Haloalkanes and Haloarenes 577

24
Haloalkanes and
Haloarenes
The replacement of H-atom(s) in a hydrocarbon, aliphatic or (b) Aryl halides : The halogen atom is attached directly to
aromatic, by halogen atom(s) results in the formation of alkyl the carbon atom of the benzene ring.
halide (haloalkane) and aryl halide (haloarene).
X X
CLASSIFICATION
On the Basis of No. of Halogen Atoms : H3C
Mono, di, tri, tetra, etc. depending on whether they contain one, Note :
two, three, four halogen atoms in structures. (a) Down the group, size of X increases, \ C– X bond length
increases down the group from F to I.
C2H5X CH2X CH2X
| | (b) Although F is more electronegative than Cl, yet dipole
CH2X CHX moment of CH3Cl is more than CH3F. This is because of
| small size of F due to which C-F bond distance (d) becomes
CH2X small in comparison to C – Cl bond distance dipole moment
mono di tri
is given as µ = q × d. Thus dipole moment of C – Cl bond is
Classification Based on Nature of C – X Bond greater in comparison to dipole moment of C – F bond.
(i) Compounds containing sp3 hybridised C–X bond METHODS OF PREPARATION OF ALKYL HALIDES
(a) Alkyl halides or halo alkanes : (i) From Alcohols
RCH2X R2CH X R3CX
1° 2° 3° R – OH + HX RX + H2O
(b) Allylic halides : In these compounds the halogen atom
is linked to an sp3 hybridised carbon atom which has a 3
C = C bond attached to it.
R – OH + PCl5 R – Cl + POCl3 + HCl
X

CH2X
Thionyl chloride method is preferred over hydrogen
(c) Benzylic halides : The tetrahedral carbon involved in chloride or phosphorus pentachloride method for the
C – X bond is linked to an aromatic ring. preparation of chloroalkanes since both the by-products
(SO2 and HCl) in this reaction being gases escape out
CH2X R
X leaving behind the chloroalkanes in almost pure state.
R' Note :
(a) Order of reactivity among HX : HI > HBr > HCl >> HF
(b) Order of reactivity among ROH : 3° > 2° > 1° > CH3OH
(ii) Compounds containing sp2 hybridised C–X bond
(c) Mixture of conc. HCl and anhydrous ZnCl2 is used for
(a) Vinylic halides : The halogen atom is attached to sp2
differentiating three types of alcohols (3° > 2° > 1°)
hybridised carbon atom of C = C bond.
under the name of Lucas reagent.
X (d) SOBr2 is less stable and SOI2 does not exist, PBr5 and
X
PI5 are highly unstable hence not used.
 EBD_7753
578 CHEMISTRY

(ii) From Alkenes Note:

CCl4 (a) Chlorination and bromination can be achieved by above

C=C + X2 C C method while iodination is done in presence of
X X oxidising agent (i.e., HNO 3 or HIO 3). Direct
A vic-dihalide flourination is highly exothermic. Thus it is done by
(X = Cl, Br)
heating alkyl chlorides with inorganic fluorides (Hg2F2,
When above reaction is carried out by using Br 2/CCl4 the AgF, SbF3 etc.).
reddish brown colour of Br2 is discharged. Therefore this
(b) Benzylic hydrogens (hydrogen present on C attached
reaction is used as a test for detection of unsaturation in
directly to benzene) are more reactive, hence easily
organic molecules.
replaced than 1°, 2° or 3° hydrogens.
C=C + HX H C C X (iv) By Halogen Exchange
(with unsymmetrical alkenes, (a) Finkelstein reaction
Markovnikov’s rule followed)
R – X + NaI acetone R – I + NaX
Alkenes react with halogen acids to form haloalkanes. The (X = Cl, Br)
order of reactivity is
(b) Swarts reaction
HI > HBr > HCl > HF
Markownikoff's rule : Alkyl chlorides/ bromides is heated in presence of a
When an unsymmetrical alkene or alkyne reacts with metallic fluoride such as AgF, Hg2F2, CoF2 or SbF3 to
unsymmetrical reagent, then negative part of reagent attach form alkyl flourides.
with that carbon atom which contains lesser number of
D
hydrogen atom during the addition. R - X + AgF ¾¾
® R - F + AgX(X = Cl, Br)
For example:
PHYSICAL PROPERTIES OF ALKYL HALIDES
Br
| (i) Lower halides are gaseous in nature whereas higher halides
CH3 - CH = CH 2 + HBr ® CH3 - CH - CH3 are either liquid or solids (having 18 or more C–atoms)
Pr opene 2 - bromopropane
(ii) Alkyl halides are colourless when pure. The bromides and
Anti-Markownikoff's rule : iodides develop colour when exposed to light.
Addition of HBr (not HCl, HI and HF) on alkenes in presence
(iii) Melting and Boiling points
of peroxides takes place in anti-Markownikoff's way
(Peroxide effect). Here addition takes place via free- The m.pts and b.pts of chlorides, bromides and iodides are
radical mechanism. higher than those of analogous hydrocarbons due to
peroxide presence of dipole-dipole interactions in them besides van
CH3CH = CH 2 + HBr ¾¾¾¾® CH3CH 2CH 2Br
der waal’s forces.
(iii) From Alkanes The m.pts. and b.pt. follows the order: RI > RBr > RCl >
By free radial halogenation RF. This is because with increase in size and mass of
hv halogen, magnitude of van der Waal’s forces also increases.
CH3CH2CH3 + Cl2 CH3CHCH3 + CH3CH2CH2Cl The b.pts of isomeric haloalkanes decrease with increase
|
Cl in branching. For isomeric alkyl halides, order of boiling
(a mixture of products point is
is obtained)
Primary > Secondary > Tertiary
However, compounds containing only one type of hydrogen
(iv) Solubility
atom can be converted into monohalogenated products in
good yield by taking excess of the concerned hydrocarbon; The haloalkanes are only very slightly soluble in water. This
is because less energy is released when new interactions
examples of such compounds are CH4, CH3CH3, (CH3)4C,
are set up between haloalkane and water molecules and these
C6H5CH3 etc. The reactivity of the alkanes follows the
are not as strong as original H-bonds in water. Haloalkanes
following order: Tertiary alkane > Secondary alkane > are completely soluble in organic solvents.
Primary alkane.
 Haloalkanes and Haloarenes 579

CHEMICAL PROPERTIES OF ALKYL HALIDES alc. KOH

R – CH 2CH(Br)CH3 ¾¾¾¾
D
®
1. Nucleophilic Substitution Reactions
R – CH 2 CH = CH 2 + R – CH = CH – CH 3
R – X + Nu ® R – Nu + X – (major) (minor)
This is also called b-elimination or Dehydrohalogenation
reaction.
The product formed is determined by Saytzeff’s rule i.e.
the preferred alkene is that which has greater no. of alkyl
groups attached to doubly bonded C-atoms. Ease of
dehydrohalogenation among halides is : 3° > 2° > 1°
(Willamson’s ether synthesis) Note :
Elimination reactions dominate over substitution when
strong base i.e., Bronsted base [e.g. NH 2- , Me 3CO - , OC 2 H 5
etc.) is used and alkyl halide is 3° or 2°.
(iii) Reaction with Metals
(a) Grignard reaction:
dry ether
R – X + Mg R – MgX
Note : (b) Wurtz reaction:
2R – X + 2Na R – R + NaX
dry ether
(c) 4CH 3 CH 2 Cl + 4 Pb / Na ¾¾¾¾ ®
(C 2 H5 )4 Pb+ 4NaCl + 3Pb
TEL
(d) With Zn dust : (Frankland reaction)
R X 2Zn X R ¾¾® R– R + ZnX2
alkane
(e) With Li :
dry ether
R – Cl + 2Li ¾¾¾¾® RLi + LiCl
Note : alkyl lithium
Alkyl lithiums react with copper halides to form higher
alkanes (Corey-House synthesis)
CuI R 'X
2RLi ¾¾¾
® R 2CuLi ¾¾¾
® R - R'
( - LiI) (1° halide)
(iv) Reduction
Haloalkanes on reduction produces alkanes frequently.
R – X + 2H ¾¾® R – H + HX
Alkane

MECHANISM OF NUCLEOPHILIC SUBSTITUTION

Nucleophilic substitution rxns can proceed via two mechanism
SN1 or SN2.
¢
¢ SN1 (Unimolecular Nucleophilic Substitution)
This reaction occurs in two steps. In first step, a carbocation is
O O formed from alkyl halide molecule. First step is slow step so it
||
Ag – O – C– R '
|| is also rate determining step. In second step, an attacking
R '– C– O – R + AgX nucleophile attacks on this carbocation and forms the final
+
K SH– product.
R – SH + KX
Ar – H + AlCl3 ® Ar – R (Friedel-craft reaction) CH 3 CH3
(ii) Elimination Reactions | | –
Slow step
(i) CH3 - C - X ¾¾¾¾® CH3 - CÅ + X
Alkyl halide loses a molecule of hydrogen halide when | |
heated with alc KOH and alkene is formed. CH3 CH3
Ter. butyl carbocation
 EBD_7753
580 CHEMISTRY

(b) For a given alkyl group, the reactivity of halide, R – X follows

CH3 the same order in both the mechanisms:
| CH3
| R – I > R – Br > R – Cl > R – F
(ii) CH3 - CÅ + O H ¾¾¾¾
Fast step
® CH3 - C - OH (c) Polar solvents favour SN1 reactions while non-polar
| | solvents favour SN2 reactions.
CH3 CH3 Stereochemical aspects of nucleophilic substitution.
If the alkyl halide is optically active, the product formed in SN1
Rate of reaction µ [(CH3)3 C – X] It is a unimolecular
reaction is always a racemic mixture. This is due to the formation
substitution reaction. of carbocations as intermediates which, being planar (sp 2
In S N1 mechanism, carbocations are formed as hybridised) can be equally attacked by the nucleophile on either
intermediate, hence more the stability of the intermediate side of the face forming two enantiomers.
carbocation, greater are chances for their formation and R2
–
hence more reactive will be the parent alkyl halide for SN1 +X : |
R2 R1 - C - Z
reaction. Hence the order of reactivity of alkyl halides R1 R2 |
| +
toward SN1 reaction follows the order : 3° > 2° > 1° R3
R1 - C - X C
When the intermediate carbocation is capable of undergoing | R2
R3 |
rearrangement, lesser stable carbocation (1° < 2° < 3°) R3 Z - C - R1
Alkyl halide Carbocation |
rearranges to the more stable carbocation and hence under (sp 3 hybridised C) (sp2 hybridised) R3
such conditions unexpected product is formed. Enantiomers in
equal amounts
Note: Allylic and benzylic halides show high reactivity
Since the nucleophile attacks from the back side and the halide
towards the SN1 reaction because carbocation formed gets
ion leaves from the front side, the product obtained will have an
stabilised via resonance.
inverted configuration [Walden inversion]. This implies that if
SN2 (Bimolecular Nucleophilic Substitution) : the alkyl halide is optically active, the product will also be optically
The rate of SN2 reactions depends on the concentration of alkyl active, although the sign of rotation may be same or different.
halide as well as nucleophile, i.e. r = k [ RX ][ Nu ] . This implies H H
that both the reactants are involved in the rate-determining step, - HO C X
H C X + OH
i.e. the reaction occurs in one step only or it is a concerted
reaction. Concerted reactions occur through a transition state H H H
transition state
(an imaginary state in which both the reactant molecules are
H
partially linked to each other).
H HO C H + X¯
é H H ù
H ê d- d- ú
Nu : + C–X ê N u - - - - C| - - - - X ú H
H ê ú (Walden inversion)
ë H û
Transition state METHODS OF PREPARATION OF ARYL AND ARALKYL
H HALIDES
H H ù
d- ú -X :
H (i) By Electrophilic Substitution
---X ú ¾¾¾® Nu – C
ú H
û
Inverted product
The nucleophile attacks from the back side of the halide ion, bulkier
the alkyl group present on the carbon bearing halogen lesser will be
its tendency to undergo SN2 reaction. Thus the reactivity of alkyl
Chlorobenzene and bromobenzene can be prepared by above
halides towards SN2 mechanism is methods whereas iodobenzene cannot be done in the same
The reactivity of alkyl halides in SN2 reactions is: way because HI formed in the reaction is a powerful reducing
1° > 2° > 3° agent due to low bond dissociation enthalpy (299 kJ mol–1).
The order of reactivity among various 1° alkyl halides is It will therefore, make the reaction reversible in nature.
CH3X > C2H5X > n – C3H7X, etc.
Bulkier the alkyl group, more is the steric hindrance in the
formation of transition state and less is the reactivity of alkyl halide.
Note :
(a) 3° alkyl halides react by SN1, 1° by SN2 and 2° by either or On account of this, HI formed in the reaction is oxidised by
both of these mechanism depending upon the nature of the carrying the reaction in the presence of iodic acid (HIO3)
alkyl halide and the reagent. or conc. HNO3.
 Haloalkanes and Haloarenes 581

