Aldehydes and Ketones

D.P.P – V
Level – I : JEE(Main) + NEET
1. (c)
The mechanism of the given reaction is as follows :
Note : HCl  H  Cl
+OH OH
O
H  C  H + H+ HCH HCH
+
Electrophile

Thus, both benzyl cyanide and benzyl isocyanide are the products of reaction but benzyl isocyanide being
the major product gives the correct option as (c).
O
||
2. (b) Coloured ppt. with 2, 4-DNP : Must have  C 
O
||
Iodoform test : Must have  C CH3
No dye formation : No Phenolic or aniline group.
Let us study the chemical nature of the functional groups present in the following compound (b)
It is a 3o-amino group (NMe2)
though aromatic which will not
CH3 respond to diazotisation (NaNO2 +
N dil. HCl/5oC). So, formation of
CH3 diazonium ion and its further reaction
with alkaline phenol or -napthol at 5-
10oC to produce a precipitate of azo-
(b) dye will not take place
It is a keto group C O and so it
responds to 2, 4-DNP test with
Brady's reagent (2, 4-dinitrophenyl
CH3 C O hydrazine) to give a raddish orange precipitate
O
It is a keto-methyl group C CH3
and hence, it responds to iodoform
test to give a yellow precipitate of
iodoform (CHI3).
Compound (c) is an alcohol and does not give positive 2, 4-DNP test. Hence, eliminated.
(a) and (b) does not have – CH3CO group and does not give iodoform test. Hence, eliminated .
1
3. (b)
NaBH4 is a selective reducing agent.

It reduces carbonyl C O group into an alcohol but cannot reduce an isolated C = C and an ester
group too.

Carbonyl O
group O OH
O CH2 C OCH3
CH2 C OCH3 NaBH4
MeOH
Ester
Isolated group
C C
4. (b)

The most suitable reagent to carry out given transformation is I2/NaOH

OH O
| Strong oxidation,  O 
||
CH3  CH  CH  CH2  C H  CH3  CH3  CH  CHCH2  C  OH  CHI3   CO 2 
6 5 4 3 2 1  Oxidative cleavage  6 5 4 3 2

Here, the haloform reaction will give following reaction :

(i) Tollen’s reagent (AgNO3 + NH4OH) is a mild oxidising agent. It does not react with  C H  CH3 group (2-
|
OH
alcohol).

(ii) Alkaline KMnO4 cannot perform the oxidative cleavage, rather it will hydroxylate the C ═ C.

OH OH OH OH
| | | |
KMnO4
CH3  CH  CH  CH2  C H  CH3 
 CH3  C H  C H  CH2  CH  CH3
6 5 4 3 2 1 OH 6 5 4 3 2 1

(iv) CrO2Cl2/CS2 will not react here.

5. (b)

In presence of strong base, acidic H can easily be removed that result in formation of anion. The resulting
anion undergoes intramolecular nucleophilic addition which on hydrolysis followed by heating gives the
O
||
required product. As ketone is more EWG than ester,   – H w.r.t.  C  undergoes condensation.

2
 3 4 5
2

6. (a)
In the given reaction, AlCl3 helps in the generation of electrophile that further undergoes ArSE2 reaction to
give the required product.

It does not show SN reaction with HCl because of double bond nature of the O – C bond, (due to + R – effect
of the – OH group.)
7. (c)
Acetal formation is nucleophilic addition reaction due to the addition of alcohols on aldehydes.
The reactivity of nucleophilic addition depends on following two factors.
 Inductive effect Greater the number of alkyl group attached to carbonyl group, greater is the electron
density on carbonyl carbon. Thus, lowers the attack of nucleophile. Hence, reactivity decreases.

3
  Steric effect As the number of alkyl group attached to carbonyl carbon increases, the attack of nucleohile

on carbonyl group becomes more difficult due to steric hinderance. Thus, the best combination is HCHO

and MeOH. The reaction is as follows :

Acetal

8. (b)

The reactant in presence of Dil. NaOH undergoes intramolecular aldol condensation reaction.

As a result on this, -hydroxyketone (A) is obtained which on hydrolysis followed by heating produces , -

unsaturated ketone (B)

2 4 6
1 3 5

More electrophillic
More as it is an aldehyde
acidic -H

4
9. (d)

10. (a)

In reaction t-BuOΘ H+ is used as a base to remove HBr and form alkene as a major product (B) via E2
elimination mechanism.
Mechanism Firstly, 1-bromoacetaldehyde undergoes protonation which is then react with t-BuO Θ H+.

(t-BuOΘ act as nucleophile and attack on carbonyl carbon). In next step, t-BuOΘ H+ act as base and accepts
proton and at last alkene is formed as major product.

