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 PREFACE
Dear readers, I feel deeply indebted to all of you for such a tremendous response to earlier editions of
this book. The revised edition of this meticulously crafted book has been written based on the latest
syllabus of both engineering and medical entrance examinations.

Some major highlights of this edition are :

• Introduction of a new chapter entitled ‘Physical Properties of Organic Compounds’.

• Addition of new challenging problems in each chapter for JEE Advanced aspirants.

• Chapter on ‘Isomerism’ has been thoroughly revised for better understanding of the topic.

• Concept strengthening Matrix questions have been added to each chapter keeping in consideration
the pattern of entrance examinations.

• Sincere efforts to remove all errors.

Almost all suggestions received from learned fellow teachers, as well as, many students have been paid
due attention and incorporated to the best possible extent. I am confident and sure this book will help
students reinforce their fundamentals of Organic Chemistry.

Suggestions from readers for further improvement of the book are welcome.

Vaibhav Trivedi
Msc-IIT-R, NET
organicvaibhav@[Link]

Dedicated
to
my Parents
 CONTENTS
Chapter 1 THE LIVING WORLD 1-8

Chapter 2 NOMENCLATURE OF ORGANIC COMPOUNDS 9-18

Chapter 3 ISOMERISM 19-50

Chapter 4 REACTION MECHANISM (General Organic Chemistry) 51-150

Chapter 5 ACID & BASE 151-168

Chapter 6 HYDROCARBON (Alkane, Alkene & Alkyne) 169-202

Chapter 7 ALKYL HALIDE & GRIGNARD’S REAGENT 203-230

Chapter 8 ALCOHOL, ETHER, EPOXIDE & GRIGNARD’S REAGENT 231-264

Chapter 9 ALDEHYDE & KETONE 265-294

Chapter 10 CARBOXYLIC ACID & ITS DERIVATIVES 295-318

Chapter 11 AMINES 319-340

Chapter 12 BIOMOLECULES 341-354

Chapter 13 AROMATIC CHEMISTRY 355-394

Chapter 14 PRACTICAL ORGANIC CHEMISTRY 395-400

Chapter 15 PHYSICAL PROPERTIES OF ORGANIC COMPOUNDS 401-404

 Main Features

1. Hybridization refers to the phenomenon of mixing of two or more than two atomic orbital of same energy (or nearly same
energy) to produce two or more than two orbital of same energy, identical shape & size.
Lone pair of electron (lp) + sigma bond pair of electron (s bp) + (–ve) charge = Hybridization
for eg.
s bp = 3 lp = 1 (–ve) charge = 0
sum = 3 + 1 + 0 = i.e. sp3 (3+1= 4)

sigma bp = 3, lp = 0, –ve charge = 0

Sum = 3 + 0 + 0 = 3 (sp2)

sigma bp = 3, –ve charge = 1, lp = 0

sum = 3 + 1 + 0 = 4 (sp3)

2. ‘N’ can acquire four states.

• (When four bonds are present then ‘N’ has +ve charge)

• (When three bonds are present then lone pair of e– is present on Nitrogen)

• (When two bonds are present on ‘N’ then there is a –ve charge along with lp on ‘N’
π
For eg. H — C σ N Here N has a lp hence hybridization of ‘N’ is sp (one lp + 1bp)
π
3. The lone pair of electron in conjugation with double bond does not consider in hybridization.
and

4. A carbon attached to one (or no) carbon atom is called a primary (1º) similarly if a ‘C’ is attached to two, three & four ‘C’ atoms
it is referred as secondary (2º) ,tertiary (3º), & quaternary (4º) carbon respectively.
5. The hydrogen attached to 1º, 2º & 3º ‘C’ atoms is called 1º, 2º & 3º hydrogen respectively.
2 Problems in Organic Chemistry

6. Starting from the simplest member of the molecular formula of the compounds of a particular class arranged in an increasing
number of ‘C’ atom then a series is obtained in which the member differ from the next member by ‘CH­­­2’ group. Such a series
is called homologues series.
1
7. Mol. Wt. of homolog ∝ boiling point ∝
solubility in water

Objective Questions

(−)
1. Which type of hybridization is absent in CH 2 = C = CH − CH = CH
(a) sp2 (b) sp (c) sp3 (d) all are present

2. How many 3° H are present in

(a) 1 (b) 2 (c) 3 (d) 4

3. Sequence of hybridization in CH3—CH = CH — CN
(a) sp3, sp2, sp, sp2, sp2 (b) sp3, sp2, sp2, sp2, sp2
(c) sp , sp , sp , sp, sp
3 2 2
(d) sp3, sp2, sp2, sp, sp2

4. which statement is false?

(a) Four carbon atoms are sp2 hybridized (b) One nitrogen is sp2 & other is sp3 hybridized
(c) It contains four secondary – H – atoms (d) One nitrogen is 2º & other is 3º
5. which statement is correct for this compound?

(a) It contains two 2ºC atoms (b) It contains two 2º ‘D’ atoms
(c) It contains 81- ‘H’ atoms (d) The ‘C’ joined with Cl is sp2 hybridized

6. which is correct?

(a) It contains four sp2 hybridized C atoms (b) It contains nine sp3 hybridized C atoms
(c) It contains two 3º – H – atoms & two sp2 hybridized ‘C’ (d) It contains ten- H-atoms & two sp2 hybridized ‘C’ atoms.

7.

In which species bold ‘C’ atom is not sp2 hybridized

(a) I (b) II (c) III (d) I & III
8. In which case state of hybridization is changing.

(a) (b)

(c) (d) (a) & (c)

 The Living World 3

9. In which case state of hybridization is changing.

−H (+) (−) −H (−) (+ )
(a) 

CH3 — CH3  CH3 — CH 2 

(b) CH3 — CH3  CH3 — CH 2

− H( + ) (−) − H( + ) (–)
=
(c)
CH 2 =
CH 
2  CH 2 CH ≡ CH 
CH (d)  CH ≡ C

10. In which case state of hybridization on each atom is retained.

(+ ) (+ )
(a)
CH 2 = CH 2 + H → CH3 — CH 2 (b)


1 ( −) (+ )
CH ≡ CH + Na  → H 2 + CH ≡ C Na
liq.
(c) (d) (b) & (c)
NH3 2
11. CH3CH 2CH 2OH CH3CHO CH3CH 2OH HCHO
I II III IV

Which statement is correct?

(a) I, II, III & IV are homolog (b) I & II, III & IV are homolog
(c) B.P. of I will be lesser than III (d) Solubility of (IV) in water will be greater than II

12. which statement is correct?

(a) Two sp hybridized ‘C’ atoms & six - 2º - H atoms are present in it
(b) Two 3ºC - atoms & two sp2 hybridized ‘C’ atoms are present in it.
(c) N is sp3 & two - 2º - C atoms are present in it.
(d) Two 3º – H – atoms, Eight – 2º – H – atoms & four – sp3 – hybridized ‘C’ atoms are present in it.

13.

State of hybridization of bold element is changing as:-

3 3 3
sp3 → sp 2 → sp 2
(a) (b) sp → sp → sp
3 2 2
sp3 → sp3 → sp 2
(c) (d) sp → sp → sp

14. correct order of bond length is :

(a) x > y > z (b) y > x > z (c) z > x > y (d) y > x = z
15. is called nitrene. Hybridization on ‘N’ is :

(a) sp (b) sp2 (c) sp3 (d) None

16. Which statement is incorrect about :

(a) Oxygen gives one of its electro pair to the empty p-orbital of 2nd carbon atom
(b) Each carbon is sp2 hybridized
(c) Each carbon has one e– in unhybridized pz orbital
(d) Except 2nd C - atom each carbon has one e– in unhybridized pz orbital

17. Which type of bond is absent in benzyne?

(a) sp2 – sp2 s bond (b) sp2 – s s bond (c) sp2 – sp2 p bond (d) sp2 – p s bond
 4 Problems in Organic Chemistry

Passage - I

Enzymes present in bacteria can convert p - amino benzoic acid in to folic acid.

N
H2N N
O H
CH2CH2COOH
N
N CH2 – NH C–N–C
H
OH
C
O OH
(Folic acid)
Answer the question from 18 to 26
18. Which statement is in favour of ‘N’?
(a) All are sp2 hybridized (b) All are sp3 hybridized
(c) Four are sp2 hybridized & three are sp3 hybridized (d) Four are sp3 hybridized and three are sp2 hybridized
19. How many ‘C’ atoms are sp2 hybridized in the folic acid?
(a) 14 (b) 21 (c) 12 (d) 15
20. How many ‘C’ are sp3 hybridized?
(a) 4 (b) 3 (c) 5 (d) 6
21. How many p bonds are present in it?
(a) 11 (b) 10 (c) 6 (d) 12
22. Number of lone pair of electron possessed by nitrogen is / are :
(a) 3 (b) 5 (c) 7 (d) None
23. How many H – atoms are present in folic acid?
(a) 19 (b) 23 (c) 18 (d) 17
24. How many ‘C = O’ bonds are present in folic acid?
(a) 5 (b) 6 (c) 4 (d) 3
25. How many ‘C’ atoms (which are not the part of ring) are sp hybridized?
2

(a) 4 (b) 3 (c) 2 (d) None

26. Ratio of N — H bond to C — H bond is :
(a) 1 : 3 (b) 4 : 7 (c) 2 : 5 (d) 2 : 9

Passage - II

H2 / Ni can reduce almost all types of multiple bonds

O OH
=
CH 2 CH — C ≡ N 
H
2 → CH CH CH NH
Ni3 2 2 2
;
|| H2
CH3 — C— CH3 
|
→ CH3 — CH — CH3
Ni
While PCC can convert alcohol (RCH2OH) in to aldehyde (R – CHO)

Consider the following compound.

Answer the question from 27 to 36

The Living World 5

27. In compound A ‘N’ does not exhibit :

(a) sp hybridization (b) sp2 hybridization
(c) sp3 hybridization (d) ‘N’ exhibits sp, sp2 & sp3 hybridization
28. In (A) carbon exhibits :
(a) sp hybridization (b) sp2 hybridization (c) sp3 hybridization (d) All of these
29. In compound (C) :
(a) All ‘N’ are sp3 hybridized (b) Two nitrogen’s are sp3 hybridized and one is sp2 hybridized
(c) All nitrogen’s are sp2 hybridized (d) One nitrogen is sp3 hybridized & two are sp2 hybridized
30. In compound (C)
(a) All ‘C’ are sp3 hybridized (b) 9 ‘C’ are sp2 hybridized & two are sp3 hybridized
(c) 9 ‘C’ are sp3 hybridized & two are sp2 hybridized (d) One ‘C’ is sp hybridized while rests are sp3 hybridized
31. In compound (C) total ‘N — H’ bonds is :
(a) 2 (b) 3 (c) 4 (d) 1
32. In compound (C) ratio of N — H to C — H bonds is :
(a) 4 : 17 (b) 4 : 15 (c) 1 : 4 (d) 3 : 17
33. How many carbon atoms of (B) are sp2 hybridized which are not the part of ring?
(a) 1 (b) 2 (c) 3 (d) None
34. In compound (B) ratio of ‘C = O’ to C = C bonds are :
(a) 2 : 3 (b) 1 : 1 (c) 1 : 3 (d) 3 : 3
35. Total double bonds present in compound (B) are :
(a) 4 (b) 3 (c) 5 (d) 6
36. In compound (B)
(a) One ‘C’ is sp hybridized 5 ‘C’ are sp2 hybridized and rest ‘C’ are sp3 hybridized
(b) On ‘C’ is sp hybridized 7 ‘C’ are sp2 hybridized and rest all are sp3 hybridized
(c) One ‘C’ is sp hybridized 8 ‘C’ are sp2 hybridized and rest are sp3 hybridized
(d) One ‘C’ is sp hybridized and rest all are sp3 hybridized

Passage - III
Succinoyl sulphathiazole was used as a chemotherapeutic agent beginning in 1942. Its structure is given below.

Answer the question from 37 to 40

37. Select the correct statement for the above compound:-
(a) Both sulphur atoms are sp2 hybridized
(b) Both sulphur atoms are sp3 hybridized
(c) One sulphur atom is sp2 hybridized & other is sp3 hybridized.
(d) One sulphur is sp3 hybridized and other is sp hybridized
38. Which statement is correct about nitrogen?
(a) All N atoms are sp2 hybridized (b) All N atoms are sp3 hybridized
(c) All N atoms are sp2 hybridized. (d) One N is sp3 hybridized while rest two N atoms are sp2 hybridized
6 Problems in Organic Chemistry

39. Total p bonds present in this compound are:-

(a) 6 (b) 7 (c) 8 (d) 9
40. Which statement is true about pentagonal ring?
(a) Both sulphur and Nitrogen are sp hybridized. (b) Both sulphur and nitrogen are sp2 hybridized
(c) Sulphur is sp3 hybridized however nitrogen is sp2 hybridized (d) N is sp2 hybridized but sulphur is sp hybridized.

Answer Key

1. (c) 2. (a) 3. (c) 4. (b) 5. (c) 6. (c) 7. (a) 8. (c) 9. (b) 10. (c)
11. (d) 12. (b) 13. (c) 14. (c) 15. (c) 16. (c) 17. (d) 18. (a) 19. (d) 20. (a)
21. (a) 22. (c) 23. (a) 24. (d) 25. (b) 26. (a) 27. (c) 28. (d) 29. (a) 30. (a)
31. (c) 32. (a) 33. (b) 34. (b) 35. (c) 36. (b) 37. (c) 38. (a) 39. (b) 40. (b)

SOLUTION
1. (c) CH2 = C = CH – CH = CH(–)
↑ ↑ ↑ ↑ ↑­ ­
sp2 sp sp2 sp2 sp2

2. (a)

3. (c)

4. (b)

Each ‘C’ atom present in ring is sp2 hybridized. Nitrogen containing positive charge is tertiary while other nitrogen is
secondary.

5. (c)

Each ‘C’ atom is sp3 hybridized

6. (c) Carbon of CO group is sp2 hybridized rest all carbon atoms are sp3 hybridized

The Living World 7

7. (a) Here negatively charged carbon is sp hybridized.

8. (c) Nitrogen in CH3CH2CN is sp hybridized while it is sp2 hybridized in
9. (b) Carbon is sp3 hybridized in ethane while it is sp2 hybridized in CH3CH2(+)

10. (c)

11. (d) Homolog should have same functional groups.
Boiling points of homolog ∝ Molecular weight
Solubility of homolog in water ∝ 1 / molecular weight

12. (b)

Except double bonded carbon atoms rest all ‘C’ are sp3 hybridized. Double bonded carbon atoms are sp2 hybridized.

13. (c)

14. (c) Hybridization % s character

sp3 25
sp2 33.33
sp 50
% s character ∝ electronegativity ∝ 1 / Bond length

Bond length of y will be lesser than z & x because due to resonance this bond will acquire partial double bond character.

15. (c) 16. (c)

Empty 'p' orbital

2 H
17. (d) sp — sigma bond
H
sp2—sp2π bond
H
H
sp2 — sp 2 sigma bond
8 Problems in Organic Chemistry

Passage – I

sp2 sp2
sp2 O
O H
NH2 sp2 CH2—CH—C—OH
N N 2
C—N—C
N CH—NH
2 H
N sp2 C—OH
sp2 OH
sp2 O

> All Carbon atoms present in ring are sp2 hybridized.

> All Carbon atoms of C = O bond are sp2 hybridized
> Rest all carbon atoms are sp3 hybridized
> Total N – H bonds = 4 , Total C– H bonds = 12
> Each N atom possesses lone pair of electrons.

Passage – II

sp3
OH H
CH—C CH2NH2 (C)

N N CH2OH
3 3

sp H H sp
sp2
sp3 sp2 O H sp

C—C CN (A)
2
sp
N N sp2 CH2OH sp
sp2 sp2
H
> In compound C total numbers of N — H and C — H bonds are 4 and 17 respectively.
> In compound B
Total number of C = O bonds = 2

Passage – III

sp2
O O sp2 sp2
HO —C—CH—CH
2 2—CHN
O
N
sp2 sp3 sp2 sp2 S—NH sp3
sp2 O S sp3
sp2 2
sp2 3
sp sp
sp 2
 Subjective Questions

(A) Write the I.U.P.A.C names of following figures.

(1) (2)

(3) (4)

(5) (6)

(7) O (8)

OH
OH OH OH

(9) (10)

(B) Draw the structures of the following.

1. 1, 3 – Dicyclobutyl propane 2. 4– tert- butyl phenol
3. Cyclo butyl pentane 4. N- methyl butanamide
5. Cyclo hexan -1 D, 2 D – diol 6. 7, 7 – Dimetyl bicyclo (2, 2, 1) heptane
7. 4, 7 – Epoxy- 4 hydroxy decanoic acid 8. 3– chloro – 4 hydroxy pentanoic anhydride
9. 4 – Ethyl – 6 nitro oct – 5 en – 3 - one 10. Bicyclo (2 ,1 0) pentane
10 Problems in Organic Chemistry

11. 3 – Bromo cyclo hexane carbaldehyde 12. 2 – Aza cyclo pentanone.

13. Cyclo butane methanoyl chloride 14. 3 – (4-nitro phenyl) cyclo hexane carboxylic acid.
15. 2 – Hydroxy ethanoic -3- bromo propanoic anhydride. 16. (2, 9), (4,7) – Di epoxy decan – 1, 10 – dioic acid.
17. 1,3.5 trimethylene cyclohexane. 18. Bis (2, 3 - trichloro methyl) cyclo hexane carbaldehyde.
19. 2, 3 – Di carboxy cyclo pentanone. 20. Spiro (3, 4) octane.
(C) Write the I.U.P.A.C. names of the following

(1) (2)

(3) (4)

(5) (CH3)3C(CH2)4COOH (6) CH3CH2CH(p – Cl – C6H4) CHBrCH2CH3

CH 2 — CH — CH—CH2COCl
(7) H3 CC[(p – Br – C6H4)]2COOH (8) | | |
COCl COCl COCl

(9) (10)

(11) (12)

(13) (14) O
N

CH3

(15) (16) CH3 – O – CH2 – CH2 – CH2OH

(17) (18)

(19) CH3 — CH OH CH Cl CO O CO CH OH CH3 (20) H — CO NCl2

(21) HCOOCHCHOHCH3 (22)

Nomenclature of Organic Compounds 11

(23) (24)

(25) —— H

(26) CH3— CO — CH = CH — C — CH — CH = CH — CONH2

O OH

(27) CH3 — CH = C H — — (CH = CH)2 — COOH (28) (CH2 = CH)4C

(29) (30)

Multiple Choice Questions

1. I.U.P.A.C. name of this compound is:-

(a) Decanoic anhydride (b) 2, 9 Epoxy decan 1, 10 dioic acid

(c) 2, 9 Di carboxy oxa cyclo nonane (d) 2, 3 Di Carboxy -2-oxa cyclo nonane

2. I.U.P.A.C name of this compound.

(a) N, N – Di methyl – 3 – chloro butanamide (b) 4 – Chloro – N, N – di methyl pentan – 2 – one

(c) 3 – Chloro – N, N – di methyl butanamide (d) 2 – Chloro – 4 – di methyl amino butanone
3. Which alphabet has I.U.P.A.C name similar to the alphabet K?
(a) W (b) X (c) Y (d) Z
4. Me2CCl CH2 CH = CH – CH = CH – COOH I.U.P.A.C name of this is:-
(a) 7-Chloro-7-methyloctan -2,4-dienoic acid. (b) 7-Chloro-7,7-dimethyl-2,-3-heptadienoic acid.
(c) 2-Chloro-2-methyl-4,5-octadiene-7-oic acid. (d) 7-Chloro-7-methyl oct-2-3-dien-1-oic acid.

5. I.U.P.A.C. name of this compound is:-

(a) Oxa – cyclo – 3 hexanone (b) Oxa – cyclo – 3 – pentanone

(c) 3 – Oxa cyclo hexanone (d) 3 – Oxa cyclo pentanone

6. I.U.P.A.C. name of is:

(a) 1, 2, 3 Trimethyl bicyclo(2, 1, 0) Pentane (b) 1, 2, 5 Trimethyl bicyclo(2, 1, 0) Pentane

(c) 1, 2, 5 Trimethyl bicyclo(2, 1, 1) Pentane (d) 1, 2, 3 Trimethyl bicyclo(2, 1, 1) Pentane
12 Problems in Organic Chemistry

7. The structure of 11’, 31’ 1” Tercyclobutane is:-

(a) (b)

(c) (d)

8. I.U.P.A.C name of it is:-

(a) 2 - Carboxy ethyl but - 3 - en -1 - oate (b) 3 – Ethoxy Carbonyl -but -3- enoic acid
(c) 3 - Ethoxy carbonyl - buten - 4 - oic acid (d) None

9. I.U.P.A.C name of

(a) Hex - 5 - ene - 1 - yne (b) Hex -1 -yne - 5 - ene

(c) Hex – 1-en -5 yne (d) Hex - 5 yne -1 - ene

10. I.U.P.A.C name of this compound

(a) 2 – Chloro – 5 – bromo - hexane. (b) 5 – Bromo – 2 – chloro hexane

(c) 2 – Bromo – 5 – chloro hexane (d) 5 – Chloro – 2 – chloro hexane
O
11. I.U.P.A.C. name of
O O
(a) Propanoic anhydride. (b) Butanoic propanoic anhydride.
(c) Propanoic butanoic anhydride. (d) 4 – Oxa octan –3, 5 – dione

12. I.U.P.A.C. name of

(a) Methyl -chloro butanoate (b) 1 – Chloro pentyl ethanoate

(c) 4 – methyl butanoate. (d) Methyl -2 – chloro butanoate.
13. Suggesst the I.U.P.A.C name of CH3 – CHClCON Cl Br
(a) 2,N-Di chloro - N- bromo propanamine. (b) 2-Chloro-N - Bromo -N - chloro propanamide.
(c) N -Bromo – 2,N- di chloro propanamine (d) N -Bromo –N- chloro 2- chloro propanamine

14. I.U.P.A.C name of I

Br
(a) 4-Bromo-3-iodo cyclohexa-1,3-diene (b) 1- Bromo-2-iodo cyclohexa-1,3-diene
(c) 1- Bromo-2-iodo-1,3-cyclohexadiene (d) (b) & (c) both are correct

15. I.U.P.A.C. name of it is:-

(a) 6-(2-Chloro cyclo hexane)-5-chloro hexane (b) 5-Chloro-6-(2-chloro cyclo hexyl) hexane
(c) 3-Chloro-1-(2-chloro cyclo hexyl) hexane (d) 2-Chloro-1-(2-chloro cyclo hexyl) hexane
Nomenclature of Organic Compounds 13

16. I.U.P.A.C name of

(a) 1 – Bromo propan – 1, 2 – di one (b) 3 – Bromo propan – 2, 3 – di one
(c) 2 – Oxo – 3 – propanoyl bromide (d) 2 – Oxo propanoyl bromide

17. I.U.P.A.C. name of

(a) 2, N- Di chloro butanamide (b) N,2-Di chloro butanamide

(c) 2-Chloro-N-chloro butanamide (d) N-Chloro-2-chloro butanamide

18. I.U.P.A.C name of CH3—CH—C—CH—COOH

| || |
OH O CONH2
(a) 2-Carboxy hydroxy 3-oxo pentanamide (b) 4-Carobamoyl-2-hydroxyl-3-oxo pentanoic acid
(c) 2-Amide-4-hydroxy -3-oxopentanoic acid (d) 2-Carbamoyl-4-hydroxyl-3-oxo pentanoic acid

19. I.U.P.A.C. name of it is:-

(a) 2-Oxo cyclo pentane carboxylic acid (b) 1-Oxo cyclo pentan-2-carboxylic acid.
(c) 1-Carboxy-2-cyclo pentanone. (d) None

20. I.U.P.A.C. name of is:-

(a) Bicyclo (7,3,3) nonane (b) Bicyclo (7,1,1) nonane

(c) Bicyclo (7,5,1) nonane (d) Bicyclo (5,1,1) nonane

21. I.U.P.A.C name of

(a) Cyclo hexanone (b) Cyclo hexyl methanone

(c) Oxy cyclo hexane (d) Cyclo hexylidene methanone
22. Which is not the name of CH3OH?
Methanol Methyl alcohol Carbinol Wood alcohol
(I) (II) (III) (IV)
(a) III & IV (b) III
(c) IV (d) I, II, III & IV all are correct

23. CH2 — CH = CH2 I.U.P.A.C. name of this is:-

(a) allyl cyclo butane (b) Propenyl cyclobutane

(c) 2 – Propenyl cyclobutane (d) 3-Cyclo butyl propene

24. I.U.P.A.C. name of

(a) Chloro – di methoxy methane (b) Dimethoxy chloro methane

(c) Methoxy chloro ethoxy methane (d) Chloro – methoxy, methoxy methane
14 Problems in Organic Chemistry

25. Probable structure for the compound 2 – Bromo ethyl – 2 – chloro propanoate is:-

(a) (b)

O CH2Br
(c) (d)
Cl
O

26. Probable structure of the compound 3 – Chloro penta - 2, 4 – dienoic anhydride is:-
(a) (CH2 = CH — = CHCO)2O (b) (CH2 = — CH = CHCO)2O

(c) CH2 = CH — CH = CH COO CO CH = — CH = CH2 (d) (a) & (c) both are correct
27. The I.U.P.A.C name of compound CH3CH2—CH—CH—CHO is :-
|| |
O CN
(a) 2 – Cyano – 3 – oxo – pentanal (b) 2 – Formyl - 3 – oxo pentane nitrile
(c) 2 – Cyano – 1, 3, pentandione. (d) 1, 3 – Di oxo – 2 – cyano pentane

28. CH3CO CH (CH3CO) COOCH3 has I.U.P.A.C name:-

(a) Methyl – 2, 2 di acetyl ethanoate (b) 2, 2 acetyl – 1 – methoxy ethanone
(c) Methyl – 2 – acetyl – 3 – oxo butanoate (d) None

Bu
|
29. I.U.P.A.C name of Pr—C—Ac
|
Et
(a) 3 – Ethyl – 3 – propyl 2 – heptanone (b) 3 – Acetyl – 3 – propyl heptanone
(c) 4 – Acetyl – 4 – ethyl nonane (d) None
30. Structure of Spiro (3, 4) octane is:-

(a) (b) (c) (d)

31. I.U.P.A.C. name of this compound is:-

(a) 1, 4, 7, 10 – Tetraoxa dodecane (b) 1, 4, 7, 10 – Tetraoxa cyclodecane

(c) 12 – crown – 4 (d) 4 – crown - 12

32. I.U.P.A.C. name of this compound is:-

(a) 2 – cyano – 4 – chloro formyl nitrobenzene (b) 4 – chloroformyl – 2 – cyano nitrobenzene

(c) 3 – cyano – 4 – nitro benzoyl chloride (d) 3 – chloro formyl – 2 – nitro benzo nitrite
Nomenclature of Organic Compounds 15

33. Which is not correctly matched?

(Compound) (IUPAC name)

(a) 2 – cyclobutyl pentane

(b) Ethane

(c) 2 – (1 – methyl butyl) cyclo butanol

OH
(d) Phenol

34. I.U.P.A.C name of H2N — N CO2H

(a) 4-Hydrazono cyclo hexanoic acid (b) 4 – Hydrazono benzoic acid

(c) 4-Hydrazono cyclo hexane-1-carboxylic acid (d) none of these
35. Which of the following groups is always taken as a substituent in the I.U.P.A.C nomenclature?
(a) — NH2 (b) — CHO (c) — NO2 (d) — CN
36. Which prefix is not suitable for –CH=CH–CH3 ?
(a) allyl (b) Propenyl (c) 2 – propenyl (d) (a) & (c)

37. I.U.P.A.C name of

(a) 2,2/-Di carbaldehyde-6,6/-di nitro bi phenyl (b) Di nitro biphenyl di carbaldehyde

(c) 6,6/-Di nitro bi phenyl-2,2/-di carbaldehyde (d) None

38. The compound

(a) 1, 2 – Bicyclo (2, 2, 2) hexandiol (b) Bicyclo (2, 2, 2) hexan 1, 2 diol

(c) Bicyclo(2, 2, 2)hexan – 2, 3 – diol (d) Bicyclo(2, 2, 2) – 5, 6 – hexandiol
39. The compound 2 – cyano penta 2 – 4 – dienal contains.
(a) 4p bonds (b) 3p bonds (c) 5p bonds (d) 6p bonds

40. I.U.P.A.C name of

(a) 2 – oxo – 5 ethoxy carbonyl cyclohexane carboxylic acid (b) 5 – Ethoxy carbonyl – 2- keto cyclohexane carboxylic acid
(c) Ethyl – 2- carboxy – 3 – oxo – cyclohexyl methanoate (d) 3 – Ethoxy carbonyl – 2- carboxy cyclo hexanone
16 Problems in Organic Chemistry

41. Cinnamic acid can be identified as:-

(a) Phenyl butenoic acid (b) 3 – Phenyl prop – 2 – en -1 – oic acid
(c) 2 – Phenyl -2 – Propenoic acid (d) 3 – Phenyl propanoic acid
42. I.U.P.A.C name of crotonaldehyde is:-
(a) Butanal (b) Butynal (c) But – 2 – enal (d) 2 – Butynal

43. I.U.P.A.C name of

(a) 2 – Chloro spiro ( 2, 5) octane (b) 2 – Chloro spiro (5, 2) octane

(c) 1 – Chloro spiro (2, 5) octane (d) 1 – Chloro spiro (5, 2) octane

44. The compound can be named as:-

(a) 1 – Oxo – 2 – carbethoxy cyclo pentan (b) 2 – Methoxy carbonyl cyclo pentanone
(c) 2 – Methoxy carbonyl cyclo pentanone (d) None
45. HCOOCHBrCH2Cl can be named as:-
(a) 1– Bromo – 2 – chloro propanoic acid (b) 2 – Bromo – 3 – chloro propanoic acid
(c) 1 – Bromo – 2 chloro ethyl methanoate (d) 1 – Bromo – 2 chloro ethyl ethanoate

46. Can be named as:-

(a) Hept–6–en–2, 4–diyne (b) Hepta – 3, 5 – dien–1– yne
(c) Hepta–2, 4 diyn–6–ene (d) Hept–1–en–3, 5–diyne

47. can be named as:-

(a) Butyl cyclo hexane (b) Pentyl cyclo hexane (c) Cyclohexyl butane (d) Cyclohexyl pentane

48. can be named as:-

(a) Cyclohexyl heptane (b) Heptyl cyclohexane (c) Cyclohexyl octane (d) Octyl cyclohexane

49. can be named as:-

(a) 4 – Cyclohexyl butanoic acid (b) 3 – Cyclohexyl propanoic acid

(c) Carboxy ethyl cyclohexane (d) Carboxy propyl cyclo hexane

50. can be named as:-

(a) 2-hydroxy butyl pentane (b) 2-hydroxy butyl hexane

(c) 2-butyl cyclobutanol (d) 2-pentyl cyclobutanol
Nomenclature of Organic Compounds 17

Answer Sheet

1. (b) 2. (c) 3. (b) 4. (a) 5. (c) 6. (b) 7. (c) 8. (b) 9. (c) 10. (c)
11. (b) 12. (b) 13. (b) 14. (b) 15. (d) 16. (d) 17. (c) 18. (d) 19. (d) 20. (d)
21. (d) 22. (d) 23. (d) 24. (a) 25. (d) 26. (a) 27. (b) 28. (c) 29. (a) 30. (d)
31. (c) 32. (c) 33. (b) 34. (c) 35. (c) 36. (d) 37. (c) 38. (c) 39. (c) 40. (d)
41. (b) 42. (c) 43. (d) 44. (c) 45. (c) 46. (d) 47. (a) 48. (a) 49. (b) 50. (d)

SOLUTIONS
(A) Write the I.U.P.A.C names of following structures
(1) 2-Cyclo butyl-5-cyclopropyl nonane (2) 7, 8-Di cyclo butyl cyclododecan-1,2-dione
(3) 1-Cyclobutyl-3-[1,1-di methyl ethyl]cyclotetradecane (4) 2, 5 Dicyclobutyl 1-methyl bicyclo (2,1,0) pentane
(5) 8, 9 Dicyclobutyl- 4, 13-di methyl hexadecane (6) 2,3-Di methyl bicyclo (2,2,0)hexane
(7) 7, 14-epoxy cyclotrideca –8, 12-dien-1, 2, 4, 6 - tetraol (8) 3, 3-Di (2-hydroxy ethyl) pentan - 1, 5-diol
(9) spiro (3, 5) nonan - 1, 3 - di thiol (10) 2, 4 Difluoro - 2, 4 di methoxy pentane
(B) Draw structures of following

(1) (2) (3)

(4) CH3(CH2)2CONHCH3 (5) (6)

(7) (8) (CH3CHOHCHClCH2CO)2O (9)

(10) (11) (12)

(13) (14) (15) HO-CH2COOCOCH2CH2Br

(16) (17) (18)

(19) (20)
18 Problems in Organic Chemistry

(C) Write the I.U.P.A.C. names of the following

(1) (3, 6), (4, 5)-Di epoxy octan-1, 8-di carboxylic acid (2) 2, 3, 5-Trimethyl bicyclo (2, 1, 0) pentane
(3) 2-[4-cyano phenyl] cyclohexanone (4) N-Ethyl N-propyl butanamine
(5) 6,6-Dimethyl heptanoic acid (6) 3-Bromo-2-(4-chloro phenyl) heptane
(7) 2, 2-di – [4-bromo phenyl] propanoic acid (8) Butan-1, 2, 3, 4-tetra carbonyl chloride
(9) 3-cyclopropyl buta-1, 3-dien-1, 4-di carboxylic acid (10) 11’, 2’1’’, 2’’1’’’-Quarter cyclopropane
(11) 2-Chloroformyl-3-methyl butanoic acid (12) 2-Aza cyclohexanone
(13) Thia – cyclohexan-2-ol (14) N-methyl aza-cyclohexanone
(15) 1-aza-4-oxa cyclohexane (16) 3-Methoxy propanol
(17) 1-[1-methyl ethyl]-3-cyclopropyl cyclohexane (18) 3, 3-Di (4-hydroxy phenyl methyl) but-3-en-1-oic acid
(19) 2-Chloro-3-hydroxy butanoic-2-hydroxy propanoic anhydride
(20) N, N-Di chloro methanamide (21) 2-hydroxy propyl methanoate
(22) Propane-1, 2, 3-tri nitrile (23) 12-crown-4
(24) Hexa-1, 3, 5-triyne (25) Methane
(26) 4-Hydroxy-5, 8-di oxo-nona-2, 6-dien-1-amide (27) 6-bromo-nona-2, 4, 7-trien-1-oic acid
(28) 3, 3-Di ethylene penta-1, 4-diene (29) 1, 2-Dicyclobutyl ethane
(30) 1-methyl butyl cyclo hexane
 Main Features

1. If two compounds have same molecular formula but different structural formulae or physical or chemical properties then they
are called isomers and the phenomenon of their existence is called isomerism. Isomerism is of two types (i) Structural isomerism
(ii) Stereo isomerism
2. Structural isomerism: In it the two isomers have different arrangement of atoms with in the molecule. Structural isomerism
is of the following types
Chain isomerism (or skeleton isomerism) These isomers have same positions of multiple bond & functional group but differ
from one another in the length of parent ‘C’ chain
CH3 — CH2 — CH2 — CH2 — OH

n – Butyl alcohol (4C) Isobutyl alcohol (3C)

Position isomerism: These isomers have same length of ‘C’ chain but differ from one another in the position of multiple bonds,
branch or functional group.
CH2 CH — CH2 — CH2 — CH3 and CH3 — CH CH — CH2 — CH3

3. Functional isomerism: These isomers have different functional groups i.e. isomers belong to different homologues series.
> CH3CH2CHO & CH3COCH3 & CH2 = CH — CH2OH
(Aldehyde) (Ketone) (Alcohol)
> CH3CH2CN & CH3CH2NC CH3CH2OH & CH3OCH3
> CH3COOH & HCOOCH3
> Ring chain isomerism is also an example of functional isomerism. For example n-butene & cylobutane, butyne & cyclo butene
Metamerism: It is due to the difference in the nature of alkyl groups attached to the same functional group.
CH3 — O — CH2CH2CH3 & CH3CH2OCH2CH3
Methyl propyl ether Di ethyl ether
Tautomerism: This type of isomerism has two functional isomers present in dynamic equilibrium.

% enol content ∝ 1/ Temperature ∝ conjugation ∝ H – bonding ∝ aromatic character

% enol content in decreasing order is as follows.
20 Problems in Organic Chemistry

> PhCOCH2COCH3 > MeCOCH2COMe > MeCOCH2COOC2H5 > MeCOCH2COO Et > MeCOCH2COOMe
> MeCOCH3
4. Stereo isomerism: When isomers have the same structural formula but differ in relative arrangement of atoms or groups in
space within the molecule, these are known as stereoisomer and phenomenon of their existence is called stereoisomerism. Ste-
reoisomerism is of two types.
(a) Geometrical isomerism: Here the isomers differ in spatial arrangements of atoms or groups around the double bonded
carbon atoms.

> Calculation of geometrical isomers:

Alkene R1(CH = CH)n R2 Geometrical isomers
(1) When n = 1 or R1 = R2 2n
n 
–1
n –1  2 
(2) When R1 = R2, n = even 2 +2
( n + 1)
–1
(3) When R1 = R2, n = odd 2n – 1 + 2 2
> Geometrical isomers possess different physical properties. Their chemical properties are similar but not identical.
> Due to good packing of trans isomers, it has higher melting point than cis isomer
Optical Isomerism (Enantiomerism):
(b)
> The isomer which does not rotate the plane of ppl is called optically inactive and which rotates the plane of ppl is
called optically active. The isomer which rotate the ppl towards left is known as laevo (l) while which rotates the ppl
to right is known as dextro (d).d & l isomers are non super imposable mirror images of each other & are known as
enantiomers The optical isomers which do not have mirror image relationship are called diastereomers
> Equimolar mixture of d & l isomers of a same compound is called dl or (+) or racemic mixture.
> Calculation of optical isomers:
(i) Compounds which have unsymmetrical molecule with one or more chiral centres. In such compounds if n is the
number of chiral carbons, then
Optically active forms = 2n, Enantiomeric pair = 2n / 2
Optically inactive form = 0
1 n –1
(ii) If it is symmetrical & n = even then optically active forms = 2n–1 enantiomeric pair = (2 )
2
n –1
Optically inactive forms = 2 2
(iii) If is symmetrical & n = odd then
n –1
Optically active forms = 2n – 1 – 2 2 = a (say)

n –1
Enantiomeric pair = a/2, Optically inactive form =
2 2
LEVEL – I

Subjective Questions
1. Draw the Fischer projections of the following.

(a) (b) (c)

Isomerism 21

(d) (e) (f)

CH3
D OH
(g) (h)
H CO (i)
H
NH NH2

( j)

2. In [Link].1 which is / are meso forms?

3. Assign the names R or S to the following.

(a) (b) (c)

Cl

(d) (e) (f)

O

O
CH2I

(g) (h) (i)

Cl

(j)
H CH2OD (k) (l)

(m) (n) (o)

22 Problems in Organic Chemistry

4. Assign the names E & Z to the following.

(a) (b) (c)

Cl—CH2 CH2CCl3
C
(d) (e) CH2COCH3 (f)
C
NHCOCH Br CH3
3

HOH2C CH2CN
(g) (h) C C (i)
OHC CH2CH2NH2
HOH2C CH2CN
( j) C C
OHC CH2CH2NH2

Multiple Choice Questions

1. Which among the following can show both the stereoisomerisms i.e. optical & geometrical?

(a) (b) (c) (d)

2. What is the relation between the following three structures?

(a) 1 & 2 are enantiomers (b) 2 & 3 are enantiomers

(c) 2 & 3 are structural isomers (d) 1 & 2 are homomers

3. I.U.P.A.C name of

(a) 2 – Chloro cyclohexan-1-ol (b) 1 D-Chloro cyclohexane-2D-ol

(c) 1-Chloro cyclohexane-2-ol (d) 2D-Chloro cyclohexan-1L-ol
4. D – form of the compound PhCHOHCH3 can be written as:-

(a) (b) (c) (d)

Isomerism 23

5. Optical rotation of the following isomer is + 36°

Which isomer will have the optical rotation equal to-36°?

(a) (b) (c) (d)

6. Consider the following compounds:-

(1) CH3NO2 (2) (3) (4)

The compounds which can also exist in its enol form is / are:-
(a) 1 (b) none (c) all (d) 1 & 3

7. How many geometrical isomers are possible for CH3 (CH = CH)3 CH3
(a) 4 (b) 5 (c) 6 (d) 8

8. How may geometrical isomers are possible for CH3(CH = CH)3C2H5

(a) 4 (b) 5 (c) 6 (d) 8

9. An optically active compound is placed in a polarimeter tube of length 5 dm & rotates ppl by 60°. If 40 gm compound is
present in 200 ml of solution then calculate specific rotation & angle of rotation of optically active compound if above solution
is diluted up to 2 lit.
(a) 60° and 12° (b) 60° and 6° (c) 30° and 12° (d) 30° and 6°

10. In which isomer plane of symmetry is present

Br

Cl H

H
(a) (b) (c) (d) OH OH

H Cl

H H
COBr

COCH3
11. F This is:-
Br

(a) R, Z (b) S, Z (c) S, E (d) R, E

24 Problems in Organic Chemistry

12. The structures shown below can be related as:

(a) Position isomers (b) Diastereomers (c) Enantiomers (d) Homomers

13. Identify the meso isomer

(a) (b) (c) (d)

14. and are:-

(a) Chain isomers (b) Positional isomers (c) Functional isomers (d) All of these
15. Which is highly stable?

(a) (b) (c) (d)

16. The number of cis–trans isomers possible for the following compound are:

(a) 8 (b) 4 (c) 2 (d) 16

17.

(a) I & II are diastereomers (b) I & III are diastereomers

(c) I, II & III, I are enantiomers (d) II & III are enantiomers
Isomerism 25

18. If (+)-2-chloro butane had specific rotation 10.6° when pure. The amount of (–) – 2 – chloro butane in the mixture of (+) &
(–)-2-chloro butane which has rotation of 7.2° would be.
(a) 49.66% (b) 50% (c) 18.5% (d) 83.9%
19. Which is optically active?

(a) (b) (c) (d)

20. Identify the species which is optically active.

(a) (b) (c) (d) NH2Cl

21. Which among the following compound has (L) configuration?

CHO
HO H
(a) (b) (c) (d)
H OH
CH2OH

22. The specific rotation of pure enantiomer is +36°. Its observed rotation if it is isolated form a reaction with 75% racemisation &
25% retention.
(a) +36° (b) +9° (c) +27° (d) Zero

23. AcCH2COOEt, AcCH2CO2Me, PhCOCH2Ac

(I) (II) (III) (IV)

Decreasing order of % enol content in the given compounds is:-
(a) I > II > III > IV (b) I > III > II > IV (c) I > IV > II > III (d) I > II > IV > III
24. How many steroisomers are possible for the following?

(a) 8 (b) 6 (c) 2 (d) 4

25. Total number of cyclic structural as well as stereo isomers possible for a compound with the formula C5H10 is:
(a) 5 (b) 7 (c) 10 (d) 6
26. Arrange the following compounds in decreasing order of heat of hydrogenation.

(I) (II) (III) (IV)

(a) I > II > III > IV (b) IV > III > II > I (c) IV > I > III > II (d) IV > III > I > II
26 Problems in Organic Chemistry

27. If stereochemistry about the double bond in the compound shown below is cis, the number of enantiomers possible for this
compound would be:
CH2BrCH – CH = CH CHBr – CH3
(a) 2 (b) 4 (c) 6 (d) 8

28. The structures given below are and

(a) Enantiomers (b) Conformational enantiomers (c) Rotamers (d) Geometrical isomers
29. How many optically active isomers are possible for CH3(CHCl)3CH3
(a) 2 (b) 3 (c) 8 (d) 6
30. How many meso forms are possible for CH3(CHCl)4C2H5
(a) 2 (b) 3 (c) 1 (d) Zero
31. Which statement is wrong for the given compound?

(a) I.U.P.A.C. name of it is 5-Bromo-hex-3-en-2-one (b) It has (S) configuration

(c) It has Z configuration (d) All are correct
32. In which solvent % enol content of CH3 CO CH2 COCH3 will be least:
(a) Benzene (b) H2O (c) D2O (d) Hexane

Passage - 1

Multiple bonds do not possess free rotation. The isomerism generated due to restricted rotation is called geometrical isomerism.
The isomer in which similar groups are on the same side of multiple bonds is called cis & isomer in which similar groups are on
the opposite side of double bond is called Trans isomer. In case of C = N & N = N Multiple bond the designation cis & Trans are
replaced by Syn & Anti respectively.
Answer the questions from 33 to 37
33. Which is Syn ethyl phenyl ketone oxime?
CH3CH2 OH
C
(a) (b) (c) (d)
N
Ph

34. Which does not contain centre of symmetry?

(a) (b) (c) (d) (b) and (c)

Isomerism 27

35. Which will not exhibit geometrical isomerism?

CH3
(a) C CHCH3 (b) (c) Ph2N2 (d)
Et
36. Which is cis isomer?

(a) (b)

(c) (d) All of these

37. Which is more stable:-

Cl
(a)
Cl Cl (b)

Cl
Cl Cl

(c) (d)

Cl
Cl

Passage II

Some times isomer does not contain chiral carbon atom but it shows optical isomerism. It is due to the presence of chiral plane.
Biphenyls and cumulenes exhibit this type of optical isomerism. Cumulenes are those unsaturated hydrocarbons which contains
consecutive double bonds.
If cumulene contains odd no. of double bond it is always optically inactive and in case of even number of double bonds it shows
optical isomerism only when it is asymmetrically substituted.
Answer the questions from 38 to 40.
38. Which is optically active:-

(a) CH3CHClCH3 (b)

(c) (d)
28 Problems in Organic Chemistry

39. Which is resolvable?

(a) (P — CH3C6H4) CH = C = CHCH3 (b) CHCl = C = CH2

(c) (d) Threo tartaric acid

40. Which does not contain plane of symmetry:-

(a) (b)

(c) (d)

Passage III

Configuration is that representation of a molecule in which relative positions of atoms or groups of atoms are shown. Configuration
does not change on rotation but changes only when bond breaks & forms in new direction. If two exchanges are made in an isomer
then configuration of isomer does not change(Retention).
Answer the questions from 41 to 43.
CH3 D OH

41. (I) (II) (III) H H

CO (IV)
NH2
NH

Which statement is correct?

(a) I & II are same (b) I & IV are same
(c) II & III are same (d) III & I are same

42. The configuration of is similar to:-

Cl
Cl Cl Cl

Cl
(a) (b) (c) (d)
Cl
Cl
Cl

43. Which statement is false for isomers?

(a) They have same molecular formulae (b) They have same vapour density
(c) They have same empirical formulae (d) All are correct
Isomerism 29

44. Which pair of isomerism is not possible together?

(a) Functional and position (b) Ring chain & functional
(c) Metamerism & functional (d) Chain & functional
45. Decreasing order of % enol content of the following compounds would be:

(1) (2) (3) (4)

(a) 2 > 3 > 4 > 1 (b) 2 > 1 > 3 > 4 (c) 4 > 1 > 3 > 2 (d) 2 > 1 > 4 > 3
46. Which is not erythro?

(a) Meso tartaric acid (b) (c) (d)

Ph
H Me
∆
47. HO2C CO2H  → A & B. Which of the following statement is true?
H Me
Ph
(a) A & B are structural isomers. (b) A & B are enantiomers
(c) A & B are geometrical isomers (d) A & B are diastereomers

48. aq
¾¾¾ ® +
NaOH

This reaction is leading to % racemisation

(a) 40% (b) 60% (c) 80% (d) 20%

49. (1) (2) (3) CH3CH2CH2COONa (4)

Resolvable compound is / are:-

(a) Only 2 (b) 1, 2 & 3 (c) Only 4 (d) 2 & 4
50. Largest % enol content will be found in:-
O

O
(a) (b) (c) (d)
30 Problems in Organic Chemistry

51. The wrong statement concerning the structure A, B & C is:

O
Et Ph Ph

Ph Et OH CH3 OCH3

(a) (b) (c)

(a) A & C are functional isomers (b) B & C can show geometrical isomerism
(c) A & B are tautomers (d) Degree of unsaturations of A, B & C are not same

52. The priority sequence for the group CH3 , C14 H3 , D & H will be in the order
(1) (2) (3) (4)

(a) 3 > 2 > 1 > 4 (b) 3 > 4 > 1 > 2 (c) 2 > 3 > 1 > 4 (d) 2 > 1 > 3 > 4
53. Alternating axis of symmetry is not present in:
D
Cl
Cl NO2
CH3 H

(a)   (b)  H H (c) D (d)

F Br
CH3
Cl Cl
H

H
54. Maximum number of atoms present in one plane of the following isomers is:

H H
C=C=C=C
HS D

(a) 8 (b) 6 (c) 9 (d) 4

55. Optical isomerism will not be exhibited by:

O O
Br Br
(a) (b) (c) P (d) P
OMe OMe
D OMe Me

56. Which pair does not represent metamerism?

Me
Cl HO Me
(a) Ph—OCO & Ph—COO (b) &
Cl
OH

(c) CH3CH2NH2 & CH3NHCH3 (d) &

57. How many structural isomers are found to be optically active obtained by the mono chlorination of methyl cyclo butane:
(a) 1 (b) 2 (c) 3 (d) 4
58. Which will have least stable enol form?
O O O
O O

(a) O (b) (c)

NO2 NO2 (d)
I I
Isomerism 31

1
H

4
59. H O Which H will involve in keto - enol tautomerism?
H
O 3
H
2
(a) Only 1 (b) 2 & 4 (c) Both (d) none

Cl CMe2CMe2H
HO
60. C C C C
F CH3 CH2CH2CH3
ClO
Configurations of these two compounds are:-
(a) Z, Z (b) E, E (c) Z, E (d) E, Z
61. How many optically active isomers are possible for 1,3,5-tri methyl cyclohexane.
(a) 2 (b) 4 (c) 6 (d) none

NHCOMe O
OH
O
62. Configuration of and are:-
H
Br
(a) RR (b) RS (c) SS (d) SR
63. Which will show enantiomerism?

Me Me Me Br Me
(a)
O NH (b) (c) (d)

Br

64. If in an organic compound two COOH groups are present on same C atom then such a compound looses one molecule of carbon
dioxide on heating.
HOOC
3
NMe2 Heating
¾¾¾¾ ®X
HOOC 1 2
COOH
In compound X configuration of C1 is:-
(a) R (b) S
(c) may be R or S (d) R & S names can not be assigned
65. The most stable form of 2 – nitro ethanol is:-

H NO2 NO2 H
H NO2 H H H OH H NO2
(a) (b) (c) (d)
H H H H H H H H
OH OH H OH
32 Problems in Organic Chemistry

66. The most stable form of 1, 2 – Di nitro ethane is:-

H NO2 NO2 H
H NO2 H NO2 H H H NO2
(a) (b) (c) (d)
NO2 H H H H NO2 H H
H H H NO2
67. The most stable form of cyclo hexane 1, 2-diol is:-
H
OH

OH
(a) (b) H
H
OH

OH H
OH H

(c) H (d) OH

H OH

OH H
68. The most stable form of 1, 2 di chloro cyclo hexane is:-
H
Cl

Cl
(a) (b) H
H
Cl

Cl
H
H
Cl
Cl
(c) (d) Cl
Cl
H

H
H
69. The most stable form of cyclo hexan – 1, 4 – di ol is:-
H
OH H
OH OH
(a)
H (b)
H

OH OH

OH H OH OH

(c)
H (d) H
H
Isomerism 33

70. The most stable form of 4 – Bromo cyclo hexanol is:-

Br OH
H
(a)
Br OH (b)
H

OH H
Br
(c) OH (d)
H

Br

71. CH3CH2CH2CHO & CH3CH—CH3

|
CHO
(a) Metamers (b) Skeleton isomers (c) Position isomers (d) Homomers
72. Total number of aldehyde & ketone possible for C4H6O are: (Excluding stereo isomers)
(a) 10 (b) 6 (c) 8 (d) 7

73. and are:-

O Ac Ac O
H H

(a) Enantiomers (b) Geometrical isomers (c) Diastereomers (d) Position isomers
74. Which will have highest dipole moment?

D Cl H H
(a) (b) (c) (d)
D Cl H H H H Cl
H

75. How many stereo isomers are possible in A & B?

Br Br
(A) (B)

(a) 2 & 2 respectively (b) 2 & 4 respectively (c) 0 & 2 respectively (d) 0 & 4 respectively
76. The absolute configurations of chiral centers 1, 2 and 5 in the following molecule are:-

Cl 4
5 3

2 OH
1
CHO

(a) 1R 2R 5R (b) 1S 2R 5S (c) 1R 2S 5R (d) 1S 2S 5S

77. Which will have very small enol content?
O O
O O O
O NO2
(a) (b) (c) (d)
O
34 Problems in Organic Chemistry

( +) (–) ( +) (–)
 CH 2 = N —O
78. CH3 — N — O 
|| |
O OH
(Nitromethane) (Aci-nitromethane)

Nitro methane is stable than aci – nitromethane because

(a) C = N bond is less stable than N = O bond.
(b) Hybridisation of ‘C’ changes from sp3 to sp2 which increases electro negativity of ‘C’
(c) Nitromethane is more stabilized by resonance than aci – nitro methane is not.
(d) Both are equally stable.
79. Maximum enol content is in:-

(a) (b) (c) CH3COCH2COCH3 (d) PhCOCH2COOCH3

80. Assertion -Conformers are not isolable at room temperature

Reason -These are unstable at room temperature
(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true
81. Assertion HDC = C = CHD can exhibit enantiomerism
Reason – It contains chiral carbon atom
(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true
82. Assertion - Me3C-NO2 can exhibit position isomerism but not tautomerism
Reason – Acidic hydrogen is absent in this compound
(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true
83. Assertion- HDC=C=C=CHD can exhibit optical isomerism
Reason- Entire molecule is planar
(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true
84. Assertion- Resolution of meso isomer in to two optically active forms is not possible
Reason- It contains plane of symmetry
(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true
Isomerism 35

85. Assertion: - % enol content in CH3CSCH3 is greater than that of CH3COCH3

Reason:-S—H bond is weaker than O—H bond because of large size of sulphur than oxygen.
(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true
86. Consider the following compound (A)

Assertion: - Compound A readily undergoes tautomerism

Reason: - Enol form of A is stabilized by H — bonding

(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true
87. Consider the following three compounds

Assertion: - % enol contents of I, II & III vary from 100 to 80 & 1.4 respectively
Reason: - In this series H – Bond becomes longer and weaker
(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true

88. Assertion: - If it is rotated along y axis its configuration does not change

Reason: - Configuration changes only when bond breaks and forms in new direction.
(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true
89. Assertion: - A mixture of cis & trans but – 2 – ene can be resolved at room temperature
Reason: - At room temp temperature cis transforms are not interconvertible
(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true
36 Problems in Organic Chemistry

O
90. Assertion: - CH3CH2O—S—CH3 & are not position isomers

O
Reason: - These are differing from each other due to the difference in the arrangement of CH2 group.
(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true

Answer Key

1. (b) 2. (d) 3. (d) 4. (b) 5. (c) 6. (a) 7. (c) 8. (d) 9. (b) 10. (b)

11. (c) 12. (b) 13. (c) 14. (b) 15. (b) 16. (a) 17. (c) 18. (a) 19. (c) 20. (b)

21. (c) 22. (b) 23. (c) 24. (c) 25. (b) 26. (d) 27. (a) 28. (b) 29. (a) 30. (d)

31. (d) 32. (b) 33. (d) 34. (c) 35. (d) 36. (d) 37. (a) 38. (d) 39. (a) 40. (c)

41. (b) 42. (c) 43. (d) 44. (c) 45. (d) 46. (d) 47. (d) 48. (c) 49. (d) 50. (d)

51. (d) 52. (d) 53. (c) 54. (a) 55. (b) 56. (b) 57. (a) 58. (d) 59. (b) 60. (c)

61. (d) 62. (a) 63. (d) 64. (d) 65. (c) 66. (a) 67. (d) 68. (c) 69. (d) 70. (a)

71. (b) 72. (d) 73. (d) 74. (a) 75. (d) 76. (d) 77. (b) 78. (c) 79. (a) 80. (c)

81. (c) 82. (a) 83. (d) 84. (b) 85. (b) 86. (c) 87. (a) 88. (d) 89. (a) 90. (a)

Multiple Choice Questions (More Than One May Correct)

1. Which of the following compounds will show geometrical isomerism?

(a) Pent – 2 – ene (b) 1 – Chloro hexene
(c) 3, 4 – Diethyl hex – 3 – ene (d) 1, 2- Di chloro ethene
2. Aldehydes and ketones on reaction with NH2OH form oximes which can exhibit geometrical isomerism.
R1 R1
C O + NH2OH H2O + C N—OH
R2 R2

Which among the following aldehyde and ketone will show geometrical isomerism after treatment with NH2OH ?

(a) (b) (c) (d)

3. Which among the following is not ‘E’ isomer?

(a) (b) (c) (d)

Isomerism 37

4. Which statement is not in favour of the following compound?

(a) It can show geometrical isomerism (b) It can show optical isomerism
(c) It possesses plane of symmetry (d) Rotation about C1 – C2 & C3 – C4 is restricted rotation
5. Select the objects which are achiral due to the presence of plane of symmetry.

(a) (b) (c) (d)

Br Cl

6. Select the objects which are achiral due to the presence of plane of symmetry as well as centre of symmetry.

(a) (b) (c) (d) None of these

7. Which is not correctly matched?

(a) & are enantiomers

(b) & are position isomers

(c) & are functional isomers

(d) and are enantiomers

8. Products (mono chlorination)

Select correct statements regarding above reaction.

(a) 4 Structural isomers are produced (b) 5 Structural isomers are produced
(c) Total number of isomers obtained in this reaction are 6 (d) Two structural isomers are optically active
38 Problems in Organic Chemistry

9. The compound which can exhibit geometrical as well as optical isomerism is/are:-

CH I
(a) (b) 2 (c) (d) None of these

10. An optically active compound is/are:-

(–)
Br
(+)
(a)
(–) Et
NH3Br (b) (c) N Br (d) None of these
(+)
CD3 Br
11. For the formula C3H6O
(a) Maximum number of possible alcohols is ‘4’ (b) Maximum number of possible Ketone is 2
(c) Maximum number of possible ether is 2 (d) Maximum number of possible aldehyde is 2
12. Compound(s) whose enol form is not possible is:

(a) (b) (c) (d)

13.

Select correct statements

(a) I & II are identical (b) II & III are identical (c) II & III are diastereomers (d) All are diastereomers
14. An optically active compound containing one chiral centre is found to exist in to two forms X & Y. The select correct
statement.
(a) Mixture of X & Y can be separated by distillation.
(b) Equimolar mixture of X & Y is found to optically inactive due to internal compensation.
(c) If 40% X & 60% Y are mixed, 80% racemisation will take place.
(d) Meso form of this organic compound is not possible.

Answer Key

1. (a), (b), (d) 2. (c), (d) 3. (a), (b), (d) 4. (a), (b) 5. (b), (c), (d)

6. (a), (b), (c) 7. (a), (b), (d) 8. (a), (c), (d) 9. (d) 10. (b), (c)

11. (a), (c), (d) 12. (b), (c) 13. (a), (b) 14. (c), (d)
Isomerism 39

LEVEL – II

Multiple Choice Questions

1. You have following four compounds

CH3CH2CHO CH2 = CHCH2OH CH2 = CHOCH3

(1) (2) (3) (4)
Select the correct statement
(a) 2 & 3 are functional isomers as well as position isomers
(b) 1 & 3 are chain isomers
(c) All are functional isomers
(d) 3 & 4 are position isomers
2. Which is not resolvable?

(a) EtNHCH3 (b) (c) POClBrI (d) All are resolvable

3. Identify the compound which has the least value of heat of combustion

(a) (b) (c) (d)

4. You have given the following transformations.

Trans –but-2-ene Cis-but-2-ene………….…….………....(1)
Anti-n-butane Gauche-n-butane…....….…………………(2)
R-butan-2-ol S-butan-2-ol ....…………….………..……..(3)
S-butan-2-ol R-butan-2-ol .....…….…..….……………....(4)
For which transformation least activation energy is needed: -
(a) 2 (b) 1 (c) 3 (d) 4
5. You have four compounds

(1) (2) (3) (4)

Geometrical isomerism will be exhibited by:-

(a) 2 & 4 (b) 1, 2 & 4 (c) All (d) None
(CH2)n
6. General representation of cyclo alkene is C C
H H
C is isomer will be more stable than trans isomer when
(a) n > 10 (b) n < 10 (c) n < 13 (d) n = 10

7.

(A) & (B) are:-

(a) Rotamers (b) Geometrical isomers (c) Enantiomers (d) Structural isomers
40 Problems in Organic Chemistry

8. Consider the following four isomers.

C2H2 BF3

(1) (2) (3) (4)

Which is correct:-
(a) 2 & 4 possess centre of symmetry
(b) 1, 2, 3 & 4 contain axis of symmetry
(c) 2 & 3 possess alternating axis of symmetry
(d) 4 contains centre of symmetry while 2 contains plane of symmetry
9. Consider the following compounds

(1) (2)

Which option satisfy for the above two?

(a) Both can show geometrical as well as optical isomerism
(b) Both can show optical isomerism.
(c) Both are chiral but only 2nd can show geometrical isomerism
(d) Both can show geometrical isomerism.

10. Consider the following compounds.

SO3H NO2

(1) (2) (3) (4)

(C2H)4

Optically active compound is / are:-

(a) Only 1 (b) 1 & 2 (c) 4, 2 & 3 (d) None

Matrix Match Questions

Each question contains statement given in two columns which have to be matched. Statement (A, B, C , D) in column I have to be
matched with statements (p, q, r, s) in column II. The answers to these questions have to be appropriately bubbled as illustrated in
the following examples. If the correct matches are A – p, A – s, B – r, B – q, C – q, D – S, then the correctly bubbled 4 x 4 matrix
should be as follows.

A p q r s
B p q r s
C p q r s
D p q r s
Isomerism 41

11. Column – I Column – II

SH
Br
(A) (p) R
H
Br

Br
HO H

(B)
HO H (q) S
Br
OH
(C)
D (r) E
H
Br
CH2I
(D) (s) Z

12. Column – I Column – II

Cl
(A) No. of positional isomers of (p) 2

(B) Total structural isomers for Pr – NH2 (q) 3

(C) Optically active isomer for dichloro cyclo hexane (r) 4
(D) Structural isomers for nitrotoluene (s) 1
13. Matrix Match
Pair of isomers Relation
Br
H I
(A) and (p) Enantiomers
I H
Br
CH3 CH3

Br CH3 CH3 Br
(B) and (q) Diastereomers
H H H
Br
Br
H

(C) and (r) Homomers

CH3 Br
CH3 and Br
(D) (s) Position isomers

Br Br CH3 CH3
42 Problems in Organic Chemistry

14. Column – I Column – II

(A) CH3COCH2D (p) optically inactive but its enolic form
can show geometrical isomerism
O
(B)
CH3CH2CHClCCH3 (q) optically active & its enolic form can show geometrical isomerism

Et
Br Br
(C) (r) can show metamerism
H H
Et
(D) CH3CH2COCH2CH3 (s) can show position isomerism

Answer Key

1. (c) 2. (a) 3. (a) 4. (a) 5. (d) 6. (b) 7. (a) 8. (c) 9. (b) 10. (b)

Answers Matrix Match

11. (A) – q, r, (B) – p, q (C) – q (D) – r

12. (A) – q (B) – r (C) – p (D) – r
13. (A) – r, (B) – s, (C) – p, (D) – r
14. (A) – p, (B) – q, r, s (C) – r, s, (D) – p, r, s

SOLUTION
LEVEL - I
1. Draw the Fischer projections of the following.
CH3 OH CH3 H
H H Cl I Cl Br Br I
(a) (b) (c) (d)
H H Cl I Br Cl H I
CH3 Br CH3 Br
CH3 CH3
H CH3
OH NH2 H Br
(e)
Br Cl (f) (g) (h)
NH H
NH2 OH H Br
I CO
CH3 CH3

Br
OH
H Cl
(i)
H NH2 ( j)
Cl H
D
Br
Isomerism 43

2. Only (g) is meso isomer as it has plane of symmetry

3. (a) F(1), CONH2(2), D(3), H(4) by using double exchange phenomenon configuration is ‘R’
(b) Cl(1), ethynyl(2), ethenyl (3), ethyl(4) by using double exchange phenomenon configuration is ‘ S’
O 2
3
3 3
COBr 1
  2 1
(c) 4 NH2 R configuration
1 4 2
4
3
1 3
Cl (3)
(d) 2 → (2) → 4 1 R configuration
(1)
O O
4 2
(4)
(e) CH2I(1), CH2F(2), CH2CH2I(3), CH2CH2CCl3(4) by using double exchange phenomenon configuration is ‘R’
Cl
(f)
2O 4 same as (d), S configuration
3

CH2I
1
(g) Cl(1), F(2), ethyl (4) – configuration is ‘S’
(h) OH(1), NHCOCH3(2), COCH3(3), CH3(4) – configuration is ‘R’
(i) Same as (c) configuration is ‘R’
( j) H(4), Cl(1), D(3), CH2OD(2) by using double exchange phenomenon configuration is ‘S’

(k)

(l) Same as (k) it is SS

3 CH3
CH3
CH3 4H Br1
4H Br1 2 S, S
H Br Br H
2
(m) → Br OH
CH3
H Br CH3
3
by using double
CH3 by using double exchange phenomenon
exchange phenomenon it is S configuration
it is S configuration
3
CH3 CH3
1 Br H 4
Br H
(n) 2 2
H Br R, R
4H Br 1
CH3 CH3
3
by using double by using double
exchange phenomenon exchange phenomenon
it is R configuration it is R configuration
44 Problems in Organic Chemistry

(o) Same as (k) (1) & (m) it is (R, S)

O O
H 2 1
2
Br COBr 1
4. (a) (b) E
E
I H 2
1
1
NH
E 1 Z
1D 2 H NH
2 COBr1 D H NH2 COBr
(c) C C C C C C2 C C
H 1 C C 2 CHO 2 H C C 2 CHO
2
F Cl F Z Cl
ans-E, Z, Z 1 1

2
2 HO CONHCH3 2 1
(d) C C 1 Z (e) CH COCH 2 2 3
1 FO NHCOCH3 Z
1 NHCOCH3
(f) Same as previous it is Z.
(g) Here out of lone pair & OH, hydroxyl group will get 1st priority. It is an‘E’.
(h) CHO (1), CH2OH (2), CH2CN (1), CH2CH2CN (2) it is E
2
H
1
(i) It is E
1

H2
1
HO18— CH2 OH 2
(j) It is E C=C
HO—CH2 OCl
2 1

Answers to Objective Questions

CH3 CH3 H CH3

1. (b) Trans isomer is optically active.

H H CH3 H
(cis) (Trans)
while cis isomer is optically inactive due to the presence of plane of sysmmetry.
2. (d) 1 & 2 are identical
H D H
D Cl
Cl D
D
Cl Cl
H
{1} H {2}

(rotate entire molecule to 120°)

3. (d)
4. (b) Phenyl group should be kept at the bottom of vertical line
Isomerism 45

5. (c) Because proposed isomer & (c) are enantiomers

COOH H
H Cl HOOC Cl
Cl (S, S) (R, R) H Cl
H
COOH Mirror COOH
O OH
6. (a) CH3 — N  O 
 CH2 N
(+)
 O
(+)

7. (c) 2n–1 + 2(n – 1) / 2 n = Number of double bond

= 23–1 + 2(3–1) / 2 = 4 + 2 = 6
8. (d) 2n = 23 = 8
9. (b) Specific rotation is a constant quantity for a particular isomer hence it should be 60° and can be calculated as:
q× 100 60°× 100
sp. rotation = = = 60°
C× 20 × 5
from q1V1 = q2V2, 60 × 0.2 = q2 × 2, q2 = 6°.
10. (b) Both the carbon atom & Boron present in the ring are sp2 hybridised.
(2)
H 'E' (1)
COBr (3) COBr

(4) COCH3
11. (c) F COCH3 F (2)
(2) 'S'
Br Br
(1) (1)

12. (b) There is no mirror image relationship between the two isomers.
CO2H
CO2H
H OH H OH
13. (c) Fischer projection of it is:- =
H OH
HO H
CO2H
CO2H
14. (b) Here length of carbon chain remains same but position of methyl group is changing.
OH

H3C OH
15. (b) It is stabilized by H – bonding
H3C H

H
16. (a)
17. (c) I = (R, R) configurations
II = (S, S) configuration
III = (S, S) configuration
Hence I, II & III, I are enantiomeric pairs
18. (a) suppose wt of mixture is 100 gm
Let amount of (+) form be x gm then amount of (–) form will be (100 – x)gm
specific rotation of (+) form = +10.6°
specific rotation of (–) form = –10.6°
46 Problems in Organic Chemistry

x (+10.6°) + (100 – x) (–10.6°) = 7.2

x = 50.34 %
(+) 2 chloro butane = 50.34 %
(–)2 chloro butane = 100 – 50.34 = 49.66 %
19. (c) Except (c) rest all possess plane of symmetry
20. (b) It is free from all type of symmetry elements while (a) possesses centre of symmetry & (c) & (d) possess plane of symmetry.
21. (c) First chiral centre from the bottom is considered
CHO
H OH
L–configuration H OH
OH H
CH2OH

22. (b) Racemic mixture has zero specific rotation thus, observed rotation will be due to retention
i.e. 36° x 25 / 100 = 9°

23. (c) Enol form of I is highly stable as its enol form is aromatic. O 
 OH

Enol forms of II , III & IV is stabilized by H- bonding.

Enol form of IV is stable than that of II & III because of more resonance (due to phenyl group)
H
OH O O
|
PhC  CHCOCH3
PhCOCH2 COCH3  OR
PhC C — COCH3
CH
24. (c) Both the rings are perpendicular to each other.
25. (b)
26. (d) Stability ∝ 1 / Reactivity ∝ 1 / heat of hydrogenation.
27. (a)
28. (b) Since these conformations have mirror image relation
29. (a) Chiral Carbon = 3
Optically active isomers= 2n – 1 – 2n – 1/2, = 23 – 1 – 23 – 1/2, = 2
30. (d) It does not have plane of symmetry.
(2) (1)
H COBr
COBr (3)

(4) COCH3
F (2)
31. (d) F COCH3
(2)
Br 'E' Br
(1)
(1)
(4)

In Fischer projection (2) (1) 'S'

(3)
32. (b) ‘CO’ group undergoes hydrogen bonding with H2O.
33. (d) OH & ethyl are on the same side of double bond
34. (c) 35. (d)
36. (d) In chair form substituents at 1, 3 positions are cis when these are located at equatorial position. Similarly substituents at
1, 2 positions are cis when one is located at equatorial position while other at axial position
Isomerism 47

37. (a) Minimum van-der-waal repulsion 38. (d) Possesses plane of symmetry.
H H
C C C
39. (a) H3C CH3

It does not contain plane of symmetry.

40. (c) It contains chiral plane 41. (b) Same as question no. 17,
42. (c) Same as question no.17 43. (d) Factual question
44. (c) Factual question 45. (d)
H
H
D CH3
Me Me
46. (d)

H3C CH3 D D Threo
H H
47. (d) On heating one mole of carbon dioxide comes out.
Ph Ph Ph
H Me H Me H Me
CO2 H

H CO2H & HO2C H
HO2C –CO 2
H Me H Me
H Me
Ph Ph Ph
(A) (B)
Both contains plane of symmetry & hence optically inactive.
Me Me Me
aq.
48. (c) H Br  H OH + HO H
NaOH
Et Et Et (60%)
(40%)
A B C

100 g of A gives 40 g of B & 60 g of C. Now 40 g of B will undergo racemisation with 40 g of C.

Hence total wt of racemic mixture will be 40 + 40 = 80 thus, 80 % racemisation will occur.
49. (d) 1st contains plane of symmetry & 3rd does not contain chiral carbon atom.
50. (d) e nol form is more stable because of extended resonance.
51. (d) Degree of unsaturation of all isomers is ‘5’.
52. (d) Higher the atomic number higher is the priority. When atomic numbers are same then higher the atomic weight higher is
the priority
53. (c) 54. (a)
55. (b) It contains plane of symmetry.
56. (b) Because these are position isomers
57. (a)
58. (d) Enol form is not stabilized by H-bonding because Iodine can not form H-bond.

OH
59. (b) Bridge ‘C’ of bicyclo compound can not have double bond until ring contains 8 ‘C’ atoms is not
possible.
1
2 HO C C E
60. (c) Out of cyclopropyl & propyl group former gets higher priority. ClO CH2CH2CH3
1 2
48 Problems in Organic Chemistry

CH3 CH3

61. (d) CH3 CH3 CH3 CH3

plane of symmetry plane of symmetry

2 NHCOMe O
O by using double 2 OH
62. (a) 1 2 3 exchange phenomenon 1 2 3 R configuration
4 it is R configuration
3 H4
Br1
63. (d) It does not contain plane of symmetry.
64. (d) Because after heating two valencies of C1 are identical.
HOOC 3 HOOC
NMe2 Heating
HOOC  NMe2
–CO 2 H
1 2 H
COOH 1
COOH
We can not assign priorities to the valencies of C1 because 2nd & 3rd carbons are identical. Thus, R-S nomenclature is not
possible.
NO2
H OH
65. (c) It is stabilized by H bonding. intra mol- H -bond

H H

H
66. (a) Nitro group can not form H bond with hydrogen of C-H bond thus, anti form is more stable
67. (d) Equatorial OH are trans to each other & can form H bond with each other.
68. (c) Both Cl are trans to each other.

OH OH
Intra molecular - H - bond
69. (d)
H H

70. (a) Since intra molecular - H - bonding is not possible thus, chair form will be more stable than boat form.
71. (b) Because position of CHO group does not change & length of carbon chain is affected.

72. (d) , 7 isomers

3 3 2
2 4 4
1 5 5 1
73. (d) O Ac Ac O
H H
Isomerism 49

1
D
74. (a) µ res = µ1+ µ2
D Cl
2
75. (d) A is optically inactive & can not show geometrical isomerism while B is optically active (one d & one l) & can show
geometrical isomerism (one cis & one trans).
76. (d) See q.n.3 (c)
77. (b) Because it has zero dipole moment & its enol form is not stabilized by H-bonding
2
O
µ res = µ1– µ2 = 0

1O

78. (c) Nitromethane is stabilized by resonance

O OH

79. (a) Enol form is aromatic & stable.

H
80. (c) Conformational energy is very small so one conformer can convert itself in to other at room temperature thus, these are
not isolable at room temperature.
H H
81. (c) It contains chiral plane CHIRAL plane C = C = C
D D
82. (a) Carbon attached with nitro group does not contain H atom
83. (d) It does not possess chiral plane.
H H
C = C = C =C
D D

84. (b) It is not the mixture of two components.

85. (b)
86. (c) Enol form is stable due to aromaticity .
87. (a) As we move from I to III distance between functional groups increases thus, H-bonds of enol forms become longer &
unstable.
88. (d)
89. (a) At room temperature cis & trans forms are not inter convertible (large energy is required)
90. (a) These are mesomers

More Than One May Correct

1. (a, b, d) 3, 4 diethyl hex-3- ene can not show geometrical isomerism because double bonded carbon atom contains two ethyl
Et Et
groups C C
Et Et
50 Problems in Organic Chemistry

2. (c, d) 3. (a, b, d)
4. (a, b) since 1st & last benzene rings contain same substituents hence it can not show geometrical as well as optical
isomerism.
5. (b, c, d) In (a) centre of symmetry is present 6. (a, b, c)
7. (a, b, d) In (a) both the isomers are optically inactive and same. In (b) both the isomers are chain isomers. In (d) both isomers
are identical.
8. (a, c, d)
9. (d (a) & (c) can not show geometrical isomerism while (b) can not show optical isomerism.
10. (b, c) In (a) chiral ‘C’ atom is absent
11. a, c, d
12. b, c
13. a, b
14. c, d d & l forms can not be separated by distillation.
LEVEL - II
1. (c) All have same molecular formula but different functional groups.
Me Me
2. (a) Because of amine inversion. N
..

Et N
..
Et
H H
3. (a) less van-der-waal forces of repulsion, more stable
alkane, least value of heat of combustion
4. (a) Conformational energy is very small. So one conformer can convert itself in to other
5. (d) There is no geometrical isomerism up to seven carbon atoms. (Cyclo heptene)
(CH2)n n= 6 to 9 cis is more stable than trans
6. (b) C C n= 10 cis & trans are equally stable
H H n > 10 trans is more stable than cis
7. (a) Rotation about single bond is free.
8. (c) See alternating axis of symmetry in your text book.
9. (b) In both the cases rings are perpendicular to each other thus, due to absence of any symmetry element both are optically
active.
10. (b) In both the cases phenyl groups are present on different plane.
 4
Reaction Mechanism
(General Organic
Chemistry)

Main Features
1. Inductive effect-
 It is defined as the displacement of sigma electrons from less to more electro negative atom.
 It is of two types viz. +I & -I effects
(–)
+I groups: -
O— > R3C — > R2CH — > RCH2 — > CH3
ss s– s+
C—C—C—C X +I group
(+ )
-I groups: - NMe3 — > NO2 > CN > SO3H > CHO > CO > COOH > COCl > COOR >
CONH2 > F > Cl > Br > I > OH > OR > NH2 > C6H5 > H
s+s+ s+ s–
C—C—C—C X —I group

 Due to – I effect acidic strengths of carboxylic acids & alcohols increase F——CH
 2 — COOH > Cl
Cl << CH2COOH > Br < CH2—COOH because –I groups help in the dissociation of OH bond
 Due to +I effect acidic strength decreases because +I groups create problem or obstruction in the dissociation of OH bond
 Due to +I effect basic strengths of amines increases while by – I effect basic strength decrease
CH3

CH3 > NH > CH3 > NH2 > NH3

 Order of basic strength (CH3)2NH > CH3NH2 > (CH3)3 N > NH3
For amines other than methyl amines R2NH > R3N > RNH2 > NH3
2. Resonance (Mesomeric effect):-
 It occurs in following five systems.
(+) (–)
(i) C C—C C (ii) C C—C (iii) C C—C (iv) C C—C (lone pair)

(v) C C—C (Free radical)

 Resonance µ ∝ Resonance energy ∝ Resonating structures ∝ Stability

3. Electromeric effect: - It is defined as the displacement of p electrons between two atoms in the presence of attacking reagent.
4. Aromaticity: - Those species which are planar, cyclic & contains (4n + 2) p delocalized electrons are called aromatic
 (4n + 2) p e– rule ( Huckel rule )
n = 0 2 p e–
52 Problems in Organic Chemistry

n = 1 6 p e–

n = 2 10 p e– 6 p e– , Cyclic & planar

n = 3 14 p e– (Aromatic)
Aromaticity ∝ Resonance energy ∝ Resonance.
5. Antiaromaticity: - The species thus called antiaromatic when shows planar cyclic and contains 4np delocalized electrons
4p e– , cyclic, planar, and hence antiaromatic.
6. Electrophile (E+):- Those species are called electrophile in which central atom has incomplete octet or central atom can re-
ceive electrons in its empty d orbital.
For eg. F+, NO2+, AlCl3, ZnCl2, PCl5, PCl3 ————— etc.
7. Nucleophile (Nu-):- These are the species in which central atom has complete octet and these can donate electrons to elelctro-
philes in chemical reaction.
•• •• •• ••
For e.g. F ,CN ,H2 O, NH3, R — O — R & R — S — Hetc.
(–) (–)
•• •• ••

8. Amphiboles: - These are the species which can favour the attack of (E+) or N u– on itself. If C forms multiple bond with another
electronegative atom then that species behaves as amphibole.
H H O
| | ||
For eq., CH3—C ≡ N, CH3 — C O, CH3 — C O, CH3 — C — OH........etc.

Free Radicalsubstitution Reaction (F.S.R.)

1. It involves three steps, chain initiation, chain propagation & chain termination. In very first step generation of free radical takes
place.
2. In halogenations of alkane numbers of products depend upon the variety of hydrogen’s present in the alkane.
mono chlorination
CH3CH 2 CH3  Cl2  CH3CH 2 CH 2 Cl  Cl3 —C HCH3
h |
Cl
3. The following is the decreasing order of case of abstraction of different kinds of hydrogens
Benzylic Hydrogen > allylic hydrogen > 3° — H > 2° — H > 1° — H > CH3 — H > vinylic —H
Benzylic carbon

CH—CH=CH—CH
2 3 Allylic carbon

Vinylic carbon
4. Attack of free radical on C—H bond is rate determining step
R — H + X* ——→ R* + H — X
5. The relative rates of formation of alkyl radicals by chlorine radical:-
3° > 2° > 1°
(5.0) (3.8) (1.0)
Bromine radical –
3° > 2° > 1°
(1600) (82) (1.0)
6. For allylic substitution NBS (N – bromo succinamide), NCS (N – chloro succinamide) can be used.
CH3 — CH = CH 2 
→ Br — CH 2 — CH = CH 2
NBS
hν
Reaction Mechanism (General Organic Chemistry) 53

Electrophilic Substitution Reaction (E.S.R)

 It is the characteristic property of aromatic compounds.