heat CHEMICAL PROPERTIES OF ARYL AND ARALKYL

2HI + 2HNO3 ¾¾¾ ® 2NO2 + 2H 2O + I 2
HALIDES
heat
5HI + HIO3 ¾¾¾ ® 3H 2O + 3I 2 (i) Nucleophilic Substitution :
Fluorination being extremely violent is difficult to control. The halogen atom is firmly attached with the benzene
Substitution in alkyl group nucleus and acquires extra stability due to resonance (+M)
effect. Hence, the halogen atom cannot be easily replaced
CH3 CH2Cl by other atoms or group of atoms. So, aryl halides are less
reactive the than alkyl halides.
Sunlight, 383K + + +
+ Cl2
Cl Cl Cl Cl

(ii) By the Decomposition of Diazonium Salts.

(a) Sandmeyer’s reaction

+ – The halogen atom is replaced by other nucleophiles under

N2 Cl Cl drastic conditions.
CuCl Cl OH
HCl + N2
(i) NaOH, 623 K, 300 atm
+ – +
N2 Cl Br (ii) H

CuBr Cl NH2
HBr + N2
200º C
2 + 2NH3 + Cu2O 2 + 2CuCl +
High
pressure
(b) Gattermann reaction: Aniline

C6 H5 N 2+ Cl –
Cu/HCl
¾¾¾¾
® C 6 H5 Cl H2O

Cl CN
C6 H5 N 2+ Cl – ¾¾¾¾
Cu /HBr
® C6 H5 Br
+ – Pyridine, 300º C
N 2 Cl I + CuCN + CuCl
(c) high pressure

KI Phenyl cyanide
+ N2
Note : Haloarenes does not undergo nucleophilic
substitution as clevage of C – X bond is difficult. When
+ –
NH2 N 2 BF4 F electron withdrawing groups like –NO2, – CN, – CHO, –
NaNO2 COOH etc. are present at ortho or para positions the bond
D
(d) + N2 + BF3 cleavage becomes easier.
HBF4
0 – 5°C (ii) Electrophilic Substitution Reactions
(a) Halogenation :
Thermal decomposition of benzenediazonium
tetrafluoroborate to give fluorobenzene is called Balz-
Schiemann reaction.
(iii) Hunsdiecker Method :

C 6 H 5 COOAg + Cl 2 (or Br2 ) ¾

¾® C 6 H 5 Cl + CO 2 + AgCl

PHYSICAL PROPERTIES OF ARYL AND ARALKYL HA- (b) Nitration :

LIDES
(i) Like alkyl halides, aryl halides are insoluble in water due to
their incapability of forming H-bonds.
(ii) Aryl halides are less polar than alkyl halides because in aryl
halides, halogen is present on sp2 hybridised carbon which
is more electronegative than the sp3 hybridised carbon of
alkyl halides.
 EBD_7753
582 CHEMISTRY

(c) Sulfonation : (iii) From carbon tetrachloride (Pyrene) :

Fe / HCl reduction
CCl4 + 2[H] ¾¾ ¾ ¾ ¾ ¾ ¾® CHCl3 + HCl
Properties
(i) Chloroform is colourless with sweet smelling, liquid.
(ii) Inslouble in water and soluble in organic solvent.
(iii) Boiling point of CHCl3 is 61ºC.
(iv) It is best solvent for fats, oil and wax.
(d) Friedel-crafts reaction : (v) On exposure to air and sunlight, chlorofrom, a colourless
heavy liquid, oxidises to carbonyl chloride (phosgene), a
highly poisonous gas used in warfare.
1 light
CHCl3 + O 2 ¾¾¾® CCl3 (OH) ¾¾® COCl2 + HCl
2 unstable
To avoid this oxidation chlorofrom is always stored in dark
coloured bottles filled to the brim to exclude any air. Further
nearly 1% alcohol is also added to destroy traces of
phosgene, if formed, to harmless diethyl carbonate.
2C 2 H 5OH + Cl 2 C = O ¾
¾® (C 2 H 5O) 2 C = O+ 2HCl
Diethyl carbonate
Uses :
(iii) Reaction with Metals:
(a) As an anaesthetic agent. However, it has been replaced by
(a) Wurtz-Fiting reaction less toxic and safer anaesthetic agents.
X R (b) CHCl3 acts as a solvent for fat, waxes, rubber etc.
+ 2Na + RX + 2NaX Iodoform (Triiodomethane) CHI3 :
CHI3 was earlier used as an antiseptic for dressing wounds. Its
(b) Fittig reaction antiseptic properties are due to the liberation of iodine when
X iodoform comes in contact with skin.
2 ether
Any compound containing CH3CO– or CH3CH(OH)– group,
+ 2Na
when heated with iodine and aqueous NaOH or NaOI (sodium
(iv) Ullmann Reaction: hypoiodite) gives yellow precipitate of iodoform, this reaction
I + 2Cu + I is called iodoform reaction.
I / NaOH
CH 3.CH(OH ).R ¾¾
2 ¾¾
¾® CH 3 .CO.R
D , in a + 2CuI I / NaOH I / NaOH
¾¾ ¾ ¾¾
® ¾¾
2 ¾¾
¾® I 3C.CO.R ¾¾
2 ¾¾
¾® CHI 3 + RCOONa
Sealed tube
Iodoform
Diphenyl Carbon Tetrachloride (Tetrachloro Methane or
POLYHALOGEN COMPOUNDS Perchloromethane) :
Chloroform Preparation :
Preparation of CHCl3
hv
(i) Haloform reaction : Aldehydes and ketones with CH3CO CHCl 3 + Cl 2 ¾¾® CCl 4 + HCl
group, and alcohols with CH3CH(OH) group give this Properties :
reaction. (i) It is a colourless, non-inflammable, poisonous liquid,
CH3 - CH - R + NaOCl ¾¾ ® CH3 - C - R + H 2O + NaX soluble in alcohol and ether.
| P (ii) On heating with steam at about 773K, it undergoes oxidation
OH O
forming carbonyl chloride.
CH3 - C - R + 3NaOCl ¾¾ ® RCOO - + CHCl3 + 3NaOH
P 773 K
CCl 4 + H 2 O (steam ) ¾¾¾® COCl 2 + 2 HCl
O Uses :
(ii) Preparation of pure chloroform :
Carbon tetrachloride is used
Cl OH (i) as a solvent for oils, fats, resins
| | NaOH (ii) in dry cleaning
Cl - C - C - H ¾¾¾®
distillation CHCl3 + HCOONa + H2O (iii) as a laboratory reagent
| |
(iv) as anthelmentic (removal of worms) for hook worms and
Cl OH
Chloralhydrate (v) as a fire extinguisher under the name of pyrene.
 Haloalkanes and Haloarenes 583

DDT
Preparation:

H Cl Cl
HH2 SO
SO4, ,
CCl3CH O + Cl3CHC
-H2O
H Cl
Cl Cl
DDT
(p, p'-Dichlorodiphenyl
trichloroethane)

Uses
It is priorly widely used as a insecticide but later researches have shown that DDT is very harmful for aquatic life as it is
non-biodegradeble.
 584

CONCEPT MAP
CHEMISTRY

EBD_7753
 Haloalkanes and Haloarenes 585

1. Under basic conditions which one suffers elimination the (a) vinyl chloride (b) benzyl chloride
most (c) chlorobenzene (d) ethyl bromide
CH3 11. When hydrochloric acid gas is treated with propene in
(a) (CH3)3 CCl (b) CH–CH2Cl presence of benzoyl peroxide, it gives
CH3 (a) 2-chloropropane (b) allyl chloride
(c) CH 3CH 2 - CH - CH 3 (d) CH3CH2CH2–CH2–Cl (c) n-propyl chloride (d) No reaction occurs
|
Cl 12. C 6 H 6Cl 6 on treatment with KOH produces