5
11. (c)

Only compound (II) which has ketonic group does not form silver mirror when treated with Tollen’s reagent.
Because Tollen’s reagent oxidises an aldehyde into the corresponding carboxylic acid. Ketones are not
oxidised by Tollen’s reagent, so the treatment of a ketone with Tollen’s reagent in a glass test tube does
not result in a silver mirror. Aldehydes give positive Tollen’s test (silver mirror test).

(I)
CHO Positive

OH Tauto O
(II) Negative
Ketone

Tauto O
(III) Positive
OH
H

O [Ag(NH3)2]+OH O O
(IV) Positive
H2O H
OH O
Hemiacetal O
12. (c)

Here, 4-methoxybenzaldehyde in series of reaction finally forms 4-(iodomethyl) phenol (A). Let us compute

the reaction step by step with mechanism as follows.

(i) In first step, oxidising agent (p-methoxybenzaldehyde) reacts with formaldehyde in presence of strong

base NaOH to give p-methoxybenzyl alcohol along with sodium salt of methanoic acid. It is known as

Cannizzaro’s reaction.

6
 +1 CH2OH
CHO
+ HCHO NaOH
Reducing + HCOONa
agent Cannizzaro
CH3O (Formaldehyde) reaction
Oxidising OCH3
agent
(p-methoxy
benzaldehyde)

(ii) In second step, deprotonation of p-methoxybnezyl alcohol in presence of sodium hydride (NaH) to form

alkoxide which further react with bromoethane in presence of DMF to give 1-ethoxymethyl-4-

methoxybenzene.

CH2O H CH2ONa CH2O CH2CH3

CH3CH2  Br
Na H (in DMF)
H2 NaBr [SN2 reaction]
(Acid-base
OCH3 reaction) OCH3 OCH3

(iii) In last step, 1-ethoxymethyl-4-methoxybenzene undergoes solvolysis reaction followed by SN2 attack of

two iodide ion (I–) to give 4-iodomethyl phenol, iodoform and iodoethane.

7
13. (d)

Compound B(C4H8O) reacts with hydroxylamine (NH2OH). So, compound B is an aldehyde or a ketone.
Again, B does not give Tollens test which indicates that B is a ketone but not an aldehyde. So, B is
O
||
CH3  C  CH2CH3  C4H8O 
2  butan  one
Compound A(C4H8Cl2) is a dihalide which undergoes hot hydrolysis (H2O/373 K) to give B, a ketone. So, A is
non-terminal geminal or dichloride and A is
Cl
|
CH3  C  CH2CH3  C4H8Cl2 
| 2,2  dichlorobu tan e
Cl
The reaction can be computed as,
Cl O H O
2H2O/373K H2O
CH3 C CH2CH3 CH3 C CH2CH3 CH3 C CH2CH3
2HCl
(B)
Cl OH 2-butanone
(A) Butane-2, 2-diol (unstable)
2, 2-dichlorobutane (Non-terminal gem-diol)
14. (a)

Sodium hypochlorite (NaOCl) is a strong oxidising agent that will convert ketone to carboxylic acid.
Since, product is carboxylic acid, therefore reactant (P) would be ketone.
OH
(i) NaOCl
(ii) H3O+
O
O But-2-enoic
(P)
acid
Pent-3-en-2-one
15. (d) Na2Cr2O7, H+/H2O beings strongest oxidising agent convert primary alcohols to carboxylic acids.

OH OH
(i) Na2Cr2O7
(ii) H+/H2O
O
Carboxylic acid
16. (c) Isobutyraldehyde reacts with formaldehyde and K 2CO3 to gives Cross Aldol reaction and form -hydroxy

aldehyde (A).

8
 -hydroxyaldehyde (A) on treating with KCN shows nucleophilic addition reaction at carbonyl group to form
-hydroxynitrile (B).

Compound (B) on hydrolysis forms carboxylic acid which then forms a stable five membered and one water
molecule is removed. This reaction is called esterification reaction.

17. (c)

Reagents used in the given reaction are BH3, H2O2/OH– are PCC.
CH3

CH2

B
CH2
CH2 CH2
Hydroboration
BH3
H3C H3C
(A)
CH3
CH2OH H2O2/OH
CHO
PCC 3
H3C
H3C
(B)

Hydroboration is done by BH3, H2O2/OH– and oxidation is done by PCC reagent.