 General mechanism of electrophilic substitution reaction is given below.
(+)
E E E E
(+) Slow
+ E ~
= (+)
(+) (+)
(Wheland complex)

H
E E
Fast (+)
(+) H +

1. Types of E.S.R.
Reaction Reagent
1. Halogenation X2/Fe or X2 lewis acid
2. Nitration conc HNO3 / conc H2SO4 or Acetyl nitrate or NO2BF4 or EtNO2
3. Sulphonation Oleum or H2SO4 + SO3
4. Friedel craft RCOCl / Anh AlCl3 or (RCO)2 O/Anh AlCl3 or RX / Lewis acid
2. Directive influence: - On the basis of it groups can be classified in to four types.
+ R (N H2, O H, N HR, O R, N COR...........)
–R (NO2, SO3H, CHO, COOH…………...)
+I (Alkyl groups)
Tautomeric (f, Cl, Br & I)
Out of these four classes+ R + I & Tautomeric groups are ortho & para directing & goups of – R class are meta directing. Groups
of –R & tautomeric class are ring deactivating on the other hand groups of + R & + I class are ring activating.
3. Introduction of third group – Here two cases may arise.
Case I: - When both groups already present have same agreement
NO2
SO3H
OH

CH3

Case II: - When both groups already present do not have same agreement then.
 When both groups are ortho Para directing, the more powerful group controls the orientation. The directing power of each
group is in the following order.
O (–) > NH2 > NR2 > OH > OMe, NHCOMe > X (halogens)
OH Cl
Me
OH

NH2 OMe
 When both groups are Meta directing, it is difficult to introduce a third group. At this time drastic conditions are required
for the introduction of third group. The following is the general order of directing power of each group, and it is the less
powerful group which controls the orientation.
Me3N(+) > NO2 > CN > SO3H > CHO > COMe > CO2H
54 Problems in Organic Chemistry

 When one group is ortho Para directing and the other is Meta directing then o, p directing group controls the orientation.
OH

SO3H

Electrophilic and free Radical Addition reactions

1. It is the characterstic property of C = C & C ≡ C systems.

2. In presence of sun light radicals are generated and free radical addition reaction takes place while in dark addition takes place
via ionic mechanism i.e. electrophilic addition occurs.
3. Electrophilic addition follows markownikoff rule on the other hand free radical addition follows anti markonikoff rule.
Br
|
CH3 — CH = CH + HBr ¾¾
® CH3 C HCH3 (95%)
(Markonikoff Product)

CH3 — CH = CH + HBr ¾¾¾¾

Sunlight
® CH3CH 2 CH 2 Br (95%)
(Anti Markonikoff Product)

4. KHARSCH EFFECT: - When unsymmetrical alkene is treated with HBr in presence of active peroxide Anti markownikoff
addition takes place.
CH3 — CH=CH 2 ¾¾¾¾¾
HBr
® CH3 — CH 2 — CH 2 — Br
(RCO) 2 O 2
(major)

5. Stereochemistry of electrophilic addition reaction:- Always anti addition takes place on alkene and alkyne
Anti addition
C is form ¾¾¾¾¾¾
® Racemic Mixture
CH3 CH3
CH3 CH3 H Br Br
in H
C C + Br 2 +
CCl4 Br
H H H H Br
CH3 CH3
Anti addition
Trans ¾¾¾¾¾¾
® Meso isomer
CH3
CH3 H in H Br
C C + Br2
CCl 4 H
H CH3 Br
CH3

Elimination Reactions

1. These reactions are the reverse of addition reaction. In these reactions double and triple bonds are produced.
–HBr
CH2 — CH 2— Br + KOH CH2 CH2
alc (Elimination)
H

CH 2 = CH 2 ¾¾¾® CH3 = CH 2 Br
+HBr
(Addition)
Reaction Mechanism (General Organic Chemistry) 55

2. Types :- Three types

 E1 (Unimolecular Elimination)
(–)
( +)
® R — CH 2 — C H 2 ¾¾¾® RCH = CH 2
Slow OH
R — CH 2 — C H 2 ¾¾¾¾
(–)
–Br –H 2O
|
Br

Rate = R [Substrate] or [alkyl halides]

 E2 (Bimolecular Elimination)
(–) OH –
H +
OH H
Slow (–)
R—CH—CH2 R— CH CH2 R— CH CH2 + H2 O + Br
–
Br Br
Rate = k [Substrate] [Base]
 E1CB (Elimination via the formation of conjugate base)
(–)
OH H (–)
OH (–) (–)
R — CH — CH2 R — CH — CH2 R— CH CH2 + Br
H2 O
Br (Slow) Br
(Conjugate base)
Rate = R [Substrate] [Base]
3. Two rules are followed in elimination reactions.
(a) Saytzeff rule: - In 1, 2 elimination reaction highly substituted alkene in formed as a major product.
H
alc KOH
CH2 — CH — CH — CH3 CH2 = CH— CH2— CH3+ CH3CH CH—CH3
Cl (Minor) (Major)
H

(b) Hoffman rule: - In 1, 2 elimination reaction less substituted alkene is formed as major product.
H
(–)
CH2 — CH — CH — CH3 OH CH2 CH—CH—CH
2 +3 CH—CH
3 CH —CH3
(Minor) (Minor)
H NMe3
(+)

Hoffman elimination generally occurs when leaving group is poor like N+Me3, P+Me3 & F etc.

AROMATICITY
LEVEL - I

Objective Questions
1. For which compound pKa is least?

COCH3 Ac
(a) (b) (c) (d)

2. Consider the following compounds

(i) (ii) (iii)

56 Problems in Organic Chemistry

Which statement is correct?

(a) (ii) & (iii) are aromatic while (i) is non aromatic (b) (i) & (ii) are anti aromatic but (iii) is aromatic
(c) All are anti aromatic (d) All are aromatic
3. Which is aromatic?

(a) (b) (c) (+) (–) (d) All of these are aromatic

4. Which is not aromatic?

Ph Ph
C
(+)
N
⊕
(a) (b) (c) (d) (b) & (c)

5. Consider the following two compounds.

(A) (B)

Which statement is correct regarding the stabilities of the above two compounds?
(a) Both are equally stable (b) B is less stable than A
(c) B is more stable than A (d) unpredictable
6. Out of following four compounds
Ph Ph Ph
Ph Ph
(+)
Me— N N–Ph
(–)
(–)
N
OMe O O CH3 O
(i) (ii) (iii) (iv)

Aromatic compounds are:-

(a) i & iv (b) i, ii, & iv (c) ii & iv (d) ii, iii & iv
7. Consider the following compounds:-

(–) (+) NMe2

C
NMe2
if planar
(A) (B) (C)

Select the correct Statement

(a) All are aromatic (b) All are anti aromatic
(c) (A) & (C) are aromatic (B) is anti aromatic (d) (C) is aromatic, (B) is anti aromatic & (A) is non aromatic
8. Consider the following dissociations
(–)
(I) C1 ——→ (+) + C1

(+)
(II) C1 ——→ (–) + C1

(+)
(III) C1 ——→ (–) + C1
Reaction Mechanism (General Organic Chemistry) 57

Identify the correct energy level diagram regarding above dissociations.

II III II
I
I I III
II P.E P.E
P.E III P.E II I
III

(a) (b) (c) (d)

T T T
T

9. Correct order of aromaticity of following compounds will be:-

(I) (II) (III)

N S O
H
(a) I > II > III (b) III > II > I (c) I ; III > II (d) II > I > III
10. Consider the following compounds.

O O S
O S
O S

(A) (B) (C)

Select the correct statement

(a) All are aromatic (b) Only (B) is aromatic
(c) (B) & (C) are aromatic while (A) is non aromatic (d) Only (C) is aromatic
11. Which with release H2 gas on reaction with ‘K’ metal

Ph Ph

(a) (b) (c) (d) both (a) and (c)

Ph Ph

12. The compound which can convert itself into aromatic compound by intramolecular rearrangement is:-
O O
HN NH O O
(a) (b) (c) (d) All of these
O O
13. Consider the following reactions:-
I
(+)
I (+)
AgNO3 (–)
1. AgI ↓ + NO3(–) 2. AgBF 4 BF4 + AgI

(–)

3. EtOK K
(+)

If rate of these reactions are R1, R2 and R3 respectively then

(a) R1 > R2 > R3 (b) R3 > R1 > R2 (c) R3 > R1 = R2 (d) R2 > R3 > R1
58 Problems in Organic Chemistry

14. Identify the species which is not aromatic:-

(+) (+)

(a) (b) (c) Fe (d)

15. Pick out the most acidic compound:-

H
H H H H H H H
(a) (b) (c) (d)

16. Which of the following species is least stable?

O NH O

(a) (b) (c) (d)

Passage – I

Cyclic compounds with planar geometry & (4n +2) p delocalized e– are called aromatic while anti aromatic if they contain 4np
delocalized e–. Consider the following compounds.

Answer the question from 17 to 22

17. Which compound is aromatic?
(a) Only A (b) B, C (c) Only C (d) C & D
18. Compound which is antiaromatic
(a) A (b) Only B (c) B, C & D (d) B & C
19. Which is neither aromatic nor anti aromatic?
(a) B (b) D (c) A & B (d) Only A
20. Compound with 4np e– is/are:-
(a) B & F (b) A, B & C (c) B & D (d) B, C & D
21. Compound with all 4np delocalized electron is/are
(a) B & C (b) Only B (c) B & D (d) None
22. Which does not have planar geometry?
(a) B (b) C & D (c) Only A (d) A & D
Reaction Mechanism (General Organic Chemistry) 59

Passage – II

Reagents LiAlH4, SeO2 & PCC can do following transformations.

O OH
|| |
LiAlH 4
 CH3 — C— CH3 ¾¾¾¾
® CH3 — CH — CH3

 CH 2 = CH — CH3 ¾¾¾
2 ® CH = CH — CH OH
SeO
2 2

OH O
| ||
 CH 2 = CH —CH — CH3 ¾¾¾
PCC
® CH 2 = CH — C— CH3

Answer the question from 23 to 25

23. The compound which can be converted into aromatic from non aromatic by SeO2 & PCC is:-

(a) (b) (c) (d)

24. The compound which can be converted into anti aromatic by treating with SeO2 & PCC is:-

(a) (b) (c) (d)

25. The compound which is aromatic but becomes non aromatic when reacts with LiAlH4
O
O O
(a) (b) (c) (d)

Passage – III

Consider the following compounds

(+)
.. N
N H
H
H
CH3O2C OCO

Answer the question from 26 to 30

26. How many rings are aromatic in this compound?
(a) 4 (b) 3 (c) 2 (d) 5
27. Number of delocalized electron present in pentagonal ring are:-
(a) 2 (b) 4 (c) 6 (d) None
28. How many rings have planar geometry (pentagonal as well as hexagonal)?
(a) 6 (b) 4 (c) 3 (d) 2
60 Problems in Organic Chemistry

29. Total delocalized p electron present in the rings of compound are:-

(a) 18 (b) 14 (c) 12 (d) 20
30. If pentagonal ring containing nitrogen has ‘x’ delocalized p electron & hexagonal ring containing nitrogen has ‘y’ p electron
then
(a) x > y (b) y > x (c) x = y (d) None

Passage – IV

Acid strength of organic compounds can be compared by comparing the relative stabilities of conjugated base or anion produced
after the release of H+ ion

HA H(+) + A(–) (conjugate base)

Higher is the stability of conjugated anion more acidic will be the acid.
Acid chaacter a 1 / pKa
Consider the following compounds

(I) (II) (III) (IV)

Answer the questions from 31 to 33

31. Which among the following can release H2 gas on reaction with NaH?
(a) I (b) II (c) IV (d) III and IV
32. Which will have least pKa?
(a) II (b) IV (c) I (d) III
33. Which among the following will favour the release of hydride ion?
(a) II (b) IV (c) Only I (d) Both I and III
34. Which statement is correct about the following two compounds?

CCl2 (–)
O
(A) (B)
CH3

(a) Both are aromatic (b) Both are antiaromatic

(c) A is aromatic while B is antiaromatic (d) A is antiaromatic while B is aromatic
35. Which is aromatic?
CMe2 NH2
(–) (+)
N
(a) (b) (c) (d)
O N O
H
Reaction Mechanism (General Organic Chemistry) 61

36. Consider the following compounds

(i) (ii) (iii)

If dipole moments of (i), (ii) & (iii) are x, y & z respectively then:-
(a) x > z > y (b) x = y = z (c) y = z > x (d) z > x > y
37. Consider the following compounds

••N ••N—H N S N O
(A) (B) (C)

Highly Aromatic compound is

(a) A (b) B (c) C (d) all are equally aromatic
38. Consider the following reaction
+
H
••N ••N—H (A) Which is correct about A

(a) A is aromatic (b) A is antiaromatic

(c) A is non aromatic (d) It is nonaromatic but planar

39. Assertion:- This compound has large dipolemoment

Reason: — C = C bond between two rings on dissociation makes the entire molecule aromatic & stable
(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true
40. Assertion: - Pyrrole is aromatic however it contains sp3 hybridised N
Reason: - It is cyclic and contains six p delocalised electrons
(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true
41. Assertion: - Cyclopropene is hydride ion donor
Reason: - The carbocation formed after the removal of hydride ion from cyclopropene is stabilized by resonance
(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true
O OH O OH
(+)
H (+)
42. Assertion:- ; H

O OH O OH
(i) (ii) (iii) (iv)
62 Problems in Organic Chemistry

Compound (i) readily isomerises to hydroquinone (ii) when treated with dilute acid but (iii) could not be isomerises to (iv)
Reason: - (ii) is aromatic while (iv) is non aromatic
(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true
Ph Ph

43. Assertion:- (i)

H COO–t–Bu
Ph Ph
(ii)
H COO–t–Bu
Compound (i), upon treatment with t – BuOK/ t – BuOD for 31 hours gave 5% D exchange at the starred hydrogen. Compound
(ii), similarly treated, and gave 22% exchange in 30 min.
Reason: - Presence of double bond makes (i) stable & irreactive
(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true

Matrix Match Questions

Each question contains statement given in two columns which have to be matched. Statement (A, B, C, and D) in column I have to
be matched with statements (p, q, r, s) in column II. The answers to these questions have to be appropriately bubbled as illustrated
in the following examples. If the correct match are A – p, A – s, B – r, B – r, C – q, D – S, then the correctly bubbled 4 × 4 matrix
should be as follows.

A p q r s
B p q r s
C p q r s
D p q r s

44. List – I (molecule / ion) List – II (Properties)

(A) Br (p) Anti aromatic

(B) Br (q) Aromatic

(+)
(C) (r) Non aromatic
(–)

Br
(D) (s) Gives ppt of AgBr with AgNO3
Reaction Mechanism (General Organic Chemistry) 63

45. List – I List – II

(A) (p) Aromatic

(+)

(B) (q) Non Aromatic

O

(C) (r) Evolve H2 with NaH

(D) B—H (s) Anti aromatic

46. List – I List – II

(A) (p) Non planar

(–)

(+)
(B) (q) Non Aromatic

(C) (r) Aromatic

(D) (s) (4n + 2)p delocalised electrons

47. Column – I Column – II

(A) (p) Aromatic

(B) (q) Non aromatic due to loss of planarity

O
EtO—C NEt2
(C) O (r) Non Aromatic because Huckel rule is not followed.
Et2N C—OEt
(–)
(D) (s) Anti aromatic
64 Problems in Organic Chemistry

48. Column – I Column – II

O (+)
(A) (P) aromatic

(B) (Q) highly unstable ion

O
(C) (R) highly unstable molecule

(–)

(D) (S) highly stable ion

Answer Key

1. (d) 2. (a) 3. (b) 4. (c) 5. (c) 6. (b) 7. (d) 8. (b) 9. (d) 10. (b)

11. (d) 12. (d) 13. (b) 14. (b) 15. (a) 16. (c) 17. (d) 18. (b) 19. (d) 20. (c)

21. (b) 22. (c) 23. (b) 24. (a) 25. (b) 26. (a) 27. (c) 28. (b) 29. (d) 30. (c)

31. (c) 32. (a) 33. (d) 34. (a) 35. (d) 36. (a) 37. (a) 38. (a) 39. (a) 40. (d)

41. (b) 42. (a) 43. (c)

Answers matrix match:-

44. (A) – r, s, (B) – r, s, (C) – p, (D) –q
45. (A) – q, r, (B) – p, (C) – q, r, (D) – r, s
46. (A) – r, s, (B) – r, s, (C) – r, s (D) – p, q, s
47. (A) – p (B) – p (C) –s (D) – q, r
48. (A) – p, s (B) – r (C) – q (D) –p

RESONANCE

Multiple Choice Questions

(–)
O
O
1. How many resonating structures are possible for the given species:-
O (–)
O
(a) 1 (b) 2 (c) 3 (d) 4
2. Which among the following is not stabilized by resonance?

(a) (b) (c) (d)

Reaction Mechanism (General Organic Chemistry) 65

3. Identify the wrong statement regarding tautomerism and resonance

(a) Tautomerism usually involves making and breaking of sigma as well as pi bonds while in resonance only the electrons in
pi bonds or lone pair on hetero atoms shift; the sigma framework is not disturbed.
(b) Tautomerism may involve a change in hybridization of atoms resulting in a change in the shape of molecule.
(c) The two tautomeric forms exist together though the equilibrium may shift to either side with a change in condition. The
tautomer has a physical reality whereas the resonating structures are imaginary.
(d) All are correct.
4. In which case a chance of resonance is least:-

NH2 NH2 NH2 NH2

(a) (b) (c) (d)

5. Which is not coplanar?

O O

(a) (b) (c) HCONH2 (d)

6. In which case lone pair indicated is not involved in resonance.

••
(a) N (b) C = N (c) CH 2 —
— CH — O— CH3 (d) ..
..S
••
H

7. Among the following identify electron-withdrawing group (in resonance).

( +) (+)
(a) —OCH = CH2 (b) — N = SH (c) —NHAc (d) —OTs
8. Consider the following species.

(–)
NO2 O F CHO

O2N NO2
(I) (II) (III) (IV)

Correct order of p e– density inside the benzene ring is:-

(a) I > II > IV > III (b) II > III > IV > I (c) III > II > IV > I (d) II > IV > III > I
9. Consider the following species.

F OH NH2 OCH3

(I) (II) (III) (IV)

Correct order of p e– density inside the benzene ring is:-

(a) IV > III > II > I (b) III > IV > II > I (c) III > II > IV > I (d) IV > II > III > I
66 Problems in Organic Chemistry

10. Compare the relative sability of following reasonating structures

(–)
O O
O
(+)
(+)

CHO CHO C
(–)
O H
(I) (II) (III)
(a) I > II > III (b) III > II > I (c) II > III > I (d) I > III > II

NH2 NH2 NH2

11. CH2 == NH

CHO
(I) (II) (III) (IV)

Among these compounds, the correct order of C – N bond lengths is:-

(a) IV > I > II > III (b) III > I > II > IV (c) III > II > I > IV (d) III > I > IV > II
12. What is the oxidation state of nitrogen in both the resonating structure respecively?

(a) –3 & – 3 (b) –3 & +3 (c) +3 & –3 (d) –3 & –4

(+)
13. O + H Stable intermediate

CH3O
Most probable structure of this intermediate would be:-

O O
(+) (+)
(a) OH (b) H (+)
O (c) CH3O (d) CH3O

CH3O CH3O
(+) H

14. Which of the following has longest C – O bond:-

(a) CH2 = CH – CH2 – OH (b) CH3 – CO– CH3
(c) CH2 = CH – OCH3 (d) CH2 = CH – CH = CH – OCH3
15. Which of the following has highest resonance energy?
O O O O

(a) (b) (c) (b)

16. Out of the following three species which of the two have equal C – O bond lengths:-
CH3COO(–) HCOO(–) HCOOH
(I) (II) (III)
(a) II, III (b) I, III (c) I, II (d) None
Reaction Mechanism (General Organic Chemistry) 67

( +) (+ )
17. (1) CH 2 = CH — CH 2 (2) CH 2 = CH — CH = CH — CH = CH — C H2
(+)

(3) (+) (4)

CH
2

Correct order of resonance energy

(a) 1 > 2 > 3 > 4 (b) 4 > 3 > 2 > 1 (c) 3 > 4 > 2 >1 (d) 2 > 4 > 1 > 3
18. Consider the following reduction process

E1 E2 E3
(1) (2) (3)

Here E1, E2 & E3 are activation energies of reduction processes of (1), (2) & (3) respectively. Relation between these activation
energies is:-
(a) E1 > E2 > E3 (b) E3 > E2 > E1 (c) E2 > E3 > E1 (d) E1 > E3 > E2
19. Resonance effect is not possible in:-
..

S
O
(a) (b) N – H (c) Both (a) & (b) (d)
.

N (+)
.

20. Out of I, II, III & IV equivalent resonating structures will be obtained in:-
(–)
2– (–) (–)
CO3 —O RSO3

(I) (II) (III) (IV)

(a) I, II & III (b) I & III (c) II & IV (d) I

21. You have three molecules as indicated below, where l1, l2 & l3 are bond lengths.

l1 l2 l3
..

..

CH2 CH — S — CH3 CH2 CH — O — CH3 CH2 CH — NH — CH3

Relation between l1, l2 & l3 would be

(a) l1 > l2 > I3 (b) l3 > l2 > l1 (c) l2 > l3 > l1 (d) l3 > l1 > l2

22. Consider the following ions.

O O(–)

(–)
(–) O
O
(II) (III)
(I)

Correct order of stability is:-

(a) III > II > I (b) I > II > III (c) I > III > II (d) I > II = III
68 Problems in Organic Chemistry

23. In whch case first resonating structure is more contributing than second resonating structure.
(–)
O
(+)
(a) CH3CONH2 and CH3 — C NH2

(+) (+)
(b) CH2 ..
CH — O — CH2 and CH2 CH — O CH2

.
(+)
Br
Br
(+)

(c) and
O (–) O
(d) and
(–)

24. Relation between bond dissociation energies of bonds a, b, c & d is:-

a c d
CH CH b CH3 — CH CH2

(a) a > b > c > d (b) d > b > a > c (c) a > d > b > c (d) a > d > c > b
25. Correct order of resonance stabilization of given anions is:-
PhSO3(–) AcO(–) PhO(–) CH2 = CH—CH = CHO(–)
(1) (2) (3) (4)
(a) 3 > 1 > 4 > 2 (b) 1 > 3 > 4 > 2 (c) 1 > 2 > 3 > 4 (d) 3 > 1 > 2 > 4
26. Compare the bond length of C — N bonds in following species

NH2 NH2

N O
O
(I) (II) (III)

(a) I > II > II (b) I > III > II (c) III > I > II (d) II > III > I
27. In the given molecule lone pair present on hetero atoms are numbered as 1, 2, 3 & 4

1N 2
N Me
O S
3 4
Correct order for these lone pairs in order of their participation in resonance will be:-
(a) 2 > 1 > 4 > 3 (b) 4 > 3 > 2 > 1 (c) 4 > 2 > 1 > 3 (d) 2 > 1 > 3 > 4
28. Correct order of stability of resonating structures given below is:-

CH 2 = CH — Cl (+ )
CH 2 — CH = Cl
(–) (–)
CH 2 — CH = Cl
(+ )

(I) (II) (III)

(a) I > II > III (b) III > II > I (c) I > III > II (d) II > I > III
Reaction Mechanism (General Organic Chemistry) 69

Passage - I

Consider the following two compounds A & B

1 2 3 4 5 6

CNH—NH O O NH

(A) (B)
Answer the questions from 29 to 32
29. In compound A correct order of electron density inside the benzene ring will be:-
(a) 1 > 2 > 3 (b) 2 > 3 > 1 (c) 2 > 1 > 3 (d) 3 > 2 > 1
30. In compound B correct order of electron density inside the benzene ring will be:-
(a) 4 > 5 > 6 (b) 6 > 4 > 5 (c) 5 > 6 > 4 (d) 5 > 4 > 6
31. The benzene ring with least electron density is:-
(a) 1 (b) 2 (c) 4 (d) 3
32. In compound B correct order of electron density inside the benzene ring when NH is replaced by S will be:-
(a) 4 > 5 > 6 (b) 6 > 4 > 5 (c) 5 > 6 > 4 (d) 5 > 4 > 6

Passage - II

When any species undergoes resonance it becomes stable. Higher the number of resonating structures higher is the stability of the
species. Resonance also affects the bond length.

Answer the questions from 33 to 36

33. Which has least dipole moment?
(a) Flurobenzene (b) Chlorobenzene (c) Bromobenzene (d) Iodobenzene
34. In which case bond length of C = O bond is least?
(a) Carboxylate ion (b) formate ion (c) Methyl acetate (d) Acetamide
35. In which case bond length of C — O bond is maximum.
(a) Carboxylate ion (b) Phenoxide ion (c) p-nitro phenoxide ion (d) 2,4 di nitro phenoxide ion
36. Pyrrole undergoes resonance as:-
(–)

(+) (+) (–)

N N N
H H H
(I) (II) (III)

Correct order of stability of these resonating structures is:-

(a) I > II > III (b) III > II > I (c) I > III > II (d) III > I > II

Answer Key

1. (d) 2. (c) 3. (d) 4. (c) 5. (d) 6. (b) 7. (b) 8. (b) 9. (c) 10. (a)
11. (c) 12. (a) 13. (a) 14. (a) 15. (b) 16. (c) 17. (c) 18. (c) 19. (d) 20. (b)
21. (b) 22. (c) 23. (c) 24. (c) 25. (c) 26. (b) 27. (d) 28. (c) 29. (b) 30. (c)
31. (a) 32. (d) 33. (a) 34. (c) 35. (b) 36. (c)
70 Problems in Organic Chemistry

REACTION INTERMEDIATES AND ATTACKING REAGENTS

(Carbocation, carboanion carbene, Nitrene, Benzyne, Electrophile, Nucleophile)

Multiple Choice Questions

1. Hybridization of negatively charged carbon in given species are respectively:-

O
CH3 (–) (–)
CH CH2 CH — CH2 (–)
CH3

(a) sp3, sp3, sp3 (b) sp3, sp2, sp3 (c) sp3, sp2, sp2 (d) sp2, sp2, sp2
2. Which is better attacking reagent (strong base) among the following?
(a) CH3O(–) (b) HCOO(–) (c) PhO(–) (d) CH2 = CH—O(–)
3. Which among the following will have least electrophilicity?
(a) BF3 (b) BBr3 (c) BCl3 (d) BI3
4. Identify the carbocation in which rearrangement is not possible.

CH3 (+)
CH3 (+)
(+)
(a) (b) (c) (d)
(+)
CH3
5. Highly stable carbocation is:-

(+)CH (+)CH (+)CH (+)CH

2 2 2 2
NH2
NO2
(a) (b) (c) (d)
NH2
NO2
6. Highly stable carbocation is:-

(+)CH 2 (+)CH2 (+)CH 2 (+)CH 2

(a) (b) (c) (d)

OCH3 NH2 NO2

7. Identify the option in which Ist intermediate is found to be more stable than 2nd

CH3 — N — CH3 CH3 — CH — CH3 (+)

(a) , (b) (+) ,

CH3 — C — CH3 CH3 — C — CH3

(+) (+)

(+)
(+)
(c) , CH — CH — CH (d) CF3(–) , CCI3(–)
3 3
Reaction Mechanism (General Organic Chemistry) 71

8. Triplet carbene has

(a) Tetrahedral geometry (b) Bent shape (c) Linear geometry (d) Trigonal planar shape
9. Which carbocation is aromatic?

(+)
NH
(a) (b) (c) (d) None
(+)
N

H
••
10. Cis–but–2–ene + C H2 (triplet) ——→ [X], [X] will be:-

H3C CH3 H3C H H3C CH3

(a) C—C (b) C—C (c) C—C (d) both b & c
H H H CH3 H H

(+ ) ••
11. Which statement is incorrect about CH3 and CH 2 (triplet)
(a) Both serve as electrophile
(b) In both the cases central carbon atom possesses 6e- in outermost shell
(c) In the both cases carbon is sp2 hybridized
••
(d) CH3+ is triangular planar however CH 2 is linear
12. Pick out highly unstable carbonium ion:-
(+ ) (+ ) (+ ) (+ )
(a) CH3 (b) (F3C) 3 C (c) F — C — F (d) CH3 CH 2
|
F
13. Highly stable carbocation is:-

( +) (+ )
(a) CH 2 = CH — CH 2 (b) CH 2 = CH — CH —OCH3
|
OCH3

( +) (+ )
(c) CH 2 = CH — CH — OCH3 (d) CH 2 = CH —CH — OCH3
| |
NMe3 OCH3
( +)

(–) (–) (–) (–)

CH2 CH2 CH2 CH2
NO2
14.
NH2 OH
(1) (2) (3) (4)

Correct order of stability is:-

(a) 2 > 4 > 1 > 3 (b) 2 > 4 > 3 > 1 (c) 2 > 3 > 4 > 1 (d) 2 > 3 > 1 > 4
15. Correct order of stability of following carbanions will be:-
(–) (–) (–)
Cl—C—Cl F—C—F
| |
Cl F
(1) (2) (3)
(a) 3 > 2 < 1 (b) 3 > 1 > 2 (c) 2 > 3 > 1 (d) 2 > 1 > 3
72 Problems in Organic Chemistry

16. Consider the following:-

H H
H H H
H O
||
(1) (2) (3) (4) CH—C—H
3

Out of these which will form highly stable carbocation by the removal of H
(a) 1 (b) 2 (c) 3 (d) 4

( +) ( +)
17. 3C( +) CH 2 = CH — CH 2 CH3 () 2C ( + ) — CH3
(1) (2) (3) (4)
In which case positive charge density is least on bold C?
(a) 3 (b) 2 (c) 1 (d) 4

(–) (–) (–) (–)

18. 3 C CH 2 = CH—CH 2 (CH 3 ) CH 2  2 C — CH3
(1) (2) (3) (4)
In which case negative charge density is maximum on C?
(a) 1 (b) 2 (c) 4 (d) 3
19. Consider the following radicals

• • •
(1) (2) (3) (4)

Correct order of stabilities of these radicals is:-

(a) 4 > 2 > 1 > 3 (b) 4 > 2 > 3 > 1 (c) 4 > 3 > 2 > 1 (d) 2 > 4 > 3 > 1
20. Which statement is incorrect about the following:-
•• •• (+ )
CH3 — N, CCl,2
•• CH3
(a) All can serve as electrophile
(b) In all cases reactive centre possesses 6e- in its outermost shell
•• ••
(c) CH3 N and C Cl2 both have two forms singlet and triplet
••
(d) All are short lived species
(i)hv
21. RN3 ¾¾¾¾¾¾® Product. Identify the product of this reaction?
(ii) Cyclohexene
R R
R R
(a) N—R (b) (c) (d)
R

22. Consider the following carbocation:-

(+) (+) (+)

(+)
(1) (2) (3) (4)

Correct order of their stability will be: -

(a) 3 > 4 > 2 > 1 (b) 3 >2 > 4 > 1 (c) 4 > 3 > 2 > 1 (d) 3 > 4 > 1 > 2
Reaction Mechanism (General Organic Chemistry) 73

23. Consider the following carbanion: -

(–) COCH3 (–) COCH 3
(–) (–)
(1) CH 2COCH 3 (2) (3) (4) CH 2 = CH — C H 2
Correct order of their stability is:-
(a) 3 > 2 > 4 > 1 (b) 3 > 2 > 1 > 4 (c) 2 > 3 > 4 > 1 (d) 2 > 3 > 1 > 4
24. More stable carbocation is:-
(a) p – Chloro benzyl carbocation (b) p – Nitro benzyl carbocation
(c) p – Methoxy benzyl carbocation (d) Benzyl carbocation
25. The most reactive carbanion among the following is:-

(–) (–)
(a) CH 2 CH2 (b)  CH 2

(–) (–)
(c) p — OMe — C6 H 4 — CH 2 (d) p — NO2 — C 6H 4 — CH 2

26. Carbocation undergoes rearrangement to get stability. In a chemical reaction following carbocation is generated as
intermediate.
CH3
(+)
C2H5 — C — C O

H
Select the correct statement regarding above carbocation
(a) It is stabilized by hydride shift towards electrophilic carbon
(b) It is quite stable and can not show rearrangement
(c) It is stabilized by methyl shift towards electrophilic carbon
(d) It is stabilized by ethyl shift towards electrophilic carbon
27. Rank the following free radicals in increasing order of their stabilities

CH2

(1) (2) (3) (4)

(a) 4 < 3 < 2 < 1 (b) 4 < 1 < 2 < 3 (c) 4 < 2 < 3 < 1 (d) 3 < 4 < 2 < 1
28. H2 gas will be liberated in

(a) + K metal (1 mole)

(b) + NaH

(c) + K metal (2 mole)

(d) Both (b) & (c)

29. Identify the species which is not an example of electrophile: -
(+ ) (+ ) (+ ) ••
(a) (C 2 H5 )4 N (b) H3 O (c) Cl (d) C Cl2
74 Problems in Organic Chemistry

30. Which of the following is most stable carbanion intermediate?

(a) (b) (–)

(–)

(–)

(–)
(c) (d) — C — CH3

C2H5

Passage - I

When H+ attacks on OH group of an alcohol carbocation is formed:-

H ( +)
R — OH ¾¾¾® R (+) + H 2 O

Rate of formation of carbocation depends on the stability of carbocation. Higher the stability of carbocation easily it can be
formed.

Answer the questions from 31 to 34.

31. In which case attack of H+ on OH is more appreciable.
F OH
F F
(a) F— C—OH (b) CH3OH (c) (d) (F3C)3COH
F F
F

32. Which of the following will give highly stable carbocation on reaction with H (+) ?

(a) Ph3COH (b) COH

3

Ph OH
| |
(c) CH 2 = C — OH (d) CH3 — C — CH = CH 2
|
Ph
33. Which will produce highly unstable carbocation on reaction with H+?
OH OH
(a) (CF3)3COH (b) CF3OH (c) (d)
OH (1)
Ph
34. OH (2)

OH (3)
Reaction Mechanism (General Organic Chemistry) 75

Correct order of ease of removal of OH by H+ is:-

(a) 3 >2 > 1 (b) 1 > 2 > 3 (c) 3 > 1 > 2 (d) 1 > 3 > 2

Passage - II

Carbocation, carbanion & free radicals are stabilized by resonance. Except carbanion, carbocation & free radical exhibit hypercon-
jugation however carbanion shows reverse hyperconjugation. Stability of free radical should be checked by resonance and I-effect
only.

Answers the question from 35 to 38

35. Consider the following carbanion
(–) (–) (–) (–) (–)
CH 2 = CH — CH 2 MeOCH = CH — CH 2 Ph 3 C CH 3 CH 2F
(1) (2) (3) (4) (5)

Correct order of their stability is:-

(a) 2 > 3 > 1 > 5 > 4 (b) 3 > 1 > 2 > 5 > 4 (c) 3 >2 > 1 > 5 > 4 (d) 3 > 5 > 2 > 1 > 4
36. Most stable carbocation is:-

(+) (+) (+) (+)

(a) (b) (c) (d)

37. In which case chances of resonance is least?

(–) (–) (–) (–)
CHCF3 CHCF3 CHCF3 CHCF3

(a) (b) (c) (d)

38. Which one of following will form with greater ease?

(a) (b)

•
(c) (d) CH 2 —
— CHCH 2 — C H 2

Passage - (III)

Answer the question from 39 to 42

+ 2Na (A) + Na (B) (X) + (Z)

[X]

39. Which is aromatic?

(a) A & Z (b) B & Z (c) Only Z (d) None
76 Problems in Organic Chemistry

40. Which is radical anion?

(a) A (b) B (c) Z (d) None
41. Which is correct about A, B & Z?
(a) A & Z are same (b) A & B are same (c) A ≠ B ≠ Z (d) All are wrong
42. Which is anti aromatic?
(a) X (b) A (c) B (d) None
43. Which intermediate is optically active?
(–) • (+ )
(a) MeCHF (b) CF2 I (c) CHFBr (d) All are optically inactive
44. If resonance effect is not considered then least stable carbocation will be:-
(+ ) ( +) ( +) (+ )
(a) 3 C (b) F3CCH 2 (c) CH 2 = CH — CH 2 (d) CH3
45. Consider the following carbocations
(+) (+)

(+)
CH2—CH 2
(1) (2) (3)
Examples of classical carbocation is /are:-
(a) 1, 2 (b) 2, 3 (c) only 3 (d) 1, 2 & 3
46. Four containers A, B, C & D contain FCH2Br, F3CBr, vinyl bromide and allyl bromide respectively now equal amount Ag+
ions are added in each container and white precipitates are formed in three containers. The container in which precipitation
does not occur is:-
(a) A (b) B (c) C (d) D
47. Which will undergo disproportionation to give alkene?
( ) (–) • ••
(a) CH3 — CH 2 (b) CH3 — CH 2 (c) CH3 — CH — CH3 (d) CH3 C H 2
(+) (+)
(+) (+) CH2 CH2
CH2 CH2
OCH3
48.
(–)
(1) (2) OCH3 OCH3 O
(3) (4)

These ions will follow the stability order:-

(a) 1 > 3 > 4 > 2 (b) 1 > 3 > 2 > 4 (c) 4 > 3 > 1 > 2 (d) 4 > 1 > 3 > 2
49. Which of the following is most unlikely intermediate?

(+)

(a) (b) (c) (d) (+)

50. How many rearrangements will occur frequently in the given carbocation?

Ac
Ac (+)
(a) 1 (b) 2 (c) 3 (d) None
Reaction Mechanism (General Organic Chemistry) 77

Matrix Match Questions

Each question contains statement given in two columns which have to be matched. Statement (A, B, C, and D) in column I have to
be matched with statements (p, q, r, s) in column II. The answers to these questions have to be appropriately bubbled as illustrated
in the following examples. If the correct match are A – p, A – s, B – r, B – r, B – q, C – q, D – S, then the correctly bubbled 4 × 4
matrix should be as follows.

A p q r s
B p q r s
C p q r s
D p q r s

51. List – I (Reaction intermediate) List – II (Available empty p – orbital / s)

(A) CH3(  ) (p) 0
••
(B) CH2 (q) 1
(C) CH3(–) (r) 2

(D) CCl2 (s) 3

52. List – I (Molecule / intermediate) List – II (Pattern of bond present)

(A) (p) sp – sp2 s bond

(B) (q) sp3 – sp3 s bond

S
(C) (r) sp2 – sp2 p bond

(+)
N2
(D) (s) sp2 – sp2 s bond

53. Column – I Column – II

(+)
CH2
(A) (p) sp2 hybridised carbon

(–)
CH2
(B) (q) sp3 hybridised carbon

CH2 — CH2
(C) (r) Most stable intermediate

(D) CH3CH2(–) (s) Intermediate is not stabilised by resonance

54. Column – I Column – II
N
D
N 
(A) → (p) Carbocation is produced

H( + )
(B) 
→ (q) H2O is produced
OH
78 Problems in Organic Chemistry

D
(C) CH2CO  → (r) N2 is produced
(D) CH (+) (–)
→ (s) SO2 is produced
D

3
C2H5 C == N == N — SO2Ph
(t) Carbene is produced

Answer Key

1. (c) 2. (a) 3. (a) 4. (a) 5. (c) 6. (a) 7. (a) 8. (c) 9. (a) 10. (d)

11. (c) 12. (b) 13. (b) 14. (d) 15. (b) 16. (b) 17. (c) 18. (d) 19. (b) 20. (c)

21. (a) 22. (a) 23. (d) 24. (c) 25. (a) 26. (b) 27. (a) 28. (d) 29. (a) 30. (b)

31. (a) 32. (b) 33. (a) 34. (d) 35. (b) 36. (a) 37. (c) 38. (c) 39. (a) 40. (b)

41. (a) 42. (d) 43. (d) 44. (a) 45. (b) 46. (c) 47. (c) 48. (c) 49. (d) 50. (c)

Answers matrix match

51. (A) – q, (B) – q, r, (C) – p (D)-q 52. (A) – s, (B) – r, s, (C) – q, (D) – p, s
53. (A) – p, (B) – p, r (C) – q, s (D) - q, s 54. (A) – r, t (B) – p, q (C) – t, (D) – r, t

Nucleophilic Substitution Reactions

Multiple Choice Questions

1. How many transition states will be observed in following transformation?

Br NH2
+ NaNH2 in water —— NaBr +

(a) 2 (b) 3 (c) 1 (d) 4

2. The reaction Ph3CBr + EtOH ——→ Ph3COEt + HBr will involve.
(a) One transition state (b) 2 - transition states
(c) 3 - transition state (d) four transition state
3. Which Statement is correct about aliphatic nucleophilic substitution reactions?
(a) In SN2 racemisation takes place.
(b) In SN1 complete racemisation occurs
(c) In SN1 partial racemisation occurs and isomer with inverted configuration forms more.
(d) In SN1 partial racemisation occurs and isomer having configuration similar to that of substrate forms more.
4. Pick out the correct order of rate of SN1 for the following compounds
Cl
Cl Ph
CH—Cl
Ph Me2CHCl

(I) (II) (III) (IV)

(a) I > II> III >IV (b) III > II > I > IV
(c) I > III > II > IV (d) III > I > II > IV
Reaction Mechanism (General Organic Chemistry) 79

5. In which case racemisation takes place.

C2H 5 C2 H5
(–) (–)
| |
OH OH
(a) CH 3 — CH—CH 2Br →
1 (b) CD3 — CH—CH 2 Br →
1
SN SN

(–)
OH
(c) CH2Br 
1
→ (d) All of these
SN

6. A species is said to be a good nucleophile if

(a) It has large size and high electro negativity. (b) It has small size and high electro negativity
(c) It has large size and less electronegativity. (d) It has small size & less electro negative.
7. Correct order of rate of SN2 is:-

(I) Cl (II) Cl (III) Cl (IV)

Cl
(a) II > III > IV > I (b) III > II > IV > I
(c) II > IV > III > I (d) I > III > II > IV
8. Correct order of rate of SN1

(I) (II)
Cl Cl

(III) Ph2CHCl (IV)

Cl

(a) III > IV > I > II (b) I > III > IV > III
(c) III > IV > II > I (d) III > I > IV > II

CH3
9. CH3 C — O — CH3 + HI (cold and dil) —— products
CH3

Select correct statement(s)

(a) This reaction occurs via SN2 path way (b) In it primary iodide is produced
(c) In this reaction 3°-iodide is produced (d) Reaction can occur by SN1 as well as SN2 path way
10. Which is correct?
H Et (–) Pr
C2H5O C2H5OH
(a) Recemisation (b) Me Walden inversion
D Br Et
Br
Et
(c) Me C2H5OH
Br Racemisation (d) All are correct

Ph
11. CD2 = CH — CH2Br is subjected to nucleophilic substitution reaction by EtO(–) in EtOH. Which of the following statement
will be most appropriate?
(a) Both SN1 & SN2 give two products. (b) Both SN1 and SN2 give only one product.
(c) SN1 gives two products but SN2 gives one product. (d) SN1 gives one product but SN2 gives two products.
80 Problems in Organic Chemistry

12. Suggest the very suitable solvent for the reaction given below
CH2Br CH2OH
NaOH
—————→

(a) H2O (b) C2H5OH (c) HCONMe2 (d) C6H6

13. In which case chances of SN2 are maximum

(a) (b) Br + C2H5O(–)(in C6H6)

(–)
Br + C 2 H5 O (in H2 O)

(c) (–)
Br + C2 H5O in DMF (d) (–)
Br + C 2 H5 O in DMSO

COOH COOH
(1) aq. NaOH
14. D Br →
+ D OH
(2) H
C2H5 C2H5
This nucleophilic substitution reaction occurs via the formation of:-
O
D COOH D COOH D COOH
δ– δ– s–
(a) (+) (b) OH Cl (c) Cls– (d) O Et
HO D
Et Et Et
15. If the compound given below is subjected to SN1 reaction by aq. NaOH then order of ease of removal of bromine will be:-

Br3
Br1
HN
Br2
(a) 1 > 2 > 3 (b) 2 > 3 > 1 (c) 3 > 2 > 1 (d) 2 > 1 > 3

I I I I
O
16. (I) (II) (III) (IV)
O
O
Ease of SN1reaction among these compounds will be in the order as:-
(a) I > III > II > IV (b) IV > III > II > I (c) III > II > I > IV (d) III > IV > II > I
17. Which among the following reaction satisfies the potential energy diagram given below?

change in
free energy

reaction
coordinates
Reaction Mechanism (General Organic Chemistry) 81

(a) Br + aq NaNH2 NaBr + NH2

(b) Br + NH3 —— H Br + NH2

CH3
CH3
(c) CH3 — CH — CH2 — Br + NH3 ——→ HBr + CH3—C—NH2

CH3

(d) + H2 O —— OH
Br

OH
aq.
18. (B) ←
aq.
 → (A), (A) & (B) are:-
NaOH Na 2CO3

Br
OH OH OH OH

(a) & (b) &

OH OH CO3Na OH
OH CO3Na OH

(c) & O (d) &

OH Br OH
CH3
C H OH
19. →
2 5 A (major), Product A is:-

CH3
CH3 OEt
| |
(a) CH3 — C— CH 2OC2H5 (b) CH3 — C— CH 2 — CH3
| |
CH3 CH3

CH3
|
(c) CH3 — C  CH 2 (d) None

20. Which one of the following will be hydrolysed with maximum rate?
Cl
(a) C6H5Cl (b) (c) CCl (d) C6H5CH2Cl
3
solvent
21. Br + NaOH ————— OH

For which solvent rate of SN2 will be maximum

(a) 100% H2O (b) 75% H2O + 25% acetone (c) 100% acetone (d) 21% H2O + 75% acetone
82 Problems in Organic Chemistry

Me
Br Br (–)
OH
22. H A is:-
in DMSO
H H
Me Me Me
OH OH H OH H H
(a) H (b) H (c) H (d) All of these

H H OH H OH OH

23. Which will yield white precipitate with AgNO3?

Cl
(a) CH2Cl (b) (c) CH2 = CH — Cl (d)
Cl

24. Which path is better for the preparation of ROH?

(–)
OH (Path I)
R—F ROH
(–) (–)
I OH
RI ROH (Path II)
(a) Path I (b) Path II (c) Both (d) None
25. Consider the solvolysis (SN1) of the following halides.
Cl
Ph
Ph Ph
(I) (II) (III) CH—Cl (IV) CHI
Ph Ph
Cl

Correct order of rate of solvolysis willl be:-

(a) II > III > I > IV (b) III > IV > II > I
(c) IV > III > I > II (d) IV > III > II > I
H
|
26. In the given reaction CH3 — C — Br  [X] will be:-
NaI
| Acetone
C2 H5
H
(a) I (b) CH3CH2 — CH2 — CH2 — I
Et
H
(c) I (d) Mixture of (a) & (c)
Et

27. Arrange the following in decreasing order of nucleophilicity in ethanol medium:-

(–) (–) (–) (–)
F Cl Br I
(1) (2) (3) (4)
(a) 1 > 2 > 3 > 4 (b) 3 > 2 > 1 > 4 (c) 4 > 3 > 2 > 1 (d) 2 > 3 > 4 > 1
28. Arrange the following groups in order of decreasing leaving groups ability for SN reaction.
(–) (–) (–) (–)
(I) CH3 SO 3 (II) CF3SO3 (III) Tert BuO (IV) I
(a) I > II > III > IV (b) IV > I > II > II (c) III > II > I > IV (d) II > I > IV > III
Reaction Mechanism (General Organic Chemistry) 83

29. Which among the following will undergo hydrolysis rapidly?

Br Br Br
Br

(I) (II) (III) (IV)

(a) I (b) II (c) III (d) IV

30. Arrange the following in decreasing order of SN2:-

Br Br Br Br

(1) (2) (3) (4)

(a) 1 > 4 > 2 > 3 (b) 1 > 4 > 3 > 2 (c) 1 > 2 > 4 > 3 (d) 1 > 3 > 4 > 2

31. CH2Br (–)

OH
OH
—————
in water

Which among the following is correct potential energy diagram for the above reaction?

G
(a) G (b)

reaction progress reaction progress

G G
(c) (d)

reaction progress reaction progress

(–) (–) (–)

32. Arrange the nucleophiles O H, Se H, and S H in order of their nucleophilicity in di methyl formamide (DMF) medium
(–) (–) (–) (–) (–) (–) (–) (–) (–) (–) (–) (–)
(a) OH  SH  SeH (b) SeH  OH  SH (c) SeH  SH  OH (d) SH  OH  SeH
84 Problems in Organic Chemistry

33. Consider the following reaction.

HOH
CH3 — CH2 — S — CD2 — CH2 — Br  → [X], [X] will be:-
(a) CH3CH2 — SCD2CH2OH (b) CH3CH2SCH2CD2OH
(c) Both (a) & (b) are correct (d) None
34. Alcohols on reaction with HX produce alkyl halides like:-
D
ROH + HX ¾¾ ® RX + H2O
How many carbocations will form as intermediates in following reaction?
OH Ph

+ HBr ——→ major product

(a) 1 (b) 2 (c) 3 (d) 4

35. Consider the following reaction
D C H OH
Me3CBr ¾¾ ® Me3C — OEt ………….. I Me3CBr →
2 5
in 25% H O
Me3C — OEt …………..II
2
C2 H5OH
Me3CBr  → Me3C — OEt …………..III
in 25% H 2O

Correct order of rate of SN1 will be:-

(a) III > II > I (b) II > III > I (c) III > I > II (d) I > II > III
36. Which is correct about the nueleophilicity of halide ion?
(a) In DMSO order of nueleophilicity is F(–) > Cl(–) > Br(–) > I(–) while in water it is I(–) > Br(–) > Cl(–) > F(–)
(b) In DMSO order of nueleophilicity is I(–) > Br(–) > Cl(–) > F(–) while in water it is F(–) > Cl(–) > Br(–) > I(–)
(c) Order of nueleophilicity is same as F(–) > Cl(–) > Br(–) > I(–) in both water & DMSO
(d) Order of nueleophilicity is same I(–) > Br(–) > Cl(–) > F(–) in both water & DMSO
37. Consider the following reactions:-
CH3
NaOH CI aq Me2 COH

Ph 3CBr  → Ph 3COH ………….. I CH  → | ………….. II
(aq) 3 Ph NaOH
Ph

Ph Ph
Br OH
NaOH NaOH
CH3—CH2Br → CH3CH2OH………….. III → ………….. IV
in DMF in DMF

Out of these four reactions in which case rate of reaction will increase by the addition of NaOH
(a) I (b) II (c) III (d) IV
38. Which among the following will undergo SN1 rapidly?
O O O O
Cl Cl Cl
(a) (b) (c) (d) H—N
O

Cl
39. Consider the following reactions:-
(I) CH3CH2Br + NaCN ——→ CH3CH2NC + NaBr (II) CH3CH2Br + AgCN ——→ CH3CH2CN + AgBr
(III) CH3CH2Br + AgNO2 ——→ CH3CH2ONO + AgBr (IV) CH3CH2Br + NaNO2 ——→ CH3CH2NO2 + NaBr
Which reaction is / are not correct?
(a) III & I (b) III, II & I (c) III (d) I, II, III & IV
Reaction Mechanism (General Organic Chemistry) 85

40. What is [X] in the following reaction:-

HOH
EtSCH 2 CH — Cl  [X]
|
CH3
Me (–)
| OH (+)
(a) EtSCH 2 CH—Cl (b) EtS—CH—CHO 2 H (c) EtS — CHMe (d) both (a) & (b)
|
CH3 CH2
CH3 CH3
+ NaOH ——→
41.

Et H Et OH
Br H

The most efficient solvent for above reaction is:-

O O
(a) H2O (b) (c) H2O + EtOH (4 : 1 ratio) (d) H2O + EtOH (3 : 1 ratio)
O O

42. The reation R — X + NaOH ——→ ROH satisfies following Ea diagram

The Ea diagram (3) belongs to

(a) R – F (b) R – Cl (c) R – Br (d) R – I

CH OH CH OH
43. (A) ←
3
(–) H Me 
3 → (B), (A) & (B) are:-
CH 2O H SO 2 4

HO Me

MeO
(a) H Me & H Me (b) H Me & H

HO OMe HO Me MeO OH HO CH3

Me MeO Me
(c) OMe & H HO (d) Me & H

H OH MeO Me MeO OH MeO OH

86 Problems in Organic Chemistry

44. For the following reaction:-

CH3 — C H — CH3  KOH 

 KCl  CH3 — CH — CH3
| (aq) |
Cl OH
100%

Rate law can be written as:-

(a) K1 [alkyl halide] [KOH] + K2 [alkyl halide] (b) K2 [alkyl halide]
(c) K1 [alkyl halide] [KOH] (d) K1 [alkyl halide] [KOH] — K2 [alkyl halide]
45. CD2 = CH — CH2 — Br is subjected to SN1 and SN2 reactions separately which of the following statement is correct.
(a) Both SN1 and SN2 give two products (b) Both SN1 and SN2 give only one product
(c) SN1 gives two products but SN2 gives only one product (d) SN1 gives one product but SN2 gives two products
46. Which among the following chloro derivative of benzene would undergo hydrolysis most rapidly with aq. NaOH ?

NO2 NO2

(a) F — Cl (b) p — Me2N—C6H4Cl (c) O2 N Cl (d) O2 N Cl

NO2
47. Match the following
Substrate Rate of solvolysis by ethanol

(A) Br (p) 10–10

(B) (q) 10–3

Br

(C) (r) 1
Br
CH3
(a) A ——→ p, ——→ B ——→ q. C ——→ r (b) A ——→ r, B ——→ q, C ——→ p
(c) A ——→ p, B ——→ r, C ——→ q (d) A ——→ r, B ——→ p, C ——→ q
48. Which sequence of nueleophilicity is correct?
(a) nBuO(–)> SecBuO(–)> tert BuO(–) (b) tert BuO(–) > SecBuO(–)> nBuO(–)
(c) SecBuO(–)> tertBuO(–)> nBuo(–) (d) SecBuO(–)> n-BuO(–)> tertBuO(–)
49. The best leaving group among the following is:-
(a) CH3COO(–) (b) CH3O(–) (c) CH3SO3(–) (d) CH ≡ C(–)
50. Among the given compounds choose the two that yield same product in SN1 reaction

Br Br

Br
Br
(1) (2) (3) (4)

(a) (1) & (2) (b) (1) & (3) (c) (1), (2) & (3) (d) (2) & (4)
Reaction Mechanism (General Organic Chemistry) 87

Et
O
51. + HI (cold and dilute) ——→ [X]

Select correct statement regarding the product [X]

(a) It is 3° alcohol (b) It is 2° alcohol (c) It is 1° iodide (d) It is optically active

I CH3

52. + NaOH (in crown ether) —— [X], the product [X] is

H H
H CH3
(a) Optically active (b)
HO H
HO CH3
(c) & can not show geometrical isomerism (d) None is correct
H H

Note: For more questions on N.S.R see hydrocarbon (chapter - 6) & alkyl halide (chapter - &)

Answer Key

1. (b) 2. (c) 3. (c) 4. (a) 5. (b) 6. (c) 7. (b) 8. (d) 9. (c) 10. (c)

11. (c) 12. (c) 13. (d) 14. (d) 15. (d) 16. (a) 17. (b) 18. (c) 19. (b) 20. (c)

21. (c) 22. (c) 23. (a) 24. (b) 25. (d) 26. (c) 27. (c) 28. (d) 29. (a) 30. (a)

31. (d) 32. (a) 33. (c) 34. (a) 35. (d) 36. (a) 37. (c) 38. (a) 39. (d) 40. (d)

41. (b) 42. (d) 43. (b) 44. (a) 45. (c) 46. (c) 47. (b) 48. (b) 49. (c) 50. (a)

51. (d) 52. (b)

Free Radical Substitution Reaction (FSR)

Multiple Choice Questions

1. + Br•——→ HBr + X •

X radical would be:-

CH2

(a) (b) (c) (d)

88 Problems in Organic Chemistry

2. Maximum numbers of products which can be obtained by the mono chlorination of methyl cyclo butane are (Excluding
stereoisomers)?
(a) 2 (b) 3 (c) 4 (d) 5
Mono Chlorination
3. (CH3)2CH — CCl2 — CH (CH3)2 → [X] (major), [X] is:-
(a) (CH3 ) 2 CHCCl 2CHCH 3 (b) (CH3)2CCl — CCl2 — CH (CH3)2
|
CH2 Cl
(c) Both a & b are in equal amount (d) (CH3)2CCl — CCl2 — CCl(CH3)2
Cl
A
4. → A may be:-
hn

(a) NCS (b) tertiary butyl hypochlorite

(c) Cl2 / hv (d) all of these
5. You have following four compounds.
CH3 CH 3 CH3 Ph
| | | |
(I) (II) CH3 — CH — CH — CH3 (III) (IV) CH3 — C — C — Ph
| |
CH3 Ph
Select those compounds which will give two products on mono chlorination by Cl2/hv (Excluding stereoisomers)
(a) II & IV (b) II & III (c) I & II (d) I, II & III

6. Rate of abstraction of these numbered hydrogen’s will follow the order

H3 H1
H2

(a) 1 > 2 > 3 (b) 2 > 1 > 3 (c) 3 > 2 > 1 (d) 2 > 3 > 1

NBS in CCl
7. CH3 — CH2 — CH = CH2 4 → [X], [X] may be:-

hn
Br
|
(a) CH3 — CH — CH  CH 2 (b) CH3 — CH = CH — CH2Br

(c) CH3 — CH2 — CH — CH 2 (d) (a) & (b)

| |
BrBr

NOCl
8. → [A], [A] is:-
hn

NO Cl N—OH
(a) (b) (c) (d) None

9. CH4 + 2CoF3 ——→ CH3F+ 2CoF2 + HF……………… (1)

NBS
CH3 — CH = CH2  → CH 2 — CH  CH 2….…………….. (2)
hn |
Br
Propanone
CH3CH2Cl + I(–)  → CH3CH2I + Cl(–) …..…………….. (3)
Bu SnH
CH3CH2Cl 
2 → CH3 — CH3 …..…………………... (4)

Which reaction is Wohl - Ziegler reaction -

(a) 1 (b) 2 (c) 3 (d) 4
Reaction Mechanism (General Organic Chemistry) 89

10. A hydrocarbon C8H18 gives only one mono chloro derivative with Cl2/hv. Hydrocarbon is:-

(a) (b) (c) (d)

11. A hydrocarbon A (vapour density = 43) on monochlorination gives chloro alkanes. If only one of
the formed chloro alkane contains chiral carbon atom then A would be:-
(a) n-hexane (b) iso hexane
(c) 2, 3-di methyl butane (d) 1, 1 - di methyl cyclobutane
12. Following steps are involved in halogenations of alkanes
X2 ——→ 2X* ……….…………………….. (1)
X* + RH ——→ R* + HX ……….…………………….. (2)
R* + X2 ——→ RX + X* …………..………………..… (3)
Which is rate determining step?
(a) 1 (b) 2 (c) 3 (d) none
13. Expected mono bromination products in the given reaction would be- (Excluding stereoisomers)

Br

2→
hn

(a) 3 (b) 5 (c) 4 (d) No Product

14. Which of the following reactions will yield 2, 2 - dibromo propane?
hn hn
(a) CH3 — HC = CH2 + 2HBr → (b) CH3CBr = CH2 + HBr →
(c) CH3 — HC = CH2 + 2HBr ——→ (d) both a & c
15. In which substrate two mono bromo derivatives will be formed by NBS/ hv /CCl4 (Excluding stereoisomers)

(a) (b) (c) (d)

Et
H O NBS
+ Cl2 h 
2 → →
16. K 2CO3 A, A will be –
1 : 2

O
CHOHBr C—COBr COCH2Br CH2 C2HBr
(a) (b) (c) (d)

Cl
17. C10H20 
2→
hn one mono chloro derivative,

So A will be-

(a) (b) (c) (d)

90 Problems in Organic Chemistry

18. Which of the following is not an example of free radical scavenger?

(a) O2 (b) Diphenyl aniline (d) Catechol (d) T.E.L
19. Iodination of alkane can be carried out by-
(a) I2 / hn (b) I2 / in CCl4 (c) I2 / HIO3 / hn (d) I2 / AlCl3
20. Iodination of alkane is difficult because:-
(a) I2 is more reactive in comparison to other halogens & hence, forms various side products
(b) Propagation step is exothermic.
(c) HI formed serves as reducing agent and reduces alkyl iodide in to alkane & I2.
(d) All are correct.
Cl
21. (CH3)2CH CH (CH3)2 2
hv
→ (CH3)2 CClCH(CH3)2 (A) % Yield of A would be:-
(a) 54.54 (b) 50 (c) 45.45 (d) cannot be predicted.
22. Hydrocarbon + Cl 2 h KOH  EtOH NBS
  
 (P)
[containing 6 carbon] [1 mol] hn

does not react with chlorine in dark

The product P would be:-
OEt
Cl Cl
(a) (b) (c) (d)
OH Br
Br Br
23. Consider the following reaction:-
CH3 — CH — CH — CH3 + Br* 
→ X + HBr
| | (free radical)
D CH3

Identify the most probable structure of [X]

D CH3
| |
• •
(a) CH3 — CH — CH — CH 2 (b) CH3 — CH — C
|
| |
D CH3 CH3
CH3
• • |
(c) CH3 — C — CH — CH3 (d) CH 3 — CH — CH — CH 3
D CH3
•
24. Consider the following CH3 — CD — CH — CH3  Br ——→ Free radical
| |
CD3 CD3
Identify the free radical predominantly produced in above reaction.
•
(a) CH3 — C — CH — CH3 (b) CH3 — CD — CH — CH3
|| | |
CD3 CD3 • CD
3 CD3
•
(c) CH3 — CD — CH — CH 2 (d) CH3 — CD — C• — CH3
| | | |
CD3 CD3 CD3 CD3

25. Which statement is correct?

(a) Chlorination of alkane is a selective reaction because chlorine free radical is highly reactive
(b) Chlorination of alkane is a selective reaction because chlorine free radical is less reactive
(c) Bromination of alkane is a selective reaction because bromine free radical is highly reactive
(d) Bromination of alkane is a selective reaction because bromine free radical is less reactive
Reaction Mechanism (General Organic Chemistry) 91

hn
26. C2H6 + Br2 → C2H5Br + HBr ………………….k1

hn
C2D6 + Br2 → C2D5Br + DBr ………………….k2

hn
C2H4 + Br2 → C2H4Br2 .………………….k3

hn
C2D4 + Br2 → C2D4Br2 .………………….k4
If k1 , k2 , k3 & k4 are the rate constants of the given reactions then:-
(a) k1 = k2 (b) k3 > k4 (c) k1 > k2 (d) k3 = k4

Answer Key

1. (d) 2. (c) 3. (a) 4. (d) 5. (c) 6. (d) 7. (d) 8. (c) 9. (b) 10. (c)

11. (c) 12. (b) 13. (c) 14. (c) 15. (a) 16. (c) 17. (c) 18. (d) 19. (c) 20. (c)

21. (c) 22. (c) 23. (b) 24. (d) 25. (d) 26. (d)

Aromatic Electrophilic Substitution Reaction

Multiple Choice Questions

1. Which among the following is the correct ptential energy diagram for sulphonation of benzene?

G ∆G
(a) (b)

reaction progress reaction progress

G
(c) (d) G

reaction progress reaction progress

92 Problems in Organic Chemistry

Ph

OH H( + )
2. + → X, X would be :-

1 mole HO

Ph Ph Ph Ph

OH Ph Ph
(a) (b) (c) (d)
Ph HO Ph Ph

O O
Ph H( + )
3. → X, the product ‘X’ would be:-

OH OH O O O
Ph
(a) (b) (c) (d) OH
O Ph
Ph OH

4. In previous reaction which intermediate will not form:-

(–) (+)
O OH O O O OH
Ph Ph
(a) (b) (c) (d)
(+)
O Ph O Ph
H

5. When 3 - Nitro acetophenone is treated with Fe/Br2 it gives.

COCH3 COCH3 COCH3 COCH3
Br Br
(a) (b) (c) (d)
NO2 NO2 NO2 Br NO2

Br

6. In which case Friedel Craft reaction by RCl / AlCl3 is not attainable.

(a) Benzoic acid (b) Salol (c) Acetanilide (d) Aniline

OH

7. Br Water
→ [A], [A] would be:-

2

SO3 H

OH OH OH OH
Br Br Br Br Br
(a) (b) (c) (d)
Br
SO3H SO3H Br SO3H
Reaction Mechanism (General Organic Chemistry) 93

8. Identify the product formed in the following transformation.

N O
→
2 5 major product

O2N

(a) (b) (c) (d)

NO2 NO3
NO2
Fuming HNO
9. 
3→
X (major), X would be :-
NO3
NO2
SO3H SO3H SO3H SO3H
O2N
(a) (b) (c) (d)
NO2 O2N
CH3 CH3 CH3 CH3
10. Consider the following reaction
O
Cl
+ ZnCl2
Cl  → P. product P would be :
one mole
N
N
O
O O O Ph
Cl
(a) (b) (c) (d) Ph
N
N N Cl N
H
H H H
4 3

11. 5 2 At which location chances of electrophilic nitration will be maximum:-

N1
H
(a) 2 & 5 (b) 4 & 5 (c) 1 (d) 1 & 2
12. 4 - Phenyl butyl chloride can be converted in to naphthalene by using:-
(a) Anhydrous AlCl3 & H+ (b) Anhydrous AlCl3 & Pd / D
(c) Cl2 / Fe & Na / Ether (d) Anhydrous ZnCl2 & H3O+
13. The major product formed when benzo trichloride is treated with [HNO3 / H2SO4 / heat] is :-
(a) o - nitro benzo trichloride. (b) m - nitro benzo trichloride.
(c) p - nitro benzo trichloride. (d) 2, 4 - Di nitro benzo trichloride.
14. Consider the following four statements
(1) Benzene does not favour the attack of Nu (–) on it self.
(2) On benzene ring E(+) can attacks easily because benzene ring is electron rich.
(3) Benzene ring does not undergo addition reaction readily because after addition reaction benzene ring looses its aromaticity.
(4) When electron with drawing groups are present on benzene ring, attack of Nu(-) on benzene nucleus becomes easy.
Out of these statements, correct statements are.
(a) 1, 3 & 4 (b) 1, 2 & 4 (c) 2 & 4 (d) All are correct
94 Problems in Organic Chemistry

8 1
9 2
7
15. Electrophilic substitution reaction in naphthalene occurs at:- 3
6 10
5 4

(a) Position - 1 (b) Position - 2 (c) Position - 9 (d) Position - 6

16. Identify the group which is meta directing for nucleophilic substitution reaction in benzene:-
(a) SO3H (b) CN (c) isopropyl (d) COOTs
17. Identify the reagents which can convert benzene in to phenyl cyclohexane:-
OH Cl
(a) & H3PO4 (b) (+)
CH2OH & H (c) & AlCl3 (d) All of these

18. In which electrophilic substitution reaction isotope effect is observed significantly.

(a) Nitration (b) Sulphonation (c) Friedel craft reaction (d) Halogenation
19. In which case o/p ratio will be maximum when subjected to Cl2 / Fe:-
F Cl I Br

(a) (b) (c) (d)

20. Which of the following compound will undergo friedel craft reaction with slower rate:-
(a) C6H6 (b) C6D6
*
(c) (d) the rate is same in all of these.
14
{*=C }

H (1 mol) H( + )
21. Iso pentyne 
2 → → [X], [X] would be:-
Ni / D C6 H 6

CH3
|
(a)  — CH2 — CH 2 — CH — CH 3 (b)  — CH — CH(CH3)2
|
CH3
(c)  —CMe 2 (d)  — CH2 — CH — Et
| |
Et CH3
22. You have following quaternary ammonium ions
(+) (+) (+)
ArNMe3 ArCH2NMe3 ArCH2CH2NMe3
(I) (II) (III)

Arrange the folowing in order of % of meta substitution

(a) I > II > III (b) II > I > III (c) III > II > I (d) I > III > II
G

FeCl3
23. + BrCl → [X] (Major)

What should be [X]if G is sec-butyl?

G G G G
Br Cl
(a) (b) (c) (d)

Cl Br
Reaction Mechanism (General Organic Chemistry) 95

(i) H ( + )
24. → [X], [X] may be:-

(ii) Ph − H

(a) (b) (c) (d) Both (a) & (c)

Φ
 

(i) FeCl
+ (5 - chloro pent - 2 - ene) 
3→
25. (ii) H ( + )
[A], [A] will be:-
(iii) Pd / D

(a) (b) (c) (d)

26. Sulphonation of benzene differs from rest of electrophilic aromatic substitution reactions because:-
(i) In sulphonation neutral electrophile attacks on benzene nucleus.
(ii) It is reversible.
(iii) It requires drastic conditions like high pressure and temperature.
(iv) It requires inert atmosphere.
The correct statement is / are:-
(a) 1, 3 (b) 1, 2, 4 (c) 1, 2 (d) 1, 2, 3 & 4
27. Correct order of electron density inside benzene ring in the following compound is:-

HOOC A O CO B O C ONH2

NO2

(a) A > B > C (b) B > C > A (c) C > A > B (d) A > C > B

(CH2 )4 — CH2Cl
28. HBF4 NO 2 Anh AlCl3
 → [X]  → [Y] would be:-

(CH2)4CH2NO2 O2N
(a) (b)
O4Cl

(c) (d)
O2N O2N

29. For the conversion of benzene in to naphthalene which reagent is not needed?
(a) Succinic anhydride / AlCl3 / H2O (b) H+
(c) Zn / Hg + HCl, Pd / ∆ (d) All are needed.
30. Select the correct statement:-
(a) Chlorination of nitro benzene is easier than nitration of chloro benzene.
(b) -CHCl2 & CCl3 groups are o & p directing.
(c) In aniline and phenol friedel craft methylation is not possible by CH3Cl & Anh. AlCl3
(d) (b) & (c) are correct
96 Problems in Organic Chemistry

31. Consider the following reaction

Et
|
C6H6 + Me3CCH2Cl 
Fe/Cl 2
Ph — CMe 2 , [W] Major


NH NH
C S EtONO C S
→
2
[X] major

NO2

COR CH3 COR CH3

H S O [ Y] major

2 2 7→

SO3H

Cl / FeCl

2 3→ [ Z] major

Cl

The product which is least likely to form -

(a) [W] (b) [X] (c) [Y] (d) [Z]

Passage - I

IPSO attack is a kind of aromatic substitution reaction in which a non hydrogen substitute in aromatic ring is substituted by other
sustituent.

Answer the questions from 32 to 36.

32. Which is not an example of IPSO attack:-
OH
OH O2N NO2
COOH
conc HNO

3→
(a) conc H 2SO 4
NO2

CH3
CH3 C CH3
(+) (+)
(b) + H + C Me3

Cl OH
NO2 NO2 O2N NO2
(c) + H2O ——→ + HCl

NO2 NO2

(d) All of these are the examples of IPSO attack.

Reaction Mechanism (General Organic Chemistry) 97

(i) i − BuCl / AlCl

33.  3→
[X], [X] would be:-
(ii) MeCl / AlCl 3
(iii) Fe / Br2
Me CMe3
CH2CHMe 2 CMe3
(a) (b) (c) (d)
Me Br Me Br
Br Br Me
34. The IPSO attack most likely to occur is:-
(a) ΦCΦ3 + H+ ——→ [CΦ3]+ + Φ - H (b) ΦC(CF3)3 + H+ ——→ Φ — H + C+(CF3)3
(c) Φ — Me + H+ ——→ Me+ + Φ — H (d) All are possible
35. Para nitro phenol can show IPSO attack when it is treated with
(a) nitrating mixture (b) Cl2 / Fe (c) Bromine water (d) All of these

CH3 CH3

36. H+ / D

→ + Me2C = CH2

CMe3
Which of the following statement is correct for this reaction:-
(a) It is ArSE (IPSO attack)
(b) It is an example of β - elimination.
(c) It is both ArSE and β - elimination
(d) None

Passage - II

o / p or m - directive influence of a group can be explained by the stability of carbocation (wheland complex or σ complex) formed
as intermediate. When electrophile attacks on substituted benzene different carbocation intermediates [Link] relative stabilities
help us in determining the directing nature of the group present on benzene ring.

Answer the questions from 37 to 40.

37. Most stable intermediate among the following is:-
NH2

NH2 CH3 NO2

E (+)
E (+)
(+) (+)
(a) (b) (c) (d) E

OMe OMe
E
(+)
+
38. 
→
E [A]

Which statement is not correct about [A]

(a) It is a sigma complex
(b) +R effect of OMe helps in the stabilization of positive charge.
(c) It has three resonating structures.
(d) Stability of [A] indicates that OMe is o/p directing group.
98 Problems in Organic Chemistry

39. Most stable intermediate among the following is:-

OH Cl OH Cl OH F OH
Cl NO2
NO2 NO2 NO2 (–)
(–)
(a) (b) (c) (–) (d)
(–)

40. Identify the most stable intermediate which should be formed during electrophilic substitution in Indole.

N
H
(+)
E (+)
E
(a) (b) (c) (+) (d)
(+) E E
N N N N
H H H H

Passage - III

Rate of aromatic electrophilic substitution depends upon the electron density inside the benzene ring. If benzene ring is substituted
by electron donating groups, electron density inside the benzene ring increases thus, E(+) attacks on ring with more efficiency and
hence rate of aromatic electrophilic substitution increases. In the same way rate of electrophlic substitution decreases if benzene ring
is substituted by electron withdrawing group.

Answer the questions from 41 to 45.

41. Rate of ArSE will be maximum in:-

NHOMe NH2
NHAc NPh2
(a) (b) (c) (d)

2
G
1 3
G G
42.
1 2 3

If G1, G2 & G3 are OMe, Cl & CHO respectively then correct sequence of benzene nucleus (1, 2 & 3) in order of their decreas-
ing electron density is :-
(a) 1 > 2 > 3 (b) 2 > 3 > 1 (c) 3 > 2 > 1 (d) 3 > 1 > 2
43. You have three substituents G1, G2 & G3 as follows
G1 = NO2, G2 = OH, G3 = Me3C
Identify the wrong statement
(a) If benzene ring is substituted by G3 then on nitration para nitro derivative will be formed as major product.
(b) Out of p — G1— C6H4 — G3 & p — G2—C6H4 — G3 former will have higher electron density in benzene ring than
later.
(c) From G3 — Ph, it is difficult to get o — G1 — C6H4 — G3 as a major product by electrophilic aromatic nitration.
(d) All are correct.
Reaction Mechanism (General Organic Chemistry) 99

44. Arrange the following compounds in decreasing order of rate of ArSE

CH3 CH2Me CHMe2 CMe3

I II III IV
(a) I > II > III > IV (b) IV > III > II > I (c) I > III > IV > II (d) III > IV > I > II
45. Highest electron density inside the benzene ring will be in:-
(a) Φ — Cl (b) Φ — F (c) Φ — Br (d) Φ — I

•
46. (+) Ph + Cu ——→ [A], [A] would be:-
(Free Radical)
N2

(–)
(+)
N = NCu
(a) (b) (c) (d)

47. For friedel craft alkylation rate law can be written as:-
Rate = K [Ar — H] [RX] [MX3]
Where MX3 is Lewis acid (Catalyst) The expected order of effectiveness of Lewis acids in friedel craft alkylation will be :-
(a) AlCl3 > BF3 > FeCl3 > SnCl4 (b) BF3 > AlCl3 > FeCl3 > SnCl4
(c) FeCl3 > AlCl3 > BF3 > SnCl4 (d) AlCl3 > FeCl3 > BF3 > SnCl4
48. Which among the following will produce 3 products on nitration by HNO3 + H2SO4?

Et Et CH3 CH3

CH3
NO2 NO2 SO3H

I SO3H
(1) (2) (3) (4) (5)

(a) 1 & 4 (b) 2, 3 & 5 (c) Only 1 (d) 2 & 5

49. What would be the least possible molecular weight of hydrocarbon which is optically active and undergoes Friedel Craft reac-
tion with RX in presence of anhydrous AlCl3?
(a) 122 (b) 108 (c) 134 (d) 132
CMe3
(+)
50. N O 2 BF4(–)
→ [A], [A] will be:-

Me3C CMe3
CMe3 CMe3 CMe3
O2N O2N NO2
(a) (b) (c) (d) both a & b
Me3C CMe3 Me3C CMe3 O2N CMe3

51. Which statement is not correct about benzene and pyrrole (C4H5N)
(a) Both are aromatic but pyrrole ring has less electron density in comparison to benzene ring.
(b) Aromatic electrophilic substitution in pyrrole is difficult in comparison to benzene.
(c) In pyrrole 3rd & 4th locations are more sensitive towards ArSE.
(d) Pyrrole has 6π delocalized electrons.
100 Problems in Organic Chemistry

OH

H( + )
52. → [X], [X] would be:-
C6 H 6

(a) O (b) (c) (d)

CD2H
53. Which of the following can show both –R & +R effect depending upon situation?
OTs NO CH == CH2 N == NH CHS
(1) (2) (3) (4) (5)
(a) 2, 3, 4 (b) 1, 3, 4, 5 (c) 1, 2, 3, 4 (d) 2, 3, 4, 5
54. Most sensitive benzene nucleus towards ArSE is present in
OCH3 OCH3
(–)
O N CH 3
(a) (b) (c) (d)

OMe CH3

2 moles of AlCl
55. 
3→
Product
CH3Cl

The product of this reaction would be:-

OMe CH3 OMe CH3 OMe CH3

CH3 CH3
(a) (b) (c) (d) Both b & c

CH3
AlCl3 EtONO 2
56. Ph — H + DCl →[X] →[Y] is:-
(Excess)
NO2 NO2
D D D
(a) C6H5NO2 (b) (c) (d)
D D NO2 D D
D D
CH3

57. ——→

CH3CO SO3H
During this transformation the reaction which should be carried out at last is:-
(a) Friedel craft acylation (b) Sulphonation (c) Friedel craft alkylation (d) Unpredictable
58. Which among the following will undergo Friedel Craft reaction (F. C. R.)?
H

N S N

(1) (2) (3) (4) (5)

(a) only 2 (b) 2 & 5 (c) 1, 2, 3, & 5 (d) All will show F.C.R.
Reaction Mechanism (General Organic Chemistry) 101

59. Which among the following can be used as a solvent in friedel craft alkylation (by RX/AlX3)?
(a) Φ — Me (b) Φ — CH2Cl (c) Φ — NO2 (d) Φ — OH

60. 

OH
Sequence of reagents required for this conversion is:-
(a) H3PO4 / ∆, & LiAlH4 (b) PCl5, alc. KOH, H+/∆ & Rh /∆
(c) H3PO4 / ∆ & Rh / ∆ (d) Both (b) & (c)
61. Which is not produced as intermediate in following transformation?
(+)
Ph H
——
CH2OH

(+)

(a) (b) (c) (+) (d)

(+)
(+)

62. What is [A] in the given reaction:-

SO3H
HO
Br
2 → [A]

NH2 water

Br SO3H
HO HO Br
(a) (b)
Br NH2 NH2
Br Br
Br Br
HO Br HO
(c) (d)
Br NH2 NH2
Br Br
63. Which among the following friedel craft reactions is not possible:-
AlCl
PhCH2Cl + Ph — H →
3 Ph2CH2 ……………..….. (1)
AlCl
Ph2CHCl + Ph — H →
3 Ph3CH ...………………... (2)
AlCl
Ph3CCl + Ph — H →
3 Ph4C .…….……………... (3)
AlCl
p — i — Bu — C6H4 — Cl + Ph — H →
3 p — i — Bu — C6H4 — Ph……(4)
(a) 2, 3, 4 (b) 3, 4 (c) 4, 1 (d) 2, 3
64. The sequence of reactions by which benzene can be converted in to 3 - ethyl - 5 - nitro benzene sulphonic acid is:-
(a) Friedel craft alkylation, Nitration, Sulphonation
(b) Sulphonation, nitration, Friedel craft alkylation
(c) Nitration, Friedel craft alkylation, sulphonation
(d) Sulphonation, Friedel craft alkylation, nitration
102 Problems in Organic Chemistry

CH2 HBr
65. → [A], [A] would be :-

acetic acid / heat
COCH3

(a) (b) (c) (d)

O OH

H( + )
CH2OH →
66. Heat [X], [X] is:-

(a) (b) (c) (d)

HCl
67. 2Ph — OH + → [A], [A] would be:-


O CH3
C C
(a) (b)
CH3

(c) HO CMe2 OH (d) HO CH2COCH 2 OH

68. The reagents required for the conversion of toluene in to 2 - (4-methyl phenyl) butan - 2 - ol is:-
(a) But - 1 - ene & H2O (b) Butan -2-ol / H3PO4 (c) Butan - 2 - one / H3PO4 (d) both (a) & (b)
69. When benzene is treated with methyl epoxy ethane in presence of (i) AlCl3 (ii) H2O a compound X (C9H12O) is formed. X will
be:-
OH
OH OCH2 CH 2 CH3
CH2OH CH2CH 3
(a) (b) (c) (d)

70. Predict the major product of bromination of the compound given below by using Br2 / FeBr3 in the dark: -
NO2

CH3
NO2 NO2 Br
NO2 NO2

(a) Br (b) (c) (d) Br

CH3 Br CH3 CH3 CH3
Reaction Mechanism (General Organic Chemistry) 103

71. Arrange the following in increasing order of rate of electrophilic nitration.

Cumene anisole Benzene Benzoic acid
(1) (2) (3) (4)
(a) 1 > 2 > 3 > 4 (b) 2 > 3 > 4 > 1 (c) 2 > 3 > 1 > 4 (d) 2 > 1 > 3 > 4
72. How many carbocations are produced during the following transformation?

(a) 1 (b) 2 (c) 3 (d) 4

73. Which among the following is the correct potential energy diagram for nitration of benzene?

∆G
(a) G (b)

reaction progress
reaction progress

G
(c) (d) G

reaction progress reaction progress

74. In which case mono substituted derivative of benzene is not produced.

(a) Benzene + N2O5 (b) Benzene + Oleum
(c) Benzene + CH3COCl + anh. AlCl3 (d) Benzene + CH3Cl + anh. AlCl3

NO2
NO2 H OH
CH3
——
75.
NHCH3 O2N N
O2N
Me

This conversion can be performed by

(a) H(+) /∆ (b) AlCl3 (c) EtOH + NaOH (d) All of these
104 Problems in Organic Chemistry

(i) CH 2 N 2
76. 3-Chloro propene 
(ii) AlCl / C H
→ [A], [A] would be:-
3 6 6

CH2 —CH2 = CH2

(a) (b)

(c) (d)

AlCl
77. + C2H5 — Cl →
3 Ph - Et

For the better yield of ethyl benzene, benzene & ethyl chloride should be taken in ratio.
(a) 1 : 15 (b) 15 : 1
(c) 1 : 1 (d) 1 : 1 & AlCl3 should be taken in excess
OH OH
NO2 steam distillation
78. + ———————→ [X], the distillate

NO2

How many products will be obtained by the sulphonation of [X] (distillate)?

(a) 1 (b) 2 (c) 3 (d) 4
79. 1 Mole of oxirane is mixed with 2-moles of benzene & catalytic amount of H3PO4 is then added product formed in this reaction
would be:-

(a) Ph2 (CH2)2 (b) PhCH2CH2OH (c) PhCH = CH2 (d) Reaction is not possible
AlCl
80. CCl4 + Benzene (excess) → 3 [X], [X] would be:-
(a) Φ2CCl2 (b) Φ3CCl (c) Φ4C (d) ΦCCl3
X
81. Ph — H + I2 → Ph — I + HI X would be:-
(a) HNO3 (b) FeI3 (c) HI (d) Fe / I2, ∆
O
Br
82. →
2 Product, Product will be:-
FeCl3

O
Br
O O
(a) (b)

O (100%) Br O (100%)
Br
O
Br O O
(c) (d) &
Br
O
O (100%) O

Reaction Mechanism (General Organic Chemistry) 105

Answer Key

1. (b) 2. (b) 3. (c) 4. (c) 5. (d) 6. (d) 7. (c) 8. (c) 9. (c) 10. (c)

11. (a) 12. (b) 13. (b) 14. (d) 15. (a) 16. (c) 17. (d) 18. (b) 19. (c) 20. (d)

21. (c) 22. (a) 23. (d) 24. (b) 25. (d) 26. (c) 27. (c) 28. (c) 29. (d) 30. (c)

31. (b) 32. (d) 33. (b) 34. (a) 35. (c) 36. (c) 37. (a) 38. (c) 39. (c) 40. (b)

41. (c) 42. (a) 43. (b) 44. (a) 45. (b) 46. (c) 47. (d) 48. (d) 49. (c) 50. (c)

51. (c) 52. (d) 53. (a) 54. (a) 55. (a) 56. (b) 57. (c) 58. (c) 59. (c) 60. (d)

61. (c) 62. (c) 63. (b) 64. (b) 65. (a) 66. (c) 67. (c) 68. (c) 69. (a) 70. (a)

71. (d) 72. (c) 73. (a) 74. (d) 75. (a) 76. (d) 77. (b) 78. (b) 79. (a) 80. (b)

81. (a) 82. (d)

Electrophilic and Free Radical Addition Reactions

Multiple Choice Questions

1. Which is correct potential energy diagram for following transformation?

G
G
(a) (b)

reaction progress reaction progress

G G
(c) (d)

reaction progress reaction progress

106 Problems in Organic Chemistry

2. CH3 — CH = CH2 + Br2 

in NaCl
→ Products
The product, not expected in this reaction is:-

Br Br Cl

(a) CH2Cl (b) CH2Br (c) CH2Br (d) All of these

KMnO
3. Cis -but- 2 – ene 
4 → [X]
273K

CH3

Me Me H OH Me
H OH
(a) H (b) (c) H H (d) Both (a) & (b)
HO OH Me OH
HO H

CH3

4. How many carbocation are produced during the following transformation?

OH
OH
+ dil H2SO4 ———→

(a) 4 (b) (c) 6 (d) 3

D D
5. C =C is subjected to halogenation by X2 / in CCl4. In which case meso isomer will be produced?
H H
(a) Iodination (b) Bromination (c) Chlorination (d) Fluorination

H /D
6.  → [A], [A] will be:-
2 

(a) (b) (c) (d)

7. CH3 — CH = CH2 + Cl2 →

3 AlCl
CH3 — CHCl— CH2 — Cl
Select the correct statement regarding the mechanism of this reaction.
(a) This reaction occurs via radical mechanism. (b) Cyclic carbonium ion is not formed as an intermediate.
(c) AlCl3 helps in the generation of Cl(+) (d) AlCl3 has no role in this reaction.
8. Consider the following compounds.