2. The total number of acyclic isomers including the (a) C 6 H 6 (b) C 6 H 6Cl 4
stereoisomers with the molecular formula C4H7Cl (c) C 6 H 3Cl 3 (d) C 6 H 6OH
(a) 11 (b) 12
13. 2-Bromopentane is heated with potassium ethoxide in
(c) 9 (d) 10
ethanol. The major product obtained is
3. Gem dihalides on treatment with alcoholic KOH give :
(a) alkyne (b) alkene (a) 2-ethoxypentane (b) pentene-1
(c) alkane (d) all of these (c) trans-2-pentene (d) cis-pentene-2
4. When two halogen atoms are attached to same carbon atom 14. When CH3CH2CHCl2 is treated with NaNH2, the product
then it is : formed is
(a) vic-dihalide (b) gem-dihalide (a) CH3 — CH = CH2 (b) CH 3 — C º CH
(c) a, w -halide (d) a , b -halide
NH2 Cl
5. Full name of DDT is (c) CH3CH2CH (d) CH3CH2CH
(a) 1, 1, 1-trichloro-2, 2-bis(p-chlorophenyl) ethane NH2 NH2
(b) 1, 1-dichloro-2, 2-diphenyl trimethylethane 15. When 2-bromobutane reacts with alcoholic KOH, the
(c) 1, 1-dichloro-2, 2-diphenyl trichloroethane reaction is called
(d) None of these (a) halogenation (b) chlorination
(c) hydrogenation (d) dehydro-halogenation
6. How many structural isomers are possible for a compound 16. Elimination of bromine from 2-bromobutane results in the
with molecular formula C3H7Cl formation of –
(a) 2 (b) 5 (a) predominantly 2-butyne
(c) 7 (d) 9 (b) predominantly 1-butene
7. Which one of the following is least reactive in a (c) predominantly 2-butene
nucleophilic substitution reaction? (d) equimolar mixture of 1 and 2-butene
(a) CH3CH2Cl (b) CH2 = CHCH2Cl 17. Light
C 3 H 8 + Cl 2 ¾¾¾® C 3 H 7 Cl + HCl is an example of
(c) (CH3)3 C – Cl (d) CH2 = CHCl
8. The compound which contains all the four 1°, 2°, 3° and 4° (a) substitution (b) elimination
carbon atoms is (c) addition (d) rearrangement reaction
(a) 2, 3-dimethyl pentane 18. The reaction of tert-butyl bromide with sodium methoxide
(b) 3-chloro-2, 3 dimethylpentane produces mainly –
(c) 2, 3, 4-trimethylpentane (a) iso-butane (b) iso-butylene
(d) 3,3-dimethylpentane (c) tert-butyl methyl ether (d) sodium tert butoxide
9. Benzene hexachloride is alc. HBr Na
19. CH3 – CH2 – CH2 – Cl ¾¾¾ ® B ¾¾¾ ® C ¾¾® D
(a) 1, 2, 3, 4, 5, 6-hexachlorocyclohexane KOH ether
(b) 1, 1, 1, 6, 6, 6-hexachlorocyclohexane In the above sequence of reactions, the product D is –
(c) 1, 6-phenyl-1, 6-chlorohexane (a) propane (b) 2, 3-dimethylbutane
(d) 1, 1-phenyl-6, 6-chlorohexane (c) hexane (d) allyl bromide
10. A compound on treatment with NaOH followed by addition 20. The compounds CHCl3 and HF lead to the formation of a
of Ag NO3 produces white precipitate at room compound of fluorine of molecular weight 70. The
compound is
temperature. The precipitate is soluble in NH 4OH . The
(a) fluoroform (b) fluoric monoxide
compound is identified as (c) fluoride dioxide (d) fluoro methanol
 EBD_7753
586 CHEMISTRY

21. When two halogens are attached to same carbon atom, it is (a) X = dilute aqueous NaOH, 20°C; Y = HBr/acetic acid,
known as : 20°C
(a) vic-dihalide (b) gem-dihalide (b) X = concentrated alcoholic NaOH, 80°C; Y = HBr/
(c) a, w -dihalide (d) a, b-dihalide acetic acid, 20°C
(c) X = dilute aqueous NaOH, 20°C ; Y = Br2/CHCl3,
22. Reaction of alkyl halides with aromatic compounds in
0°C
presence of anhydrous AlCl3 is known as : (d) X = concentrated alcoholic NaOH, 80°C; Y = Br2/
(a) Friedel Craft reaction (b) Corey house synthesis CHCl3, 0°C
(c) Kolbe’s synthesis (d) Beckmann rearrangement 30. n-Propyl bromide on treatment with ethanolic potassium
23. Chlorobenzene gives aniline with : hydroxide produces
(a) NH3 + Cu2O (b) NH3 + H2SO4 (a) propane (b) propene
(c) propyne (d) propanol
(c) NaNH2 (d) None of these
31. The compound which forms acetaldehyde when heated with
24. In the following sequence of reactions
dilute NaOH, is
AgCN Reduction (a) 1, 1-dichloroethane (b)1, 1, 1-trichloroethane
C 2 H 5 Br ¾¾¾¾ ® Y ; Y is
® X ¾¾¾¾¾
(c) 1-chloroethane (d)1, 2-dichloroethane
(a) n-propyl amine (b) isopropylamine
32. The number of structural and configurational isomers of a
(c) ethylamine (d) ethylmethyl amine
bromo compound, C5H9Br, formed by the addition of HBr
25. Ethanol can be prepared more easily by which reaction ? to 2-pentyne respectively are
(i) CH 3 CH 2 Br + H 2 O ¾¾
® CH 3 CH 2 OH (a) 1 and 2 (b) 2 and 4
(c) 4 and 2 (d) 2 and 1
(ii) CH3CH 2 Br + Ag 2O (in boiling water) 33. Chlorination of toluene in the presence of light and heat
followed by treatment with aqueous KOH gives
¾¾
® CH3CH 2OH (a) o-cresol (b) m-cresol
(a) by (i) reaction (c) p-cresol (d) benzyl alcohol
(b) by (ii) reaction 34. Isobutyl magnesium bromide with dry ether and ethyl
alcohol gives :
(c) Both reactions proceed at same rate
(d) by none (a) CH 3 CHCH 2 OH & CH 3CH 2 MgBr
|
26. The reaction conditions leading to the best yields of C2H5Cl CH3
are :
UV light
(b) CH3 CHCH3 & MgBr(OC2 H5 )
(a) C2H6 (excess) + Cl2 ¾¾¾¾® |
CH3
dark
(b) C2H6 + Cl2 ¾room
¾ ¾ ¾ ¾ ¾¾®
temperatur e (c) CH3CHCH = CH 2 & Mg(OH)Br
|
UV light CH3
(c) C2H6 + Cl2 (excess) ¾¾¾¾®
UV light (d) CH 3 CHCH 3 & CH 3CH 2 OMgBr
(d) C2H6 + Cl2 ¾¾¾¾® |
27. The best method for the conversion of an alcohol into an CH3
alkyl chloride is by treating the alcohol with 35. During debromination of meso-2,3-dibromobutane, the
(a) PCl5 major compound formed is
(b) dry HCl in the presence of anhydrous ZnCl2 (a) n-butane (b) 1-butene
(c) SOCl2 in presence of pyridine (c) cis-2-butene (d) trans-2-butene
(d) None of these 36. Which of the following isomeric heptanes can yield seven
28. (CH3)3CMgCl on reaction with D2O produces : different monochlorinated products upon free radical
(a) (CH3)3 CD (b) (CH3)3OD chlorination?
(c) (CD3)3CD (d) (CD3)3OD. (a) 3-methylhexane (b) 2,2-dimethylpentane
(c) 2-methylhexane (d) 2,3-dimethylpentane
29. Identify the set of reagents 'X' and 'Y' in the following set 37. Benzene reacts with n-propyl chloride in the presence of
of transformations anhydrous AlCl3 to give
X Y (a) 3 – Propyl – 1 – chlorobenzene
CH3 - CH 2 - CH 2 Br ¾¾® Product ¾¾® CH3 - CH - CH3 (b) n-Propylbenzene
|
Br (c) Isopropylbenzene.
(d) No reaction occurs
 Haloalkanes and Haloarenes 587

38. Methyl bromide reacts with AgF to give methyl fluoride (a) N, N-dimethyl aniline
and AgBr. This reaction is called (b) phenyl lithium (C 6 H 5Li)
(a) Finkelstein reaction (b) Swarts reaction
(c) Fittig reaction (d) Wurtz reaction (c) para chloro-N, N-dimethyl aniline
39. Bromobenzene reacts with Mg in dry ether to give a (d) meta chloro-N, N-dimethyl aniline
compound (A) which further reacts with ethanol to yield 47. To prepare 3-ethylpentan-3-ol the reagents needed are –
(a) phenol (b) benzene (a) CH3CH2MgBr + CH3COCH2CH3
(c) ethylbenzene (d) phenyl ether. (b) CH3MgBr + CH3CH2CH2COCH2CH3
40. Phenyl magnesium bromide reacts with methanol to give (c) CH3CH2MgBr + CH3CH2COCH2CH3
(a) a mixture of toluene and Mg(OH)Br (d) CH3CH2CH2MgBr + CH3COCH2CH3
(b) a mixture of phenol and Mg(Me)Br 48. Which one of the following alkyl halides has the lowest
(c) a mixture of anisole and Mg(OH)Br boiling point?
(d) a mixture of benzene and Mg(OMe)Br (a) n-Butyl chloride (b) iso-Butyl chloride
41. In alkaline hydrolysis of a tertiary alkyl halide by aqueous (c) sec-Butyl chloride (d) tert-Butyl chloride
alkali, if concentration of alkali is doubled, then the 49. When phenyl magnesium bromide reacts with tert -butanol,
reaction rate of constant temperature the product would be
(a) will be doubled
(a) benzene (b) phenol
(b) will be halved
(c) ter-butylbenzene (d) ter-butyl phenyl ether
(c) will become four times greater
50. Which Chloride is least reactive with the hydrolysis point
(d) will remain constant
42. Bromination of toluene gives of view
(a) only m-substituted product (a) CH3Cl (b) CH3CH2Cl
(b) only p-substituted product (c) (CH3)3CCl (d) CH2 = CH – Cl
(c) mixture of o-and p-substituted products 51. 2-Bromopentane is treated with alcoholic KOH solution.
(d) mixture of o-and m-substituted products The major product formed in this reaction and the type of
43. On sulphonation of C6H5Cl reaction respectively are
(a) m-chlorobenzenesulphonic acid is formed (a) pent-2-ene, b-elimination
(b) benzenesulphonic acid is formed (b) pent-1-ene, b-elimination
(c) o-chlorobenzenesulphonic acid is formed (c) 2-pentanol, nucleophilic substitution
(d) mixture of o- and p-Chlorobenzenesulphonic acid is (d) pent-1-ene, nucleophilic substitution
formed 52. Chloropicrin is obtained by the reaction of
44. An alkyl halide with molecular formula C 6 H13 Br on (a) steam on carbon tetrachloride
dehydrohalogenation gave two isomeric alkenes X and Y (b) nitric acid on chlorobenzene
with molecular formula C6H12. On reductive ozonolysis, (c) chlorine on picric acid
X and Y gave four compounds CH3COCH3 , CH3CHO,
(d) nitric acid on chloroform
CH3CH2CHO and (CH3)2CHCHO. The alkyl halide is
(a) 2-bromohexane
(b) 2, 2-dimethyl-1-bromobutane 53. Cl
(c) 4-bromo-2-methylpentane C–CCl3
(d) 3-bromo-2-methylpentane
45. Silver benzoate reacts with bromine to form Cl H
COOBr
The above structural formula refers to
(a) BHC (b) DNA
(a) (b)
(c) DDT (d) RNA
54. The pesticide DDT slowly changes to
COOAg (a) CCl3-CHO and chlorobenzene
(b) p, p'-Dichlorodiphenylethene
(c) p, p'-Dichlorodiphenyldichloroethane
(c) (d) C 6 H 5Br
Br (d) p, p'-Dichlorodiphenyldichloroethene
55. Which one of the following on hydrolysis produces a
46. What is the product of the following reaction ? ketone?
Cl (a) Isobutylidene chloride
(b) Secondarybutylidene chloride
(CH ) NLi (c) Benzylidene chloride
¾¾ ¾
3 ¾
2 ¾®
?
(CH 3 ) 2 NH (d) Ethylidene chloride
 EBD_7753
588 CHEMISTRY