9
18. (a)


O O

CH3MgBr + Cul
(1, 4-addition)

O O

19. (b)

O OH
NaCN
(P) + COOH
HOAc
Cl Cl
OH O H
(i) 2MeMgBr
EtOH OC2H5
P O (ii) H3O+ C
H+
Cl Cl OH
(Q) (R)
20. (15)

EtO CH2 CH O
NH3/H+(NH4Cl)

EtO CH2 CH NH
KCN

NH
EtO CH2 CH
CN
H2SO4/H+

NH
EtO CH2 CH
CO2H
HNO3 + H2SO4 (2eq)

O2N
NH2
EtO CH2 CH
CO2H
NO2 AC2O

10
 O
O2N
NH C CH3
EtO CH2 CH
C OH
NO2
O
EtOH/H+/

NO2 O
NH C CH3
EtO CH2 CH
C OEt
NO2
O
H2(Pd)/C

NO2 O
NH C CH3
EtO CH2 CH
C OEt
NO2
O
HNO2

+
N2 O
NH C CH3
EtO CH2 CH
CO2Et
NaI
+
N2

I O
NH C CH3
EtO CH2 CH
C O C2H5
I O
[mf C15H19NO4I2]

21. (2) As per the conditions given, the compounds do not have acidic or basic component to be dissolved in basic or

acidic medium. It has at least one unsaturated bond to be hydrogenated. The molecules do not have

C = O or CHO functional group.

CH CH O CH3

cis-and trans-isomers,
of this compound.

22. (c) A-III, B-IV, C-I, D-II

11
Level – II : JEE(Advanced) / AIIMS / KVPY / Olympiad

23. (a) Lower ketone protected first.

O O OH OH
HO +
H+ LAH H3O
+

O HO
O O O O O

24. (c)

CH3 CH3 CH3

S S CH3 Br S CH3 HS
C C C
C O +
H S S CH3 S CH3 HS
(A)

25. (b)

Ph Ph S H2/Ni
Ph S CH3CH2Br
S C C Ph CH2 CH2 CH3
C
S S
H S H3CH2C
(Ist intermediate)

26. (d) -Halogenation

 HOCl  HCl
Cl2  H2O 

O
O
Cl
H + HOCl+ + H 2O
O O
HO Cl+ Cl
H2O

27. (a)

Aldol condensation. (Intramolecular)

O O

OH , 
O
O O
H2C
H

12
28. (b)

CH3 CH3
KOH + H2O
O H
 CH3
H
C CH3
O
O

29. (a) Acid Catalysed

Aldol condensation (Proceeds via enol intermediate)

C
H2
O

30. (c) Michael Addition

O O
H C C2H5O H C
CH2 CH
H C C2H5OH H C
O O
(A)

H H
+
CH2 CH C O CH2 CH C O

O O
H H
H C H C
+ +H+ CH2 CH C O
CH + CH2 CH C O CH H
H C H C

O O

O
H
H C
CH CH2 CH2 C O
H C
O

31. (a)
O O
C2H5O
+ C2H5OH
(X)

13
 + 
CH2 CH C N CH2 CH C N

O O
+  +H+ CH2 CH C N H
+ CH2 CH C N

O
CH2 CH2 C N

1, 4-addition first. CH2 CH C N

Then tautomerisation

+
CH2 CH C N
32. (d)
All -H replaced.
O O O
  +  D
OD D OD

All -H will be replaced by D in this way.

33. (d)
Benzoin Condensation
(Refer to its Mechanism in class notes)
34. (a)
O O H
MnO2 KCN/EtOH
CH2OH C H Ph C C Ph
H2O
(X) Benzoin OH
condensation
35. (c)

O O O + O
 + Br C O
C C Br C O Br exchange
2KOBr OBr
CH2 C
H of C CBr3
C active C Br C C Br
O methylene O O O
Br
replaced
by Br O O

 C O 2H+
C OH
OBr
CBr4
(x) C O C OH

O O
1, 4-dicarboxylic
(y) acid
 (Blanc's
Rule)
O
C
O
C
O

14
 O
 +
C ONa + CHBr3 (X and Y)

C ONa+
O
O
C
O (Z) By Blanc's Rule
C
O
36. (a) Baeyer Villiger Oxidation. (Refer to its mechanism in class notes)

37. (b) Baeyer Villiger Oxidation. (Refer to its mechanism in class notes).

38. (d) Baeyer Villiger Oxidation. (Refer to its mechanism in class notes).

39. (b) Baeyer Villiger Oxidation. (Refer to its mechanism in class notes).

40. (a) Baeyer Villiger Oxidation, followed by Hydrolysis

O O
|| ||
Ph  C H  C  O CH3 (X) , Ph C H C  OH (Y) , CH3OH (Z)
(EWG) | |
Ph Ph
(EWG)
41. (c) Baeyer Villiger Oxidation. (Refer to its mechanism in class notes).
42. (c) Favorskii Type Reaction :
O O
O O
C OH
Br Br OH + H+ COOH Favorskii type reaction

(A)
43. (b)
O O COOH Favorskii type
O Br2/H2O
O HO + H+ COOH
rearrangement
Br Br
44. (c) NaH forms more stable or more substituted enolate. LDA forms less stable or less substituted enolate

O O O
O O CH3
O if CH3 CH3 
LDA NaH CH3 CH3 CH3
+ Lighter
LiN[CH(CH3)2]
Bulky (A) enolate
Less more
substituted substituted
enolate
45. (c) Aldehyde protected preferrably.