Ph2C = CH2 (CH3)2C = CH2 Ph2C = CHCF3

1 2 3
Correct order of rate of electrophilic addition reaction is:-
(a) 1 > 2 > 3 (b) 3 > 2 > 1 (c) 1 > 3 > 2 (d) 3 > 1 > 2
9. The compound with highest heat of hydrogenation is:-

(a) Me2C = CH2 (b) Cis – 2 – butene (c) Trans – 2 – butene (d) 1, 3 – Butadiene
Reaction Mechanism (General Organic Chemistry) 107

10. CH2 = CH2 + H2 → CH3 — CH3

Ni
D
It is an example of:-
(a) Free radical addition reaction (b) Eleclrophilic addition reaction
(c) Nucleophilic addition reaction (d) Molecular addition.

11. Acetylene ——→

This reaction can be performed by:-

(a) CH2 = C = O / hv (b) CH2N2 / hv (c) CH2I2 / Zn (Cu) (d) All of these

CH = CH 2 H( + )
12. → [A] Major, [A] will be:-
EtSH

SEt
(a) SEt (b) (c) SEt (d)
SEt
13. Consider the following reactions.
Br
hn
+ HBr 
→
(1) (2) Cl
+ HCl →
Peroxide SEt hn
(3) + C2 H 5SH → (4) + HBr → Br

The reaction with wrong product is / are:-

(a) 2 (b) 2 & 3 (c) 3 (d) 1 & 4

(+)
14. H3O
 → [A], [A] would be:-

OH CH2OH CH2OH

(a) (b) (c) (d)

CH3
OH OH OH
15. When cyclo hexene is treated with chlorine water followed by aq NaOH, another compound [X] is produced. The compound
[X] can be identified as:-
OH Cl Cl
(a) (b) (c) O (d)
OH OH Cl

(i)Cl / H O
16. →
2 2 [A], [A] would be:-
(ii)Na 2CO3

OH Cl
(a) (b) (c) O (d) CO3
OH OH
108 Problems in Organic Chemistry

17. Which statement is correct about A & X?

CH3 CH3
| |
dil
Ph — CH — C  CH 2  A
H 2SO4
[X]
(a) On dehydration ‘A’ gives alkene (major product) which can show stereoisomerism
(b) ‘A’ is optically active alcohol and contains 2- chiral carbon atoms.
(c) On reduction by H2 / Ni compound ‘X’ gives optically active hydrocarbon which contains one chiral carbon atom.
(d) ‘A’ is an optically inactive alcohol.

Ac
18. CH—CH 3 + HBr ——→ [A], [A] may be:-
NC
Ac Ac
(a) CH2— CH3 (b) CH—CHBr—CH 3
NC NC
Br
OH
Ac
(c) CH—CH 2 —CH2Br (d) CH3 C Br
NC CH—CH—CH3
NC
Br
19. (O2N)2 C = CH — CH3 [A]
Which statement is not correct about [A]
(a) HBr will add on it according to Markonikoff rule (b) Addition of HBr on [A] will give antimarkonikoff product
(c) It will favour nucleophilic addition (d) Both (b) & (c)

H( + )
20. → [A], [A] will be:-
D 2O

D OD D
(a) (b) (c) (d)
OD OD OD

Cl
21. 2 → [A], [A] is:-

H 2O
OH
OH Cl
Cl
Cl
(a) (b) Cl (c) (d)
Cl
Cl

O (+)
H3O
22. CH3—CH—CH—CH3 ————→ .....................(1)
Ni
—
cis-CH3—CH—CH—CH 3 + D2 ————→ .....................(2)
∆
in CCl4 .....................(3)
tans-CH3—CH==CH—CH3 + Br2 ————
CH3
CH3
in CCl
4 .....................(4)
H + Br2 ————→
H

Racemic mixture will be produced in:-

(a) 1 & 4 (b) 2 & 3 (c) 1, 3, & 4 (d) 3 & 4
Reaction Mechanism (General Organic Chemistry) 109

23. In the reaction given below [X] is an organic compound & can be identified as:-
hn
( Ph2CH)2N2 + Br2 → [X],
(a) Ph2CHNBr—NBr — CHPh2 (b) Ph2CHNBr2
(c) Ph2CHBr (d) All of these

H
(+) A
D2O
24 D
(+) A & B respectively are :-
H2O
B
OD D
D
(a) (b) ,
,
OD OD
OD
D OD OH
OH
(c) , (d) ,
OH D

25.
dil H SO
Ph ——————
2 4
→ [X], Major
Excess

How many chiral ‘C’ atoms are present in [X]?

(a) 3 (b) 4 (c) 5 (d) 6
26. When 2 – iodo – 1 – phenyl propene is subjected to addition reaction with HI in dark, an organic compound [X] is formed which
is:-
(a) 1, 2 – Di iodo – 1 – Phenyl propane (b) 2, 2 – Di iodo – 1 – Phenyl propane
(c) 1 – Phenyl propene (d) Both (a) & (b)
* 14 
27. CH 2 = CH — CH = C* H2 [A] C == C  If 1 mol of [A] is treated with 1 mol HBr in dark then expected product/s will
be:-  
Br Br
| |
(a) C H 2 = CH –CH — C H3 = CH –CH — C• H3
•
(b) C H 2

(c) BrCH 2 CH  CH — CH3 & BrCH 2 CH  CH — CH 3 (d) All of these

* *

Ph 3
28.
1
2
Here double bonds are numbered as 1, 2 & 3. The correct order of these double bonds towards eletrophilic attack is:-
(a) 1 > 2 > 3 (b) 3 > 2 > 1 (c) 1 > 3 > 2 (d) 3 > 1 > 2
Me
29. + HBr ——→ [A], major [A] will be:-
Ph

Br Me Me H

Me Br H Me
(a) (b) (c) (d)
Ph Ph Ph Ph
H H Br Br
110 Problems in Organic Chemistry

H( + )
30. CH2 = CH2 + H2O → CH3CH2OH
For this reaction rate law is:-

(a) Rate = k [CH2 = CH2] [H+] (b) Rate = k [CH2 = CH2] [H2O] [H+]

(c) Rate = k [CH2 = CH2] (d) Rate = k [CH2 = CH2] [H2O]

31. The intermediate of the reaction is: -
Phenyl ethylene + ICl ——→ Product
I Cl
I Cl
( ) | ( ) | (+) (+)
(a) Ph — CH — CH 2 (b) Ph — CH — CH 2 (c) Ph—CH —CH2 (d) Ph—CH—CH 2

32. Correct order of reactivity of the following halogens and interhalogens towards electrophilic addition to C = C is:-
(a) BrCl > Br2 > IBr > I2 (b) Br2 > I2 > BrCl > IBr (c) BrCl > IBr > Br2 > I2 (d) IBr > Br2 > BrCl > I2
33. Which of the following compounds is most reactive towards electrophilic addition reaction?

(a) CH2 = CH2 (b) (F3C)2C = CH2

NO2

(c) NC — CH = CH — CHO (d) O2 N CH = CH 2

NO2

34. An alkene (A) on reduction gives an optically active alkane of least molecular weight & on treatment with H+ gives 3° carbo-
nium ion which can not show rearrangement. What should be the structure of (A) if it can show geometrical isomerism?

(a) CH3CH2CH(CH3)CH = CH — CH3 (b) CH3CH2CH(CH3)CH2 — CH = CH2

(c) CH2 = CH — CH(CH3)CH2 — CH = CH2 (d) CH3 CH  CCH 2CH 2CH 3

|
CH3
35. End product of the following reaction

O O + HBr (1mol) ——→ is :-

(a) O O (b) HO OH (c) Br OH (d) O OH

Br Br OH Br
36. When Cis- but-2-ene is treated with Br2 in carbon tetra chloride medium the product formed will be:-
(a) (2 R, 3 S) di bromo butane (b) (2 R , 3 R) di bromo butane
(c) (2S, 3 S) di bromo butane (d) Mixture of (2 R, 3 R) & (2 S, 3 S) di bromo butane

Answer Key

1. (d) 2. (a) 3. (d) 4. (c) 5. (d) 6. (a) 7. (c) 8. (c) 9. (b) 10. (d)

11. (d) 12. (c) 13. (a) 14. (b) 15. (c) 16. (a) 17. (c) 18. (b) 19. (d) 20. (b)

21. (a) 22. (a) 23. (c) 24. (d) 25. (c) 26. (c) 27. (d) 28. (c) 29. (d) 30. (a)

31. (c) 32. (a) 33. (a) 34. (d) 35. (b) 36. (a)
Reaction Mechanism (General Organic Chemistry) 111

Elimination Reactions
Multiple Choice Questions

EtOH + KOH
1. → [X], [X] will be:-


Cl

(a) (b)

(c) Both (a) & (b) (d) No product will form

CH3
2. + alc KOH ————— major product

Cl

(a) (b) (c) (d)

(  )(–)

3. (CH 3 )4 NOH  Products

Which product will not form in this reaction?

(a) CH3OH (b) Me3N
(c) H2O (d) No product will form in this reaction

conc H3PO4
4. A, the product A would be
∆

(a) (b) (c) (d)

H PO
OH 
3 4→
5. D
Major [P], [P] would be:-

(a) (b) (c) (d)

2 4 conc H SO
6. CH3CH2CH2OH ——————→
∆
CH3CH==CH2 + H2O

(a) E1 pathway (b) E2 pathway (c) E1cb pathway (d) Unpredicable

112 Problems in Organic Chemistry

7. Select the reaction in which chances of SN1 are maximum

(a) I + EtNH2 —→ Product (b) + NH2(–) —→ Product
(–) I
(c) + C2 H5 O —→ Product (d) I + C2H5OH —→ Product
I
Ph
8. CH3CHI—CH + alc KOH —→ X (major), [X] would be:-
Me
Erythro
Me Me
H Me Me H
H OH H OH
(a) (b) (c) (d)
Ph H H Ph
Ph Me H Me
Me Me
9. Number of possible products obtained by the acid catalysed dehydration of 3-methyl-pentan-2-ol is (do not consider stereoisomers):-
(a) 1 (b) 2 (c) 3 (d) 4
OH

dilute
10. → [X], [X] can be identified as:-
acid

OH
OH
(a) (b) (c) (d)

H
(+) (–)
Heat
11. Ph NMe3OH 
→ [X] Major, [X] will be:-
Ph
(a) (b) Ph (c) (d) None of these.
Ph
12. The sp3 hybridised carbon atom can not bear two groups which interacts with each other as shown below & elimination
occurs:-
OH H-bond
C ——————→ H2O + C == O
OH

OH H-bond
C ——————→ HF + C == O
F
(+)
OH H3O
Predict the final product of the following reaction:-
Cl

(a) (b) O (c) (d) O

O O
Reaction Mechanism (General Organic Chemistry) 113

13. Which alkyl halide would you expect to be least reactive in an E1 reaction?
(a) CH  CH —CH — CH (b) Ph — CH — CH3
2 3 |
|
Br Br
(c) CH
2  C — CH 2 — CH3 (d) Ph — CH2 — CH2Br
|
Br
(i) H / Ni / D
14. Substrate  2
(ii) CH I(excess)
→ 1, 3 – butadiene + Me3N Substrate will be:-
3
(iii) AgOH / D

NH2
(a) (b) (c) (d)
N N N
H H H
H D
Br
[X]
15. (Product) , [X] would be:-
D Br
H
H D H D H
I
D
(a) (b) (c) (d) Both (b) & (c)
I H
D H D H D

16.

In this reaction % of [X] & [Y] are respectively:-

(a) 15 % & 85% (b) 50 % & 50% (c) 85 % & 15% (d) 55 % & 45%

Passage - I

Acid catalysed dehydration of alcohol follows E1 mechanism. In it carbocation is formed as intermediate. Rate of dehydration of
alcohol depends on two factors viz stability of carbocation & acid strength of H present at adjacent position to positively charged
carbon atom in intermediate.

Answer the following questions from 17 to 19

17. Consider the following alcohols
OH OH OH OH

NMe2 NO2
NO2
(1) (2) (3) (4)

Correct order of rate of acid catalysed dehydration will be:-

(a) 1 > 2> 3> 4 (b) 2> 1 > 3 > 4 (c) 3 > 2 > 4 > 1 (d) 3 > 2 > 1 > 4
18. Correct order of rate of acid catalyzed dehydration if nitro group is replaced by methyl group
(a) 1 > 2 = 4 > 3 (b) 2 > 1 > 3 > 4 (c) 3 > 4 > 2 > 1 (d) 2 = 4 > 3 > 1
19. Correct order of rate of acid catalyzed dehydration if dimethylamino group is replaced by methyl group
(a) 1 > 2> 3> 4 (b) 2> 1 > 3 > 4 (c) 3 > 2 > 4 > 1 (d) 3 > 2 > 1 > 4
114 Problems in Organic Chemistry

20. Match the following

Reaction Product
Br

alc KOH
(A) Me → (p)

OH CH2
H PO

3 4→
(B) D (q)
F
3°BuO(–)
(C)  → (r)
(a) A —→ p, B —→ q, C —→ r (b) A —→ q, B —→ p, C —→ r
(c) A —→ r, B —→ p, C —→ q (d) A —→ r, B —→ q, C —→ q
O OH (–) O
OH
21.  → H2O +
D
This reaction occurs via:-
(a) E1 mechanism (b) E2 mechanism (c) E1CB mechanism (d) E2 as well as E1CB

22. CH3CH2ONa + 60° C

——— +
Br OEt

[X] [Y]
In this reaction % of [X] & [Y] are respectively:-
(a) 75% & 25% (b) 25% & 75% (c) 50% & 50% (d) almost 100% [X] is produced
23. Main products of reactions 1 & II are respectively:-
CH OH
(I) Et3CBr ————3

25°C
CH3
(II) C—H + NaSH 50°C
————
Br CH OH
3

Et
CH3 CH3

(a) Et3COMe and (b) Et2C==CH2 and

H Et H Et
SH SH
CH3 CH3

(c) Et3COMe and (d) Et2C==CH2 and

H SH H SH
Et Et

Matrix Match Questions

Each question contains statement given in two columns which have to be matched. Statement (A, B, C , D) in column I have to be
matched with statements (p, q, r, s) in column II. The answers to these questions have to be appropriately bubbled as illustrated in
the following examples. If the correct match are A - p, A - s, B - r, B - r, B - q, C - q, D - S, then the correctly bubbled 4 x 4 matrix
should be as follows.
Reaction Mechanism (General Organic Chemistry) 115

A p q r s
B p q r s
C p q r s
D p q r s

24. Reaction Graphs

(A) E1 (p) Rate

Base

Free
(B) E2 (q) Energy
Temp

(C) SN1 (r) Rate

Base

(D) SN2 (s) Rate

25. If r1 & r2 are rate of reactions then match the following. substrate
Column - I Column - II
H PO
CH3 CH2 OH 3 →
4
alkene
∆ (r1)
(A) (p) Follows saytzett rule
H 2SO4
CD3 — CH 2 — OH → alkene
∆ (r2)
( )
H
CH3CH2 CH 2OH  alkene
 (r1)
(B) ( )
(q) r1  r2
H
CH3CHOHCH3  alkene
 (r ) 2
OH
|
H( +)
Ph — CHCH3 → alkene
∆ (r1)
(C) (r) r1 > r2
( +)
H
CH3CH2 CH 2OH → alkene
∆ (r ) 2

CH3 H
(+)
C—CH2—CH 3 alkene
CH3  (r1)
(D) OH (s) r1 < r2
CH3 H
(+)
CH—CH—CH3 alkene
CH3  (r2)
OH

Answer Key

1. (d) 2. (b) 3. (c) 4. (c) 5. (b) 6. (b) 7. (a) 8. (c) 9. (c) 10. (b)
11. (a) 12. (b) 13. (c) 14. (b) 15. (c) 16. (c) 17. (d) 18. (c) 19. (d) 20. (c)
21. (c) 22. (d) 23. (b)
116 Problems in Organic Chemistry

Answers Matrix Match

24. A → r, s ; B → p, s, q ; C → s, r ; D → q, s, p
25. A → q ; B → s ; C → r ; D → p, r

Multiple Choice Questions (More Than One May Correct)

1. Identify the compound whose resonating structure can show geometrical isomerism:-

O
(a) CH3CONHCH3 (b) (c) NH2CONHNH2 (d) PhCONH2
NH

2. Identify the species where resonance is not possible:-

(–) (+) (–) (–)

(a) CH 2Cl (b) (c) F (d) CH 2 CHO

3. In which case 1st resonating structure is more stable than 2nd

(–)
O O
( ) ( )
(a) CH3 — C O — CH3 — C  O (b) — (–)

(+)
(–)
(c) (–) — (d) —
(+) (+)
O O O O
(+)
4. Which is not correctly matched?
(a) CO32– ——→ Bond order of C — O bond is 3/2 (b) CH3COO(–) ——→ Bond order of C — O bond is 4/3
(c) ClO4(–) ——→ Bond order of Cl —O bond is 7/4 (d) PO43– ——→ Bond order of P — O bond 5/4
5. In which case 1st species has more resonance energy than 2nd.
O
O
(a) , (b) ,
O O
(+)
(c) PhCOO(–), PhO(–) (d) (+)

6. Correct order of leaving group character is :-

(a) CCl3COO(–) > CH3COO(–) > CH3O(–) > PhO(–) (b) OTs(–) > CH3SO3(–) > PhO(–) > OH(–)

(c) CCl3COO(–) > PhO(–) > CH2 = CH — O(–) > CH3O(–) (d) HCOO(–) > PhO(–) > CH3COO(–) > CH3O(–)
7. Which among the following is/are aromatic?

CH3 H
O CH3
B N
NH N
(a) (b) (c) (d)
N O N N O

H H H
Reaction Mechanism (General Organic Chemistry) 117

N2
8. Which statement is not in favour of
N1

H
(a) It is aromatic (b) It looses its aromaticity when 1st nitrogen reacts with H+
(c) 2nd nitrogen is less basic than 1st nitrogen. (d) It becomes antiaromatic when H+ ion attacks on 1st nitro-
gen
9. The compound from which NH2(–) can not abstract H+ is/are:-
(a) CH3CH3 (b) CH2 = CH2 (c) CH3OH (d) HCOOH

CH3 CH3 CH3

| | |
 CH3 — C — CH 2 CH3  CH3 — C  CH — CH3
10. CH3 — CH —CH — CH3  Reagent
| | (Y)
Br OCH3
(X)

Which are true statements about reagent & products (X & Y)?
(a) ‘X’ forms when CH3O(–) / CH3OH is treated with the substrate at elevated temperature.
(b) ‘Y’ forms when CH3O(–) / CH3OH is treated with the substrate at elevated temperature .
(c) ‘X’ forms when substrate is treated with CH3OH.
(d) ‘X’ forms when substrate is treated with CH3O(–) / DMSO.
11. Select the true statements regarding the following four reaction intermediates.
(+) (–)

(I) (II) (III) (IV)

(+) (–)

(a) All are aromatic (b) II is less stable than I

(c) IV is more stable than III (d) III is aromatic while II is antiaromatic
12. Which of the following compound will not give Friedel craft acylation under ordinary conditions?
SO3H CH3 NO3
NO2
(a) (b) (c) (d)
NO2
NO2

13. Under what conditions chances of SN1 are maximum:-

(a) When medium is polar (b) When base is weak
(c) When medium is polar aproteic (d) When substrate is tertiary
14. Under what conditions chances of E1CB are maximum:-
(a) When substrate contains poor leaving nucleophile. (b) When attacking base is strong
(c) When attacking base is poor (d) Substrate contains good leaving nucleophile

CH3

15. Which among the following statement is not correct about xylenes CH3 ?

(a) Ortho xylene on mono nitration gives only one product

(b) Para xylene on mono nitration gives only one product
(c) Meta xylene is thermodynamically most stable than ortho and para xylenes
118 Problems in Organic Chemistry

(d) Among all xylenes para derivative has maximum melting point.
Cl

16. product;-

Cl
Product of this reaction is/are

(a) (b) (c) (d)

R H
(–)
17. R—C ≡≡ C + H—C 50°C
———→ Products
C—Br
H
R
Which statement is correct regarding this reaction?
(a) R—C ≡≡ H will produce as one of the product
(b) Alkene is produced as major product which can not show geometrical isomerism
(c) Reaction occurs via E1CB path way
(d) Reaction occurs via E2 path way
18. In which case first alkene is more stable than 2nd are

(a) (b) ,
,

(c) , (d) ,

19. In which case I species is stable than 2nd

(a) S S , O O (b) CF3(–), CCl3(–)

(–) (–)

(–) (–)
O O O

(c) CF3CH2(–), CCI3CH2(–) (d)

,

20. In which case 1st species has more heat of hydrogenation than 2nd

(a) (b) ,
,

(c) (d) ,
Reaction Mechanism (General Organic Chemistry) 119

Answer Key

1. (a), (b), (c) 2. (b), (c) 3. (b), (c) 4. (a), (b) 5. (b), (c)

6. (b), (c) 7. (a), (b), (d) 8. (c), (d) 9. (a), (b) 10. (b), (c)

11. (b), (d) 12. (a), (b), (d) 13. (a), (b), (d) 14. (a), (b) 15. (b), (c)

16. (a), (b) 17. (a), (d) 18. (a), (b), (c) 19. (a), (c), (d) 20. (a), (c)

LEVEL - II

Multiple Choice Question

1. Which will have largest Ea?

(a) + HCl —→ (b) + HCl —→

Cl Cl

(c) + HCl —→ (d) All have same Ea?

Cl
2. Arrange the following in increasing order of stability.
(+) (+)

Ph 3 C( ) (+)

(1) (2) (3) (4)

(a) 1 > 2 > 3 > 4 (b) 2 > 4 > 3 > 1 (c) 1 > 3 > 2 > 4 (d) 1 > 2 > 4 > 3
3. In which case 1st carbocation is not stable than 2nd.

(+) (+)
(a) & (b) &
(+)
O O
(+)

(+)
(+)
&
(c) (d) &
(+)
(+)

4. Hexa chloro cyclohexane can have number of isomers. If one of its isomer given below is treated with three moles of alcoholic
KOH,another compound [X] is formed . Select the correct statement about [X].
Cl
Cl Cl
3 moles of alc KOH
→ [X]

Cl Cl
Cl
(a) It is aromatic (b) Its degree of unsaturation is four
(c) It is tri chloro benzene (d) Reaction is not possible
120 Problems in Organic Chemistry

H (+)
5. → P, P is :-
D

(a) (b) (c) (d)

OH
B
6. OH This compound on nitration with nitrating mixture (HNO + H SO ) gives meta derivative because.
3 2 4

(a) This compound takes H(+) ion from nitrating mixture and converts itself in to Ph — B O and since B O is – R group
thus, meta derivatives are obtained.
(b) B is electron deficient & abstracts electron from benzene ring to complete its octet thus, benzene ring acquires +ve charge
at o & p positions & consequently meta derivatives are formed.

(c) Nitric acid is an oxidizing agent. It oxidizes PhB(OH)2 in to PhB O. Since B O is –R group thus, meta derivatives
are obtained.
(d) both (a) & (c)
7. Rate of nitration will be maximum in:-

(a) (b) Me

(c) (d)

8. Which resonating structure is least stable?

(+)
O O O
(a) (b) (c) (d) (b) & (c) are equally unstable.
(–)
O O O
(–)

9. Acetate, nitrate, Carbonate and ClO4(–) ions are stabilized by resonance. Due to resonance bond order & bond length of species
affect. Select the correct statement.
(a) Bond order of C — O bond in carbonate ion is equal to that of N — O bond in nitrate.
(b) Bond order of Cl — O bond in ClO4(–) is equal to that of N — O bond in nitrate ion.
(c) Bond order of C — O bond in acetate ion is equal to that of Cl — O bond in ClO4(–) .
(d) Bond order of C — O bond in acetate ion is equal to that of N — O of nitrate ion.

CD3 SiH3
CD3
10. (+) (+) CD3 (+)
(+) SiH3
CD3 CD3 SiH3

(1) (2) (3) (4)

Arrange these carbocations in decreasing order of stabilities
(a) 4 > 2 > 3 > 1 (b) 1 > 4 > 3 > 2 (c) 1 > 2 > 4 > 3 (d) 4 > 3 > 1 > 2
Reaction Mechanism (General Organic Chemistry) 121

11. Identify the case where -ve charge is least delocalized

(–) (–) (–) (–)

CH2 CH2 CH2 CH2
CH3 CF3
(a) (b) (c) (d)
CN
NO2 CHO
(–) (+) (+)
•
CH2 CH2 CH2 CH2

12.
CH3
(1) (2) (3) (4)
Correct order of stability
(a) 1 > 2 > 3 > 4 (b) 2 > 1 > 4 > 3 (c) 4 > 3 > 1 > 2 (d) 4 > 3 = 2 = 1
13. Which is not correct about 1 & 2 :-
D b
a D
D D
(1) (2)
(a) Both are antiaromatic (b) Bond lengths a ≠ b
(c) Both are same compounds (d) Resonance decreases their stabilities
14. Which of the following has non planar geometry?

(–)

(a) (b) (c) (–) (d) All are nonplanar

15. Which is not aromatic?

(–)

(a) (b) (c) (d) All are aromatic

(–)
16. Which is not correct about cyclo butadiene?
(a) It reacts with sodium rapidly. (b) It does not undergoes dimerisation below 4°C
(+)
(+)
(c) Resonance energy of is greater than cyclo butadiene

(d) All are correct statements.

17. You have four compounds.

CCl3
O CCl3
O
CH3COCH2COOC2H5
CCl3 O
(1) (2) (3) (4)
These compounds on treatment with base produce base. Identify the compound/s which can’t form planar carbanion.
(a) 2, 3 & 4 (b) Only 4 (c) 1, 2, 3 & 4 (d) 2 & 3
122 Problems in Organic Chemistry

CH3 CH3
H( + )
| |
18. CH3 — C — CH 2 — C — CH 3 → (A) Major + (B) Minor
| | Heat
CH3 CH3

Which is correct about A & B?

CH3
CH3 |
(a) (CH3)3CCH = C and (CH 3 ) 3 CCH 2 — CC  H2
Minor
Major CH3

CH3 CH3
|
(b) (CH3) 3CCH = C and (CH 3 ) 3 CCH2 — C  CH 2
CH3 Major
Minor

CH3 CH3
|
(c) (CH3 ) 3 CCH = C and (CH 3 ) 3 CCH 2 — C  CH 2
CH3 50%
50%

CH3
(d) Only one product (CH3 ) 3 CH = C will form
CH3

19. How many products (including stereoisomers) will be formed in the following reaction?

D H

H SO

2 4→
Product
170°C
OH

(a) 1 (b) 2 (c) 3 (d) 4

20. How many geometrical isomers will be formed in the previous question?
(a) 0 (b) 1 (c) 2 (d) 3

21. Which is not correct about SN2?

(a) Rate of SN2 is directly proportional to the dielectric constant of medium.
(b) Rate of SN2 is directly proportional to the nature of leaving group
(c) Rate of SN2 is inversely proportional to the steric hindrance present in substrate

Rate Rate
(d)

[base] [substrate]

22. Which reaction is most likely to occur?

(a) RX + NaOH (in C6H6) ——→ ROH
(b) RX (in C6H6) + NaOH (aq) ——→ ROH
(c) RX + NaOH (in crown ether) ——→ ROH
(d) Both (b) & (c)
Reaction Mechanism (General Organic Chemistry) 123

23. In the given figure graphs are plotted for SN1 & SN2 in polar as well as in non polar mediums. Graph 1 is plotted in polar me-
dium while graph 2 is plotted in non polar medium. Select the correct statement.

SN2 SN1

G1 1 G1 G2 1
G2
2 2

(a) For SN1 ∆G1 > ∆ G2 because substrate is more solvated than the transition state
(b) For SN2 ∆G1 > ∆ G2 because transition state is more solvated than the substrate
(c) For SN2 ∆G2 > ∆ G1 because substrate is more solvated than the transition state
(d) For SN1 ∆G2 > ∆ G1 because substrate is more solvated than the transition state
15% aq solution of ethyl alcohol
24. 2–Chloro butane → product
In this reaction 70% racemisation takes place. % of inverted product would be:-
(a) 30 (b) 70 (c) 35 (d) 65

Answer Key

1. (a) 2. (d) 3. (d) 4. (d) 5. (c) 6. (b) 7. (d) 8. (b) 9. (d) 10. (a)

11. (a) 12. (b) 13. (c) 14. (d) 15. (d) 16. (d) 17. (b) 18. (b) 19. (b) 20. (a)

21. (a) 22. (c) 23. (c) 24. (d)

SOLUTIONS
Level - I
(AROMATICITY)
Ac
Ac (–)
( )
1. (d)  H +

aromatic and stable
2. (a) (i) is non planar because of repulsion between ‘H’ atoms as shown below

H H

repulsion
124 Problems in Organic Chemistry

(+)
3. (b) — (–)

(Both the rings follow Huckel rule & hence it is aromatic)

sp3hyd
4. (c) Non planar due to sp3 hybridization

5. (c) B is non aromatic (non planar) & A is antiaromatic

6. (b) Due to resonance (iii) becomes antiaromatic

Ph Ph
Ph Ph

— antiaromatic
(–)
(–)
CH3 O
CH3 O

7. (d) (A) is not planar (B) has 8πe– (C) has 10πe–
(+) (–)
(–) NMe2
C
(+) NMe 2
(B)

8. (b) Order of stabilities of ions produced from I, II & III is III > I > II.
9. (d) O is more electronegative so it does not give its lone pair of electrons easily for resonance hence it is least aromatic. How-
ever electronegativity of S is lesser than O & N hence resonance energy of thiophene will be more & thus, aromaticity of
II will be large.(exceptional case)
10. (b) (B) follow Huckel rule and planar (C) also follows Huckel rule but not planar because S is bigger in size & does not fit in
the hole created by rings. (A) is not planar due to H—H repulsion as shown below -

H H

O
Ph Ph Ph Ph
(+)
(–) K
11. (d) + 2K —— H2 +
(–)
Ph Ph Ph (+) Ph
K
(+)
(–) K
(+)
(–) K
+ 2K —— H2 +
Reaction Mechanism (General Organic Chemistry) 125

12. (d) In these compounds tautomerism takes place.

O
OH
HN NH

 N N
O O
HO OH
O

13. (b) The products formed in 1,2 & 3 reactions are non aromatic, antiaromatic & aromatic respectively.
14. (b) does not obey Huckel rule.
+
15. (a) Because after removal of H it converts in to an aromatic species

H H (–)

 ( )
 H +
aromatic

16. (c) Because it is antiaromatic (less stable)

(–)
O O
(+)
antiaromatic

17. (d) (A) is non aromatic because one of its ‘C’ is sp3 hybridised
18. (b)
19. (d) 20. (c) 21. (b) 22. (c)

OH O
SeO PCC
23. (b) 
2 
aromatic

24. (a) Same as question no. 23

O OH sp3
LiAlH

4
25. (b) (non planar & non aromatic)

1 2 3
N
N
4 H
26. (a) H
H 5
CH3O2C OCO

Rings 1, 2, 3 & 6 are aromatic.

27. (c) 6πe–, two from lone pair of e– & four from two double bonds
28. (b) Ring 1, 2, 3 & 6 have planar geometry
29. (d) Total e– present in 1, 2, 3 & 6 rings
126 Problems in Organic Chemistry

30. (c) Pentagonal ring contains 6πe– where as hexagonal ring also contains 6πe–

NaH
———→
–H (–) Na
(+)
2

31. (c)

aromatic

32. (a) 33. (d)

(–) O
O (–)
34. (a)  Aromatic
CH3 CH3

Cl Cl
(–)
CCl2 C
 (+)
Aromatic

35. (d) It undergoes tautomerism immediately.

(–)
36. (a) (+) (–)
(+) (–) (+)

aromatic antiaromatic nonaromatic

order of stability:- Aromatic > non aromatic > antiaromatic hence x > z > y
37. (a) N is less electronegative in comparison to O thus, for A resonance energy is high hence it is highly aromatic

H
(+)
38. (a) ••N—H  H—N ••N—H (A)
••N

A is planar & follow Huckel rule.

39. (a) See q.n. 36
40. (d) The lone pair of electron present on N undergoes resonance with double bonds & makes pyrrole planar
(+)
(–)
——— H
41. (b)
+

aromatic and thus, stable

42. (a) (ii) is aromatic while (iv) is non aromatic

43. (c) (i) forms less stable antiaromatic species as an intermediate while (ii) forms stable non aromatic species as intermediate.

Ph Ph Ph Ph

(–) (–)
COO–t–Bu COO–t–Bu
antiaromatic & less stable nonaromatic
Reaction Mechanism (General Organic Chemistry) 127

RESONANCE
(–) (–) (–)
O (–)
O O O O O O O

1. (d)
(–)
O O O
(–) O O
(–)
O
(–)
O O

2. (c) Cyclobutadiene has rectangular shape and hence does not favour resonance

(More stable) (Less stable because

double bonds are long)

3. (d) factual question

4. (c) Two tertiary butyl groups present at ortho position creates problem in resonance by disturbing the co -planarity of com-
pound. (Steric inhibition to resonance)
5. (d) Carbon adjacent to CO groups is sp3 hybridized
(+)
6. (b) 7. (b) CH2= CH—N=SH (+)CH — CH N — SH
 2

8. (b) electron density will be least in I because nitro groups are electron withdrawing groups and it will be maximum in II be-
cause O(–) is +R group
9. (c) electron density will be least in (I) because F is a tautomeric group (–I & + R effects) while other groups are +R groups and
order of +R effect is:- NH2 > OH > OMe
10. (a) I is more stable an it is non polar. II is more stable than III because opposite charges are close to each other.
11. (c) (III) does not show resonance hence C — N bond has maximum length. (II) & (I) shows resonance hence C — N bond
acquires partial double bond character thus, bond length decreases. Out of (I) & (II) C—N bond length will be less in I
because CHO (—R) group favours resonance in (I).
12 (a) 13. (a)
14. (a) Because C — O bond is a single bond and free from resonance
O OH
Tautomerism

15. (b)

Aromatic compound has more resonance energy.

16. (c) Because in (I) & (II) resonance takes places

O O(–) Oδ –
|| (–) | ||
H — C— O ←→ H —C = O  H —C ....... Oδ –

17. (c) In 3rd case sigma resonance takes place hence it has largest R.E. Out of 1st , 2nd & 4th last species possesses more R.E as it
is aromatic in nature.

(+)  (+)

CH CH sigma resonance

18. (c) First species is antiaromatic so E1 should be least. Second species is conjugated diene thus, stable and hence E2 is greater
than E3.
128 Problems in Organic Chemistry

19. (d) Bridge head can not bear double bond.

20. (b)
21. (b)
22. (c) In 1st case both the resonating structures contain-ve charge on electronegative O atom thus, it is highly stable. (III) is more
stable than (II) due to more resonance.
(–)
O O
←——→
(–)
O O
23. (c) 24. (c)
25. (c) 1st has 3 resonating structures 2nd has two resonating structure & in each resonating structure negative charge is present on
electronegative oxygen atom hence 1st & 2nd are more stable than 3rd & 4th . In between 3 & 4, former is more stable
due to more resonance.
26. (b)
27. (d) When lone pair of electron present on 2nd ‘N ‘undergoes resonance +ve charge comes on ‘N’ which is stabilized by + I
effect of methyl group thus, lone pair of electron present on 2nd N will be more delocalized than 1st ‘N’. Lone pair present
on ‘O’ will be less delocalized in comparison to that of both the nitrogens because ‘O’ is more electronegative than ‘N’.
Chances of resonance will be least in ‘S’ because of less favourable 2p (carbon)–3p (sulphur) overlapping
28. (c) (II) violates octet rule as ‘Cl’ contains 10 electrons in its outermost shell.
Passage-I (29 to 32)
Group C = NH is —R group & decreases electron density inside the benzene ring. NH & O are +R group & increase the electron
density inside the benzene ring.
Passage-II (33 to 36)
33. (a) in fluoro benzene resonance occurs effectively as 2p of F can easily overlap with 2p of ‘C’ hence due to more double bond
character bond length decreases. Consequently dipole moment is least.
O (–) O
|| | ( )
34. (c) CH3 — C— O — Me  CH3 — C  O — Me
It is less favourable because electronegative ‘O’ atom acquires positive charge.
35. (b) due to less favourable resonance in phenoxide ion in comparison to other ions
36. (c) (I) is non polar hence highly stable. Out of (II) & (III) later is stable because opposite charges are closer to each other.
REACTION INTERMEDIATES AND ATTACKING REAGENT:-
1. (c)
2. (a) Besides (a) rest all are stabilized by resonance. [Stability ∝ 1 / reactivity]
3. (d) In BI3, B is more electron deficient because in it chances of back donation of e– is least
4. (a)
5. (c)
+R effect of NH2 stabilizes +ve charge present on CH2 group
6. (a)
At meta position, resonance does not occur only I effect is considered. OCH3, NH2 & NO2 all have –I effect at meta
position
7. (a) First spfecies is stabilised by resonance while second species is stabilised by seven hyperconjugative structures.

8. (c) H C H
sp hybridisation
9. (a)

triplet carbene CH2 CH2

10. (d) CH3  H3C CH3 it can undergo two types of rotations
H3C C C
C C H H
H H
Reaction Mechanism (General Organic Chemistry) 129

CH2 CH2 CH2

H3C CH3 rotation
 H3C CH3  H3C CH3
C C C C C C
H H H H H H

CH2 H CH3
CH2 C C
H3C CH3 
rotation H CH3  H3C H
C C C C CH2
H H H 3C H
11. (c) In triplet carbene ‘C’ is sp hybridized.
(+)
12. (b) F3C C CF3

CF3
Due to – I effect of CF3 group positive charge density on ‘C’ increases consequently stability decreases.
( ) ( ) ( )
13. (b) CH 2  CH — CH  O CH3  CH 2  CH — C H — OCH3  CH 2— CH  CH — OCH3
It has 3 resonating structures
14. (d) Electron with drawing effects make anions stable
(–) (–) (–)
CH2 CH2 CH2
NO2

NH2 OH
(–I effect) (–R effect) (–I effect)

15. (b) 3rd is aromatic hence highly stable . In 1st case resonance is possible as carbon can donate its negative charge to empty d
orbital of chlorine. Such kind of resonance is not possible in 2nd because d orbital is absent in ‘F’.
(+)

16. (b) aromatic & stable

17. (c) Due to more resonance +ve charge spreads over different ‘C’ atoms.
18. (d) Except ‘3’ rest all shows resonance thus, delocalization of –ve charge takes place.
19. (b) number of resonating structures ∝ stability
20. (c) nitrene is not found in singlet & triplet states
(+) ••
hν cycohexene
21. (a) R — N — N ≡ N  → R — N  → N—R
••

22. (a) number of resonating structures ∝ stability of species

23. (d) 2nd is aromatic thus, more stable than 3rd . Out of 1st & 4th former is more stable as one of its resonating structures acquires
negative charge on oxygen.
24. (c) + R effect of methoxy group helps in the stabilization of positive charge.
(+) CH CH2 CH2 CH2
2

(+) (+)

(+)

OCH3 OCH3 OCH3 OCH3

CH2

(+) OCH3
130 Problems in Organic Chemistry

25. (a) This ion is least stable because -ve charge is not stabilized by resonance.
26. (b) Given carbocation is already stable because of resonance
CH3 CH3
•• ••
C2H5 —C—C==O ←——→ C2H5—C—C≡≡ O
(+) •• (+)

H H
27. (d)
28. (d) See question number 11 in the topic aromaticity.
29. (a) ‘N’ can not form five bonds as it does not contain d– orbital. So tetra ethyl ammonium can not receive electron pair from
nucleophile.
30. (b)
31. (a) Here resonance stabilized carbonium ion is formed.
F (+) (+)
H(  ) F—C—F F=C—F
F C—OH  
–H 2O
F F F

(+)
32. (b) C is highly stable carbonium ion due to sigma resonance
3
33. (a) Carbonium ion generated by (a) is destabilized by strong (–I) effect of CF3.
34. (d) Stability of carbocation ∝ number of resonating structure
35. (b) See Q 15 & 18
36. (a) In (c) & (d) resonance is not possible because of SIR effect.
37. (c) Substitution at ortho position cerates hindrance in resonance by disturbing the planarity of species.
38. (c) All are independent of resonance hence stability of free radical will depend on + I effect.
+ I effect ∝ Stability of free radical
Passage-III (39 to 42)
(–) (–)

2Na →2e + 2Na +


→ Aromatic
(X) (A)
(–) •
+
2Na →2e + 2Na

→
(X) (B)
(–) (–)
(–) •
+ aromatic
disproportionation
→
nonaromatic
(B) (X) (Z) or (A)

43. (d) Although carbanion has pyramidal shape yet it does not show optical isomerism because in carbanion rate of flipping of
negative charge is very high.
H 3C CH3
H C  C H
F F
44. (a) Because phenyl group is –I group.
45. (b) the carbocation in which formation of ring or opening of ring take place are referred as classical carbocations.
46. (c) Due to resonance C — Br bond acquires partial double bond character which is difficult to break.
(–)
CH2=CH—Br  CH2—CH=Br
(+)
Reaction Mechanism (General Organic Chemistry) 131

Reduction

47. (c) (CH3) 2 C + (CH3) 2 C CH3—CH = C2H + CH3—CH 2CH3

Oxidation

48. (c) + R effect of —O(-) is greater than that of OMe group. At meta position OMe shows –I effect thus 2nd is less stable than
1st.
49. (d) bridge carbon atom can not bear positive charge.
50. (b) same as Q.26
••
51. Carbene (C H 2 ) can show sp2 (singlet) as well as sp (triplet) hybridization. Hence in singlet carbene one ‘p’ Orbital is
available while in triplet carbene two –p orbitals are available. (See [Link].8)
52. Compound B is benzyne & it has sp2 – sp2 pi bond.
H

H
sp 2—sp2 pi bond
H
H

NUCLEOPHILIC SUBSTITUTION REACTIONS:-

1. (b)
Et
(–) (+ ) |
–Br EtOH
2. (c) Ph 3CBr 
→ Ph 3C........Br 
→ Ph 3 C → Ph 3C ...... OH
TS–1 TS− 2
(+ ) (+ )
–H ( + )
Ph 3C — OEt ←
 Ph 3C — OEt ...... H ←
 Ph 3 — O EtH
TS −3

3. (c) In SN1 intimate ion pair forms which also favours the formation of inverted product.
4. (a) For SN1 reaction, stability of carbonium ion is considered. Carbonium ion formed by I is highly stable.
(+)
(+) Ph (+) (+)
C > > CH > Me2CH
3 Ph
less stable
Highly stable

5. (b) For racemisation substrate must be chiral. In (a) racemization does not occur because rearrangement in carbocation gives
rise to optically inactive product.
C2 H5 C2 H 5
|
SN1 (+)
C2 H5
CH 3 — CH — CH 2 Br → CH3—C—CH 2 |
→ CH3 — C — CH3
( +)
H

C2 H5
| (–)
CH 3 — C — CH 3 OH
|
OH optically inactive
6. (c) Factual question
st
7. (b) In 1 due to resonance C—Cl bond acquires double bond character thus , chances of nucleophilic substitution reaction will
be least in it. Rate of SN2 will be maximum in 3rd because it is primary alkyl halide. Out of 2nd & 4th rate of SN2 will be
more in 2nd because the ‘C’ which is attached with ‘Cl’ is less sterically hindered.
8. (d) Rate of SN1 ∝ stability of carbocation.
Out of 1st & 4th rate will be more in 1st because substrate is sterically hindered & can release leaving group very easily to
remove steric hindrance.
132 Problems in Organic Chemistry

CH3 CH3 H
(+) 1
SN
9. (c) CH3—C—O—CH3 + H ——→ CH3—C —O—CH3
(+) —CH3OH
CH3 CH3

CH3 (–) CH3

(+)
I
CH3—C—I ←—— CH3—C
CH3 CH3
10. (c) In (a) SN2 reaction will occur because base is strong & substrate is 1° alkyl halide similarly in (b) SN1 occurs hence in (a)
& (b) will show inversion & racemisation respectively.

Pr CH3 Pr CH3 Pr OC2H5

Et C2 H5OH(weak base) +
Br → Et Et

(3° alkyl halide) OC2H5 CH3

11. (c) In SN1 carbonium ion is formed which undergoes resonance hence two products can form
(+)
CD2= CH —CH2Br SN1 EtO– CD2 = CH—CH2OEt
–Br
(–) CD2= CH—CH2

(+)
CH2= CH—CD2OEt EtO– CD2 —CH = CH 2

12. (c) This reaction will occur by SN2 pathway because substrate is a primary alkyl halide thus for this polar aprotic medium is
required. Dimethyl formamide (DMF) i.e. HCONMe2 is a polar aprotic medium .Another example of polar aprotic me-
dium is DMSO.
13. (d) Substrate is 1° alkyl halide, base is strong & medium is polar aprotic, these three conditions increase the chances of SN2

O (–)
O O
COOH C
14. (d) D Br OH(–) D Br
–H2O
O Products
C2H5 Et Et
D

15. (d) Carbonium ions formed by the release of Br (1) & Br (2) are stabilized by [Link] formed by the release of
Br (3) is less stable because it does not undergoes resonance.
16. (a) Rate of SN1 ∝ stability of carbocation
17. (b) It involves three transition states.
18. (c) It is the case of neighbouring group participation. Here epoxide formation occurs.

OH O(–)

NaOH
–H2O
O

Br Br
In such case halo group can be replaced to OH group by using aq. Na2CO3

OH OH

aq Na2CO 3

Br OH
Reaction Mechanism (General Organic Chemistry) 133

CH3 CH3 ( +)
SN 1 (+) Methylshift CH3 — C — CH 2 CH3
19. (b) CH3 CH2Br
–Br
(–) CH3 CH2 |
CH3 CH3 CH3

OEt
| C2H5OH
CH3 — C —Et
|
CH3
20. (c) This is SN1 reaction. [ Rate of SN1 ∝ stability of carbocation ]
21. (c) It is SN2, thus, requires less polar solvent to avoid caging of nucleophile
22. (c) Since DMSO favours SN2 hence inversion takes place.
23. (a) Precipitation occurs via SN1 pathway. Since (a) will undergo SN1 easily hence it will easily form precipitates with
AgNO3
24. (b) Since iodide is better leaving group as well as better attacking reagent hence path II is best.
25. (d) Solvolysis is a SN1 process hence solvolysis of 1st is not possible as bridge carbon can not carry positive charge. Out of 4th
& 3rd later undergoes solvolysis more rapidly as iodide is a better leaving group than chloride
26. (c) SN2 mechanism occurs hence inversion in configuration takes place(Finkelstein reaction).
27. (c) In protic solvent nucleophilicity is proportional to the size of ion
28. (d) Leaving ability of any group is proportional to its stability
29. (a) Hydrolysis occurs via SN1 pathway & (I) will form highly stable intermediate(aromatic carbocation)
30. (a)
31. (d) It involves 4 carbocations & five transition states
OH
(+)
(–) (–)
(–) (+) (+)
–Br
—CH2Br ——— OH
—CH2 ——— ——— ——— ———

32. (a) in polar aprotic medium nucleophilicity is proportional to basic character.

33. (c) It is an example of neighbouring group participation.
(–) (+) (+)
–Br HOH
CH—CH—S CH—Br CH3CH 2—S —CH2 CH3C2 H—S CH2
3 2 2 CH3CH2SCH2CD2OH
CD2 CD2 CD2
(+) HOH

CH3C2H—S CH2 CH3CH2SCD2CH2OH
CD2
34. (a) Carbocation so produced can not show rearrangement as it is stabilised by resonance
(+)

Ph

(Highly stable)

35. (d) Since nucleophilic substitution reaction has ionic mechanism thus, polar medium favours nucleophilic substitution reaction.
36. (a) Same as question 32 & 27
37. (c) Because it occurs via SN pathway Rate = R [alkyl halide] [OH–]
2

38. (a) First compound forms aromatic carbocation.

39. (d) NaCN is an ionic compound hence cyanide ion attacks from its ‘C’ site so cyanides are formed while AgCN is a covalent
compound (Ag — CN) so ‘C’ site is not free to attack. CN attacks from its ‘N’ site consequently iso cyanides are formed.
Similarly from NaONO, R — ONO is formed & from Ag — ONO, R — NO2 is formed.
134 Problems in Organic Chemistry

40. (d) Same as question no. 33

41. (b) Crown ether captures Na(+) easily & releases OH(–) & hence SN2 occurs easily

O O
(+)
Na (Na+ ion trapped inside crown ether)
O O

42. (d) R—I dissociates easily to produce carbocation as ‘I’ is a good leaving group
(+) H(+) •• (+)
H O CH3OH CH3 HO H
CH3 HO
•• (B)
43. (b) H3C H3C H3C—O(+) H MeO H
O
H
••
(–) CH3 H CH3OH CH3 H
CH3O •• (A)
H3C (–) O MeO HO MeO
O
Hence (A) forms via SN2 pathway while (B) via SN1 pathway
44. (a) In case of 20 alkyl halide reaction may occur through SN1 as well as SN2 pathway hence

Overall rate = K 1 [ alkyl halide] [Nu] + K 2 [alkyl halide]

2 1
SN SN
45. (c) In SN1 carbonium ion is formed which undergoes resonance hence two products form in SN1.
46. (c) Presence of nitro group makes benzene ring electron deficient hence nucleophile (H2O) can attack rapidly on benzene
nucleus even it can be hydrolysed by warm water.
47. (b) Since bromine is present at bridge carbon atom hence hydrolysis will occur by SN2 pathway.
Rate of SN2 ∝ 1 / (steric hindrance at reactive centre)
Since A is less sterically hindered thus, rate of hydrolysis will be maximum in it
48. (b) Nucleophilicity is proportional to basic character.
49. (c) It is highly stabilized by resonance thus, it is a good leaving group.
Et Et
Et Et I
(–)
(+) (+) OH OH
O O(+) I
50. (a) 51. (d) + H ———→ ———→ ———→

52. (b) It is an example of SN2 & thus inversion in configuration occurs.

FREE RADICAL SUBSTITUTION REACTION

1. (d) It is more stable due to resonance & + I effect.

Cl2 CH2Cl Cl +
hν + +
2. (c) Cl Cl

3. (a) Number of primary hydrogens are more

4. (d) All reagents can perform allylic substitution.
Reaction Mechanism (General Organic Chemistry) 135

Cl Cl
Cl2
5. (c) h +

CH3 CH3
H3C CH3 Cl2 | |
CH—CH hν CH3 — CCl — CH(CH3) 2 + (CH3)2 CH — CH — CH 2 Cl
H3C
CH3

6. (d) Ease of abstraction of hydrogen depends upon the stability of f ree radical formed after the abstraction of hydrogen

7. (d) CH 3 — CH2 — CH = CH2 →

NBS
CH3—CH—CH = CH2 CH3—CH = CH—CH2
Br
CH3—CHBrCH = CH2
CH3CH = CHCHBr Br

h •
NOCl  N O  Cl• , Cl HCl +
8. (c)
N—OH
NO Tautomerism
NO

9. (b) factual question 10. (c) All hydrogens are identical.
11. (c) molecular wt. of alkane = 43 x 2 = 86 i.e. C6H14
It would be 3- methyl pentane
Cl
Cl2 Cl
Cl
+ + +
Cl
12. (b) Abstraction of hydrogen by halogen radical is rate determining step.
Br
Br
13. (c)
Br
CH2 Br

14. (c) This reaction occurs by electrophilic addition and follows markownikoff’s rule.
Br

15. (a) and

Br
HO OH O
2Cl aq
16. (c) Ph — Et 
2 → Ph — CCl Me 
2 → –H2 O
hν K 2CO3 Ph—C—Me Ph—C—Me
unstable
O
Ph—CCH2Br NBS

17. (c) All hydrogens are identical.

18. (d) TEL ( tetra ethyl lead) is a free radical generator
19. (c) Iodination of alkane is rervsible reaction because HI forms in this reaction acts as reducing agent & hence makes the
reaction reversible.
 CH3 I + HI
CH 4 + I2 

136 Problems in Organic Chemistry

Hence iodination of alkane is carried out in presence of HIO3 or HNO3 (oxidizing agents)
HIO
CH 4 + I4 
3 → CH I + HI
3

5HI + HIO3  → 3I2 + 3H 2 O

20. (c) See question no. 19
21. (c) In chlorination rate of abstraction of hydrogen is:-
1° : 2° : 3° = 1 : 3.8 : 5
Cl2
(CH3 )2 — CHCH(CH3 ) 2  →(CH3 )2 — CClCH(CH3 )2 + CH3 — C — CH(CH3 ) 2
hν |
A45.45%
CH 2 Cl
1°H / 3°H = (12 × 1) / (2 × 5) = 12 / 10 = 6 / 5
% of A = [5 / (6 + 5)] x 100 = 45.45 %
22. (c) The hydrocarbon is cyclohexane which on reaction with chlorine forms chloro cyclohexane which on elimination forms
cyclo hexane
Cl
Cl2
 alcKOH

NBS

h

Br
23. (b) It is 3° free radical & highly stable due to inductive effect.
24. (d) Strength of C — D bond is more in comparison to C — H bond hence Br can break C — H bond from 3° ‘C’ and form 3°
free radical which is stable due to more +I effect.
25. (d) Chlorine free radical is highly reactive than bromine free radical
Reactivity ∝ 1 / Selectivity
26. (d) Since C—H or C—D bond is not breaking thus rate of reaction will be unaffected.

AROMATIC ELECTROPHILIC SUBSTITUTION REACTION

1. (b) See mechanism in your text book.
Ph Ph Ph
2. (b) OH (+) (+) Ph
H C6H6
—H2O
HO HO HO
(+)
O O O OH O OH
H(  ) Tautomerisation

Ph  Ph Ph
3. (c)
H
(–)
O O (–)
O O
→ → →
Ph (+) Ph
O O Ph
O O Ph
H
H H
4. (c) See mechanism in 3rd question
5. (d) Because both COCH3 & NO2 have same agreement at the location where Br is attached.
6. (d) Aniline, because it reacts with catalyst & benzene ring gets deactivated
•• ( ) (–)
PhN H 2  AlCl3   Ph NH 2 
 Al Cl3

(Lewis base) (Lewis acid)

7. (c) Br of Br2 water can replace —R groups.

Reaction Mechanism (General Organic Chemistry) 137

crowded
3 1
8. (c) no alpha H atom
no alpha– H– atom
2
4
Ring activation due to 2nd carbon is more thus; nitration should take place at 4th position
9. (c) Both (a) & (c) can form but later can form with greater ease due to lack of steric hindrance
10. (c) ZnCl2 will remove chlorine atom near to nitrogen because of the formation of more stable carbocation
4 3 (–)
11. (a)  (+)  (+) (–)
5 2
N N N

H H H
(1) (2) (3)

Out of 2nd & 3rd, later is more favorable because opposite charges are closer to each other hence E+ attacks at 2nd & 5th
position.
CH2
CH2
12. (b) AlCl 
Pd/ 
CH2 
3
–2H 2
Cl
CH2

13. (b) –CCl3 is meta directing group due to reverse hyperconjugation.

14. (d) Factual question
E (+)
E
(+)
15. (a)
(2)
(1)

Out (1) & (2), former is more favourable than later

16. (c) It is ring activating groups and increases e– density at o & p position so incoming Nu- can not attack at o & p position
and ultimately Nu– attacks at meta position.

OH (+)
H ( )
 C H

6 6
17. (d) –H 2O

(+)
(+)
( ) ring
H
CH2OH  CH2  C H

6 6
opening

Cl
(+)
C H

3 AlCl 
6 6

18. (b) Factual question (see energy profile diagram of sulphonation of aromatic compounds in your text book)
19. (c) Because –I effect of iodine is least so ortho position is less deactivated (i.e. less positively charged).
20. (d) Because rate determining step of ArSE does not involve breaking of C — H or C — D bond.

21. (c)
138 Problems in Organic Chemistry

22. (a) In ‘I’ group shows electron withdrawing effect while in II & III case ‘CH2’ is present which can show hyperconjugation
with benzene ring.
23. (d) Sec- butyl group is o/p directing group hence reaction will occur at para position because sec- butyl group is sterically
hindered. In BrCl, Br+ serves as electrophile hence (d) is obtained.

( )
24. (b) H
 C H
ring opening

(+) 
6 6
ArSE
(+)

25. (d) CH3 — CH  CH — CH2 — CH 2 Cl 

FeCl3
C6 H 6
H ( )

(+)

Pd/ 


26. (c) In sulphonation SO3 a neutral electrophile attacks on benzene ring & reaction is reversible. Hence to avoid reversibility
we use oleum in place of H2SO4
27. (c) Ring (C) is attached with two +R group hence it has maximum electron density. (B) has less electron density than (A)
because – R effect of NO2 group is decreasing electron density inside the benzene nucleus.
28. (c) First Nitration occurs at para position & then friedel craft reaction occurs.
(+)
(CH2) 4— CH2Cl (CH2)4 C2H
(CH2) 4 —CH 2Cl
AlCl
NO ( ) 
3

2
NO2 NO2

(+)

O2N O2N

O O
O
H ( ) (+)
29. (d) +O O

3 AlCl
COOH  CO
H 2O

Zn  Hg
Pd
 
 HCl

O
30. (c) See question no. 6
31. (b) Because the benzene ring which is directly attached with ‘S’ is activated thus, nitration should take place on this ring.
32. (d)
(–) ( )
33. (b) CH3 — CH — CH 2 Cl  CH3 — CH — CH 2( )  CH3 — C — CH3 
AlCl3 H shift C6 H 6
| | |
CH3 CH3 CH3
(+) Br Fe/Br2 CH3Cl/AlCl 3
CH3—C—CH 3 +
CH3 CH3
CH3

34. (a) Leaving E+ is more stable.

35. (c) Bromine water can remove –R groups like NO2 from benzene ring
Reaction Mechanism (General Organic Chemistry) 139

OH OH

Br2water Br Br

NO2 Br
36. (c) Here H ion attacks on benzene nucleus & displace Me3C+ ion which on elimination gives alkene
+

i.e. IPSO attack followed by beta elimination takes place

37. (a) Positive charge is stabilized by + R effect of NH2 group
38. (c) It has four resonating structure
39. (c) – R effect of NO2 stabilizes negative charge.
40. (b) +ve charge can be stabilized by lone pair of electrons present on nitrogen.
41. (c) Due to more +R effect benzene ring is highly activated.
42. (a) OMe is + R group, CHO is – R group however Cl has two effects + R & – I
43. (b) p - G2C6H4 — G3 will have higher electron density because both G2 & G3 are electron donating groups
44. (a) CMe3 can not show hyperconjugation hence in (IV) electron density inside the benzene ring is least thus, rate of ArSE will
be small in it.
45. (b) Because 2p of F can easily overlap with 2p of ‘C’ of benzene ring hence due to more resonance electron density is maxi-
mum in fluoro benzene.

(+) (+)
46. (b) –H
(+)
N2 H
Cu
–CuH
–H

47. (d) Strength of lewis acid depends upon the electron deficiency on central atom.SnCl4 is poor lewis acid as Sn has complete
octet. In BF3 back donation of electrons from F to boron decreases electron deficiency of B thus, it is also a weak lewis
acid
48. (d)
H

C C2H5
49. (c)
CH3
50. (c) It is an example of IPSO attack.
CMe3 CMe3
(+)
NO 2 (+)
+ Me3C
Stable
Me 3 C CMe 3 Carbonium ion
Me3C NO2
51. (c) Following resonating structure of pyrrole is favourable because distance between –ve & +ve is least hence ArSE occurs at
2nd & 5th position.
4 3
(–)
5 (+) 2
N1
H
OH
(+)
(+)
H (+) C6H6
52. (d)
(+)
140 Problems in Organic Chemistry

53. (a)
(–)
54. (a) —O has strongest + R effect.
(–) (+)
OMe CH3 AlCl—OMe
3 CH3

AlCl3
55. (a) Deactivated ring
1 2

Thus reaction occurs on 2nd ring

56. (b) Reaction of Ph—H with DCl is a kind of friedel craft reaction as a result of which dutereated benzene is produced which
on nitration produces (b)
57. (c) alkylation should be performed al last because CH3 is o/p directing group, while in product all groups are present meta to
one another.
58. (c) 1, 2, 3 & 5 are aromatic compounds & hence can undergo ArSE.
59. (c) Because nitro benzene is least sensitive towards ArSE as nitro group deactivates the benzene nucleus
(+)
PCl5 alc. KOH H Rh
60. (d) heat

OH Cl
heat with H3PO4

61. (c)
62. (c) Br of Bromine water can replace –R group (like SO3H)
63. (b) in 3rd reaction product is sterically hindered that is carbon can not bear four phenyl groups on the other hand in 4th case
generation of carbonium ion is difficult.

SO3H SO3H SO3H

64. (b) Sulphonation Nitration F.C.R

NO2 Et NO2

OH OH
CH2COCH 3 CH2C—CH 3 CH3
(+)
(+)
65. (a) H


–H2O

66. (c) Ring opening will occur in it.

(+) (+)
H H

(+)
CH2OH (+) CH
2

OH OH
O O
(+) (+)
H PhOH H PhOH
67. (c) (+) HO OH

(+)
OH
Reaction Mechanism (General Organic Chemistry) 141

O OH OH
|| ( ) |
68. (c) CH3CH 2CCH3 
H Toluene
 CH3CH 2 — C — CH3   CH3 CH2 C—
( )
Me Me

H
AlCl3 C6 H 6 H2O
69. (a) (+) OAlCl3 OH
O (+) O OAlCl3
AlCl3

70. (a) Reaction will occur on that benzene ring which is activated thus, bromium ion attacks on the ring which is attached with
Me group. Since para position is sterically hindered hence ortho derivative will produce as a major product.
71. (d)
(+)
CH2 CH2 CH= CH2 (+) CH2 CH2 CH CH CH3
H
72. (c)
CH3 CH3

(+)
CH2 CH2 C CH2 CH3

CH3
(+) CH2
CH2
C
CH2CH3
CH3 (+)
—H

73. (a) See mechanism in your text book.

74. (d)

75. (a) Due to presence of two NO2 groups benzene nucleus becomes e– deficient and can favour the attack of nucleophile.
NO2 OH NO2 OH NO2 OH
(–)

NHCH3 N—CH 3
O2N NHCH3 O2N (+) O2N (+)
H H

NO2 NO2 OH
(+)
H
∆
N—CH3 N—CH3
O2N O2N
CH2
CH2N2 AlCl3 (+) C6 H 6
76. (d) CH2= CH—CH2Cl CH2—CH—CH 2 Cl

77. (b) Factual question

78. (b) [X] is ortho nitro phenol.
142 Problems in Organic Chemistry

H
(+)
O O
79. (a) (CH2)2
(+) CH2C2HOH (+)
H benzene H
benzene
Oxirane Oxirane
80. (b) Carbon can not bear four phenyl groups due to steric hindrance thus, Ph4C can not form.
81. (a) HI formed in this reaction is a good reducing agent which makes the reaction reversible hence during the iodination of
benzene HI should be oxidized in to iodine by some oxidizing agents like HNO3 & iodic acid

O +R group
82. (d) Hence ArSE will occur according to +R group

O –R group

ELECTROPHILIC & FREE RADICAL ADDITION

(+)
CH2
(+)
1. (d) H (+)
(+)

OH OH2 H2O
(+)
(+)
+ H

It involves four intermediats and thus five transition states will be achieved.
Br
Br 2 +
2. (a) CH3—CH = CH2 CH3—CH—CH 2
(–)
Cl
Br(–) from NaCl

CH3—CH—CH2Br CH3—CH—CH2Br
Br Cl

3. (d) KMnO4 gives syn hydroxylation

CH3
H3C CH3 OH OH H OH
KMnO 4
C =C 273 K CH3 OR
H H OH H
H H Meso isomer
CH3
4. (c)
Anti addition
5. (d) Cis alkene 
→ Racemic mixture
Syn addition
Trans alkene 
→ Racemic mixture
Syn addition
Cis alkene 
→ Meso isomer
Anti addition
Trans alkene  → Meso isomer
All addition reactions of alkenes with halogens are the example of anti addition but fluorination is syn addition hence (d)
is correct.
H2(Steric repulsion) H

H2(no Steric repulsion) H
6. (a)

Hexagonal ring will not show ring opening reaction because it does not possess strain.
Reaction Mechanism (General Organic Chemistry) 143

 AlC4(–)  Cl(  )
7. (c) AlCl3  Cl2 
(+)
Cl Cl
(–)
(+) AlCl4
CH3—CH = CH2+ Cl CH3—CH—CH 2 AlCl3 + CH 3—CH—CH2Cl

8. (c) Since carbocation forms as an intermediate in electrophilic addition reaction hence, rate of electrophilic addition reaction
will depend upon the stability of carbocation.
( +)
E( +)
Ph 2 C = CH 2 
→ Ph 2 C — CH 2 E ................... (A)
(A) Is highly stable due to resonance of +ve charge with benzene rings
E ( )
(CH3 )2 C  CH 2   Me2 C( ) — CH 2 E ................... (B)
(B) is also stable due to hyperconjugation
( )
E ( )
Ph 2 C  CHCF3 
 Ph 2C — CHCF3
|
E
(C) is more stable than (B) but less stable than (A) because of – I effect of CF3 group hence rate of E.A.R. will be more in (1)
& least in (2) i.e. 1 > 3 > 2
9. (b) Stability of alkene ∝ 1 / Reactivity ∝ 1 / Heat of hydrogenation

CH3 — CH = CH — CH3 is less the all four operation.

CH2 H CH3
10. (d) + (Molecular addition)
CH2 H CH3

11. (d) All reagents will produce carbene

••
CH
••
CH
2 2
CH CH

(+)
— (+)
12. (c) 2 H 3 Ring opening
(+)

H
SEt H
(+) S EtSH +
(+) Et

13. (a) HCl does not exhibits Antimarkownikoff addition.

(+)
O OH
CH2OH CH2OH CH2OH
(+) (+)
H H 2O –H
14. (b)
(+)
OH CH3
(+) 2
OH
15. (c) Cl2 + H2O gives HOCl
(–)
OH (–)
O
OH
–H2O
O
Cl Cl

OH OH
Na C O
16. (a)
Cl OH
144 Problems in Organic Chemistry

CH3 CH3 CH3 CH3 CH3 CH3 CH3

| | ( ) | | | | |
H Re arrangement H 2O
17. (c) Ph — C H — C  CH 2  Ph — C — C — CH3  Ph — C —C HCH3   Ph —*C — CHMe2
(optical active) | ( ) ( ) |
H OH
(optical active)A

A contains only one chiral carbon atom. On dehydration it produces Ph(Me)C = CMe2 which can not show optical as well
as geometrical isomerism

CH3 CH3 CH3 CH3

| | | |
Ph — CH — C 
— CH — CH — CH3 only one chiral carbon atom
H2
CH 2  Ph
Ni/  *
18. (b) CN & Ac groups are - R groups & decrease the electron density in C == C moiety.
Consequently C == C moiety favours the attack of nueleophile.
Ac (–) Ac (–) (+) Ac (–)
H
C=CH—CH 3 +Br CH—CHBrCH3 C—CH—CH 3
NC NC NC
19. (d) NO2 group is electron withdrawing group &Brdecrease electron density of C = C moiety hence nueleophilic addition reac-
tion will occur on it. Consequently antimarkownikoff addition takes place.
OD
(+)
(+)
Ring opening D2O
20. (b) H (+) (+)
–D

21. (a) Cl2 water gives HOCl

(+)
(+) (–) (+) OH
Cl
(+) Cl Rearrangement Cl OH Cl

22. (a)

23. (c) Ph2CH—N = N—CHPh2 h 2Ph2CH

Br 2
2Ph2 CHBr
–N2

OD
(+)
(+)
D2O
24. (d) H
(A)
H
(+) D OH
(+)
D HO
2

D (B)

25. (c) Product of this reaction wll be

OH
* *
PH * *
OH
* *
OH C = chiral carbon

26. (c) Same as question no.1

(+) (+) (–)
27. (d) CH2= CH—CH=CH2 H CH2=CH—CH—CH3 Br CH2= CH—CHBrCH3

(–)
(+)
CH2—CH =CH—CH 3 Br
CH2BrCH= CH—CH3
Reaction Mechanism (General Organic Chemistry) 145

(+) (+) (–)

CH2= CH—CH=CH2 H CH3–CH—CH =CH 2 Br CH3CHBrCH = CH2

(+) (–)
Br
CH3CH =CHCH 2Br
CH3—CH =CH—CH 2
28. (c) When E(+) attacks on ‘1’ , a highly stable carbocation is formed. Thus, 1st double bond will be highly reactive. Out of 2nd
& 3rd, later is more reactive because it is cis while 2nd is more stable & less reactive as it is trans isomer more stable.
H H
Me Me Me
(+) (–)
29. (d) H Br

Ph (+) Ph Ph
Br
( ) ( ) ( )
30. (a) CH 2  CH 2 
H
Slow
H 2O
 CH 2 — CH 2 
Fast
 H  CH3CH 2 OH

Since slowest step contains CH2 = CH2 & H+ hence rate law is Rate = K [CH2 = CH2] [H+]
31. (c) I+ serves as electrophile as it is less electronegative than Cl
32. (a) Since electrophilicity of Br+ is greater than I+ because of less electronegativity of I than Br thus, BrCl is more reactive than
IBr. Further interhalogens are less stable than halogens hence order of reactivity is: - BrCl > Br2 > IBr > I2
33. (a) In (a) C == C moiety is not attached with electron with drawing group.
CH3 CH3
| ( +) |
34. (d) CH3 — CH = CCH 2 CH 2 CH3 →
H
CH3 — CH2 — CCH 2 CH 2 CH3
[can show geometrical isomerism] ( +)

CH3
reduction |
CH 3 — CH 2— CHCH2CH2CH3 [opticaly active]
*

(+) (+)
35. (b) O O H
O OH O OH
(+)

(–)
Tautomerism Br
O OH O OH

Br Br
CH3
H Br
36. (a) Br2in CCl 4
Br H

CH3
The product of this reaction has configuration [2R, 3S]

Elimination Reactions:-
1. (d) At bridge ‘C’ atom double bond does not form until parent ring contains 8 ‘C’ atoms (Bredit’s rule)
2. (b) In hydrohalogenation anti elimination takes place
CH3

H H alc KOH CH3

——————

H Cl H
146 Problems in Organic Chemistry

(+)
CH3
(–) 
3. (c) H3C—N— CH 3 OH CH3OH + (CH 3 )3N
CH3

(+)
(+)
(+) (+)
4. (c) H –H
(+)

(+)
(+) (+)
H Rearrangement –H
5. (b) OH –H2O (+)

6. (b)
7. (a) For SN1 substrate should be 3° & base should be weak.
Me
Me H
I H (–)
OH
8. (c) Also see q.15 Ph H
H Me
Me

OH CH3 CH3 CH3

| | () ( ) | () |
 CH 2  CH CHCH 2 CH3
H –H
9. (c) CH3 — CH — CH — CH 2 CH3 
 CH3 — CH CH — CH 2 CH3 
–H 2O

CH3 CH3
(+)
CH3CHCHCH 2CH 3 CH3CH 2 CCH2CH 3
(+)
(+)
(+)
–H –H

CH2 CH3

CH3CH2 —C—CH2CH 3 CH3CH = C—Et

10. (b) See question no. 52 in electrophilic substitution reaction.

11. (a) Anti elimination will take place.
OH (+)
H (+)
————
—H2O
Cl Cl

H2O
12. (b) ————
Cl (+) Cl
OH2
(+)
(+)
–H
———— O
–HCl
Cl
OH

13. (c) Because it will produce least stable carbonium ion.

Reaction Mechanism (General Organic Chemistry) 147

H/Ni
2 CH3I AgOH
excess (+) (–)
N N N N OH
(+)
H H H3C CH3 H3C CH3

14. (b) H2 O + N(CH3 )3 + ∆ CH3I ∆

(+) (–) AgOH
N OH N
H3C CH3 H3C CH3
CH3

Br I
H D
H D (–) H D (–) H D
15. (c) I I OR
D H D H D H D H
Br I
16. (c) Base is sterically hindered thus elimination product will produce more than substitution product.
Passage (17 to19)
Acid catalysed dehydration of alcohols involves formation of carbocation as intermediate
Rate of dehydration depends upon 2 factors
1. Stability of carbocation formed in rate determining step
2. Acidic nature of H attached to the carbon adjacent to positively charged carbon atom
3rd will provide stable carbocation (resonance stabilized) thus, it will dehydrate more easily
OH
(+) (+)
H
–H2O
NMe2 NMe2 (+)NMe2
stable due to resonance
4th will provide highly unstable carbocation as positively charged carbon atom is attached with electron withdrawing NO2
[Link] of 1st & 2nd dehyration process is rapid in later as it contains more acidic hydrogen.
OH
(+) (+) H
H More acidic due to electron
withdrawing effect of NO2 group
NO2 NO2
Out of 1st & 4th rate of dehydration will be more in 1st because formation of carbocation occurs in slowest step & 1st
provides more stable carbocation.
20. (c) In (B) saytzeff rule is obeyed while in (C) hoffman rule is obeyed.
In A anti elimination occurs as follows:-
OH
(+) (+)
H H More acidic due to electron
withdrawing effect of NO2 group
NO2 NO2
21. (c) Since OH is a poor leaving group in basic medium thus, base will abstract ‘H’ to produce conjugate base(E1CB)
22. (d) Tertiary halide on reaction with strong base favours elimination reaction & since temperature is also large thus 100% elimi-
nation product will be obtained.
23. (b) In 1-2 elimination reaction leaving groups should be anti periplanar to each other hence rotation about single bond occurs
in the following manner.
Ph Ph Ph
Ph Ph H Me
H Br Br
free rotation OR
Me H about single bond Me H Me Ph Ph
Ph H H
148 Problems in Organic Chemistry

MORE THAN ONE MAY CORRECT

1. a, b, c
2. b, c
In (a) Cl can receive -ve charge in its vacant d orbital. In (b) + ve charge can not be delocalized because bridge head ‘C’ can not
bear double bond.

(+)
–H (+)
(+)

(not possible)

3. b, c
4. a, b In carbonate ion bond order is 4/3 while bond order is 3/2 in acetate ion.
5. b, c
6. b, c
7. a, b, d b & d will show aromaticity after tautomerism
8. c, d
9. a, b because alkyl and alkenyl ions are stronger bases than NH2(–)
10. b, c X & Y are formed nia SN1 and elimination reactions respectively.
11. b, d II & III are antiaromatic & aromatic species respectively while I & IV are non aromatic species
12. a, b, d In these three cases benzene ring is deactivated.
13. a, b, d In polar proteic medium attacking base is caged solvent molecules by the help of hydrogen bonding and becomes
weak.
14. a, b 15. b, c, d
Cl

16. a, b + 2NaNH2 — 2NaCl + 2NH3 + +

Cl
17. a, d 18. a, b, c 19. a, c, d
20. a, c

LEVEL-II
1. (a) Trans alkene is more stable so it has less energy thus, more energy will be required to achieve transition state
(+)
(+)
2. (d) 1st is stable as it can show sigma resonance

3rd is least stable as it can not show resonance it is stabilized by three hyperconjugative structures.

Antiaromatic
3. (d)
(+)
4nπ electrons

4. (d) This reaction is not possible because anti dehydrochlorination is not possible
Reaction Mechanism (General Organic Chemistry) 149

H
5. (c) H(+) H3C (+)
–CH3
(+)

(+)
H3C CH3
(+)

H
OH (+) OH
B B
6. (b) OH OH

6- valence electrons 8- valence electrons

7. (d) When two benzene rings are connected with each other by the help of covalent bond then resonance occurs as follows.

(+)

Deactivated ring
(–)
Activated ring

This kind of resonance is possible only when both the rings are present in the same plane. This resonance is maximum in
(d) because CH2 group holds both the benzene rings in the same plane which is not possible in (a) & (b)
(+)
O
8. (b) Lone pair present on oxygen repels negative charge.
(–)
O

9. (d) Bond order = No. of covalent bonds involved / No. of resonating structure
10. (a) + I effect of SiH3 is greater than CD3 which is further greater than CH3
11. (a) – R effect of CN will not work at meta position.
12. (b) Carbanion is stable than carbocation & radical as negatively charged carbon atom possesses 8e’s in its outermost shell.
Out of free radical & carbocation former is stable than later as radical needs only one electron to complete its octet while
carbocation needs 2 electrons to complete its octet
13. (c) Cyclo butadiene has rectangle shape hence bond lengths a & b are not equal & both are different compound
14. (d) All have 4nπ electrons so they all are antiaromatic & stable. Hence they loose their planarity & becomes non aromatic and
stable
15. (d) π- electrons present at periphery are considered.
16. (d) Since cyclobutadiene has rectangular shape hence chances of resonance are low thus, it has less resonance energy .It is
antiaromatic in nature thus, it dimerises easily at above 4°C as follows:-

2- moles

This is Diels -Alder reaction.

CCl3 CCl3
CCl3 –H
(+) CCl3
17. (b) O O
(–)
150 Problems in Organic Chemistry

Since negative charge is present at bridge ‘C’ thus, it can not be delocalized hence this carbanion will be nonplanar.
18. (b) Both the alkenes are almost equally stable
CH3 CH 3
|
A (CH3)3CCH =C and B (CH 3 ) 3 CCH 2 — C  CH 2
CH3 5  hyperconjugative structure
6- hyperconjugative structure

But removal of 2nd hydrogen is more difficult in comparison to due to more steric hindrance around it thus, B is major &
A is minor
CH3 H2 CH3
| | |
CH3 — C — CH — C — CH2— H1
| |
CH3 OH

D H D H H D

19. (c)

optically inactive optically active

20. (a) See chapter - 3, q.n. - 6, level - II

21. (a) In polar medium (large dielectric constant) salvation of base takes place thus, nucleophilicity deceases consequently rate
of SN2 decreases.
22. (c) In (a) NaOH does not dissociate in non polar medium so reaction is not possible. In (b) RX is present in a non polar medium
while NaOH is dissolved in water (polar medium) so both solutions do not mix & reaction does not occur. In (c) NaOH
dissociates easily because sodium ion is caged in crown ether.

O O
(+) (–)
Na RX + OH ROH
O O

23. (c) In case of SN2 :-
δ δ
RX + Nu ( )

→ Nu .........R.......... X
more polar & more more polar & more solvated
solvated

In case of SN1:-
δ δ
RX → Nu .........R.......... X
less polar & more more polar & more solvated
solvated
24. (d) In racemic mixture 35% d form & 35% l form will be present thus, % inverted product = 35 + 30 = 65
 Acid & Base
5
Main Features

 H O(+) +
HA + H2O  A(–)
3
(acid) (Conjugate base)

Acid Strength ∝ Stability of conjugate base

Basic Strength ∝ Stability of the species formed after protonation
Factors affecting acid or basic strength

> Acid Strength ∝ [- I effect]

∝ 1 / [+ I effect]
> Basic Strength ∝ [ + I effect ] ∝ 1 / [ - I effect ]
> Polarity of medium ∝ acid / basic Strength
> % s character ∝ electronegativity
∝ acid Strength
∝ 1 / basic Strength
> Aromaticity & Hydrogen bonding also affect the acidic or basic strength. Here some compound are arranged in order of their
decreasing pKa values:-
Alkane > Terminal alkene > benzene > alkyl amines > NH3 > RCN > terminal alkyne > ester > ketone > alcohol (3° > 2° > 1°)
> H2O > CH3NO2 > PhOH > PhSH > p - nitro phenol > RCOOH > PhCOOH > HCOOH > RSO3H > HNO3 > H2SO4 > HCl >
HBr > HI

LEVEL - I

Multiple Choice Questions

1. Which among the following is least basic:-

(a) CH2 CH — NH2 (b) CH3 — C — NH 2 (c) CH3 — NH2 (d) Cl — CH2 — NH2
||
O
2. The compound having least pKa is:-

(a) (b) (c) (d)

152 Problems in Organic Chemistry

OH OH COH
2
COOH
NO2
3.
NO2
NO2
(1) (2) (3) (4)

Correct order of acid strength is:-

(a) 2 > 4 > 3 > 1 (b) 4 > 2 > 1 > 3 (c) 4 > 3 > 2 > 1 (d) 4 > 2 > 3 > 1

NH2 NH2 COOH

NH2
NO2
4.
CH3
CH3
(1) (2) (3) (4)

Correct order of basic strength is:-

(a) 3 > 1 > 2 > 4 (b) 3 > 2 > 1 > 4 (c) 1 > 2 > 3 > 4 (d) 4 > 3 > 1 > 2
5. Arrange the following compounds in decreasing order of basic strength:-
NH2 NH2
CH3
CH3CONHCOCH3 CH3NH2

(1) (2) (3) (4)

(a) 4 > 2 > 3 > 1 (b) 4 > 1 > 3 > 2 (c) 2 > 4 > 1 > 3 (d) 4 > 2 > 1 > 3
O O Cl
6.
CH3
N N N N
H H H H
(1) (2) (3) (4)

Correct order of basic strength is:-

(a) 2 > 1 > 3 > 4 (b) 2 > 3 > 1 > 4 (c) 2 > 1 > 4 > 3 (d) 3 > 2 > 4 > 1
7. Arrange the following substituted benzoic acids in decreasing order of acid strength:-
CO2H CO2H
CO2H CO2H
OMe

OMe
OMe
(1) (2) (3) (4)
(a) 1 > 2 > 3 > 4 (b) 1> 2 > 4 > 3 (c) 1 > 4 > 2 > 3 (d) 2 > 1 > 4 > 3
8. Carbonic acid, H2O, Phenol, FCO2H
(1) (2) (3) (4)
Correct order of acid strength is:-
(a) 1 > 4 > 3 > 2 (b) 2 > 1 > 3 > 4 (c) 2 > 4 > 1 > 3 (d) 4 > 1 > 3 > 2
2
NHCl
O
9.
H–N
3 N
1
Correct order of basic character of these nitrogens is:-
(a) 1 > 2 > 3 (b) 2 > 1 > 3 (c) 3 > 2 > 1 (d) 2 > 3 > 1
Acid & Base 153

(3)
HOOC
10. (1)
OH
(2) OH NO2

1, 2 & 3 are H+ donating sites. Correct order of ease of removal of H+ is:-

(a) 3 > 2 > 1 (b) 3 > 1 > 2 (c) 1 > 3 > 2 (d) 3 > 1 > 2
O (2)
(1) (3)
11. N
N
N

H H
Highly basic nitrogen is:-
(a) 3 (b) 2 (c) 1 (d) 1 = 2 > 3

12.
N N N N
H H H H
(1) (2) (3) (2)
Correct order of basic strength is:-
(a) 2 > 1 > 4 > 3 (b) 2 > 1 > 3 > 4 (c) 1 > 2 > 4 > 3 (d) 1 > 2 > 3 > 4
(1)
NMe

13.