56. Pure chloroform is prepared by (c) RX + Mg ® RMgX

(a) distilling chloral hydrate with aqueous sodium (d) RX + KOH ® ROH + KX
hydroxide 67. Benzene reacts with CH3Cl in the presence of anhydrous
(b) heating ethanol with bleaching powder AlCl3 to form:
(c) heating acetone with bleaching powder (a) chlorobenzene (b) benzylchloride
(d) reducing carbon tetrachloride (c) xylene (d) toluene
57. The organic compound used as feedstock in the synthesis 68. Trichloroacetaldehyde, CCl 3 CHO reacts with
of chlorofluorocarbons is chlorobenzene in presence of sulphuric acid and produces
(a) CH2Cl2 (b) CHCl3 :
Cl
(c) CH3Cl (d) CCl4
58. If chloroform is left open in air in the presence of sunlight,
it gives
(a) carbon tetrachloride (b) carbonyl chloride
(c) mustard gas (d) lewisite
59. On warming with silver powder, chloroform is converted (a) Cl C Cl
into
(a) acetylene H
(b) hexachloroethane
(c) 1,1,2,2-tetrachloroethane OH
(d) ethylene
60. Cl2 reacts with CS2 in presence of I2 to form (b) Cl C Cl
(a) CHCl3 (b) CCl4
(c) C2H5Cl (d) Cl3C – NO2 Cl
61. Reaction of chloroform with KOH in presence of a primary
aromatic amine is called : (c) Cl CH Cl
(a) carbylamine reaction (b) reduction
(c) hydrolysis (d) Wurtz reaction CCl3
62. The product formed by heating iodoform with KOH is :
(a) HCHO (d) HCOOK Cl
(c) CH3COOK (d) CH3CHO
(d) Cl C Cl
63. Ethyl alcohol is used as a preservative for chloroform
because it :
CH2Cl
(a) prevents aerial oxidation of chloroform
(b) prevents decomposition of chloroform 69. Which one is most reactive towards SN 1 reaction ?
(c) decomposes phosgene to CO and Cl2 (a) C 6 H 5 CH(C 6 H 5 )Br
(d) removes phosgene by converting it to ethyl carbonate
64. When chlorobenzene is reacted with acetyl chloride in the (b) C6 H5 CH(CH3 )Br
presence of anhydrous AlCl3, the major product formed is (c) C6 H5C(CH3 )(C6 H5 )Br
(a) 2-chloroacetophenone (d) C6 H5CH 2 Br
(b) 3-chloroacetophenone 70. In the following sequence of reactions
(c) 4-chloroacetophenone
(d) 1, 4-dichlorobenzene KCN 3 ® H O+
CH3 - Br ¾¾¾® A ¾¾¾¾
65. In a SN2 substitution reaction of the type
LiAlH
4 ® C,
R - Br + Cl - ¾¾¾ ® R - Cl + Br -
DMF
B ¾¾¾¾ the end product (C) is :
ether
which one of the following has the highest relative rate ? (a) acetone (b) methane
(a) CH3 – CH2 – CH2Br (b) CH3 - CH - CH 2 Br (c) acetaldehyde (d) ethyl alcohol
| 71. Which of the following is the correct order of decreasing
CH3 SN2 reactivity?
(a) R2CHX > R3CX > RCH2X
CH3 (b) RCHX > R3CX > R2CHX
| (c) RCH2X > R2CHX > R3CX
(c) CH3 - C - CH 2 Br (d) CH3CH2Br (d) R3CX > R2CHX > RCH2X.
| (X is a halogen)
CH 72. Iodoform can be prepared from all except :
3
(a) Ethyl methyl ketone
66. Which of the following reactions is an example of (b) Isopropyl alcohol
nucleophilic substitution reaction?
(c) 3-Methyl 2-butanone
(a) 2 RX + 2 Na ® R – R + 2 NaX
(d) Isobutyl alcohol
(b) RX + H2 ® RH + HX
 Haloalkanes and Haloarenes 589

73. Which one of the following is not an allylic halide? 75. Consider the following bromides :
(a) 4-Bromopent-2-ene Me Me
(b) 3-Bromo-2-methylbut-1-ene Me Br Me
(c) 1-Bromobut-2-ene Br Br
(d) 4-Bromobut-1-ene (A) (B)
74. The organic chloro compound, which shows complete The correct order of SN1 reactivity is
stereochemical inversion during a SN2 reaction, is (a) B > C > A (b) B > A > C
(a) (C2H5)2CHCl (b) (CH3)3CCl (c) C > B > A (d) A > B > C
(c) (CH3)2 CHCl (d) CH3Cl

1. Which chloro derivative of benzene among the following NaCN Ni / H

would undergo hydrolysis most readily with aqueous 5. CH 3 CH 2 Cl ¾¾ ¾
¾® X ¾¾ ¾
¾2®Y

sodium hydroxide to furnish the corresponding hydroxy Acetic

Y ¾¾ ¾
¾® Z
derivative? anhydride

Z in the above reaction sequence is

NO2
(a) CH3CH2CH2NHCOCH3
(a) O N
2 Cl (b) ON
2 Cl (b) CH3CH2CH2NH2
(c) CH3CH2CH2CONHCH3
NO (d) CH3CH2CH2CONHCOCH3
2
6. Bottles containing C6H5I and C6H5CH2I lost their original
labels. They were labelled A and B for testing. A and B were
(c) MeN
2
Cl (d) C6H5Cl. separately taken in test tubes and boiled with NaOH solution.
The end solution in each tube was made acidic with dilute
2. The alkyl halide that undergoes SN1 reaction more readily HNO3 and then some AgNO3 solution was added. Substance
is B gave a yellow precipitate. Which one of the following
(a) ethyl bromide (b) isopropyl bromide statements is true for this experiment ?
(c) vinyl bromide (d) n=propyl bromide (a) A was C6H5CH2I
(b) B was C6H5I
3. CH 3 - CH 2 - C H - CH 3 obtained by chlorination of
| (c) Addition of HNO3 was unnecessary
Cl
(d) A was C6H5I
n-butane, will be
7. Which of the following is the correct method of
(a) l-form (b) d-form preparation of methyl fluoride?
(c) meso form (d) racemic mixture (a) CH4 + HF ® (b) CH3OH + HF ®
4. Aryl halides do not undergo nucleophilic substitution (c) CH4 + F2 ® (d) CH3Br + AgF ®
reactions under ordinary conditions because 8. The structure of the major product formed in the following
1. approach of nucleophile is retarded reaction
2. carbon carrying halogen atom is sp3 hybridised CH2Cl
NaCN
3. the substrate molecule is destabilised due to resonance is
DMF
4. partial double bond character between carbon and
I
halogen
CH2Cl CH2CN
(a) 2 and 4 only (b) 1 and 4 only
(a) (b)
(c) 2 and 3 only (d) 2, 3 and 4 only
CN I
 EBD_7753
590 CHEMISTRY

CH2CN CH2Cl HBr

KCN
(c) (d) 15. Isobutene ¾peroxide
¾ ¾¾® A ¾¾¾®
CN
CN dil. H SO
I B ¾¾¾2¾¾
4®
C + inorganic salt D
9. Identify Z in the following series
C and D are
Alc. KOH Br2 KCN
C 2 H 5 I ¾¾ ¾ ¾
¾® X ¾¾
¾® Y ¾¾¾® Z (a) Me 2 CH.CH 2 COOH, ( NH 4 ) 2 SO 4
(a) CH3CH2CN (b) NCCH2–CH2CN (b) Me 2 CH.COOH, ( NH 4 ) 2 SO 4
(c) BrCH2–CH2CN (d) BrCH=CHCN
10. Which of the following pairs is/are correctly matched? (c) Me 2CH.CH 2 COOK, NH 4OH
Reaction Product (d) Me 2CH.CH 2 COOK, K 2SO 4
I. RX + AgCN RNC
II. RX + KCN RCN 16. How many isomeric naphthylamines are expected in the
following reaction ?
O
III. RX + KNO2 R–N Br
O NaNH , NH
¾¾¾¾
2 ¾¾
3®
IV. RX + AgNO2 R–O–N = O – 33°C
(a) Only I (b) I and II
(a) two (b) only single product
(c) III and IV (d) I, II, III and IV
(c) four (d) three
11. Identify Z in
17. 2-phenyl-2-hexanol can be prepared by Grignard synthesis.
aq. NaOH
CH 3CH 2 CH 2 Br ¾¾¾¾¾
®X The pair of compounds giving the desired product is
Al O Cl / H O
¾¾2¾ ¾3 ® Y ¾¾2¾¾ 2¾® Z

(a) Mixture of CH3CHClCH2Cl and CH3CHOHCH2Cl C

(b) CH3CHOHCH2Cl (a) Br and Ph CH 3
(c) CH3CHClCH2OH
(d) CH3CHClCH2Cl
12. Which compound in each of the following pairs is most
reactive to the conditions indicated ? C
(b) Br and Ph
CH 2 Br CH 3
Br
(A) and (B) (KOH in CH3OH)
(c) Ph and PhBr
(d) None of these
CH 3 CH 3 18. Which will undergo SN2 reaction fastest among the following
Cl Cl halogen compounds?
(C) and (D) (NaNH2 in NH3) (a) CH3CH2F (b) CH3CH2Cl
CH 3 (c) CH3CH2Br (d) CH3CH2I
(a) A and C (b) B and C 19. In the following sequence of reactions
(c) A and D (d) B and D
P +I Mg HCHO
13. The correct kinetic rate equation for the addition- CH 3CH 2 OH ¾¾¾
2 ® A ¾¾¾® B ¾¾¾¾
®
ether
elimination mechanism of nucleophilic aromatic
H O
substitution C ¾¾¾
2 ®D
(a) rate = K [aryl halide] [nucleophile] the compound D is
(b) rate = K [aryl halide] (a) propanal (b) butanal
(c) rate = K [aryl halide] [nucleophile]2 (c) n-butyl alcohol (d) n-propyl alcohol.
(d) rate = K [ nucleophile] 20. X in the following reaction is –
14. Which of the following reagents react readily with
CH3 - C - H CCl4
bromobenzene ? Br2 + || ¾¾¾ ®X
(a) NaNH 2 / NH 3 at - 33°C H - C - CH3

(b) (CH 3 )2 NH at. 25°C (a) (+) 2, 3-Dibromobutane

(b) (–) 2, 3-Dibromobutane
(c) CH 3CH 2ONa at. 25°C (c) Rac. 2, 3-Dibromobutane
(d) NaCN / DMSO at. 25°C (d) Meso-2, 3-Dibromobutane
 Haloalkanes and Haloarenes 591

21. Consider the reactions :

CH2Br
(i) C H OH
(CH 3 ) 2 CH - CH 2 Br ¾¾2 ¾¾¾
5 ® CH2Br
(CH 3 )2 CH - CH 2OC 2H 5 + HBr (c) (d)
CH3
C H O-
(ii) (CH 3 ) 2 CH - CH 2 Br ¾¾2 ¾5 ¾¾
® CH3

(CH 3 )2 CH - CH 2OC 2 H 5 + Br - DIRECTIONS for Qs. 23 to 25 : These are Assertion-Reason

type questions. Each of these question contains two statements:
The mechanisms of reactions (i) and (ii) are respectively : Statement-1 (Assertion) and Statement-2 (Reason). Answer these
(a) SN1 and SN2 (b) SN1 and SN1 questions from the following four options.
(a) Statement-1 is True, Statement-2 is True, Statement-2 is a
(c) SN2 and SN2 (d) SN2 and SN1 correct explanation for Statement-1
22. Compound (A), C8H9Br, gives a white precipitate when (b) Statement-1 is True, Statement-2 is True ; Statement-2 is
warmed with alcoholic AgNO3. Oxidation of (A) gives an NOT a correct explanation for Statement-1
acid (B), C8H6O4. (B) easily forms anhydride on heating. (c) Statement-1 is True, Statement-2 is False
(d) Statement-1 is False, Statement-2 is True
Identify the compound (A).
23. Statement-1 : CHCl3 is stored in dark bottles.
Statement-2 : CHCl3 is oxidised in dark.
CH2Br C2H5 24. Statement-1 : Addition of bromine to trans-2-butene yields
(a) (b) meso-2, 3-dibromobutane
Br Statement-2 : Bromine addition to an alkene is an
electrophilic addition.
CH3
25. Statement-1 : CCl4 is not a fire extinguisher.
Statement-2 : CCl4 is insoluble in water.