 + OH O
HO OMgBr O
O O O + CH3
O CH3 H3O
O O CH3MgBr H
HO
H H
H H+

15
46. (c) No change in configuration. (Baeyer – Villiger Oxidation)
O (ERG) CH3 O

R''COOOH R''C O  O + H+ 3o 1o

Ph C CH3
EWG
H
O
O OH
H+ R''C O  O
RC R' RC R'
+

R' O R'
RC O  O C R'' RC O + R C OR' + H+
O
OH O H O
R''C O

47. (a) Baeyer Villiger Oxidation. (Refer to its mechanism and find that O 18 will be used in ester formation).


48. (b) CH2N2   : CH2  N2 (Carbene formation)

O O O
CH2 Baeyer Villiger Oxidation O
insertion

49. (c) Beckmann Rearrangement

O H O
+
C C C H
H2N  OH PCl5 N H2O N N
O N OH
H2O
 H+
oxime

50. (a) Beckmann Rearrangement. Group Anti to –OH migrates.

N OH + H H H
N OH2
+H+ N O N
LAH

(X) (y)

51. (d)

O
S S S S S S R R'' + SH SH
S
R H R R''
R
(P) (Q) (R) (S)

16
52. (c) 1, 4-addition

O O



CN CN
C2H5O
H2C HC
C2H5O
CN CN

O O H O
CN
+ CN
+H CN
+ HC 
C C
CN CN CN
H H

53. (b,d)

O
AlCl3
2H for H.C. Friedel craft
Strong o,p- reaction
(P) directing C O

HO
O (Q)
Clemmenson reduction
Zn/Hg/HCl

H3PO4
HO
O Cyclisation
O C

(R)
(1) CH3MgBr
(2) H+/H2O

H2SO4
HO

CH3 (H2O)
(S)

17
54. (a)

+ CHI3

55. (c)

O O
|| ||
H  C  H  CH3  C  H 
conc. NaOH
 HCOONa  CH3CH2OH
O O O
|| || ||
This is Cannizzaro reaction. Note out of H  C  H and CH3  C  H, H  C  H will be preferrably attacked by
Θ
OH in first step and it will release H⊝ to CH3CHO
56. (a)

57. (d)
Only – CHO group gets oxidized to – COOH group by Br2/H2O.
CHO COOH
Br2 / H2O
H OH H OH
CH2OH CH2OH
Glyceraldehyde (Chiral compound)
58. (b)
Williamson’s synthesis reaction.

59. (a)
H O H O
Br (i) Alc. KOH HgSO4
Br H C C Ph H C C Ph CH3 C
Ph (ii) NaNH2 (X) H2SO4

Conc.
HNO3/H2SO4
H3C O
C

NO2

18
60. (d)

1. O3
2. Zn/H2O O
CHO

The product has a aldehyde group

(which is not aromatic aldehyde)
 Gives Fehling’s test.
Products of options (a), (b) and (c) are
CHO
(Aromatic aldehyde)

(Ketone)
O
CHO
(Aromatic aldehyde)

and none of them give Fehling’s test.

61. (12)
+ +
OH HO OH OH

O O N N N N
O3 (excess) NH2OH  
 
then Zn/H2O
O O N N N N

OH HO OH OH
+ +
(P)
sp3 carbon atom of ring
has least angle strain.
So, total 12 atoms are sp2 hybridised (4 C atoms, 4N atoms and 4 O atoms).

62. (a,c)
O O O
O C CH2 CH2 C OH CH2 CH2 CH2 C OH
O O
Zn/Hg, HCl
AlCl3
SOCl2
(P) (Q) O
CH2 CH2 CH2 C Cl

Zn/Hg O AlCl3
HCl
Hydrocarbon (S) (R)
63. (d) P  3; Q  4; R  5; S  2
O
Zn - Hg/HCl
(1) Ph C CH3 Ph CH2 CH3
Acetophenone

19
 O
CH3 C Cl CH3
(i) KMnO4,
KOH/ H2Pd -BaSO4
(2)
(ii) SOCl2 Rosenmond
Tolune Tolune reaction (S)

CH3 CHO
CH3-Cl CrO2Cl2
(3)
Anhy.AlCl3 AcOAc/
Etard reaction (P)

NH2 N2Cl- Cl
NaNO2/HCl Cu/HCl
(4)
273 - 278 K Gattermann
reaction
(Q)
OH Cl
Zn/D Co/HCl
(5)
AlCl3
Gattermann (R)
Koch reaction

20