(3)
(2)
Bu—N Nac

Correct order of basic strength of these nitrogens is:-

(a) 2 > 1 > 3 (b) 2 > 3 > 1 (c) 1 > 2 > 3 (d) 1 > 3 > 2

14. Identify the least acidic alcohol

OH OH
OH
H H
H NO2 H H

H H H H
H NO2
H NO2
H
(3)
(1) (2)

(a) 2 (b) 1 (c) 3 (d) all are equally acidic

15. The compound having least pKb or large pKa is:-

NH2 NH2
|
(a) C = NH 2 (b)
H2N—CH—NH 2 (c)
H2N—C CH 2 (d) Ph—N—NH 2
H2N | |
NH2 Ph
16. From the following reactions
NH3  CH  CLi
CH  CH  LiNH 2 

 CH  CH  LiOH
CH  CLi  H 2 O 
154 Problems in Organic Chemistry

Predict which of the following orders regarding base strength is correct?

(–) (–) (–) (–) (–) (–)
(a) CH  C  OH  NH 2 (b) CH  C  NH 2  OH
(–) (–) (–) (–) (–) (–)
(c) OH  NH 2  CH  C (d) OH  CH  C NH2
17. Consider the following reactions
RONa  H 2 O 
 ROH  NaOH

RONa  NaNH 2 
 RONa  NH3

Predict, which of the following order regarding base strength is correct

(–) (–) (–) (–) (–) (–) (–) (–) (–) (–) (–) (–)
(a) OH  NH2  RO (b) NH 2  OH  RO (c)
OH  RO  NH 2 (d) OH  RO  NH2
18. Correct order of acid strength is:-
H
CH=C
H H (3)

H C C CH
(2)
H(1)
(a) 1 > 2 > 3 (b) 2 > 3 > 1 (c) 2 > 1 > 3 (d) 1 > 3 > 2
19. Correct order of ease of removal of H+ is:-
(+)
(1) OH

C—H

(+)
NO2H COOH
HO (3)

(a) 3 > 1 > 2 > 4 (b) 2 > 4 > 3 > 1 (c) 3 > 2 > 1 > 4 (d) 2 > 3 > 4 > 1
20. Which will have least pKa?

(a) (b) (c) OH (d) H2SO4

SH COOH
(+) 2 (+)

21. Which will have maximum pKa?

(a) (b) (c) (d) Phenol

SH OH COOH
22. Strongest base among the following is:-
(a) BuLi (b) LiNH2 (c) CH3ONa (d) HCOONa
23. Which reaction is not possible?
(a) 2CH3COONa + H2SO4 ——→ Na2SO4 + 2CH3COOH
(b) HCOOH + CH3OK ——→ HCOOK + CH3OH
(c) CH ≡ CNa + CH3OH ——→ CH ≡ CH + CH3ONa
(d) LiNH2 + CH2 = CH2 ——→ CH2 = CHLi + NH3
24. Which is strongest acid among the following?
(a) HCOOH (b) 2, 4, 6 trinitro phenol
(c) FCH2COOH (d) CH3COOH
Acid & Base 155

25. FCH2COOH Cl2CHCOOH CH3COOH HCOOH ClCH2COOH

(1) (2) (3) (4) (5)
Correct order of acid strength is:-
(a) 1 > 5 > 2 > 4 > 3 (b) 5 > 1 > 2 > 4 > 3 (c) 2 > 1 > 5 > 4 > 3 (d) 5 > 2 > 1 > 4 > 3
26. Which statement is not correct?
(a) Oxalic acid is stronger acid than formic acid
(b) Formic acid is stronger acid than succinic acid
(c) Fumaric acid is stronger acid than maleic acid
(d) Fluoro ethane is stronger acid than Chloro ethane
27. Which of the following ‘O — H’ bond has least bond energy?
(4)
COO—H (1)
CH—O—H
2
Cl
H—O—CH2 C
(3)
CH3 O—H
(a) 1 (b) 2 (c) 3 (d) 4
28. Correct order of case of removal of marked ‘H’ will be:-
1 3
H H
H
CH2 COOH
4
2H

(a) 1 > 2 > 3 > 4 (b) 1 > 4 > 2 > 3 (c) 4 > 1 > 2 > 3 (d) 4 > 1 > 3 > 2
29. Out of 1, 2, 3 & 4 which can with draw H from sp hybridized carbon of propene
+ 3

(–)
COO (2)

(–)
(–)
(3)
(–) C C (1)
O

(a) 1 (b) 2 (c) 3 (d) 4

30. Strongest base among the following is:-
(a) Me3N (b) Me2NH (c) Me4NOH (d) NaOH
31. Identify the correct statement?
(a) p – nitro phenol is less acidic than ortho nitro phenol
(b) Picric acid is less acidic than formic acid
(c) pKa of maleic and fumaric acid is same
(d) Dichloro acetic acid is stronger acid than fluoro acetic acid
OH OH
OH OH
Cl
32.
Cl Cl
(1) (2) (3) (4)
Correct order of p is:-
Ka

(a) 4 > 3 > 2 > 1 (b) 4 > 2 > 1 > 3 (c) 4 > 1 > 2 > 3 (d) 4 > 3 > 1 > 2
156 Problems in Organic Chemistry

OH OH
OH OH
OMe
33.
OMe OMe
(1) (2) (3) (4)

Highly acidic compound is:-

(a) 1 (b) 2 (c) 3 (d) 4
34. Which is not a monoacidic base?
(a) Urea (b) Methyl amine (c) Ethylene diamine (d) NH2CH2CO NH2
3 5.  C  NH p — NO2 — C 6H 4C — NH2 m — CH3 — C 6H 4C — NH2
| || || CH3 CONH2
NH2 NH NH
(1) (2) (3) (4)

Correct order of basic strength is:-

(a) 3 > 1 > 2 > 4 (b) 4 >3 > 1 > 2 (c) 3 > 1 > 4 > 2 (d) 4 > 3> 2 > 1
36. Which reaction is not possible?

(a) + +
N N N N
H (+) (+)
H H H
() (–) (–)
(b) ( NH3 )HSO 4  Me2 NH 
 MeNH 2 HSO4  NH 2
() ()
(c) C  NH  H   C N H2

| |
NH2 NH2

(–)
(d) + OH H2 O +
N N
(+)
H
37. Consider the following amines:-
NMe2 NMe2 Me
NH2 Me Me NH2

Me
(1) (2) (3) (4)

Correct order of basic strength is:-

(a) 4 > 2 > 3 > 1 (b) 2 > 4 > 3 > 1 (c) 3 > 4 > 2 > 1 (d) 3 > 2 > 4 > 1
38. Weakest base among the following is:-
(a) n-BuLi (b) AcCH2(–) (c)
FCH2(–) (d) i - Pr carbanion
39. Consider the following compounds:-

N Et3N FNH2 Me2NH

(1) (2) (3) (4)
Correct order of basic strength is:-
(a) 1 > 4 > 2 > 3 (b) 4 > 1 > 3 > 2 (c) 4 > 2 > 1 > 3 (d) 2 > 1 > 4 > 3
Acid & Base 157

(–) (–)
40. Which statement is not correct about OH & SH :-
(–) (–)
(a)
SH is better leaving group than OH
(–) (–)
(b)
OH is stronger base than SH
(–) (–)
(c) Conjugate acid of OH is stronger acid than conjugate acid of SH
(–) (–)
(d) Nucleophilicity of SH is large in comparison to OH in polar protic solvents

41. The decreasing order of relative basic strength of following:-

Me3CO(–) MeO(–) Me2N(–) BuLi
(1) (2) (3) (4)
(a) 1 > 2 > 3 > 4 (b) 4 > 1 > 2 > 3 (c) 4 > 3 > 1 > 2 (d) 3 > 1 > 2 > 4
42. Consider the following compounds:-
O
O O
Ac3CH Me3COH

(1) (2) (3) (4)

Correct order of acid strength will be:-
(a) 3 > 4 > 2 > 1 (b) 3 > 4 > 1 > 2 (c) 3 > 1 > 2 > 4 (d) 4 > 1 > 3 > 2
43. Which among the following is highly basic:-
NH NH
(a) (b) (c) (d)
O
N N
Me H

44. NH NH
N O N Me
Me H
(1) (2) (3) (4)

Correct sequence of basic strength is:-

(a) 1 > 4 > 3 > 2 (b) 1 > 4 > 2 > 3 (c) 4 > 1 > 2 > 3 (d) 4 > 3 > 1 > 2
45. Which among the following is least basic:-
NO2
( ) O Cl
(a) (b)
C5 H5 NMe (c) (d)
N N N
Cl Cl Cl

46. Identify the wrong statement

O
N
(a) is basic but not (b) is less basic then
N O NH
N

O CF3
O O O
(c) is less acidic than (d)
F3 C OH is less acidic the CH3COOH
CF3
158 Problems in Organic Chemistry

47. Correct sequence of acid strength of the following four compounds will be:-
CO2H CO2H CO2H CO2H
Me Me

Me Me
NO2 NO2 SO3 H NO2
(1) (2) (3) (4)

(a) 3 > 1 > 2 > 4 (b) 3 > 1 > 4 > 2 (c) 1 > 3 > 2 > 4 (d) 3 > 2 > 1 > 4
48. Which statement is correct regarding the acid strength of the following organic and inorganic compounds?
(a) Sulphonic acids are more acidic than carboxylic acids
(b) BCl3 is more acidic than BF3
(c) Acetone is more acidic than acetaldehyde
(d) All are correct
49. Pick out the wrong statement.
(a) (CH3)3SiCH2COOH is more acidic than Me3CCH2COOH
(b) Fumaric acid is more acidic than maleic acid.
(c) Chloroform is more acidic than Fluoroform.
(d) In CH3CONH2, Hydrogen attached with N is more acidic than hydrogen attached with C
50. Which among the following is highly basic?

(a) O CH3 (b) (c) (d)

N N N
N
Ac CH3 H
H
51. Which among the following is least acidic?
(a) FCO2H (b) FSO3H (c) FCH2OH
FOH (d)
52. If pKb of CH3CN, CH3CHO and CH3OCH3 are x, y & z respectively then
(a) x > y > z (b) y > z > x (c) z > x > y (d) z > y > x
53. Which is not expected to be a good carbon acid?
O
O O O
(a) CH3COCH2COOC2H5 (b) (c) (d) NO2 — CH(COOCH3)2

54. Which has maximum pKa?

CO2H CO2H
CO2H NO2
(a) (b) (c) (d)
N CO2H N N

55. Select the wrong statement.

(a) Acetamide is less basic than aniline
(b) Pyridine -2-carboxylic acid is more acidic than Pyridine -3-carboxylic acid
(c) BCl3 is stronger acidic than AlCl3.
(d) GaCl3 is stronger acid than ZnCl2
56. Which among the following is strongest base?
(a) Cyclohexa – 2, 4 – dinone (b) Propene
(c) Acetone (d) 4 – Oxa cyclohexa 2, 4 dienone
Acid & Base 159

Cl
H
57. The reagent which can abstract H is:-

(a) HCOOK (b) CH3OK (c) FONa (d) CH3Li

58. Salicylic acid is stronger acid than p - hydroxyl benzoic acid because of
(a) Resonance effect (b) Steric hindrance
(c) Intra molecular – H– Bonding (d) Hydration energy.
59. Match the following
Acid pKa
FC CF3
(A) 3 (p) 5.40
CF3 OH
(B) 2, 4, 6 - trinitro phenol (q) 0.7
(C) AcOH (r) 6.60
(D) COOH (s) 4.76
O
(a) A → q, B → q, C → p, D → s (b) A → r, B → q, C → s, D → p
(c) A → r, B → q, C → s, D → p (d) A → p, B → q, C → s, D → r
60. Match the following
Acid Approx pKa
O
HO
(A) Squaric acid (p) 1
HO
O
(B) RSO3H (q) –1
(C) HClO4 (r) 0.0
(D) H3BO3 (s) 9.27
(a) A → p, B → r, C → q, D → s (b) A → s, B → q, C → r, D → p
(c) A → s, B → r, C → q, D → p (d) A → p, B → q, C → r, D → r
61. Assertion: - para chloro phenol is more acidic than para-fluoro phonol.
Reason: - (–I) effect of F is greater than Cl.
(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true
62. Assertion: - salicylic acid is stronger acid than p-hydroxy benzoic acid
Reason: - salicylate ion is stabilized by H-bonding.
(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true
63. Assertion: - 2nd dissociation constant for sulphuric acid is smaller than 1st dissociation constant.
Reason: - resonace stabilization of sulphate ion is lesser than that of bi sulphate ion.
(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true
160 Problems in Organic Chemistry

64. Assertion: - para chloro benzoic acid is more acidic than benzoic acid.
Reason: - +R effect of Cl group is not prominent thus due to –I effect of Cl para chloro benzoic acid is more acidic
(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true
65. Assertion: - Hydroxide ion can withdraw hydrogen from benzene .
Reason: - basic strength of alkenyl carbanion is greater than hydroxide ion
(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true

Answers Key

1. (b) 2. (c) 3. (c) 4. (a) 5. (b) 6. (a) 7. (d) 8. (a) 9. (a) 10. (a)

11. (a) 12. (a) 13. (a) 14. (b) 15. (a) 16. (d) 17. (c) 18. (c) 19. (a) 20. (d)

21. (b) 22. (a) 23. (d) 24. (b) 25. (c) 26. (d) 27. (d) 28. (d) 29. (c) 30. (c)

31. (d) 32. (a) 33. (b) 34. (c) 35. (a) 36. (a) 37. (b) 38. (b) 39. (a) 40. (c)

41. (c) 42. (c) 43. (c) 44. (d) 45. (b) 46. (c) 47. (d) 48. (d) 49. (a) 50. (c)

51. (d) 52. (a) 53. (b) 54. (a) 55. (b) 56. (d) 57. (d) 58. (c) 59. (d) 60. (a)

61. (b) 62. (a) 63. (a) 64. (a) 65. (d)

Multiple Choice Questions (More Than One May Correct)

1. In which case 1st compound is more acidic than 2nd.

(a) CF3COOH, HCOOH (b) PhOH, CH CH

(c) Me3CCOOH, CCl3COOH (d) F COOH Cl OH

2. In which case 1st compound is more acidic than 2nd

COOH COOH
(a) Cl OH F OH (b)
NH2 NH3
(+)

(c) OH (d) COOH

O2N OH H3C COOH
NO2 CH3
3. Which sequence of basic strength is not correct?
(a) PhO(–) > CH3O(–) > NH2(–) > HCOO(–) (b) CH3O(–) > NH2(–) > CH C(–) > PhO(–)
(c) (CH3)3CO(–) > CH3COO(–) > HCOO(–) > HSO4(–) (d) CH3(–) > CH2 = CH(–) > NH2(–) > OH(–)
Acid & Base 161

4. Which statement is wrong about the following compound?

4
OH
1
2 COOH
OH
3
HO NO2
(a) 4th is least acidic hydrogen
(b) Most acidic hydrogen is 1st
(c) 2nd hydrogen is more acidic than 3rd hydrogen
(d) 4th hydrogen remains unreactive when 1 mol of this compound reacts with 3 moles of NaOH.
5. In which case 1st compound is more basic than 2nd:-

NH2 NMe2 NMe2

(a) NH2 (b)
CH3
NO2
NH = C — NH2 ,
(c) H 2 N — CHNH 2 (d) (CH3)3N, Et2NH
| |
NH2 NH 2
CH3
O
6.
N N N
H H
(I) (II) (III)
Which is/are correct statement/s?
(a) III is more basic than I & II. (b) I & II are aromatic compounds
(c) I is more basic than III (d) II is more basic than III
7. In which of the following reactions, forward reaction is favoured:-
(a) CH3C ≡ CH + BuLi  CH3C ≡ CLi + BuH
(b) HCOOH + CH3CH 2 ONa  HCO 2 Na + EtOH
(c) PhSO3 Na + CH ≡ CH PhSO3 + CH ≡ CNa

(–)
H 2SO 4 + OH (–)
(d) H 2S O 4 + H 2 O 
8. Which among the following will produce antiaromatic species after the removed of H(+)

Ph Ph
(a) (b) (c) (d)
(+) Ph (–) Ph

9. In which case 1st is stronger acid than 2nd.

COOH
OH COOH
O2N NO2 COOH
(a) (b)
OCH3
OCH3
NO2
COOH COOH
COOH COOH
CH3
(c) (d)
CH3 Cl
CH3
162 Problems in Organic Chemistry

Answer Key

1. (a), (b), (d) 2. (a), (d) 3. (a), (b) 4. (c) 5. (b), (c)

6. (a), (b) 7. (a), (b) 8. (a), (c) 9. (a), (b), (c), (d)

LEVEL - II

Multiple Choice Questions

1. Arrange the following in decreasing order of acid strength.

O
O
O O O O O O
O O
F Cl
(1) (2) (3) (4) (5)

(a) 2 > 1 > 3 > 4 > 5 (b) 1 > 2 > 3 > 4 > 5 (c) 1 = 2 > 3 > 5 > 4 (d) 2 > 1 > 3 > 5 > 4
2. Which is true regarding the basic strength of the two amines given below?
N N

(1) (2)

(a) Both are equally basic.

(b) 2nd is less basic than 1st because in 1st case amine inversion is not possible.
(c) 1st is more basic than 2nd because in 2nd case N is sterically hindered.
(d) 2nd is more basic than 1st because in 1st case amine inversion takes place.
3. Your have three species PhNH3(+) (1), CH3NH3(+) (2) & CH3COOH (3) Correct order of their pKa will be :-
(a) 2 > 3 > 1 (b) 2 > 1 > 3 (c) 3 > 2 > 1 (d) 3 > 1 > 2
4. Strongest carbon acid among the following is:-
F
S NH O
(a) (b) (c) (d)
S N F O
H
H1
2H
5. Most acidic hydrogen
3H
H4
(a) 1 (b) 2 (c) 3 (d) 4
6. Correct sequence of bond energies of C — H bonds in the following compound will be:-
O H2
H1

H4 H3
(a) C — H4 > C — H2 > C — H3 > C — H1 (b) C — H2 > C — H3 > C — H4 > C — H1
(c) C — H4 > C — H1 > C — H3 > C — H2 (d) C — H2 > C — H1 > C — H3 > C — H4
Acid & Base 163

7. Which statement is correct regarding the acid strength of following three compounds?
(1) HO O O—H(2) O H (4)

HO O (3) HO O
(a) H(3)is more acidic than H(4)
(b) H(1) is less acidic thanH(2)
(c) H(4) is more acidic than H(2)
(d) H(3) is less acidic than H(1) but more acidic than H(2)
8. In which case Ist is more acidic than 2nd
OH OH OH OH

(a) & (b) &

Cl F
OH OH CMe3 Et

(c) & (d)

&
MeO OMe
F Cl
9. In which case Ist compound is more basic than IInd compound.

NH2
(a) & N (b) CH3CONHCOCH3 & CH3CONHCOPh

N NH2
(c) & NH=CH (d) H2O & NH3
N NH3

10. Which nitrogen will pick up H(+) rapidly?

H
N NH2
(a) (b) (c) (d) MeCONHCOCH2ME
N
H
11. Which will not form zwitter ion?
(a) p – NH2C6H4SO3H (b) p – NH2C6H4 — COOH
(c) p – CH2NH2C6H4SO3H (d) NH2CH2COOH
Hint: - The ion which contains positive as well as negative charge is called zwitter ion for e.g.

Answer Key

1. (a) 2. (b) 3. (b) 4. (a) 5. (b) 6. (b) 7. (c) 8. (b) 9. (a) 10. (a)

11. (b)
164 Problems in Organic Chemistry

SOLUTION
Level – I
1. (b) Resonance makes the NH2 group less basic however resonance also occurs in (a) but resonance in (b) is more favourable
because electro negative ‘O’ atom acquires negative charge. Hence due to more extent of resonance (b) is least basic.
(+ )
CH3 — C—N H 2←→ CH3 —C = NH 2
••
|| |
O O(–)

(+)
2. (c) H + aromatic & stable
(–)

3. (c) Phenols are less acidic than carboxylic acids hence 1 & 2 are less acidic than 3 & 4. Out of 1 & 2, later is more acidic
because NO2 is electron with drawing group & helps in the dissociation of OH bond.
Similarly out of 3 & 4th later is more acid due to more –I effect as well as – R effect of NO2 group at ortho position.
4. (a) The methyl group raises the electron density more at ortho & para position than at meta. Thus, the carbon atom para to the
methyl group has a high electron density, & the lone pair on the nitrogen atom therefore is prevented, to some extent, from
entering in to resonance with the ring. A methyl group raises the electron density at meta position to a very small extent.
Hence resonance with the ring of the NH2 group at this position is prevented less than for the p- position. Consequently, a
methyl group in the ring increases the basicity of the aniline, more so from the p- position than from meta
NH2
NH2
CH3NH2
NH2
5. (b)
NH3 Cl
ortho effect +R & –I effect ( +I effect)
(1) (2) (3) (4)

4 > 1 > 3 > 2 3rd is placed after 4 & 1 because Cl in ring deactivating group.
6. (a) 3 & 4th are less basic than 1 & 2nd because lone pair of electron present on N is delocalized. Out of 3 & 4th former is more
basic them later because electron –I effect of Cl decreases electron density on ‘N’. Out of 1 & 2nd is more basic due
to + I effect of methyl gruoup.
7. (d) 2nd & 1st are almost equally acidic because –I effect in 2nd will be equal to that of +R & ortho effect in 1st.
8. (a) acid strength ∝ stability of conjugate base
9. (a) –R effect of CO group makes 3rd nitrogen least basic. Out of 1st & 2nd later is less acidic because (–I) effect of Cl group
decreases electron density on N atom.
10. (a) Carboxylic acid is more acidic than phenols. Out of 1st and 2nd later is less acidic due to presence of intra molecular –H
bonding
11. (a) 1st is least basic because lone pair of electron present on ‘N’ undergoes resonance with CO group. Out of 3rd and 2nd former
is more basic as its lone pair undergoes resonance only with one double bond
12. (a) 3rd is least basic because lone pair of electron present on N is delocalized. Out of 1, 2 & 4th, 4th is least basic because N is
sp2 hybridized thus, it is more electronegative & can not donate its lone pair of electrons easily. 2nd is more basic than 1st
because of more +I effect.
13. (a) 3rd is least basic as lone pair of electron present on N is not localized and takes part in resonance with CH3CO
group(Ac).
14. (b) 1st is least acidic due to the presence of intramolecular H bonding
15. (a) Because after protonation intermediate so formed is stabilized by resonance
•• (+ )
NH2 NH2 NH2
| (+ ) | ||
H 2 N — C = NH → H 2 N —C = N H 2 ←→ H 2 N—C — N H 2
H •• •• ••
( +)
Acid & Base 165

(–) (–)
(–) (–)
CH ≡ CH + N H2 ←
→ NH3 + C ≡ CH NH 2 > C ≡ CH
(less basic)
(More basic)
16. (d)
(–) (–) (–) (–)
→ OH + CH ≡ CH
CH ≡ C + H 2 O ← CH ≡ C > OH
(More basic)(less basic)

Therefore overall sequences will be:-

(–) (–) (–)
NH 2 > CH ≡ C > O H
17. (c) Same as previous.
18. (c) % S character electronegativity.
Triple bonded carbon atom is more electronegative than double & single bonded carbon atom due to 50% S character so it
can withdraw electrons very easily from C—H bond. Consequently 2nd is most acidic
19. (a) Stability of conjugate base acidic character.
20. (d) Mineral acids (H2SO4, HCl, HNO3 ) are stronger acids than other.
21. (b) Alcohols are less acidic than thiols because ‘S’ is bigger in size thus ‘S—H’ bond has less bond energy than ‘O—H’ bond
22. (a) Alkanes are poor acid but their anions are strong base.
23. (d) CH2 = CH(–) is stronger base than
24. (b) Because electron with drawing effect of 3-NO2 groups helps is dissociation of ‘O—H’ bond.
25. (c) Negative I effect enhances acidic character
(–) (–)
26. (d) CH 2 Cl is stabilized by resonance while CH 2 F is not because Cl can receive electrons of –ve charge in its empty d
orbital.
27. (d) Acidic character ∝ 1 / Bond energy
28. (d) Carboxylic acid is more acidic than alkane & alkene.1st is more acidic than 2nd & 3rd because it forms an aromatic
anion.
29. (c) Because alkyl carbanions are more basic than alkenyl carbanion
30. (c) Me4NOH is more ionic in comparison to NaOH because of less polarization as the size of Me4N+ is so large in comparison
to Na+
31. (d) Stability of conjugate base ∝ acidic character
32. (a) Out of 2 & 3 former is more acidic as Cl can not show resonance at meta position
33. (b) At meta position OMe group shows electron withdrawing effect.
34. (c) Because it contains two NH2 groups (basic groups) although urea & NH2CH2CO NH2 also contain two NH2 groups yet lone
pair of electron present on one NH2 group undergoes resonace with CO group.
35. (a) 4th is least basic because lone pair of electrons present on ‘N’ take part in resonance with CO group. Out of 1, 2 & 3, 3rd is
more basic because +I effect of CH3 increases electron density on ‘N’ 2nd in less basic than 1st because of the presence of
electron withdrawing NO2 group. Thus sequence of basic strength is 3 > 1 > 2 > 4
H
N N
36. (a) Because is more basic than

37. (b) 2nd is more basic then 3rd because groups present at ortho position create hindrance in resonance (steric inhibition to
resonance) thus, lone pair of electrons present on ‘N’ does not undergo resonance with benzene ring easily & available
for protonation.
38. (b) –ve charge undergoes resonance which is more favourable as electronegative element ‘O’ acquires negative charge.
O O(–)
|| (–) |
CH3 — C— CH 2 → CH3 —C = CH 2
39. (a) 1st is more basic than 2nd & 4th because in 1st case amine inversion takes place.
40. (c) H2S in stronger acid than H2O
166 Problems in Organic Chemistry

41. (c) CH3OH is stronger acid than Me3COH Me2 NH & BuH hence methoxide ion is least basic. BuH is least
acidic hence its conjugated base i.e will be strongest base. Since Me3COH is stronger acid than Me3NH hence
(–) (–)
(CH3 )3 CO will be stronger base than (CH3 ) 2 N

42. (c) Ac3C(–) is highly stabilized by resonance.

O O
(–)
CH3 — C — C — C — CH3

O == C — CH3
43. (c) Because lone pair of electron present on ‘N’ are localized & (c) is 2° amine which is more basic than 3° amine (a)
44. (d) 2nd is least basic because of delocalization of lone pair of electrons present on N with CO group. 4th & 3rd are more basic
than 1st as 1st is 3° amine
45. (b) ‘N’ does not contain lone pair of electron.
(–) O (–)
O O O
46. (c) is stabilized by extended resonance while is not

47. (d) Sulphonic acid is more acidic than carboxylic acid. 2nd is more acidic than 1st due to ortho effect. 4th is least acidic because
at meta position methyl group shows + I effect.
48. (d) BF3 is less acidic than BCl3 due to back bonding. Acetone is more acidic than acetaldehyde because
(–)
CH3CHO 
base
→ C H 2 CHO ←→ CH 2 = CH — O(–) less substituted
alkene & less stable
(–)
→ CH 2 COCH3 ←→ CH 2 = C — CH3
base
CH3COCH3  more substituted
| alkene & more stable
O(–)
49. (a) + I effect of (CH3)3 Si- is greater than Me3C–
50. (c) Lone pair of electrons present on nitrogen is localized.
51. (d) Anion formed after the removal of H+ ion is not stabilized by resonance (alkoxide ion PhCH2O(–)).
52. (a) N of CH3CN is sp hybridized hence more electronegative while oxygen of MeCHO & MeOMe are sp2 & sp3 hybridized
respectively. So oxygen of MeOMe is least electronegative.
Electronegativity ∝ 1 / basic character
53. (b) Conjugate base is not stabilized by resonance as bridge carbon atom can not bear double bond.

54. (a) Due to the presence of intra molecular H—bonding

CO
N
HO
55. (b) Same as previous question.
O (+)OH OH OH OH
(+) (+)
56. (d) H
(+)
O O O O O
(+)
highly stabilized by resonance
57. (d) Same as q.n.22
58. (c) Salicylate ion is stabilized by H– bonding as:-
(–)
COOH CO—O
OH (+) O—H intra mol—H
–H bonding
Acid & Base 167

59. (d) Acid strength ∝ Stability of conjugate base

60. (a) Acid strength ∝ Stability of conjugate base
61. (b) See question 49
62. (a) See question 58
63. (a) Resonance stabilization of sulphate ion is lesser than that of bi sulphate ion
64. (a) + R effect of Cl group is not prominent as 3p of Cl does not overlap effectively with 2p- of carbon thus due to – I effect of
Cl para chloro benzoic acid is more acidic.
65. (d) hydroxide ion is poor base than alkenyl anion

More Than One May Correct

1. (a), (b), (d) 2. (a), (d) 3. (a), (b)

4. (c) Second hydrogen is less acidic than 3rd hydrogen because 2nd hydrogen forms intramolecular hydrogen bond with
NO2 group
5. (b), (c) In (b) 1st is more basic than 2nd amine because in 1st amine SIR (Sterric inhibition to resonance) takes place in (c)
1st is more basic than 2nd amine because in 1st amine after protonation resonance takes place
(+ ) (+ )
H( + )
NH = C — NH 2 → NH 2
|
= C| — NH 2 ←→ NH 2 — C| = NH 2
NH2 NH2 NH2
6. (a), (b) 7. (a), (b) 8. (a), (c)
(–)
Ph (+) Ph
H + Antiaromatic
(+) Ph (+) Ph

(–)
(+)
H + Aromatic

(–)
(+)
H + Antiaromatic

(–)
Ph (+) Ph
H + Aromatic
(–) Ph (–) Ph
9. (a), (b), (c), (d)

LEVEL - II

1. (a) 2. (b) 2nd is less basic than 1st because 2nd amine undergoes inversion

i—Pr i—Pr
i—Pr N N i—Pr
i—Pr i—Pr

3. (b) Check the stability of the anion formed after the removal of H+

S
4. (a) sulphur can receive electrons of negative charge in its d orbital
(–)
S
168 Problems in Organic Chemistry

(–)
5. (b) (–)
aromatic ring

6. (b) Acid strength ∝ 1 / Bond energy of C-H bond

7. (c) Acid strength ∝ Stability of conjugate base
8. (b) CMe3 does not has hyper conjugation effect
9. (a) Pyrrole is less basic because its lone pair undergoes resonance & makes the ring aromatic. Thus its lone pair of electron is
least available for protonation.
H
H (+) H
N (+)
N
10. (a) H

antiaromatic & less stable nonaromatic & stable

11. (b) Lone pair of amino group is delocalized and COOH attached with benzene ring is least acidic due to -R effect
 6
Hydrocarbon
(Alkane, Alkene
& Alkyne)

Main Features

REACTION CHART FOR ALKANE

Preparation Properties
NaOH AlCl3 Chain isomers (at least 4 C atoms)
R—COONa or RCOOH CaO, ∆ HCl

Na/Ether Pyrolysis
RX Lower alkane & alkene

Zn/Ether Al2O3 or
RX Mo2O3 600°
Aromatic Compound

Zn/Hg +HCl
RCOR or RCHO X2
A hvν
RX
NH2 NH2
NaOH, ∆ L
K
A
N O2
Current
RCOONa E ∆
CO2+ H2O

H2O conc. HNO3

RMgX 400°C R—NO2

(+)
Zn + H conc. H2SO4
RX ∆ RSO3H

Red P
RCOR or RCHO or ROH HI
170 Problems in Organic Chemistry

REACTION CHART FOR ALKENE

Preparation Properties
(+)
Zn dust H2O/H Alcohol (M.A.)
RCHXCH2X heat X2
alc. KOH RCHXCH2X
RCH2CH2X heat HX
(+) RCHXCH3 (M.A.)
H /heat HBr
R—CH2CH2OH A Peroxide RCH2CH2Br (A.M.A.)
Partial Reduction L cold KMnO4
R—C CH RCH(OH)CH2OH [Syn addition]
K
R—CH—COOK E CH2
Electric CH2N2
N R—CH — CH2
R—CH—COOK Current
E hot KMnO4
Carboxylic acid
RCH2CHX2 Zn dust S O3/H2O
heat aldehyde & ketone
Zn, ∆
Hoffman elimination O3/H2O, ∆
Carboxylic acid
Pyrolysis
MeCH2OCOCH3 High P & T Polymers
Catalyst
B2H6
A. M. A Antimarkownikoff addition RCH2CH2OH (A.M. A.)
H2O2/OH(–)
M.A. Markownikoff addition H2/Ni
alkane
200-300°C
S2Cl2
CH2ClCH2SCH2CH2Cl Mustard gas
Hg(OAc)2
Alcohol (M.A.)
NaBH4
Br2/500°C
CH2 = CHCH2Br
or NBS
allylic substitution
per acid
hydrolysis
RCH(OH)CH2OH [Anti addition]

REACTION CHART FOR ALKYNES
Preparation Properties
Ag. heat H2/Ni
CHC 3(2-moles) alkane
H2(1mole)
alc. KOH alkene
CH2Br—CH2Br or NaNH2 Hg+2/H
(+)

H2O
Aldehyde or ketone (M. A.)
alc. KOH
CH3CHBr2 or NaNH2 A HOCl
CI2CHCHO (M. A.)
Zn dust L Fe/heat
Benzene [For acetylene]
CHBr=CHBr heat K Trimerisation
H2O Y Fe/heat
Cal. or Mag. Carbide Dimerisation
[For acetylene]
N
E Cold KMnO4
CH3X
CHO—CHO or vicinal di ketones
CH CNa S
Hot KMnO4
(i) CH3Mgl. Zn Carboxylic acid
CH3—C CH (ii) CH3X Ozonolysis
Carboxylic acid
X2
RCX2—CHX2
M. A Markownikoff addition AsCl3
CHCl=CHAsCl2 Lewsite gas
A. M. A Antimarkownikoff addition CO + H2O
R—CH = CHCO2H
Ni(CO)4
NH4OH + CuCl2
R—C CCu
Only for terminal alkynes
Tollen’s reagent
NaBH4 R—C CAg
Only for terminal alkynes
B2H6/H2O2
aldehyde or ketone (A.M.A.)
NaOH
2HX RCX CH (M.A.) 2 3
Hg(OAc)2
NaBH4 aldehyde or ketone (M.A.)
Hydrocarbon (Alkane, Alkene & Alkyne) 171

LEVEL - I

Multiple Choice Questions

(i) NBS / hν (i) Current

→ →
1. (ii) alkaline X (ii) aq KOH Y, Y is:-
KMnO 4 &heat 623K,200atm

(a) CH3CHO (b) CH2 = CH — CH2 — OH

OH
(c) HOOC —CH = CH — COOH (d) HOOC
HOOC
Ph  C  COOH NaOH Hg 2+
2. || ¾¾¾¾ ®[X] ¾¾¾¾ ®
CH3  C  COOH Current H3O(+)

Final product of this transformation is:-

O OH
(a) Ph (b) Ph (c)
Ph (d)
Ph
O OH
CH3 CH3
(i) NaNH H / Pd / BaSO MnO(-)
3. CH3CH 2 C º CH ¾¾¾¾¾
(ii) EtBr
2 ® ¾¾¾¾¾¾
2 4 ® ¾¾¾¾ 4 ®
ice cold

Final product of this reaction

(a) is optically active (b) contain three chiral ‘C’ atoms
(c) is optically inactive (d) is a racemic mixture
4. Which will have least rate of dehydrobromination?
Br
Br
(a) (b) (c) (d)
Br Br
CH3
Cl

Na/Et2O
5. (A) (A) & (B) respectively are:-
Br
(i) Mg/Et2O
(B)
(ii) H2O

Cl Cl

(a) , (b) ,
Br Br
Br Br

(c) , (d)
,
Cl Cl
Zn Zn
6. (A) →
Me2O (B) →
∆ But - 2 - ene (A) will be:-

(a) CH 2 — CH — CH — CH3 (b) CH3 — CH2Cl (c) CH3CHCl2 (d) CH3CCl3

| |
Cl Cl
172 Problems in Organic Chemistry

Me Me
7. C=C 
4 2OsO / H O
→ (A), (A) would be:-
H H
OH
OH
H OH Me Me H
(a) Me (b) H OH (c) (d) All of these
Me Me H Me
H
H OH OH

8. Which product is unexpected in the following reaction?

3  (i) O
CH3 — C = C — CH3 
(ii) H O, ∆
→ Product,
2
O OH
|| |
(a)
CH3 — C— C— CH3 (b) AcOH (c) CH3 — C—C = CH 2 (d) MeCHO
|| ||
O O
9. Pick out the reaction which is not stereospecific
(–) Hg(OAc)
KMnO4 / OH
(a) Cis – 2 – butene  2 → Product
→ Product (b) Trans – 2 – stilbene 
NaBH 4

3 (i) PhCO H Br
(c) Trans – stilbene  → Product 2 →
(+ ) (d) Cis – stilbene 
in CCl Product
(ii) H 2O / H 4

2 2CH N in presence of N
2 → Product
10. Cis – stilbene 

Ph Ph Ph H H H
(a) C — C (b) C—C (c) C—C (d) Both (a) & (b)
H H H Ph Ph Ph
CH2 CH2 CH 2

1 mol
11. → (A), (A) would be:–
H2

(a) (b) (c) (d)

dilute [X]
12. →
H 2SO4 (Major)

H2SO4 OH
OH
HSO4
(a) (b) (c) (d)
Hydrocarbon (Alkane, Alkene & Alkyne) 173

hν Peroxide
13. CH 4 + CI2 →(A)  → (B), (B) would be:–
Cyclo octa-1, 5-diene
1 : 3

(a) (b) (c) (d)

CCl3 CCl3 CCl3

CCl3
14. CH3 — CH = CH2 + HI (Solid) ——→ [X] will be:–
(a) CH3CH2CH2I (b) 2 – Iodo propane
(c) Both (a) & (b) (d) No product will form
15. How many structural isomeric alkenes are possible for the fomula C3H4Br2?
(a) 3 (b) 4 (c) 5 (d) 2
16. Buta – 1, 3 – diene can be converted in to But – 2 – ene by:–
(a) LiAlH4 / Ether (b) Na / Liquid NH3 (c) Na / C2H5OH (d) B2H6 / AgNO3
17. Which alkene will produce CH3COCOCH2CHO & OHC — CH2 — COCH2CH2CHO on ozonolysis followed by hydroly-
ses?

(a) (b) (c) (d)

18. Which among the following will have largest heat of hydrogenation?

(a) Trans –2–butene (b) Isobutene (c) (d)

19. Which among the following will undergo dehydrochlorination rapidly:–

(a) 2 – chloro pentane (b) 3 – chloro but – 2 – ene
(c) 1, 5 – dichloro pentane (d) 1 – chloro – 4 – Phenyl pentane

20.

These compounds are dehalogenated by Zn /∆ . The correct order of ease of these compounds for dehalogenation is:–
(a) 1 > 2 > 3 (b) 1~ 2 > 3 (c) 3 > 2 > 1 (d) 3 > 2 ~1
21. Which will give four products when subjected to mono chlorination. (only structural isomers)
(a) n –pentane (b) Iso – butane
(c) Methyl cyclo pentane (d) 1, 2 – Dimethyl cyclo propane
22. Identify [Y] in the following reaction.

CH3CH 2 MgCl + [Y] → 44800ml of alkane at S.T.P + other products


(unknow)
(a) Ethylene glycol (b) Succinic acid
(c) HO3S — CH2 — CH2 — SO3H (d) All of these

hν
23. Cl2C = C = O → A B, A & B are:–

CHCl2 CCl2 Cl
•• •• ••
(a)
C Cl2 , (b) C2Cl2, Cl (c) C Cl2 , (d) C Cl2 , Cl
CCl2
Cl
174 Problems in Organic Chemistry

24. Arrange the following hydrocarbons in decreasing order of their acid strength
Propyne, Ethyne, But – 2 – yne Ethene
(1) (2) (3) (4)
(a) 2 > 1 > 3 > 4 (b) 2 > 1 > 4 > 3 (c) 1 > 2 > 4 > 3 (d) 1 > 2 > 3 > 4
25. 1 mol of hydrocarbon ‘A’ gives 4 moles CO2 on combustion. It can decolourise Br2 water. A gives B when treated with Pd/C.
B can also decolourise Br2 water. A can react with Tollens reagent but B can not. A & B are:–
(a) , (b) , (c) , (d) ,

2 5 KOH in C H OH
26. ΦCH 2 Cl →[X] , [X] may be:–
(2 − Moles)

(a)
Φ — CH — CH 2 — Φ (b) ΦCH2 — CH2 Φ (c)
ΦCH = CH Φ (d) 2 moles of PhCH2OH
|
Cl
27. Which product will not form in the following reaction?
CH3 — C — CH 2 — CH = CH 2 → O3 ,H 2O
Product
|| ∆
CH 2

(a) HCOOH (b) CH3COCH2COOH (c) Me2CO (d) All are possible

∆ NaOH Pd O3
CHO
28. A + maleic acid → → →  →3 | (A) will be:–
CaO / ∆ ∆ H 2O + Zn CHO

CH 2
(a) || (b)
(c)
(d) Ethene
CH 2

29. Which product is not possible in the reaction given below?

H( + )
CH2 = CH — CH = CH2 → Product
D 2O

(a)
CH3 — CH — CH CH 2 (b) CH3 — CH = CH — CH2OD
OD

CH 2 D — CH — CH = CH 2
(c) (d) Both b & c
|
OD

30. Which among the following will liberate two moles of CO2 gas on oxidative ozonolysis followed by heating?

(a) (b) (c) (d)

Mg(1mol)
31. BrCHDC º C - CHD - Br ¾¾¾¾¾
® Product
Ether

Product of this reaction

(a) can release alkane with ROH (b) can show geometrical isomerism
(c) can show optical isomerism (d) can show geometrical as well as optical isomerism

H PO A MnO (–)
4 → NaOH
32. Butan – 1, 4 – di – ol 3 4→
 →  → Butane. (A) is:–
∆ ∆ ∆ CaO, ∆
•• •
(a)
C H 2 (b)
CH3 (c) C2H2 (d) C2H4
Hydrocarbon (Alkane, Alkene & Alkyne) 175

33. Which reaction is / are not possible among the following?

∆ ∆
+ CH2=CH2 ...................(1) + CH2 =CH2 ...................(2)

+ iso butene Heat ...................(3) ...................(3)

O ∆
+
O

(a) 1 & 3 (b) 1, 2 & 4 (c) only 1 (d) 1 & 4

(i) NaNH
2 → X  (i) NaNH
2 → Y  0°C
34. Acetylene 
(ii) (CH ) Br (ii) Ni –B (–)
→ Z , Z is:–
2 4 2 2 MnO4

CHOHCH2OH C=O OH
(a) (CH2)4 (b) (CH2)4 (c)
Br(CH 2 )4 CH — CH 2 OH (d)
CHOHCH2OH C O= |
OH
OH

35. Correct order of boiling points of n – hexane, n– pentyne, iso – pentyne, iso pentene, iso pentane is:–
(a) n – hexane > n – pentyne > iso pentyne > iso pentene > iso pentane
(b) n – pentyne > iso pentyne > iso pentene > n – hexane > iso pentane
(c) n – hexane > iso pentyne > n – pentyne > iso pentene > iso pentane
(d) n – pentyne > iso pentyne > n – hexane > iso pentene > iso pentane

CN

∆
36. + [X], X is:–
CH3
CH3 CH3
CN
CN CH3

(a) Me (b) Me

Me CH3 Me

CN
Me
(c) Me CH3 (d) Me

Me CH3

CN

37. Which of the following alkene is highly statble?

(a) (b) (c) (d) (a) & (b)

176 Problems in Organic Chemistry

38. Consider the following reactions:–

........................ (1) ...................... (2)

...................... (3) ...................... (4)

The reaction /s in which alkene will not form is /are:–

(a) 2 (b) 1 & 2
(c) 1, 2, 3, 4 (d) Alkene will produce in all cases
39. 2 moles of acetylene are passed through red hot iron tube followed by heating with acetylene gives X. The product obtained by
the ozonolysis of X will be:–

OHC CHO
(a) (b) CHO
OHC CHO |
CHO
(2 moles)

COH
(c) OHC — CH2 — CH2 — CHO (d) |
C OH
(3moles)

40. CH CH = CHD 

NBS
→ product of this reaction would be:–
3

(a) CH2Br CH = CHD (b) CH3 CH = CHBr (c) CH2 = CH CHDBr (d) both a & c

H
CH3 CH3ONa(in DMSO)
41.  → X, X is:–
Br heat

H
D
H
H H
CH3
CH3 CH3
(a) (b) (c) (d)
H CH3
H D D H
D H

CH3
H Br I(–)
42. Br H  → X, X is:–
in Me2CO

CH3

CH3 CH3
H I H I CH3 CH3 H CH3
(a) I H (b) H I (c) C C (d) C C
H H H H
CH3 CH3
Hydrocarbon (Alkane, Alkene & Alkyne) 177

COONa
Current
43. ¾¾¾¾
® [X] dim erisation
¾¾¾¾¾® [Y]
COOK
COONa
Current
COOK ¾¾¾¾ ® [Z]

O
Aromatic products are
(a) All (b) Y & Z (c) X & Y (d) Z

(i) Na / liq NH
3 → ortho-Xylene, A is:–
44. A 
(ii) A / ∆
(iii) Pd / ∆

(a) (b) CH2 = CH2

(c) CH3 — CH = CH — CH3 (d) CH2 = CH — CH = CH2

45. The reaction in which anti addition occurs is:–
Ni
(a) RCH = CHR + H2 → RCH2CH2R (b) RCH = CHR + F2 (in CCl4) 
→ RCHF — CHFR
Cold PBA
(c) RCH = CHR → RCHOH CHOHR (d) RCH = CHR 
(+ )
→ RCHOH CHOHR
KMnO4 H3O

CH3
H NAOEt
46. → product
Br
H
H3C
H
The product of this reaction is:–

CH3 CH3
H H
(a) (b) (c) (d)
CH3 H CH3 H
CH3 CH3

47. Which is ordered correctly for heat of hydrogenation:–

(a) > (b) >

(c) > (d)

>

48. By the ozonlysis of cis – jasmone propanal & 3, 4, 7 – trioxo heptanal are produced, the structure of cis jasmone will be:–
O
(a) O (b)

(c) (d)
178 Problems in Organic Chemistry

O
49. 
→

This conversion can be performed by:–

(a) PBA (b) Br2 / water & NaOH (c) air / Ag / ∆ (d) All of these
50. An alkene A on ozonolysis gives dicarbaldehyde. When A is subjected to hydrolysis followed by acid catalysed dehydration
compound B is produced which on ozonolysis gives diketone. A will be:–

(a) (b) (c) (d) CH = CH2

51. In which alcohol acid catalysed dehydration is not possible via E1 mechanism:–

(a)
(CF3 )2 — COH (b) CF2MeOH (c)
Φ2CMeOH (d)
CH3 — CH — OH
| |
CH3 CH3

52. In which case 1st compound has higher melting point than 2nd.
Cl Cl Cl Cl
Cl
(a) & (b) CH3COONa & NaCl (c) & (d) both (a) & (b)
Cl
Cl Cl
53. The compound with highest value of heat of combustion is:–

(a) (b) (c) (d)

(+ )
54. ΦCH (OH) C ≡ CH  H3O
→ CH =CHCHO
Which intermediate will not form during the course of above reaction?
+ (+ ) (+ )
ΦC H C ≡ CH (b)
(a) ΦCH= C= C H (c)
ΦCH(OH) C = CH 2 (d) All are correct
55. Identify the unexpected product in the following reaction:–

Me Br
2 →
 Product
in NaCl

Br
Cl Me
Me
(a) (b) Me (c) Br (d) All products are possible
H
H H
Br
Br Br

Cl2 →
56.  A, Product A is:–
in CCl 4

H Cl H Cl Cl
Cl
H Cl H Cl
(a) (b) (c) (d) None
Hydrocarbon (Alkane, Alkene & Alkyne) 179

H3C COOR
∆ heat strongly
57. + → 
→
COOR
The end product of this reaction is:–
Me CO2R Me CO2R
(a) (b)
CO2R CO2R

Me
CO2R Me CO2R
(c) (d) & CH 2 = CH 2
CO2R CO2R

CH Cl(excess)
3 2 4 → (i) C H / ∆
58. N 
→  E
AgOH/∆ (ii) Pd / ∆
CH3

The end product ‘E’ of the reaction is:–

(a) (b) (c) (d)

59. Which isomer of pentane will produce three mono chloro derivatives (including stereoisomers)

(a) (b) (c) (d) None

MeO(–)
60. 
in MeOH/∆
→ [X]
Br H

Br
MeO(–)

in MeOH/∆
→ [Y]
H
(X) & (Y) are
(a) Same alkyne (b) Cumulated diene & alkyne respectively
(c) Alkyne & cumulated diene respectively (d) Same cumulated diene
61. Wurtz reaction will be observed in:–

OH OH
CH ≡ C — CH 2 Cl (b)
(a) (c) CH3CHCl2 (d)
Cl
Br
62. A Hydrocarbon ‘A’ (C6H10) on reduction with limited quantity of H2 gives another hydrocarbon B. B on mono chlorination
gives two isomers. A is :–
CH3

(a) (b)
CH3 CH3 (c) (d) All of these
180 Problems in Organic Chemistry

63. Rank the following in decreasing order of rate of E2.

Et Et Et

Cl Cl Cl

(1) (2) Et (3)

(a) 1 > 2 > 3 (b) 2 > 3 > 1 (c) 3 > 1 > 2 (d) 2 > 1 > 3

NH2

Li / liq NH
3→ H 2 / Ni
64.  (B)  → (C)
CH OH 3
(A)
Correct order of basic strength of A, B & C is:–
(a) B > C > A (b) B > A > C (c) C > B > A (d) A > B > C
65. Styrene (Phenyl ethylene) + Chloro methoxy methane ——→ Product P. P would be:–
(a) Ph—CH(OCH3)CH2CH2Cl (b) PhCH(CH2Cl)CH2OCH3
(c) Ph–CH(CH2OCH3)CH2Cl (d) Ph–CHCl(CH2)2OCH3

Hg(OAc)2, THF
NaBH4
A
Me H
H OH
(–)
66. THF/BH3
X
H2O2, OH
C
Me H
Me H H OH
CH3COOH
B
Me
H

Out of A, B & C which product is wrong?

(a) A (b) B (c) C (d) All are wrong products

(CH2)3Br
67.
CH2Br

Sequence of reagents required for this conversion is:–

(a) [Link] 3, Pd/D (b) Na / ether, Pd / Heat
(c) Mg, ether, H3O+, Pd, heat (d) both (a) & (b)
68. Identify the product of following rearrangement
CH3

O H SO

2 4

CH3

(a)
O (b)
OH (c)
OH (d)
Hydrocarbon (Alkane, Alkene & Alkyne) 181

Passage– I

LiAlH
4 → B  dil H SO
2 4 → C → D H( + ) ,Heat
A 
Compound D on ozonolysis gives heptan – 2, 6 – dione

Answer the following questions from 69 to72

69. Compound D would be:–

(a) (b) (c) (d)

70. Compound C would be:–

OH OH OH
(a) (b) (c) (d)
OH
71. Compound B would be:–

(a) (b) (c) (d)

72. Compound A would be:–

(a) (b) (c) (d) Both (a) & (c)

Cl Cl
Cl

Passage–II

An alkyl halide (X) C4H8Br2 gives (A) when treated with alcoholic KOH. A gives B when fused with KOH at 197°C .When (A) &
(B) are treated with NaNH2 (C) & (D) are formed respectively. (D) On treatment with HCl gives (E). (E) On reaction with (C) can
produce (D). Compound (A) & (B) have same degree of unsaturation (A) can react with Tollen’s reagent but (B ) can not. However
both (A) & (B) forms same compound (F) on hydration.

Answer the questions from 73 to 79

73. Compound X is
(a) 2,3 – di bromo butane (b) 1,1 di bromo butane (c) 1, 4 di bromo butane (d) All of these
74. Compound A is:–
(a) Butyne (b) But–2–yne (c) Buta–1, 3–diene (d) But–2–ene
75. Compound B is
(a) Butyne (b) But–2–yne (c) Buta–1, 3–diene (d) But–2–ene
76. Compound C is:–
(a) Cis–but–2–ene (b) Trans–but–2–ene (c) Butylide ion (d) None of these
77. Compound D is:–
(a) Cis–but–2–ene (b) Trans–but–2–ene (c) Butylide ion (d) Butene
78. Compound E is:–
(a) 2 – chloro butane (b) 2, 2 di chloro butane (c) Both (a) & (b) (d) 1 – chloro butane
79. Compound F is:–
(a) Butanal (b) Butanol (c) Butanone (d) Butan–2–ol
182 Problems in Organic Chemistry

Passage – III

Consider the following three reactions.

H O( + )
3
Reaction - 1 → A

2 6B H
Reaction - 2  (–)
→ B
H 2O2 , OH

oxymercuration
Reaction - 3  → C

Answer the questions from 80 to 84

80. The reaction which occurs via rearrangement in carbocation.

(a) 1 and 3 (b) 1 only (c) 3 only (d) 2 only
81. Pick out the correct statement about A, B & C?
(a) A and B are same and different from C (b) A and C are same and different from B
(c) C and B are same and different from A (d) All are different
82. C is heated with sulphuric acid and product so obtained is shaken with dilute phosphoric acid to get another product D
(a) A and D are same (b) B and D are same (c) C and D are same (d) A B C D all are different
83. Select the correct statement.
(a) A B & C will produce same product on acid catalysed dehydration
(b) B & C will produce same product however A will produce different product on acid Catalysed dehydration
(c) A & C will produce same product however B will produce different product on acid catalysed dehydration
(d) B & A will produce same product however C will produce different product on acid catalysed dehydration
84. Which is regeoselective?
(a) Acid catalysed hydration of alkene (b) oxymercuration of alkene
(c) Hydroboration oxidation of alkene (d) All of these

Passage – IV

Consider the following process

NaNH
2→ A
A  B → C
If A is a chloro compound can decolorize boromine water & on vapourisation 1.49 g of A gives 448 ml vapour at S.T.P. then

Answer the question from 85 to 90

85. Molecular wt. of A is:–

(a) 37.25 (b) 74.5 (c) 98.5 (d) 76
86. Compound A is:–
(a) 2 – chloro propene (b) 1– chloro propene (c) 3–chloro propyne (d) 1– chloro propyne
87. Compound B is:–
(a) Cl CH2C ≡ CNa (b) Cl CH2CH = CH2 (c) Propyne (d) CH2 = C = CH2
88. Compound C is:–
(a) 1.4 di chloro hex – 2 – ene (b) 6–chloro hexa–1, 4–di–2–yne
(c) 6–chloro hexa–1, 4–di–yne (d) 1– chloro hex – 2–yne
Hydrocarbon (Alkane, Alkene & Alkyne) 183

89. A will not show:–

(a) Reaction with Tollen’s reagent (b) Wurtz reaction
(c) Ozonolysis (d) Hydration reaction
90. Which is correct about A & C?
(a) A can react with ammonical cuprous chloride but C can not
(b) C can react with ammonical cuprous chloride but A can not
(c) A can react with Tollen’s reagent while C can not
(d) Both A & C can react with Tollen’s reagent as well as ammonical cuprous chloride

Passage – V
Fe/∆ A A
(A) (B) Heat (C) Heat (D)
2 moles O3/Zn/ H2O

2 moles of glyoxal
Answer the questions from 91 to 93
91. Compound (A) is:–
(a) Propyne (b) Ethyne (c) Ethene (d) Propene
92. Compound (C) is:–

(a) (b) (c) (d)

93. Compound (D) is:–

(a) (b)

(c) (d)

94. Match the following

Characterstic of Compound Molecular wt
1. Optically active alkane with least molecular wt A 98
2. Alkene with least [Link] which can not exhibit geometrical isomerism
& becomes optically active after hydrogenation B 100
3. Alkene with least [Link] & optically active C 84
(a) 1 – B, 2 – A, 3 – C (b) 1 – A, 2 – B, 3 – C
(c) 1 – C, 2 – B, 3 – A (d) 1 – C, 2 – A, 3 – B
95. Which is / are not correctly matched?

A gives Diels alder with ethane

HOOC COOH
B gives meso tartaric acid with cold KMnO4

C gives trans but 2 – ene on reaction with Pd / C / H2

(a) A (b) B & C (c) A & C (d) All are mismatched
96. Consider the following compounds:–

(1) (2) (3)

Correct order of their heats of combustion will be
(a) 1 > 2 > 3 (b) 2 > 1 > 3 (c) 3 > 2 > 1 (d) 3 > 1 > 2
184 Problems in Organic Chemistry

OH
CH2 C CH2
(+ )
H
97. CH3 CH2 NH2 →(X) product
Heat

CHO

X(major product) would be:–

CH2 C CH CH C CH
(a)
CH3 NH2 (b)
CH3 CH2 NH2
CH2

CHO CHO

NH
CH2 C CH2 CH2 C CH3
(c)
CH3 CH NH2 (d) CH3 CH2

CHO CHO

CH3MgBr Br2 water

98. CH3 — CH —CH — CH3  → (A) CH3 — CH CH — CH3  → (B)
| | ∆ aq KOH
OH Br

CH3 — CH = CH — CH3  CH3 — CH = CH — CH3 

2 Cl water PAA
→ (C) → (D)
aq K 2CO3

Select the correct option.

(a) A = B = C ≠ D (b) A = B = D ≠ C (c) B = D ≠ A ≠ C (d) A ≠ B ≠ C ≠ D

99. Identify the product which is least likely to form:–

Br
2 → Product

in NaCl

Br
(a) Br (b)
Br
Br

(c) Br (d) All are possible

Cl
Hydrocarbon (Alkane, Alkene & Alkyne) 185

100. Identify the alkene which will not provide the following alcohol upon oxymercuration – demercuration.

OH

(a) (b) (c) (d) None of these

101. CH 2 CH 2 2H SO

4


Major product of this reaction would be:-

(a) (b) (c) (d)

AlCl —HCl
102. Assertion: – CH3 — CH2 — CH3 
3 → No product:–
25°C
Reason: – For product formation temperature should be 300°C.
(a) Assertion is true, Reason is true: Reason is a correct explanation for assertion
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
103. Assertion: – In pyrolysis of alkane lower alkenes and alkanes are formed
Reason: – Disproportionation of free radial takes place in this reaction
(a) Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is true, Reason is False
(d) Assertion is false, Reason is true
104. Assertion: – Methyl isonitrile can not be reduced to Dimethyl amine by Sabatier senderson reduction
Reason: – Sabatier senderson [Link] a kind of syn – molecular addition while above reduction requires nascent H
(a) Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
Na
105. Assertion :– (C6H5)3CCl + chlorobenzene (C6H5)4C → (C6H5)4C
Ether
The product (C6H5)4C does not form in this reaction
Reason: – In chloro benzene resonance occurs and C – Cl bond acquires double bond character which is difficult to break.
(a) Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion.
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
106. Assertion: – Methane has largest Calorific value among all hydrocarbon nevertheless it is not used in L.P.G.
Reason: – When it comes out from the cylinder it does not convert it self in to gas and remains in liquid state
(a) Assertion is true, Reason is true: Reason is a correct explanation for assertion
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
186 Problems in Organic Chemistry

107. Assertion: – Hyrdrogenation of compound (given below) by Pd / H2 (1mol) gives an optically inactive compound.
Me H

H
H
Reason: – It is a kind of anti addition
(a) Assertion is true, Reason is true: Reason is a correct explanation for assertion
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
108. Assertion: – n – Butane on mono chlorination gives three products which on distillation gives 2 products,
Reason: – On distillation association takes place
(a) Assertion is true, Reason is true: Reason is a correct explanation for assertion
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
109. Assertion: – Addition of bromine on fumaric acid yield enantiomers.
Reason: – Bromination of alkene is an example of electrophilic addition.
(a) Assertion is True, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is True, Reason is False
(d) Assertion is False, Reason is true
OH
(+ )
H /∆
110. Assertion : – → A (Product)

(A) does not give addition with Cl2 / CCl4 (in dark)
Reason: – A contains phenyl group which does not show addition with Cl2 in dark.
(a) Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true

Answer Key

1. (a) 2. (d) 3. (b) 4. (b) 5. (d) 6. (c) 7. (d) 8. (d) 9. (d) 10. (d)
11. (b) 12. (c) 13. (d) 14. (d) 15. (a) 16. (b) 17. (a) 18. (c) 19. (b) 20. (c)
21. (c) 22. (d) 23. (d) 24. (b) 25. (b) 26. (c) 27. (b) 28. (c) 29. (c) 30. (a)
31. (b) 32. (d) 33. (c) 34. (d) 35. (b) 36. (d) 37. (c) 38. (d) 39. (a) 40. (d)
41. (a) 42. (d) 43. (a) 44. (d) 45. (d) 46. (b) 47. (d) 48. (c) 49. (d) 50. (c)
51. (a) 52. (a) 53. (c) 54. (c) 55. (c) 56. (a) 57. (d) 58. (b) 59. (c) 60. (a)
61. (c) 62. (b) 63. (c) 64. (c) 65. (d) 66. (a) 67. (b) 68. (c) 69. (a) 70. (c)
71. (a) 72. (d) 73. (b) 74. (a) 75. (b) 76. (c) 77. (b) 78. (a) 79. (c) 80. (b)
81. (d) 82. (a) 83. (a) 84. (c) 85. (b) 86. (c) 87. (a) 88. (c) 89. (b) 90. (d)
91. (b) 92. (d) 93. (a) 94. (a) 95. (c) 96. (a) 97. (a) 98. (b) 99. (b) 100. (c)
101. (a) 102. (c) 103. (a) 104. (a) 105. (b) 106. (a) 107. (c) 108. (c) 109. (d) 110. (a)
Hydrocarbon (Alkane, Alkene & Alkyne) 187

Multiple Choice Questions (More Than One May Connect)

1. Which among the following compound can produce two moles of ethane when 1 mol of the compound reacts with excess of
EtMgBr?
OH
(a) CH3CH = CH2 (b) (c) (d) Buta -1,3-diene
OH
2. Maleic acid on neutralization by NaOH followed by electrolysis gives ‘X’, ‘X’ on reaction with:-
(a) Cl2/H2O can produce dichloro ethanal (b) MnO4(–) / 0°C can produce glyoxal
(c) H2O/H(+) can produce ethanol (d) O3 followed by hydrolysis can produce acetic acid
3. Which statement is true about addition reactions?
(a) Unsymmetrical alkenes on reaction with HCl give markownikoff product in presence of sun light
(b) C2H5SH shows KHARASCH effect in presence of active peroxide
(c) When addition reaction occurs via the formation of free radicals, antimarkownikoff product is obtained as major product
(d) C C bonds on addition reaction with I2 can not produce vicinal di iodide
4. Which among the following reagent is not suitable for the following transformation?
H
|
→ CH3 — C = C— CH3
CH3 — C ≡ C — CH3 
|
H
(a) Na/liquid NH3 (b) P - 2 Catalyst (c) Pd / C (d) H2 / Ni

OH
CH3 H
R
5. → R may not be:-
H CH3
OH

HCOOOH / H3O(+)
(a) (b) OsO4 / H2O2 (c) Cold MnO4(–) (d)
CH3COOH / H3O(+)

6. Buta1, 3 diene + HBr 

→A + B
(1 mol)

A & B are primary and secondary allyl bromides. Select the true statement/s:-
(a) A is thermodynamically controlled product (b) B is thermodynamically controlled product
(c) A is kinetically controlled product (d) B is kinetically controlled product
7. In which case 1st compound has higher value of heat of hydrogenation than 2nd compound.

(a) (b) , CH3CH = CH—CH3

(c) , (d) None of these

8. In which of the following case optically active compound is produced.

CH3 CH3
| |
(b) CH3 — CH — CH = CH 2 
Hg(OAc)
(a) CH CH 2 + HBr 
C2 H5 —C H —= → Product 2 → Product
NaBH 4
CH3 CH3
| |
(c) CH3 — CH — CH =
Cl2 dil H 2SO4
CH 2  → Product (d) C2 H5 —CH — CH = CH 2  → Product
in CCl4
188 Problems in Organic Chemistry

9. Which of the following can show Diels - Alder reaction?

(a) (b)
(c) (d)
O
10. In which case meso isomer is produced.
4 KMnO
(a) in CCl4
+ Cl2  → Product (b) → Product
0°C
H
KMnO4 | Cl
(c) → Product (d) Ph — C = C— Ph  2 →
Product
0°C in CCl 4
|
H

Answer Key

1. (b), (c) 2. (a), (b) 3. (a), (b), (c), (d) 4. (b), (c), (d) 5. (b), (c)

6. (a), (d) 7. (d) 8. (b), (c) 9. (a), (b), (c), (d) 10. (c), (d)

LEVEL - II

Multiple Choice Questions

1. Predict the product of the following reaction.

dil H SO
2 4→
 Product

OH

(a) (b) (c) (d)

HO
OH

OH
2. Which intermediate will not involve in the following reaction.
H( + ) Me Ph
= CH 2 →
2mec
|
PH

Me Me
CH2
Ph
(+ ) | (+ ) (+ ) Me2 C C–Me
(a)
Me2CPh (b)
Me2 C — C —CH 2 (c)
MeC — CH 2 — CMe (d)
+ Ph
| | | |
Ph Me Ph Ph

3.
(1) (2) (3) (4)
Arrange the following compounds in decreasing order of their calorific values.
(a) 1 > 2 > 3 > 4 (b) 4 > 3 > 2 > 1 (c) 4 > 2 > 1 > 3 (d) 4 > 2 > 3 > 1
Hydrocarbon (Alkane, Alkene & Alkyne) 189

4. Oxygen is free radical scavenger or eater because.

(a) It is paramagnetic in nature
(b) Bond dissociation energy of O = O bond is small
(c) Free radicals form stable paramagnetic compounds with oxygen
(d) It decreases velocity of free radicals
5. Which is not correct about wurtz reaction?
(a) Rate of reaction is maximum in 1° alkylhalide & least in 3° alkyl halide because in 3°
alkyl halide chances of disproportionation is more
(b) Dry ether is used so that Na does not react with it
(c) By the addition of O2 reaction does not stop but slows down
(d) All are correct
6. Select the reaction with wrong product
Br Na Br Na
(a) 
→ (b) 
→
dry Ether dry Ether
Br Br

Na
(c) 
→ (CH2)n (d) All are correct
Br Br dry Ether

Na
7. ICHDC2CHDI → X, [X] is:-
THF
(a) An alkyne and can react with tollen’s reagent
(b) Optically active
(c) alkyne and can not react with tollen’s reagent
(d) Not optically active but can show geometrical isomerism
8. Select the reaction with wrong produced
COOK
Current
(a) →
COOK

Current
(b) (CH3)3CCOONa  → (CH3 )3 CC(CH3 )3
100%

Current
(c) KOOC COOK →

KOOC
(d) Current
→
COOK

Current
9. CH3 — C H — CH 2 — COONa  → [X], [X] would be:-
|
Cl
(a) CH3 — CHClCH2CH2CHClCH3 (b)
CH3 — C H — CH 2 Cl
|
CH3 —CH—CH 2Cl
Cl
|
CH3 — C = CH 2
(c) (d) CH3 — CH — CH3
|
Cl
190 Problems in Organic Chemistry

10. How many structural alkenes on hydrogenation can give following alkane?

(a) 11 (b) 19 (c) 10 (d) 12

11. Which will not decolourise bromine water?

(a) (b)
(c) (d) CF2 = CF2

Matrix Match Questions

Each question contains statement given in two columns which have to be matched. Statement (A, B, C , D) in column I have to be
matched with statements (p, q, r, s) in column II. The answers to these questions have to be appropriately bubbled as illustrated in
the following examples. If the correct match are A – p, A – s, B – r, B – r, B – q, C – q, D – S, then the correctly bubbled 4 x 4 matrix
should be as follows.
A p q r s
B p q r s
C p q r s
D p q r s

12. Compounds Hybridization on Carbon

(A) Mg2C3 (p) sp
(B) CaC2 (q) sp2
(C) CH2CO (r) sp3
(D) CH2 = CH— CH = NH (s) sp3d
13. Column - I Column - II
HOCl
(A) CH2 = CClCHO 
→ Product (p) optically active

3 H O( + )
(B) CH2 = CH — SiH3 → Product (q) Nucleophilic addition reaction
2 → Product Br
(C) CH2 = CH — CH2 — CH3  (r) Electrophilic addition
hν

3 → CCl Br
(D) CH2 = CH — CH3 
Peroxide Product (s) Markownikoff addition

14. List - I (Oxidation) List - II (Product)

3 2 O ,H O
(A) CH3COCH2CH = CHCH3 →
heat (p) CH3CHO

hot KMnO4
(B) (CH3)2C = CHCH3  → (q) CH3COOH

3 2 → O ,Zn,H O
(C) (CH3)2C= CHCH3  (r) CH3COCH3
heat

3 O ,Zn
(D) (CH3)2C = CHCH2COCH3  →
H O, heat (s) CH3COCH2CHO
2
Hydrocarbon (Alkane, Alkene & Alkyne) 191

15. Column - I Column - II

(A) (p) Na / liq NH3 / Paraftin, heat

(B) (q) Solid KOH

(C) (r) Na / liqNH3 / CH3OH

(D) (s) Na / liq NH3

Answer Key

1. (a) 2. (b) 3. (c) 4. (a) 5. (d) 6. (d) 7. (d) 8. (b) 9. (b) 10. (a)

11. (d)

Answers Matrix Match

1 2. (A) - p, r (B) - p (C) - p, q (D) - q 13. (A) - q, (B) - p, r, s (C) - p, (D) - p

14. (A) - q, r (B) - q, r (C) - r, p (D) - s, r 15. (A) - p, q, (B) - r, (C) - s, (D) - r

SOLUTION
Br Br
(–)
NBS KMnO4 COO(–) Kolbey’s
1. (a) electrolysis
CH2=CH—Br
COO
Tautomerism KOH
CH2CHO CH2=CH—OH 623 K, 200 atm

2. (a) [X] = Ph - C º C - CH3 and last product is Ph - CO - CH 2 CH3

Et-Br
3. (c) CH3CH 2C º CH + NaNH 2 ® CH3CH 2C º CNa ¾¾¾¾
® CH3CH 2C º C - Et

(meso isomer)
4. (b) On dehydrobromination it will produce cyclobutadiene which is less stable because it is antiaromatic.
Cl
Na / Et O
2 →
5. (d) 
Br Wurtz reaction

RBr is more reactive than RCl towards Grignard’s reagent formation

192 Problems in Organic Chemistry

Cl Cl
Cl
Mg H 2O
→  →
Et 2O –MgBrOH
Br MgBr
Wurtz reaction Wurtz reaction
Cl Cl
Zn | | Zn / ∆
6. (c) 2CH3CHCl2 → CH3 — CH — CH — CH3  → CH3CH = CH — CH3
Ether

7. (d) OsO4 gives syn hydroxylation. cis alkene on syn addition produces meso isomer; options (a) (b) & (c) all are meso isomers
hence all are correct.
O O
O3
8. (d) CH3—C C—CH3 CH3—C—C—CH3
H2O2
2CH3COOH
H2O
O O
Tautomerism
CH3—C—C=CH2
9. (d) Halogenations of alkene is anti addition. cis alkene on anti addition forms mixture of enantiomers i.e. racemization takes
place hence (d) is not stereo specific.
Note: - See question no. 5. topic electrophilic and free radical addition in chapter - 4
10. (d) In the atmosphere of N2 triplet carbene is formed. (see question no. 10 topic reaction intermediate in chapter -04 )
11. (b) Less substituted alkene is less stable and hence undergoes reduction easily. Benzene ring does not undergo reduction
because after reduction it loses its Aromaticity
(+)

(+) (+)
H ring opening H2O
12. (c) OH

13. (d) •
RCOOOCOR 
→ 2RCO O

• • • •
RCO O 
→ R + CO 2
R + CHCl3 
→ RH + C Cl3

CCl3 CCl3
• RH
+ C Cl3 • –R•
•

CCl3
or

CCl3

14. (d) HI solid does not undergo addition reaction with alkene.

Br Br Br
Br
15. (b) Br Br Br Br

(+)
(–) Na NH3 •
16. (b)
CH2 = CH—CH= CH2
Na
CH2 = CH —CH—CH2 –NaNH2 CH2=CH—CH—CH3
(+)
(–)Na
NH3 Na •
CH3—CH =CH—CH3 –NaNH2 CH2—CH=CH—CH3 CH2—CH=CH—CH3
Hydrocarbon (Alkane, Alkene & Alkyne) 193

O ozonolysis
17. (a) O
O  → CH3COCOCH2CHO + OHCCH2COCH2CH2CHO
O
O
O

18. (c) Heat of hydrogenation ∝ Number of double bonds

19. (b) Because on dehydrohalogenation conjugated alkene will form which is stable due to resonance.

Cl
20. (c) 3rd will undergo dehalogenation rapidly because after dehalogenation resonance stabilized alkene i.e. CH2 = CH — CH =
CH — CH = CH2 forms. 1st will undergo dehalogenation slowly because it forms cyclo propane which is less stable due
to ring strain. 2nd also gives alkene on dehalogenation but resonance stabilization of CH2 = CH — CH = CH2 is less in
comparison to the alkene given by 3rd compound. Thus, rate of dehalogation is 3 > 2 > 1
1
2

21. (c) 3

22. (d) 1mol of gas at S.T.P. occupies 22400 ml volume.

Moles of gas liberated = 44800 / 22400 = 2
Hence Y should have two active hydrogen’s glycol, succinic acid & ethylene disulphonic acid, all contain two active
hydrogen’s Hence (d) is correct.

hν ••
23. (d) CCl2 CO → CO + C Cl2
Di chloro carbene
Dichloro carbene undergoes addition reaction with alkene.

+ CCl2 Cl
Cl
24. (b) Acid strength ∝ 1 / stability of conjugated base
(A) (B)

25. (b) Pd/C

Reallens
t
gen

Partial reduction
To

CAg

(A) decolourises Br2 water which indicates presence of multiple bond. (A) reacts with Pd / C which indicates presence of
triple bond & since (A) reacts with Tollen’s reagent hence triple bond must be present at the terminal.
(–)
alc
26. (c) Ph — CH 2 Cl → Φ — CH — Cl
KOH Stabilised by resonance
Cl
(–)
alc KOH
ΦCHCl + Φ —CH2—Cl Φ—CH=CH—Φ
(–)

Cl Φ—CH2—CH—Φ Elemination
dicarboxylation
27. (b) CH3COCH 2COOH 
→ CH3COCH3 + CO2
Heat

CH—COOH COOH
28. (c) + Diels Alder NaOH
CaO/∆
CH—COOH COOH

CHO O3/H2O/Zn Pd/∆

3 –2H2
CHO
194 Problems in Organic Chemistry

29. (c) See question no. 27 topic - Electrophilic & free radical addition, Chaptor -04.
30. (a)
31. (d)

This product is cumulated diene and can show geometrical isomerism

H( + )
32. (d) CH 2 — (CH 2 )2 — CH 2 → CH 2
∆
= CH — CH = CH 2
| |
OH OH
(–)
D. Alder MnO4 COOH Decarboxylation
+ Reaction –2CO2
COOH

33. (c) Trans alkenes do not undergo Diels Alder reaction.
34. (d) (–)(+)
C Na
NaNH2 (–)(+) Br(CH ) Br NaNH2
CH CH CH CNa –NaBr2 4 CH C(CH2)4Br C—(CH2)4—Br

OH CH C
0°C Ni2–B
(CH2)4 (CH2)4 – NaBr
MnO4
CH C
OH
Y X
35. (b) boiling point ∝ van-der-waal’s forces of attrations ∝ surface area

36. (d)

37. (c) Bredt’s rule: - A bridged bicyclo compound can not have a double bond at bridged carbon untill ring contains at least 8
carbon atoms.
38. (d) In 1st reaction base is sterically hindered thus alkene will produce via elimination reaction
In 2nd case alkene will produce due to iodination - deiodination. In 3rd & 4th cases dehydrobromination & debromination
take place respectively.
39. (a) CH = CH CH = CH
dimerisation dimerisation
CH = CH CH = CH

OHC CHO O3/Zn/H2O

OHC CHO
• •
40. (d) CH3CH=CHD NBS
CH2CH=CHD CH2=CHCHD

BrCH2CH=CHD HBr HBr CH2=CHCHDBr

Br
H H H
41. (a) E2 Me
Me anti elimination
H
H
D
Hydrocarbon (Alkane, Alkene & Alkyne) 195

42. (d) Trans alkene will produce via anti elimination reaction.
43. (d)

2 NaNH
44. (d) CH2 = CH — CH = CH2(A) → CH3 — CH = CH — CH3 (But-2-ene)
For this conversion See question no. 16. This but-2-ene undergoes Diels alder with A to produce o-xylene i .e. o-methyl
toluene o - xylene

Pd/∆ o-xylene
+ –2H2

(A)
O OH
(+)
H3O
45. (d) R—CH= CH—R PBA
R—CH—CH—R R—CH—CH—R
OH
46. (b) Same as question no. 41
47. (d) Cyclo butane has more strain in its ring hence it is more reactive than cyclo hexane.
(a) is incorrect because cis form will have greater heat of hydrogenation than trans form.
(b) is incorrect because former alkene is more stable than later because of resonance.
(c) is incorrect because benzene is more stable due to Aromaticity.
48. (c) 49. (d)

O3
50. (c)
H2O/Zn/∆ CHO
CHO
(+) (+)
(+) (+)
H H2O OH H /∆
(+)

O
Ozonolysis

O
51. (a) Because (a) gives less stable carbocation
(+)

(F3C)2 C—CH3 (unstable due to strong -I effect of CF3)
52. (a) Melting point ∝ closed packing
Out of cis and trans forms later has higher mp than former because molecules of trans isomer are closely packed.
⇒ Trans - but-2-ene

⇒ Cis-but-2-ene
(poor packing)
Thus, option (b) & (d) are wrong. The para substituted benzene has linear geometry & such molecules are closely packed
in their solids state.
Cl Cl Cl

⇒ Closely packed

Cl Cl Cl
Cl Cl Cl

⇒ Poor packing
Cl Cl Cl
Hence (a) is correct
196 Problems in Organic Chemistry

53. (c) As it has high molecular weight

(+) (+) (+)
54. (c) PhCHOHC C H
–H2O PhCHC CH PhCH=C=CH
H2O
PhCH=CH CHO PhCH=C=CH
OH
55. (c) Bromination of alkene is a kind of anti addition. So bromine atom should acquire axial position (c) option is incorrect
because in it Br atoms acquires axial & equitoral positions i.e. syn addition
Ha
1
Note:- H
e
2 H
e

Ha

At 1, 2 position
(a, a) → Trans, (a, e) → Cis,
(e, e) → Trans (e, a) → Cis

56. (a) Although in chlorination of alkene anti addition takes place yet in the given reaction syn addition occurs due to steric
hindrance.
(–) H
Cl Cl Cl
(+) Cl
H
Cl
2→
 steric hindrance 
→

57. (d) If product of Diels -Alder reaction is heated ‘C’ chain forming bridge in bicyclo compound comes out from compound in
the form of alkene.
CO2 R
Me COOR Me CO2R
(+) Me
+ H + CH2 = CH 2
COOR CO2 R
CO2 R
58. (b) Hoffman elimination followed by Diels - Alder reaction See question no. 14, topic Elimination reaction, chapter - 04.
59. (d)
60. (b)
61. (c) Wurtz reaction is carried out by Na which is very sensitive towards active ‘H’. Except (c) rest all compounds contain
active hydrogen (acidic ‘H’) so (a), (b) & (d) will remove hydrogen on reaction with Na metal.
ONa
OH
+ Na 1/2 H2 +
Br
Br

(–) ( + )
CH ≡ C — CH 2 Cl + Na 
→ ClCH 2 — C ≡ C Na + 1/ 2H 2

OH ONa
+ Na + 1/2 H2

Cl Cl
Hydrocarbon (Alkane, Alkene & Alkyne) 197

62. (b) CH3 CH3 CH3 CH3

Cl
H2/Ni Cl2/hv
+
CH3 (A) CH3 CH3 CH3 CH3 CH3 CH3 CH2Cl

63. (d)
NH2 NH2 NH2
64. (c) Birch reduction H2/Ni

(A) (B) (C)

(c) is highly basic because lone pair of electron present on ‘N’ are localized and does not take part in resonance. (A) & (C)
both have delocalized lone pair of electron but (A) is less basic than (B) because of more delocation of electron due to the
presence of three double bonds.
65. (d) CH3OCH2Cl can dissociate by two ways
(–) ( + )
First way:- CH OCH Cl 
→ CH3 O + C H 2 Cl
3 2
(+) •• (+)
CH—Cl CH2 = Cl
••

2 ••
(–) (+ )
Second way:- CH — OCH Cl ←→ Cl + CH O CH
3 2 3 2

•• ( + ) (+ )
CH3 — O CH2 ←→ CH3 — O
••
= CH 2
(B)

Resonance stabilization of (B) is greater than (A) because 3p of Cl will not overlap with 2p of carbon effectively

(+ ) (+ )
Cl(–)
= CH 2 + CH 2 OMe 
PhCH → Ph C HCH 2 CH 2 OMe → PhChClCH 2 CH 2 OMe
(Styrene)

66. (a) (A) is wrong because in oxymercuration, Markownikoff rule is followed.

67. (b) Wurtz reaction followed by dehydrogenation.
68. (d)

Passage - I

(69 to 72)

(+)
(+) (+)
LAH H
Cl
A B
H2 O
LAH

O O (+)
(+)
ozonolysis H
A OH
∆
Cl D C
198 Problems in Organic Chemistry

Passage - II

(73 to 73.9)

Since A is terminal alkyne hence it can react with Tollen’s reagent.

Passage - III

(80 to 84)
Reaction 1st is hydration reaction. Here carbocation is formed as an intermediate which may show rearrangement as
follows:-
(+) HO
2
(+)

(+) OH
Reaction 2nd is hydroboration. Here antimarkownikoff addition of water takes place.
hydroboration

OH
rd
Reaction 3 is oxymercuration where markownikoff addition (without rearrangement) takes place.
oxymercuration

OH

Passage - IV

(85 to 90)
48 ml vapours has wt. = 1.49 g
22400ml vapours will have wt. = 1.49 x 22400 / 448 = 74.5 g
Thus, molecular wt of A = 74.5g
A os a chloro compound hence it should have Cl atom (at. wt. = 35.5 g)
Therefore remaining carbon chain will have wt. = 74.5 - 75.5 = 39 g
Thus, compound A should be 3- chloro propyne.
Cl NaNH (+) Cl A
2 Na (–)
A B C
Cl
Hydrocarbon (Alkane, Alkene & Alkyne) 199

A can not show Wurtz reaction because it contains acidic hydrogen which can liberate hydrogen gas with sodium metal.
A & C both can exhibit substitution reaction with Tollen’s reagent as well as with ammonical cuprous chloride as both are
terminal alkynes.

Passage - V

(91 to 93)
C2 H 2(2 moles) ∆ A B
Fe ∆ ∆
A
B C D
ozonolysis

2 moles of CHO–CHO
CH 2CH3
|
94. (a) Optically active alkane with least mol. wt. (100) CH3 — C H — CH 2 CH 2 CH3

CH 2
||
CH3CH 2 — C — CH 2 CH 2 CH3
Least molecular wt. (98) can not show geometrical
Isomerism but becomes optically active after reduction
CH3
|
alkene with least [Link](84). & optically active CH 2 = CH 2 — C H — CH 2 CH3
95. (c) In compound A both double bonds are anti to each other hence it can’t show Diels- Alder reaction
Pd/C/H H H
2
syn addition
(C)
96. (a) Heat of combustion ∝ 1 / stability of compound
97. (a) When acid reacts with OH group, A is formed which undergoes hydride shift to produce more stable carbocation B
(+) (+)
CH2CCH 2 CH2CHCH
CH3 NH2 CH3 NH2
CH2 CH2

A B

CHO CHO
Thus due to the formation of B, product (a) is obtained.
(–)
OH O
98. (b) CH3 MgBr CH3MgBr
A
Br Br O
OH
Br2 water aq KOH B
O
Br
OH OH
Cl2 water K2CO3 C
Cl OH

PAA D
O
200 Problems in Organic Chemistry

Br
(+)
99. (b) Br2

(–) (–)
Br Cl
Br Cl

Br Br

100. (c)
Oxymercuration
OH
101. (b)
102. (c) Propane can not exhibit isomerisation reaction because for chain isomerism molecule should have at least 4-carbon
atoms.
isomerisation

isomerisation no isomer will form
103. (a) Disproportionation of free radial produces alkane & alkene
LIAlH4 → CH NHCH
104. (a) CH3 NC  3 3
This reduction is not possible by H2 / Ni because in this reduction unsymmetrical addition of hydrogen occurs on triple
bond for which nascent hydrogen is required.
105. (b) The product Ph4C is sterically hindered thus, difficult to form.
106. (a) When CH4 comes out from the cylinder it does not convert it self in to gas and remains in liquid state.
107. (c) It is a kind of syn addition & after reduction moslecule becomes achiral because of absence of chiral carbon atom.