Exemplar Questions CH3

1. The order of reactivity of following alcohols with halogen |
acids is .............. . (d) CH3CH2 – C – OH
|
(A) CH3CH 2 — CH 2 — OH CH3

(B) CH3CH 2 - CH - OH 3. Identify the compound Y in the following reaction.

| +
NH3 N 2 Cl
CH3 Na NO 2 + HCl
¾¾ ¾ ¾ ¾ ¾® Cu Cl
¾ ¾ 2¾ ¾
2® Y+ N
273- 278 K 2
CH3
| Cl
(C) CH3CH2 – CH – OH
| (a) (b)
CH3
(a) (A) > (B) > (C) (b) (C) > (B) > (A) Cl
(c) (B) > (A) > (C) (d) (A) > (C) > (B) Cl
2. Which of the following alcohols will yield the
corresponding alkyl chloride on reaction with concentrated (c) (d)
HCl at room temperature?
Cl
Cl
(a) CH3CH 2 — CH 2 — OH
4. Toluene reacts with a halogen in the presence of iron (III)
(b) CH3CH 2 - CH - OH chloride giving ortho and para halo compounds. The
| reaction is
CH3 (a) electrophilic elimination reaction
(b) electrophilic substitution reaction
(c) CH3CH2 – CH—CH2OH (c) free radical addition reaction
|
CH3 (d) nucleophilic substitution reaction
 EBD_7753
592 CHEMISTRY

5. Which of the following is halogen exchange reactions? (a) (i), (ii), (iii) and (iv) (b) (i), (ii) and (iii)
(a) RX + NaI ® RI + NaX (c) (ii), (iii) and (iv) (d) (i), (iii) and (iv)
10. Which of the following structures is enantiomeric with the
(b) C C + HX C C
|| molecule (A) given below?

|
| |
H X H
CH3
(c) ZnCl C
R — OH + HX ¾¾¾¾
2®R — X + H O
2 Br
H5C2(A)
CH3 CH3 CH3
Fe H
(d) + X 2 ¾¾¾ ® H
dark C2H5 C
X (a) C (b)
Br
CH3 H3C Br C2H5
H Br
+ Br H
X (c) C (d) C
6. Which reagent will you use for the following reaction? H3C C2H5 CH3
H5C2
CH3CH2CH2CH3 ® CH3CH2CH2CH2Cl + CH3CH2CHClCH3 11. Which of the following is an example of vic-dihalide?
(a) Cl2 /UV light (a) Dichloromethane (b) 1, 2-dichloroethane
(b) NaCl + H2SO4 (c) Ethylidene chloride (d) Allyl chloride
(c) Cl2 gas in dark 12. The position of Br in the compound CH3CH = CHC(Br)
(d) Cl2 gas in the presence of iron in dark (CH3)2 can be classified as .............. .
7. Arrange the following compounds in the increasing order (a) allyl (b) aryl
of their densities. (c) vinyl (d) secondary
Cl 13. Chlorobenzene is formed by reaction of chlorine with
benzene in the presence of AlCl3. Which of the following
(i) (ii) species attacks the benzene ring in this reaction?
(a) Cl – (b) Cl+
(c) AlCl3 (d) [AlCl4]–
Cl Br 14. Ethylidene chloride is a/an ................ .
(a) vic-dihalide (b) gem-dihalide
(iii) (iv) (c) allylic halide (d) vinylic halide
15. What is 'A' in the following reaction?
Cl Cl
CH2 — CH — CH2
(a) (i) < (ii) < (iii) < (iv) (b) (i) < (iii) < (iv) < (ii)
(c) (iv) < (iii) < (ii) < (i) (d) (ii) < (iv) < (iii) < (i)
8. Arrange the following compounds in increasing order of + HCl A
their boiling points. (a) CH2 — CH — CH2
CH3
(i) CH — CH2Br (ii) CH3CH2CH2CH2Br
Cl
CH3

CH3 (b) CH2 — CH2 — CH2 — Cl

|
(iii) H3C — C| — CH3
Br
(c) CH2 — CH — CH3
(a) (ii) < (i) < (iii) (b) (i) < (ii) < (iii)
(c) (iii) < (i) < (ii) (d) (iii) < (ii) < (i) Cl
9. In which of the following molecules carbon atom marked
with asterisk ( * ) is asymmetric?
H D (d) Cl
CH — CH2 — CH3
(i) C* (ii) C*
I Cl I Cl
Br Br
H H
16. A primary alkyl halide would prefer to undergo .................
(iii) C* (iv) H C* (a) SN1 reaction (b) SN2 reaction
OH CH3 CH3
C2H 5 C2H 5 (c) a-elimination (d) racemisation
 Haloalkanes and Haloarenes 593

17. Which of the following alkyl halides will undergo SN1 25. Which of the following compounds will give racemic mixture
reaction most readily? on nucleophilic substitution by OH – ion?
(a) (CH3 )3 C — F (b) (CH3 )3 C — Cl
Br
(c) (CH3 )3 C — Br (d) (CH3 )3 C — I |
18. Which is the correct IUPAC name for (i) CH3 — CH — Br (ii) CH3 — CH — CH3
| |
CH3 — CH — CH 2 — Br ? C2H5 C2H5
|
C2H5
(iii) CH 3 — CH — CH3Br
(a) 1-bromo-2-ethylpropane |
(b) 1-bromo-2-ethyl-2-mehylethane C2H5
(c) 1-bromo-2-methylbutane (a) (i) (b) (i), (ii) and (iii)
(d) 2-methyl-1-bromobutane (c) (ii) and (iii) (d) (i) and (iii)
19. What sh ould be th e correct IUPAC name for Direction (Q. No. 26 to 29) : In the questions 26 to 29 arrange
diethylbromomethane? the compounds in increasing order of rate of reaction towards
(a) 1-bromo-1, 1-diethylmethane nucleophilic substitution.
(b) 3-bromopentane
(c) 1-bromo-1-ethylpropane Cl Cl Cl
(d) 1-bromopentane NO2
20. The reaction of toluene with chlorine in the presence of 26. (i) (iii)
(ii)
iron and in the absence of light yields ............ . NO2
CH2Cl CH3 (a) (i) < (ii) < (iii) (b) (iii) < (ii) < (i)
Cl (c) (i) < (iii) < (ii) (d) (iii) < (i) < (ii)
(a) (b)
Cl Cl Cl
CH3
(c) H 3C Cl (d) Mixture of (b) and (c) 27. (i) (ii) (iii)
CH3
21. Chloromethane on treatment with excess of ammonia yields
mainly (a) (i) < (ii) < (iii) (b) (i) < (iii) < (ii)
(c) (iii) < (ii) < (i) (d) (ii) < (iii) < (i)
æ CH3ö
(a) N, N-dimethylmethanamine çCH3 —N ÷ Cl
è CH3ø Cl Cl
O2N NO2
(b) N - methylmethanamine (CH3 — NH — CH3)
(c) methanamine (CH3NH2) 28. (i) (ii) (iii)
(d) mixture containing all these in equal proportion
22. Molecules whose mirror image is non – superimposable NO2 NO2
over them are known as chiral. Which of the following
molecules is chiral in nature? (a) (iii) < (ii) < (i) (b) (ii) < (iii) < (i)
(a) 2 - bromobutane (b) 1 - bromobutane (c) (i) < (iii) < (ii) (d) (i) < (ii) < (iii)
(c) 2 - bromopropane (d) 2 -bromopropan - 2 - ol
Cl Cl Cl
23. Reaction of C6H5CH2Br with aqueous sodium hydroxide
follows .......... . CH3
(a) SN1 mechanism 29. (i) (ii) (iii)
(b) SN2 mechanism
(c) Any of the above two depending upon the temperature
CH3 CH3
of reaction
(d) Saytzeff rule
(a) (iii) < (ii) < (i) (b) (ii) < (i) < (iii)
24. Which of the carbon atoms presents in the molecule given
below are asymmetric? (c) (iii) < (ii) < (i) (d) (i) < (iii) < (ii)
30. Which is the correct increasing order of boiling points of
OH H O
HO | | | || the following compounds?
1 2 4
1 - iodobutane, 1 - bromobutane, 1 - chlorobutane, Butane
|| C — C — C — C |
3

| | H (a) Butane < 1-chlorobutane < 1- bromobutane <

O H OH
1 - iodobutabe
(a) 1, 2, 3, 4 (b) 2, 3
(b) 1 - iodobutane < 1 - bromobutane < 1 - chloroubutane
(c) 1, 4 (d) 1, 2, 3
< Butane
 EBD_7753
594 CHEMISTRY

(c) Butane < 1 - iodobutane < 1 - bromobutane < CH3 CH3

1 - chlorobutane
(d) Butane < 1 - chlorobutane < 1 - iodobutane < (d)
1 - bromobutane and
CH3 Br CH3
31. Which is the correct increasing order of boiling points of
the following compounds? Br
1 - bromoethane, 1 - bromopropane,1 - bromobutane, 33. In which of the following compounds, the C - Cl bond
Bromobenzene ionisation shall give most stable carbonium ion? [2015]
(a) Bromobenzene < 1 - bromobutane < 1 - bromopropane
< 1- bromoethane H
(b) Bromobenzene < 1 - bromobutane < 1 - bromopropane CH — Cl
< 1- bromobutane H3C
(c) 1 - bromopropane < 1 - bromorpropane < 1 - bromoethane C — Cl
(a) H3C (b)
< Bromobenzene CH3
(d) 1 - bromoethane < 1 - bromopropane < 1 - bromobutane
< Bromobenzene H H 3C H
(c) C — Cl (d) C — Cl
NEET/AIPMT (2013-2017) Questions O 2NH2C H H 3C

32. What products are formed when the following compounds 34. In an SN1 reaction on chiral centres there is : [2015 RS]
is treated with Br2 in the presence of FeBr3? [2014] (a) 100 % racemization
(b) inversion more than retention leading to partial
CH3 racemization
(c) 100 % retention
(d) 100 % inversion
CH3 35. For the following reactions : [2016]
(1) CH3CH2CH2Br + KOH ®
CH3 CH3 CH3CH=CH2+KBr + H2O
Br (2) H3C CH3 H3C CH3
(a) and + KOH + KBr
CH3 CH3 Br OH
Br Br
CH3 CH3 + Br2
(3)
Br Br Br
(b) and Which of the following statements is correct ?
CH3 CH3 (a) (1) and (2) are elimination reaction and (3) is addition
reaction
CH3 CH3
(b) (1) is elimination, (2) is substitution and (3) is addition
Br reaction
(c) and (c) (1) is elimination, (2) and (3) are substitution reactions
CH3 CH3 (d) (1) is substitution, (2) and (3) are addition reaction
Br
 Haloalkanes and Haloarenes 595

Hints & Solutions

6. (a)
EXERCISE - 1 7. (d) Among the given structures, CH2 = CHCl is least
1. (b) In basic conditions, the reactivity by elimination increases reactive.
from 1° carbocation to 3° carbocation. So, (CH3)3CCl As reaction of substitution involves breakage of
suffers elimination the most among the given choices. carbon-halogen bond. Here the carbon is vinylic
Note: Elimination reactions are of two types E1 and carbon hence is sp2 hybridised. The bond length is
E2. Reactivity by E1 and E2 mechanism increases in shorter than single bond and has a very high bond
the same order but due to different reasons. The rate energy. This is because of resonance:
of E2 depends upon the concentration of base and rate H H H H
of E1 depends upon the nature of base. ¬¾®
H – C = C – Cl H – C – C = Cl
Here we can not decide whether the reaction is – +
proceed via E1 mechanism or E2 mechanism because Also vinylic carbocation is very less stable.
nothing is given about the basic conditions. Thus option (d) is correct choice.
2. (b) C4H7 Cl is a monochloro derivative of C4H8 which In structure CH2 = CHCH2Cl, allylic carbon is present.
itself exists in three acyclic isomeric forms. Allylic carbocation is infact stabilized by resonance.
CH3 1°
CH3 1°
CH3
| 1° 2° 1°
CH3CH 2CH = CH 2 CH3CH = CHCH3 CH3 - C = CH 2 8. (b) CH3 – CH – C – CH2 – CH3
I II III 3° 4°
(Its four C 's are (It has 2 types (It has 2 types Cl
different) of carbon) of carbon) 3-Chloro-2,3-dimethylpentane
Four monochloro derivatives of I 9. (a)
Cl Cl - - -
| | 10. (b) Halides Cl , Br , I React with AgNO3 to give
*
CH 2 CH 2 CH = CH 2 CH3 CHCH = CH 2 AgCl ¾¾ ® soluble in NH4OH
(optically active) AgBr ¾¾ ® spraringly soluble in NH4OH
d and l isomers
AgI ¾¾ ® Insoluble
Cl and the C – Cl bond is weakest in benzyl chloride [(sp3)
|
CH3CH 2 C = CH 2 CH 3 CH 2 CH = CHCl hybridised carbon is attached to Cl]
cis and trans isomers 11. (a) Peroxide effect is observed only in case of HBr.
Hence total isomers from I = 6 Therefore, addition of HCl to propene even in the
Two monochloro derivatives of II presence of benzoyl peroxide occurs according to
Cl Markonikov’s rule :
Cl
| | HCl
CH 2 CH = CHCH3 CH 3 C = CHCH3 CH3 - CH = CH 2 ¾¾¾¾¾¾¾
®
Benzoyl peroxide
cis and trans isomers cis and trans isomers
Hence total isomers from II = 4 CH 3 - CHCl - CH 3
Two monochloro derivatives from III
H Cl Cl
CH 2Cl CH3 Cl H |
| |
CH3 - C = CH 2 CH3 - C = CHCl H Cl
12. (c) + KOH ¾¾¾¾
-3HCl
®
Grand total of acyclic isomers = 6 + 4 + 2 = 12 Cl H
|

3. (a) Gem dihalides on treatment with alcoholic KOH gives Cl Cl

H
alkyne as follows : Cl H Cl
alc.KOH 13. (c) Potassium ethoxide is a strong base, and 2-
R , CH 2 CX 2 ¾¾ ¾¾↑ RC º CH bromopentane is a 2º bromide, so elimination reaction
,2HX
| predominates
H
OC H -
CH 3 CH (Br )CH 2 CH 2 CH 3 ¾¾ ¾¾®
2 5
4. (b) CHCl 2 CH 2 Cl
| | CH 3 CH = CHCH 2 CH 3 +CH 2 = CHCH 2 CH 2 CH 3
CH3 CH 2 Cl Pentene - 2(major) trans Pentene -1(min or ) cis

(gem-dihalide) (vic-dihalide) Since trans- alkene is more stable than cis.thus

trans-pentene -2 is the main product.
Cl NaNH
14. (b) CH 3 — CH 2 — CHCl 2 ¾¾ ¾¾®
2
5. (a) CCl3CH D

® CH 3 — C º CH
Cl NaNH2
CH 3 — CH = CHCl ¾¾ ¾¾
D Final Product
(DDT)
 EBD_7753
596 CHEMISTRY

15. (d) Alcoholic KOH, reduces haloalkane into alkene by the 27. (c) The best method for the conversion of an alcohol into
process dehydrohalogenation an alkyl chloride is reaction of the alcohol with thionyl
CH 3 - CHBr - CH 2 - CH 3 + KOH (Alc) chloride (SOCl2) in the presence of pyridine.
Pyridine
¾¾¾® CH 3 - CH = CH - CH 3 R – OH + SOCl2 ¾¾¾¾¾ ® RCl + SO2­ + HCl­
- HBr SO2 and HCl being gases escape leaving behind pure
Br alkyl halide.
|
Alc. KOH
16. (c) CH3 - CH - CH 2 - CH3 ¾¾¾¾¾ ® 28. (a) (CH3 )3 C - MgCl + D 2 O ¾¾
®
CH3 - CH = CH - CH3 + HBr (CH3 )3 C - D + Mg(OD)Cl
Alc NaOH
The formation of 2-butene is in accordance to 29. (b) CH3–CH2–CH2Br 80° C
CH3–CH=CH2
Saytzeff’s rule. The more substituted alkene is formed (X) acetic acid
HBr, 20° C
in major quantity. (Y)
17. (a)
CH3–CH–CH3
18. (b) 3° halide on reaction with strong base (CH3OQ )
undergo elimination reaction and forms alkene as major
Br
product.
ethanolic KOH
CH3 CH 2 30. (b) CH3 - CH 2 - CH 2 Br ¾¾¾¾¾¾
® CH3 - CH = CH 2
| n - Propyl bromide - HBr Propene
Q ||
CH3 - C - Br + HBr
® CH3 - C
CH3O 31. (a) 1, 1-dichloroethane on heating with dil. NaOH gives
¾¾¾¾
| Strong base | acetaldehyde.
CH3 CH3 Cl OH
3° Halide | |
dil NaOH
alc. CH3 — C — H ¾¾¾¾¾® CH3 — C —H
19. (b) CH3 – CH2 – CH2 – Cl ¾¾¾
® CH3CH = CH 2 | |
KOH (B) Cl OH
¾® CH3CHO + H2O
Br CH3 CH3 32. (b) Addition of HBr to 2-pentyne gives two structural
| Na
HBr
¾¾¾ ® CH3 - CH - CH 3 ¾¾® | | isomers (I) and (II)
(C) ether CH 3 CH - CHCH 3 HBr
(D) CH3 - C º C - CH 2 CH 3 ¾¾¾
®
20. (a) CHCl 3 + 3HF ¾ ¾® CHF3 + 3HCl CH3C(Br) = CHCH 2 CH 3 + CH3CH = C(Br)CH 2CH3
wt. of CHF3 = (12 + 1 + 19 × 3) = 70 (I) (II)
Each one of these will exist as a pair of geometrical
21. (b) CHCl 2 CH 2 Cl isomers. Thus, there are two structural and four
| |
CH3 CH 2 Cl configurational isomers.
CH3 CH2Cl CH2OH
gem-dihalide vic–dihalide
22. (a) Friedel Craft reactions are examples of aromatic 33. (d) Cl2, h u aq. KOH
electrophilic substitution. In this, a Lewis acid (like
AlCl3 , FeBr3 etc.) is used as catalyst. Toluene Benzyl chloride Benzyl alcohol

C2 H5OH
AlCl
C 6 H 6 + CH 3Cl ¾¾¾3 ® C 6 H 5CH 3 + HCl 34. (b) (CH3)2 CHCH2MgBr ¾¾ ¾¾® (CH3)2 CHCH3
OC2H5
200°C
23. (a) C6 H5Cl+NH3 +Cu 2O ¾¾¾¾
pressure
®
+ Mg
C 6 H 5 NH 2 + 2CuCl + H 2O Br
AgCN Reduction 35. (d) Debromination is a trans-elimination reaction.
24. (d) C2H5Br ¾¾¾¾ ® C2H5NC ¾¾¾¾¾ ® meso- 2, 3-Dibromobutane on debromination gives
Ethyl bromide Ethyl isocyanide trans-2-butene.
C2H5NHCH3 36. (a) 3-methlhexane can yield seven different
Ethyl methyl amine monochlorinated products upon free radical
25. (b) Heavy metal ions, particularly Ag+, catalyse S N1 chlorination.
7
reaction because of presence of empty orbital. CH3
+ 6 5 4 3| 2 1
CH3CH 2Br + Ag H3C–H2C–H2C–CH–CH2–CH3
+
[CH3CH2 .... Br .... Ag] CH 3
– |
Anhyd .
slow + 37. (c) C 6 H 6 + CH 3CH 2 CH 2 CI ¾¾ ¾
¾® C6 H 5 - CH - CH 3
CH3CH 2 OH CH 3CH 2OH AlCl 3
(–AgBr) from H 2O
Isopropyl benzene
26. UV light
(a) C2H6 + Cl2 ¾¾¾¾ 38. (b) CH3Br + AgF—® CH3F + AgBr
® C2 H 5 Cl+HCl
 Haloalkanes and Haloarenes 597

Mg 48. (d) The boiling points of alkyl chlorides increases with

39. (b) C6 H 5Br ¾¾¾ ® C6 H 5 MgBr increase in molecular weight. In case of isomeric alkyl
CH CH OH chloride, the order of boiling point is
¾¾¾¾¾¾
3 2 ® C6 H 6 + CH 3CH 2OMgBr primary > secondary > tertiary
40. (d) CH 3 OH + C 6 H 5 MgBr ¾ ¾® CH 3 O.MgBr + C 6 H 6 49. (a) Grignard reagents react with compounds containing
41. (d) SN1 (Unimolecular nucleophilic substitution) : a cti ve h ydr ogen t o for m h ydroca r bon s
Although it is a two step process, the rate of reaction corresponding to alkyl (or aryl) part of the Grignard
depends only upon the first (slow) step which involves reagent.
ionization of the alkyl halide to form carbocation. Hence C6H5MgBr + Me3COH ¾¾® C6H6 + Me3COMgBr
rate of reaction depends only upon the concentration of 50. (d) CH 2 < CH , Cl
the alkyl halides, r = k[RX] and is independent of the (Vinyl Chloride)
concentration of the nucleophile which adds on the The halogen atom in vinyl chloride is not reactive as
carbocation in the second (fast) step. in other alkyl halides. The non-reactivity of chlorine
atom is due to resonance stabilisation. The l.P. on Cl-
-X- :Z atom can participate in delocalisation (Resonance) to
R - X ¾¾® R + ¾® R - Z
(slow) (fast) give two canonical structure.
42. (c) –CH3 group is o, p–directing. Π ∗
43. (d) –Cl is o, p–directing. CH 2 < CH , Cl ¾¾
↑ CH 2 , CH < C l
44. (d) CH3 — CH — CH — CH2 — CH3 alc. KOH
½ ½ 51. (a) CH3 CH2 CH CH CH3 –HBr
CH3 Br
3-bromo-2-methyl Pentane H Br
2-bromopentane
dehydrohalogenation
CH 3 — CH 2 — CH == CH — CH 3
H3CC CH — CH2CH3 + H3C— CH — CH = CHCH3 2-pentene
½ ½
CH3 CH3 These reactions are known as b-elimination.
52. (d) Chloropicrin is nitrochloroform. It is obtained by the
(X) (Y)
nitration of chloroform with HNO3.
ozonolysis ozonolysis
(conc.) HNO
HCCl3 ¾¾¾¾¾¾
3
® O2 NCCl3
H3C
C O (CH3)2CHCHO Chloroform Chloropicrin
H3C 53. (c) 54. (d)
+
+ CH3CHO CH3 CH3
2° OH
CH3CH2 — CHO 55. (b) [OH ]
–