108. (c) H H
Me Me
Pd/H 2
H H
H
H H H
mono chlorination +

A B
Cl Cl
optically active
distillation

B d & l isomers

H COOH

COOH Br2 Br H Br
COOH
109. (d) HOOC anti addition
HOOC OR
H
H Br
Br
COOH

110. (a) A is ethyl benzene & benzene ring does not undergo addition reaction easily.

MORE THAN ONE MAY CORRECT

1. (b, c) hydrogen of [= C - H ] is not acidic in nature

2. (a, b) X is acetylene 3. (a, b, c, d)
4. (b, c, d) only sodamide provides anti addition
5. (b, c, d) only performic acid [HCOOH] provides anti hydroxylation
Hydrocarbon (Alkane, Alkene & Alkyne) 201

6. (a, d)

+ HBr +
Br Br
[A] [B]

7. (d) Heat of hydrogenation  ∝ 1 / Stability

8. (b, c) In (a) 3 - bromo - 3 - methyl pentane is formed while in (d) 3 - methyl pentan - 3 - ol is formed & both are optically
inactive as they do not contain chiral carbon atoms.
9. (a, b, c, d 10. c, d

LEVEL - II

(+)
(+) (+) H2 O
HO
H
1. (a)

(+) (+)
2. (b) MeC =CH 2 H
MeC — CH3
Ph (A) Ph

Me Me
Me—C—CH2 Me—C—CH2
+ C—Me C—Me
(+) (+)
Ph Ph
Me
Me Ph
(+) Me
–H

3. (c) Calorific value  ∝ heat of combustion  ∝ Molwt  ∝ Van-der-waal forces of attractions

4. (a) Free radicals and O2 both are paramagnetic in nature because of presence of unpaired electron thus they combine to form
diamagnetic species.
5. (d) See wurtz reaction.
6. (d) In wurtz reaction if more than 6 C atoms are present & halogens are present at terminals then polymer is formed other wise
cylo alkanes are formed.

Na
dry Ether (CH2)n

Br Br

• •
7. (d) I—CHD—C C—CHD—I Na
CHD—C C—CHD
H H
C=C = C
D D

Current +
8. (b) (CH3)3CCOONa  → disproportionation
202 Problems in Organic Chemistry

9. (b) If α –carbon possesses halogen then rearrangement in free radical takes place.
•
CH3—CH—CH2COONa Current CH3—CHCH2 COO

Cl Cl
•
dimerisation CH3CHCH2Cl CH3—CH—CH 2
Cl

10. (a) Double bond can be placed at numbered positions

9
10
2 3 5 11
6
1 4 7 8

11. (d) Due to strong -I effect of fluorine CF2 = CF2 becomes electron deficient thus, can not undergo electrophilic addition
reaction with bromine water.
 7
Alkyl Halide &
Grignard’s Reagents

Main Features
ALKYL HALIDE & GRIGNARD’S REAGENT

Preparation Properties

LAH alkene [For 3° halides]

LAH
alkane [For 1°& 2°halides]
X2 Ag2O
alkene or alkyne Ether
inCCl4
HX Moist Ag2O
alkene or alkyne Alcohol
Red P + X2 A AgCN
ROH RNC
L
PCl5/PCl3/SOCl2 K NaCN
ROH RCN [For 1°& 2°halides]
Y
Anh ZnCl2 + HCl L Na / Pb
Et4Pb
ROH
(2°, 3° alcohols) H alc KOH
Alkene
RX + NaI Acetone A
L aq KOH
(for alkyl iodides) Alcohol
RX + AgF I
D Mg / Ether
(for alkyl fluoride) RMgX
RCOOAg + Br2 heat E
Na / Ether alkane
(for alkyl bromides)
alkene NBS Zn / Ether
alkane
( For allylic halides)
(+)
X2 Zn / H
alkane alkane
hv
AgNO2
RNO2
NaNO2
RONO [For 1°& 2°halides]
RONa
ROR [For 1°& 2°halides]
204 Problems in Organic Chemistry

Multiple Choice Questions

1. Consider the following reaction:–

(1) CH3Br (0.1M) + OH (–)(0.2M) → Br (–) + CH3OH
(2) Ph3CBr (0.1M) + CH3OH (0.2M)  → Ph3COMe + Br (–)
(3) CH3CH2Br (0.1M) + OH (–)(0.4M) 
→ CH3CH2OH + Br (–)
(4) Ph3 CBr (0.1M) + OH (0.3M) 
(–) → Ph3COH + Br (–)
If R1, R2, R3 and R4 are the rates of the reactions 1, 2, 3 & 4 respectively then:–
(a) R2 = R1 (b) R3 = R4 (c) R2 = R4 (d) R1 ≠ R2 ≠ R3 ≠ R4
(i) Mg/Ether
Ag/∆ Fe/∆ (B)
2. CH3Cl 
(+ )
→ (A) → (B) → (C) 
∆
→ (E)
(ii) HCHO/H3O
(iii) NaOCl 2 mole

The end product E is:–

(a) (b) (c) (d)

3. Here four reactions are given below for the preparation of alkyl bromide.
HBr HBr
1. CH2 = CH2 → EtBr 2. CH3 — CH = CH2 → i — PrBr
in CCl4 in CCl4

HBr HBr
3. CH3CH = CHCH3 → MeCHBrEt 4. (CH3)2C = CH2 
in CCl
→ Me2CBrCH3
in CCl 4

If these reactions have rates R1, R2, R3 & R4 respectively then correct order of rates of reaction will be:–
(a) R1 < R3 < R2 < R4 (b) R1 < R2 < R3 = R4 (c) R1 < R2 < R4 < R3 (d) R1 < R4 = R3 < R2
4. In the following reaction the most probable product is :-
Cl

H CH3
NaOH
 →
CH3 H in DMSO

n-Pr
OH CH3 n-Pr OH

H CH3 H OH H CH3 H CH3

(a) (b) (c) (d)
CH3 H CH3 H CH3 H n-Pr CH3

n-Pr n-Pr OH H

5. Which reaction is the example of entertainment technique?

CH Cl 3 → RMgX CH F
RX 3 → RMgX
+ Mg  RX + Mg 
(a)
(X = F,Br,I) Ether (b)
(X = Cl,Br,I) Ether

CH3Br 3 CH I
RX + Mg  → RMgX RX + Mg → RMgX
(c)
(X = Cl,F,I) Ether (d)
(X = F,Cl,Br) Ether

6. Correct order of boiling points of the following halides would be:–

CH3Cl, CH2Cl2, CHCl3, CCl4
(1) (2) (3) (4)
(a) 1 > 2 > 3 > 4 (b) 3 > 2 > 1 > 4 (c) 4 > 3 > 2 > 1 (d) 2 > 3 > 1 > 4
Alkyl Halide & Grignard’s Reagents 205

OH
lucas
7. 
→ Product is:–
reagent

CH3
Cl
Cl

(a) (b) (c) (d)

CH3 CH3

8. Which is thermodynamically controlled product for the following reaction?

O
(+)
H3O
+ CH3MgCl Product is :-
(Major)

OH O
CH3
(a) (b) (c) (d) All are possible
CH3
9. Which among the following will have highest boiling point:–
(a) CH3CH2F (b) CH3CHF2 (c) CH3CF3 (d) CF3CF3
10. Correct sequence of dipole moment is:–
(a) CH3F > CH3Cl > CH3Br > CH3I (b) CH3I > CH3Br > CH3Cl > CH3F
(c) CH3F > CH3I > CH3Br > CH3Cl (d) CH3Cl > CH3F > CH3Br > CH3I

∆
11. CH3COOAg + Br2 → AgBr + CO2 + CH3Br
This reaction is called Borodine Hunsdecker reaction. If in this reaction Br2 is replaced by I2 then the product will be:–
(a) CH3COI (b) CH3I (c) CH3COOCH3 (d) No reaction
(–)
12. CH3F OH CH3OH ...................(A)
(i) NaI
(–) CH3OH ...................(B)
(ii) OH

If R1 & R2 are the rates of reaction A & B respectively then

(a) R1 = R2 (b) R1 > R2 (c) R1 < R2 (d) R1 R2
13. Product and mechanism of the following reaction would be :-
H

Br
Finkelstein reaction

→

t-Bu
H
H
H H I
I
(a) H , SN1 (b) I , SN1 (c) H, SN2 (d) , SN2

I t-Bu
t-Bu H H
t-Bu H t-Bu
206 Problems in Organic Chemistry

14. Which among the following will not show haloform test:–
(a) CH3COCH2COOC2H5 (b) (CH3)3COH (c) 2 – Butanol (d) Both (a) & (b)
15. List the following alkyl halide in decreasing order of SN2 reactivity:–
Me Me Me
Cl
(1) Cl (2) Pr (3) Pr (4)
Cl I
D

(5) Cl

(a) 3 > 2 > 4 > 5 > 1 (b) 2 >3 > 5 > 1 > 4 (c) 5 > 3 > 2 > 1 > 4 (d) 5 > 3 > 2 > 4 > 1
16. Which among the following will not produce ethane when treated with ethyl magnesium halide:–
(a) CH3SH (b) Propyne (c) C2H5CH = CH2 (d) C2H5OH
17. Identify the product of following reaction.

Br
+ AgNO3 + HO2 Product
Br
OH
O O
Br
(a) (b) OH (c) (d)
NO3 OH

Ac
18. NaOCl A + B electric current C
(ppt)

The compound (C) is:–

(a) (b) (c) & (d) both a(major) & c(minor)

19. tert – butyl chloride on treatment with lithium aluminium hydride will provide:–
(a) Iso butane (b) Iso butene
(c) 2, 2, 3, 3 – Tetramethyl butane (d) no reaction takes place

CH3
| Hoffman
20. CH3 — CH —CH — CH3  → (B) HBr
(C)
E limination
| HBr/hv
Cl
(A) (D)

Correct order of rate of SN1 for A, C & D will be:–

(a) A > C > D (b) C > D > A (c) A = C > D (d) C > A > D
CO2
21. RMgX (B) (A)
(C) + other product
H3O(+)
(A)
C2H5OH
(E) + other products
Which statement is correct;–
(a) (C) is an ester (b) (E) & (B) are same compounds
(c) (C) & (E) are same compounds (d) (E) is ether
Alkyl Halide & Grignard’s Reagents 207

22. In Finkelstein reaction when Acetone is replaced by water then

(a) Reaction occurs in forward direction via SN1 pathway
(b) Reaction occurs in forward direction via SN2 pathway
(c) Reaction occurs in backward direction because sodium halide formed in right hand side is soluble in water & can not ppt
out
(d) Reaction occurs in backward direction because sodium halide formed in right hand side is insoluble in water

(i) NBS (A)/ ∆

23. (A)  →(B)  → (B) will be
(ii) alc KOH

(a) (b) (c) (d)

HBr(I − mole)
24. → A Product A will be :
Br
Br Br
(a) (b) (c) (d) both a & c

Br

25. 
Mg
→[X] →[Y]
PhOH
THF

The product [Y] of this reaction is

O OH
(a) (b) (c) (d)

26. Which of the following reaction is least likely to occur?

Moist [Link]
(a) EtBr 
→ EtOH (b) EtBr → EtNO2
Ag 2O

Silver nitrite Pb/ Na

(c) EtBr 
→ EtNO2 (d) EtBr 
→ Et4Pb

(i) B H /OH(–)
2 6
27. Me 
(ii)SOCl
→ A, Product A is :–
2

H Me Me Me
(a) H (b) (c)
H (d) Cl
Me Cl H Cl
Cl Cl H
208 Problems in Organic Chemistry

28. What will be the product of given reaction?

CH3

H OH
HBr
Br H 
→ Product

CH3

CH3 CH3 CH3 CH3

H Br H OH H Br H OH
(a) (b) (c) (d)
H Br H Br Br H Br H

CH3 CH3 CH3 CH3

29. 0.037 gm of alcohol was added to CH3MgBr and the gas evolved has volume equal to 11.2 cm3 at S.T.P. This alcohol gives
haloform test ,thus, alcohol would be:–
(a) CH3CH2OH (b)
CH3 — CH — CH3 (c) iso butyl alcohol (d) n — Propyl alcohol
|
OH

30. Which reaction results in the formation of a pair of enantiomers?

Br
H
H O CH OH
(a) 
2
→ (b) 
3
→
H Br

NaCN
(c) (d) 
in DMF
→
Br NaOH

in DMSO
→ H Br
CH3
CH3

31. ROH + HBr 

→ H2O + RBr
In which case first alcohol is more reactive towards HBr than second one:-

OH CH2OH and
(a) and OH (b)
OH
OH O

(c)
Me 2 C – CH 2 CH3 and CH3 – CH – Et (d) and
| |
OH OH OH

32. Consider the following compounds

NH2CHBrCH3 AcNHCHBrCH3 NH2CHBrNH2 NH2CHBrOH
(1) (2) (3) (4)
If K1, K2, K3 & K4 are the rate constant for the solvolysis of 1, 2, 3 & 4 respectively then
(a) K1 > K2 > K4 > K3 (b) K4 > K3 > K1 > K2 (c) K3 > K4 > K1 > K2 (d) K3 > K4 > K2 > K1
33. CHCl3 can be converted in to methyl chloride by using:–
(a) Zn / H2O (b) Zn / HCl (aq) (c) Zn / HCl (alc) (d) H2 / Ni
Alkyl Halide & Grignard’s Reagents 209

34. Match the following:–

Reaction End Product

current
(A) CHCl3 + KOH(Excess)  →
→ X  (1) Mesitylene

(i) alcKOH(ii) NaNH

2
(B) Ethylene di chloride → (2) Hydrogen gas
(iii) Butadiene/∆

Na/liq NH3
(C) Bromo benzene  → (3) Cyclohexene
EtOH

(i)alc KOH & NaNH

2→
(D) 1,1–di chloro propane  (4) 1–Bromo cyclo hexa – 1, 4 – diene
(ii) Fe/heat

(a) A 
→ 2; B 
→ 4 ;C 
→ 1; D 
→ 3 (b) A 
→ 2; B 
→ 3; C 
→ 1; D 
→1

(c) A 
→ 2 ; B 
→ ;3 C 
→ 4; D 
→ 1 (d) A 
→ 1 ;B 
→ 2 ; C 
→ 1; D 
→ 4

35. Consider the following E1/SN1 reaction

Br

CH3 H O + C H OH
H 
2 2 5
→ Products
∆

CH3

Which product is not possible?

OH CH3

OH
(a)
H
CH3 (b) H (c) H (d) H

CH3 CH3 CH3 CH3

36. Identify the reaction in which benzene does not form as an end product:–

(i)Ag/ ∆ 2(i)H O
(a) Acetone →(A) ↓ → (b) CaC2 →
(–)
OI (ii)Fe/ ∆ (ii)Fe/ ∆

(i) ∆
(c) 1, 3 – Butadiene + ethene → (d) In all cases benzene is formed.
(ii)Pd/ ∆

NOCl Moist Ag O
2 →(P),
37.  → 
(+ ) Product P is :–
CH2NH2 H /∆

(a) (b) (c) (d)

CH—O
2 2
210 Problems in Organic Chemistry

COCH3
(–)
OI
38. → ppt + (A), (A) will be :–

COCH2I
(–) (–)
(–) COO COO COCH3
COO
(a) (b) (c) (d)
ICH2OC
(–)
COO COCH2 OI COCH2 OI

H (A)
NaC
39. CH3—CH—CH2Cl AgC (A) & (B) would be :
N
(Major)
CH3 (B)

CH3 CH3
(a)
CH3 —C—CN & CH3 —C—NC (b)
CH3 —CH—CH2CN & CH3—CH—CH2NC
CH3 CH3 CH3 CH3

CH3 CH3 CH3

(c) CH3 —C—CN & CH3—CH—CH2NC (d)
CH3—CH—CH2CN & CH3—C—NC
CH3 CH3 CH3

40. When Ethylene dichloride is treated with alc KOH followed by NaNH2 (A) is formed. (A) on treatment with tertiary butyl
chloride forms (B) which on reduction with H2 / Ni gives (C), (C) will be:–

(a) (b) (c) (d)

H
H H
Br CH3ONa
41.  → (A) + (B) , (A) & (B) are :–
in CH3OH Major Minor

H H D H Ph H Ph H
(a) C =C & C =C (b) C =C & C =C
Ph H Ph H H H H
D
Ph H Ph H Ph H Ph H
(c) C = C & C =C (d) C =C & C =C
H D H H H H H D
42. An alkyl Magnesium bromide on reaction with ethyl alcohol forms a hydrocarbon ‘X’ which occupies 0.2872 lit per gm at
S.T.P. Grignard reagent will be :–
(a) C2H5MgBr (b) PhMgBr (c) CH2 = CHCH2MgBr (d) (CH3)2CHMgBr
43. Which graph is incorrect?

(a)
Rate For Ph3CBr + OH(–) 
→ Product

Base
Alkyl Halide & Grignard’s Reagents 211

(–)
(b)
Rate For (CH3)2CHBr + O H (in acetone) 
→ Product

Base

(c)
∆G For PhCHDBr + EtOH 
→ Product

Reaction progress

(d)
∆G For Me2(Et) COTs + NH3 
→ Product

Reaction progress

44. Correct order of rates of dehydrohalogenation of following halides is:–

Cl
(I) (II) CH3 — CH2 — CH2Cl (III) CH3 — CH — CH 2 — CH3 (IV) CH2 = CH — CH2 — CH2Cl
|
Cl
(a) III > II > IV > I (b) I > IV > III > II (c) III > IV > II > I (d) I > III > IV > II
45. At 25°C chloro benzene can be converted in to acetophenone by treating it with:–
(a) KCN & CH3MgBr / H3O(+) (b) CH3COCl / Na / Ether
(c) Mg / Ether & CH3CHO / H3O , mild oxidation
(+)
(d) All of these
Hint–2° alcohols on mild oxidation produce ketone
46. 1 – Bromo – 4 – chloro butane is treated with Mg (1 mol) / Ether to give (A).Which among the following represents A ?

MgBr MgCl
(a) Cyclo butane (b) Cl (c) Br (d)

47. 2 – Bromo – 3 – chloro butane on Finkelstein reaction will provide.

(a) 2 – chloro – 3 iodo – butane (b) 1, 2 – Di methyl ethylene
(c) Di methyl acetylene (d) 2, 3 – Di iodo butane
48. ∆H1 , ∆H 2 , ∆H3 & ∆H 4 are the enthalpies of dissociation of C–X bond of the following four halides:–

Cl

→ (+) 
→ (+)
Cl ∆H1 ∆H2

Br

→ (+) 
→ (+)
I ∆H3 ∆H4
212 Problems in Organic Chemistry

Which order is correct?

(a) ∆H1 > ∆H3 > ∆H2> ∆H4 (b) ∆H1 > ∆H2 > ∆H3> ∆H4
(c) ∆H2 > ∆H1 > ∆H3> ∆H4 (d) ∆H2 > ∆H3 > ∆H4> ∆H1

Q.49 A + HCl 
→ 1-chloro-1,2-dimethyl cyclo hexane (A) can be :-

OH

(a) (b) (c) (d) All of these

Passage – I

Compound (A) is optically active and gives (B) on treatment with (KOH + H2O) compound (B) is also optically active. (B) On
heating with phosphoric acid gives (C) which does not show geometrical isomerism. When (C) is subjected to ozonolysis (O3 / Zn,H2O, heat)
(D) & (E) are obtained. (D) & (E) on treatment with OI(–) give precipitates. These precipitates are removed by filtration and filtrates
of (D) and (E) are then treated with soda lime, (D) gives (F) while (E) gives methane .Compound (F) can be obtained by heating
cyclo hexane with Al2O3 | Cr2O3.

Now answer the questions from 50 to 53.

50. (F) would be:–

(a) (b) (c) (d)

51. (A) and (B) are:–

Φ 2 CHCCl(CH3 )2 , Φ C(Me) — CHMe2 (b)

(a) ΦC2 H5 — CClCHMe2 ,
|
OH

(c) Φ — CH — CClMe2 , Φ — C(OH)CHMe2 (d)

Φ3C — CClMe2 , Φ 2 C — CHMe2
| | |
Me Me OH

52.
(C) would be: –
Ph Ph Ph Me
Φ 2 C = CMe2 ,
(a) (b) Ph (CH3) C = CMe2 (c) C = C (d) C =C
Ph Me Et Ph

53. (D) and (E) are:–

(a) PhCOPh, CH3COCH3 (b) Ph2CO, CH3COPh (c) PhCOCH3, CH3CHO (d) PhCOCH3, CH3COCH3

Passage – II

Consider the following halides:–

CH3 — CHCl — CHCl — CH3 CH 2 — CH 2 —CH 2 — CH 2 CH3 — CH2 — CH2CHCl2
| |
Cl Cl
(1) (2) (3)
These halides can undergo substitution and elimination reaction now
Alkyl Halide & Grignard’s Reagents 213

Answer the question from 54 to 59

54. On treatment with Zn/Ether cyclo alkane will be formed by:–

(a) 1 & 2 (b) 3 (c) 2 (d) 1

55. (3) can be converted in to (1) by:–

(a) Zn / Ether, Zn /∆, O3 / Zn, H2O, PCl5 (b) aq KOH, LiAlH4 / Ether , H3PO4 /∆ ,Cl2 in CCl4
(c) alc KOH(Excess), heat , Pd / C , Cl2 / in CCl4 (d) All of these

56. Which two alkyl halides on treatment with KOH (alc) will give same product:–
(a) 1 & 2 (b) 2 & 3 (c) 3 & 1 (d) None

57. Which alkyl halide will form higher alkene on treatment with Zn / THF / heat :–
(a) 1 (b) 2 (c) 3 (d) 1 & 2

58. The alkyl halide which on treatment with alc KOH followed by CH3MgBr can liberate CH4
(a) 1 (b) 2 (c) 3 (d) None

59. Halide which can give two different bromides when treated with alcoholic KOH followed by HBr
(1 mol) is / are –
(a) 1 (b) 3 (c) 1 & 2 (d) 2

Passage – III

ICl Finkelstein reaction H3O (+)

B C D P, Cl2, heat
(i) Mg in ether HCl
A G
(ii) H2 O
E
E

Answer the questions from 60 to 63

60. Compound B would be:–

I Cl Cl Cl
(a) (b) (c) I (d)
Cl I I Cl

61. Compound C would be:–

I Cl
(a) (b) (c) (d)
I I I

62. Compound E would be:–

OH
(a) I (b) (c) (d) Cl
OH

63. Which is wrong statement about the given passage?

(a) E & F are identical (b) F & G are position isomers
(c) E & G are identical (d) A & C are identical
214 Problems in Organic Chemistry

Passage–IV

Propyne NBS (A) 1 mol (B) PhMgBr (C) Mg (D)

HBr Ether
Succinic Anhydride CO2
(F) (Diels Alder)
(E) (+)
H3O

Answer the Questions from 64 to 67

64. Compound (B) is:–

Br
Br
Br Br
(a)
Br Br (b) Br (c) (d) Br

65. Compound (C) is:–

Br Br Br

Ph
(a)
Br (b) Ph (c) Ph (d) Ph
66. Compound (E) is:–
COOH
HOOC
Ph
CO2H

(a) COOH (b) (c) (d)

67. Compound (F) is:–
O
OH O
OH
(a) COOH (b) HOOC OH
OH
CH—
2
CH—
2

O HOOC O

OH OH

(c)
PhCH2 OH (d) PhCH2

COOH OH

Current Acetone/KOH
68. (A) + Brine → (B) → Hypnotic medicine, (A) will be:–
(a) CH2 = CH2 (b) CH3COONa (c) C2H5OH (d) CH3CH2COONa
69. Identify the reaction in which alkyl chloride is not form as product:–
(i) AgOH SOCl
→
CH3COOH  .......... (1) 2→
CH3CHOHCH3  .......... (2)
(ii) X 2 / ∆
FeCl P + Cl / ∆
3→
Φ — H + Cl2  ......... (3) 2 →
Φ —CH 2 OH  .......... (4)
(a) 1 (b) 4 (c) 1 & 3 (d) 1, 2 & 3
Alkyl Halide & Grignard’s Reagents 215

70. The reaction in which carbene does not form as an intermediate:–

(a) (Me3CO)3 Al
+ CHCl3  → CCl2

(b) Reimer Tieman reaction

(c) Carbyl amine reaction
(d) CHCl3 + CH3COCH3 + KOH (alcoholic) 
→ Chloretone
71. Assertion – Tert butyl chloride on rection with AgCN produces tert Bu –CN
Reason – this reaction occurs via SN1 pathway
Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(a)
Assertion is true Reason is true: Reason is not a correct explanation for assertion
(b)
Assertion is true, Reason is False
(c)
Assertion is false, Reason is true
(d)
72. Assertion – Tert butyl chloride on rection with NaCN produces tert Bu –CN
Reason – Cyanide ion is a strong base & favours elimination reaction
Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(a)
Assertion is true Reason is true: Reason is not a correct explanation for assertion
(b)
Assertion is true, Reason is False
(c)
Assertion is false, Reason is true
(d)
73. Assertion – Alkyl halides on reaction with moist Ag2O forms alcohols & not ethers
Reason – Ag2O undergoes hydrolysis to form silver hydroxide
Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(a)
Assertion is true Reason is true: Reason is not a correct explanation for assertion
(b)
Assertion is true, Reason is False
(c)
Assertion is false, Reason is true
(d)
74. Assertion – R– butan–2–ol on reaction with SOCl2 becomes R– 2–chloro butane
Reason – This reaction occurs via SN1 pathway
Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(a)
Assertion is true Reason is true: Reason is not a correct explanation for assertion
(b)
Assertion is true, Reason is False
(c)
Assertion is false, Reason is true
(d)
75. Assertion: – Boiling point of CH3F is lesser than CH3I
Reason: – Boiling point of alkyl halides is proportional to polarisability and I has good polarizing power in comparision to that
of F.
Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(a)
Assertion is true Reason is true: Reason is not a correct explanation for assertion
(b)
Assertion is true, Reason is False
(c)
Assertion is false, Reason is true
(d)
76. Assertion: – Dipole moment of CH3Cl is greater than CH3–F
Reason: – F has less electron affinity than Cl
Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(a)
Assertion is true Reason is true: Reason is not a correct explanation for assertion
(b)
Assertion is true, Reason is False
(c)
Assertion is false, Reason is true
(d)
216 Problems in Organic Chemistry

Mg
77. Assertion: – PhCH2Br → Ether PhCH2MgBr
This reaction is not possible.
Reason: – PhCH2Br Undergoes nucleophilic substitution reaction with PhCH2MgBr to produce PhCH2CH2Ph
(a) Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
78. Assertion: – In proteic solvent order of nucleophilicity of halide ions is I(–) > Br(–) > Cl(–) > F(–)
Reason: – In polar proteic medium ion–dipole attraction takes places. F(–) is strong base hence due to more ion dipole attraction
it is arrested by solvent molecules.
(a) Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is true, Reason is False
(d) Assertion is false, Reason is true
79. Assertion: – The relation nucleophilicity proportional to basicity holds in protic solvent but not valid in aprotic solvent like
DMSO
Reason: – If the solvent is protic it forms H – bond with nucleophile but aprotic solvent like DMSO con not form H – bond
with nucleophile.
(a) Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is true, Reason is False
(d) Assertion is false, Reason is true
80. Assertion: – In SN1 reaction 100% racemisation occurs.
Reason: – Here initmate ion pair is formed
(a) Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is true, Reason is False
(d) Assertion is false, Reason is true
81. Assertion: – DMF is aprotic solvent
Reason: – C –H bond is not polar
(a) Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is true, Reason is False
(d) Assertion is false, Reason is true

Answer Key

1. (c) 2. (b) 3. (a) 4. (b) 5. (d) 6. (c) 7. (b) 8. (b) 9. (a) 10. (d)
11. (c) 12. (c) 13. (d) 14. (d) 15. (d) 16. (c) 17. (c) 18. (d) 19. (b) 20. (d)
21. (c) 22. (c) 23. (d) 24. (b) 25. (b) 26. (b) 27. (c) 28. (c) 29. (c) 30. (b)
31. (c) 32. (c) 33. (b) 34. (c) 35. (d) 36. (d) 37. (d) 38. (b) 39. (d) 40. (b)
41. (b) 42. (b) 43. (d) 44. (b) 45. (c) 46. (a) 47. (b) 48. (a) 49. (d) 50. (c)
51. (c) 52. (b) 53. (d) 54. (c) 55. (c) 56. (a) 57. (c) 58. (c) 59. (c) 60. (b)
61. (d) 62. (d) 63. (b) 64. (b) 65. (d) 66. (c) 67. (a) 68. (c) 69. (c) 70. (d)
71. (d) 72. (d) 73. (a) 74. (c) 75. (a) 76. (c) 77. (a) 78. (a) 79. (d) 80. (d)
81. (a)
Alkyl Halide & Grignard’s Reagents 217

Multiple Choice Questions More Than One May Correct

1. Which of the following reactions will produce an aromatic product?

O
Fe
(a) + HBr (b) Pr opyne 
→
heat
(1 mol)

Cl
VO
(c) alc KOH (d) 2 5
n − hep tan e →
773K,10 − 20atm

O
2. The method which can not be used for the preparation of propane is:–
(a) Wurtz reaction (b) Frank – land reaction (c) Finkelstein reaction (d) Corey – House reaction

3. The substrate which can produce a di iodide on finkelstein reaction is:–

Cl
Cl
Cl Cl
(a) (b) (c) (d)
I
I
I I
4. Which of the following can exhibit Wurtz Reaction?

O OH
(a) (b) (c) Cl — CH2 — NH2 (d) CH3 CH — C
|
Cl CH = CH 2
Cl
5. Which statement is true about the products A & B present in the following reaction scheme?

I(–) 2CH = CH—CH Cl

2 →(B)

→ ZnCl2
Acetone (A)
Br
I
(a) A can decolourise Br2 water (b) B decolourise Br2 water
(c) (B) on hydrolysis produces optically active product. (d) (A) is a di iodide

••
6. CHCl3 + (X) 
→ C Cl2
(X) would be:–
(a) alc NaOH (b) Me3CO(–) (c) Pyrrole (d) All of these

7. (X) + CaOCl2 + H2O 

→ Sweet smelling liquid
‘X’ would be:–
O
O
Ac
(a) (b) (c) (d) CH2ClCOCH3
218 Problems in Organic Chemistry

8. Which of the following reagent is not required during the following transformation?
Cl

I
COOH

(a) NaOH / CaO, ∆ (b) NaI / acetone (c) H2 / Ni / heat (d) KOH + H2O
9. Permanent dipole moment is shown by:–
O

Cl Cl Cl Cl
(a) (b) Br (c) Cl (d)
10. Pick out the correct equations

(a) CH3OCH3 + CH3Br + Zn 

→ C2 H 6

CH3CH — CH3 + C2 H5OH + KOH 

(b) → propene
|
Br

AlCl + HCl
(c) CH3CH 2 CH 2 CH 2 Br + Zn + H ( + )  3
→(A) 
→

(d) CHCl3 + KOH + CH3COCH3 + C2H5OH 

→ (CH3)2COHCCl3

11. X + NaOH + I2 
→ Yellow ppt + sodium adipate, X would be:
(a) octan – 2, 7 – dione (b) 7 – oxo heptanoic acid (c) HOOC (d) `
O O O

Answer Key

1. (a), (b, (c), (d) 2. (a), (b), (c) 3. (b), (c) 4. (a), (d) 5. (b), (c)

6. (a), (b) 7. (a), (b), (c), (d) 8. (d) 9. (a), (b), (d) 10. (a), (b), (c), (d)

11. (a)

LEVEL – II
(+ ) (+ )
→ R ( + ) + H 2 O .....................(1)
1. R — OH 2  → N 2 + R (+ )
R N 2  ...................(2)

If these reactions have rates R1 & R2 then:–

(a) R1 = R2 (b) R1 > R2 (c) R2 > R1 (d) R1  R2
2. Select the compound which can give substitution reaction with aq NaOH at room temperature
(a) PhCl (b) MeI (c) Me3CI (d) Me3CBr
3. The rate of nucleophilic substitution of an alkyl halide RX in 75% EtOH & 25% acetone is given below:–
Rate = 1.67 × 10–6 [RX] [Base] + 0.05 × 10–6 [RX]
Calculate fraction of SN2 when [Base] = 1M
(a) 90% (b) 3% (c) 10% (d) 97%
Alkyl Halide & Grignard’s Reagents 219

4. The reaction in which 4 products can form (including stereo isomers) is:–

ICl HCl HCl DCl

(a)  → (b) → (c)
 CD3 
→ (d) 
→
5. Match the following
Reaction Product % yield
Br
+ HBr 1. (p) 2

Br
2. (q) 52

3. Br (r) 46
1. (a) 1 → r, ; 2 → p; 3 → q (b) 1 → q; 2 → p; 3 → r (c) 1 → p; 2 → q; 3 → r (d) 1 → r; 2 → q; 3 → p

Comprehension

Consider the following reactions

Cl Cl
al KOH al KOH
(a) → A (b) → B
Me Me

Cl Cl
Me Me
alc KOH (excess) alc KOH (excess)
(c) 
→ C (d) 
→ D
Me Me

Cl Cl
Cl

Me
alc KOH (excess)
(e) 
→ E
Me

Cl

Answer the following questions:–

6. Which product is least stable?
7. Which product has least value of heat of hydrogenation?

LiNH2
8. CH3OH [X]

Out of A, B, C, D & E which is similar to that of [X]

9. Arrange A, B, C, D & E in increasing order of their stabilities

Matrix Match Questions

Each question contains statement given in two columns which have to be matched. Statement (A, B, C , D) in column I have to be
matched with statements (p, q, r, s) in column II. The answer to these questions has to be appropriately bubbled as illustrated in the
following examples. If the correct match are A – p, A – s, B – r, B – r, B – q, C – q, D – S, then the correctly bubbled 4 x 4 matrix
should be as follows.
220 Problems in Organic Chemistry

A p q r s
B p q r s
C p q r s
D p q r s

10. Reaction Mechanism / Stereochemistry

Ph
(A) C—Br + NH3 Product (p) SN1
Et
Me
Br
(B) in CCl4 Product
2
(q) SN2

(C) CH3CH2Br + KOH (aq) Product (r) Racemisation

Cl
2 →
(D)  Product (s) Meso product
in CCl 4

11. List – I (Reaction) List – II (Production)

OH Br
HBr
(A) 
→ (p)

Br
HBr
(B)  → (q)
hν

Br
HBr
(C)  → (r)
peroxide

NBS Br
(D) → (s)
hν

12. Reaction Reagent

(A) → iso butene

(CH3 )3 CBr  (p) LiAlH4

(B) → Pr— H
i — pr — I  (q) KOH + C2H5OH

(C) → i — Pr— I
i — Pr— Br  (r) I(–) / Acetone

(D) iso pentene → Iso pentane (s) Wilkinson Catalyst

13. Alkane Number of monochloro derivatives

produced (only structural isomers)

(A) (p) 1

(B) (q) 2
Alkyl Halide & Grignard’s Reagents 221

(C) (r) 3

(D) (s) 6

14. Alkane Number of mono chloro

derivatives Produced
(A) (p) 2
(B) (q) 3

(C) (r) 4
(D) (s) 5

Answer Key

1. (c) 2. (b), (c), (d) 3. (d) 4. (a) 5. (d)

6. Product A 7. Products a & b 8. None 9. A < B < E < C = D

Answers matrix match

10. (A) – p, r (B) – r (C) – q (D) – s 11. (A) – p, q, s (B) – p (C) – q (D) – r
12. (A) – p, q, (B) – p (C) – r (D) – s 13. (A) – r, (B) – s, (C) – r, (D) – q
14. (A) – p, (B) – q, (C) – p, (D) – q

SOLUTION
1. (c) Reaction 2nd & 4th are going on by SN1 pathway which is independent of concentration of base hence both will have same
rate because concentration of alkyl halide is same.
1st and 3rd are going on by SN2 depends upon concentration of base hence R1 will be different from R3 because
concentration of base is different.
(+)
2. (b) CH3Cl Mg. Ether
CH3MgCl HCHO, H 3 O
CH3CH2OH Haloform CHCl3 Ag. heat

CH CH Fe, heat
∆ CH CH(B)
(2 mol)
(E) (C)
3. (a) Rate of reaction ∝ Stability of carbocation
4. (b) In DMSO SN2 reaction takes place
5. (d) CH3I is very sensitive towards Grignard’s reagent formation. Hence to increase the rate of formation of Grignard’s reagent
small amount of CH3I is added. This is called entertainment technique.
6. (c) As no. of halogens increases boiling point decreases (Except fluorides)
222 Problems in Organic Chemistry

7. (b) Anh ZnCl2 + HCl is called Lucas reagent

OH
(+)
(+)
(+) (–) Cl
H Cl
–H2O

O OMgCl OH
CH3 CH3
(+)
H3O
8. (b) + CH3MgCl

Kinetically controlled product

O OMgCl OH O
(+)
CH3MgCl H3O Tautomerism

CH3 CH3 CH3

Thermodynamically
controlled product

9. (a) See question no. 6

10. (d) Dipole moment = charge on dipole (q) × distance between opposite charges (d)
Br & I have low electro negativities hence value of q is too small thus; dipole moment is less. Out Cl & F, C — Cl bond
has large bond length is comparision to C — F bond however q for F is greater than that of Cl but product q × d for CH3Cl
is found to be greater than that of CH3F
11. (c) If Br2 is replaced from I2 in Hunsdecker reaction ester is formed. This reaction is called Smith simonini reaction.
12. (c) Because nuclophilicity of I is greater than that of F. I is a good attacking reagent as will as good leaving group.
13. (d)
14. (d) See mechanism of haloform reaction in your text book.
15. (d) 1st is 3° alkyl halide so rate of SN2 will be least in it. Rest all are 2° alkyl halide but 3rd contain ‘I’ which is a good leaving
group hence rate of SN2 is maximum it 3rd case. Out of 2nd & 4th, later is sterically hindered halide because near to Cl two
methyl groups are present. So formation of pentavalent transition state is difficult in it in comparison to 2nd. similarly Cl of
5th is less stericallly hindered than that of 4th hence rate of SN2 will be 3 > 2 > 5 > 4 > 1
16. (c) It does not contain acidic hydrogen.

5 Br Br
1
6 OH
17. (c) Br Ag
(+) 4 (+) 6 2 (+) H2O
–AgBr 1 Br 3
Br 3 2 5
4

18. (d) Haloform gives CHCl3 (A) & cyclo hexyl carboxylate ion (B) which undergoes Kolbey’s electrolysis as follows:–

• current (–) –CO2

COO COO • Cyclohexyl free radical

Disproportionation +
Cyclohexyl free radical 
→

Dimerisation
Cyclohexy Free radical  →
Alkyl Halide & Grignard’s Reagents 223

19. (b) 3° alkyl halides undergoes elimination reaction by LiAlH4

LiAlH
4 → (CH ) C = CH
(CH3)3CCl  3 2 2

20. (d) CH3CH(CH3)CHClCH3 .……….….………(A)

(CH3)2CHCH2CH2Br …………………..… (D)
(CH3)2CBrCH2CH3 …….………….….… (C)
Since rate of SN1 depends upon the stability of carbocation hence (C) will undergo SN1 rapidly because it will provide
highly stable carbocation while D will undergo SN1 with slower rate because it gives primary carbonium ion as intermediate
which is less stable.

21. (c) (B) = RCOOH

RCOOH + RMgBr 
→ RH + Other Product
(B) (A) (C)

RMgBr + C2 H5OH 
→ RH + Other Product
(E)

22. (c) In this reaction NaCl or NaBr or NaF is formed along with alkyl iodide

in water
RX + NaI 
→ NaX + RI
[X = Cl,Br,F]
In water NaCl , NaBr & NaF are soluble thus can not precipitate out.
While in acetone these are insoluble due to their more ionic character thus; precipitate out.

in acetone
RX + NaI NaX + RI
Soluble
in acetone insoluble in acetone

Br

23. (d) NBS alc KOH + D-Alder

(A)

24. (b) Product formed is stabilized by resonance.

THF
25. (b) PhBr + Mg 
→ PhMgBr

PhMgBr + PhOH + PhOMgBr

(–) • •
26. (b) O N O nitrite is an ambident nucleophile because it can attack from its O as well as N site.
NaNO2 is an ionic compound so O site of nitrite is free to attack on halide hence ethyl nitrite forms as:–

(formNaNO )
EtBr + (–) ONO → 2 Br + EtONO
Ag – ONO is a covalent compound so nitrite can not attack from its oxygen site because covalent bond is present between
silver and oxygen. Hence nitrite attacks from its nitrogen site & nitro alkane is formed
••
EtBr + Ag—ONO Et—NO2+ AgBr
224 Problems in Organic Chemistry

Me

B2H6 Me H2O2/Base Me
27. (c) Me H H
H H
BH2—H BH2 OH

Me
SOCl2
H
H
Cl

CH3 CH3 CH3 CH3

(+) (+) (–)
H OH H H OH2 (+) Br H Br
28. (c) Br
Br H H Br H
••
• • Br H
CH3 •• CH3 CH3
CH3

29. (c) Volume of gas = 11.2 cm3

Moles of gas = 11.2 / 22400 = 0.0005
0.0005 moles of gas are obtained from = 0.037 gm alcohol 1 mole of gas will be obtained from = 0.037 / 0.0005 = 74
Hence molecular wt of alcohol = 74 gm
Therefore alcohol will be (CH3)2CHCH2OH
30. (b)
31. (c)
32. (c) Solvolysis is SN1 reaction. Observe the stability of carbocations formed by 1, 2, 3, & 4
33. (b) Zn / HCl reduces chloroform partially.

Zn / HCl (aq) 
→ 4(H)

Zn / HCl (alc) 
→ 2(H)

Zn/HCl(aq)
CHCl3 + 4(H) 
→ CH3Cl + 2HCl

Zn/HCl(aq)
CHCl3 + 2(H) 
→ CH2Cl2 + HCl

Zn/H O or H /Ni
2 2
CHCl3  → 3HCl + CH4
34. (c)
35. (d) During elimination reaction more stable or more substituted alkene is produced.
36. (d) (c) is Diels–Alder reaction

(a)
CH3COCH3 Haloform
CHCl3

Fe, heat Ag heat

C6H6 CH ≡ CH

Hydrolysis
(b) CaC2  → ACETYLENE 
→ 6 6
Alkyl Halide & Grignard’s Reagents 225

37. (d) NOCl is called Tilden reagent and can convert amine in to halide.

NOCl Ag2O moist

CH2NH2 CH2 —Cl CH2OH

heat (+) Ring opening (+)

(+) H
(+)
H CH2 –H2O

38. (b) Haloform reaction

(–) ••
39. (d) C N is an ambident nucleophile
NaCN is an ionic compound so CN can attack from ‘C’ site. In NaCN, CN behave as strong base hence reaction occurs via
SN2 pathway therefore CH3CH(CH3)CH2CN is formed.
In Ag–CN, C is joined with Ag by covalent bond so CN attacks from lone pair present on N atom. Now CN becomes weak
base and reaction occurs via SN1 pathway
1
SN (+ ) Rearrangement (+ )
CH3 — C H — CH 2 — Cl ? CH3 — CH — CH 2 ————————→ CH3 — C — CH 3
| | |
CH3 CH3 CH3

CH3
|
•• CH3 — C — NC + Ag ( + )

AgCN
|
CH3

alcKOH
40. (b) CH 2Cl — CH 2Cl → Acetylene

(–) ( + )
CH ≡ CH + NaNH 2 
→ CH ≡ C N a + NH3

CH3 CH3
(–) | |
CH ≡ E limination
C + (CH3 )3 C – Cl 
Reaction
→ CH3 — C =
CH 2 
H 2 / Ni
→ CH3 —C H — CH3

41. (b) Bond energy of C — D bond is greater than that of C — H bond so former is more difficult to break in comparison to later.
The alkene in which D is present will be major product.
42. (b) 0.2872 lit of gas has weight = 1 gm
22.4 lit of gas will have weight = 22.4 / 0.2872, = 78
Hence molecular weight of gas RH = 78 Mol. Wt. of R = 77
Hence R will be C6H5 (12 × 6 + 5 = 77) Hence Grignard reagent is C6H5MgBr

RMgBr + C2H5OH 
→ RH + other product
[Link] = 78

43. (d) this is SN1 reaction hence1st step should be RDS and endothermic but in the proposed graph 1st step is exothermic.
44. (b) rate of dehydrohalogenation ∝ stability of product formed
226 Problems in Organic Chemistry

Ph
CH3CHO
45. (c) PhCl + Mg (Ether) PhMgCl CH3—CH—OMgCl

Ph
(+)
mildoxidation H3O
PhCOCH3 CH3—CH—OH

Cl

+ Mg (Ether) (+)
46. (a) Br MgBr(–)
Cl
(A)

Acetone
47. (b) CH3 — CHBr — CHClCH3 + 2NaI → CH3CHICHICH3 
→ CH3CH = CHCH3 + I2
Unstable

48. (a) Enthalpy of dissociation ∝ 1 / ease of formation of carbocation

OH
(+) Cl
(+) (+)
H Methyl shift
49. (d) –H2O

Passage – I

50 to 53

Al2O3, heat
(F)

Hence (D) should be PhCOCH3 (acetophenone)

haloform sodalime
→ PhCOO(–) 
PhCOCH3  → PhH
(D) (F)

haloform sodalime
→ CH3COO(–) 
CH3COCH3  → CH 4
(E)
Hence (C) would be:–
CH3 CH3
C=C Ozonolysis PhCOCH3 + CH 3 COCH3 (E)
Ph CH3
CH3 CH3
| |
Ph — C — CH(CH3 ) 2 → Ph — C = C(CH3 ) 2
H3PO4
| (C)
OH
CH3 CH3
| 1 |
SN *
Ph — *CH — CMe2
→ Ph — *C — CHMe2 , Here C = Chiral carbon atom
| KOH |
Cl OH
(A) (B)
Alkyl Halide & Grignard’s Reagents 227

Passage - II

(54 to 59)

Zn, heat
54. (c) ClCH 2CH 2CH 2Cl  →

55. (c) CH3—CH2CH 2CHCl 2 alc KOH KOH (alc)

heat

Cl
Cl2 Pd/C
heat H2
(1) Cl

56. (a) CH3CHCl—CHClCH 3 alc KOH

CH2= CH—CH=CH2

alc KOH
CH2CH 2CH2—CH 2 Cl
Cl

57. (c) It will form oct–4–ene.(Frankland reaction followed by dechlorination)

58. (c) (3) on treatment with alcoholic KOH forms terminal alkyne (See question no. 55)
CH3CH2C ≡ CH + CH3MgBr ——→ CH4 + CH3CH2C ≡ CMgBr
59. (c) From question no. 56 it is clear that by alcoholic KOH halides form butadiene. This butadiene on reaction with HBr (1 mol)
can form two products as:–

(+) (+) (+)

H
CH2=CH—CH=CH3 CH3—CH—CH=CH2 CH3—CH=CH—CH2
(–) (–)
Br Br

CH—CH—CH=CH
3 2 CH3CH=CHCH2Br
Br

Passage – III

(60 to 63)

Cl I
(+)
ICl finkelstein H3O

I I
A B C
Mg in ether
Cl Cl
H2O P, Cl2, heat
Cl OH
E MgI G D
228 Problems in Organic Chemistry

Passage – IV

(64 to 67)
A is 3– bromo propyne which on reaction with 1 mol of HBr gives (B) BrCH2—CBr = CH2
Now allylic bromine of B undergoes substitution reaction with PhMgBr to produce (C)
Which is Ph CH2—CBr = CH2. Compound (D) is grignard’s reagent Ph CH2—CMgBr = CH2
Which on reaction with carbon dioxide produce Ph CH2—C(COOH) = CH2
68. (c) By the electrolysis of aq NaCl (brine), Cl2 librates & NaOH is Produced.
C2H5OH + Cl2 ——→ CH3CHO + 2HCl
CH3CHO + 3Cl2 ——→ 3HCl + CCl3CHO
CCl3CHO + NaOH ——→ CHCl3 + HCOO Na
CHCl3 + acetone ——→ Chloretone
(Hypnotic medicine)
69. (c) 1→ Borodine– Hunsdecker reaction. In it alkyl bromines are formed.
3→ Here aryl halides is formed.
70. (d) Here tri chloro carbanion is formed which attacks on carbonyl group of acetone .
71. (d) In this BuNC will form(See q. n 39)
72. (d) Substrate is sterically hindered & base is strong so cyanide ion will give elimination product with
3°–BuCl thus; instead of alkyl cyanide alkene is formed

73. (a) Ag 2 O + H 2 O 
→ 2AgOH

AgOH + RX 
→ AgX + ROH

74. (c) Here intimate ion pair is formed thus, retention occurs.
75. (a) Boiling point of alkyl halides is proportional to polarisability and I has good polarizing power in comparison to that of F.
76. (c) Bond length of C—Cl bond is larger than bond length of C—F bond.
77. (a) PhCH2Br undergoes nucleophilic substitution reaction with PhCH2MgBr to produce PhCH2CH2Ph
78. (a) In polar proteic medium ion–dipole attraction takes places. F(–) is strong base hence due to more ion dipole attraction it is
arrested by solvent molecules.
79. (d) In protic solvent nuceophile is caged by solvent molecules by H—bonding thus, in protic solvent
Nuceophilicity ∝ 1 / Basicity
80. (d) Here initmate ion pair is formed. Hence racemisation occurs along with retention.
81. (a) Di methyl formamide (DMF) does not contain acidic hydrogen (C–H bond is not polar)
HCON(CH3)2 .........D.M.F

More than one may correct:–

O OH OH OH OH
(+) (–)
H Br
1. a, b, c, d
(+)
Br Br
O O O O OH
(Aromatic)
Alkyl Halide & Grignard’s Reagents 229

CH3
Fe
Propyne heat
(Aromatic)
H3C CH3

Cl
alc KOH

O O OH
(Aromatic)

2. a, b, c
3. b, c In (a) but–2–ene is formed while in (d) benzene is formed
4. a, d (b) & (c) contain active hydrogen
5. b, c Compound A is benzene while B is PhCH2CH = CH2
6. a, b Pyrrole is not a strong base
7. a, b, c, d CHCl3 is sweet smelling liquid and the proposed reaction is haloform reaction. Since all a, b, c & d contains CH3CO
linkage hence all will undergo haloform reaction.

Cl
NaI NaOH/CaI H/Ni
2
8. d) Acetone ∆ ∆
I
COOH COOH

9. a, b, d (c) is a symmetrical trans alkene hence it has zero dipole moment.

10. a, b, c, d 11. a

LEVEL –II

1. (c) N2 is inert gas thus good leaving group.

2. (b) Due to resonance C — Cl bond acquires double bond character & hence Ph—Cl does not undergo substitution.

1.67 × 10 –6 [RX] × 1 × 100

3. (d) % SN 2 = 97%
1.67 × 10 −6 [RX] × 1 + 0.05 × 10 –6 [RX]

H I I H H I I H
4. (a)
H Cl Cl H Cl H H Cl
(D.D) (L.L) (D.L) (L.D)

Br
(+) (+) (–)
H Br
+ 46%
5. (d)
(–) (+) (+)
Br
resonance
Br (More Stable)
2%
52%
230 Problems in Organic Chemistry

Comprehension

H
Cl Cl
H alc KOH
 → Me alc KOH
H (Anti elimination) H  →
H (Anti elimination)
Me
Me (A) H Me
(B)
Me
Similarly C is
Me

Me
D is
Me

Me
E is
Me

2LiNH
Compound X is formed by Birch reduction as:– →
CH 2OH

6. (a) 7. (a) & (b) 8. None 9. A < B < E < C = D
 Alcohol, Ether,
Epoxide Grignard’s
Reagents 8
Main Features

Reaction Chart for Alcohol

Preparation Properties

(+)
H2O/H CrO3 or PCC
Alkene aldehyde or ketone (mild oxidation)
or PDC

Aldehyde or ketone
or ester or acid LAH KMnO4
RCOOH ( strong oxidation)
halide or carboxylic
acid
A (+)
ROH/H
Fermentation L RCOOR ( Esterification)
Sugar
C
Fermentation O (–)
Starch RCOCl / OH
H RCOOR (Acylation)
NaNO2+HCl O (–)
RNH2 (RCO)2O / OH
L RCOOR ( Acylation)
O3/H2O S
Alkene NH3/Al2O3
NaBH4 RNH2
B2H 6 (+)
Alkene H
H2O2 / OH(–) RCH = CH2
170°C
(+)
Ester H 2O / H
(+)
H
O (+)
RCH2CH2OCH2CH2R
H3O 140°C
CH2–CH2 + RMgX ( not for 3°alc)
PCl5 /PCl3 /SOCl2
RCHO or (+) RCl
H3O
RCOR + RMgX Red P + HI
alkane
232 Problems in Organic Chemistry

Reaction Chart for Ether & Epoxide

Preparation Properties

(+)
H / 140°C HI (cold & dil)
ROH RI + ROH
Ag2O HI (hot & conc)
RX E 2RI
H
RONa T H2SO4
RX H R—O—R
(+)
(+)
(1° or 2°) E H2O / H
R 2ROH
S PCl5 / heat
2RCl
SOCl2 or PCl
heat RCl

Reaction Chart for Epoxide

Preparation Properties
(+)
heat H3O
CH2=CH2 + Ag + 1/2O2 CH2OH—CH2OH
E
PAA P HCl
CH2=CH2 CH2Cl—CH2OH
O (+)
NH3 / H
CH2—CH2 X CH2NH2—CH2OH
aq KOH I
Cl OH D RMgX
H3O
(+) RCH2CH2OH
E
S
PCl5
heat CH2Cl—CH2Cl

LEVEL - I

Multiple Choice Questions

CH2NH2
(i)Tildent reagent

+
→
1. (ii)aqKOH (iii) H ,heat A, Compound (A) will be:-
CH2OH OH

(a) (b) (c) (d) CH3

2. OH group of ROH is a good leaving group in:-

(a) Basic medium (b) Acidic medium (c) Neutral medium (d) Presence of sun light
OH

Br 3CH MgBr
3. → X
heat
In this reaction X would be:-
Br
O
(a) (b) (c) CH4 (d) Both b & c
Alcohol, Ether, Epoxide Grignard’s Reagents 233

4. How many intermediate carbocations are involved during the following transformation?

H( + )
OH → Alkene (major product)
Heat

(a) 1 (b) 2 (c) 3 (d) 4

5. In which case epoxide will form as product:-

OH

OH H( + ) NaOH + H O
2 →
(a) → (b) 

OH OH H( + )
(c) → (d) All of these

6. Most Stable form of 4-nitro cyclo hexanol is:-

NO2 NO2

(a) H H (b)
OH
OH
NO2
OH NO2
(c) H H (d) OH H

H PO
3 4→
7. Which product is not expected for  Products?

OH OH

(a) (b) (c) (d) (b) & (c)

COCH3 O COCH3

(AcO) Pb
4 → (B) 
8. (A)  → + ve haloform test (A) may be:-
(a) (CH3CH2CHOH)2 CH2 (b) CH3CHOHCHOHCH3
(c) CH3— CHOHCOCHOHCH3 (d) (b) & (c)
H

H( + )
9. OH → ?
OH

H
Product of this reaction will be:-
(a) Cyclo pentan carbaldehyde (b) 2 - Hydroxy Cyclohexanone
(c) Cylco hexanone (d) All of these
234 Problems in Organic Chemistry

10. Correct order of acid catalyzed dehydration to produce alkene in the following compounds will be:-

OH
|
OH CH 2 = CH — CH = CH — CH — CH3
(1) (2)

CH 2 CH — CH — CH3
Φ3COH OH

(3) (4)
(a) 1 > 2 > 3 > 4 (b) 3 > 1 > 2 > 4 (c) 3 > 2 > 1 > 4 (d) 1 > 2 > 4 > 3
11. Consider the following reduction.
NaBH 4
O 
→ Product
D ether,H( + )

Product of this reaction will be:-

(a) Optically active (b) diastereomer
(c) Product forms with partial racemisation (d) meso
12. Consider the following reduction.
D NaBH 4
O  → Product
ether,H( + )

Product of this reaction will be:-

(a) Optically in active diastereomeric pair (b) Optically active diastereomeric pair
(c) Product forms with partial racemisation (d) Product forms with 100% racemisation
13. In which reaction product will not exhibit haloform test.

lead tetra acetate

(a) CH3COCH2CHOHCHOHCH2COCH3  → Product

4 H(+) /KMnO
(b) CH3CH2OH → Product

CH 2CHO
|
CH3 C = CCH3
O3
(c) → Product
| H 2O/Zn, heat
CH 2CHO

(d) Products of all reactions will not show haloform test.

OH O
14.

This oxidation can be performed by:-

(a) Aluminum tert- butoxide (b) Hot KMnO4 (c) Jones reagent / 35°C (d) (a) & (c)

OH
|
15. Φ 2 — C — CH3 + Ac Cl 
→ X + Y, X & Y are :

CH3 CH3
CH3 CH3
| |
| |
(a) Φ 2 C — Ac + HCl (b)
Φ 2 COAc & HCl (c) Φ 2 C — Cl & AcOH (d)
Φ 2 C — COOH + CH3Cl
Alcohol, Ether, Epoxide Grignard’s Reagents 235

H
SOCl
Pr OH  2
in dioxane
→ CH3CH—Pr
|
Cl
16. CH3
Configuration of product will be:-
(a) R (b) S (c) Racemic mixture (d) Unpredictable
17. Consider the following reagents:-
Al2O3 / 350°C H2SO4 / 1400C (CH3)2SO4 / NaOH CH2N2
(1) (2) (3) (4)
Methyl alcohol can be converted in to dimethyl ether by using
(a) 1, 2, 3 & 4 (b) 1, 2 & 3 (c) 1 & 2 (d) 1, 2 & 4

CH3 SOCl2

18.  OH—— Configuration of ‘A’ & ‘B’ will be:-

P + Br2
H 

(a) R, S (b) S, R (c) S, S (d) R, R

Φ Φ
| |
19. CH3 — CH — CHOHCH3 
→ CH3 — C — CH 2 — CH3 , Here A will be:-
(A) |
Cl
(a) Sarret reagent (b) Lucas reagent (c) SOCl2 (d) All of these

Passage I

An organic compound A (C7H13OCl) contains one four membered ring whose two opposite corners are substituted by two group, one
of which is Cl. This Compound reacts with lucas reagent immediately. This compound gives B & C on treatment with aq Na2CO3 &
aq KOH respectively. Compound (B) can react with Sarret reagent. (A) On reaction with dilute sulphuric acid gives D(minor) which
can react with lucas reagent with in 5 minutes. When (D) is subjected to heat in presence of H(+) (E) is formed which can decolourise
Br2 water. (E) On treatment with KMnO4, heat gives (F). (F) Gives haloform test & on treatment with excess of CH3MgBr followed
by hydrolysis (F) gives (G) which can not react with Sarret reagent.
Answer the questions from 20 to 26.
20. Compound (A) is:-

CH—Et OH
OH OH
(a) (b) (c) (d) OH

Cl Cl Cl Cl

21. Compound (B) is:-

OH CH —Et
OH
OH
(a) (b) (c) O (d)

OH
OH OH
236 Problems in Organic Chemistry

22. Compound (C) is:-

O OH OH
(a) (b) O (c) (d)

OH OH
23. Compound (D) is:-

OH OH OH
OH Cl

(a) Cl (b)
Cl (c) (d)
Cl

24. Compound (E) is:-

(a) Cl (b)
Cl (c) Cl (d) Cl

25. Compound (F) is:-

COCH3 COCH3
CHO COCH3
COCH3
(a) Cl (b) Cl CHO (c)
Cl (d) None

26. Compound (G) is:-

COH(CH3)2 COHMe2
COHMe2
CHOCH3
(a)
Cl (b) Cl

COCH3
COHMe2 CHOHMe

CHOHMe
(c) Cl (d) Cl

Passage II

An organic compound (A) on hydrolysis gives (B) along with ethyl alcohol & on treatment with LiAlH4 (A) gives (C) & ethyl
alcohol. Compound (B) can be converted in to (C) by the help of LiAlH4. Compound (C) gives two moles of CH4 while (B) gives
one mole of CH4 when treated with excess of [Link] (C) does not give lucas test under ordinary condition. Com-
pound (A) on treatment with excess of CH3MgBr/H3O+ gives (D) which gives haloform test but when (D) is treated with PCC fol-
lowed by CH3MgBr(excess) / H3O+ compound (E) is formed which does not give haloform test.
Alcohol, Ether, Epoxide Grignard’s Reagents 237

Answer the questions from 27 to 31.

27. Compound (A) is:-

(a)
HO COOC2H5 (b) EtO2C CO2Et
OH
(c) OHC COOEt (d) CH—CO2Et

28. Compound (B) is:-

OH OHC
(a) (b)
COOH COOH

COOH
CH2OH
(c) HOOC (d)
HOH2C

29. Compound (C) is:-

COOH
CH2OH
(a) (b) HOOC
HO2C

CH2OH
(c)
HOH2C (d) HOCH OH
2

30. Compound (D) is:-

COOMgBr
(a)
OH (b) HO CHOHCH3

OH CHOHCH3 CHO
(c) (d)
Ac

31. Compound (E) is:-

(a) Me2HOC COHMe2 (b)

HO COHMe2

(c) HOH2C COHMe2 (d) None

Passage III

An organic compound (A) can decolourise Br2 water but does not react with Pd / CaCO3 / H2. (A) gives (B) on treatment with hot
KMnO4 followed by reaction with NaBH4 / Ether. (A) Gives (C) on treatment with cold KMnO4. (B) Gives blue colouration in
victor maeyer test. (B) gives (E) when heated with H3PO4 followed by treatment with hot KMnO4. When alkaline solution of (E) is
electrolysed ethane is formed. (C) On reaction with H3PO4 gives (D) which does not give victor maeyer & lucas test.

Answer the question from 32 to 36.

32. Compound (A) will be:-

(a) (b) (c) (CH3)2C = C(CH3)2 (d) EtC ≡ CEt

238 Problems in Organic Chemistry

33. Compound (B) will be:-

OH
OH CH3 O
(a) (b) (c) CHOH (d)
CH3
34. Compound (C) will be:-

OH OH OH

(a) (b)

OH
OH OH

(c) (d) Me2COHCOHMe2

35. Compound (E) is:-

(a) Pentanoic acid (b) Propane 1,3- di carboxylic acid
COOH
(c) HOOC (d) HOOC — CH = CH — COOH
36. Compound (D) will be:-
O

(a) (b) (c) (d)

O

Passage - IV

An organic compound (A) gives 3 moles of CH4 when one mole of it reacts with excess of CH3MgBr. Compound (A) on dehydration
gives (B). (B) gives +ve Br2 water test but -ve haloform test. (B) on reaction with CH2N2 gives (C) which on reaction with LiAlH4
followed by H3O+ gives cyclo propyl methanol. Compound (B) on reaction with cold KMnO4 gives (D). (D) Can be converted in to
(A) by treatment with LiAlH4/Ether/H+.

Answer the question from 37 to 40.

37. Compound (A) is:-

OH OH
OH OH
OH
(a) (b) OH (c) (d)

HO OH OH CH2OH HO OH
38. Compound (B) is:-
O
(a) (b) CH2 = CH—CHO (c) (d)

OH OH
Alcohol, Ether, Epoxide Grignard’s Reagents 239

39. Compound (C) is:-

OH
(a) CHO (b) (c) (d)

OH OH
40. Compound (D) is:-
O O
HO OH

(a) (b) (c) (d) CH2OHCHOHCHO

HO OH HO O CHO
41. Ether (A) when reacts with cold HI gives alcohol & iodide. Alcohol does not give haloform test but iodide can give haloform
test (A) Will be:-
O—CH2
(a) AcCH2– O (b)
COCH2I

(c) Ph—O—CH2 (d) All of these

Ac

42. Which is not an example of SN2 reaction:-

Br Br
NH2 (b) HI
(a) CH3OC2 H5 → CH3I + EtOH
NH3
 →
Methanol
O OH

Cl OEt
AgNO3
(c)  → (d) PhONa + CH3Br PhOCH3 + NaBr
EtONa

43. Correct order of boiling point is:-

(a) n — BuOH > i — BuOH > 2° — BuOH > 3°— BuOH (b) n — BuOH > 2° — BuOH > i — BuOH > 3° — BuOH
(c) n — BuOH > 2° — BuOH > 3° — BuOH > i — BuOH (d) n — BuOH > i — BuOH > 3° — BuOH > 2° — BuOH
44. 2 — Cyclohexyl butan — 2 — ol can’t be prepared by:-
Ac MgBr
Ether Ether
(a) + EtMgBr 
(+ )
→ (b) + Ethyl methyl ketone 
(+ )
→
H3O H3O

CHOHEt Ag, heat MeMgBr I Mg COCl

(c) →  → (d) → X  2→
H O( + ) 3 THF excess
(+ )
H3O

OH NO2

45. One mole of Ac COCHI2

OH
is treated with NaOH / I2 and then acidified, the product obtained after the removal of precipitates is treated with 3 moles of
NaOH and another salt (A) is formed (A) will be:-
240 Problems in Organic Chemistry

ONa NO2 OH NO2

(a) NaOOC COCHI (b) NaOOC COONa

ONa ONa

ONa NO2 ONa NO2

(c) NaOOC COONa (d) HOOC COONa

OH ONa

2 H CrO
4
46. R2CHOH  → R2CO
In this oxidation colour of the solution changes from
(a) Orange to Red (b) Red to Blue
(c) Orange to Blue - Green (d) Orange to white
47. Which is not correctly matched:-

DMSO PCC
(a)
RCH 2 OH  → RCHO (Swern oxidation) (b) R 2 CHOH → R 2 CO(Sarret oxidation)
in CH Cl 2 2

3 CrO H 2CrO4
RCH 2 OH →
(c) RCHO (Colling oxidation) (d)
RCH 2 OH  → RCHO (Robin oxidation)
Pyridine in acetone
C OOH
Br |

48.
D KOH DMSO
→ (A) 
CH 2 = CH — CH 2CH 2OH →
hot
C H2
 → (B) KMnO 4 |
H DMSO
CH 2 —COOH
H
OH
D D O
(a) (A) & (B) both are (b) (A) is & (B) is
H
H H
H H OH
D D O D D
(c) (A) is & (B) is (d) (A) is & (B) is
OH OH H
H H H H
49. Consider the following reagents:-
(i) LiAlH4 / Ether / H+ (ii) CH2N2 / H3O+
(iii) NaOH / CaO, mono chlorination, aq KOH (iv) B2H6 / THF
For the conversion of cyclo propane carboxylic acid to cyclo propyl methanol we can use.
(a) (i), (iv) (b) (ii), (i), (iii), (iv) (c) only (i) (d) (i) & (iv)

(A)
50. CH = CHCHO PhCH2CH2CH2OH, Here (A) is:-

(a) LiAlH4 / Ether / H+ (b) H2 / Ni (c) NaBH4 / Ether (d) (a) & (b)
51. Which reaction is least likely to occur ?
(–) (–) + Me COH 
(a) → CH3OH + CH3COO(–) (b)
CH3 O + CH3COOH  Me2 CHCO 3 → Me3CO(–) + Me2 CHOH
(–) (−) (–)
NH 2(–) + EtOH 
(c) CH 2 = CH + BuOH 
→ Et O + NH3 (d) → Bu O + CH 2 = CH 2
Alcohol, Ether, Epoxide Grignard’s Reagents 241

52. An alcohol (A) on heating with Cu / 300°C gives (B). (B) on oxidation gives (C). (C) on reaction with CH3MgBr / H3O+ gives
(A). (A) will be:-
OH
OH

(a) (b) (c) OH (d) OH

CH3 O CH3MgBr Cu
53. C—CH2 (+ )
→ (A)  →
300°C (B) Here (B) is:-
CH3 H3O

O
||
CH3 — C = CHCH3
(a) (CH3)3CCHO (b) (c) (CH3)2CHCOCH3 (d)
CH3 — C CH 2 CH 2 CH3
|
CH3
C2H5SH, MeOH
(C)
CH3MgBr/H3O(+)
54. (B)
MeOH, H(+)
(A)
O
Out of (A), (B) & (C) the compound which will not give victor maeyer test is:-
(a) (A) & (C) (b) (B) & (A) (c) (C) (d) (B) & (C)
55. Which among the following reaction is not possible:-

(a)
CH 2 = CHCH 2CH 2OH 
O3
Me S

→ HCHO + CHO
2 |
(CH 2 )2 OH

(b)
CH 2 = CH — CH 2CH 2OH 
DMSO
→ CH 2 = CHCH 2 — CHO

(c)
CH 2 = CH — CH 2CH 2OH 
MnO2
→ CH 2 = CHCH 2 CHO

C OOH
|
(d)
CH 2 = CH — CH 2CH 2OH →
hot
KMnO
C H2
4 |
CH 2 —COOH
56. What will be the order of reactivity of following compounds with Grignard’s reagent?

CH3CHO O

(I) (II) (III)

(a) I > II > III (b) III > II > I (c) II > I > III (d) II > III > I
O
TsCl 3 CH O(–)
OH → (B) 
→(C)
57. Pyridine
Me
(A)
Identify the correct statement
(a) Configurations of (A) & (C) are same
(b) When (A) converts in to (B) configuration does not change
(c) From (A) to (B) configuration changes but when (B) converts in to (C) configuration remains same
(d) All have same configuration
242 Problems in Organic Chemistry

58. Consider the following two reactions having R1 & R2 rates of reactions respectively.
R
RMgX O
¾¾¾¾ ® RMgX
¾¾¾¾ ®
(1) H3O(+) (2)
R H3O(+) OH

(a) R1 > R2 (b) R2 > R1 (c) R1 = 2R2 (d) R1 = R2

OH OH

Phosphoric acid
59. CH3 Br → [X], product

[X] would be:-

CH3
O O

(a) (b)
CH3 Br Br

O O

(c) (d)
CH3 Br
CH3

Br

60. When cyclo hexane is added in ethanol then which of the following will happen
(a) Heat is evolved & boiling point does not change (b) Heat is absorbed and boiling point increases
(c) Heat is evolved and boiling point decreases (d) Heat is absorbed and boiling point decreases

3 2CH MgBr
61. (A) 
→ (B) If B is acetone then A would be:-

(a) CH3COCl (b) CH3COOC2H5 (c) CO(OC2H5)2 (d) All of these

O O O

62. CH3 CH3 CH3 H H H

(1) (2) (3)

Correct order of bond angle is:-

(a) 1 > 2 > 3 (b) 2 > 3 > 1 (c) 3 > 2 > 1 (d) 2 > 1 > 3

63. The common cyclic ether containing least number of carbons is:-
(a) Oxolane (b) Oxetane (c) Oxane (d) Dioxane
Alcohol, Ether, Epoxide Grignard’s Reagents 243

O
H( + )
64. → Product, Product of this reaction will be:-
H 2O

CH2OH CH3
OH
OH
(a) (b) CH2OH (c) (d)
CH3 OH CH3
OH OH OH

65. H SO
2 4→ (A), (A) is:-

o

HO
(a) (b)
OH

(c) (d)
OH OH

66. Identify the correct esterification reaction,

Here O18 = O*

* * H( + ) * * * H (+ )
* 1
(a) RC O OH + R1OH 

 1
 RC O OR + H 2 O (b) RCO 2 H + R1 O 

 RCO O R + H 2 O
H 

(+ )
*
(c) RCOOH + R1 O H *
 RCOOR + H 2 O (d) all are correct


H  1

OH HI Zn

→ →
67. excess Ether P, Product P is:-
OH

(a) (b) (c) (d)

(+)
+ H3O CH2OH
68. CH3OH +
O
CHO
OMe
In this reaction which intermediate will not form during the mechanism.

(a) (b) CH2OH (c) (d) None of these

O O—H
(+)

H—OMe HO OCH3 OCH3

(+)
244 Problems in Organic Chemistry

COOCH3
Ph Ph
H( + )
69. → A, Product (A) would be:-

Ph
Ph Ph
COOH
Ph Ph
CO
(a) (b)
Ph Ph Ph
Ph Ph

O OCH3
Ph Ph Ph
(c) (d)

Ph Ph
70. Which ether will not react with dil HI at room temperature ?

(a) (CH3)3COC (CH3)3 (b) CH2OH (c)

Φ2O (d) All of these
O

Anh
6 6 → C H
71. + HCHO + HCl 
ZnCl
→(A) 
dil H SO (B), (A) & (B) respectively are:-
2 2 4

CHO CHO CH2OH

CH2
(a) & (b) &
Ph 2

CH2OH CH2OH CHO CHO

(c) & (d) &

Cl Ph
Ph
72. The product obtained by the acid catalysed hydrolysis of cyclo propyl oxirane is:-
OH

CH2OH
(a)
HOCH2 OH (b) CHOH (c) both (a) & (b) (d)
CH2OH

H( + )
73. →[P] major
OH Heat

CH3
[P] would be:-

(a) Toluene (b) (c) (d) Reaction is not possible

CH3 CH3
Alcohol, Ether, Epoxide Grignard’s Reagents 245

74. Match the following

Compounds Dipole moment
(A) Et2O (i) 1.18 D
(B) n - Pr - Cl (ii) 2.10 D
(C) n - Pr - CHO (iii) 2.72 D
(D) n - BuOH (iv) 1.63 D
Correct option is:-
(a) A→ (i) ; B→ (ii) ; C → (iii) ; (D) → (vi) (b) A→ (iv) ; B→ (iii) ; C → (ii) ; (D) → (i)
(c) A → (iii) ; B → (ii) ; C→ (iv) ; (D) → (i) (d) A → (iii) ; B → (ii) ; C → (i) ; (D) → (vi)
75. Assertion- Benzyl ethyl ether on reaction with dilute & cold HI produces benzyl iodide
Reason- This reaction occurs via SN2 pathway
Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(a)
Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(b)
Assertion is true, Reason is false
(c)
Assertion is false, Reason is true
(d)

R O
2 → RMgX
76. Assertion: - RX + Mg 

R OR2
Here RMgX is present in the form of Mg
X OR2
Reason: - Due to-I effect of halogen Mg is electron deficient thus, receive electrons from ether.
Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(a)
Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(b)
Assertion is true, Reason is false
(c)
Assertion is false, Reason is true
(d)
77. Assertion- acylation of alcohol by acid halide is carried out in basic medium
Reason- base neutralizes HCl produced in the reaction and avoid the formation of alkyl halide
Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(a)
Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(b)
Assertion is true, Reason is false
(c)
Assertion is false, Reason is true
(d)
78. Assertion- OH group is better leaving group than I in acidic medium
Reason- In acidic medium OH of alcohol picks up proton and comes out in the form of water
Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(a)
Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(b)
Assertion is true, Reason is false
(c)
Assertion is false, Reason is true
(d)
79. Assertion: - Rates of acid calatysed dehydration of CH3CH2OH & CD3CH2OH are almost equal.
Reason: - Breaking of C—H or C—D bond is not rate determining steps.
Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(a)
Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(b)
Assertion is true, Reason is false
(c)
Assertion is false, Reason is true
(d)
246 Problems in Organic Chemistry

80. Assertion: - Solubility of butyl alcohols follows following order.

CH3 CH3
| |
CH3 — C — OH > CH3CH 2 — CH — OH > CH3 — CH 2CH 2CH 2OH
|
CH3

Reason: - As branching increases surface area decreases and solubility increases.
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
81. Assertion: - Melting point of cyclo hexanol is greater than that of hexan – 1 – ol
Reason: - Cyclo hexanol has less molecular wt. than hexan – 1 – ol
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
82. Assertion: - Dipole moment of cyclo hexanol is lesser than phenol
Reason: - In phenol resonance takes place & C - O bond acquires partial double bond character.
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true

OH OH
83. Assertion: - does not undergo pinacole-pinacolone rearrangement.

Reason: - Due to resonance one C - OH bond becomes C = O

(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true

Answer Key

1. (a) 2. (b) 3. (d) 4. (b) 5. (d) 6. (c) 7. (c) 8. (d) 9. (a) 10. (d)
11. (d) 12. (b) 13. (d) 14. (a) 15. (c) 16. (b) 17. (b) 18. (a) 19. (b) 20. (c)
21. (b) 22. (a) 23. (d) 24. (a) 25. (c) 26. (b) 27. (c) 28. (b) 29. (c) 30. (c)
31. (a) 32. (b) 33. (b) 34. (c) 35. (c) 36. (a) 37. (b) 38. (b) 39. (a) 40. (d)
41. (d) 42. (c) 43. (a) 44. (d) 45. (b) 46. (c) 47. (d) 48. (c) 49. (d) 50. (d)
51. (b) 52. (c) 53. (b) 54. (d) 55. (c) 56. (d) 57. (b) 58. (b) 59. (d) 60. (d)
61. (c) 62. (a) 63. (b) 64. (a) 65. (c) 66. (b) 67. (b) 68. (a) 69. (c) 70. (c)
71. (b) 72. (b) 73. (a) 74. (a) 75. (c) 76. (c) 77. (a) 78. (a) 79. (a) 80. (a)
81. (b) 82. (d) 83. (a)
Alcohol, Ether, Epoxide Grignard’s Reagents 247

Multiple Choice Questions (More Than One May Correct)

1. Which of the following will not release H2 on reaction with Na metal?

C CH=CH2
CH
(a) Me2O (b) n - BuOH (c) (d)
O
OH
2. Which of the following will give yellow precipitate with NaOI?

(a) OH (b) (c) O (d) OH

O
3. Which of the following transformation is not possible by NaBH4?

(a)
O OH

(b) COOEt CH2OH + EtOH

O OH
(c)

CHO CH2OH
O O
(d) EtOH
O
4. Which will undergo oxidation by IO4(-)?
OH
OH OH CH 2OH
|
(a) (b) C = O (c) (d)
OH | OH OH
CH 2OH
OH
5. In which of the following case alkane is producing.
110°C
(a) Glycerine + EtMgBr 
→ (b) Glycerine + oxalic acid 
→

Red P + HI (i) SOCl

2 
(c) CH3 — CH — CH3 → (d)  →
| (ii) Na / Me2O
OH
OH

6. Which is not the preparation of epoxide:-

Cl
2 Cl / Water
(a) →
aq Na 2CO3 (b)
 →
HO

PAA
(c) → (d) C H 2
heat
|| + Ag + 1/ 2O 2 
→
CH 2
7. Which among the following will not be oxidized by CrO3?
(a) 2-Methyl propan 2- ol (b) PhOH
(c) 3-Phenyl propan-2-ol (d) CH3CH2OCH2CH3
248 Problems in Organic Chemistry

8. In which case products formed are not according to reaction?

(a) ∆
Gycerine + conc H 2SO 4 → CH3CHO (b) PhCH = CHCHO + LAH 
→ PhCH 2CH 2CH 2OH
D
O LAH OH
(c) → PhCH 2OH + CH3OH
PhCOOCH3 + NaBH 4  (d) 
(+ )
→
D
9. Which of the following is not the preparation of alcohol?
aq KOH
Sucrose + H3O( + ) 
(a) → (b) Cl →
OH

3 O / H O / NaBH
2 4 →
(c)  (d) Sucrose + yeast 
→

10. Which of the following will not show Lucas test?

(a) Phenol (b) OH

CF3
CF3
CF3
(c) OH (d) OH

Answer Key

1. (a), (d) 2. (c), (d) 3. (b), (d) 4. (a), (b) 5. (a), (c), (d)

6. (a), (b) 7. (a), (b), (d) 8. (a), (c), (d) 9. (a), (b) 10. (a), (b), (d)

LEVEL - II
CH2OH
1. CHOH + CH3MgBr 
→ 44.8 lit CH4 + [X], [X] would be:-
CH2SH
(1 mol)
CH2OMgBr CH2OMgBr CH2OH CH2OMgBr
(a)
CHOMgBr (b)
CHOH (c) CH2OMgBr (d)
CHOMgBr
CH2SMgBr CH2SMgBr CH2SMgBr CH2SH

2. Which among the following will consume more than two moles of Grignard’s reagent?
OH O
O O

OEt
(a) (b) (c) (d)
O OH
O COOH O
Br
3. Dehydration of alcohol is performed by concentrated H ion. It involves 3 transition states (TS)1 (TS)2 & (TS)3. If free energy
(+)

changes for these transition states are ∆G*1, ∆G*2 & ∆G*3 respectively them:-

∆G*1 > ∆G*2 > ∆G*3 (b)

(a) ∆G*2 > ∆G*3 > ∆G*1 (c) ∆G*3 > ∆G*2 > ∆G*1 * * *
(d) ∆G 2 > ∆G 1 > ∆G 3
Alcohol, Ether, Epoxide Grignard’s Reagents 249

Et

CH MgBr
4. ¾¾¾¾¾
3 ® Product
H O( +)
3

O
Products in this reaction will be
(a) Emnantiomers (b) Stereoisomers (c) Diastereomers (d) Geometrical isomers
O
CH MgBr
5. ¾¾¾¾¾
3
( +)
® [X]
H3O

Select correct statement regarding [X]

(a) It contains two chiral ‘C’ atom
(b) It can show geometrical isomerism
(c) On acid catalysed dehydration [X] givens [Y] which can not show geometrical isomerism
(d) [X] contains plane of symmetry
6. Consider the following reactions
CH3
| H (+ )
1.
CH3CH 2CH 2 — C — CH 2OH → Major Product
| ∆
CH3
CH3
| H( + )
2.
CH3 — C — CH 2 — (CH 2 )2 — CH3 → Major Product
| ∆
OH
H( + )
3.
i — Bu — CH 2 — CH — CH3 → Major Product
| ∆
OH
CH3
| H( + )
4.
CH3 — CH —CH — CH 2 Et → Major Product
|
OH

Reaction with same major product is / are:-

(a) 1, 2, 3 & 4 (b) 2, 3 & 4 (c) 1 & 3 (d) 2 & 4
7. Consider the following reactions.

CH2OH
OH
H( + ) H( + )
1. → Product 2. HO OH → Product
∆ ∆

Cl

Cl Cl
OH H( + ) Zn dust
3. → Product 4. → Product
OH ∆ heat
Cl Cl
Cl
250 Problems in Organic Chemistry

Cl

Cl Cl
Zn dust
5. → Product
heat
Cl Cl

Cl
Reaction in which benzene is formed as a product is / are:-
(a) 1, 2, 3, 4 & 5 (b) 1, 3 & 5 (c) 1 & 5 (d) 1, 2, 3 & 4
8. Consider the following acid catalysed transformation.

OH

H(+)
→
∆
OH O

Following intermediates are expected in this transformation

OH
(+)
1. 2. 3. 4.
OH (+) OH (+) (+)
OH
OH

5. (+)

The intermediate which is not produced during this transformations is / are :-

(a) 2, 3 & 5 (b) 3, 4 & 5 (c) 2, 3, 4 & 5 (d) Only 4th
9. Alcohols are prepared in following reactions.