CCl2 C
Hunsdiecke r reaction CH3CH2 CH3CH2 OH
45. (d) C 6 H 5 COOAg + Br2 ¾¾ ¾¾ ¾¾ ¾¾®
2° Butylidene Chloride unstable
C 6 H 5 Br + CO 2 + AgBr
CH3
Cl N(CH 3 ) 2
[– H 2O]
C=O
CH3CH2
46. (a) + (CH3 ) 2 NLi ¾(¾
CH3 ) NH
¾¾ ¾® + LiCl
Butanone
distil
47. (c) 56. (a) CCl3·CH(OH)2 + NaOH ¾¾¾® CHCl3 + HCOONa + H2O
CH3 – CH2 – Mg – Br + CH3 – CH2 SbCl5
57. (d) 3CCl4 + 2 SbF5 ¾¾¾¾ ® 2SbCl3 + 3CCl 2 F2
C=O freon -12
CH3 – CH 2 C,FeCl3
CCl 4 + 2H ¾¾¾¾¾
® 2HCl + CCl 2 F2

CH2 – CH 3 58. (b) CHCl3 + 1 O 2 ¾¾¾

Light
® CCl(OH)3 ® COCl 2 + HCl
CH3 – CH 2 2 unstable

C – O Mg Br D
59. (a) HCCl3 + 6Ag + HCCl3 ¾¾® HC º CH + 6AgCl
CH3 – CH2 anhy. AlCl3
OH
60. (b) CS2 + 3Cl2 ¾¾¾¾¾ ® CCl 4 + S2 Cl2
or SbCl5
HOH
–Mg 2S2 Cl2 + CS2 ¾¾ ® CCl4 + 6S
Br 61. (a) This is carbylamine reaction
CH2– CH 3 ArNH 2 + CHCl3 + 3KOH
CH3 – C H2
1o aromatic amine
C – OH
CH3 – CH 2 ®
® Ar - N = C+ 3KCl + 3H 2 O
¾¾
3-ethylpentan-3-ol isocyanide
 EBD_7753
598 CHEMISTRY

62. (b) CHI3 + 3KOH ¾¾® CH(OH)3 + 3KI Cl

iodoform ¯ 68. (c) Cl 3C–C=O + conc. H2 SO4
KOH
HCOOK ¬¾¾¾ HCOOH + H 2 O
H Cl
63. (d) CHCl3 on exposure to air forms phosgene which is
poisonous gas and removed by converting it into diethyl
carbonate (which is non-poisonous substance). Cl
Cl C–C=O conc. H SO
Cl2C – CH
O 2 / light
CHCl3 ¾¾¾¾ ¾ ® COCl2 + HCl H Cl
Cl
Phosgene (Poisonous)
DDT
COCl2 + 2C2H5OH ¾¾
® (C2H5)2CO3 + 2HCl 69. (c) SN1 reactions involve the formation of carbocations,
Diethyl carbonate (non-poisonous) order of stability of carbocation is 3° > 2° > 1° hence
higher the stability of carbocation, more will be the
Cl Cl reactivity of the parent alkyl halide. Moreover the
tertiary carbocation formed from (c) is stabilized by
COCH3 two phenyl groups.
Anhy AlCl
64. (c) + ClCOCH3 ¾ ¾ ¾ ¾ ¾3 ¾
® +
KCN H 3O
70. (d) CH3 - Br ¾¾¾ ® CH3 - CN ¾¾¾¾ ®
2-Chloro acetophenone (A)
(minor) LiAlH
4 ® CH - CH - OH
CH3 - COOH ¾¾¾¾ 3 2
Cl (B) (C)
Ethyl alcohol
71. (c) In SN2 mechanism transition state is pentavalent. Thus
+ + HCl bulky alkyl group will be sterically hindered and smaller
alkyl group will favour the SN2 mechanism. So the
COCH3 decreasing order of reactivity of alkyl halides is
RCH2X > R2CHX > R3CX
4-Chloro acetophenone (major) 72. (d) Iodoform test is given by methyl ketones,
acetaldehyde and methyl secondary alcohols.
[Note : Para product predominates over the ortho
CH3 CH CH2 OH
product]
65. (d) For such a reaction the rate of SN2 substitution reaction CH3
is maximum in case of CH3 CH2 Br because SN2 Isobutyl alcohol is a primary alcohol hence does'nt
mechanism is followed in case of primary and secondary give positive iodoform test.
halides i.e., SN2 reaction is favoured by small groups 73. (d) 4-Bromobut-l-ene is not an allylic halide
on the carbon atom attached to halogens so order of BrH 2C —CH 2 —CH== CH 2
4 - Bromobut -1-ene
SN2 substitution reaction will be 74. (d) SN2 reaction is favoured by small groups on the carbon
CH3 CH2 Br > CH3 CH2 CH2 Br > atom attached to halogen.
So, the order of reactivity is
CH3 CH 3Cl > (CH 3 ) 2 CHCl > (CH 3 ) 3 CCl
| > (C 2 H 5 ) 2 CHCl
CH3– CH – Br > CH3 – C – Br
| | SN2 reaction is shown to maximum extent by primary
CH3 CH3 halides. The only primary halides given is CH3Cl so
the correct answer is (d).
i.e. option (d) is correct.
75. (a) + –
Me Br ionisation +Br
66. (d) It is a nucleophilic substitution reaction as here stronger Me
nucleophile OH– is replacing weaker nucleophile X– (A)

Me Me
CH3 ionisation Me
+ + Br –
Br
Anhyd. (B)
67. (d) + CH3Cl +HCl3
AlCl3
Me
Toluene ionisation Me –
Me + Br
Friedel Craft’s reaction. Me +
Br
(C)
 Haloalkanes and Haloarenes 599

Since SN1 reactions involve the formation of carbocation 7. (d) Fluoroalkanes are difficult to prepare directly because
as intermediate in the rate determining step, more is the flourination of hydrocarbons with pure F2 gas occurs
stability of carbocation higher will be the reactivity of explosively. Therefore these are prepared by treating
alkyl halides towards SN1 route. Now we know that alkyl chloride or bromide with salts such as Hg 2F2, AgF.
stability of carbocations follows the order : 3° > 2° > 1°, The reaction is called swarts reaction.
so SN1 reactivity should also follow the same order. CH3Br + AgF ® CH3F + AgBr
3° > 2° > 1° > Methyl (SN1 reactivity) CH2Cl CH2CN
NaCN
8. (b) ¾¾ ¾
¾®
EXERCISE - 2 DM F

1. (a) Cl in 2, 4, 6-trinitrochlorobenzene is activated by three I I

NO2 groups at o, and p-positions and hence undergoes Nuclear substitution will not take place.
hydrolysis most readily.
2. (d) This reaction occurs in two steps. In first step, a 9. (b) C 2 H 5 I ¾alc. KOH Br2
¾ ¾ ¾® CH 2 = CH 2 ¾¾¾®
carbocation is formed from alkyl halide molecule. First KCN
step is slow step so it is also rate determining step. In BrCH 2 - CH 2 Br ¾¾¾® CNCH 2 .CH 2 CN
second step, an attacking nucleophile attacks on this 10. (b)
carbocation and forms the final product. 11. (b)
Thus the stability of the carbocation influences the rate aq. KOH Al O
CH 3 CH 2 CH 2 Br ¾¾ ¾¾® CH 3CH 2 CH 2 OH ¾¾2¾
¾3®
of reaction. More stable the carbocation, higher is its heat
rate of formation. Thus those alkyl halides which form
stable, 3º carbocations undergo SN1 reaction readily. Cl / H O
Thus, t-butyl bromide is the favourable substrate. CH 3 CH = CH 2 ¾¾2¾ ¾ 2¾® CH .CHOH .CH Cl
3 2
CH3 CH3 12. (a) In the first case the reaction gives side chain
| | – substitution product which is easier in A. In the second
Slow step
(i) CH3 - C - X ¾¾¾¾® CH3 - CÅ + X case the reaction will proceed by benzyne mechanism
| |
CH3 CH3 for which ortho position w. r. to Cl must have H-atoms.
Ter. butyl carbocation Cl Nu Cl
Nu Cl
CH3
| CH3 Nu:
| 13. (a) ¾ ¾¾®
Å Fast
(ii) CH3 - C + O H ¾¾¾¾ step Slow
® CH3 - C - OH
| |
CH3 CH3
Nu
Rate of reaction µ [(CH3)3C – X] Nu Cl
Cl / hn Fast
3. (d) CH3 — CH2 — CH2 — CH3¾ ¾ ¾¾®
2
¾¾
¾® + Cl

CH3 CH3 Rate µ [C 6 H 5Cl] [ Nu :] =

H — C — Cl + Cl — C — H K [Aryl halide] [nucleophile]

C2H5 C2H5 Br NaNH / NH

d l 14. (a) ¾¾¾ ¾
2 ¾¾3®
+ HBr
Racemic mixture H
50% d form + 50% l form HBr
H 3C
Cl• may attack on either side and give a racemic mixture 15. (a) H 3C C= CH 2 ¾¾ ¾¾®
peroxide
CH– CH 2 Br
H 3C H 3C
of 2-chloro butane which contain 50% d form and 50%
l-form. KCN H 3C
4. (b) Aryl halides are less reactive towards nucleophilic ¾¾¾® CH – CH 2 – C º N
H3 C
substitution because of the partial double bond character
of carbon-halogen bonds. It is also partly due to H 3C
dil. H SO
repulsion between the electron cloud of the benzene ring ¾¾¾¾¾
2 4® CH– CH 2 – COOH
and the nucleophile. H3 C

5. NaCN
(a) CH3CH 2 Cl ¾¾¾¾ ® + ( NH 4 ) 2 SO 4 .
Br
Ni / H
CH3CH 2 CN + NaCl ¾¾¾¾
2®
16. (a) NaNH / NH
¾¾ ¾ ¾
2 ¾¾3®
(X) – 33°C
CH 3CH 2 CH 2 NH 2 ¾¾ ¾ ¾ ¾
¾®
( CH 3CO ) 2 O
(Y ) NH 2
CH 3CH 2 CH 2 NHCOCH3 ∗ CH 3COOH NH 2
NH
(Z) ¾¾¾
2® +
6. (d)
 EBD_7753
600 CHEMISTRY