D( + ) H (+ ) D( + ) H( + )
1. CH3CH = CH2 → 2. CH3CH = CH2 → 3. CH3CH = CH2 → 4. CH3CH = CH2 →
H 2O D 2O D 2O H 2O

Select the correct statement regarding these reactions.

(a) Except 4th reaction two products are formed in rest of the reactions.
(b) In 1st & 2nd reactions two products are formed
(c) In 2nd reaction two products are formed
(d) In 1st and 3rd reactions two products are formed

CH3

NaNO2 + HCl
10. i–Pr CH2NH2  → [ X]

i–Pr
We have following statements about the proposed reaction.
1. [X] is optically active 2. [X] gives red colour in victor maeyer test
H( + ) ozonolysis
3. [X] shows haloform test 4. [X] →[Y] → O + CHO
Heat
Alcohol, Ether, Epoxide Grignard’s Reagents 251

Out of these four statements correct statements are:-

(a) 1 & 4 (b) 1, 2, 3 & 4 (c) 1,3 & 4 (d) 2,3
11. Nucleophilic addition of Grignard’s reagent is not possible in
O
O O
OH || || C–OH
CH - C - CH - C - CH3 (c) CH COCOCH
(a) (b) 3 2
3 3
(d)

Matrix Match Questions

Each question contains statement given in two columns which have to be matched. Statement (A, B, C , D) in column I have to be
matched with statements (p, q, r, s) in column II. The answer to these questions have to be appropriately bubbled as illustrated in the
following examples. If the correct match are A – p, A – s, B – r, B – r, B – q, C – q, D – S, then the correctly bubbled 4 × 4 matrix
should be as follows.
A p q r s
B p q r s

C p q r s

D p q r s

12. Select the reagents form list -II by which you can differentiate the pairs of compounds given in List I
List - I List - II

(A) & (p) Na

OH OH

(B) & (q) Br2 water

OCH3 CH2OH

(C) & (r) KOI

HO—CH—CH3 OH

(D) & (s) Anhydrous ZnCl2 + HCl

OH CH2OH

13. List - I (Reaction) List - II (Product)

LiAlH
4→
(A) 
(+ ) (p)
O H OH

CH MgBr
3
(B) 
(+ )
→ (q)
O H3O OH
252 Problems in Organic Chemistry

(C) OH OH
→ (r)
O CH MgBr
3

(+ )
H3O

O
LiAlH 4→

(D) H( + ) (s)
OH

14. List - I (Reaction) List - II (Missing Reagent)

CH3
CHO
?
(A) (p) Zn / Hg + HCl

?
(B) PhCH = CH — CHO 
→ Ph(CH2)3OH (q) H2 / Ni

?
(C) PhCH = CH—CHO 
→ PhCH = CH—CH2OH (r) NaBH4 / Ether / H(+)

?
(D) CH3CH = CH—CHO 
→ CH3CH2—CH2CH2OH (s) LiAlH4/Ether/H(+)

15. List - I (Compond) List - II (Test)

OH
(A) (p) Evolve H2 with Na metal

(B) (q) Yellow ppt with KOI

OH
(C) CH2OH (r) +ve victor Maeyer test

(D) OH (s) +ve lucas test at room temperature

16. Organic compounds W, X, Y and Z are formed in following chemical reactions.
CH3
| NaNO + H SO AgNO
2 2 4 3→ X
Ph 2CIC(OH)(CH3 )2 
CH3 — C — CH 2 NH 2 → W
|
CH3
AgNO3 Ag cold and dilute HI
Ph 2CIC(OH)(CH3 )2  → X W  →Y Me3COCHMe2 
→ alkyl Iodide + Z
heat
Select the reactions from list II which is exhibited by W, X, Y and Z
List - I (Compounds) List - II (Reactions)
(A) W (p) Can give yellow ppt with KOBr
(B) X (q) infinitely soluble in water
(C) Y (r) Decolourise Br2 water
(D) Z (s) Evolve H2 with sodium metal.

Answer Key

1. (b) 2. (a), (b), (c) 3. (b) 4. (b), (c), (d) 5. (b), (c), (d)

6. (a) 7. (d) 8. (b) 9. (d) 10. (a)

11. (a), (b), (d)

Alcohol, Ether, Epoxide Grignard’s Reagents 253

Answers matrix match

12. (A) - s, (B) - p, (C) - r, (D) - q,s 13. (A) - p, (B) - q, (C) - s, (D) - s
14. (A) - p, (B) - q, s, (C) - r, (D) - q 15. (A) - p, (B) - p, r, s (C) - p, r (D) - p, q, r, s
16. (A) - s, (B) - p, (C) - r, (D) - p, q, s

SOLUTION
NOCl aq KOH
1. (a)
CH2NH2 CH2—Cl CH2OH

heat (+) Ring opening (+)

(+) H
(+)
–H CH2 –H2O

2. (b) Because in acidic medium it removes H2O & generates carbocation

(+ )
(+ ) → H 2O + R ( + ) (Carbocation)
ROH + H  → R OH 2 

OH OMgBr O

CH3MgBr
3. (d) Br CH4 + Br

O
Heat
ring opening

(+)
(+)
H
4. (d) OH 1
(+)
hydride
shift 2

(+)
–H

H
•• (+)
H( + ) OH
••

OH OH O

→ (+) –H( + ) ••
5. (d) –H 2O 
→ 
→

OH O(–)
O
Cl Cl
NaOH

→ 
→
••
OH H
••

(+)
(+) O O
(+) (+)
OH + H –H

6. (c) Due to intra molecular H– bonding.

ON O2H
H H Intramolecular–H–bonding

254 Problems in Organic Chemistry

7. (c) It is an example of pinacole - pinacolone rearrangement

(+) (+)
H H

(+)
OH OH OH OH (+)

(+) (+)
OH OH
(+)
–H (+)
–H

COCH3 O

(a) (b)

4 → 2CH CHO  (AcO) Pb

8. (d) CH3CHOHCHOHCH3  3 → + ve haloform test

4 (AcO) Pb
CH3CHOHCOCHOHCH3 → 2CH3CHO + CO 2 
→ + ve haloform test

H H
(+)
OH (+ )
9. (a) →
H
OH OH
H H
Here H - migration does not occur because always anti migration takes place hence contraction in ring occurs.

H OH CHO
(+) (+)
–H( + )

→ 
→
OH
H

10. (d) Acid catalyzed dehydration occurs by E1 pathway hence for arrangement stability of carbonium is considered. 3rd can not
produce alkene on acid catalyzed dehydration.
11. (d) Product is optically inactive due to the presence of plane of symmetry.
D H D OH
OR

H OH H H
OH H
D D
12. (b) H OR OH

13. (d) In a & c active methylene compounds are produced while in b acetic acid is produced . Both active methylene compounds
& acetic acid are inactive towards haloform test.
14. (a) At - tert - butoxide can oxidize 2° alcohol in to ketone without affecting double bond jones reagent at 0° C behaves as mild
oxidizing agent but above 25° C it can oxidize multiple bond.
Alcohol, Ether, Epoxide Grignard’s Reagents 255

OCOCH3
|
15. (c) Φ 2C(OH)CH3 + CH3COCl 
→ Φ CCH3 + HCl

The ester formed in this reaction is easily attacked by H+ of HCl

(+ )
OCOCH3 H– O COCH3
| | (+ )
Φ 2 C — CH3 + H ( + ) 
→ Φ 2 — C — CH3 
→ CH3COOH + Φ 2 C CH3
(resonance
stabilized)

(+ )
Φ 2C CH3 + Cl(–) 
→ Φ 2 C CH3
|
Cl

16. (b) Alcohols can be converted in to halides by SOCl2, PCl5, PCl3 & P + X2. In case of SOCl2 configuration of the reactant does
not change after reaction (Retention)
Hence in the given question configuration of reactant & product will be same

4
H
2 1
Pr Cl
‘S’
3CH3

17. (b) CH2N2 can not methylate less acidic hydrogen of aliphatic alcohols
18. (a) Alcohols can be converted in to halides by SOCl2, PCl5, PCl3 & P + X2. In case of SOCl2 configuration of the reactant does
not change after reaction (Retention) while in case of P + Br2 inversion in configuration takes place (see q.n. 16)
19. (b) Anhydrous ZnCl2 + HCl is called Lucas reagent

H
(+) (+) (+)
H rearrangement CH3—C—CH2—CH3
CH3CH(Ph)CHOHCH3 –H O CH3C—CH—CH3
2
Ph
Ph Cl
(–)
Cl
CH3—C—CH2—CH3
Ph

Passage - I

(20 to 26)
 PCC in CH2Cl2 is called sarret reagent. It can oxidize 1° and 2° alcohols in to aldehydes and ketones respectively.
 (D) reacts with Lucas reagent with is 5 minutes. It means it is 2° alcohol
 (D) on dehydration gives (E) which can decolourise Br2 water. Hence E is alkene.
 F gives haloform test hence F must have ‘CH3CO’ linkage.
 G does not react with sarret reagent (PCC in CH2Cl2) hence it is a 3° alcohol.
 (A) reacts with Lucas reagent immediately hence it is 3° alcohol.

256 Problems in Organic Chemistry

Passage - II
(27 to 31)
 (C) does not gives Lucas test under ordinary conditions it indicates that it is primary alcohol.
 (D) gives haloform test hence (D) must have CH3CO linkage.
 (D) should have either 1° or 2° alcoholic group because it is oxidized by PCC.
 E does not give haloform test hence it should be 3° alcohol & (D) should be 2° alcohol.
 (A) on hydrolysis gives alcohol hence it may be an ester.
 Since (B) given are mole & (C) given two moles of CH4 on treatment with CH3MgBr hence (B) contains 2OH groups

Hydrolysis
OHC COOEt OHC COOH + C2H5OH
(A) (B)
LiAH4

LiAlH4
HOCH2 CH2OH + C2H5OH
(C)
OH CH3
(A) CH3MgBr (Excess)
CH3CH C—CH3 +ve haloform test
H2O(+)

(D) OH

O CH3 OH OH
CH3MgBr (Excess)
CH3—C C—CH3 CH3—C C—CH3
H3O(+)
OH CH3 (E) CH3
–ve haloform test
Alcohol, Ether, Epoxide Grignard’s Reagents 257

Passage - III

(32 to 36)
 A decolourises Br2 water but does not react with Pd/CaCO3 hence it may be an alkene.
 B gives blue colour in victor maeyer test thus B must be a 2° alcohol.
 Alkaline solution of (E) on eletrolysis gives ethane thus, (C) should be a carboxylic acid
 (D) does not give victor maeyer test and lucas test hence (D) is not an alcohol.
O OH
(+)
• Hot KMnO4 NaBH4 H , heat

(A) (B)
cold KMnO4
OH(–), Electrolysis
COOH Hot KMnO4
CH2 = CH2 + 2CO2
(E)COOH
OH OH OH
3 2 (+)
(+)
1 (+) OH 1 O
H 1 4 2
(D)
4 5
5 3
(C)

Passage - IV

(37 to 40)
 A contains 3 - active hydrogen’s because it produces 3 moles of CH4 when reacts with Grignard’s reagent
 (B) Gives -ve haloform test but positive Br2 water test it indicates that (B) contains C - C multiple bond.
 B is obtained by the dehydration of A hence (B) must be an alkene.
CH2OH CH2
H2SO4 CH2N2 LiAlH4
CHOH CH CHO CH2OH
CH2OH CHO
(A) (B) (C)

H2O (+) (+)

CH2OH CH2 H
(+)
–H

Cold KMnO4 CH2—CH—CHO LiAlH4 CH2—CH—CH2

(B)
OH OH (D) OH OH OH (A)

AcCH2—O cold AcCH2I + OH

41. (d) HI

+ve haloform test

O—CH2 cold HI ICH2 + phenol
COCH2I COCH2I

+ve haloform test

258 Problems in Organic Chemistry

O—CH2 cold HI ICH2 + phenol

Ac Ac

+ve haloform test

Cl (+)
OEt
Ag (+) EtONa
42. (c) –AgCl, SN1 Hydride
shift

43. (a) Boiling point ∝ surface area

OH
I Mg MgI COCl2
44. (d) THF H3O(+)

excess

45. (b) OH adjacent to NO2 is less acidic due to intramolecular H–bonding.

OH NO2 OH NO2
haloform and
Ac acidification HO2C
COCHI2 COOH

OH OH
OH NO2

3 moles of base
NaOOC COONa

ONa

46. (c) Orange (H2CrO4) to Blue - Green

47. (d) H2CrO4 in acetone in called jones reagent, thus, it is jones oxidation
48. (c) In presence of DMSO, SN2 reaction occurs
Br H
KOH,DMSO DMSO
D D D O
H OH
H H H
49. (d)
50. (d) However LiAlH4 does not reduce C = C bond but LiAlH4 reduces C = C bond when it is present in conjugation with phenyl
group.

LiAH4
CH = CH—CHO CH2—CH2—CH2OH
H2/ Ni

51. (b) Because Me3CO(-) is stronger base than Me2CHO(-). So Me2CHO(-) can not remove H(+) from Me3COH

(+)
52. (c) OH Cu, 300°C
OH Oxidation
OH
CH2MgBrH3O
(A)
(A) (B) (C)
Alcohol, Ether, Epoxide Grignard’s Reagents 259

53. (b) CH3 O CH3 OMgBr (+) CH3 OH

CH3MgBr H3O
C—CH2 C—CH2CH3 C—CH2CH3
SN2
CH3 CH3 CH3

Cu,300°C
CH3—C = CH—CH3
CH3
(+)
H , CH3OH
1
(A)
SN OCH3
(+)
OH
CH3MgBr, H3O
54. (d) 2 (B)
SN

O OH
C2H5SH, MeOH
2 (C)
SN

H5C2S OH
Since B & C are tertiary alcohols hence they will not exhibit victor maeyer test
55. (c) Because MnO2 oxidises allylic alcohol.
56. (d)
O O O
OH OTs Me
(–)
TsCl, Pyridine CH3O
57. (b) –HCl 2 + OTs
(–)

SN
(A) Me (B) Me (C) OCH3
From (A) to (B) configuration does not change. From (B) to (C) inversion in configuration occurs because reaction occurs
via SN2 pathway.
58. (b) This reaction is an example of SN2 reaction. In first substrate steric hindrance is more, thus, rate of reaction will be less
59. (d) Migrating aptitude of phenyl group is greater than p–Br–C6H4–
OH OH OH
H
(+) (+)

CH3 Br CH3 Br

OH
(+)
(d) –H
(+)
CH3 Br

H C 2 H5 C 2 H5
| | |
60. (d) C2 H5 — O.......H — O.......H — O..... ( Before addition of cyclo hexane)

C2H5OH C2H5OH (After addition of cyclo hexane)

It is an example of non ideal solution with positive deviation. In ethanol hydrogen bonds are present when cyclo hexane is
mixed in it H–bonds get broken down for this heat is absorbed.
260 Problems in Organic Chemistry

Boiling point ∝ H - Bonding

Hence due to breaking of H - bonds, heat is absorbed & b.p. decreases

O O
|| ||
CH3MgBr
CH3MgBr
61. (c) H5C2 O — C OC2 H5 → CH3 — CO 2 H5  → Acetone(B)

62. (a) In each case oxygen contains two lone pairs of electrons thus, due to lp–lp repulsion contraction in bond angle takes place
. This contraction in angle will be maximum in water & minimum in di methyl ether because size of methyl group is larger
than hydrogen

lone pair lone pair

repulsion
•• ••
O

Group Group

O O
63. (b) O
O O
Oxetane Oxolane Oxane Dioxane

(+)
O O–H CH2OH CH2OH
64. (a)
(+)
H H2O
(+)
–H(+)

OH

(+)
(+)
65. (c) H

O (+) OH
OH

(+)
–H

OH

(+)
O OH OH OH
|| (+)
66. (b) R — C— O — H + H ( + ) 
1* 1*

 ROH
 R—C—OH 
 R—C—OH  ROH
 R—C—OH2
1
O(+) O—R
1 * *
R H
O OH
(+) (+)
–H * 1 * 1 –H
R—C—OR 
 R—C—OR
(+)

67. (b) OH
HI (Excess)
I HI I
–I2

OH I
(Frank land reaction) Zn, Ether
Alcohol, Ether, Epoxide Grignard’s Reagents 261

(+) –H2O
H2O
68. (a) H (+) H
O O OH OH
(+)
OMe MeO OH2 MeO OH
OMe
unstable

CH2OH –MeOH
CHO

(+) H
COOCH3 COO (+)
O
CO
CH3
Ph Ph Ph Ph Ph Ph
(+)
H –CH3OH ArSE
69. (c)

Ph Ph Ph Ph

•• (+)
O—Ph O—Ph
70. (c) •• ••
(–)

Due to double bond character in C - O bond this ether does not react with HI

71. (b) HCHO + HCl 

→ CH 2OHCl
(+ )
→ ZnCl3(–) + CH 2OH
CH 2OHCl + ZnCl2 
(+)
(+) CH2OH (+) CH2
H C6H 6
+ CH2OH Ph2CH2
A B

H
(+)
O (+)
O •• OH OH
••

H2O
72. (b) CH—CH2
H
CH—CH2 CH—CH2

CH3
73. (a) (+) (+)
H –H
OH (+)
(+)
CH3 CH3 CH3
74. (a)
75. (c) Reaction occurs via SN1 pathway because PhCH2+ is formed.
76. (c) Solvation of grignard’s reagent takes place by ether
77. (a) Base neutralizes HCl which is produced during acylation and avoid the formation of alkyl halide

Me3COH + CH3COCl 
→ Me3COCOCH3
(+ ) (+ )
–CH COOH Cl(–)
Me3COH + H ( + ) (from HCl) 
→ Me3C — OCOCH3 
3
→(CH3 )3 C → Me3CCl
|
H
Hence to avoid the formation of alkyl halide base should be added to neutralized acid (HCl)
(+)
78. (a) In acidic medium OH (alcoholic group) converts itself into O H 2 & release water.
79. (a) Breaking of C – H or C – D bond is not rate determining steps. In slowest step breaking of C– O bond takes place
262 Problems in Organic Chemistry

80. (a) As branching increases, surface area of hydrocarbon part (hydrophobic part)decreases so solubility increases
81. (b) Molecules of cyclohexanol are more closely packed in comparison to that of hexan–1–ol

•• (+)
O—H O—H
82. (d) •• ••
(–)

Due to resonance bond length of C– O bond decreases thus dipole moment of phenol is found to be lower than that of cyclo
hexanol.
83. (a) Due to resonance it acquires C = O bond hence, no need to show pinacole-pinacolone rearrangement

•• (+)
OH OH OH OH
••

(–)

More than one may correct:-

1. a, d
2. c, d (a) can not show haloform test as it is 30 alcohol while is (b) CH3CO linkage is absent.
3. b, d
4. a, b (c) & (d) are not vicinal diols so these alcohols can not show oxidation with IO4(-)
5. a, c, d
6. a, b
7. a, b, d CrO3 can oxidize 1° and 2° alcohols
8. a, c, d
9. a, b
10. a, b, d Except (c) rest all give unstable carbocation

LEVEL -II

1.
CH2OH More acidic hydrogen

CHOH less acidic (2°alc)

CH2OH More acidic hydrogen

Since 44-8 litre CH4 is liberated thus 2 active hydrogens are removed by grignard’s reagent. Hence (b) option is correct.
2. (a) a, b, c

3. (b)
(TS)2
(TS)3
(TS)1

P.E

(+) (+)
ROH2 R alkene

Thus ∆G*2 > ∆G*3 > ∆G1*

Alcohol, Ether, Epoxide Grignard’s Reagents 263

4. (b) b, c, d
OH CH3
O CH3 OH

+
Me Mg Br

(+) →
H3O
Et Et Et

5. (b, c, d)

O
R OH
Rmgx

H O
→
2 [X]

(+)
H
R OH  →
D

[X] can show geometrical isomerism as : -

Because [X] contains plane of symmetry hence it can not show optical isomerism
6. (a) In 1st reaction propyl shift occurs.

CH3 CH3
(+) (+)
H CH3CH2CH2–C–CH2
CH3CH2CH2 —C—CH2OH
CH3 CH3

(+) (+) CH3 (+)

CH3 –H C—CH2CH2CH3
C=CH—CH2CH3
CH3
CH3

(+)
CH2OH CH2
(+) (+)
7. (d) H –H
–H2O
(+)
(1)

OH OH OH OH
(+) (+) (+)
H (+) –H
OH –H2O OH OH OH
OH (3)

CH2OH OH OH
(+) (+)
H –H

(1) (+) (+)

In 4th Case anti elimination is not possible hence here benzene does not form?
264 Problems in Organic Chemistry

(+)
(+)
H
8. (b) –H2O ••
OH
OH OH + ••

(+)
–H

+
O O
H
(+) *
D
9. (d) (1) CH3 —=
CH CH 2 → CH3 — CH — CH 2 D
H 2O |
OH
(opticallyactive)(d & 1 isomers)

(+)
H
(2) CH3 —=
CH CH 2 → CH3 —CH — CH3
D 2O |
OD
Optically inactive (Only one product)

D( + ) *
(3) CH=
3CH CH 2 → CH 2 —CH — CH 2 D
D 2O |
OD
(Opticallyactive) (d & 1 isomers)

H( + )
(4) CH=
3CH CH 2 → CH3 — CH — CH3
H 2O |
OH
(Optically inactive)

CH3 CH3 CH3

(+)
10. (a) i-pr CH2NH2
NaNO2 + HCl
i-pr CH2 i-pr CH2 i–Pr
(+)

i-pr i-pr
CH3
H2O
i-pr CH2 i–Pr
optically active
OH

(+)
CH2I CH2 OH O

OH Ag
(+) OH
11. (b)
 Aldehyde & Ketone
9
Main Features
Reaction Chart for Aldehyde & Ketone
Preparation Properties
266 Problems in Organic Chemistry

LEVEL - I

Multiple Choice Questions

NaBH H+
1. (A) 
Ether
4 → (B) 
D
→ no reaction, Here (A) is :-
|
↓
Blue colour in victor
Maeyer test
O

CO2C2H5
(a) CHO (b) (c) (d)

O
2. Choose the answer that has the following compounds located correctly in the separation scheme. Propanone - A , Methanol - B,
AcOH – C.
Pass through NaHSO
A
+
B +
C → ppt + Solution 
3 → ppt + solution
Ca(OH)2 (3)
vapours (1)

ppt (1) ppt (2) solution (3)
(a) A B C
(b) B C A
(c) C B A
(d) C A B

LiAH / Ether
3. 
4
(+) →(X), (X) wiil are:-
COPh H

OH

CH—Ph
CHOHPh
(a) (b) O

Ph
CHOHPh

(c) O (d) OH
4. Cyclo petntanone can be converted in to 5 – Hydroxy pentanoic acid by:-
(a) hot KMnO4 (b) SeO2, H3O+ (c) NH2OH/H3O+ (d) CH3CO3H & H3O+

5. OHC COCH3 OHC CH2CH3

It can be performed by:-

(a) glycol / H+, Zn / Hg + HCl, H3O+ (b) N2H4 / OH– followed by H+
(c) OH / ∆ , H2 / Ni
–
(d) (a) & (c)
6. An organic compound reacts with Tollen’s reagent but undergoes Baeyer villager oxidation. The compound is:-
O
(a) C2H – CH2 – COCH3 (b)

(c) CH3 – CHO (d) CH3COCH3

Aldehyde & Ketone 267

7. Consider the following processes

Process - I B2H6 / H2O2 / OH–, Al (OEt)3
Process - II Pd - C / H2, Hot KMnO4, CH3OH / H+
Process - III HgSO4 / H+, CH3COOH / O3
Propyne can be converted in to methyl ethanoate by using the process:-
(a) I, II, III (b) II, III (c) I, III (d) II

8. Identify the reaction which is not the preparation of ketone

Gilaman
(a)
CH3COCl → Product
reagent

(b) Hot KMnO 4 Product

→

Al(OEt)3 CH3MgBr(excess)
(c)
CH3CHO →  (+) →
H3O

(d) End product of all reactions is ketone

9. The reaction in which hydride shift does not occur is:-

H O( + ) OH OH (–)
(a) 
3
→ (b)
ΦCHO → ΦCH 2 IG + ΦCO 2(–)

H( + )
(c) → (d) None
D
OH
Ca(OH)
10. CH3CHO + HCHO 2
→ Products of this reaction will be:-
D
(1 : 4)

(a) (CH2OH)3CCOO– + (CH2OH)3CCH2OH (b) (CH2OH)4C + HCOO–

(c) CH3COO– + CH3OH (d) (CH2OH)3CCHO
11. Which reaction is not correct?
(–)
OH
(a)
CHO — CHO → HOCH 2 — COO(–)
(–)
(b) OH
PhCOCHO → PhCHOCOO(–)
n
NaOH Sol
(c) 2Me2 CHCHO  → Me2 CHCO 2(–) + Me2 CHCH 2 OH
200°C
(d) All are correct

12.

(1) & (2) are respectively:-

(a) CH2 = C = O & Br2 in CCl4 (b) H2|Pd|C & CHBr3 + KOH
(c) Na|NH3 & CHBr3 + KOH (d) CH2N2 & HBr (2 moles)
268 Problems in Organic Chemistry

(+)
(i) ΝΗ3/Η
(A)
(i) CH3MgBr/H3O(+)

(i) Φ3P = CH2

13. Cyclopentanone (+)
(B), which statement is correct :-
(ii) H3O
(+)
LiAIH4/ Ether/H
(C)
(a) (A) is ketone however (B) & (C) are alcohols
(b) (B) &(C) gives blue colour however (A) does not produce any colour in victor maeyer test
(c) (B) & (C) are same compounds and give blue colour in victor Maeyer test however (A) is primary amine
(d) (A), (B) & (C) all are identical
14. Arrange the following four compounds in order of their rate of addition with NaCN / H(+)
CHO CHO
CHO CHO
MeO
NO2
OMe
1 2 3 4

Correct order of rate of addition with HCN is:-

(a) 2 > 1 > 3 > 4 (b) 1 > 2 > 3 > 4 (c) 2 > 3 > 1 > 4 (d) 3 > 4 > 1 > 2
15. Cyclo pentene is treated with cold KMnO4 followed by lead tetra acetate to give (A) when (A) is heated with Ba(OH)2 the
product obtained will be:-
(–)
COO OH
(a) (b) (–) (c) (d)
CH2OH COO CHO

16. HCHO can be separated from the mixture of HCHO, CH3COCH3 & CH3CHO by treating the mixture with;-
(a) NaHSO3 (b) 2, 4 DNP (c) Semi carbazide (d) [Ag (NH3)2] (+)
17. Pyroligneous acid does not contain
(a) HCHO (b) CH3CHO
(c) CH3CH2OH (d) All of these are absent in pyroligneous acid
18. Which will not show reducing property with tollens & fehling solution?
I - Hemi acetal of acetaldehyde II - acetal of formaldehyde
III - Hemi ketal of acetone IV - formic acid
(a) III & II (b) II, III & IV (c) I, II, III & IV (d) I & II
19. Which base catalysed reaction is least likely to occur?

O
EtONa
(a) + 
→
D

O
EtONa
(b) + 
→
D

O CO2Et
EtONa
(c) CH3COCH2COOC2H5 + 
→ |
D Ac – C = CMe2

(d) (a) & (b)

Aldehyde & Ketone 269

20. Which will not exhibit cannizaro reaction?

CHO CHO

(a) Ph – COCHO (b)

(c) (d) All of these can show cannizaro reaction

21. Which among the following is called Tollen’s reaction?

OH (–)
(a) (CH3 )2 CHCHO + HCHO 
→ Me2 C — CH 2 OH + HCOONa
1 : 2 |
CH2OH

CH3CHO + [Ag(NH3 )2 ]( + ) OH (–) 

(b) → Other + Ag ↓ + CH3COO(–)
Product

OH COOH

OH (–)
(c) 
→
H 2O

O O

(d) CH ≡ CH + Ag 2 O 
→ H 2 O + AgC ≡ CAg

Passage - I

An organic compound (A) [C8H8O] gives (B) & (C) on reaction with NH2OH / HCl. (B) & (C) give (D) & ( E) on reaction with
sulphuric acid with formula (C8H9NO). When (D) is boiled with alcoholic KOH an oily compound (F) separates out. (F) Rapidly
reacts with acetyl chloride to reproduce (D). (E) on boiling with KOH followed by acidification gives a white solid (G). If benzoic
acid is produced by the oxidation of (A) then:-
Answer the questions from 22 to 27.
22. (B) & (C) is the mixture of:-
(a) Syn and anti PhCH2CH = NOH (b) Syn and anti Ph(CH3)C = NOH
C3H7
(c) Syn and anti NOH (d) both (a) & (b)
C4H9
23. Compound (D) is:-
(a) CH3CONHPh (b) PhCONHCH3 (c) PhCH2NHCHO (d) PhCH2NHCH3
24. Compound (F) is an :-
(a) aliphatic amine (b) aromatic amine (c) aliphatic aldehyde (d) aliphatic ketone
25. Compound (A) when subjected to heat with aq KOH another compound (H) is formed. Which is correct about the newly formed
compound (H) :-
(a) (H) can show addition with sodium bi sulphite (b) (H) can decolourise bromine water
(c) (H) can not exhibit haloform test (d) All of these
26. Compound (G) is:-
(a) Benzoic acid (b) Acetic acid (c) Phenyl acetic acid (d) None of these
270 Problems in Organic Chemistry

27. Compound (H) on ozonolysis can produce:-

(a) Benzophenone (b) Benzoic anhydride (c) Acetic anhydride (d) none of these

Passage - II

For Aldol / Ketol condensation aldehyde and Ketone must contain a – H – atom. This reaction is base catalysed. Base removes
acidic a – H – atom and forms carbanion. This carbanion produces aldol / Ketol when attacks on other aldehyde or ketone on the
other hand cannizaro reaction is exhibited by those aldehydes which do not contain a – H – atom.
Answer the question from 28 to 33.

28. The compound containing most acidic a – H – atom is:-

(a) AcOH (b) CH3NO2 (c) CH3SO3H (d) CH3CHO

29. Which will not show aldol as well as connizaro reaction?

O CH3
O
(a) (b) PhCOCHO (c) H (d) All of these
Me
H

30. The compound which can undergo cross aldol with HCHO is:-

NO2

(a) PhCOCHO (b) O (c) CH3NO2 (d) None of these

31. Intra molecular aldol / ketol is not possible in:-

(a) H5C2OOCCOCOCOOC2H5 (b) PhCOCHO
(c) CH3COCHO (d) All of these can not show intra molecular aldol

OH ( − ) LAH
32. (A) → (P) → (Q)

D

If Q does not decolourise bromine water then A would be:-

O
(a) PhCH2CHO (c) CH3COCHO (c) (d) CH3NO2

OH ( − )
33. CH3CHDCHO 
→ Product, The product of this reaction would be:-

D OH H
| | |
(a)
CH3 —C — CH — CHDCH3 (b) CH3 — C — CHOHCHDCHO
| |
CHO CHO

CHO
CH3 |
(c) C = CHCHDCHO (d) CH3 —CH — CHOD CHD CHO
OHC
Aldehyde & Ketone 271

Passage - III

An organic compound (A) is highly volatile. (A) On reaction with HI gives two products (B) & (C). (C) gives red colour in victor
Maeyer test but when (C) is heated with H+ followed by dilute sulphuric acid, it gives (D) which immediately reacts with Anhydrous
ZnCl2 + HCl. (B) on treatment with C2H5OH + KOH followed by O3 / Me2S gives (E). (E) can gives haloform test. (E) When heated
with NaOH gives (F). (F) Also gives haloform test & can decolourise Br2 water.
Answer the question form 34 to 39.
34. Compound (A) is:-

O O–CH3
(a) (b) O (c) (d) O—CH2—Ph

35. Compound (C) is:-

OH OH
(a) (b)
(c) PhCH2OH (d) OH

36. Compound (D) is:-

OH
(a) (b) OH (c) (d)
Ph — C — CH3
|
OH OH
37. Compound (E) is:-

O CHO CHO COCH3

(a) (b) (c) (d)
CHO CHO
CHO
38. Compound (F) is:-
O
CHO
Ac CHO
(a) (b) (c) (d)

39. Compound (B) is:-

CH3 I
I I
(a) I (b) (c) (d)

Passage - IV

(A) (B)
HO CH2OH MeO CH2OH (V)

OH OH
(D) (C)
MeO CH–CHOH MeO CH–CHCO2Et
Me Me
Answer the questions from 40 to 43
40. A would be:-
(–)
(a) CH3OH / H+ (b) CH3OH / Al2O3 (c)
O H/ MeCl (d) All of these
272 Problems in Organic Chemistry

41. B would be: -

O
||
(a) CH3 – CH2COOH (b) CH3 — C CH 2 OH
(c) PCl5, Mg / Ether (d) MnO2
42. Compound (C) is:-
(a) H+ (b) CH3CH2COOEt/OH–

(c) H3O+ (d) CH3 — C— CO 2 Et / OH −

||
O
43. Compound (D) is: -
(a) NaBH4 / Et2O / H+ (b) LiAlH4 / Et2O / H+ (c) DlBAL – H at – 78° C (d) (b) & (c)
44. An organic compound (A) can react with tollen’s to give (B) which on heating gives (C). Compound (C) does not give haloform
test. (A) Would be:-
CHO
(a) CH3COCH2CHO (b) CH2 (c) Both (a) & (b) (d) None
CHO
O
(i) Glycol (1mole)/H (+)
45.  → (A) Product, (A) will be; –
(ii) NaBD 4 / H 2O
(iii) H3O( + )
O
OD O OH O
D

(a) (b) (c) (d)

O OD O OH D
46. Identify the compound for which rate of hydration is least
O

(a) (b) O (c) MeCOCOCOMe (d) MeCHFCOCHFMe

(i) dil H 2SO 4

47.  → (A)
(ii) Al2O3 / D
O O
Which statement is not correct about (A)
(a) It will react with Benedict’s solution and 2, 4 – D.N.P. (b) It will decolourise Br2 water.
(c) It will react with Br2 water but not with [Ag(NH3)2](+) (d) It will not show iodoform test
48. Two unknowns, X & Y both having molecular formula C4H8O, give the following results with four chemical tests.
Br2 Water Na metal Chromic acid Lucas reagent
X decolourise Bubbles Orange to Green No reaction
Y no reaction no reaction no reaction no reaction
X & Y are:-
OH
(a) OH & CHO (b) & CHO

OH

(c) & CH3CH2COCH3 (d)

OH & CH3CH2COCH3
Aldehyde & Ketone 273

49. An organic compound (A) on hydrolysis by aq KOH gives another compound B. B gives cannizaro reaction with NaOH. What
is (A) if (A) can exhibit haloform test?
(a) PhCCl2CHO (b) CHCl2CHO (c) CH3CCl2CHO (d) CH3COCHCl2
50. Acetaldehyde can be converted in to an optically active compound
(a) By treating it with LiAlH4/Ether/H+ (b) By treating it with (i) KCN (ii) H3O+
(c) By heating it with aq NaOH (d) By treating it with OH(–) / D followed by H2 / Ni
51. By the help of formaldehyde we can not prepare
(a) Urotropin (b) Bakelite (c) Farmose (d) Phorone
52. In which of the following cannizaro reaction products are not proposed correctly.
OH (–)
(a) HCHO + PhCHO 
→ HCOO– + PhCOO– + CH3OH + PhCH2OH
(–)
CHO CH2OH CO2
(–)
OH (–)
(b)
PhCHO + PhCH2OH + + PhCO2 +

OMe OMe OMe

(c) CHO (–)

OH COO( −)
| 
→ |
CHO CH2OH

(−)
OH
(d) PhCOCHO  → PhCHOCOO(–)

H O18
53. CH3COCH3 →
2
(+) P
trace of H

Product P of this reaction would be:-

(a) No chemical reaction takes place but acetone dissolves in water due to H – Bonding
(b) CH3CO18CH3

OH
|
(c)
CH3 —C— CH3
|
OH
18

(d) Reaction occurs & the end product P is CH3COCH3

54. The order of acidity of the compounds A–C is:-
O O O
NO2 CO2Et
A B C
(a) A > C > B (b) C > B > A (c) B > C > A (d) B > A > C
55. Out of A, B & C the product which will not show Cannizaro reaction with NaOH is:-

(a) CH ≡ CH 
SeO aq KOH
2 →(A) (b) (B)
CHCl2
O
(c) Ethene 
3 →(C) (d) None of these
H 2O
274 Problems in Organic Chemistry

OH
(i) N 2O 4 / CHCl3
CH—Φ 
n →(P)
56. (ii) Zn/Hg Conc HCl, D

OH
Product P of this reaction will be:-
OH
CH—Φ
(a) (b)

CH2—Φ
CH2—Φ
(c) (d)
Cl

OD
CH2OH CHD
57.

This conversion can be performed by:-

(a) MnO2, LiAlH4 / D2O (b) N2O4 / CHCl3, LiAlH4 / D2O
(c) MnO2, NaBD4 / H2O (d) N2O4 / CHCl3, NaBD4 / D2O

58. OH (1) Mg/ether PCC

+ HI (excess) [X] [Y] [Z]
OH (2) HCHO
(3) H3O(+)

(a) [Z] can show cannizaro reaction (b) [X] is a di iodide

(c) [Z] can show self aldol condensation (d) [Z] contains two CHO group.

=
(i) CH CHCO Et / D
59. 
2 2 → [X]
(ii) O3 , CH3 –S–CH3
(iii) OH (–)

Product [X] of this reaction would be:-

CO2Et OH
CH2OH
(a) (b)
(–)
COO CO 2 Et O

(c) (d) None

60. The reaction in which disproportionation takes place is:-

Na OH (–)
(a) (CH3)3CBr → (b) CH3CHO + PhCHO 
→
Ether
(c) Ketol condensation (d) (a) & (b)
Aldehyde & Ketone 275

61. In a cannizaro reaction the intermediate which is the best hydride ion donor is:-

H H
| |
p — NO 2 — C6 H 4 — C— O(–)
(a) (b) p — OCH3 — C6 H 4 — C — O
(–)
| |
O(–) O(–)

(–) OH
O (–)
CH (–) O—C—H
O
(c)
NH2 (d)

O2N NO2
NH2 NO2

62. Which is wrong about cannizaro reaction:-

(a) Dianion can form as intermediate
(b) It follows 3rd as well as 4th order kinetics.
(c) It requires concn base and hydride ion transfer occurs in it.
(d) Attack of base (OH–) is the rate determining step.
63. Select the correct order of reactivity of following compound towards RMgX
(a) CH3COCH3 > CH3CH2CHO
(b) CH3CONH2 > CH3COCl

(c) CH3CO SO3H  > CH3CO OCH3

(d) CH3COOCH3 > CH3CON(CH3)2

+ CH3COCH = CH 2 
NaOH
64. → (P)
D
O

Here P is:-
OH
CH = CH2
C
CH3
(a) (b) (c) (d)
CHCOCH=CH2 O O O

65. Which among the following will not show cross aldol with formaldehyde?
(a) Glyoxal (b) nitro methane (c) cyclopentadiene (d) 3–oxo butanal
66. Which will have least pKa?
(a) Di chloro acetaldehyde (b) Tri fluro acetaldehyde (c) Fluro acetaldehyde (d) Acetaldehyde
67. Match the following
Compound Properties
(A) Methyl cyclo hexanol (1) disproportionation by caustic soda
(B) Glyoxal (2) Haloform as well as tollen’s test
(C) 2- oxo propanal (3) gives alkene with Ag/ 673K
(D) Nitro methane (4) negative bendict’s test but gives
aldol with HCHO
(a) A-3 B-4 C-2 D-1 (b) A-3 B-1 C-2 D-4 (c) A-4 B-3 C-2 D-1 (d) A-4 B-3 C-1 D-2
276 Problems in Organic Chemistry

68. Match the following

Compound Tests
(A) Di chloro butan-2-one (1) –ve haloform & fehling tests but +ve 2,4 DNP test
(B) Formic acid (2) +ve haloform but -ve fehling test
(C) Di ethyl ketone (3) gives Hg on reaction with corrosive sublimate
(a) A–3 B–1 C–2 (b) A–3 B–2 C–1 (c) A–1 B–3 C–2 (d) A–2 B–3 C–1

69.

Product of this reaction would be:-

(a) (b) (c) (d)

OH
(i) NH OH
X  →Y
heated with silver metal 2
70. (ii) H3PO 4

Compound Y is:-
(a) An imine (b) cyclic amide
(c) cyclic secondary amine containing one C=C bond (d) alkane

Passage - V

Answer the questions 71 & 72 from the following reaction scheme.

(i) C H / D
(A) ← 2 4
(+)
NaOH

→(B)
(ii)H /D D
O O
71. Compound (A) is.
Et Et Et Et
(a) (b) (c) (d)
OH OH OH OH
72. Compound (B) is. Et

(a) (b) (c) (d)

COOD
73. CH3CO CH CH3 ∆ [X]
CF COOH
[Y] 3

Identify wrong statement.

(a) Both [X] & [Y] are optically active (b) [Y] is an ester
(c) [X] is an optically active ketone (d) [Y ] is optically inactive ester

O
74.

This conversion can be performed by:-

(a) (i) Ph3PCH2, (ii) LiNH2 with CH3OH (b) (i) LAH (ii) 1 Mol H2 / Ni
(c) (i) HCHO / OH(–), (ii) Red P + HI (d) (i) LAH, (ii) H+ / heat , (iii) NaNH2 with CH3OH
Aldehyde & Ketone 277

75. The compound which will not show geometrical isomerism after acidification:-
(a) Ph(CH3)CO (b) Ph(CH3)CNH (c) CH3CHO (d) CH3CHS
76. The compound which can show geometrical isomerism after acidification is :-
CH3 O
Et
(a) O (b) (c) CH—C—(i–Pr) (d)
S CH3 NH
77. Which is correct for following reactions?

O OH
K K

1→
← 
3→
← CN
K2 K4
O
(a) K1 > K3 (b) K3 > K1 (c) K3 = K1 (d) K4 = K2

(i) LiAlH / Ether / H ( + )

78. PhCH = CH—CHO  4 → (A)
(ii)PCC in CH Cl (iii) OH 2 2
(–)
OH (B)

Here (A) and (B) are:-

(a) Same, PhCH = CH — CH2OH + PhCH = CHCO2 anion
COH OH
| |
(b) Same, Ph — CH 2 — CH — CH — CH 2 CH 2 Ph

CHO
|
(c) Different, A is PhCH 2 —CHCH — (CH 2 )2 Φ & B is ΦCH = CHCH2OH + ΦCH = CHCO2 anion
|
OH

(d) Different, B is ΦCH 2 — CH — CH — (CH 2 )2 Φ & A is ΦCH = CHCH2OH + ΦCH = CHCO2–

| |
CHO OH

OH (–)
79. CH3 — CH = CH — CHO 
D

→ Product, Product of this reaction is:-
(a) CH3CH2 = CHCOO– & CH3CH = CHCH2OH
CH3 — CH 2 — C = CH — CH = CH — CH3
(b)
|
CHO
(c) CH3 — CH = CH — CH = CH — CH = CH — CHO
(d) Reaction is not possible
80. Assertion - Ketones have slightly higher bp than the isomeric aldehydes
Reason - Presence of two + I group in ketone makes C = O bond polar
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
81. Assertion-Neo butyl alcohol can show Haloform test
Reason- Halogens are weak oxidizing agents & can not oxidize tert- alcoholic group
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
278 Problems in Organic Chemistry

82. Assertion- Tri chloro ethanal can not exhibit cannizaro reaction
Reason -It undergoes haloform test
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
83. Assertion- Tri chloro ethanal can show hydration reaction & can form gem di ol
Reason -strong -I effect of chlorine atoms makes carbon of carbonyl group more electropositive
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
84. Assertion- formic acid can show reducing properties
Reason - It is stronger carboxylic acid than other non substituted aliphatic carboxylic acid
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true

O O O O
O / H O / Zn
85. Assertion:- 
3 2 → +
Boil
(A)
H (B)
H
Along with (A) & (B) CH3COCHO also forms
Reason: - A & B on reaction with Zn / H2O undergo rearrangement to given CH3COCHO
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
86. Assertion: - Cyclo propanone undergo addition with HCN more easily in comparision to that of acetone
Reason: - Cyclo propanone contains strained ring.
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
O OH
87. Assertion:- CH3—C—CH 2 —CH3 CH3 —C = CH—CH3
(A)

OH
CH2= C—CH2—CH3
(B)
Out of A & B, (B) is less favourable tautomeric form than (A).
Reason: - A is more substituted alkene & hence more stable
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
Aldehyde & Ketone 279

OH
O O
(+)
H
88. Assertion:- → +
heat

OH (A) (B)
OH
Out of A & B, B does not form.
Reason: - H+ attacks on C = O and not on OH group because in C = O oxygen acquires –ve charge due to resonance.
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
O
∆
89. Assertion: - [X], [X] can not release CO2 on reaction with NaH CO3
COOH
Reason: - [X] does not contain COOH group
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
90. Assertion: - Cl2C(OH)2 is unstable and produce phosgine along with H2O but CCl3CH(OH)2 does not loose water.
Reason: - In CCl3CH(OH)2 intera-molecular H - bonding presents.
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
LiAlH
91. Assertion: - CH2 = CH — CHO 
4→
(A)
LiAlH 4
PhCH = CH — CHO  → (B)
(A) gives Br2 water test but (B) does not.
Reason: - (B) does not contains CHO group.
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
92. Assertion: - Zn/Hg/HCl converts Acetone to propane but Mg/Hg/H2O can not convert acetone to propane.
Reason: - Mg/Hg/H2O converts acetone to pinacole
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
93. Assertion: - R2C(OH)(OMe) easily looses methyl alcohol along with ketone but R2C(OMe)does
not loose di methyl ether along with R2CO
Reason: - Di methyl ether is more volatile than MeOH
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
280 Problems in Organic Chemistry

Answer key

1. (c) 2. (d) 3. (c) 4. (d) 5. (a) 6. (a) 7. (b) 8. (c) 9. (c) 10. (b)
11. (d) 12. (b) 13. (b) 14. (c) 15. (d) 16. (a) 17. (d) 18. (a) 19. (a) 20. (d)
21. (a) 22. (b) 23. (a) 24. (b) 25. (d) 26. (a) 27. (b) 28. (b) 29. (a) 30. (c)
31. (d) 32. (a) 33. (a) 34. (b) 35. (a) 36. (b) 37. (d) 38. (b) 39. (a) 40. (c)
41. (d) 42. (b) 43. (b) 44. (b) 45. (c) 46. (b) 47. (c) 48. (d) 49. (b) 50. (b)
51. (d) 52. (a) 53. (c) 54. (c) 55. (c) 56. (d) 57. (d) 58. (a) 59. (a) 60. (a)
61. (c) 62. (d) 63. (c) 64. (c) 65. (a) 66. (a) 67. (b) 68. (d) 69. (b) 70. (b)
71. (b) 72. (b) 73. (d) 74. (a) 75. (b) 76. (b) 77. (a) 78. (c) 79. (c) 80. (a)
81. (d) 82. (a) 83. (b) 84. (b) 85. (c) 86. (b) 87. (a) 88. (a) 89. (a) 90. (a)
91. (b) 92. (a) 93. (b)

Multiple Choice Questions (More Than One May Correct)

1. Which among the following can show Tollen’s test?

OH
| OCH 3
(a) CH3CHO (b) PhCHO (c) CH3 — CH — F (d)
CH3—CH
OH
2. Which among the following can’t show Fehling test?

(a)
CH3 —CH — OCH3 (b) CH3COCH3 (c) PhCHO (d) CHO
|
OH
3. CH3CH = N NH2 is called acetaldehyde hydrazone. Which is not true about it?
(a) It can produce methane on reaction with conc. H2SO4.
(b) In can not show geometrical isomerism
(c) This compound can show geometrical isomerism after protonation.
(d) On heating with NaOH it will produce ethane
4. In the context of following road map which statement is correct?
O
CF3CO3H LiAlH4
(A) (B)
D2O
(X) Ph3PCH 2
(C)
(a) Reaction (X) to (A) is Baeyer villiger oxidation (b) Reaction (X) (C) is tollen’s reaction
OH O
D while (C) is O
(c) (B) is (d) while (B) is
O O
5. Which of the following compound is not required in the preparation of urotropin?
(a) HCHO (b) CH3CHO (c) NH3 (d) CH3NH2
6. In which of the following case plastic is not formed.
H( + ) high P & T
(a) n(HCHO + PhOH) → (b) n(CH2 = CHCl) 
→
very dilute alkali
(d) n HCHO 
→
dry HCl gas
(c) CH3COCH3 →
Aldehyde & Ketone 281

7. Which among the following reagent are required for the transformation of ethene in to CH4?
(a) O3 / H2O / Zn / ∆ (b) Zn / Hg + HCl
(c) H2 / Ni (d) NaOH / CaO / ∆
Cr O 2 − PCC
CH 2 OH  OH (–)
H (+)
8. (B) ← → (A) → (D) → (E)
2 7
|
CH2OH
Select the correct statement:-
(a) (D) is CH2OH – COO(–) (b) (B) & (E) are same compounds
(c) (A) is glyoxal (d) (E) on oxidation gives (B)
9. LiAlH4 can reduce:-

O O O
|| ||
(a) (b) CH3 — C— CH 2 — C— CH3
O
O
||
(c) CH2 = CH — NCH3 (d) CH3 — C— OCH3

Answer Key

1. (a), (b), (c), (d) 2. (b), (c) 3. (a), (b) 4. (a), (d) 5. (b), (d)

6. (c), (d) 7. (a), (b) 8. (a), (c), (d) 9. (a), (b), (d)

LEVEL - II

Comprehensions

Comprehension - I

1. Which hydrogen is most acidic?

(a) 1 (b) 2 (c) 3 (d) 4
2. Arrange these hydrogens in decreasing order of pKa values
3. Write the mechanism of the proposed reaction and identify the product formed in it.
282 Problems in Organic Chemistry

Comprehension - II

Consider the following aldehydes

CH3 — CH = CH CHO CH2 = CH — CHO
(A) (B)
4. Identify the correct reactions
Base Base
(a) A 
→ C
annizaro reaction (b) B 
→ C
annizaro reaction
Base Base
(c) A 
→ Aldol reaction (d) B 
→ Aldol reaction
Base Base
(e) A + B 
→ Cannizaro reaction (f) A + B 
→ Aldol reaction

5. Write a mechanism for the following transformation.

Ba(OH)
2
→
A + PhCH = CHCHO D Ph(CH = CH)3CHO (87%)

H O( + )
B + CH3MgBr  → C + D
3
6.
Select the correct statements
(a) Both C & D can show haloform test (b) Both C & D can show Victor maeyer test
(c) Out of C & D, one can show Tollen’s test (d) Both C & D can react with Br2 water
7. Provide the missing reagents & products.

C
HO CH2OH MeO CH2OH

A PCC

D
HO CHO ∆ CH2(COOEt)2
E
B
(–) (–)
O COO

&
(–)
O CH2OD

O (limited) NH ( − )

3
→(A) 
2 →(B)
Zn, H 2O,
8.
What is B? Write mechanism for the transformation (A → B)
9. You have following aldehydes
NO2

CCl3CHO Ph3CCHO F CHO F CHO

NO2
(1) (2) (3) (4)
Select the compounds which can show cannizaro
Aldehyde & Ketone 283

Matrix Match Questions

Each question contains statement given in two columns which have to be matched. Statement (A, B, C , D) in column I have to
be matched with statements (p, q, r, s) in column II. The answers to these questions have to be appropriately bubbled as illustrated
in the following examples. If the correct match are A – p, A – s, B – r, B – q, C – q, D – S, then the correctly bubbled 4 × 4 matrix
should be as follows.
A p q r s
B p q r s
C p q r s
D p q r s

10. List - I (Reaction) List - II (Missing reactant & reagent)

(A) NH 2 NH 2 / OH (–) / D
→ penta-2,4-dienal (p)
CH3CHO + ? 

O
COOH COOH
?
(B) (q) Zn / Hg + HCl
Cl Cl

OH OH
Ph Ph (–)
(C) ? (r) OH / D
O Ph Ph

(D) → But − 2 − en − 1 − al
CH3CHO  (s) CH 2 = CH — CHO / OH(–)
11. List - I (Reaction) List - II (Type of Reaction & Product)
(A) 2, 4- dimethyl hepane (p) Decarboxylation
Al2 O3–CrO 3
Product
∆
(B) (q) Mesitylene

(C) (r) Phorone

dry HCl gas

(D) Acetone → Product (s) Aromatization
D

12. List - I (Reaction) List - II (Reagent)

(A) Ethene 
→ Oxirane (p) Ag, air, heat
Acetone 
→ Methylacetate
(B) (q) Ph3PCH2
Ethanal 
→ Ethyl acetate
(C) (r) Me3CO(–)K(+)

(D) Acetone 
→ isobutene (s) PAA
284 Problems in Organic Chemistry

13. Select the reagents from list II by which you can differentiate the pairs of compounds given in list I
List - I List - II
CHO
(A) & [Ag(NH3 )2 ]( + )
(p)

O CHO
(B) & (q) KOI

Ac CHO
(C) & (r) Cu +2 / OH (–)

O CHO
(D) & (s) 2, 4 – DNP

14. Pair of Compounds Reagent by which distinction can be made

OH
(A) OH & (p) Na

(B) OH and Acetone (q)

O
OH
(C) and (r) NaBrO
OH
(D) and (s) PhNHNH2

Answer Key

1. (d) 2. 2>3>1>4
4. (b), (c) & (f) 6. (c) & (d)
7. A is PCC (or other mildoxidizing agent), B is OD(–)

D = MeO CHO C = CH2N2

E = MeO CH = CH(COOEt)2

8. Compound B is 9. None
OH

Answers matrix match

10. (A) – s, (B) – q, (C) – p, (D) – r 11. (A) – q, s, (B) – q, (C) – p, q, (D) – r
12. (A) – p, s, (B) –s, (C) – r, (D) – q 13. (A) – r, (B) – p, r (C) – p, q, r, (D) – s, p
14. (A) – r, (B) – p, s, (C) – p, r, s, (D) –p, q, r
Aldehyde & Ketone 285

SOLUTIONS
LEVEL-I
OH
O

H,(+) heat
NaBH No Reaction
1. (c) 
4→

(B)
(A) Blue colour in victor Maeyer test

Alcohol (B) can not undergo dehydration because bridge ‘C’ can not bear double bond.
2. (d) In ppt(1) acetic acid separates as [Link]
2AcOH + Ca(OH)2 ——→ 2H2O + Ca(OAc)2
After separation solution contains MeOH & propanone. Propanone separates as propanone sodium bi sulphite (ppt-2)
O SO3Na
|| |
NaHSO

CH3 — C— CH3 
3→
CH3 — C — CH3 ppt–2
|
OH
Thus, solution contains methyl alcohol.
3. (c) Reduction followed by pinacole pinacolone rearrangement takes place.
Ph
ring opening
H (+) (+)
LiAlH / Ether

4 → → OH
COPh (+) CHPh CHPh
H
(+)
OH OH OH OH
Ph (+)
–H

OH
O O
COOH
O
CH3CO3H H3O( + ) OH
4. (d) 
→ 
→

OH (+) O
Zn–Hg + HCl
5. (a) OHC COCH3 OH, H
CH COCH3
O

(+) O
H3O
OHC Et CH Et
O
Tollen’s Reagent
6. (a) HC ≡ C — CH2COCH3  → AgC ≡ C — CH2COCH3
Since it has ketone group hence it will undergo Baeyer villiger oxidation.
7. (b) In II-process propyne undergoes partial reduction to give propene which on oxidation by KMnO4
Gives acetic acid which undergoes esterification with methyl alcohol to give methyl [Link] III- process propyne gives
acetone on hydration which undergoes Baeyer villager oxidation to produce methyl acetate.
8. (c) CH3COCl + (CH3)2CuLi (Gilman reagent) ——→ CH3COCH3 + CH3Cu + LiCl
O
hot, KMnO 4

O
Al(OEt) CH MgBr(excess)
CH3CHO  3 → CH3COOC2 H5 
3 →(CH3 )COH
Tishenko reaction H3O( + )

286 Problems in Organic Chemistry

9. (c) Here methyl shift takes place.

(+)
H methyl (+) ∆
shift –H(+)
(+)
OH
O(–)
(–) (–) |
OH HCHO H 2O
10. (b) CH3CHO  
→ CH 2 CHO  → H — CH — CH 2 CHO  → HOCH 2 — CH 2 CHO
–H 2O

CH2OH CH2O(–)
| | (–) (–)
H O HCHO OH
H 2 C — C H — CHO ←
2  HOH C — CHCHO ←
2  HOH 2 C — CHCHO
–H2O

CH2OH
(–) |
OH, HCHO
HOH 2 C — C — CHO (P)
|
CH2OH
This is Cross aldol condensation. Now (P) does not contain a - H atom so further addition of HCHO will lead to cross
cannizaro reaction
OH (–)
→(HOCH 2 )4 C + HCOO(–)
(HOH 2 C)3 CCHO + HCHO 

11. (c) is exceptional case

12. (b)

NH NH2
CH3MgBr CH3
NH3
(+)
H3O (A)

O
OH
13. (b)
Ph3P =CH 2 H3O (+)
(B)

OH
LiAlH4
(C)

Since (B) & (C) are 2° alcohols hence they will produce blue colour in victor maeyer test (A) is primary amine which is
inactive towards victor Maeyer test.
14. (c) Addition of HCN on carbonyl compound is nucelophilic addition reaction
Rate of nucleophilic addition ∝ electropositive character of ‘C’ of carbonyl group
OH
15. (d) cold KMnO 4 (AcO) 4 Pb CHO Aldol

CHO CHO
OH
16. (a) HCHO on reaction with NaHSO3 produces white precipitates of formaldehyde sodium bi sulphite
17. (d) By the destructive distillation of wood pyroligneous acid is formed along with wood tar & waste gases. This acid contains
acetone, methyl alcohol & acetic acid.
Aldehyde & Ketone 287

18. (a) Hemi acetal of acetaldehyde is unstable & dissociates in to alcohol & acetaldehyde. Thus, it shows reducing properties.
 O 
 || 
HCOOH also shows reducing properties because it contains CHO as well as COOH group  H — C— OH 
(–)

19. (a) + EtO(–)  → EtOH +

Formation of cyclo propenyl anion is not possible as it is antiaromatic & unstable.
20. (d) Since all compounds do not contain ‘a’ H atom thus, all can show cannizaro reaction
21. (a) The reaction in which aldol and cannizaro reactions both occur simultaneously is called Tollen’s reaction.

Passage - I

(22 TO 27)

Passage - II

(28 To 33)
28. (b) Became after the removal of α – H atom carbanion is formed which is stabilized by resonance.
(–) (–)
 H 2 O + CH 2 NO 2
CH3 NO 2 + O H 

O O(–)
(–) || |
CH 2 — N — O ←→ CH 2 =(N+ ) — O
( + )

29. (a) Because it is phenol

30. (c) See question no. 28.

O O(–) OH
|| (–) | |
H 2O
31. (d) H — C— H + CH 2 NO 2 
→ H —CH — CH 2 NO2 (–) → CH 2 — CH 2 NO 2
–OH

(–)
OH ,heat
32. (a) PhCH 2 CHO → Ph — C
Aldol |
= CHCH 2 Ph 
LiAlH 4
→ Ph — C H — CH 2 CH 2 Ph
|
CHO (P) CHO
Compound (P) can be reduced to by LiAlH4 here it should be noted that double bond in conjugation of phenyl group can
be reduced by LAN. Since (P) does not contain C = C bond hence it can not decolourise Br2 water
33. (a) It is aldol condensation base will break C -H bond & not C -D bond as we know that former has less bond energy than
later.
288 Problems in Organic Chemistry

(–) (–)
 H 2 O + CH3 CDCHO
CH3CHDCHO + O H 

O O(–)
(–) || |
H O
CH3CDCHO + CH3CHD — C— C 
→ CH3 — CHD —C HCD — CHO 
2 → CH CDCHOHCHDCHO
3
| |
CH3 CHO

Passage - III

(34 TO 39)
 A is highly volatile & can react with HI to give two products hence a may be an ether.
 (C) gives red colour in Victor maeyer test hence (C) is 1° alcohol.
 (D) reacts immediately with Lucas reagent hence D is 3° alcohol.
 E & F can show haloform test hence both should have CH3CO linkage.

Passage - IV

(40 TO 43)
(–) (–)
OH MeCl
OH CH2OH –H2O O CH2OH MeO CH2OH

CH3CH2COOEt, OH MnO2
MeO CHOHCHCO2Et Aldol
MeO CHO
Me
LiAlH4
Product

CHO CHO
44. (b) CH2 Tollen's reagent
CH2 heat
–CO2
CH3COOH –ve haloform test
CHO CHO
(A) (B)
Aldehyde & Ketone 289

Steric hindrance
O O OH OH
D D
(+) (+)
45. (c) glycol, H NaBD4 H3O
H2O

O O O O O O

46. (b) (c) & (d) forms stable hydrates as they are stabilized by intramolecular H- bonding . Thus rate of hydration will be maxi-
mum in these two cases. Although hydrates of both (b) & (c) are not stabilized by H bonding yet hydrates of (a) will be
more stable because of decrease in angle strain. Hence rate of hydration will be least in (b)
(+)
H3O
47. (c) –H2O
OH OH OH CHO OH
OH OH OH
HO O
H
OH
(+)
H, heat

CHO
(A) Contains double bond hence it will decolourise Br2 water. Due to the presence of CHO it will show all reducing proper-
[Link] Tollen’s & Bendict’s Solution Due to the presence of CHO group it will undergo condensation with 2, 4 - DNP &
semicarbazide.
48. (d) CH2 = CH – CH2CH2OH will decolourise Br2 water because it has C = C bond. It will react with Na because it has OH
group. OH group can be oxidized by chromic acid. Since it has 1° alcoholic groups hence it will not react with Lucas
reagent CH3CH2COCH3 can not decolourise Br2 water & can not react with Na because of the absence of C = C bond &
OH group chromic acid can not oxidise keto group.
OH (–) (–)
49. (b) CHCl2CHO 2KOH HCCHO –H O CHOCHO OH OOC–CH2OH
–2KCl 2
OH (Cannizaro)

OH (–) OH (–)
→ CHCl3 + HCOO(–)
CHCl2 CHO + Cl2 
→ CCl3CHO 

O( − ) OH
| |
KCN H3O( + )
50. (b) CH3CHO → CH3 CHCN 
→ CH3 — CH — COOH
(A)
Compound A is lactic acid and optically active due to the presence of chiral carbon atom
51. (d) Phorone is prepared by acetone, by treating it with dry HCl gas (dehydrating agent)
52. (a) Reactivity of base is more towards aliphatic aldehyde than aromatic aldehyde.
(–)
O O
(–)
H—C—H + OH H—CH—OH

O( −)
(–)
O O
|
Ph—C—H + H —CH—OH 
→ HCOOH + Ph — C — H 
→ HCOO(–) + PhCH 2 OH
|
H
(+)
O OH OH OH
|| 18 (+)
53. (c) CH3 — C— CH3 + H ( + )  H2•O• –H
••

→ CH3—C—CH 3 CH—C—CH
3 3 CH3—C—CH 3
(+)
18 OH2 18 OH (P)

Product P will not loose H2O because C — O & O — H bonds have high bond energies
18 18

54. (c)
55. (c) CH 2 = CH 2 
O3
H 2O
→ HCOOH 
→ –ve cannizaro reaction

CH ≡ CH 
2 → CHO — CHO  SeO
→ +ve cannizaro reaction
290 Problems in Organic Chemistry

56. (d) N2O4/CHCl3 can oxidise 2° benzylic alcohol in to ketone.

N2 O4/CHCl 3
OH CHOHPh PhCO OH

Zn/Hg+HCl
Cl CH2Ph

O (–)
O(–) OD
|| | |
N 2O 4CHCl3 D from D 2O
57. (d) PhCH 2 OH 
→ Ph — C— H  → Ph —C — H 
→ Ph —CHD
NaBD 4 |
D

58. (a)

OHC
59. (a) CH2
Diels-Alder ozonolysis
+
CHCO2Et
OHC
CO2Et CO2Et
CO2Et
(–)
CH2OH OH
Cannizaro

COO(–)

60. (a) In wurtz reaction free radical generation takes place thus, in reaction (a) free radical will undergo disproportionation
61. (c) +R effect of NH2 group helps in the dissociation of C — H bond
62. (d) Migration of hydride ion is rate determining step.
Rate = (aldehyde)2 (base) & some times kinetic studies show that Rate = (aldehyde)2 (base)2
63. (c)
64. (c) It is an example of cross aldol condensation.
O
(–) (–) H2O
OH
CH2 = CH—C—CH 3
–H2O (–)
O O O CH O O CH OH
3 3

(–)
OH
–H2O
O O CH O O CH O
2 3
O (–)
(–)
(–)
H2O OH, heat

Aldehyde & Ketone 291

65. (a) Glyoxal & formaldehyde both are independent from alpha hydrogen atom thus, these two will show cross aldol
condensation
(−)
base
66. (a) CHCl2 CHO 
→ C Cl2 CHO (highly stabilised by resonance as well as –I effect of Cl)

67. (b) A is tertiary alcohol hence undergoes dehydration by Ag / 573 K. B does not contain alpha H atom thus, it will show
disproportionation (cannizaro). C has MeCO linkage thus, it will exhibit haloform. D does not contain CHO group so it
will not react with bendict solution but can show cross aldol as follows:-
(−)
OH (–)
CH3 NO 2 
→ CH 2 NO 2 + H 2 O
stabilized by resonance

O O(–) OH
(–) | |
OH (–)
H—C—H CH2NO2 
→ H — C — H 
→ H — C — H 
→ CH 2
H 2O
Heat
= CH 2 NO2
| |
CH2 NO2 CH2 NO2
68. (d) Formic acid can show reducing properties as it contains CHO as well as COOH group
HCOOH + 2HgCl2 ——→ 2HCl + CO2 + Hg2Cl2
Hg2Cl2 + HCOOH ——→ 2Hg ↓ + 2HCl + CO2

69. (b).

(+)
OH O NOH N—OH2
(+)
Ag/573K NH2OH H
70. (b) backman
rearrangement
H
N N N
O OH HO (+)
2

71. (b) & 72. (b) Solution of these two question is given below

tautomerism C2H4

∆
O O OH OH

H
+ OH OH
(–)
∆

O O (A)
intramolecular O
aldol
CH= CH2
(B)
292 Problems in Organic Chemistry

73. (d)

O
wattig Birch
74. (a) reaction reaction
Ph (+) Ph H
75. (b) NH H
N can not show geometircal isomerism
(+) H
CH3 CH3
76. (b) Same as previous.
77. (a) Attack of cyanide ion is easy on cyclo propanone as carbon CO group is more electropositive.
78. (c) (B) forms via cannizaro reaction
LiAlH PCC
= PhCH CH — CHO 
4 → PhCH CH CH OH 
→ Ph(CH 2 )2 CHO
2 2 2

(–)
PhCH 2 CH — CH(CH 2 )2 Ph OH
(A) | |
CHO OH

(–) (–)
79. (c) → CH 2 CH = CH — CHO
OH
= CH3CH CH — CHO 
–H 2O
(–)
O O
(–)
CH3CH = CH—C—H + CH2CH = CH—CHO CH3—CH = CH—CH—CH2CH=CH—CHO
OH H2O
(–)
CH CH=CH—CH=CH—CH=CH—CHO –H O CH3CH = CH—CHCH2CH= CH—CHO
OH, heat
3 2

80. (a)
81. (d) Neo butyl alcohol is 3° alcohol & can not be oxidized in to ketone by mild oxidizing agents like halogens thus, can not
exhibit haloform test.
82. (a) See mechanism of haloform reaction from your text book
83. (b) Hydrate of tri chloro ethanal is stabilized by intra molecular H - bonding
Cl H–O
Cl—C —— C—H
Cl H–O
84. (b) See Question Number 68
O O O O
85. (c) O3/H2O/Zn
+
Boil
(A) H (B) H

O O
O3/H2O/Zn
+ CH3COCHO
Boil
H H
86. (b) Because of less steric hindrance around CO group.
87. (a) A is more stable due to more hyperconjugation.
88. (a) H+ attacks on C = O and not on OH group because in C = O oxygen acquires –ve charge due to resonance.
89. (a)
90. (a) See Question Number 83
Aldehyde & Ketone 293

91. (b) Double bond present in conjugation with Ph group can be reduced by LAH thus, B is PhCH2CH2CH2OH & can not show
bromine water test.
92. (a) See acyloin condensation in your text book
93. (b) OH is attracted by OMe by H bonding so bond angle reduces thus, to remove strain R2C(OH)(OMe) looses MeOH
More than one may correct:-
1. a, b, c, d
F
CH3—CH HF + CH3CHO
(unstable)
OH (+ve tollen’s test)

OCH3
CH3CH CH3OH + CH3CHO
OH (+ve tollen’s test)
(unstable)
2. b, c 3. a, b 4. a, d

5. b, d 6HCHO + 4NH3 
→ (CH 2 )6 N 4 + 6H 2 O
(urotropin)

6. c, d In (c) phorone is formed while in (d) farmose is formed (mixture of saccharides)

O3 / H 2O / Zn Zn / Hg + HCl
7. a, b C2 H 4  → HCHO  → CH 4
D
2–
Cr2O7 PCC NaOH (–)
8. a,c,d COOH—COOH CH2OH—CH 2OH CHO—CHO CH2OH—CO 2
acidification
CH2OH—COOH
9. a, b, d LAH can not reduce C—C multiple bond.

LEVEL -II

1. (d) Acid strength ? stability of Conjugate base

2. 2 > 3 > 1 > 4
pKa α 1 / acid Strength

3.
(–)
O O O
(–)
PhCCH2CH3 + CH2 = C—C—CH 2 PCC
Ph—C—CH2CO—C = CH2
CH3 CH2CH3 CH3
OH
(–) H2O
OH
PhC=CHCOC = CH 2 Ph—C—CH2CO—C = CH2
∆
Et CH3 CH2C3H CH3
4. (b) (c) & (f)
(–) (–)
OH
5.
=
CH3CH CHCHO → CH
= 2 — CH CHCHO –H 2O

O
(–)
PhCH = CH—C—H + CH2CH = CHCHO

294 Problems in Organic Chemistry

(–)
O OH
H2O
PhCH = CH—CH—CH2CH =CHCHO PhCH=CH—CH—CH2CH =CH—CHO
(–)
OH
PhCH=CH—CH =CH—CH = CH—CHO
∆

6. (c) & (d) CH2= CH—C—H+CH3MgBr

OMgBr OMgBr
CH3—CH 2 —CH=C—H CH2= CH—C—H
CH3
(+) (+)
H3O H3O

OH
CH3CH2—CH = CH—OH CH2= CH—CH—CH3
Can show haloform &
vector Maeyer test

CH3CH2CH2CHO
can show tollens test

7. A = PCC (or other mild oxidizing agent)
B = OD(–)

D = MeO CHO

E = MeO CH=CH(COOEt)2

8. Double bond is more sensitive towards ozonolysis

O
C—H NH 3
(–) (B)
O OH
(–)

9. None of these can show cannizaro reaction. 1 gives haloform, in 2 & 4 CHO group is sterically hindered. In 3rd case
st nd th

migration of hydride ion is difficult because of presence of electron withdrawing groups.

 10
Carboxylic Acid &
Its Derivatives

Main Features

REACTION CHART FOR CARBOXYLIC ACID ACID DERIVATIVES

Preparation Properties
(+)
H3O NH3
RCH2CN RCH2CONH2
heat
(+)
H3O PCl3/PCl5/SOCl2
RCH2CONH2 RCH2COCl
(+)
H2O ROH/H
RCH2COCl RCH2COOR
(+) N3H
H3O
(RCH2CO)2O H2SO4 RCH2NH2
hot KMnO4 P2O5
Alkane / alkyne RCH2COOH (RCH2CO)2O
heat
CARBOXYLIC
KMnO4 ACID Na
RCH2CH2OH RCH2COONa + 1/2 H2
KMnO4 FeCl3
Aldehyde Fe(OOCCH2R)3
KMnO4 (Blood red colouration)
Ketone heat NaHCO3
CO2+H2O+RCH2COONa
aq KOH
RCH2CX3 H(+) NaOH / CaO
RCH3(Decarboxylation)
(+)
H3O
Ester LAH
RCH2CH2OH
P + X2
H2O RCHXCOOH [ HVZ ]
296 Problems in Organic Chemistry

Multiple Choice Questions

(–)
O O (i) OH
1. (+) (A), Compound (A) is:-
(ii) H
CH2CO2H

OH
OH O
(a)
O (b)
O
CH2COOH
OH OH O
(c) O (d)
O
O

2. Consider the following compound,

COOH
S COOH
HOOC — CH2 — (CH2)3CONH

COOH
O
How many chiral ‘C’ atoms will be present in the compound after heating?
(a) 5 (b) 6 (c) 4 (d) 3
3. Which reaction product is not expressed correctly?

EtO( )
–
CH 2O + 2CH 2 ( CO 2 Et ) 2 
(a) ( +) →
H EtO2C CO2Et
O
O
EtO(–)
(b) + CH 2 ( CO 2 Et ) 2 
( +) → H3O
O
O

EtO( )
–
(c)
HCHO + 2CH3COCH 2CO 2 Et 
( +) → H

CO2H

( +)
CH 2 ( CO 2 Et ) 2 
(d) H3O
→ CH3COOH
Heat
OH
H (4)
O O
HOH2CCO
4. Given the structure of ascorbic acid (vitamin C) (3)
Which proton is most acidic? HO OH
(2) (1)

(a) 1 (b) 2 (c) 3 (d) 4

Carboxylic Acid & Its Derivatives 297

5. CH3CONHCH3 NaOBr Product ……………………… (1)


→
CH3CON (CH3)2 NaOBr
 → Products ……………………… (2)
Products of reaction (1) & (2) are
(a) CH3NH2 & CH3NH2 (b) CH3NH2 & CH3NHCH3
(c) CH3CONBrCH3 & No reaction (d) CH3CONBrCH3 & CHCl3 + (CH3)2NCOO(–)
6. Formic acid can be distinguished from acetic acid by:-
(a) NaHCO3 (b) NaOBr
(c) NaOH + CuSO4 (d) Na
7. An organic compound does not show haloform test but reacts with sodium to give H2 gas. Compound gives blood red coloura-
tion with neutral FeCl3. Organic compound is:-
(a) (CH3)3COH (b) HCOOH
(c) acetylene (d) AcOH
8. Calomel can be converted in to mercury by:-
(a) Lactic acid (b) Oxalic acid
(c) Pyruvic acid (d) Formic acid
9. γ - hydroxy butanal can be converted in to γ - lactones by:-
(a) H+ / Cr2O72–, H3O+ (b) KMnO4/H+, H3O+
(c) Alkaline CuSO4, H+ / heat (d) All of these

D
10. + 2 – acetyl propenoic acid  → product

Product of this reaction will be:-

COOH Ac
(a) (b) COOH

Ac COOH
(c) (d)
Ac
EtONa
11. CH3COOC2H5  → Product,
Product of this reaction would be:-
( +)
( – ) Na
(a) CH3COCH2COOEt (b) CH3COCHCOOEt
(c) CH3COCH2 — COH(OEt)2 (d) CH2(COOEt)2
12. In which of the following case only one molecule of active methylene compound is formed:-
EtONa EtONa
(a) CH3COOCH3 + EtCO2Et 
H( )
+
→ (b) HCOOEt + CH3COOEt 
( +) →
H

EtONa EtONa
(c) CH3COOMe + CH3COOEt  → (d) (CH3)3CCOOC2H5  →
H( ) H( )
+ +

O
LiAlH / Ether
NaBH 4 
4
( +) →
13. (A) ←
O O H (B), (A) and (B) are:-
O CH2OH CH2OH
(a) , CH2OH (b) , CH2OH
OH OH HO O O HO
O OH OH
(c) , (d) Both are
CH2OH CH2OH
HO O HO HO
298 Problems in Organic Chemistry

14. Ethyl acetate can be converted in to acetone by:-

(a) CH3MgBr (Excess), H3O+ (b) EtONa / H+, H3O+ / heat
(c) OH– / H2O, CaO/NaOH , heat (d) HCHO / OH(–) / heat
15. Rate of decarboxylation of following carboxylic acid will follow :-
COOH COOH CH COOH COOH
3

O
O O

(1) (2) (3) (4)

(a) 1 > 2 > 4 > 3 (b) 4 > 3 > 2 > 1 (c) 4 > 2 > 1 > 3 (d) 4 > 2 > 3 > 1
16. CH MgBr ¾¾¾¾¾
(1) SO3
®[X]
3 ( +)
(2) H3O

(1) CO
CH3MgBr ¾¾¾¾¾¾
2 ®[Y]
(2) dil H 2SO 4

Select correct statement
(a) [X] and [Y] are same compounds
(b) pKa of [X] is lesser than that of [Y]
(c) [X] can release CO2 on reaction with NaHCO3 while [Y ] can not
(d) [Y] can release CO2 on reaction with NaHCO3 while [X] can not.

P2O5 / heat
17. (A) (B), (A) would be :-
(+)
H3O

(a) (CH3CO)2O or CH3CONH2 (b) (CH3CO)2O or CH3COOH

(c) CH3COOH or CH3CONH2 (d) CH3CONH2 , or C2H5OH
COBr
(i) Ag2O
[X]
18. (ii) H2O / Heat
CHO O (i) Pd / BaSO4
[Y]
(ii) H2CrO4 / Heat

(i) H2O / Heat

[Z]
(–)
(ii) N2H4 / OH / Heat

COBr O

X ⇒ Y ⇒ Z ⇒
(a)
O CH3
O
(b) X & Y are & Z is

(c) X, Y & Z all are

(d)
X= Z ≠ Y
Carboxylic Acid & Its Derivatives 299

CHO

19. Which statement is not correct about ?

CONH2
(a) It can be converted in to amino acid by treating it with NaOBr, Ag2O, H+
(b) Its IUPAC name is 2 – formyl cyclohexanamide
(c) It shows bi uret test.
(d) It is amphoteric in nature
O OH
20. CH3COEt PrCOOH

(1) (2) (3)
Correct order of boiling points would be:-
(a) 1 > 3 > 2 (b) 2 > 3 > 1
(c) 3 > 1 > 2 (d) 3 > 2 > 1
21. (R) – 2 – butanol is treated with Ac2O to get another product [X], [X] will have:-
(a) R configuration
(b) S – configuration
(c) Equimolar mixture of R & S will be obtained
(d) Both R & S will form will be produced in larger amount.

Passage – I
Ethyl acetoacetate and malonic ester are used for the synthesis of various important organic compound like ketone & substituted
carboxylic acid. It contains active methylene (CH2) group. If contains acidic hydrogen and can be replaced as:-
.. (–)
Base
CH3COCH2COOC2H5 CH3COCHCO2Et
R
R–X
CH3COCHCO2Et
This alkyl substituted ethyl acetoacetate on hydrolysis produces acids
dil NaOH
CH3COCHCO2Et (+)
CH3COCH—COOH
H
R R
Now answer the questions from 22 to 27
22. CH3COCH 2CO 2 Et (1 mole) (i) EtONa / Br
Br (P), P is:-
(+)
(ii) H3O /∆

(a) CH3COCH2CH2CH2COCH3 (b)

Ac
COOH
(c) (d) 5 – Hydroxy pentan – 2 – one
Ac
23. CH2(COOC2H5)2 is also an active methylene compound. It can be converted in to adipic acid (butane-1,4-di carboxylic acid)
by:-
(a) EtONa, CH2I2, NaOH / H+, heat (b) EtONa, CH2ICH2I, H3O+ / heat
(c) H3O+, heat , EtONa , (CN)2 (d) H3O+
24. Malonic ester CH2(COOEt)2 can be converted in to CH3CH = CH – COOH by treating malonic ester with
(a) EtONa / CH3CHO / heat, H3O+ / heat (b) EtONa / CH3Cl, H3O+ / heat
(c) EtONa / CH2Cl2, H3O+, heat, alc KOH (d) All of these
300 Problems in Organic Chemistry

(+)
EtONa H3O O3
25. CH3COCH2COOC2H5 RX CH3COCHCOOC2H5 –C2H5OH
X
H2O

R
CH3COCOOH + HCOOH + CH3COCH2CH2COOH

RX would be:-
XCH = CH — C = CH2
(a) (b) XCH2CH = CCH3CH = CH2
CH3
(c)
XCH2 — C — CH = CH — CH3 (d) XCH — C = CH — CH = CH
2 2

CH3 CH3

26. CH3COCH2COOC2H5 Can be converted in to 1, 3 di ketone by treating it with

(a) EtONa / CH3COCl, H3O+ / heat (b) EtONa / CH3COCH2COCl, H3O+ / heat
+
(c) EtONa / CH3CH2COCl, H3O / heat (d) EtONa / CH3COCH2CH2COCl, H3O+/ heat
27. Which will form active methylene compound when treated with CH3OH / H+
O

COOH
(a) CH3COCH2CH2COOH (b)

(c) CH3CH2COOH (d) (CF3)3CH2COOH

Passage - II

An organic compound (A) containing six membered ring gives (B) when treated with KOH + C2H5OH. (B) Gives (C) when
subjected to heat with KMnO4. (C) Releases CO2 with NaHCO3 & gives (D) & (F) when treated with [CaO / heat] &
[CH2N2/heat] respectively.(D) gives (E) when heated with Ca(OH)2. (E) further gives (D) when treated with [N2H4/ heat] followed
by ozonolysis. On the other hand (F) gives (G) when treated with EtONa/ H+. (G) Also gives (D) by [H3O+ / heat]. If compound (A)
on reduction with LiAlH4 gives hydrocarbon then
Answer the questions from 28 to 34.
28. Compound (A) is:-
Br
O
(a) (b)
Br O

Br

(c) (d)

29. Compound (B) is:-

OH
(a) (b)
COOH

O
(c) (d)

30. Compound (C) is:-

(a) Adipic acid (b) Glutaric acid
(c) Succinic acid (d) Oxalic acid
Carboxylic Acid & Its Derivatives 301

31. Compound (D) is:-

O
(a) (b) O
O

(c) (d) MeCOMe

32. Compound (E) is:-

O
O

(a) (b)
O OH
O
(c) (d)

33. Compound (F) is:-

(a) Dimethyl adipate (b) Dimethyl Glutarate
(c) Dimethyl Succinate (d) Dimethyl Oxalate
34. Compound (G) is:-
CO2CH3 CO2Me

(a) (b)
O
O
CO2Me
O
(c) (d) None

Passage - III
H( )
+
2A + B 
→ C
(A) Can not show haloform test but can reduce schiff’s reagent.A can not show aldol condensation but its oxidized form can show
reducing properties. Compound B can be obtained by partial reduction of the alkyne which can not show tollen’s test. If compound
B contains 4 carbon atoms then
Answer the questions from 35 to 42.
35. Compound (A) is:-

(a) CHO (b) CH3—CH—OMe

OH
(c) PhCHO (d) HCHO
36. Compound (B) is:-
(a) CH3CH2CH = CH2 (b) CH3CH = CH CH3
(c) Iso butene (d) CH2 = CH—CH = CH2
37. Compound (C) is:-

O O O O
(a) (b)

O O O O
(c) (d)
302 Problems in Organic Chemistry

38. Which intermediate will not form during the formation of (C) from (A) & (B)?
OH (+)
(a) (b) CH2OH
(+)
(+)
O O H
(+)
(c) (d) H O O

39. How many optical isomers are possible for (Y) ?

H O( )
+

( B) + ( CN) 2 → ( X ) 
 3 → ( Y)
(a) 2 (b) 3 (c) 4 (d) 5
40. Which statement is not correct about (Z) & (W)?
( i) alkaline CuSO
→4
( W)
(B) Hot KMnO 4
→ ( Z) , (A) ( +)
( ii) H
(a) pKa of (W) is lesser than that of (Z)
(b) Both can show reducing properties
(c) (Z) gives blood colouration with neutral FeCl3
(d) (W) produces mercury on reaction with corrosive sublimate
41. What is (P) in the following reaction?
+ HCl

( Y) 
NaOH / CaO
→ ( I)
AlCl
→ ( P)

3

(a) (b)
O

(c) (d) O O
CH3 CH3
42. (Y) is subjected to heat to produce another organic compound R. Which is correct about (R)?
(a) It is a carboxylic acid (b) It is optically active
(c) It is an anhydride (d) It is an ester
43. Consider the following reagent:-
NH3 / heat NH2OH PCl5 / heat Na / heat
(1) (2) (3) (4)
Which among the above reagents will react with both the functional group of lactic acid?
(a) (3) (b) (4) (c) (1), (2), (3) & (4) (d) (3) & (4)
44. An organic compound on treatment with NH3, NaOBr & NaNO2 + dil H2SO4 gives cyclo pentanol.
Organic compound will be:-

(a) (b) COCl

COOH

(c) (d) Both (b) & (c)

CH2COCl
Carboxylic Acid & Its Derivatives 303

H O( )
+
45. ( A) 
3 → ( B) Na
→ 2 moles of H gas
2
(1 mol) (1 mol)

COOEt CO2Et

(a) (b)
CN
OH

OH
HO (CH2)3Ac HO (CH2)4Ac
(c) (d)
HO EtO2C
CH2CH = NH CN

Br
(1) 1 mol Mg
46. [X]
(2) D2O
I
[X] would be:-
D
D
(a) (b)
I
D

(c) (d) None of these

Br

47. Consider the following processes.

Process (1) C2H5OH / H+, LiAlH4, PCC
Process (2) NaBH4, Cu / 300°C
Process (3) PCl5, LiAlH4, CrO3 / H2SO4
Process (4) SOCl2, Pd / BaSO4
The process by which acetic acid can be converted in to acetaldehyde is/are:-
(a) 1, 2, 3, 4 (b) 1, 4
(c) 1, 3, 4 (d) 2

LiAlH
48. → (X), (X) would be:-

O D O
O
CH2OD CH2OD
(a) (b) CH2OD
CH2OH
CD2OD CHDOD
(c) CH2OD (d) CH2OD
304 Problems in Organic Chemistry

CONH2 (+)
P2O5 H3O
49. (CH2)2 ∆
(B) (C)
(A) H2O2
CONH2 (D)
(–)
OH
(+)
H3O NH3
(E) (F)
∆

Which statement is not correct?