O 23. (c) CHCl3 is stored in dark bottles to prevent oxidation of

CHCl3 in presence of sunlight.
17. (a) C + Mg Br ¾
¾® 24. (b)
25. (d) CCl4 is used as a fire extinguisher. The dense, non
Ph CH 3 combustible vapours cover the burning substance and
OH prevents the availability of oxygen around burning
O MgBr material.
1
2
Ph C CH 3 EXERCISE - 3

|
|
H2 O
C ¾¾¾
® 4
CH 3 6
Ph 3 Exemplar Questions
5
2 – phenyl -2-hexanol 1. (b) Alchols and h alogen acid react thr ough S N 1
18. (d) Smaller the R group reactivity will be higher towards mechanism.
SN2 reaction. For alkyl halides containing similar alkyl +
group better will be the leaving group, more facile is CH3 —CH 2 —CH 2 —OH ® CH3 —CH2 —CH+ OH -
the nucleophilic substitution reaction.
Amongst the halide ions, the order in which the leaving In this case, 1° carbocation is formed. It is least stable.
groups depart follows the sequence : So, here SN2 mechanism is followed. In this SN2
I– > Br– > Cl– > F– mechanism a transition state is observed in which
It is because of this reason that the order of reactivity a - carbon is linked with two nucleophilies.
of haloalkanes follows the sequence : + –
iodoalkanes > bromoalkanes CH3— CH2 — CH — OH ® CH3— CH2 — CH — OH
> chloroalkanes > fluoroalkanes | |
CH3 CH3
P + I2
19. (d) CH3CH 2 OH ¾¾¾ ® CH3CH 2 I 2º Carbocation (more stable than 1º carbocation)
A
CH3 CH3
Mg HCHO | |+
¾¾¾® CH3CH 2 MgI ¾¾¾¾
® –
Ether
(B)
CH3— CH2 — C — OH ® H3C — CH2 — C + OH
CH 2 CH3 | |
CH 2 CH 3
| | CH3 CH3
H2 O
H - C - OMgI ¾¾¾ ® H - C - OH 3° carbocation (most stable)
| |
H Greater the stability of carbocation, greater will be the
H
(D) possibilities of attack of X– ion on the carbocation.
n - propyl alcohol Order of stability of carbocation is : 3° > 2° > 1.
So order of reactivity will be C > B > A.
CH3 H CH3 2. (d) Reaction of alcohols with conc. HCl at room
C Br temperature follows SN1 mechanism.
20. (d) H
|| + Br2 The attack of nucleophile to the carbocation is possible
C H Br
(trans reagent) only on stable carbocation as at room temperature only
H CH3 CH3 3° carbocation is stable.
(Meso) Step I
(trans-2-butene)
21. (a) A strong nucleophile favours the SN2 reaction and a CH3 CH3
weak nucleophile favours the SN1 reaction. | | –

First reaction is SN1 reaction because C2H5OH is used CH3 CH 2 C OH ® CH3 CH2 CÅ + OH
| |
as solvent which is a weak nucleophile. CH3 CH3
Second reaction is SN2 reaction because C2H5O– is
strong nucleophile. Step II
CH2Br CH3 CH3
22. (d) Alcholic |r s |
AgNO3
AgBr¯ CH3 — CH2 — C + Cl ® H3C — CH2 — C—Cl
A CH3 | |
CH3 CH3
Oxidation
3. (a) Sand meyer’s Reaction
COOH CO +
D NH3 N2 Cl Cl
O Na NO + HCl
¾ ¾ ¾2 ¾ ¾® Cu 2Cl2
¾ ¾ ¾® +N2
COOH CO 273- 278 K

Acid (B) Phthalic Anhydride (Y)

 Haloalkanes and Haloarenes 601

4. (b) benzene < chlorobenzene < dichlorobenzene <

FeCl3 r s r s bromochlorbenzene
Cl – Cl Cl – Cl – FeCl3 Cl + FeCl4 8. (c) Greater the surface area, greater will be the boiling point
CH3 of a compound. Surface area decreases with increases
CH3 CH3 in branching.
r s H
+ Cl – Cl – FeCl3 rds Increasing order of boiling point
Cl or Å
r CH3
H Cl H3C
H3C C CH3 < CH — CH2Br
H3C
Br
CH3 CH3 < CH3CH 2 CH 2CH 2 Br
H
+ Cl or + 9. (b) Carbon atom in which all four valencies are different is
known as Asymmetrical/chiral.
H Cl 10. (a) Enantiomers are the steroismers which are related to
each other as non – superimposable mirror images.
FeCls
4 FeCls
4
The enantiomer of molecule (A) is
Mirror
CH3 CH3
Cl H H
CH3 H3C
C C
H5C2 Br Br C2H5
Cl
As electrophile Cl+ attacks on electron rich benzene
ring and substitutes hydrogen. So, the reaction is 11. (b) Halides in which two halogen atoms are present on the
electrophilic substitution reaction. two adjacent carbon atoms are known as vic - dihalides.
5. (a) Halogen exchange reactions are those reactions in H
which one hailde replaces another (Finkelstein reaction). | CH 2 — CH 2
6. (a) It is a substitution reaction which involves the Cl — C — Cl | |
replacement of 1° and 2° hydrogen of alkanes by | Cl Cl
H
chlorine. It occurs in presence of ultraviolet light. 1, 2 - dichloroethane
Dichloromethane
·
UV
Step 1 : Cl — Cl ¾ ¾ ¾® 2C l H Cl
light | | Cl
· H — C— C — H |
C l + CH 3 — CH 2 — CH 2 — CH 3 ® CH 3CH 2 CH 2 | | C H 2 — CH = CH 3
· H Cl
— C H 2 + HCl Ethylidene chloride
Allyl chloride
Step 2 :
·
CH3 — CH 2 — CH 2 — C H 2 + Cl 2 ® 12. (a) Compounds in which the halogen atom is bonded to
· sp3 hybridised carbon atom next to carbon carbon-
CH3 — CH 2 — CH 2 — CH 2 Cl + C l double bond are known as allyl halides.
· CH3 CH = CHC ( Br ) ( CH3 ) 2
CH3 – CH2 – C H – CH3 + Cl2 ®
-
Cl 13. (b) ® [ AlCl 4 ] + Cl+
AlCl3 + Cl2 ¾¾
| ·
CH3 – CH2 – CH – CH3 – C l Cl
+
Step 3 : + Cl
· ·
CH3 — CH 2 — CH 2 — C H 2 + C l ® Chlorobenzene

CH3CH 2 CH 2 CH 2 Cl 14. (b) If halogen atoms present on the same carbon atom
then they are known as gem – dihalides or alkylidene
· ·
CH3 - CH 2 - C H - CH3 + Cl ® halides.
15. (c) Addition of HCl takes place in accordance with
Cl
| Markownikoff's rule.
CH3CH2 CH – CH3 CH2 — CH — CH2 CH2 — CH — CH3
7. (a) Density is directly related to molecular mass. More the
molecular mass, more will be the density of the Cl
compound. The order of molecular mass is + HCl
 EBD_7753
602 CHEMISTRY

16. (b) It would prefer to undergo SN2 reaction. 25. (a) All those compounds which follow SN1 mechanism
SN2 reactions occur if there is less steric crowding during nucleophilic subsitution reaction will give
on a - carbon of alkyl halide. In case of primary aklyl racemic mixture.
halides, steric crowding is very less. So, it would prefer Order of reactivity of alkyl halides for SN1.
to undergo SN2 reaction. 3° > 2° > 1° CH3 X
17. (d) All compounds are tertiary alkyl but bond formed
Thus, CH3 — CH — Br contains a 2° carbon so
between carbon and iodine (C — I) is weakest bond |
due to higher difference in size of carbon and iodine. C 2 H5
18. (c) IUPAC name
gives a racemic product.
2 1
CH3 — CH — CH2 — Br 26. (c) The substitution is faster if the electron withdrawing
3
| group is at ortho and para position because electron
CH2 density is high at these positions as chlorine is
| electron donating group which increase electron
CH3
4 density at ortho and para position. Therefore, it has
partial double bond character, and is not easy to break.
1-bromo-2 methylbutane
In compound (ii) and (iii) both has one electron
Br withdrawing group but in compound (ii) electron
| withdrawing (— NO2 ) group is present at ortho
19. (b) H3 C— H 2 C— H C — C H 2 — C H3
1 2 3 4 5 position, so rate of reaction in compound (ii) is more
than that of (iii) while (i) has no electron withdrawing
IUPAC name is 3-bromopentane.
group.
20. (d) Toluene react with chlorine in presence of iron and
27. (d) If electron releasing group is present at ortho or para
in absence of light, by substitution on benzene ring.
position it decreases the rate of nucleophilic
CH3 CH3 CH3 substitution reaction. In compound (iii) electron
releasing group is present at meta position w.r.t.
Cl
Fe chlorine, so the impact is nothing but in compound
+ Cl2 ¾ ¾® + (ii) it is present at ortho position.
Toluene o-chlorotoluene 28. (d) If electron withdrawing group is present at ortho and
Cl para position then the nucleophilic substitution
p-chlorotoluene reaction rate increases.
29. (c) If electron releasing group is present at ortho and para
21. (c) CH3Cl + NH3 ® CH3 NH 2 + HCl position w.r.t. to chlorine it decreases the rate of
Excess Methanamine
nucleophilic substitution reaction.
22. (a) Carbon in which four bonds are different is known as 30. (a) Greater the surface area, greater will be the
Chiral carbon. intermolecular forces of attraction and
1 2 3 4 intermolecular forces of attraction is directly
H3C — CH — CH2— CH3
| proportional to boiling point. Surface area is larger for
Br larger size of halogen.
(2- bromobutane) 31. (d) Boiling point is directly proportional to size of the
Å molecule. All contains same halogen atom but different
23. (a) In C6H5CH2Br carbocation is C6 H5 C H 2 which is hydrocarbon part. Larger the different hydrocarbon part
stable due to resonance. larger the boiling point.

CH3 NEET/AIPMT (2013-2017) Questions

Å
CH 2 Å CH 2 CH2 CH2 32. (c) Methyl group is ortho para directing but due to steric
hind rance effect, generated by two CH3 groups
Å Å substitution will not take place on position (I). Hence
only two products are possible.
CH2
CH3
+
III I

24. (b) If carbon atom has all four valencies with four CH3
II
different groups then it is called as asymmetric/chiral
carbon.
 Haloalkanes and Haloarenes 603

i.e. CH3 CH3 So attack from below or above the plane can take place.
Br2
If 50% attack below and above the plane of carbocation take
FeBr3
place than 100% racemization occurs but it may not be
CH3 CH3 highly probable.
Br i.e. if inversion occurs more than retention leading to partial
(A) racemization.
CH3 35. (b) (1) CH3CH2CH2–Br + KOH
Br
® CH3CH=CH2 + KBr + H2O
+ This is dehydrohalogenation reaction which is an
CH3 example of elimination reaction.

(2) H3C CH3 H3C CH3

33. (a) Tertiary butyl chloride will give the most stable tertiary C + KOH ® C + KBr
carbonium ion among the other given compounds
Br OH
H3C – H3C
C Cl
Cl +
C Replacement of Br– by OH– is substitution reaction
thus it is a nucleophilic substitution reaction.
H3C CH3 H3C CH3 Br
t-butyl carbonium ion
(3) + Br2 ®
34. (b) In SN 1 reaction, carbocation a planar species as Br
intermediate is formed. Above reaction involves addition of Br 2 across double
bond. Thus it is called addition reaction.
R1
Nu
Å
C R3
Nu
R2