(a) (F) and (A) are same
(b) (C) and (E) are same and can be converted in to (A) by NH3 / Heat
(c) (D) and (A) are same and can be converted in to (C) by H3O+
(d) All are correct
50. The reaction in which ester does not form is -
H( )
+
(a) AcBr + BuOH 
→ Product
PCC Al( OEt )
(b) Amyl alcohol 
→ (X) →
3
Product
(c) HO — CH2 — CHOHCH2OH + HNO3  →
(d) In each case ester is produced
51. Consider the following four compounds.
O O O O

CH3 — C — NH2 CH3 — C — O — C — CH3 CH3 — C — OCH3

(1) (2) (3)

Decreasing order of bond lengths of C = O bond would be:-
(a) 2 > 3 > 1 (b) 1 > 3 > 2
(c) 3 > 2 > 1 (d) 2 > 1 > 3
52. Consider the two carboxylic acids
Product :- (CH3)3C COOH (CH3)3 SiCOOH
(1) (2)
Select the correct statement
(a) (pKa)2 > (pKa)1 (b) (pKa)1 > (pKa)2
(c) (pKa)1 = (pKa)2 (d) None of these

O
CN (+)
H3O
53. HOOC COOH [X]
∆
ClOC
O
Select the correct statement
(a) X will give effervescence of CO2 with NaHCO3
(b) X will produce alkane when treated with Zn / Hg + HCl
(c) X will produce symmetrical diketone when heated with sodalime
(d) All are correct
54.
Assertion: - Rate
. of decarboxylation of ethanoic acid is greater than propanoic acid.
.
Reason: - CH3 is less stable CH3CH2
(a) Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
Carboxylic Acid & Its Derivatives 305

55. Assertion:- Vont Hoff’s factor for carboxylic acid is more in aqueous medium but least in benzene
Reason: - In benzene RCOOH is present in its associated form while in water it is gets dissociated in to caboxylate and hydro-
nium ions
(a) Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
NaOH
56. Assertion: - RCOOH  → RH
heat
This reaction requires the presence of CaO
Reason: - CaO absorbs the released CO2 in the reaction and forms CaCO3.
(a) Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
C2H5
heat
57. Assertion:- CH3 — C — COOH 
→ Product
COOH
In this reaction two products are formed
Reason: - Due to rearrangement CH3 — C ( COOH ) converts in to the mixture of
2
|
C2 H5
CH3 — C ( COOH ) 2 and HOOCCH 2 — CH — COOH
| |
C2 H5 C2 H5
Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(a)
Assertion is true Reason is true: Reason is not a correct explanation for assertion
(b)
Assertion is true, Reason is false
(c)
Assertion is false, Reason is true
(d)
58. Assertion: - rate of decarboxylation of fluoroacetic acid is greater than that of chloro acetic acid
Reason: - fluoro methyl carbanion is less stable than chloro methyl carbanion.
(a) Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
59. Assertion: - decarboxylation by sodalime in 4-methoxy phenyl acetic acid occurs rapidly in comparison to that of 4- nitro
phenyl acetic acid.
Reason: - Rate determining step involves the formation of carbanion.
(a) Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
306 Problems in Organic Chemistry

→ ( A ) + ( B) 
dil H 2SO 4 soda lim e
60. Assertion:
= CH 2 CH — OCOEt  → Et − H
A does not release H2 on reaction with Na
Reason: - A is an aldehyde.
(a) Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
COOH

soda lime
61. Assertion:- → Product

Br
This reaction gives decalin as a product
Reason: - carbanion is formed as intermediate which undergoes SN2 reaction
(a) Assertion is true, Reason is true: Reason is a correct explanation for assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true

Answer Key

1. (a) 2. (c) 3. (b) 4. (a) 5. (d) 6. (c) 7. (d) 8. (d) 9. (c) 10. (c)
11. (b) 12. (b) 13. (c) 14. (b) 15. (a) 16. (b) 17. (c) 18. (b) 19. (b) 20. (c)
21. (a) 22. (b) 23. (b) 24. (a) 25. (b) 26. (a) 27. (d) 28. (c) 29. (b) 30. (a)
31. (a) 32. (a) 33. (a) 34. (c) 35. (d) 36. (b) 37. (c) 38. (c) 39. (b) 40. (b)
41. (b) 42. (c) 43. (d) 44. (d) 45. (d) 46. (d) 47. (b) 48. (b) 49. (c) 50. (d)
51. (b) 52. (a) 53. (b) 54. (b) 55. (a) 56. (a) 57. (c) 58. (d) 59. (d) 60. (a)
61. (a)

Multiple Choice Questions More Than One May Correct

1. Which among the following can’t show Fehling test?

(a) HCOOH (b) CH3COOH
(c) CH3CH2COOH (d) PhCOOH
2. Which is not the preparation a chiral molecule?
Red P + Br
CH3CH — COOH 
2→
NBS
H 2O
(a) | =(b) CH 2 CH — CH 2 — CH3 
→
CH3

LiAlH Red P + Br
(c)
HOCH 2 — CH — COOH  4 PhCH 2COOH 
( + ) → (d)
2→

| H H 2O
CH3
Carboxylic Acid & Its Derivatives 307

3. Which is not correct about X ?

COOH
OHC ∆
COOH X
O
(a) X can show haloform test
(b) X can give brisk effervescence with NaHCO3
(c) X can not show Fehling test
(d) X contains one CHO one keto and one COOH group
4. In which case 1st compound is more acidic than 2nd.
(a) PhCOOH, CH3COOH (b) CH3SO3H, HCOOH
(c) CH3CH2CH2COOH, CH3OH (d) CH3OH, CH3NH2
5. Which among the following is not the preparation of ester?
∆ H2O2
(a)
CH3COOAg + I2 (b) CH3CN (–)
OH
PAA
(c)
CH3COCH2CH3 (d) OH + CH3COCl
6. In which case products formed are not according to reaction?
(+)
H
(a)
CH3COOH + CH3OH H2O + CH3COOCH3
(+)
H
(b)
CH3COOH + CH3OH H2O + CH3COOCH3
(+)
H
(c)
CH3COOH + CH3OH H2O + CH3COOCH3
(+)
H
(d)
CH3COOH + CH3OH H2O + CH3COOCH3
7. Which is correct statement about A, B & C ?
(–)
MnO 4 Red P + Br2
CH3CH2CH2OH (B) (C)
(+) H2O
H
(A)
(a) A is more acidic than (B) (b) C is more acidic than A & B
(c) C can not show Wurtz reaction (d) B is more acidic than A & C
8. The reaction by which acetic anhydride can be prepared is:-
P2O5
(a)
Acetyl chloride + Sod. acetate heat
(b)
Acetic acid heat
+
260°C H
(c)
Glycerine + oxalic acid (d) CH3COOEt + CH3OH
9. In which case products formed are not according to the reaction:-
+
(a) Glycerine + fatty acid Oil & fat (b) fatty alcohol + fatty acid Oil & fat
+
H H
+
(c) Glycerine + fatty acid Wax (d) fatty alcohol + fatty acid Wax
+
H H

10. Which among the following can not show HVZ reaction?
(a) PhCOOH (b) CH3CHBrCOOH
(c) CH3CBr2COOH (d) PhCOCOOH

Answer Key

1. (b), (c), (d) 2. (a), (c) 3. (a), (b), (c), (d) 4. (a), (b), (c), (d) 5. (b), (d)

6. (a), (b), (c) 7. (b), (c) 8. (a), (b) 9. (b), (c) 10. (a), (c), (d)
308 Problems in Organic Chemistry

LEVEL - II

Comprehension

1. Write the product (organic compounds) of following dehydration

COOH ∆
COOH ∆
(a)
(CH2)2 P1 (b)
(CH2)3 P2
COOH COOH
COOH ∆
(c)
(CH2)4 P3
COOH
2. Write mechanisms of (a), (b) & (c) ([Link]. 1 )
3. CH2Br Mg (1 Mol) H3O
(+)
C
(A) (B)
THF
CH2Br
neutral
Blood red (D)
FeCl3
Colouration
Identify A, B, C & D

Matrix Match Questions

Each question contains statement given in two columns which have to be matched. Statement (A, B, C, and D) in column I have
to be matched with statements (p, q, r, s) in column II. The answer to these questions has to be appropriately bubbled as illus-
trated in the following examples. If the correct match are A — p, A — s, B —r, B — q, C — q, D — S, then the correctly bubbled
4 x 4 matrix should be as follows.
A p q r s
B p q r s
C p q r s
D p q r s

4. List - I Comprise of reagent for given compounds (X) List - II indicates the possible products (s)
COOC2H5

match List - I with List - II O

OH Cl

List - I List - II
(CH2)2OH

OH
(A) LiAlH4
(p)
OH CH2OH

COOC2H5

(B) Luke warm water (q) O

OH
COOH
Carboxylic Acid & Its Derivatives 309

COOEt
OH
(C) NaBH4 (r)
OH CH2OH

COOC2H5

O
(D) Cu/300°C (s)
Cl

5. List - I (Reaction) List - II (Reagent required)

(A) (p) CH3MgBr (2 mol) / H3O(+)

COOH NH2

O
(B) (q) EtMgBr / H3O(+)
OMe
OH

O O
(C) (r) NH3 / D then KOBr
MeO OMe

O
(D) (s) N3H / H2SO4

OH (t) MeMgBr (2 moles)

6. Column-I Column-II
O
CN
(A) dil H 2SO 4
 → (p) Product contains ketonic group
∆

(B) 2 4→
(i) KCN / H SO
 (q) Product contains CONH2 group
(ii) H 2O 2 / NaOH

O
H O( +)

3 →
∆
(C) (r) Product contains COOH group
NC CN

CN

NH2 OH
HONO
(D) →
 (s) Product contains OH group
∆
310 Problems in Organic Chemistry

7. Reaction Name of reaction

(A) CBr3COCH3 + NaOH → (p) Haloform reaction
(B) CH3CONH2 + NaOH + Br2 → (q) Hoffman degradation
(C) CH3COCH3 + KOH + Br2 → (r) Aldol condensation
(D) CBr3CHO + NaOH → (s) Cannizaro reaction

Answer Key

O
O
O
O
1. P1 = O P2 = O P3 =

3. A = ethane B = ethanol C = KMnO4 D = (CH3COO)3Fe

Answers matrix Match

4. (A) — p (B) — q (C) — r (D) — s 5. (A) — r, s (B) — p (C) — t (D) — q

6. (A) — p, r (B) — q, s (C) — p, r (D) — p 7. (A) — p (B) — q (C) — p (D) — p

SOLUTIONS
LEVEL - I

O
OH OH H
H OH OH
O O basic hydrolysis esterification O
1. (a) MeCHO +
OH
(–)
CH2CO2
CH2CO2H

2. (c) Because compound will lose two molecules of carbon dioxide one from left hand side and other from right hand side to
produce :-

S
HOOC—CH2—(CH2)3CONH * *
COOH
*
*
O

Base (–)

3. (b) CH2(CO2Et)2 CH(CO2Et)2

Carboxylic Acid & Its Derivatives 311

(–)
O OH
O
(–) H2O
+ CH(CO2Et)2
CH(CO2Et)2
CH(CO2Et)2
(–) (–)
O O O
Base

C(CO2Et)2 C(CO2Et)2 CH(CO2Et)2

(–)

OH (+)
H2O H3O

CO2H
C(CO2Et)2
OH CO2H

4. (a) Because when it removes -ve charge comes on oxygen which is stabilized by resonance.
OH Br2
5. (d) CH3CONHCH3 –H2O
CH3CONCH3 CH3CONBrCH3 (Hoffman Bromamide)

In CH3 — CON(CH3)2, H is absent on ‘N’ hence it can not undergo Hoffman Bromamide reaction however it undergoes
haloform reaction because it contains CH3CO linkage:-

NaOBr or (–)
CH3 CON(CH3)2 CHCl3 +(CH3)2NCOO
NaOH + Br2

CHCl3

6. (c) Because formic acid contains CHO as well as COOH group & can show reducing properties with fehling solution
(CuSO4 + NaOH).

O
H—C — O – H acid group

aldehyde gp.

7. (d) Since compound gives blood red colouration with neutral FeCl3 hence it should have COOH group. Option b & d may
correct but HCOOH does not react with neutral FeCl3 hence (d) is correct.

8. (d) HgCl2 + HCOOH 

→ 2Hg + 2HCl + CO2
(Calomel) ( Mercury)

(–) (+)
CHO CuSO4 + NaOH COO H COOH

9. (c) OH OH OH
O

Diels-Alder
10. (c) + heat + CO2
Ac COOH
Ac
312 Problems in Organic Chemistry

11. (b) This is claisen condensation:-

(–)
CH3COOC2H5 + EtONa ——→ EtOH + CH2COOC2H5

(–)
O O
(–)
CH2COOC2H5 + CH3 — C — OC2H5 CH3 — C — OC2H5
CH2CO2Et
(–)
CH3 — COCH2CO2Et + EtO

If we do not add H(+) at the last of the reaction then EtO(–) will remove H(+) from CH3COCH2CO2Et

(–) (–)
as:- CH3COCH2COOEt + EtO CH3COCHCOOEt + EtOH

12. (b) Except (b) in all cases mixture of active methylene compound will form however in (d) condensation is not possible

O NaBH4 O LiAlH4 OH
13. (c)
CH2OH
OH O O O HO

NaBH4 can not reduce ester group but LiAlH4 can reduce ester as well as ketone group.

(+)
14. (b) CH3COOC2H5 EtONa, H
CH3COCH2COOC2H5
Claisen Condensation
(+)
heat H3O
CH3COCH3 CH3COCH2COOH – C2H5OH
– CO2

15. (c) Carbanion is formed as an intermediate in decarboxylation. Since (a) gives more stable carbanion thus decarboxylation of
4th acid occurs rapidly & it is too slow in 3rd case

16. (b) [X] = CH3SO3H [Y] = CH3COOH

P2O5, heat
17. (c) CH3COOH (CH3CO)2O
(+)
H3O

COBr Ag2O COBr H2O COOH ∆

18. (b) OHC O O O – CO2 O
(X)
HOOC HOOC
∆
Pd, BaSO4 CHO H2CrO4 COOH
OHC O HOOC O

+ (–)
H3O COOH ∆ N2H4,OH

OHC O O
OHC
(Z)
Carboxylic Acid & Its Derivatives 313

19. (b) Its IUPAC name is 2 — formyl cyclo hexan carboxamide

20. (c) Boiling point of Carboxylic acid will be higher due to H — bonding

O HO
Pr—C C—Pr
O—H O
Here two H — Bonds are present in between two molecules. After 3rd, 1st will have higher boiling point than 2nd due to
H — bonding.

H
O O
OH O

21. (a) Because configuration changes only when bond breaks and forms in new direction.

H4 H4
1 Ac2O 1
H3C OH –AcOH
H3C OAc
3 3
CH2CH3 CH2CH3
2 2
[R] [R]

(–) BrCH2CH2Br
EtONa
22. (b) CH3COCH2CO2Et CH3COCHCO2Et CH3COCHCO2Et
CH2CH2Br
Ac COOH (+)
H3O (–)
EtONa
CH3CO—CCO2Et CH3COCCO2Et
CH2CH2 – Br
heat
– CO2 Ac

(–) CH2I -CH2I (1 mol)

23. (b) CH2(COOC2H5)2 EtONa
CH(COOC2H5)2
2-moles

COOH
CH2CH CH2CH(COOC2H5)2
COOH H3O(+) SN
2

–4C2H5OH
COOH
CH2CH CH2–CH(COOC2H5)2
COOH
CH2CH2COOH
heat (Adipic acid)
CH2CH2COOH

(–)
O
(–) CH3CHO
24. (a) CH2(COOEt)2 EtONa
–EtOH CH2(COOEt)2 CH3—CHCH2(COOEt)2
OH
H3O
(+) EtOH
heat
CH3CH=CH(COOEt)2 CH3—CHCH2(COOEt)2
COOH heat
CH3CH=CH COOH –CO CH3CH=CHCOOH (Crotonic acid)
2
314 Problems in Organic Chemistry

OH H (+)
H3O
25. (b) CH3COCH2COOC2H5 EtONa
RX
CH3COCHCOOC2H5
CH2CH=CMeCH=CH2

CH3COCH(COOH)CH2CH=CMeCH=CH2
X
ozonolysis

CH3COCOOH + HCOOH + CH3COCH2CH2COOH

(–)
26. (a) CH3COCH2CO2Et CH3COCHCO2Et
EtONa CH3COCl
RX
CH3COCHCO2Et
COCH3
(+)
heat H3O
CH3COCH2COCH3 –CO2 CH3COCH—COOH
1 2 3
(1, 3 di Ketone) COCH3

27. (d) (CF3)3C — CH2 — COOCH3 active methyl group

Electron with drawing groups

Passage - II

(28 to 34)

 (C) releases CO2 with NaHCO3, Thus, (C) must be a carboxylic acid.
 Since (A) on reduction with LiAlH4, gives hydrocarbon hence (A) must be a 1° or 2° alkyl halide.

alc KOH KMnO4,heat COOH (Adipic acid)

COOH
Br (C)
(B)
CaO CH2N2

O COOCH3
heat COO
–CaCO3 Ca COOCH3
COO
(F)
Aldol, Ca(OH)2 (D) (F)
+
ozonolysis EtONa, H Claisen Condersation
O CO2Me
(–)
N2H4, OH O

(E) (G)
Carboxylic Acid & Its Derivatives 315

Passage - III

35 to 42

 Since A can reduce schiff’s reagent hence it should contain CHO group & since its oxidized form can show reducing properties
thus, it should be formaldehyde.
 Since B is obtained by reduction of the alkyne which can not reduce thus, B should be 2-butene

Pd / C
→ (B)

 Z & W are acetic acid & formic acids respectively.

 I is butane & on isomerisation it gives isobutene (P)

••
(+) (+) CH2OH CH2OH
••
HCHO + H CH2OH B A
(+)
(+)
O=CH2
H
O O (+)
(C)
O O
CN (+)
COOH
H3O
B + (CN)2 (Y)
CN COOH
it contains two chiral carbon atoms

43. (d) OH ONa

Na
COOH COOH
Cl
COCl

44. (d) NH3 NaOBr

COCl CONH2 NH2

OH (+) NaNO2+ H2SO4

H2O

NH3 NaOBr
CH2COCl CH2CONH2 CH2NH2

H2O (+) NaNO2 + H2SO4

(+)
OH CH2
316 Problems in Organic Chemistry

OH OH
HO (CH2)4Ac HO (CH2)4Ac 4-moles of Na
45. (d) acidic hydrolysis

EtO2C HO2C
CN COOH
ONa
NaO (CH2)4Ac
+ 2H2
NaO2C
COONa

46. (d)

Rest all amide produce resonance stabilized amines. Hence (a) will provide least yield of carboxylate ion on hydrolysis.
47. (b) See chemical reactions in your text book
(–)
CHO
H from LiAlH4 O(–) D2O
48. (b) O
(–)
O O O
H
(–)
H O
CH2OD CH CHO
D2O OD (–) OD
H
CH2OD

CONH2 CN (+) CO2H

P2O5 H3O
49. (c) (CH2)2 heat
(CH2)2 (CH2)2
CONH2 CN CO2H
(A) (B) (C)
H2O2OH
(–) CO2H
(CH2)2
CO2H
(D)
(+) COOH CONH2
H3O NH3, heat
(CH2)2 (CH2)2
COOH CONH2
(E) (F)

50. (d) In (c) tri nitro glycerine is produced which is a nitro ester.
51. (b)
52. (a) Because electron donating effect of Me3Si is greater than Me3C.
O O
CN COOH
53. (b) HOOC COOH (+)
H 3O HOOC COOH
ClOC ∆
HOOC [X]
O O
O

Zn-Hg+HCl Heat

[X]
O
Carboxylic Acid & Its Derivatives 317

54. (b) In decarboxylation reaction carbanion is formed as an intermediate

O
(–) (–)
R—C—O CO2 + R
(–) (–)
R + H2O RH + OH
Stability of carbanion ∝ rate of decarboxylation.
55. (a) In benzene two molecules of RCOOH are associated with each other by the help of H Bonding.
O
(–)
56. (a) R—C—O(–) CO2 + R
(–) (–)
R + H2O RH + OH

CO2 + CaO CaCO3

COOH COOH
57. (c) C2H5
heat
C—COOH CH3 + C2H5
CH3 H C2H5 H CH3
COOH
58. (d) See question number 54
59. (d) See question number 54

H OH
dil H2SO4
60. (a) CH2=CH—OCOEt CH2=CH—OH + EtCO2H soda lime Et—H
hydrolysis
tautomerism

CH3CHO

COOH
(–)

soda lime
61. (a)

Br Br
More than one may correct:-
1 b, c, d 2. a, c
COOH
OHC COOH ∆ OHC
3. a, b, c, d O O
4. a, b, c, d Organic compounds can be arranged in their decreasing order of acid strength as follows:-
RSO3H > HCOOH > RCOOH > PhOH > H2O > ROH > RNH2
H O / OH (–)
b, d CH3CN 
2 2 → CH3CONH 2
5.
OH + CH3COCl OCOCH3 + HCl Cl +CH3COOH
6. a, b, c See mechanism of esterification in your text book
Br
(–)
OH MnO4 HVZ
7. b, c (+) COOH COOH
H
[A] [B] [C]

Order of acid strength is C > B > A

8. a, b 9. b, c
10. a, c, d In (a), (c) & (d) alpha ‘H’ atom is absent
318 Problems in Organic Chemistry

LEVEL -II

O O O
(+)
C—OH C—OH2
1 & 2 (CH2)2 (CH2)2 (–) O P1
C—OH COO
O O

O O O
(+)
C—OH C—OH2 O
(CH2)3 (CH2)3 (–) P2
C—OH COO O

O
O O
(+)
C—OH C—OH2 O
(CH2)4 (–) H2O + CO2 + P3
C—OH C—O
O O
(–) (+)
3.
CH2Br Mg (1 mol)
CH2Mg Br
(THF)
CH2=CH2+ MgBr2
CH2Br CH2—Br (A)

(+)
H3O KMnO4 neutral
CH2 = CH2 EtOH CH3COOH FeCl3
(CH3COO)3Fe
(Blood red)
 Amines
11
Main Features

Reaction Chart for Amines

Preparation Properties

LAH or H2/Ni NaNO2 + HCl Alcohol / nitroso amine

RNO2 or Sn+HCl [ 1°amine / 2° amine]
(for 1° amine)
alc NH3 CH3COCl Acylation
RX
(for 1° and 2° amines)
LAH or N2/Ni CS2/HgCl2
RCONH2 RNCS (Mustard oil test)
(for 1° amine) A (for 1° amine)
M CHCl3
Imine/schiffs base
LAH or H2/Ni
I KOH
RNC
N (for 1° amines)
Gabriel Phthalimide E PhSO2Cl Hinsberg test
S KOH
(for 1° amines) (for 1° and 2° amine)
LAH or H2/Ni
RCN(for 1° amine)
CH3Br (in excess)
(CH3)4NBr
NH3
ROH(for 1° amine) Al2O3 (for all amines)
H2O2
RCONH2(for 1° amine) KOBr or H2SO5 R3N→O
(for 3° amine)
N3H COCl2
RCOOH(for 1° amine) H2SO4
RNCO
(for 1° amines)
RNC(for 2° amine) LAH
Hoffman elimination
RMgX + ClNH2
320 Problems in Organic Chemistry

LEVEL - I

Multiple Choice Questions

C H ONa
1. Urea (A) + Diethyl malonate 
2 5 → (B)
110°C

Which is correct about the basic strength of A & B?

(a) (pKb)A = (pKb)B (b) (pKb)A > (pKb)B (c) (pKb)A < (pKb)B (d) (pKb)A ; (pKb)B

2. Identify (X) in the following reaction:-

OH
C H OH
+ NH2NHCONH2 →
2 5
75°C,8hr (X)
COCH3
OH
ONHNHCONH2
(a) (b) C= NHNCONH2
COCH3
CH3
OH
ONHCONHNH2
(c) (d) C=NCONHNH2
COCH3
CH3
3. Rank the following compounds in order of basic strength.

O O O

N N N N
(1) CH3 (2) CH3 (3) H (4) CH3

(a) 2 > 3 > 4 > 1 (b) 2 > 3 > 1 > 4 (c) 3 > 2 > 1 > 4 (d) 3 > 2 > 4 > 1

CH3
|
(i) LiAlH
4. CH3 — C(NO 2 )C(OH)Me2  4
(ii) NaNO + H SO
→ Product
2 2 4

Product of this reaction would be:-

CH3 CH3 CH3

CH3 CH3 | | |
(a) | | CH 2 = C — C = CH 2
(b) CH3 — C — C — CH3 (c) Me3CAc (d)
CH3 — C = C — CH3 | | |
OH OH CH3

5. Cyclobutyl Ethanoic acid is treated with N3H / H2SO4 and the product formed in this reaction is further treated with potassium
nitrite & dilute sulphuric acid to give [X] , [X] would be:-
(a) Cyclobutyl Methanol (b) Cyclo pentanol
(c) Cyclobutyl ethanol (d) Nitrosocyclo butyl methanamine
110°C
6. Carbamide + N2H4 
Amyl alcohol
→ (X), (X) will not react with

(a) Carbinol (b) AcH (c) Formalin (d) Acetophenone

Amines 321

7. Consider the following reactions.

KBrO NaN / ∆
EtCONH 2 → Product .............(1) CH3CH 2COCl 3 → Product .............(2)
H O 2

LiAlH 4 (i) NH
AcNH 2  → Product .............(3) CH3CHO  3
(ii) LiAlH
→ Product .............(4)
4

The reaction in which ethyl amine forms as a product is/are:-

(a) 1, 3 & 4 (b) 1, 2 & 4 (c) 1 & 3 (d) 1, 2, 3 & 4
8. Caffeine is found in tea leaves. It contains four nitrogens. Correct sequence of basic strength of these nitrogens is:-
O (1) CH3
(4)
CH3—N N

(2)
O N (3) N

CH3

(a) 1 > 2 > 3 > 4 (b) 2 > 1 > 3 > 4 (c) 1 > 4 > 3 > 2 (d) 1 > 3 > 4 > 2
9. 3° — butyl alcohol can be converted in to 3° butyl amine conviently by:-
(a) PCl5, NaNH2 (b) HCN + H2SO4
(c) AcCl / C2H5N & NH3 / Heat (d) All of these
10. The reaction which can not be performed by H2 / Ni is:-

(a) CH3NO2 
→ CH3NH2 (b) CH3CONH2 
→ CH3CH2NH2

Φ CH = CH — CN 
(c) — → ΦCH 2 — CH 2CH 2 NH 2 (d) CH NC 
3
→ CH3NHCH3

NaNO2
11. (A) (C) –ve victor maeyer test
+ve mustard oil test
(B) (D) Blue colour in vector maeyer test
NaNO2
HCl

(A) and (B) are respectively.

CH3 CH3
NH2 |
|
(a) CH3 — C — NH 2 , CH3—N— CH3 (b) , CH3 — C — NH 2
| |
|
CH3 Et CH3

CH3 NH2
| Et
|
(c)
CH3 CH — CH 2 NH 2 , (d) ,
CH3 —CH — NH 2
CH2NH2

12. Which product will not form when primary amine reacts with sodium nitrite & HCl ?
(a) Alcohol (b) Alkylhalide (c) Alkene (d) Chloramine
13. Which of the following is the weakest bronsted base ?

N
(a) (b) (c) (d)

O
322 Problems in Organic Chemistry

14. Mitomycin C is an anticancer agent & used to treat stomach and colour couch. Its structure is
2
O CH2OCONH2
1
H2N
OMe
N 3
O 4 NH
Which is correct about mitomycin C?
(a) It contains 5 chiral carbon atoms (b) 3rd nitrogen is highly basic
(c) It contains 3 chiral carbon atoms (d) 4th nitrogen is highly basic
15. Arrange the following compounds in decreasing order of boiling point
(a) (CH3)3N < CH3NHEt < PrNH2 < PrOH (b) (CH3)3N < PrNH2 < PrOH < MeNHEt
(c) PrNH2 < MeNHEt < Me3N < PrOH (d) Me3N < MeNHEt < PrOH < PrNH2
16. Strongest acid among the following is:-
H
NH2
N SO NH
(a) (b) (c) (d) 2 2

N
17. Consider the following reactions
(i) L.A.H
® [A] Benzonitrile ¾¾¾¾¾¾¾
dil H 2SO 4 ® [B]
CH 2 = CH 2 + (CN)2 ¾¾¾¾¾ (ii) MeCl / NaOH

OH O NH2
(i) AgNO 2
+HI (excess) 
→   → [C]
(+)
(ii) Fe / H H ( ) H / Pd
+  
2  [D]
OH
Out of A, B, C & D the product (s) the product which can show Hoffman mustard oil test is/are:-
(a) B & D (b) only D (c) A, B & D (d) Only C
18. Identify (X) in the following reaction.
(+)
(i) LaH (ii) H / heat
ClCOCH 2CH 2CH 2 NH 2 
→(X)
(iii) NaOH

H
H
N
N CH3
(a) N—CH3 (b)
CH3 CH3 (c) (d)
N—H

19. Identify [Y] in the following reaction

O
O [Y]
+
NH2
O

O O OH OH
NH
(a) O (b) NH (c) NH (d)
NH O OH O
OH
Amines 323

20. The reaction in which ketone does not form.

(i) KMnO (i) CH3MgBr
(CH3 )2 CHNH 2 
(a) + → Product (b)
4
CH3CN  + → Product
(ii) H3O (ii) H3O

(i) NaNO 2 + HCl

(c)
i − Propylamine  → Product (d) In all cases ketone is formed
(ii) Cu / ∆

Passage - I

Reserpine is a natural product belonging to the family of alkaloids. Clinical application of it is in treatment of hypertension and
nervous and mental disorders

N
MeO N H
H
H
H O
O—C— OMe
MeO2C
OMe
OMe
(Reserpine)
OMe

Reserpine breaks in to products when subjected to hydrolysis as follows

OH
OH

Reserpine + H3O + → A + 6MeOH + HOOC OH

Answer the question from 21 to 23
21. Which is correct about the basic nature of nitrogen atoms ?
(a) ‘N’ of pentagonal ring is more basic than that of hexagonal ring
(b) ‘N’ of pentagonal ring is less basic them that of hexagonal ring
(c) Both are equally basic
(d) ‘N’ of hexagonal ring can show amine inversion
22. Chiral ‘C’ atoms present in reserpine are:-
(a) 4 (b) 5 (c) 6 (d) 7
23. When 2 moles of aqueous NaOH are added in to one mole of (A) then product formed would be:-

N (+) (–) N
(a) (b) Na O N
HO N
(–) H
Na+

NaO2C OH NaO2C OH
OH OH

N (+) (–) N
(c)
HO N (d) N
Na O (–)
H
(–) (+)
O Na OH
NaO2C NaO 2C
OH OH
324 Problems in Organic Chemistry

Passage - II

CH I Ag O ∆ H SO heat
N − methyl peperidine 
3 → P →
2 Q 
→ R 
2 5 → S 
→T
H 2O

Answer the question from 24 to 28

24. Compound P is:-

(+) (+)
(a) (+) (b) (c) N I(–) (d) N I(–)
N (–) N (–)
I (+) I H3C CH3 H3C CH3

25. Compound Q is:-

(a) (b) (c) (+)

(–) (d)
(+)
(+) (+) OH (–)
N N N N OH
(–) (–)
H 3C CH3 H3C CH3
CH3 O CH3 O

26. Compound R is:-

(a) (b) (c) (d)

N N NMe2 NMe2

27. Compound S is:-

(a) (+) (b) O (c) O (d) (+) (–)

N (–) N N N—O
O
28. Compound T is
(a) Buta - 1, 3 - diene (b) Penta - 1, 4 - diene
(c) Penta - 1, 3 - diene (d) (CH3)2 N+ = CH — CH2 — CH = CH2

Passage - III

∆ OH (–) , heat H O
CHI(CH2)3NHMe 
→ A → B →
2 2 C
∆

N
Answer the question from 29 to 31

29. Compound A is:-

CH (+) CH=CH(CH2)2NHMe
(CH2)3 N
(a) (+) (b) H (c) (d) None of these
N N N
N CH3
CH3 H
Amines 325

30. Compound B is:-

OH I
CH CH (+)
(CH2)3 (b) N N
(a) (+) (+) (CH2)3 (c) (d)
N N N CH3 CH3
N H N N
CH3 Me

31. Compound C is:-

OH
O
N
(a) CH2CH=CH2 (b) (c) (d)
N N N OH N
N N
OH OH

Passage - IV

A nitrogen containing compound (with four carbon atoms) can have two isomers (A) & (B). (A) & (B) On treatment with Fe +
HCl give (C) & (D) respectively. Both (C) & (D) produce same compound (E) on treatment with sulphuric acid and sodium nitrite.
Compound (C) on treatment with KMnO4 followed by hydrolysis gives (F). (E) And (F) don not give haloform test. (F) Gives (G)
when treated with NaBH4 & thionyl chloride. Now (E) is treated with aqueous NaOH & then with (G) to produce (H). (H) Further
gives (E) when mixed with dilute sulphuric [Link] H can decolourise bromine water then:-

Answer the question from 32 to 40

32. Compound (A) is:-

(a) NO2 (b) NO2 (c) NO2 (d)

NO2
33. Compound (B) is:-

(a) NO2 (b) NO2 (c) NO2 (d)

NO2

34. Compound (C) is:-

NH2
(a) NH2 (b) (c) NH2 (d)
NH2

35. Compound (D) is:-

NH
(a) NH2 (b) 2 (c) NH2 (d)
NH2

36. Compound (E) is:-

OH
(a) (b) OH (c) (d) OH
OH
37. Compound (F) is:-
CHO
(a) CHO (b) (c) (d) NO
O
326 Problems in Organic Chemistry

38. Compound (G) is:-

CH2Cl
(a) Cl (b) CH2Cl (c) (d) NHCl

39. Compound (H) is:-

(a) (b)
CH2—O (c) (d) OCH2

40. Compounds which exhibit enantiomerism

(a) (F) & (G) (b) (B) (c) (H) (d) None
41. Consider the following amines.
Et CH2NH2
| CH3
CH3 — C — Pr (2)
(1) | (3) CHD2 – CH2 – CHDNH2 (4)
| CD3CHCH 2 NH 2
NH2

Amine/s which will exhibit optical isomerism after the treatment with NaNO2 + H2SO4 is / are:-
(a) 1, 2 (b) 1, 3 (c) 1, 3, 4 (d) Only 1
42. Match the following:-
Reaction Product
(i) HONO
(A) PrNO2 
(ii) NaOH
→ (1) Blue Colour

(B) MeNO2 Cl + NaOH


2 → (2) Red Colour
(i) Sn + HCl
(C) EtNO2 
(ii) HONO (iii) KOCl
→ (3) Chloropicrin

(i) HONO
(D) Me2CHNO2 
→ (4) Chloroform
(ii) NaOH

A B C D A B C D
(a) 5 3 4 1 (b) 2 3 4 1
(c) 2 4 3 1 (d) 2 4 1 3
43. The method which does not offer preparation of 1° amine is:-
H
(b) CH3CHO + CH3 NH 2 
2 →
(a) Gabriel Phathalimide Pd / ∆

CH3 (i) KMnO

∆
CH—NH2 
H 4→
(CH3 )2 CO + NH3 
(c) → 
2→
(d) (ii) H ,Pd 2
Pd
CH3
44. The compound whose one mole will react with three moles of Ac2O is:-
O CN
NH2
HN NH
(a) (b) (c) (d) None of these
O O N COOH HO OH

45. Least basic amine among the following is:-

N—H

(a) N•• (b) Pr3N: (c) (d)

••
N
H
Amines 327

46. A primary amine on treatment with NaNO2/HCl gives alcohol which on dehydration followed by ozonolysis gives two com-
pounds. One of them gives +ve iodoform test but negative tollen’s test whiles other gives +ve tollen’s test but negative iodoform
test. If alcohol does not produce any colour in victor maeyer test then structure of amine will be:-

(a) (b) (c) NH2 (d) NH2

NH2
NH2

47. Weakest base among the following is:-

H H

N N
N N
(a) (b)
CH3 CH (c) (d) H C2H5
CH3 3 C2H5

48. Which of the following is the IUPAC name of C3H7NC?

(a) Propyl isocyanides (b) Carbyl amino butane (c) Carbylamino propane (d) Butyro isonitrile

49. HNCO on tautomerism will produce

(a) Cyanuric acid (b) Cyanic acid (c) Isocyanic acid (d) Cyanogen

50. The reaction in which amine does not produce is:-

–AgI KOH (i) P + I
(a) CH3OH 
CH3I + AgNCO → X → Product (b)
2 → Product
(ii) NH 3

(i) CH NH
(d) CH3COCH3 →
KOH 3 2
(c)
CH3 NCO → Product Product
(ii) H / Ni 2

51. Me4N + OH– is:-

(a) Amphoteric (b) stronger base than NaOH
(c) Basic in nature but lesser than NaOH (d) Neutral in nature

nBu nPr
| |
52. CH3 — C — CH —C — CH3 ¾¾¾¾¾
nitrous acid
® major product (X)
| | |
Et NH2 Et

[X] would be:-

nBu nPr nBu OH
| | | |
(a)
CH3 — C — CH —C — CH3 (b) CH3 — C — CH —C — CH3
| | | | | |
Et OH Et Et nPr Et

nBu nPr OH nPr

| | | |
(c)
CH3 — C —CH —C — CH3 (d) CH3 —C— CH —C — CH3
| | | | | |
OH Et Et Et nBu Et

53. If boiling points of CH3NO2, CH3ONO and CH3COOH are x, y & z respectively then
(a) z > x > y (b) y > x > z (c) z > x = y (d) z > y > x
328 Problems in Organic Chemistry

O
(CH2)2CN H

2 → Product,
[Link]
54.

Product of this reaction will be:-

OH O OH
(CH2)3NH2 (CH2)3NH2 (CH2)2CN
(a) (b) (c) (d)
N
H

D
14
KBrO
CONH2 →
55. C O Product
H
Product of this reaction will have:-
(a) ‘R’ configuration (b) ‘S’ configuration (c) Both R & S configuration (d) product is optically inactive
(i) H O /OH(–)
2 2 (i) H2O/H2SO4
56. (A) (ii) KBrO (B) (C) (ii) N3H, Heat
[X]
KBrO

By the help of [X] carbonyl compounds can be identified select the correct statement.
(a) (A) is carbamide & B is cyanogens (b) (B) is NH2CN & A is Cyanogen
(c) (A) is Cynogen & (C) is NH2CN (d) (B) is NH2CN but (C) is Carbamide

57. Assertion- aliphatic amines can not form RN2 + Cl– with NaNO2 + HCl while aromatic amines form diazonium salts
Reason- Aliphatic diazonium salts are not stabilized by resonance
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
58. Assertion-aniline can not be prepared by Gabriel phthalimide reaction while phenyl methyl amine can
Reason- Aniline is less basic than phenyl methyl aniline
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
59. Assertion- acetamide is amphoteric in nature
Reason- Due to resonance NH2 group acquires positive charge and oxygen acquires negative charge so when acid is added it
attacks on oxygen and when base attacks it removes water from NH2
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true
60. Assertion- Although acetamide contains CH3CO linkage yet it does not form iodoform
Reason- C—H bond is more polar than N—H bond
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is frue, Reason is false
(d) Assertion is false, Reason is true
Amines 329

61. Assertion- 2nd acylation of primary amine is difficult

Reason- After first acylation N of primary amine becomes sterically hindered
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true

62. Assertion- Aniline (aqueous solution) can precipitate FeCl3 in to ferric hydroxide but same is not true for methyl amine
Reason- In aniline the lone pair of electrons take part in resonance in benzene ring while lone pair of electron of methyl amine
is localized.
(a) Assertion is true, Reason is true: Reason is a correct explanation for Assertion.
(b) Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(c) Assertion is true, Reason is false
(d) Assertion is false, Reason is true

Answer Key

1. (c) 2. (b) 3. (d) 4. (c) 5. (b) 6. (a) 7. (d) 8. (b) 9. (b) 10. (d)
11. (c) 12. (d) 13. (a) 14. (b) 15. (a) 16. (d) 17. (d) 18. (c) 19. (d) 20. (d)
21. (b) 22. (c) 23. (b) 24. (a) 25. (c) 26. (c) 27. (a) 28. (b) 29. (b) 30. (c)
31. (c) 32. (b) 33. (a) 34. (b) 35. (a) 36. (b) 37. (a) 38. (b) 39. (a) 40. (d)
41. (b) 42. (b) 43. (b) 44. (a) 45. (b) 46. (a) 47. (b) 48. (c) 49. (b) 50. (a)
51. (b) 52. (d) 53. (a) 54. (a) 55. (a) 56. (c) 57. (a) 58. (b) 59. (a) 60. (c)
61. (c) 62. (d)

Multiple Choice Questions More Than One May Correct

1. Water insoluble amine is:-

(a) Me2NH (b) PhNH2 (c) Ph2NH (d) Ph3N
2. Which statement is not correct about acetamide?
(a) It is amphoteric in nature (b) On hydrolysis it produces primary amine
(c) On heating with NaOH it gives NH3 (d) On heating with P2O5 it gives carbyl amine
3. Which among the following pair can not be differentiated by Hoffman mustard oil test?
(a) Ph2NH, Me3N (b) MeCONH2, Me2NH (c) MeNH2, i-Pr-NH2 (d) EtNH2, Me2NH
4. Which is resolvable?
(+ )
(a) CH3CH2CH2CH(Et)NH2 (b) CH3 NHD (c) CH3NHC2H5 (d) CH3NH CH3
|
Et
5. Which is not the preparation of secondary amine?
heat LaH
(a)
CH3CHO + NH 2OH  →
→  (b) Gabriel Pthalimide reaction
LAH
(c) CH3CONHCH3  → (d) CH3 NH 2 + CH3Br(2moles) 
→
330 Problems in Organic Chemistry

6. Aliphatic 1° amine:-
(a) is more soluble in water in comparison to alcohol of comparable molar mass
(b) has pyramidal shape
(c) has more boiling point than RCOOH
(d) has sp3 hybridised ‘N’ atom
7. Which is correct about the following road map?

LAH NaNO + HCl

→[A] 
2 →[B]

NO2

(a) A is optically inactive (b) B is optically inactive (c) A is optically active (d) B is optically active
8. Which of the following reaction is least likely to occur?

(a)
(CH3 )2 NH + CHCl3 + KOH 
→(CH 2 )2 CNC

NaBH 4
(b)
CH3CONH 2  → CH3CH 2 NH 2

(c)
CH3 NH 2 + CH3COCl 
→ CH3CONHCH3 + HCl

pyridine
(d)
PhNHCOCH3 + CH3COCl 
→(CH3CO)2 NPh + HCl

9. Which is not in the favour of Gabriel pthalimide reaction?

(a) It is the method for the preparation of pure primary amine
(b) Aromatic amines can not be prepared by this method
(c) All aromatic amines (except aniline) can be prepared by this method
(d) 2° & 3° amines can also be prepared by this method

H
KOBr
CONH 2 → product
10.

CH3

(a) Product of this reaction can show geometrical isomerism

(b) Product of this reaction contain plane of symmetry
(c) Product of this reaction can show both geometrical & optical isomerism
(d) Product of this reaction is a secondary amine.

O
NC CN
11. 3 (i) H O(+)
NC CN 
→ [X]
(ii) N3H +H 2SO 4

NC CN CH3

Which is correct about [X]?

(a) It is optically active (b) It bears 3 chiral ‘C’ atom
(b) It contains only ketone as functional group (d) It contains one ketone & one NH2 group
Amines 331

OH NH2 NO2 CH2NH2

12.
OH
(1) (2) (3) (4)

(a) (1) is strongest acid while (4) is strongest base (b) (4) is strongest base
(c) (3) is strongest acid (d) (3) is weakest acid while (4) is strongest base

Answer Key

1. (b), (c), (d) 2. (b), (d) 3. (a), (b), (c) 4. (a), (b) 5. (a), (b), (d)

6. (a), (b), (d) 7. (a), (d) 8. (a), (b), (d) 9. (c), (d) 10. (a), (b)

11. (a), (d) 12. (b), (c)

LEVEL - II

Comprehension

Comprehension - I

H ( )
CH3 MgBr *CO 2 
SOCl NH3
[A] [B] 2 [C]  [E]


NaOI H / BrO()
[F]  [D]
2 
Pd / BaSO 4
Precipitates [G]

1. What is ‘F’ ?
2. Can ‘G’ show Hoffman mustard oil test
3. Out of A, B,...............G, which contains isotopic carbon i.e. *C
4. Which will show Tollens’s test among B, C, D, E & F ?

RCONH 2 + Br2 + KOH ¾¾

® RNH 2
5.
x : y : z

What is the ratio x:y:z ?

Comprehension - II

Consider the following reactions.

OH
|
KOBr
CH3 — CHCONH 2 →(A)

NH 2CONH 2 
→ (B)
332 Problems in Organic Chemistry

NaNO 2 + HCl
 → (C)
N
H

OH
|
(i) CrO , ∆
CH3CHCH 2CONH 2  3 → (D)
(ii) NaNO + HCl, ∆
2

(a) A (b) B (c) C (d) D

6. A can undergo condensation with:-
(a) B (b) C (c) D (d) None
7. B can undergo condensation with:-
(a) A (b) C (c) D (d) All of these
8. Which is yellow coloured solution ?
(a) A (b) B (c) C (d) D

B
9. A → E
NaOH,∆

B
→ F
D NaOH,∆

E & F are:-
(a) Optical isomers (b) Geometrical isomers (c) Homomers (d) Homologues

Comprehension - III

(+)
KHSO4 Aniline H
Glycerine (A) (B) (C)
∆
[O] –H2O
(E) (D)

10. Which is highly aromatic?

(a) C (b) D (c) E (d) All are equally aromatic
11. Total number of chiral carbon atoms present in C is:-
(a) 2 (b) 3 (c) 4 (d) 1

Answer Key

1. CHI3 2. yes 3. A, B, C, D & E 4. (d) 5. x : y : z = 1 : 4 : 1

6. (a) 7. (a) & (c) 8. (c) 9. (d) 10. (c)

11. (d)
Amines 333

SOLUTIONS

NH2 EtOOC NH—CO

–2EtOH
1. (c) CO + CH2 CO CH2 B
A NH2 EtOOC NH—CO

In B lone pair of electron present on N are more delocalized in comparison to that of urea because each lone pair takes part
in resonance with two carbonyl group, hence B is less basic than A.

OH OH
(–)
O •• •• •• C2H5OH
O
2. (b) NH2NHCONH2 75°C, 8 hr
C 1 2 3 C—NH2NHCONH2
(+)
CH3 CH3
OH
OH
C=NHNCONH2 ∆
–H2O
OH
C—NHNHCONH2
CH3
CH3

Out of 1st 2nd & 3rd nitrogens, 2nd & 3rd nitrogens can not participate in condensation as lone pair of electrons present on
nitrogens is deloclised & take part in resonance with CO group.

3. (d) 1st & 4th are less basic as lone pair of electron is delocalized (resonance with CO group). 3rd is more basic than 2nd because
secondary amines are more basic than tertiary amines.

4. (c) It is a kind of pinacole-pinacolone rearrangement

CH3 CH3 CH3

LiAlH4 HNO2
CH3—C(NO2)C(OH)Me2 CH3—C(NH2)C(OH)Me2 CH3—C—C(OH)Me2
OH
pinacole pinacolone rearrangement
(CH3)3CCOCH3 (+)
H

(+) (+)
CH2COOH CH2NH2 CH2
N3H HNO2
5. (b)
H2SO4
H2O
(+)
OH OH2

6. (a) X is semicarbazide which gives condensation with (b),(c) & (d) but not with (a) (carbinol is MeOH)

Heat H 2O
7. (d) RCOCl + NaN3 
→ RCON3  → RNCO  → RNH 2

8. (b) 4th N is least basic as its lone pair of electrons are highly delocalized with two carbonyl groups. Lone pair of electrons
present on 3rd N are also delocalized with one carbonyl thus, it is less basic than 1st and 2nd.
9. (b) This is Ritcher reaction.
334 Problems in Organic Chemistry

10. (d) Reduction of an organic compound by H2 / Ni is an example of molecular addition.

CH3CN + 2H – H 
→ CH3CH 2 NH 2

In isocyanide molecular addition is not possible.

Me Me Me
NaNO2+HCl (+)
11. (c) Me— CH—CH2—NH2 Me— CH—CH2 Me— CH—CH3
A (+)
H2O
Me
negative Vector maeyer test Me— CH—CH3
OH C

NaNO2+HCl OH blue colour in Victor

maeyer test
CH2NH2

12. (d) When primary amine reacts with sodium nitrite & HCl carbocation forms. If it is attacked by chloride ion alkyl halide
forms & alcohol forms if water attacks on carbocation. If H+ ion is removed from carbocation alkene is formed.

13. (a) Lone pair of electron present on nitrogen is highly delocalised.

14. (b) It contains 4 chiral carbon atom. 3rd nitrogen is more basic than 4th because lone pair of electrons present on 4th nitrogen is
delocalized.

O
O ••
CH2OC—NH2
H2N
* OMe
* *
N
NH
O *

15. (a) Boiling point ∝ surface area

Boiling point of alcohol is greater than amine due to strong H– bonding . Since O is more electronegative than N thus,
alcohol forms stronger H– bond in comparison to amine.

16. (a) Lone pair of electron present on nitrogen are less delocalised in comparison to other.

17. (d)

(+)
18. (c) ClCOCH2CH2CH2NH2 LAH OHCH2CH2CH2CH2NH2 H ••
NH2
(+)OH2
(+)
–H
(+) (+)
N N
H H H
Amines 335

O O (+) O
NH2 NH
O ••
19. (d) NH2
O O O [Y]
O(–) OH

(+)
H3O
20. (d) MeCN + CH3MgBr  → MeCOMe

(+)
KMnO4 H3O
Me2CHNH2 Me2C=NH MeCOMe

NaNO2+HCl Cu,heat
i-PrNH CH3CHOHMe
2

21. (b) Because lone pair of electron of nitrogen in pentagonal ring is not localized

N
22. (c) MeO *
N H
H *
H *
H * * O
* OMe
MeO2C O—C—
OMe
OMe
(Reserpine)
OMe

(+) (–)
N NaO N
23. (b) OH N 2 moles of NaOH N
H H
A
(+) (–)
HO2C OH NaO2C OH
OH OH

Passage - II

(24 to 28)
CH3I Ag2O, H2O Heat H2SO5
(+) (+) (+)
(–) NMe2
N N I
(–) N OH N
R (–) S
CH3 P Q O
heat

Me2NOH +
T
336 Problems in Organic Chemistry

Passage - III

(29 to 31)

(–)
Heat OH O2H2
I (+) (+)
∆
N MeNH N N N N
CH3 H
A B Me

Heat
C (+)
N N N N
(–)
OH O
Me Me

Passage - IV

(32 to 40)
 Compound A & B may be nitro compound because they can react with Fe + HCl & the product formed after reaction can react
with nitrous acid.
 E & F do not show haloform test hence both does not contain MeCO linkage or both may be 30 alcohol.
 Since H decolourises bromine water hence it should have C-C multiple bond.

NO2 Fe + HCl NH2 NaNO2+ H2SO4

OH
A C E
Fe + HCl NaNO2 + H2SO4
NO2 NH2
B D
NH2 (+)
KMnO4
CH=NH H3O
CHO
C F
C
NaBH4 SOCl2
CHO CH2OH CH2Cl
F G
NaOH G
OH ONa
E H
(+)
H3O
OH
E

40. (d) All are optically inactive because no one have chiral carbon atom.
41. (b) 2nd on treatment with nitrous acid will produce optically inactive alcohol.

CH3 CH3 CH3 CH3

| | | |
NaNO 2 + H 2SO 4
→ CD3CHCH 2( + ) 
H 2O
CD3 CHCH 2 NH 2  → CD3 —C — CH3 
→ CD3 —C — CH3
(+ ) |
OH

42. (b) See victor mayer & haloform tests in your text book.
43. (b) 2° amine is formed.
Amines 337

44. (a) It on tautomerism becomes aromatic

O OH
HN NH tautomerism N N
A
O O
HO OH
Since A has 3 OH groups thus, it can react with 3 moles of Ac2O.

45. (b) Sterically hindered tertiary amine & can show amine inversion

NaNO2+HCl (+) ozonolysis

46. (a) H
NH2 OH Heat

+ve haloform but –ve Tollen's test MeCOMe + EtCHO

–ve haloform but +ve Tollens test

47. (b)

48. (c) Factual question

 N ≡ C — OH
49. (b) O = C = N — H 

(–) ••
50. (a) NCO Ambidentate nucleophile
••

In AgCNO, nitrogen site is not free to attack because it is a covalent compound (Ag-NCO) Thus reaction occurs as-

KOH
MeI + AgNCO 
→ MeONC → not a primary amine

51. (b) Factual question

52. (d) Migrating tendency of groups follow the following order n butyl > n propyl > ethyl > methyl

53. (a) In acetic acid two H bonds are present between two molecules. In nitro methane there is one H bond in its tautomeric
structure.

H
O O
N N
(CH2)2CN H2/Pd (CH2)3NH2 Heat H2 / Pd
54 (a) Heat –H2O

3 3
D D
1 14 2 2 14 1
KBrO
C O CONH2 C O NH2
55. (a)
H4 H4
S configuration R configuration

56. (c) CN H O / OH (–) CONH 2 NH 2 COOH CN


2 2 →
KBrO
→ N H H O( + )
| | | (X) ←
3
 | ←
3
 | ( C)
CN H 2SO 4 NH2
CONH2 NH2 NH2
338 Problems in Organic Chemistry

57. (a) Aliphatic diazonium salts are not stabilized by resonance however resonance occurs in aliphatic diazonium salts.
(+) (–) (+) (–) (+) (–) (+) (–)
N N N N N N N N
(+) (+)

(+)

58. (b) For the preparation of aromatic amines pthalimide has to react with aromatic halide which is not favourable reaction be-
cause in aromatic halide C-X bond acquires double bond character due to resonance, which is difficult to break.

59. (a) Due to resonance NH2 group acquires positive charge and oxygen acquires negative charge so when acid is added it attacks
on oxygen and when base attacks it removes water from NH2

(–) (–)
O O O
(+) (–)
OH
Me—C—NH2 Me—C NH2 base Me—C NH
(+)
H
OH
(+)
Me—C NH2

60. (c) C–H bond is less polar than N–H bond thus, base removes H from N–H bond & not from C–H bond.

61. (c) After first acylation N is attached with COMe group so lone pair of electron present on N becomes delocalized as it under-
goes resonance with CO group and can not attack easily on 2nd RCOCl molecule.

62. (d) Aniline is poor base than methyl amine & can not precipitate FeCl3

(+ ) (–)
CH3 NH 2 + H 2O 
→ MeNH3 + OH

(–)
2Fe+3 + 6OH 
→ 2Fe(OH)3 ↓ Brown ppt

More than one may correct:-

1. b, c, d (b),(c) & (d) contain hydrophobic ‘Ph’ group which make them insoluble in water.

P2O5/∆
2. b, d CH3CONH2 CH3CN
(+)
H3O
CH3COOH + NH3

3. a, b, c Hoffman mustard oil reaction is the characteristic property of primary amines

4. a, b In both the cases chiral centers are present while (c) & (d) are not resolvable due to amine inversion.

5. a, b, d

6. a, b, d RCOOH has more boiling point than amine because two intramolecular hydrogen bonds are present between two
molecules of RCOOH

NaNO2 + HCl
7. a, d LAH

NO2 NH2 OH
Optically inactive Optically active
Amines 339

8. a, b, d 9. c, d

H H
KOBr
10. a, b CONH 2 → NH2

CH3 CH3

Product is optically inactive as it contains plane of symmetry

11. a, d product of this reaction is

* *

CH3 NH2

It is optically active and bears two chiral carbon atom.

12. b, c

LEVEL -II

Question No. 6 to Question No. 8

OH OH H–Bonding
KOBr –NH3
CH3CHCONH2 CH3—CH—NH2 CH3CHO (A)
(Unstable)

KOBr
NH 2CONH 2 → NH 2 NH 2 (Hydrazine)
(B)

NaNO2 + HCl

N N (C)
H NO
(2°amine) (yellow liq)

CrO3
CH3CHOHCH2CONH2 CH3COCH2CONH2

NaNO2 + HCl
CH3COCH3 ∆
CH2COCH2COOH
(D)
340 Problems in Organic Chemistry

wolf Kishner reduction

9. (d) A 
→ Ethane (E)

wolf Kishner reduction

B 
→ Propane (F)

E & F are homologues

Question No. 10 to Question No. 12

KHSO4 PhNH2
Glycerine ∆ CH2=CH—CHO PhNHCH2CH2CHO
(A) (B)

(–)
O OH
H O

•• (+)
N N N
(C)
H H H
(O) –H2O
–H2O
N N
(E) (D)
H

Only E is highly aromatic Q.10 (c) C is highly basic Q.11 (b)

 Biomolecules
12
Main Features
REACTION CHART FOR BIOMOLECULE

Modern definition of carbohydrates: - These are polyhydroxy aldehyde or ketone. Carbohydrates on hydrolysis produce poly
hydroxyl aldehyde & ketone.

In modern classification carbohydrates are also called as saccharides

Carbohydrates

Mono Saccharides Oligo Saccharides Poly Saccharides

(Di, tritetra
, Saccharides...........etc)

Test Mono Saccharides Di Saccharides Poly Saccharides

(1) Mutarotation Show mutarotation Except sucrose rest all show Don’t show
mutaroation mutarotation

(2) Tollen’s & +ve Except sucrose rest all show –ve
Fehling’s test Tollen’s & Fehling test

(3) Br2 water test Except ketose rest all show Except sucrose rest all show –ve
Br2 water test Br2 water test
Molish test: - Carbohydrates give violet colour on treatment with conc. H2SO4 & α - naphthol.

Epimers: - A pair of diastereomers that differ only in the configuration about of a single carbon atom are said to be epimers for eq.
CHO CHO

H OH H OH

HO H HO H

H OH HO H

H OH H OH

CH2OH CH2OH
342 Problems in Organic Chemistry

Anomers: - The two sugars that differs in configuration only for the carbon that was the carbonyl carbon in the open form is called
as anomers

H OH HO H

H OH H OH

HO H HO H

H OH H OH

H O H O

CH2OH CH2OH

Mutarotation: -
• α & β – D glucose have specific rotation +112° & 18.7° respectively. When either of these forms are dissolved in water
specific rotaion of solution is found to be + 52.7°. Thus, specific rotation of α & β – D glucose decrease and increase re-
spectively. This change of optical rotation with time is called mutarotation.
• If a carbohydrate show mutarotaion indicates that it exists in two anomeric forms α & β .
Protein: -
(a) Biuret test: - Alkaline solution of protein treated with a drop of aq. CuSO4, bluish – violet colour is developed
(b) Ninhydrin test: - Protein on treatment with ninhydrin give a solution having colour ranging from deep blue to violet
pink.

LEVEL - I

Multiple Choice Questions

1. HO2CCH2CHNH2COOH is called aspartic acid
If pKa of α – COOH is 1.88 pKa of α – NH3+ is 9.60 & pKa of side chain is 3.65 then isoelectric point of aspartic acid will be:-
(a) 5.74 (b) 2.77 (c) 6.13 (d) 3.65
2. (+)
H3N (CH2)4— CH COOH β
α
NH3
(+)
γ
pKa of the sites α, β & γ are 10.79, 2.18 & 8.95 Iso electric point will be:-
(a) 9.87 (b) 5.07 (c) 6.5 (d) 2.18
3. Which is not a reducing sugar?
CH2OH CH2OH
O H H O H
H
H H
(a) OH H O H OH (b)
OH OH

H OH OH H
CH2OH CH2OH CH2OH

H O H O H O H O H
CH2OH
H H H
(c) OH H O CH2 (d) OH H O H
H OH OH
OH H OH OH OH
H

H OH H H H OH H OH
Biomolecules 343

4. Which is incorrect about fructose?

(a) It gives Bendict’s test
(b) It gives CO2 with HIO4
(c) It forms Glucosazone when treated with Phenyl hydrazine
(d) It reacts with bromine water
5. Which one of the following is optically inactive?
(a) Leucine (b) Proline (c) Arginine (d) Glycine
6. Fructose gives Fehling test because:-
(a) Ketonic group present in it can be oxidized by fehling solution
(b) Ketonic group converts in to CHO gp by enolization
(c) Ketal form of fructose changes in to open chain structure which is sensitive towards base present in fehling solution
(d) Fructose does not give fehling test
7. Iso electric point of alanine is 6. At what pH value, maximum concentration of zwitter ion will be present
(a) greater than 6 (b) lesser than 6
(c) equal to 6 (d) pH = 8
8. One mole of sucrose will consume
(a) Six moles of AcCl (b) Eight moles of AcCl
(c) Five moles of AcCl (d) Ten moles of AcCl
9. Consider the following four carbohydrate molecules
CHO CHO CHO CHO
H OH H OH HO H HO H
HO H H OH HO H H OH
H OH HO H H OH H OH
H OH H OH H OH HO H
CH2OH CH2OH CH2OH CH2OH

(A) (B) (C) (D)

Epimeric pair is:-
(a) (A) & (B) (b) (A) & (D) (c) (C) & (B) (d) (C) & (A)
10. If a compound shows mutarotation then:-
(a) It confirms that it will exist in two anomeric forms
(b) It will always provide α – D glucose units on hydrolysis
(c) Compound will always contain aldehyde as well as ketone group
(d) All of these
11. Which is not dextro rotatory compound?
(a) Glucose (b) mannose (c) Fructose (d) Sucrose
12. Which statement is correct reagarding the difference between glucose & fructose?
(a) Glucose & fructose forms different - osazones
(b) Glucose on reduction gives sorbitol while fructose gives a mixture of sorbitol and mannitol.
(c) Fructose does not undergo oxidation by periodate while glucose is oxidized by it
(d) Glucose exhibits muta rotation but fructose does not.
13. The reagent by which we can prove that ketonic group is present at second location in fructose is:-
(a) Zymase (b) LiAIH4 (c) HNO3/∆ (d) H2 / Ni
14. Which is D(+) mannose ? If mannose is epimer of D(+) Glucose.
CHO CHO CHO CHO

H OH H OH HO H HO H
H OH H OH HO H H OH
(a) (b) (c) (d)
H OH HO H H OH H OH
H OH H OH H OH H OH
CH2OH CH2OH CH2OH CH2OH
344 Problems in Organic Chemistry

15. The reagent by which we can prove that glucose contains straight 'C' chain of six C atom is:-
(a) Na – Hg / alcohol (b) IO4– (c) Br2 water (d) Red P + HI
16. NaOH CaO pass in
Amino acid → gas  → 0.1999 kg (salt)
(1mole) ∆ lime water
evolved
Amino acid has:-
(a) Two NH2 groups (b) One COOH group (c) Two COOH groups (d) Three COOH groups
17. HNO 2 NaOH / CaO
Amino acid  → (A) → Ethyl alcohol,
∆
Amino acid is:-
(a) Glutamic acid (b) Glycine (c) Lysine (d) Aspartic acid
18. The carbohydrate with β - Glycosidic linkage is:-
(a) Lactose (b) Maltose (c) Amylopectin (d) Sucrose
19. Structure of amylose is:-
CH2OH CH2OH CH2OH CH2OH
O H H O OH O
(a) H O H O (b) H O H O
OH H OH H OH H OH H
n H n
H OH H OH H OH H OH
CH2OH CH2OH CH2OH CH2OH
O H O O O
(b) H O H O (d) H O H O
OH H OH H OH H OH H
H H H
n n
H OH H OH H OH H OH
20. The compound whose trinitrate is called gun - cotton is:-
(a) Sucrose (b) Gulose (c) Cellulose (d) Lactose
21. Compound Property
(A) amylopectin (1) Milk sugar
(B) Lactose (2) dextrorotatory
(C) Sucrose (3) 1, 4 & 1, 6 glycosidic linkage
(D) Alanine (4) L - Configuration
Correct matching is:-
(a) (A)→3; (B)→4 ; (C)→1 ; (D)→ 2 (b) (A)→3; (B)→1 ; (C)→2; (D)→ 4
(c) (A)→2; (B)→3 ; (C)→2 ; (D)→ 4 (d) (A)→3; (B)→4; (C)→2 ; (D)→ 1
22. Glycine can be converted in to methane by:-
(a) Heat, H3O+, Zn/Hg + HCl
(b) H2SO4 + NaNO2, KMnO4, NaOH/CaO
(c) LiAlH4, NaIO4
(d) HNO2, NaOH/CaO / heat, Red P + HI
23. Correct Structure of β – D – fructose is:-
HOH2C O CH2OH HOH2C O OH
(a) H HO (b) OH HO
H H H CH2OH
OH H H H
H O CH2OH HOH2C O OH
(c) HOH C H
HO
(d) H HO
2 OH H CH2OH
OH H OH H
24 Which among the following direct the synthesis of protein as well as responsible for the transfer of genetic information?
(a) Amino acids (b) Nucleic acids
(c) Pyruvic acid (d) Carbohydrates specially cellulose
Biomolecules 345

25. Which statement is correct regarding the difference between DNA and RNA?
(a) RNA contains Adenine guanine, Thymine and uracil while DNA contains Adenine, uracil Thymine & guanine
(b) RNA contains deoxy ribose while DNA contains oxyribose
(c) RNA contains Adenine cytosine, uracil and guanine while DNA contains Adenine cytosine, guanine and Thymine
(d) RNA contains phosphate while DNA does not
26. Vitamin Source
(A) H (p) Butter
(B) K (q) Yeast
(C) D (r) Green leafy vegetable
(D) A (s) Cod liver oil
Correct matching is:-
(a) (A)→2; (B)→3; (C)→ 4; (D)→1 (b) (A)→3 ; (B)→2; (C)→1; (D)→4
(c) (A)→2; (B)→4; (C)→ 3; (D)→1 (d) (A)→1; (B)→3; (C)→ 2; (D)→4
27. Which statement is correct?
(a) Hormones not produced by body & may be stored in the body to fight out the diseases
(b) Vitamins may be stored in the body to fight out diseases
(c) Vitamins are not stored in the body but are continuously produced
(d) Both hormones and vitamins are stored in the body
28. Molecular formula of pentasaccharide would be:-
(a) C30H52O26 (b) C30H72O36 (b) C5H10O5 (d) C30H60O30
29. Nucleotide contains
(a) Base + Sugar (b) Base + Sugar + Phosphate
(c) Sugar + Phosphate (d) Base + Phosphate
30. Glucose contains 5 – OH groups. This fact can be proved by treating glucose with
(a) Br2 water (b) Ac2O/H+
(c) Phenyl hydrazine (d) Zymase
31.
n
conc
(A)
HCl
Glucose
concn H2SO4
(B)
∆
(A) and (B) are :-
(a) Pyruvic acid & black mass (b) leavulic acid & Ethanol
(c) Pyruvic acid & Ethanol (d) leavulic acid & black mass
32. concn
(A)
HCl
Glucose
concn H2SO4
(B)
∆
HCl & H2SO4 are:-
(a) Oxidizing agent (b) Reducing agent (c) Dehydrating agent (d) Polymerizing agent
HNO3
33. Fructose  → oxalic acid + [X]
(O)
optically active
LiAlH (i) A
[X] 
4 → → Glycerine
(ii) B

A & B are respectively:-

(a) Br2 water & NaBH4 (b) HCN & H3O+
(c) HNO3 & NaOH / CaO,∆ (d) All of these
346 Problems in Organic Chemistry

34. Consider the following three carbohydrates:-

CHO CHO

H OH H OH CH2OH
HO H HO H H O
H OH
H OH HO H OH H
OH OH
H OH H OH
H OH
CH2OH CH2OH
(A) (B) (C)

The carbohydrate which does not have D configuration is:-
(a) C (b) A & B (c) B (d) All have D configuration
35. Which is correct about sucrose?
(a) It is non reducing non sugar (b) It is reducing non sugar
(c) It is non reducing sugar (d) It is reducing sugar
36. Honey contains:-
(a) Glucose + sucrose + water (b) Glucose + Lactose + water
(c) Glucose + fructose + water (d) Glucose + galactose + water
37. Which will not react with Tollen’s reagent?
(i) Glucose (ii) Fructose (iii) Sucrose (iv) hemi acetal of CH3CHO
(v) hemi acetal of propanone
(a) iv & v (b) iii, iv & v (c) i, ii & iii (d) iii & v
38. Consider the following reagents
A→PCl5 B→ KCN C→H3O+ D→ Red P + Br2 E→ NH3
Which reaction is correct?
(i) D
(a) AcOH 
(ii) B (iii) C
→ Glycine

CH2OH (i) A
(b) H2N—CH → Aspartic acid
(ii) B (iii) C
CH2OH
CH2OH (i) A
(c) H2N—CH → Aspartic acid
(ii) B (iii) C
OH
(i) A
(d) AcOH → Glycine
(ii) E

39. Which among the following will not produce D - glucose on hydrolysis?
(a) Amylose (b) Cellulose (c) Sucrose (d) Galactose
40. β – D – Glucopyrarose is:-
OHCH2 OH OH CH2OH
C CH2OH C CH2OH
H OH H O OH H OH H O OH
(a) HO H (b) H
H (c) HO H (d) H
H
OH OH
H OH OH H HO H OH OH
H O H OH H O H OH
CH2OH CH2OH
41. Isoelectric point is:-
(a) Potential difference (b) dissociation constant
(c) pH (d) Amount of current passed in the solution.
Biomolecules 347

Passage - I

Base of one nucleotide undergoes H - bonding with base of other nucleotide to give rise to formation of primary structure of DNA.
Guanine forms 3 - H bonds with cytosine while adinine forms two H - bonds with Thymine.
Answer the question from 42 to 44
42. What will be the sequence of bases on the strand of DNA that would be complementary to strand having the following se-
quences of bases?
T T A G G A T A?
(a) A A C T T C A T (b) A A T U U T A T (c) A A T C C T A T (d) T T A G G A T A
43. We have two samples of DNA
Sample – 1 M. P. = 340 K
Sample – 2 M. P. = 300 K
Which statement is correct?
(a) G C contents in sample – 1 are more than that of sample – 2
(b) A T contents in sample – 1 are more than that of sample – 2
(c) G C contents in sample – 1 are lesser than that of sample – 2
(d) A T contents in sample – 1 are lesser than that of sample – 2
44. Suppose RNA has double helix structure like DNA. What will be the sequence of bases on the strand of RNA that would be
complimentary to strand having the following sequence of base?
AA C C G AA G G
(a) A A G G C T T C A (b) U U G G C U U C C
(c) T T G G C T T C C (d) A A G G C U U C A

Passage - II

CHO
HO H HCN / H3O( + ) (i) Heat
H OH  →(A) + (B) →(C) + (D)
(ii) NaBH 4

CH2OH
D - Threose
Answers the questions from 45 to 47
45. Which is not correct?
(a) A & B are Epimers (b) C & D are Epimers
(c) C & D are anomers (d) A & B are hydroxy carboxylic acids
46. Which is correct?
(a) (A) is aldo pentose (b) (C) is aldo tetrose
(c) (D) is aldo pentose (d) (B) is aldo tetrose
47. The reaction D – Threose  → (A) + (B) is:-
(a) Stereo Selective (b) Stereo Specific
(c) Rearrangement reaction (d) Racemisation
48. A carbohydrate should contains at least
(a) 3 – carbon atoms (b) 4 – carbon atoms
(c) 5 – carbon atoms (d) 6 – carbon atoms
49. When a carbohydrate reacts with HIO4 it gives one glyoxal two formic acid and one molecule of formaldehyde. The carbo-
hydrate is:-
(a) keto hexose (b) Aldo pentose
(c) Aldo hexose (d) keto pentose
348 Problems in Organic Chemistry

z
50. C x (H 2 O) y  → xC + yH 2 O
if x = y = 6 then z would be:-
(a) Zymase (b) H2SO4 (c) HNO3 (d) Na – Hg / alcohol
51. The compound which does not exist as a & b forms are:-
(a) Glucose (b) Fructose (c) Maltose (d) Sucrose
52. Which among the following can not show mutarotaion?
CH2OH CH2OH

H O H H O H
H H
(a) OH H O H OH (b)
OH OH

H OH OH H

(c) (d)

53. Which is water insoluble:-

(a) amylose (b) gulose (c) galactose (d) amylopectin
54. The carbohydrate which does not contain b- anomer of any mono saccharide is:-
(a) Cellulose (b) Lactose (c) Sucrose (d) Maltose
55. Match the following
Compound Configuration
HO H
HO H
HO H
α – L – Glucose
(A) (1) H OH
H O
CH2OH
H OH

H OH
β – D – Glucose
(B) (2) HO H
H OH
O H
CH2OH
H OH
HO H
HO H
(C) Epimer of β – D – glucose (3)
H OH
O H
CH2OH
HO H
H OH
(D) Epimer of α – L – glucose (4) HO H
H OH
H O
CH2OH
(a) A→3; B→ 2; C→1; D→4 (b) A→2; B→ 1; C→4; D→3
(c) A→2; B→ 4; C→1;D→3 (d) A→3; B→ 4; C→1; D→2
Biomolecules 349

Answer Key

1. (b) 2. (a) 3. (a) 4. (d) 5. (d) 6. (b) 7. (c) 8. (b) 9. (d) 10. (a)
11. (c) 12. (b) 13. (c) 14. (c) 15. (d) 16. (c) 17. (d) 18. (a) 19. (a) 20. (c)
21. (c) 22. (d) 23. (d) 24. (b) 25. (c) 26. (a) 27. (b) 28. (a) 29. (b) 30. (b)
31. (d) 32. (c) 33. (c) 34. (d) 35. (c) 36. (c) 37. (d) 38. (c) 39. (d) 40. (b)
41. (c) 42. (c) 43. (a) 44. (b) 45. (c) 46. (c) 47. (d) 48. (a) 49. (b) 50. (b)
51. (d) 52. (a) 53. (d) 54. (d) 55. (c)

LEVEL - II

Comprehension
Consider the following compounds
H CH2OH H CH2OH
OHO OHO
HO HO
(A) H
CH2OH (B) H
OH
HO H OH HO H H
H OH
CH2OH
HO O CH2OH
(C) HO O
O
OH
OH HO
OH
1. Which can reduce tollen’s reagent?
(a) Only A (b) Only B (c) A & B (d) A, B & C
2. Which can not exist in anomeric form?
(a) A & C (b) B & C
(c) A & B (d) All can exist in anomeric forms.
3. Which can not decolourise Br2 water?
(a) A (b) B (c) C (d) A & C
Ag 2O dim ethyl sulphate
4. C  → D  → E, D & E. are respectively
(ii) acidification aq NaOH
H CH2OH H CH2OH
H CH2OH CH2OH
HO O H OH MeO O H OMe
(a) H O H & H O
HO COOH MeO COOH
OH OH OH OMe
OH MeO
H H
H H
CH2OH CH2OMe
HO O MeO O
(b) H & H CH2OMe
O CH2OH O OMe
OH OH OMe
HO MeO
H
HO OH COOH MeO OMe COOMe
CH2OH CH2OMe
OH H CH2OH OMe CH2OMe
HO OH MeO
(c) & OMe
O H O H
HO OH OH COOH MeO COOH
OMe
HO OH MeO OMe
(d) None of these
350 Problems in Organic Chemistry

Multiple Choice Questions

ach question contains statement given in two columns which have to be matched. Statement (A, B, C , D) in column I have to be
E
matched with statements (p, q, r, s) in column II. The answers to these questions have to be appropriately bubbled as illustrated in
the following examples. If the correct match are A - p, A - s, B - r, B - r, B - q, C - q, D - S, then the correctly bubbled 4 x 4 matrix
should be as follows.
A p q r s
B p q r s
C p q r s
D p q r s

5. arbohydrate
C Phenomenon / Reaction observed
(A) Amylose (p) Blue colouration with I2
(B) Glucose (q) decolourise Br2 water
(C) Sucrose (r) Can reduce tollen’s reagent
(D) Fructose (s) Can not Exist in anomeric form

6. Carbohydrate Structure
CH2OH
H O H
(A) β – D – Glucose (p) H
OH H
OH OH
H OH
CH2OH
H O OH
(B) Epimer of α – D – mannose (q) H
OH H
OH H
H OH
CH2OH
H O OH
(C) α – D – Glucose (r) H
OH HO
OH H
H H
OH
H—C
H OH
(D) β – D – Mannose (s) HO H
H OH
H O
CH2OH

Answer Key

1. (d) 2. (d) 3. (a) 4. (b)

5. A – p, B – q, r, C – s, D – r 6. (A) – q, (B) – p, s, (C) – p, s, (D) – r

Biomolecules 351

SOLUTION
1. (b) Isoelectric point is the average of pKa of similar groups .

Iso electric point = (1.88 + 3.65) / 2 = 2.77

2. (a) Iso electric point = (10.79 + 8.95) / 2 = 9.87

3. (a) Because none of the hemiactal linkage is free

4. (d) Keto group can not be oxidized by bromine water

5. (d) NH2CH2COOH glycine

6. (b) Fructose in presence of OH(–) ion gives mixture of glucose, fructose & mannose. This is called Lobry – de –bryun –van–
ekenstein rearrangement.

7. (c) At pH = 6 zwitter ion is present because pH = 6 is isoelectric point and amino acid does not move towards any electrode

8. (b) Because it has 8 OH groups.

CH2OH
O
H H
H
alpha- D- glucose OH H
OH
H OH O
HOH2C O α–β glycosidic linkage

beta- D- fructrose H OH
H
CH2OH
OH H

9. (d) CHO CHO

Epimeric carbon
H OH HO H
HO H HO H
H OH H OH
H OH H OH
C CH2OH A C CH2OH
10. ( a) Muta rotation is the phenomenon in which anomeric forms (α & β forms) change their optical rotation spontaneously when
dissolved in water. For e.g. specific rotation of pure α –D glucose is +113° & that of pure β-D glucose is –19° but when
either of these forms are dissolved in water specific rotation is found to be + 53° thus, mutarotation indicates that carbohy-
drate exists in α & β forms
11. (c) Fructose is laevo rotatory compound.

12. (b) CHO CH2OH CH2OH CH2OH

H OH H OH OH H O
HO H [H] HO H + HO H [H] HO H
H OH H OH H OH H OH
H OH H OH H OH H OH

CH2OH CH2OH CH2OH CH2OH

D-glucose sorbitol mannitol D-fructose
352 Problems in Organic Chemistry

13. (c) Fructose breaks in to two acids (oxalic & tartaric acids) in which ratio of carbon is 2:[Link] indicates that keto group is pres-
ent at 2nd location.
[O]
CH2OHCOCHOCHHOHCHOHCH2OH → COOH—COOH + HOOC—CHOHCHOH—COOH

14. (c) Mannose is the epimer of α – D– glucose

15. (d) Glucose on reduction with Red P + HI gives n–hexane

16. (c) 0.1999 kg CaCO3 = 200 g CaCO3

= 2 mol CaCO3

Thus, amino acid contains 2 moles of COOH group.

COOH COOH
HNO2 decarboxylation
17. (d) HOOC—CH2—CH COOH—CH2CH EtOH
NH2 OH

18. (a) 19. (a) 20. (c)

21. (b) Lactose is called milk sugar as it is found in the milk of all mammals. Alanine is amino acid & except glycine all amino
acids are found in L configuration.

HNO 2 decarboxylation [H]

22. (d) H 2 NCH 2COOH  → H 2OCH 2COOH → CH3OH  → CH 4

23. (d) 24. (b) 25. (c) 26. (a)

27. (b)

28. (a) [Glucose] × 5 – 4 H2O = C30H52O26 29. (b) Base + Sugar + Phosphate

30. (b) One mole of glucose consumes 5 moles of Ac2O.

31. (d) Concentrated H2SO4 is a good dehydrating agent.

concn H SO concn HCl

C6 H12O6 
2 4 → 6C + 6H O
C6 H12O6 
2 → leavulic acid

32. (c) Dehydrating agent 33. (c) Fructose on oxidation gives oxalic as well as tartaric acid

CH2OHCOCHOHCHOHCHOHCH2OH [O]
COOH–COOH + HOOC–CHOHCHOH–COOH
fructose Tartaric acid [X]
COOH CH2OH COOH CH2OH
CHOH LAH CHOH HNO3 CHOH Sodalime CHOH
CHOH CHOH CHOH Heat
CH2OH glycerine
COOH [X] CH2OH CH2OH

34. (d) All have D configuration because at 2nd last carbon atom H is on the left.

35. (c) Since it is sweet in taste hence it is sugar but it can not reduce tollen’s reagent thus, it is non reducing.

36. (c) Glucose + fructose + water

Biomolecules 353

37. (d)
CH2OH CH2Cl KCN CH2CN
38. (c) H2N—CH PCl5
H2N—CH H2N—CH
OH Cl CN
(+)
CH2COOH H3O
H2N—CH
COOH

39. (d) Galactose is monosaccharide. 40. (b)

41. (c) It is that pH at which amino acid does not migrate towards any electrode.

42. (c) A A T C C T A T (Thymine forms H bonds with Adenine & Cytosine with Guanine)

43. (a) Melting point ∝ extent of H - bond.

44. (b) A A G G C T T C A (in RNA in place of thymine, uracil is present)

CN CN
Passage-II (45 to 47) CHO
H
H OH HO
HO H HCN HO H HO H
H OH H OH H OH
CH2OH CH2OH CH2OH
(+)
H3O

COOH COOH
A H OH HO H B
HO H HO H
H OH H OH
CH2OH CH2OH

release of H2O Heat

CO CO
H OH OH H
HO H HO H
H O H O

CH2OH CH2OH

CO CO CHO CHO
H OH OH H H * OH H * OH
NaBH4 H
HO H + HO H HO + HO H
H O H O H OH H OH
CH2OH CH2OH CH2OH
CH2OH C D

Starred carbons are epimeric carbons.

45. (c) C & D are epimers but not anomers.

46. (c) (D) is aldo pentose 47. (d) Both A & B are formed in equal amounts

48. (a) Cx (H2O)y Here x = 3 to 8 (not for poly saccharides)

354 Problems in Organic Chemistry

49. (b) CHO

OH CHO
HIO4
OH + 2HCOOH + HCHO
OH CHO
CH2OH

50. (b) Dehydration of glucose 51. (d) Sucrose 52. (a)

53. (d) Starch contains two parts. One part is water soluble (amylose) & 2nd part is water insoluble (amylopectin). Gulose &
galactose are mono saccharides & soluble in water

54. (d) It contains two units of α – D– glucose. 55. (c)

LEVEL -II

1. (d) A is fructose B is glucose while C is Maltose.

2. (d) All can show muta rotation thus all can exist in anomeric forms i.e. α & β forms.

3. (a) In basic medium fructose converts in to glucose & exhibits tollen’s and fehling test but it can't show Br2 water test because
Br2 water cannot convert fructose in to glucose.

H
4. (b) CH2OH
O Hemiacetal but enguaged in
HO bonding
H
H CH2OH
HO OH O Hemiacetal site & shows tollen’s
H O test
OH
HO OH
H
CH2OH
O
HO
Ag2O H
(C) acidification O CH2OH
OH OH
HO
H
HO OH COOH
H CH2OMe (D)
O
MeO
CH2OMe
O
MeO OMe OMe Methylating agent

MeO OMe COOMe

 Aromatic Chemistry
13
Main Features
Preparation Properties
R NaOH / CaO
Ph heat
Aromatic electrophilic
COOH substitution
3Cl2 / hv
(+) (–) boil PhCCl3 (For toluene)
H3PO2
PhN2Cl or C2H5OH,∆
KMnO4 PhCOOH
boil (For C6H5R)
R (+) or
H3O
Ph R 3Cl2 / hv
SO3H C6H6Cl6
(For benzene)
Zn dust
Ph — OH ∆ V2O5/O2 CHCO
500°C O
CHCO
Anh. AlCl3 CrO2Cl2
(For benzene)
C6H6 + RCl PhCHO
Fe (+) (For toluene)
Acetylene (3-moles) ∆ D / D2O
D
Al2O3 / Cr2O3
n-hexane
600°C, 10 –15 atm
ArN2X
PhN2Ar
PhMgX + H2O
Preparation Properties

(i) CrO2Cl2 +ve tollen’s test

PhCH3 in CS2
+
(ii) H3O PCC CuSO4
PhCH2OH or Cu /∆ NaOH
–ve Fehhing’s & Bendict’s test
ZnCl2 NaOH
PhH+ CO + HCl CHO PhCOONa + PhCH2OH
H2O/∆ LAH
PhCHCl2 PhCH2OH

PhCN
DI BAL–H ARSE at meta location
KCN PhCH — COPh
Benzoin
OH
KMnO4
PhCOOH
Ac2O / AcONa
PhCH = CHCOOH
H3O(+)
[Perkin’s reaction]
356 Problems in Organic Chemistry

Preparation Properties
FeCl3 aq NaOH
PhH + X2 [X= Cl,Br] (+) PhOH
673K, 200 atm, H
Cu
PhN2X + HX [X= Cl,Br] Cu /∆
or CuCl Ph – Ph [Ullman reaction]
X (For iodobenzene)
PhN2Cl + KI
[For iodo benzene] ARSE at ortho and para locations
∆ Na/Ether
PhN2Cl + HBF4 Ph - Ph [Fittig reaction]
X=Cl, Br
[For fluoro benzene]
F&I
RX / Na
Catalyst Ether Ph – Ph + Ph – R + R – R
PhH + O2 + HCl [Wurtz-Fittig reaction]
[Raschig’s process]
Mg/Ether
PhMgX

Preparation Properties
(+)
673K, 200 atm H /Na2Cr2O7
PhX + NaOH (+)
O O
H
Br2 water
PhN2Cl + H2O Boil White ppt of 2,4,6 tri
bromo phenol
OH (+)
NaNO2+HCl PhN2Cl
PhN2Cl t > 8°C Pyridine PhN2 OH
(Orange)
OH NaOH / CaO (+)
HCHO/H
∆ PHENOL Bakelite plastic
COOH
FeCl3 3
NaOH /∆ [Fe(OPh)6] –[violet colouration]
PhSO3Na H
(+)
dil HNO3 OH
air Ph o & p derivatives
PhCHMe2
H3O+/∆ NO2
concn HNO3
Picric acid [2,4,6-tri nitro phenol]
Zn /∆
C6H6 [Reduction]
PCl5
C6H6Cl + POCl3 + HCl

Preparation Properties

hot
PhCH2R KMnO4 NaOH/CaO
∆ C6H6
hot
PhCH2OH or PHCHO KMnO4
ARSE at meta position
COOH NH3 / heat
hot PhCONH2
PhCOCH3 KMnO4

Na
PhCOONa + 1/2H2
H3O(+)
PhCN N3H
H2SO4
PhNH2
(i) KOH
PhCCl3 (+)
(ii) H
NaHCO3
PhCOONa + CO2 + H2O
Aromatic Chemistry 357

(i) NaOH/∆
(ii) H
(+) PhOH
SO3H SO3Na
oleum aq NaOH NaCN/∆
∆ PhCN

NaCl/∆
PhCl

H3O(+)
∆ PhH

Preparation Properties

conc HNO3
conc H2SO4 Sn+HCl or
PhNH2
Fe+HCl or H2/Ni
NO2
or L.A.H.
EtONO2
ASRE at meta location
Fuming HNO3 Strongly acidic medium
pass electric current
p–OH–C6H5–NH2
(+) (–) weakly acidic medium
NO2 BF4 Ph–NH2
pass electric current

acetyl nitrate Zn + NaOH

CH3OH PhN2Ph
Azo benzene
Zn + NaOH
PhNH–NH–Ph
Hydrazo benzene
O
Na2AsO3/NaOH
PhN=N–Ph
Azoxy benzene

Preparation Properties
Sn+HCl or PhCOCl
PhNO2 PhNHCOPh
Fe + HCl or H2/Ni
or L.A.H. PhSO2Cl (–)
KOH PhSO2NPh (Hinsberg test)
NH2
Na (–) (+)
NH3 / Cu2O PhNHNa + 1/2 H2
PhCl heat
CHCl3 / OH(–)
NH3 + ZnCl2
PhNC (carbyl amine)
PhOH heat
ANILINE NaNO2 + HCl
PhN2Cl (Diazotisation)
KOBr 0-5°C
PhCONH2
NaNO2 + HCl
PhMgBr NH2Cl t > 8°C
PhOH

(+)
H / Na2Cr2O7
O O
Br2 in CCl4
o & p bromo aniline
Br2 water
white ppt of
2,4,6-tri bromo aniline
(i) AcCl
o & p nitro aniline
(ii) HNO3 + H2SO4
(iii) Hydrolysis

H2PtCl6
[PhNH3]2 [PtCl6]

358 Problems in Organic Chemistry

Preparation Properties
KI solid
PhI + N2 + HCl

Cu or CuCl
HX PhX + N2 + HCl ( X= Cl ,Br)
N2Cl
NaNO2 + HCl HBF4
PhNH2 PhF + N2 + BF3
0-5°C
boil with water PhOH
EtOH or
H3PO2 + H2O benzene
+
PhNH2, H
p–NH2–C6H4–N2Ph [coupling reaction]
pH 4-5
(yellow dye)
PhOH, OH(–)
p–OH–C6H4–N2Ph [coupling reaction]
pH 9-10
(orange dye)

PhH + NaOH
Ph-Ph [Gomberg reaction]

Zn + HCl Zn + HCl
PhNHNH2 PhNH2
Na2SO3 / H2O
PhNHNH2
KCN / CuCN
PhCN
(i) HBF4
PhNO2 + N2 + NaBF4
(ii) NaNO2 / Cu

LEVEL - I

Multiple Choice Questions

NH2 NO2

1.
NH2 NH2
For this conversion sequence of reagents required is:-
(a) (i) KMnO4 (ii) Na2S (b) (i) H+/K2Cr2O7 (ii) NH4HS
(c) (i) Caro’s acid/HNO3/H2O2 (ii) Sn + HCl (d) (i) CF3CO3H (ii) Na2S
NaNH 2
2. ortho – Bromo toluene  → (A)
NaNH
ortho – Bromo anisole 
2→ (B)
(A) & (B) are:-
OCH3 CH3 NH2
CH3 NH2 NH2 Br
&
&
(a) NH2 (b)
CH3 OCH3 CH3 OCH3
NH2 NH2
& &
(c) NH2 (d) NH2
Aromatic Chemistry 359

(i) NaOH / CO Br
3. Phenol 
(+)
2 → X →
2
Water
Y,Compound Y is : −–z
(ii) H

OH OH OH OH
Br COOH COOH Br Br Br COOH
(a) (b) (c) (d)

Br Br Br
4. Identify the correct reaction.
NH2 NH2
Cl OH Cl OH
(a) + H2O + HCl (b) + H2O + HCl
Warm O2N NO2 Warm
O2N NO2
NH2 NH2
Cl OH
O2N NO2 O2N NO2
(c) + H2O HCl +
Warm

NO2 NO2
(d) None, because Cl present on Benzene nucleus can not be removed by H2O.
I I
5.
(A)

Br Br
(B)

(A) And (B) are:-

(a) Both are Cu / ∆ (b) A = Cu /∆ B = Zn + Et2O
(c) A = Zn + Et2O B = Cu /∆ (d) Both are Fe + HCl
6. Idenify the product of the following reaction.
Product
NO2

(i) KMnO / ∆
→
4 Product
(ii) NaOH + CaO

(a) Nitrobenzene (b) Benzene (c) CO2 + H2O + NO2 (d) o – nitro benzoic acid
7. Select the incorrect reaction.
NH2 O
Me Me
(i) 3 moles of CH Cl +
(a) PhNH 2 
3 → Na 2Cr2O7 / H
(ii) Heat (iii) NaOH (b) PhNH 2  →

Me O
NH2 NH2
NO2
conc HNO3 NaNO 2 + HCl PhNH 2
(c) PhNH 2  → + (d) PhNH 2  →[X]  → yellow ppt.
conc H 2SO 4 0°C

NO2
360 Problems in Organic Chemistry

8. Consider the following reactions.

NaNO 2 FeCl
CH3 NH 2  → CH3 N 2Cl .......(1)
CCl4 + 4Ph — H → Ph 4C + 4HCl .......(2)
HCl

(i) KMnO
PhNH 2 + CH3Cl →
3 AlCl
o − Me − C6 H 4 — NH 2 .......(3) Anthracene 
4 → C6 H 6 .......(4)
(ii) NaOH / CaO, heat

Reactions with wrong products are:

(a) 1 & 3 (b) 1, 2, 3 & 4 (c) 1, 2 & 3 (d) 4, 1 & 3

CH Cl dil H SO Br / D
CH2 → 3

2 4
→ →
2
[X]
9. Anh. AlCl3 D Fe
Major
C NH

O
[X] would be:-
Br Br
CH2 CH2
(a) (b)
NH2 C OH C OH
CH3 NH2 CH3
O O
Br

CH2
(c) (d) None of these

NH2 CH3

CH3 NH2
NO2 NO2
10. →(A) ,
H 2S/ NH3 H S/ NH
 
2 3 →(B)
50°C

NO2 NO2

(A) & (B) are:-

CH3 NH2 CH3 NH2

NH2 NH2 NO2 NH2
(a) & (b) &

NO2 NO2 NH2 NH2

CH3 NH2 CH3 NH2

NO2 NH2 NH2 NO2
(c) & (d) &

NH2 NH2 NO2 NH2

SO3H NaOH (C)

H (+)
11. NaOH

→ [X]
NaCN
(A) (B)
H3O(+)

Correct sequence of acid strength is:-

(a) A > B > C (b) B > A > C (c) C > A > B (d) A > C > B
Aromatic Chemistry 361

NH2
CHCl dil HCl
12. 
3 → 
→ X, X would be
KOH Heat

Cl

(+)(–)
(a) Cl NH2Cl (b) Cl NH2 (c)
Cl CN (d)
Cl NC

∆ (A)
V 2O 2
13. HO
2 2∆
(B)
NaNH2
(C)
CH3OH
Cl2
FeCl3
(D)

Which is correct about A, B, C & D ?

(a) All are non aromatic (b) ‘C’ is a conjugated diene
(c) A & B are non aromatic while (C) & (D) are aromatic (d) A, B & C are non aromatic but (D) is aromatic

14. What product will be obtained when 2 – methyl – 2 – phenyl propane is subjected to oxidation by MnO4– / H+ followed by
decarboxylation by NaOH / CaO / heat ?
(a) Benzene (b) Propane (c) Iso butane (d) Methane

15. Consider the following three derivatives of toluene

CH3 CH3 CH3

NO2

NO2
NO2
(1) (2) (3)

Their dipole moments will follow the sequence.

(a) µ1 > µ2 > µ3 (b) µ2 > µ3 > µ1 (c) µ2 > µ1 > µ3 (d) µ3 > µ2 > µ1

16. Aniline can be converted in to m-methyl nitro benzene by using:-

(a) NaNO2 + HCl (0°C), NaNO2 / Cu, CH3Cl / AlCl3 (b) CF3COOOH, CH3Cl / AlCl3
(c) NaNO2 + HCl (0°C), CH3Cl / AlCl3, NaNO2 / Cu (d) All of these

17. Which among the following is / are meta directing

( + ) (–)
– N 2 Cl,
– CCl3, – NHAc, –CHCl2

(a) All of these (b) 1, 2 & 3 (c) 1 & 2 (d) 1, 2 & 4

OH
CO (i) H SO

2 4→
18. + O (ii) NaOH (X)
CO
Product [X] will be:-
362 Problems in Organic Chemistry

OH
O OH
OH
C COO(–)
C
(a) (b)
C
C
O
O
OH
OH
CO
O
(c) C (d) None of these
OH

OH
19. How many mono nitro derivatives will be obtained by the nitration of [X] ?
OH

(i) Br (aq)
 2 → (X)
(ii) Zn, heat

(a) 1 (b) 2 (c) 3 (d) 4

(+) (–)
(+) NO 2 BF4
H
20. Phenol + Benzoic acid  (X) → (Y) major, (Y) would be:-
→
COOPh
COOPh COOPh COOPh
(a) (b) (c) (d)
NO2
NO2 NO2 NO2

MeO OMe

(i) H3O,( + ) rearrangement

OMe 
21. → (X), (X) would be:-
(ii) Br2 (aq)
OMe
OH OH OH OH
Br Br Br Br Br
(a) (b) (c) (d)
HO OH OH OH Br O
Br Br
22. o - cresol is treated with allyl chloride and product obtained is exposed to sun light. What would be the end product ?
OH CH2—CH=CH2
H3C CH2—CH=CH2 CH3
(a) (b)

OH OCH3
CH3 CH3
(c) (d)

CH2—CH=CH2
Aromatic Chemistry 363

23. Which product is unexpected in the following reaction ?

OAc OCOPh

AlCl3
+ Products

Et Me
OH OH
Ac COPh
(a) (b) (c) (d) All products are possible

Et Et
Hint: - Fries rearrangement is intermolecular as well as intramolecular

+ (CN)2 C = C(CN)2 
∆
24. → Products

Product of this reaction is:-

NC CN
CN
CN
CN CN
(a) (b)
CN
CN
CN
CN
(c) (d) No reaction occurs
CN
CN
OH
OH
Zn(CN) H O
→
2 
2 →
25. & HCl
OH
OH
CHO
Electrophile of this reaction would be:-
(+ ) (+ ) (+ )
(a) HOC Cl CH = NH (d)
(b) CHO (c) Zn(CN

26. 3 – Hydroxy phenol (Resorcinol) in basic medium reacts with benzene diazonium chloride to give [X], [X] on acidification
gives [Y], [Y]
OH OH OH
OH
N2Ph
(a) N2 (b) (c) (d)
OH N2Ph HO ON2Ph
OH

27. Bismark brown (Y) is an azo dye which can be prepared as follows:-
NaNO 2 + HCl / 0°C
Meta phenylenediamine  →[X]

[X] + metaphenylenediamine 
→[Y]
1 : 2
364 Problems in Organic Chemistry

Identify bismark brown:-

NH2 NH2
NH2 NH2 N=N N=N
N=N
(a) (b)
H2N NH2

NH2 NH2 NH2 NH2

N=N N=N N=N

(c) (d)
NH2 H 2N H2N NH2

28. Reaction with wrong product is:-

N2 SO3H

(i) NaNO + HCl / 0°C


2 →
(a) Sulphanilic acid (ii) α− Naphthyl amine

NH2

ONa
(i) NaOH
(b) Beta - Naphthol 
( + ) (–) →
(ii) Ph N2 Cl

N2Ph

NH2

(i) NaNO + HCl / 0°C N2 SO3H

(c) Sulphanilic acid 
2 →
(ii) α− Naphthyl amine

N2Ph
ONa
(i) NaOH
(d) Beta - Naphthol 
( + ) (–) →
(ii) Ph N2 Cl

NH2
OH
Hints:-
beta-Naphthol
Alpha- Naphthyl amine

CO 2 H( + )
29. PhOH 
Base
→ → [X]

H2N S NaNO 2 + HCl

NH2  →
0°C [ Y]

Pyridine
X (1-mole) + Y)  → Anthracene yellow
Anthracene yellow will be;-
(–)
(–) COO
OOC

(a) HO N2 S N2 OH
Aromatic Chemistry 365

OH OH
(–)
OOC
(b) (–)
N2 S N2 COO

OH OH
OHC CHO
N2 S N2
(c)

(–)
(d)
(–)
OOC N2 S N2 COO

EtONO
30. 2 → Products

O O

Product of this reaction will be:-

O NO2 O OEt O
NO2
(a) (b) (c) (d)
O O O O O O

Br CHO
MeO OH
31.
MeO OH
This conversion can be best performed by:-
(a) CH3Br / Na / Et2O, H3O+, CrO2Cl2 (b) Mg/Et2O, CH2O, H3O+, Cu /∆
+
(c) H3O , CHOCl / AlCl3 (d) Zn(CN)2 / HCl / H3O+
NO2
CH3
1 mol EtSNa
32. 
D
→ Product
Cl
Cl
The product of above reaction would be:-
NO2 NO2 NO2 NO2
CH3 CH3 CH3 CH3
(a) (b) (c) (d)
SEt Cl EtS Cl SEt
SEt Cl SEt
Cl
NH O
33. (A) + Na 
3 →(B) 
3 → CH COCH CHO
3 2
EtOH Me2S

Compounds (A) is:-

(a) o-xylene (b) m-xylene (c) p-xylene (d) mesitylene
366 Problems in Organic Chemistry

34. Identify the product [X] of the reaction given below:-

∆
OD + D2SO4 ( in heavy water)  → [X]

OD
OD OD
D D
(a) D D (b) (c)
D D (d) All of these
D D
D D
KHSO C H NH
35. Glycerine 
4 →(A) 
6 5
(+)
2 →(B) , Compound (B) is:-
∆ H , heat

(a) CH2 = CH — CH = NPh (b)

N
H
NH—CH—CH2CH3
(c) CH2 = CH — CH = O (d)
OH
36. Which intermediate will not form in the course of the reaction given below?
OH O
| ||
KCN
2PhCHO → Ph — CH — C— Ph

O(–) OH O OH O(–)
| | (–) || | |
(a) Ph — C — N (b)
Ph —C— CN (c)
Ph — C — C— Ph (d)
Ph — C — CH — Ph
| (–) | |
CN CN CN
37. Consider the following four compounds.
4 3
8 1 8 9 1 4 3
7 2 7 2 5 2
N1 5 2
6 3 3
6 S
5 4 5 10 4 H 1
Naphthalene Anthracene Pyrrole Thiophene

Which statement is correct regarding the nitration of these compounds ?

(a) In naphthalene nitration occurs at 1st position (b) In anthracene nitration occurs at 9th position
(c) In pyrrole nitration occurs at 3rd position (d) In thiophene nitration occurs at 4th position

HNO
38. 
3→
(X), (X) would be:-
N H 2SO 4
S
NO2
HNO3
(a)  → (b) N (c)
NO2 N (d) All of these
H 2SO 4
S S

AcONO
39. CO →
2 Product
S N
Major product of this reaction would be:-

(a)
O2N CO (b) CO
S N NO2
S N
O2N NO2

(c) CO (d) CO
S N S N
Aromatic Chemistry 367

40. Match the following

Reaction Colour
FeCl3
(A) Phenol → (1) Orange

+
–
Ph N 2 Cl
(B) Phenol  (–) →
(2) Red
OH

NaNO
(C) Phenol 
2 → (3) Violet
H 2SO 4

K 2S2O8
(D) Phenol  → (4) Colourless

Correct matching is:-

(a) A→3 B→ 4 C→ 2 D→ 1
(b) A→3 B→ 1 C→ 4 D→ 2
(c) A→3 B→ 4 C→ 1 D→ 2
(d) A→3 B→ 1 C→ 2 D→ 4

Note: - Phenol on oxidation with K2S2O8 gives a mixture of catechol & quinol this reaction is called Elbs persulphate oxidation:-

41. Which reaction will yield naphthalene as an end product?

heat (i) Bayers reagent

(a) Benzyne + 1, 3 – butadiene (X)  → (X) 
(+) → Product
(ii) H

(i) AlCl H( + ) / ∆
(b) Ph(CH2)3COCl  →(X) 
→ Product
3
(ii) LiAlH 4

I
Cu / ∆
(c) 2 moles of → Product
I

(d) All of these

42. Identify the product of following oxidation reaction

hot KMnO4
 → product

HOOC COOH
(a)
HOOC COOH (b)
HOOC COOH

CHO HO OH
(c) (d)
CHO HO OH

43. In the reaction of p-chloro toluene with sodamide, the major product is
(a) o-Toluidine (b) m-toluidine (c) p-toluidine (d) p-chloro aniline
44. Which will not give 1, 3 5 - T.N.B. as a product ?
(i) KMnO (i) conc HNO
(a) 2, 4, 6, T.N.T. →
4
(ii) NaOH / CaO / ∆ Product (b) Phenol  3→
(ii) Zn & heat
Product

CF CO H (i) HNO / H SO
(c) meta phenylenediamine 
3 3
HNO + H SO , heat
→ Product (d) m - nitro benzylalc  3
(ii) KMnO
2 4→
Product
3 2 4 4
(iii) N3H / H 2SO 4
368 Problems in Organic Chemistry

KOH
45. T.N.T. + benzaldehyde  heat
→ Product
Product of this reaction would be:-
NO2

(a) No reaction takes place (b) O2N CN = CH + H2O

NO2

NO2 CHO
NO2
CHO CH2
(c) O2N CH2 (d)
O2N NO2
NO2

46. When aniline is heated with H2SO4 at 453 K, compound [X] forms which on treatment with (i) Ac2O/Br2 (ii) H3O+ at 100°C
/ NaOH gives [Y], What is [Y]
NH2 NH2 NH2
NH2
Br Br
(a) (b) (c) (d)
Br SO3H
Br
SO3H SO3H

47. Aniline can be distinguished from phenol by:-

(a) Br2 water (b) Zn dust / ∆ (c) C6H5N2Cl / NaOH (d) All of these

PCl5
48. Ph-COOH [A] [B] Ph-COOOH [C]
ZnCl2
[Y]

[Y] would be:-

(a) PhOH (b) PhCOONa (c) PhCOOOH (d) PhCOOH
49. We would like to convert Benzaldehyde in to 3 – bromo – 4 – nitro toluene. Which sequence of reagent is suitable for this
transformation ?
(a) Zn / Hg+HCl, Br2 /Fe, HNO3 / H2SO4 (b) Br2 / Fe, HNO3 / H2SO4, Zn / Hg + HCl
(c) Br2 / Fe, Zn / Hg + HCl, HNO3 / H2SO4 (d) Zn /Hg+HCl, HNO3 / H2SO4, Fe / Br2
50. Would like to convert Benzoic acid in to 3, 4, 5 tri bromo benzaldehyde which sequence of reagent is suitable for this transfor-
mation.
(a) LiAlH4, Br2 / Fe, Cu /∆ , Br2 / Fe, Br2 / Fe (b) Br2 / Fe, LiAlH4, Br2 / Fe, Br2 / Fe, Cu /∆
(c) LiAlH4, Cu /∆ , Br2 / Fe, Br2 / Fe, Br2 / Fe (d) Br2 / Fe, Br2 / Fe, Br2 / Fe, LiAlH4, Cu / ∆

NaNO + H SO
51. Aniline 
2 2 4 → (A)
273K

(i) dil H SO
CH2(OEt)2 
(ii) HCl, A
2 4 →(B)
(iii) Boil with water

Compound (B) would be:-

OH OH
OH NH2 CH2OH
(a) (b) (c) (d)
CH2OH
CHO CH2OH
Aromatic Chemistry 369

52. Nitro benzene can be converted in to cyclo hexan – 1, 2, 3, 4, 5 pentadiol by:-

(a) HNO3 / H2SO4 / t > 180°C, LiAlH4, NaNO2 + HCl (t > 8°C)
(b) Fuming HNO3 / H2SO4, heat, Fe + HCl, NaNO2 + H2SO4 (0°C), H2O / boil
(c) NaNH2 / CH3OH, LiAlH4, HONO, KMnO4 (0°C)
(d) HNO3 / H2SO4 / t > 180°C, LiAlH4, H2 / NI, NaNO2 + HCl (t > 180°C)

Na / NH (l) H (1 mol)
53. Toluene 
3 → 
2
Ni / ∆
→(X)
CH3OH

Which is the most correct structure of [X] ?

(a) (b) (c) (d)

CH3
(i) NaNH / MeOH
54. →
2 (X), (X) would be:-
(ii) KMnO 4 (0°C)
SO3H

Me OH
HO OH Me OH OH
Me Me
OH OH OH SO3H
(a) H (b) HO (c) H H (d) HO
H OH
SO3H SO3H SO3H
H HO H
OH OH
H H H OH
OH
55. Consider the following compounds.
SO3H CH3 CH3 SO3H

D D

D D
D
(1) (2) (3) (4)
Correct order of rate of nitration will be:-
(a) 3 > 2 > 4 > 1 (b) 2 = 3 > 1 > 4 (c) 2 > 3 > 4 > 1 (d) 3 = 2 > 1 = 4

(i) H O( + )
56. 
3
→ (X), (X) would be:-
(ii) HCl / rerrangement

O OH OH OH
Cl Cl Cl Cl
(a) (b) (c) (d)
H H Cl Cl
O OH OH

OCH2CH=CH2

∆
57.  → (X), (X) would be:-

OH OH OH OH
CH2—CH=CH2 OCH2—CH=CH2
(a) (b) (c) (d)

CH2CH=CH2 CH2CH=CH2
370 Problems in Organic Chemistry

58. Benzene ring can be halogenated by using interhalogens. Identify the product of the following halogenation reaction.
O O

ICl
 → Product

O O O O O O O O

I
(a) (b) (c) (d)

I Cl I
59. C6H6 C6D6
(1) (2)
If K1 & K2 are the rate of aromatic electrophilic substitution in 1 & 2 then select the correct statement
(a) In case of nitration K1 > K2 (b) In case of sulphonation K1 = K2
(c) In case of sulphonation K1 > K2 (d) In case of nitration K1 < K2

Passage - I

Consider the following molecules

OH OH
CH2OH
OH OH

(A) (B) (C) (D) (E)

Answer the questions from 60 to 69
60. Which is not aromatic alcohol ?
(a) Only B (b) (B), (C), (D) & (E) (c) (B), (C) & (D) (d) (B) & (D)
61. Which will release CO2 on treatment with sodium bi carbonate ?
(a) (A), (C) & (D) (b) (C), (D) & (E) (c) Only (A) (d) None
62. (B) & (C) can be distinguished by:-
(a) Neutral FeCl3 (b) Br2 water (c) NaOCl (d) Anhydrous ZnCl2 + HCl
63. (D) and (E) can be distinguished by:-
(a) Neutral FeCl3 (b) NaOCl (c) Victor maeyer test (d) All of these
64. The alcohol which will not undergo acid catalysed dehydration to give hydrocarbon is / are:-
(a) (A) & (E) (b) (A), (E) & (D) (c) (A), (C), (D) & (E) (d) Only (A)
65. Alcohol that can able to produces violet colouration with neutral FeCl3 is:-
(a) Only (A) (b) (A), (C), (D) & (E) (c) (A) & (E) (d) (A) & (D)
66. Order of stability of carbocations formed by given alcohols when treated with H+ is:-
(a) A > B > C > D> E (b) D > C > B > E (c) E > C > D > B (d) D > C > E > B > A
67. Benzene ring with highest electron density is:-
(a) (A) (b) (E) (c) (C) (d) (D)
68. Correct order of acid strength is:-
(a) A > E > B > C > D (b) A > E > C > D > B (c) A > C > D > E > B (d) A > E > D > C > B
Aromatic Chemistry 371

69. Which will provide highly stable alkene on acid catalysed dehydration ?
(a) (D) (b) (E) (c) (B) (d) (C)

Passage - II

Na 2S NaNO2 (281K)
Dinitrobenzene (B) (G)
H2SO4
(A)
NaNO2 + HCl (273 K)

HCl KNO2
(D) Cu (C) (E)

H2O/heat

(F)

Answer the questions from 70 to 74

70. Compound (A) is:-
(a) 1, 2-di nitro benzene (b) 1, 3-di nitro benzene (c) 1, 4-di nitro benzene (d) All of these
71. In this passage two compounds, which are identical are:-
(a) A & E (b) G & F (c) B & E (d) A & E as well as G & F
72. Compound (B) is:-

NH2
(a) 2-nitro aniline (b) 3-nitro aniline (c) H2N NH2 (d)
SH
73. Which among the following will produce highly explosive compound on mono nitration ?
(a) F (b) E (c) G (d) C
74. Compound (F) can be converted in to(B) by using:-
(a) Zn / heat, EtNO2, CF3COOH (b) Zn / heat, EtNO2, (NH4)2S
(c) EtNO2, Zn / heat, LAH (d) All of these

Passage - III

Alumina, 600°C (i)Cl2 / Fe (ii) Mg,Ether

C6H14(A) (B) (G)
Oxide of Cr (iii) D2O

(does not decolourise Br2 water) (+)

Propanol /H

(+)
H3O air
(E) + (F) (D) (C)

does not give gives

haloform test haloform test

Answer the questions from 75 to 81

75. Compound (A) is:-

(a) iso hexane (b) n - hexane (c) neo hexane (d)

372 Problems in Organic Chemistry

76. Compound (B) is:-

(a) Benzene (b) (c) (d) Toluene

77. Compound (C) is:-
(a) Styrene (b) Cumene (c) Stilbene (d) Ethyl benzene
78. Compound (D) is:-
(a) Ph — CH2O2H (b) PhCMe2O2H (c) PhCH2CH2CH2OH (d) Ph(CH2)3O2H
79. Compound (E) is:-
(a) Phenol (b) 1 – Propanol (c) Acetone (d) Propanal
80. Compound (F) is:-
(a) Phenol (b) Propanol-2-ol (c) Acetone (d) Ethanal
81. Compound (G) is:-
Cl
OH OD
(a) C6H5D (b) (c) (d)

Passage - IV

An organic compound (A) C7H8O, is insoluble in aq NaHCO3 but soluble in NaOH.

(A) On treatment with Br2 water gives (B) (tribromo derivative)
Answer the question from 82 to 84
82. Compound (A) is:-
OH
OCH3 OH
CH3

(a) (b) (c) CH3 (d) All of these

83. Compound (B) is:-
OCH3 OH OH
Br Br Br Br OH Br Br
Br Br
CH3
(a) Br (b) Br (c) (d) Br
84. What will be (A) if it does not dissolve in NaOH but shows reactions given in the passage?
OCH3
OH OH OH
CH3
(a) (b) (c) (d)
CH3
CH3

Passage -V

Pyrrole on treatment with alkaline chloroform followed by heating with H+ gives (B) & (C). (B) can react with 2, 4 DNP but (C)
can not. (B) on reaction with NaOH form (E) & (F). (E) on reaction with H2SO4 & soda lime gives (X). (F) can be converted in to
(B) by (Ag/heat). (C) on reaction with Mg/ ether followed by treatment with H2O gives (Y).
Aromatic Chemistry 373

Answer the questions from 85 to 90

85. Compound (B) would be:-
CHO
Cl
(a) CHO (b) (c) (d)
N N N
H H
86. Compound (C) would be:-

Cl
(a) CHO (b) CH2OH (c) (d)
N N Cl
N N
H H
87. Compound (F) would be:-
CH2OH
(a) CH2OH (b) (c) (d)
N N N N
H H CH2OH
88. Compound (E) would be:-
(–)
COOH COO
(a) COOH (b) COO
(–)
(c) (d)
N N N N
H H H H
89. Compound (Y) would be:-
(a) Pyridine (b) Pyrrole (c) Pyrolidine (d) Piperidine
90. In Passage- V identical compounds are:-
(a) X & Y (b) X, Y and Pyrrole (c) Pyrrole & X (d) Pyrrole & Y

Passage - VI

Seven compounds are present in seven buckets named A, B, C, D, E, F & G.

NaNO2+
PhOH AgNO2 PhNH2
HCl
(A) (B) (C) (D)

i–Pr–I n–Pr–I NaOH

(E) (F) (G)

A cotton shirt is immersed in these containers in the order as given in questions. Identify the colour developed on shirt in each
case.
Answer the questions from 91 to 94
91. D→ B (ice cold)→ A→ G
(a) Yellow (b) Orange (c) Red (d) Blue
92. D→ B (ice cold)→ D→ G
(a) Yellow (b) Orange (c) Red (d) Blue
374 Problems in Organic Chemistry

93. E→C→B→G
(a) Red (b) Blue (c) Yellow (d) Orange
94. F → C → B→ G
(a) Red (b) Blue (c) Green (d) Orange

PCl ZnCl N H
95. o − (COOH) − C6 H 4 − CH 2 – Ph 
5
→ [A] 
2
→[B]  2 4
NaOH in glycol / D
→[C]

[C] would be
O O

(a) (b) (c) (d)

O
96. Match the following:-
Compound Nature
(A) Picric acid (1) Highly acidic
(B) m-Toludene (2) Acidic
(C) p-Toludene (3) More basic
(D) o-Cresol (4) Less basic
Correct option is:-
(a) A–1B–2C–3D–4 (b) A–1B–3C–4D–2 (c) A–1B–4C– 3D–2 (d) A–2B–1C–4D–3
97. Match the following:-
Reaction Product
(A) Raschig’s (1) Chloro benzene
(B) Schotten Bauman (2) Salicylic acid
(C) Kolbe’s (3) Cinnamic acid
(D) Reimer Tieman’s by CCl4 (4) Benzanilide
(E) Perkin
Correct option is:-
(a) A-1 B-1 C-2 D-4 E-2 (b) A-1 B-4 C-2 D-2 E-3
(c) A-4 B-2 C- 2 D-3 E-1 (d) A-4 B-1 C-2 D-3 E-2
98. Match the following:-
Product of reaction Comparison of Acidic Nature of Products
(i) fuming HNO , Conc H SO
(A)
Ph – CH3 →
3 2 4 (A) (1) Highly acidic
(ii) KMnO 4

Dil HNO
Ph – OH 
(B)
3 →(B)
(2) Good acidic
Conc HNO
(C)
Ph – OH →
3 (C) (3) Acidic
CrO Cl
Ph – CH3 
(D) 2 2 →(D)
(4) Not acidic

(a) A–2 B–3 C–1 D–4 (b) A–2–B–4–C–1 D–3 (c) A–1 B–2 C–3 D–4 (d) A–1 B–3 C–2 D–4

99. Consider the following reaction.

(+)
(i) aq NaOH H 2 ,Ni (i) H , Heat
(W) → (X)  →(Y)  →(Z)
SO3H (ii) fuse with NaOH, H (+) Heat (ii) H3O( + )

Aromatic Chemistry 375

Now match the following

Compound Test
W 1. Red Colour with FeCl3
X 2. No Colour in Victor Maeyer
Y 3. Blue Colour in Victor Maeyer
Z 4. Violet colour with FeCl3
Correct option is:-
(a) W – 1 X – 2 Y – 3 Z–4 (b) W – 1 X – 4 Y – 3 Z – 2
(c) W – 4 X – 2 Y – 4 Z – 3 (d) W – 4 X – 4 Y – 2 Z – 3
100. Assertion: - Friedel craft reaction of Aniline by CH3Cl / AlCl3 is not possible.
Reason: - Lone pair of electron present on nitrogen is not localised.
Assertion is True, Reason is true: Reason is a correct explanation for Assertion.
(a)
Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(b)
Assertion is True, Reason is False
(c)
Assertion is False, Reason is True
(d)
101. Assertion: -Benzaldehyde does not give Fehling test.
Reason: - It undergoes Cannizaro reaction.
Assertion is True, Reason is true: Reason is a correct explanation for Assertion.
(a)
Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(b)
Assertion is True, Reason is False
(c)
Assertion is False, Reason is true
(d)
102. Assertion:- Nitration of benzene & C6D6 occur with the different rates.
Reason: - Breaking of C–H & C–D bonds do not occur in rate determining step.
Assertion is True, Reason is true: Reason is a correct explanation for Assertion.
(a)
Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(b)
Assertion is True, Reason is False
(c)
Assertion is False, Reason is true
(d)
103. Assertion:-When aniline is subjected to nitration by conc HNO3 & H2SO4 meta nitro aniline is formed in considerable
amount.
Reason: - NH2 is o/p directing but ring deactivating group.
Assertion is True, Reason is true: Reason is a correct explanation for Assertion.
(a)
Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(b)
Assertion is True, Reason is False
(c)
Assertion is False, Reason is true
(d)
104. Assertion:-Benzene does not undergo addition reaction easily.
Reason: -Benzene losses it’s aromaticity after addition reaction & becomes less stable.
Assertion is True, Reason is true: Reason is a correct explanation for Assertion.
(a)
Assertion is true Reason is true: Reason is not a correct explanation for Assertion
(b)
Assertion is True, Reason is False
(c)
Assertion is False, Reason is true
(d)
376 Problems in Organic Chemistry

Answer Key

1. (d) 2. (d) 3. (c) 4. (c) 5. (b) 6. (a) 7. (c) 8. (c) 9. (b) 10. (c)
11. (d) 12. (b) 13. (d) 14. (c) 15. (d) 16. (d) 17. (c) 18. (b) 19. (a) 20. (c)
21. (c) 22. (a) 23. (d) 24. (b) 25. (c) 26. (c) 27. (b) 28. (b) 29. (a) 30. (c)
31. (b) 32. (b) 33. (c) 34. (b) 35. (b) 36. (c) 37. (b) 38. (c) 39. (a) 40. (d)
41. (a) 42. (a) 43. (b) 44. (d) 45. (b) 46. (c) 47. (c) 48. (a) 49. (c) 50. (a)
51. (d) 52. (c) 53. (c) 54. (b) 55. (d) 56. (c) 57. (a) 58. (d) 59. (c) 60. (b)
61. (d) 62. (c) 63. (c) 64. (a) 65. (a) 66. (d) 67. (a) 68. (b) 69. (a) 70. (b)
71. (d) 72. (b) 73. (b) 74. (b) 75. (b) 76. (a) 77. (b) 78. (b) 79. (a) 80. (c)
81. (a) 82. (a) 83. (d) 84. (a) 85. (b) 86. (c) 87. (a) 88. (b) 89. (a) 90. (c)
91. (b) 92. (a) 93. (b) 94. (a) 95. (a) 96. (c) 97. (b) 98. (d) 99. (b) 100. (b)
101. (a) 102. (d) 103. (c) 104. (a)

Multiple Choice Questions (More Than One May Correct)

1. Phenol can not exhibit:-

(a) Liberman’s nitroso test (b) Neutral FeCl3 test (c) Bromine water test (d) Biuret test

H ( + ) / Na Cr O O O
2. [X] 
2 2 7
→

[X] may be:-

(a) Aniline (b) Phenol (c) m- hydroxy phenol (d) p-amino phenol
3. Phenol & aniline can not be differentiated by:-
(a) Neutral FeCl3 test (b) Bromine water test (c) Victor maeyer test (d) Coupling reaction
NHOH
(+)
4. H
[X] X may be :-

(a) Aniline (b) p-Hydroxy aniline (c) o-hydroxy aniline (d) m-hydroxy aniline
5. Both phenol & methyl alcohol can show:-
(a) Reaction with sodium bi carbonate (b) Reaction with sodium
(c) Acylation reaction (d) Reduction with zinc dust
6. Which of the following will undergo diazotization reaction?
NHPh CH2CH2NH2 CH2NH2
CH3
(a) (b) (c) (d) None of these

7. Phenol can be prepared by:-

(a) The hydrolysis of benzene diazonium salt
(b) Decarboxylation of salicylic acid
(c) Hydrolysis of chloro benzene by aq NaOH/25°C
(d) Fusing sodium benzene sulphonate with NaOH pellets followed by acidifications
Aromatic Chemistry 377

8. Correct order of basic character is:-

H
O
N
(a) > (b) > (c) > (d) None of these
N N N N N N
H H H H H H
9. The product of acid hydrolysis of A & B can be distinguished by :-
[A] CH3 — C — OCOPh [B] CH3—CH = CH OCOPh
||
CH2

(a) Cu+2 / NaOH (b) [Ag(NH3)2]OH (c) NaCN / HCl (d) Victor Maeyer test

10. The appropriate reagent for the following transformation is:- RCOOH  → RNH
2
(a) Ammonia / heat (b) (i) NH3 / heat (ii) KBrO / heat
(c) Hydrazoic acid(in acidic medium) (d) (i) LAH (ii) Ammonia / Al2O3
11. In the following transformation A & B are:-
CH3
Li / liquid NH 1 mole of H

3 → A 2
→B
MeOH Ni / heat

(a) B is CH3 (b) B is CH3 (c) A is CH3 (d) A is CH3

12. In following scheme of reactions Z would be:-

* Cl
alc. KOH [X]
→[Y] 
→[Z]
ZnCl2
[X]

* * * * *
(a) (b) (c) (d)
* *

Answer Key

1. (d) 2. (a), (b) 3. (b), (c) 4. (b), (c) 5. (b), (c)

6. (d) 7. (a), (b), (d) 8. (a), (b), (c) 9. (a), (b) 10. (b), (c)

11. (b), (d) 12. (b), (c)

LEVEL - II
1. Select the reaction with correct product
AlCl FeCl
(a) Ph — H + n — Pr — Cl →
3
PhCH2CH2CH3 (b) Ph — H + n — Pr — Cl →
3
PhCH2CH2CH3
AlCl ,H O
(c) Ph — H + nPr — Cl 
3 2 →
PhCH2CH2CH3 (d) None of these
378 Problems in Organic Chemistry

2. You have following four compounds

O O O O
O O O O O O
O O S S

(1) (2) (3) (4)

If R1, R2, R3 & R4 are the rate of nitration of 1, 2, 3 & 4 respectively then:-
(a) R1 > R2 > R4 > R3 (b) R1 > R4 > R3 > R2 (c) R1 > R4 > R2 > R3 (d) R1 > R2 > R3 > R4
3. Select the reaction which is most likely to occur:-.

(a) Me3CCOCl + PhH + Anhydrous AlCl3 

→ Ph — CMe3
∆
(b) PhNO2 + CH3COCl + Anhydrous AlCl3  → m  — NO2 — C6H4COCH3
AlCl
(c) PhOH + CH3Cl →3 p — CH3 — C6H4 — OH
(d) All are possible

Comprehension

Comprehension - I

Nitration of benzene nucleus is carried out by HNO3 & H2SO4 as:-

NO2
conc. H2SO4
+ HNO3

Identify P1 to P7
OH P1 + P2
4. + concn HNO3 
→ (Major) (Minor)

OH

5. + concn HNO3 + concn H2SO4 

→ P3

NH2

NO2BF4
6. P4
low temp
NO2BF4
High temp
P5

Cl

N O
7. →
2 5 P6

NO PF
8. ••
5 6 → P (Thermodynamically controlled product).
 7
N
H
Aromatic Chemistry 379

Comprehension - II

Since benzene ring is electron rich hence it does not favour the attack of nucleophile. When electron with drawing groups are present
on benzene ring attack of nucleophile on ring becomes easy as intermediate anion is stabilized by electron with drawing groups.

Cl OH
aq NaOH,H ( + )
→
High + T&P

Cl OH
O2N NO2 O2N NO2
H 2O
+ (warm) 
→

NO2 NO2

Identify P1 to P4

Cl
Cl
MeSNa
9.  → P1
in DMF

CN
(–)
F O

10. + 
→P
2

NO2

NO2
(–)
11. + N H 2 
→ P3 + P4
Cl (Major) (Minor)

12. Consider the following reactions

NO2 NO2 NO2 NO2

(–) (–)
+ CH2=CH—O .... R1 + CH2=CH—O .... R2

F OCH = CH2 Cl OCH = CH2

NO2 NO2 NO2 NO2

(–) (–)
+ CH2=CH—O .... R3 + CH2=CH—O ..... R4

Br OCH = CH2 I OCH = CH2

If R1, R2, R3 & R4 are the rates of reaction then arrange them in decreasing order.
380 Problems in Organic Chemistry

13. Consider the following reactions

NO2 NO2 NO2
NO2

+ MeSNa
+ MeSNa ................ R1 ................ R2
F F Cl Cl
Cl Cl SMe
SMe
NO2 NO2 NO2 NO2

+ MeSNa ................ R3
+ MeSNa ................ R4
Br Br I I
Cl SMe Cl SMe

If R1, R2, R3 & R4 are the rates of reaction then arrange then in decreasing orders.

Matrix Match Questions

Each question contains statement given in two columns which have to be matched. Statement (A, B, C, D) in column I have to be
matched with statements (p, q, r, s) in column II. The answer to these questions has to be appropriately bubbled as illustrated in the
following examples. If the correct match are A - p, A - s, B - r, B - q, C - q, D - S, then the correctly bubbled 4 x 4 matrix should be
as follows.

14. Pair of compound Reagent for distinction

OH OH
(A) & (p) KOH / I2

NH2
CONH2
(B) & (q) PhN2Cl with Pyridine

NH2
NH2
(C) & (r) neutral FeCl3

OH
CHOHCH3
(D) & (s) Br2 water
Aromatic Chemistry 381

15. List - I List - II

CH3 CH3
(A) NaNH

2→ (p) Aryne Mechanism
Cl NH2

SO3H SO3H
Cl
(B) KNH

2→ (q) Anhydrous AlCl3
NH2

CH3 CH3

(C) (CH ) CCl


3 3 → (r) Nucleophilic Substitution

CMe3

(D) 
→ (s) Intermediate carbocation is form

16. List - I List - II

NHCOC6H5
(A) (p) Gives Phenol or air oxidation followed by hydrolysis.

CHMe2
(B) (q) Benzanilide

OCOPh
(C) (r) Formed by schotten Bauman reaction

CCl3
(D) (s) Shows reverse hyperconjugation

17. List - I List - II

NO2

(A) (p) Gives p – benzoquinone with H+/Na2Cr2O7

NH2

(B) (q) In a strongly acidic medium when current is passed it gives

p – hydroxyl aniline

OH

(C) (r) Gives coupling reaction but not react with neutral FeCl3

COCH3
(D) (s) Can not show coupling reaction but reacts with NaHSO3
382 Problems in Organic Chemistry

18. Match the products W, X, Y and Z in list - I with list - II

List - I List - II
CrO3
(A) PhCH2OH3  → W (p) Shows addition reaction with Cl2/CCl4

CrO
(B) PhCHOHCH3 
3 → X (q) Negative fehling test

LiNH
(C) PhNH2  2→
CH OH
Y (r) Can react with hydroxyl amine
3

NO2
(D) Z (s) Contains two C = C bonds
O2N
NO2

19. List - I List - II

Ph
(A) Ph (p) Gives ketone on oxidation
OH

(B) (q) Gives epoxide on dehydration with H2SO4

OH OH

(C) Ph (r) Can show Diels Alder reaction with

NH2

(D) (s) Turns brown on reaction with H2SO5

20. List - I List - II

(A) Corbolic acid (p) Phenol
(B) Oil of winter green (q) Phenyl salicylate
(C) Given white ppt with Br2 water (r) p - Hydroxy benzanilide
(D) Paracetamol (s) Anisole

Answer Key

1. b, 2. c, 3. a,

O O NO2 NO2
NO2
NO2
4. + 5. 6. P4 P5
P2 HO P1 P3
O O
NO2

Cl Cl
NO2
7. & 8.
NO2
N
NO2 H
For 9, 10, 11, 12 &13 See Solution.
Aromatic Chemistry 383

Answers matrix match

14. (A) – q, r, s, (B) – q, s, (C) – q, s, (D) – p, q, r, s 15. (A) – p, r (B) – p,r, (C) – q, s, (D) – q, s
16. (A) – q, r, (B) – p, (C) – r, (D) – s 17. (A) – q, (B) – p, r, (C) – p, (D) – s
18. (A) – q, r (B) – q, r, (C) – p, q, s (D) – p, q 19. (A) – p, r, (B) – p, (C) –p, q (D) – p, s
20. (A) – p, (B) – q, (C) – p, s, (D) – r

SOLUTION
NH2 NO2 NO2
CF3CO3H Na2S
1. (d)
NH2 NO2 NH2
CH3 CH3 CH3 CH3 (+)
Br (–) .. (–) NH3
NH2 NH3
2. (d) –NH3, –Br (–) (+) or
(–)
NH3
less stable due More stable
to +I effect of CH3
CH3 group
NH2

OCH3 OCH3 OCH3 (+)

OCH3
Br (–) NH3 (–)
NH2 NH3
or
–NH3, –Br (–) (–) (+)
NH3
OCH3 More stable due to
-I effect of oxygen

NH3
3. (c) X is salicylic acid which is obtained by kolbe reaction of phenol. Since COOH is electron withdrawing group hence on
reaction with Br2 water IPSO attack occurs & COOH is replaced by Br.
OH OH
COOH Br Br
Br2 water

(X) (Y)
Br
Br of bromine water can replace –R groups.
4. (c) Nucleophile does not attack on benzene ring because benzene nucleus is electron rich. So as substitutions with –R groups
increases on benzene ring, benzene ring becomes electron deficient and favours the attack of nucleophile. Water is a poor
nucleophile hence it can’t replace Cl from benzene through necleophilic substitution reaction. H2O can do it only when all
ortho & para positions are substituted by electron with drawing groups like NO2.
5. (b) A = Cu (Ullman reaction)
B = Zn + Et2O (Fitting reaction)
NO2 electron rich NO2 NO2
COOH
6. (a) KMnO4, heat NaOH, CaO
heat
COOH
electron dificient
KMnO4 attacks on electron rich benzene nucleus.
384 Problems in Organic Chemistry

7. (c) Along with o & p products meta derivative also forms with 47%
8. (c) 1st is wrong because aliphatic amine can not form stable di azo salt 2nd is wrong because single carbon atom can not bear
4 phenyl groups due to steric hindrance. 3rd is wrong because benzene ring is deactivated as aniline reacts with AlCl3 to
(+ ) (–)
produce Ph NH 2 AlCl3

Br
CH3Cl
 → CH2
9. (b) CH2 AlCl3

C NH C NH

O O
H
OH

Br
CH2

CH3
COOH NH2
10. (c) NH3 + H2S is used for partial reduction of aromatic nitro compounds
11. (d) (B) is phenol (C) is benzoic acid & (A) is benzene sulphonic acid. The acid strength of these compounds will follow the
following order A > C > B
dil HCl
12. (b) Cl Cl hydroloysis Cl NH2

CHCO Cl
13. (d) A = O C= B= D=
CHCO

Ph
decarboxylation
14. (c) oxidation
COOH

CH3 CH3 CH3

NO2
15. (d)
NO2
θ =120° θ =60° NO2 θ = 0°

Dipole moment ∝ 1 / θ
16. (d)
17. (c) CCl3 is meta directing group due to reverse hyperconjugation
18. (b) X is phenolphthalein .In basic medium (NaOH) it converts it self in to (b)
Br Br
19. (a) X is

Br
Here all positions are identical hence, only one product will be obtained afer mono nitration.
Aromatic Chemistry 385

20. (c) Benzoic acid & phenol on esterification produces phenyl benzoate (X)

OCOPh OCOPh OCOPh

NO2(+)
+
NO2 NO2
Majo due to less
steric hinderence

MeO OMe HO OH
H3O(+) –2H2O
21. (c) OMe OH
OMe OH
OH OH O
Br Br Tautomerism
Br2 water

OH OH O
Br

OH OCH2CH = CH2
CH3
– HCl CH3
22. (a) + CH2 = CH – CH2Cl

CH2
O CH O OH
H
CH3 CH3 CH2—CH = CH2 CH3 CH2CH = CH2
CH2

(+) (+)
23. (d) In it two electrophiles are generated by AlCl3,CH3CO and PhCO . Hence both the electrophiles can attack on both the
benzene nucleus consequently all products are possible.
24. (b) 9th & 10th positions of anthracenes are more reactive hence Diels – Alder reaction will occurat 9th & 10th position.

25. (c) Zn(CN)2 + 2HCl 

→ ZnCl + 2HCN
2

H — CN + H(+)  → CH(+) = NH
26. (c) N2Ph can not enter at 2nd position due to steric hinderence. N2Ph will attach at 6th position because at this location as it is
less sterically hindred & both the OH groups have same agreement.
OH
1
less Chances 2 6 More Chances
3 5
HO 4
(RESORCINOL)
NH2 N2Cl
diazotisation
27. (b)
NH2 N2Cl

NH2 (+) (+) NH2

N2 N2

H2N NH2
Also see previous question.
OH
28. (b) more sensitive position
for electrophilic attack
386 Problems in Organic Chemistry

OH
2
3 1 COOH
29. (a) (X) is salicylic acid both OH & COOH groups have common agreement at 5th position hence coupling
4 6
5
will occur at 5th position.
COOH COOH
(+) (+)
HO N2 S N2 OH

Oa
3
4 2
30. (c) a is – R group however b & c are +R groups all these three have common agreement at 2nd position
5
1 b
O
cO 6

hence nitration will occur at 2nd position.

31. (b)
32. (c) See aromatic nucleophilic substitution in your text book.
CH3 CH3

Birch reduction ozonolysis

33. (c) CH3COCH2CHO

CH3 CH3

34. (b) OD is ortho para directing group thus, D+ attacks at ortho para locations.
35. (b) A is acrolein CH2 = CH — CHO
(–)
O H
C
O = C—H CH H
HO
.. CH CH2
NH2 NH NH
CH2 (+) 2
(+) O tautomerism
OH OH
ARSE (+) H
H H
NH NH
N
H
(+)
H , heat

N
H
36. (c) It is benzoin condensation
(–)
O O OH
(–)
Ph–C–H + CN Ph—C—H PhC—CN
(–)
CN (–)
(–) OH O
O OH O OH
Ph–C–H + PhC—CN Ph—CH—C—CN Ph—CH—C—CN
(–)
OH Ph Ph
(–)
–CN
BenzoinPh—CH—COCN
Aromatic Chemistry 387

37. (b) In thiophene and pyrrole ARSE occurs at 2nd location. See q. No. 11 Chapter -04 topic electrophilic substitution reaction.
4 3

38. (c) 5 N 2 nitration can occur at 2nd & 5th positions but at 2nd position H is absent hence substitution is not possible at 2nd
S
1
position consequently nitration occurs at 5th position.
39. (a) Since electronegativity of S is lesser than N so extent of resonance by lone pair with double bond is maximum in thiophene
part hence electrophile will attack on thiophene part.
40. (d) See test of phenol
OH
41. (a) +
D–Alder Cold KMnO4
OH

H(+), heat
(Naphthanlene)

42. (a)
43. (b) NO2 group is o/p directing for nuclceophilic substitution. 44. (d)
45. (b) It is an example of Cross aldol condensation.
(-)
CH3 CH2
O2N NO2 O2N NO2
(–)
+ OH H2O +

NO2
NO2
NO2 NO2 (–)
O O
(–)
O2N CH2 + Ph—C—H O2N CH2 — CH —Ph
NO2 NO2
NO2 NO2 OH
(–)
OH, heat H2O
O2N CH = CH—Ph O2N CH2—CH—Ph
–H2O

NO2 NO2
(+) (–)
NH2
NH2 H2SO4
NH3HSO4
46. (c) 453 K
–H2O

NH2 NH2
(+) SO4H
Br H3O, NaOH Br
Ac2O + Br2
100°C

SO3H

47. (c) C6H5N2Cl on coupling reaction with phenol gives orange coloured dye while yellow coloured dye with aniline.
PCl5
48. (a) PhCOOH PhCOCl
(A)
Baeyel villiger C6H6
PhCOOPh PhCOPh
Oxidation (B) AlCl3
(C)
PhCOCl + PhOH 
→ PhCOOPh
(A)
[Y]
388 Problems in Organic Chemistry

49. (c) Benzaldehyde on bromination gives meta bromo benzaldehyde which on reduction with zinc amalgam & HCl gives meta
bromo toluene which finally gives 3 – bromo – 4 – nitro toluene on nitration
CHO CH2OH CH2OH CHO CHO CHO
Br2 Br2 Br2
50. (a) LAH
Fe
Cu
∆ Fe Fe

Br Br Br
Br Br Br Br

NH2 (+) (–)

N2Cl
NaNO2 + H2SO4 meta directing group
51. (d)
A
OEt OH OH
CH2 dil H2SO4 –H2O
CH2 HCl
–2EtOH CH2O H—C—H
OEt OH Formaldehyde (+)
OH
(+) N
2Cl
(–)
boil with water A
HOCH2
HOCH2

NO2 NO2 NH2

Birch reduction LiAlH4

52. (c)
OH OH
HO OH
Baeyers HONO
reagent
HO OH
1
Birch reduction
53. (c) (A)
2
Since 2nd is less substituted alkene hence it is less stable & undergoes reduction easily in comparison to 1st .
H (1 mol)
(A) 
2 →
Ni, heat

OH
Me
CH3 CH3 H
Birch reduction Cold KMnO4 OH
54. (b) HO
Synaddition
SO3H SO3H SO3H
H OH
H
55. (d) Rate of reaction will be least in 1 & 4 as SO3H is ring deactivating group. While rate of reaction will be large in 2 & 3 as
methyl group is ring activating group. Since isotopic effect is not observed in nitration thus rate of reaction will follow the
order 3 = 2 > 1 = 4
O (+) OH
H3O
56. (c) O O O O
O OH –H2O
OH
HCl

Cl
OH
See [Link]. 35, topic electrophilic addition, chapter 04
Aromatic Chemistry 389

57. (a) See Question Number 22

58. (d) –R group O O +R group

Activated ring

59. (c) Isotopic effect is observed only in case of sulphonation.

Passage - I

(60 to 69)
60. (b) For aromatic alcohol OH group should be directly linked to the benzene nucleus.
61. (d) This is the property of carboxylic acid. Phenol & aliphatic alcohols do not release carbon dioxide with NaHCO3
62. (c) (C) will give haloform test with NaOCl.
63. (c) (D) is 3° alcohol and will not give any colouration in victor maeyer test while ‘E’ is primary alcohol & produce red coloura-
tion in victor maeyer test.
64. (a) A & E can not form alkene by acid catalyzed dehydration.
65. (a) Aromatic alcohols give violet colouration with neutral FeCl3.
66. (d) Phenol can not form cation on reaction with H(+) hence 1st option is not correct. Carbocation formed by (D) is highly stable
due to resonance as well as hyperconjugation.
(+)
(+)
(+) (+)

From (D) From (C) From (E) Only From (B) not
Resonance & more Resonance & Stabilized by Stabilized by

hyperconjugation hyperconjugation resonance resonance

67. (a) Due to +R effect to OH group.

68. (b) 69. (a)

Passage - II

(70 to 74)
NO2 NO2 NO2

Na2S NaNO2 + HCl

t > 8°C
NO2 NH2 OH
(A) (B) (C)

NaNO2 + HCl, 0°C

NO2 NO2 NO2

HCl KNO2, Cu
Cu
Cl N2Cl NO2
(D) (C) (E)
NO2
H2O, boil

NO2
(F)
Compound ‘E’ on mono nitration will form tri nitro benzene which is highly explosive [T.N.B]
390 Problems in Organic Chemistry

Passage - III

(75 to 81)
Cl
Cl2
MgCl
n – Hexane aromatisation Mg, Ether
Fe
(A)
(+)
CH3CH2CH2OH, H
D2O
–H2O
CH3 D
CH3 O–O–H CH3 CH3
air (G)
(C)

OH
(+)
H3O
CH3COCH3 +
(F) (E)
(gives haloform test) (doesnot gives haloform test)

Passage - IV

(82 to 84)
OH ONa

NaOH

(A) CH3 CH3

OH
Br Br
Br2, water

CH3
Br (B)

When (A) is insoluble in NaOH then it will be anisole.
Br
OCH OCH3
3 Br water
→
2
Br Br

Passage - I

(85 to 90)
Cl MgCl
CHCl3, NaOH Mg, Ether
(+)
+
N H CHO
N N N
H (A) H
(B) (C)
H2O

NaOH

H2SO4 (Y) N
(–) +
sodalime COO CH2OH
N N N
(X) (E) (F)
H H H
Aromatic Chemistry 391

91. (b) Coupling reaction

92. (a) Coupling reaction
93. (b) Victor maeyer test of aliphatic alcohol
94. (a) Victor maeyer test of aliphatic alcohol
95. (a)
96. (c) A–1 B–4 C– 3 D–2
97. (b) A–1 B–4 C–2 D–2 E–3
98. (d) Compounds A, B, C & D are 2,4,6-tri nitro benzoic acid, para or ortho nitro phenol 2,4,6-tri nitro phenol & benzaldehyde
respectively.

99. (b)

100. (b) AlCl3 reacts with aniline (Lewis acid - base reaction) thus, benzene ring gets deactivated.
(–)
AlCl3 + PhNH 2 
→ PhNH 2 
→ AlCl3
(Acid) Base

101. (a) 2PhCHO + NaOH 

→ PhCH 2OH + PhCOONa
(from fehling solution)

102. (d) Nitration of C6H6 & C6D6 occur with same rate because breaking of C— H & C — D bonds is not the part of rate deter-
mining step.
103. (c) Due to protonation by nitrating mixture (nitric acid & sulphuric acid) NH2 group becomes NH3(+) which is electron with
drawing and meta directing group.
104. (a) Benzene losses it’s aromaticity after addition reaction & becomes less stable

More than one may correct:-

1. (d) Biuret test is shown by the compounds containing CONH2 linkage.

2. (a, b) 3. b, c

(+)
NHOH NH—OH2 NH NH
(+) (+)
H
4. (b, c) –H2O

H2O H2O (+)

NH2 NH2
HO

OH
5. (b, c)
6. (d) Diazotisation reaction is shown by aromatic amine & not by aliphatic amine as aromatic diazonium salts are stabilized
by resonance.
7. (a, b, d ) Chlorobenzene can not be hydrolysed by aqueous NaOH at room temperature. Fusion of sodium benzene sulphonate
with NaOH pellets gives sodium phenoxide which on acidification gives phenol
392 Problems in Organic Chemistry

8. (a, b, c) In (a) first compound is more basic than 2nd because it becomes aromatic after protonation.
(+)
O OH OH
(+)
H Aromatic
N N N (+)

H H H

H O( + )
9. (a, b) [A] 
2 → MeCOMe + PhCOOH
(–ve tollen's & fehling 's test)

H O( + )
[B] 
3
→ EtCHO + PhCOOH
(–ve tollen's & fehling 's test)

CH3 CH3
10. (b, c) 11. (b, d) [A] [B]

* Cl *
alc. KOH
12. (b, c) [Y]

[X]
* *
(+) (+)
alc. ZnCl2
[X]

[Y] [Y]
* *

* *

LEVEL -II

(+ )
(–)
1. (b) [FeCl4 ] [CH3CH 2 CH 2 ] is formed, This is weak ion pair thus, rearrangement does not occur because these ions do not
get separated.
2. (c) In 1 & 4 benzene rings are activated and moderately activated respectively. While in 2 & 3 benzene rings are moderately
deactivated.
(+ )
AlCl
Me3CO( + ) 
Ph –H
3. (a) Me3COCl →
3 → CO + Me3 C → Ph – CMe3

OH O
O2N
NO2
4. + conc.HNO3 +

P2 HO P1
O NO2

OH O

nitrating mixture
5.

NH2 P3
O
Aromatic Chemistry 393

NO2

6. P4

NO2
P5

7. N2O5 is a nitrating agent.

Cl Cl Cl
NO2
N2O5
&

NO2

nitration
8. NO2
N N
H H
Cl SMe
Cl (–) Cl
MeS
9.

CN CN

10. No reaction because base is sterically hindered.

11. Here benzyne mechanism takes place.

NO2 NO2
(–)
NH2
– NH3
Cl
NH3 NH3
NO2 NO2
(+)
(–) NH3
(+) (–)
NH3
(More Stable) (Less Stable)

NO2 NO2
NH2

NH2
(Major) (Major)
394 Problems in Organic Chemistry

X Base

12. Here following type of intermediate is formed (–) - I effect of X stabilizes the intermediate hence rate of reactions
will follow the following order.
R1 > R2 > R3 > R4 > R5 NO2

X Base
Cl
13. (–) It is more stable than others because -ve charge can go to empty d orbital or chlorine thus order is:-

NO2
R2 > R1 > R3 > R4
 Practical Organic
Chemistry 14
Main Features
Detection of elements (Lassaigne test): - Organic compound is fused with sodium metal and then fusion mixture is mixed in boiled
distilled water. Boiled solution is now filtered. This filtered solution is called sodium extract (S.E.). Elements present in organic
compound get converted in to their sodium salts as follows:-
Na + C + N 
→ NaCN
2Na + S 
→ Na2S
Na + X 
→ NaX [ X = Cl , Br ,I , F]
Na + C + S + N 
→ NaCNS
Test of Nitrogen: -
S.E. + FeSO4 + conc H2SO4 boil & cool
now add FeCl3 + conc HCl (Prussian blue colouration)
FeSO4 + 2NaOH 
→ Fe(OH)2 + Na2SO4
Fe(OH)2 + 6NaCN 
→ Na4[Fe(CN)6] + 2NaOH
Na4[Fe(CN)6] + FeCl3 
→ Fe [Fe(CN) ] + 3NaCl
4 6 3
(Pr ussian blue)

Test of Sulphur: -
(i) S.E. + sod. Nitro prusside (deep violet colouration)
Na2S + Na2[Fe(CN)5NO] 
→ Na4[Fe(CN)5NOS]
(ii) S.E. + dil CH3COOH + lead acetate (black ppt)
Na2S + (CH3COO)2Pb 
→ PbS ↓ +2CH3COONa
(black)

When both sulphur & nitrogen are present

S.E + FeSO4 + NaOH + boil & cool + FeCl 3 + conc HCl ( blood red colouration)
NaCNS + FeCl3 
→ [Fe(CNS)]Cl + NaCl
2
(Blood red)

Test of Halogen
S.E + dil HNO3 + AgNO3 (Precipitates)
NaCl + AgNO3 
→ AgCl + NaNO3
White ppt
396 Problems in Organic Chemistry

NaBr + AgNO3 
→ AgBr + NaNO3
(Dirty yellow ppt)

NaI + AgNO3 
→ AgI + NaNO3
(Bright yellow)
Precipitates of AgCl & AgBr are soluble in liquid. NH3 but precipitates of AgI are insoluble in liquid. NH3.

LEVEL - I

Multiple Choice Questions

1. For the detection of nitrogen in urea (Lassaigne test) some times we add naphthalene for better result because
(a) Naphthalene breaks urea easily.
(b) In urea % of C is small so naphthalene helps in the formation of more cyanide ions.
(c) Naphthalene forms nitro naphthalene which can show test of nitrogen easily by aq. FeSO4
(d) Naphthalene reduces melting point of urea
2. X + resorcinol + conc H2SO4 ∆ solution
pour in a solution
Red-green fluoroscence
containing aq NaOH
X would be:-
(a) Phthalic acid (b) p - nitro toluene
(c) Salicylic acid (d) Phenolphthalein
3. Phenol and acetic acid can be distinguished by:-
(a) Haloform (b) Neutral FeCl3
(c) Na (d) (a), (b) & (c)
4. Choose the answer that has the following compounds located correctly in the separation scheme.
Citric acid - A, Benzophenone - B, Benzoic acid - C
A + B + C water water soluble + Insoluble Portion saturated NaHCO3

Solution (–1)

dil HCl
Compound (–3) Soluble Portion + Insoluble

InNaHCO3(–2)
1 2 3 1 2 3
(a) A B C (b) C B A
(c) B C A (d) A C D
5. Choose the answer that has the following compounds located correctly in the separation scheme.
Succinic acid (A), Anthracene (B), Salicylic acid (C)
water NaHCO3
A+B+C water soluble + Insoluble
Solution (–1)
dil HCl
(3) Soluble Portion + Insoluble
Portion(–2)
1 2 3 1 2 3
(a) A B C (b) C B A
(c) C A B (d) A C B
Practical Organic Chemistry 397

6. Lassaigne test for the detection of nitrogen does not hold well for:-
(a) NH2OH (b) NH2NH2 (c) N3H (d) All of these
7. Lassaigne test for the detection of nitrogen will fail in case of:-
(a) Guanidine (b) 2, 4 - DNP (c) Carbyl amine (d) Tilden reagent
8. Formic acid and acetic acid can be differentiated by:-
(a) Calomel (b) NaHCO3 (c) Na (d) CH3OH / H(+)
9. Formaldehyde and acetaldehyde can be differentiated by:-
(a) Phenol / dil NaOH (b) [Ag(NH3)2]OH
(c) NH2NH2 in glycol / NaOH (d) All of these
OH OH
10. & can be differentiated by:-

(a) KOBr (b) NaNO2 + H2SO4 (c) Na (d) Cu+2 / OH(–)

11. PhN2Cl some times does not show positive lassaigne test for Nitrogen because.
(a) It dissociates PhN2(+) & Cl(–) ion so Nitrogen does not come in solution in form of NaCN
(b) On heating it decomposes to give N2 gas.
(c) PhN2Cl is stabilized by resonance and thus Nitrogen does not come in the solution easily.
(d) It sublimes on heating thus can not form fusion extract.
12. A + AgNO3 
→ AgCl
A would be:- white ppt

(a) PhN2Cl (b) Me3N(+)Cl(–) (c) PhCH2Cl (d) All of these

13. Match the following
Column - I Column - II
(A) Acetaldehyde 1. heat/NaOH/CuSO4
(B) Glucose 2. NaHSO3
(C) HCOOH 3. Molish test
(D) Urea 4. HgCl2
A B C D A B C D
(a) 1 2 3 4 (b) 2 3 4 1
(c) 4 1 3 2 (d) 3 2 4 1
14. Match the following
Column - I Column - II
(A) Glucose 1. HgCl2
(B) Phenol 2. concn H2SO4
(C) CH3NH2 3. concn H2SO4 + NaNO2
(D) HCOOH 4. HgCl2/CS2
A B C D A B C D
(a) 4 2 1 3 (b) 2 3 4 1
(c) 2 3 1 4 (d) 4 3 2 1
398 Problems in Organic Chemistry

Passage - I

Mixture (A + B + C)

Dissolved in water & filter

Soluble (A) Insoluble

(B) & (C)
wash with water dried
and then add saturated
solution of NaHCO3

Soluble (C) Insoluble (B)

Answer the question from 15 to 17

15. Compound A would be:-
(a) Benzophenone (b) Aniline
(c) Pthalic acid (d) NH2CSNH2
16. Compound B when heated with conc sulphuric acid gives yellow coloured solution. Compound B is :-
(a) Acetic acid (b) Benzene
(c) Toluene (d) Benzophenone
17. Compound C on on heating produces another compound which produces a pink coloured solution on reaction with
(i) Phenol / H2SO4 (ii) NaOH
COOH OH

(a) NH2 (b) OH

COOH

(c) COOH (d) All

Passage - II

(A + B + C)
water

water soluble A water insoluble B + C

Saturated NaHCO3

Insoluble - B Soluble - C
dil-HCl

C
Practical Organic Chemistry 399

Answer the question from 18 to 20

18. Compound C is fairly soluble in hot water but not is cold water. Compound C is:-
COOH
(a) CH3COOH (b) (c) para di chloro benzene (d) Citric acid
O2N
19. Compound B has zero dipole moment.
COOH
(a) para di chloro benzene (b) (c) PhNH2 (d) meta di chloro benzene
HOOC
20. A gives foam with NaOH. A would be:-
(a) Citric acid (b) meta di chloro benzene (c) aniline (d) Phthalic acid

Answer Key

1. (b) 2. ( a) 3. (b) 4. (a) 5. (a) 6. (d) 7. (d) 8. (a) 9. (a) 10. (b)
11. (b) 12. (d) 13. (b) 14. (b) 15. (d) 16. (d) 17. (c) 18. (b) 19. (a) 20. (a)

SOLUTION
LEVEL -I
1. (b) In urea % C is low so nitrogen of urea does not convert in to cyanide easily. For this either we have to use two or more
ignition tubes for fusion mixture or we have to use naphthalene along with urea in ignition tube.

OH OH
2. (a) HO HO HO O OH
H2SO4
H H
O C
O
C
O
C
C
O
NaOH
Phthalic anhydride Red-green fluoroscence

3. (b) Phenol gives violet while acetic acid gives blood red colouration on treatment with neutral FeCl3
4. (a) Citric acid is soluble in water (1) Benzoic acid is insoluble in water due to the presence of hydrophobic benzene ring but
forms PhCOONa with sod. bi sulphite white NaHCO3 (2)
5. (a) Same as above.
6. (d) Carbon is absent in all compounds.
7. (d) Carbon is absent in NOCl.
8. (a) Formic acid shows reducing properties.
Hg2Cl2 + 2HCOOH 
→ 2HCl + CO2 + 2Hg↓ (grey)
9. (a) Formaldehyde form a very hard plastic (Bakelite) with Phenol & H(+) ion.
10. (b) Phenol shows liberman’s nitroso test with NaNO2 + H2SO4.
11. (b) On heating PhN2Cl evolves N2 so cyanide ion formation does not occur.
400 Problems in Organic Chemistry

12. (d) All of these.

13. (b) Acetaldehyde gives addition reaction with sod. bi sulphite & forms white crystals. Urea on heating gives biuret which
turns violet by NaOH & aq. CuSO4. Formic acid can reduce Hg2Cl2. (sec. [Link]. 8)
14. (b) Glucose + H2SO4 (concn) 
→ Carbon black
Phenol + H2SO4 + NaNO2 
→ liberman’s nitroso test
CH3NH2 + HgCl2 + CS2 
→ Mustard oil reaction
HCOOH + 2HgCl2 
→ 2HCl + CO2 + Hg2Cl2 (grey)
15. (d) Thiourea is water soluble due to H bonding.
16. (d) Benzophenone on sulphonation gives meta acetyl benzene sulphonic acid which is yellow in colour
17. (c) Pthalic acid on heating produces phallic anhydride which further produces phenolphthalene on reaction with PhOH &
sulphuric acid. Phenolphthalene gives pink colouration in basic medium.
18. (b) 19. (a)
20. (a) Since it gives foam with NaOH thus it must have COOH group. Hence it is citric acid.
 15
Physical
Properties of
Organic Compounds

Main Features

There are two types of forces

(a) Primary forces: Ionic and covalent bonds. Former is stronger than later.
(b) Secondary forces:

H – Bonding > dipole – dipole attraction > other van-der waal forces

Van-der waal forces a Molecular weight

Melting Point: Melting point of ionic compound is greater than covalent compound.
NaCl = 801°C CH3CH2CH2CHO = – 90°C
M.P. of ionic compound a Lattice energy
In case of covalent molecules, following factors are responsible
M.P. a Packing
a Molecular weight
a Dipole moment
a Intermolecular forces of attractions
Boiling Point: B.P. of ionic compound is greater than covalent compound.
In case of covalent molecules, following factors are responsible
B.P. a Mol wt.
a Intermolecular forces of attractions
a Surface area
B.P. of halides a Polarisability (I > Br > Cl > F)
B.P. of chlorides, bromides and iodides increases as number of halogen atom in organic compound increases but b.p. of fluorides
decreases when number of fluorine atoms increases.
Solubility in water: a 1/Mol. wt.
a Dipole – dipole or ion – dipole attraction
a Dipole moment
In general for organic compound having comparable molecular weight solubility order is :
RCOOH > RNH2 > ROH > RCOR > RCHO > ROR
Solubility of chain isomers a 1/surface area
CH3CH2CH2CH2CHO < CH3 — CH — CH2CHO

CH3
402 Problems in Organic Chemistry

Problems (Multiple Choice)

1. Compound with largest melting point is :

(a) CH3(CH2)5Cl (b) LiCl (c) CH3COOH (d) CH3OH
2. Least boiling point will be exhibited by
(a) CH3Cl (b) CH3Br (c) CH3I (d) CH3F
3. Which is insoluble in water?
(a) Urea (b) Methyl bromide (c) Chloroform (d) Both (b) and (c)
4. In which case dipole – dipole attraction is present
(a) CHCl3 and Acetone (b) CHCl3 and H2 (c) CH3COONa and T.H.F. (d) HF + NaCl
5. Correct order of dipole moment of the following organic compounds is:-
CH3 CH3 CH3
NO2

NO2
NO2
(1) (2) (3) (4)

(a) 3 > 2 > 1 > 4 (b) 3 > 2 > 4 > 1 (c) 1 > 2 > 3 > 4 (d) 1 > 2 > 4 > 3
6. If µ1, µ2, µ3 and µ4 are the dipole moments of alkenes as shown below then select correct statements regarding following four
alkenes
Cl H H CH3 H CH3 Cl CH3
C=C C=C C=C C=C
H Cl CH3 H Cl H H H
(1) (2) (3) (4)

(a) µ1 > µ2 (b) µ4 > µ3 (c) µ1 = µ2 = µ3 = 0 (d) µ1 = µ2

7. Which among the following will have largest melting point?
(a) CH3COONa (b) CH3CH2COONa (c) HCOONa (d) CH3CH2OH
8. Compounds having infinite solubility in water is
(a) Iso propyl alc (b) Phenol (c) Acetone (d) Both (a) and (c)
9. Organic Compound Melting Point
A. n – Pentane (1) 324°C
B. Butanal (2) –96°C
C. Butan – 1 – ol (3) –90°C
D. Sod. Acetate (4) –130°C
Correct matching is :
(a) A → 4, B → 3, C → 2, D → 1 (b) A → 4, B → 2, C → 1, D → 3
(c) A → 3, B → 2, C → 1, D → 4 (d) A → 4, B → 3, C → 1, D → 2
10. Consider the following two carbonyl compounds where l1 and l2 are the bond lengths of ‘C – O’ bond
O O
Ketone l1 l2 Aldehyde
C C
CH3 CH3 Et H
(a) l1 > l2 (b) Ketone is more polar than aldehyde
(c) Aldehyde has more boiling point than ketone (d) Ketone has less % enol content than aldehyde
Physical Properties of Organic Compounds 403

11. Out of CH3CH2CH2OH, CH3COCH3, CH3OCH2CH3 and CH3Cl the compound which is completely insoluble in water is :
(a) CH3CH2CH2OH (b) CH3COCH3 (c) CH3OEt (d) CH3Cl
12. The compound which makes partially miscible solution when added in to water is
OH
NH2
(a) CH3SO3H (b) CH3CH2OH (c) (d)

13. Which pair of organic compound is completely insoluble in water?

(a) PhNH2 and CH3F (b) CH3CH2OCH2CH3 and CH3F

(c) and PhOH (d) and CH3F

OH OH
14. Among the following compound the compound with highest M.P. is :
CH3CH2CH2COONa NaCl CH3CH2COOH
OH
OH
(I) (II) (III) (IV)
(a) I (b) II (c) III (d) IV
15. Boiling points of CH3CH2F, CH3CF3 and CF3 – CF3 are respectively –
(a) –32°C, –47°C and –78°C (b) –78°C, –47°C and –32°C (c) –47°C, –32°C and –78°C (d) –78°C, –78°C and –32°C
16. Select correct statement

OH
(a) has more m.p. than

(b) 3° alcohol has more m.p. than 1° and 2° alcohols of same molar mass
(c) 1° amines are more soluble in water in comparison to alcohols having comparable molar mass
(d) All are correct
17. CH3CH2OH is more soluble in water in comparison to CH3OCH3 because
(a) Alcohols are more polar than ethers
(b) Alcohol can form hydrogen bonds with water while ether can not form hydrogen bond with water
(c) Alcohol dissociates in water while dissociation of ether is not possible
(d) Alcohol forms more hydrogen bonds with water in comparison to ether
18. Which is an example of negative deviation?
(a) C2H5OH + H2O (b) CHCl3 + CH3COCH3
OH
(c) C2H5OH + CH3OH (d) +

19. Arrange the following in order of boiling point :

CH3F CH3Br CH3I

F
(1) (2) (3) (4)
(a) 4 > 3 > 1 > 2 (b) 4 > 3 > 2 > 1 (c) 1 > 4 > 3 > 2 (d) 1 > 2 > 3 > 4
20. Compound with largest boiling point is :
(a) CH3COOC2H5 (b) CH3CHO (c) CH3COOH (d)
404 Problems in Organic Chemistry

21. Compound with maximum solubility in water is :

(a) (b)

(c) O (d) All are insoluble in water

N

22. Out of hexane, pentane, butane and propane, the alkane having second highest melting point is :
(a) Butane (b) Hexane (c) Propane (d) Pentane
23. But-2-en 1, 4 dioic acids exists in two forms as shown below

CH – COOH HOOC – CH

CH – COOH CH – COOH
Maleic acid Fumaric acid

Select correct statement

(a) pKa of maleic acid is lesser than that of fumaric acid (b) Maleic acid is more soluble in water than fumaric acid
(c) Fumaric acid has more M.P. than maleic acid (d) All are correct
24. Select correct statement for following halides

Cl Cl Br I

(I) (II) (III) (IV)

(a) B.P. of IV is lesser than III

(b) Dipole moment of III is lesser than IV
(c) Dipole moment of II is greater than I
(d) Except II rest all halides undergo SN reaction with aq NaOH frequently
25. Which will have maximum solubility in water?
(a) CH3OCH3 (b) OH

(c) CH3CHF2 (d) NH2

NH2

Answers Key

1. (b) 2. (d) 3. (d) 4. (a) 5. (a) 6. (d) 7. (c) 8. (d) 9. (a) 10. (b)

11. (d) 12. (d) 13. (a) 14. (b) 15. (a) 16. (d) 17. (d) 18. (b) 19. (c) 20. (c)

21. (d) 22. (a) 23. (d) 24. (d) 25. (a)