C HEMISTRY E XPERTS

(JEE Main & Advanced)

HALOGEN DERIVATIVES

DR. SHARAD KOTHARI PIYUSH MAHESHWARI BRIJESH JINDAL

(SK SIR) (PMS SIR) (BJ SIR)
 ABOUT EDUCATORS

DR. SHARAD KOTHARI

• MSc., PhD, NET, JRF
• 18 year experience of IIT JEE in Organic Chemistry
• Ex. Senior Faculty of Vibrant Academy, Kota and Bansal Classes, Kota

PIYUSH MAHESHWARI
• BE (Hons.)
• 11 year experience of IIT JEE in InorganicChemistry
• Author of 'Super Problems in Inorganic Chemistry',
• Ex. HOD Bansal Classes, Kota
• Ex. Senior Faculty of Vibrant Academy, Kota and Allen Career Institute, Kota

BRIJESH JINDAL
• BTech Jaipur MNIT
• 11 year experience of IIT JEE in Physical Chemistry
• Ex. Senior Faculty of VibrantAcademy, Kota, Allen Career Institute, Kota and Bansal Classes, Kota

Page # 2
 HALOGEN DERIVATIVES

r ts r ts
x pe CONTENT x pe
ry
E ry
E
i st i st
e m e m
h
CS.No Ch Pages

1. Exercise-1 04
2. Exercise-2 10
3. Answer Key 39

t s t s
er er
E xp E xp
ry ry
i st i st
e m e m
Ch Ch

t s t s
p er p er
E x E x
r y r y
i st i st
e m e m
Ch Ch
Page # 3
 HALOGEN DERIVATIVES

s
tEXERCISE-1 (Subjective Questions) ts
r r
pe
x compounds according to their reactivity with alc silver nitrate. x pe
Q.1
y E
Arrange following
ry
E
s t rchloride, sec butyl chloride and Butyl chloride.
t-Butyl
st
e mi e m i
CQ.2h Propose a mechanism for the following reactions-
OH
Ch
CH3
CH3
C—Br H

2O

CH3
CH3

Q.3

What are (A) & (B) and explain their stereochemistry.

t s t s
er
pthe subsitution reaction of 2-bromobutane and OH¯ in 75% ethanol and 25%x Hp2O at
The rate lawxfor er
Q.4
ry
25°C is E ry
E
i st i st
e mRate = 4 × 10–5 [ ] [OH¯] + 1.0 × 10–5 [ e m
Ch h
]
Br Br
C
What % of the reaction take place by the S 2 mechanism when [OH¯] = 1.00 M
N

x
If answer is x% then fill in OMR sheet
10
Q.5 Out of the followings how many compounds are more reactive than CH3 – CH2 – Br towards SN2
reaction.
Br
H3C– I Br
I Br

Ph – CH2 – I H3C I H 3C  C  CH 2  I
||
O

NaOCH
Q.6  3  I
CH 3OH
t s t s
p er p er
E x E x
r y r y
i st i st
e m e m
Ch Ch
Page # 4
 HALOGEN DERIVATIVES

Q.7 s write the mechanism of each of the following reactions

Predict the product(s) and
ts
e rHIt(1mole) r
p pe
Ex E x
excess HI
 
r yO ry
(i) (ii)
st st
O

m i m i
e e
CQ.8h HBr
 KCN
 Major product.
Ch
H 2O 2

Major product is

Q.9 CHC–CH2–CH=CH2, adds up HBr to give CHC–CH2–CHBr–CH3 while CHC–CH=CH2 adds

up HBr to give CH 2  C – CH  CH 2 .
|
Br

Q.10 Find out the total no. of products (including stereo) in the given reaction :
CH3

NBS, CCl4 Products.

Peroxide, 

Q.11 What are the products of the following reactions ?

t s t s
er
p + HBr A er
(a) PhCH = x
E
CHCH (b) + HI  B E xp
ry ry
3

i st i st
e m e m
Ch (c) + HBr Peroxide
  C (d) + HClhD
C
Q.12 Write all the monochlorinated products (including stereo) of isohexane.

Q.13 With the help of following data show HBr exhibits the peroxide effect.
H10/kJ mol–1 H20/kJ mol–1
   
H–X X + CH2 = CH2  X CH2 – C H2 XCH2– C H2 + H–X  XCH2CH3 + X

HCl –67 + 12.6
HBr –25.1 – 50.2
HI +46 –117.1

Q.14 How many dibromo derivative can be obtained by Cyclobutane.

t s t s
p er p er
E x E x
r y r y
i st i st
e m e m
Ch Ch
Page # 5
 HALOGEN DERIVATIVES

scompound(s) gives haloform reaction (or Iodoform test with NaOH + I2). ts
rt
Q.15 Which of the following
p e p er
x E
O
x E
y ||
y
tr tr
(1) (2) CD3  C  CD3
i s i s
e m e m
Ch Ch
CHI2
O
O O OH
|
(3) O O (4) H 3C  CH  C  OH
||
O
O
O O
(5) (6)

O O O
|| || ||
(7) CH 3  C  CCl3 (8) CH 3  C  O  C  CH 3
Cl

t s t s
er CH 3  CH 2  CH  CH 3
er
(9) (10)

E xp |
E xp
ry ry
OTs
st st
O
m i O O
| | ||
m i
e e
Ch Ch
(11) CH 3  C  C  OH (12)
O

Q.16 Iodoform gives precipitate withAgNO3 on heating while CHCl3 does not.

Q.17 On electrolysis of aqueous ethanolic solution of sodium chloride gives sweet smelling liquid (X). (X)
gives isocyanide test and condenses with acetone to from hypnotic (Y). What are (X) and (Y)?

Q.18 Consider following compounds and give number of compounds which can show iodoform reaction.

O
O OH
Ph  C  CH 3 CH3 – CH2 – OH
||
O
O
H 3C  C  OH H 3C  C  C  OH
s s
rt t
||
er
| | ||
O
p e O O O O p
r y Ex r y E x

m ist m i st
e e
Ch Ch
Page # 6
 HALOGEN DERIVATIVES

CH3–CH2I reacts moresrapidly with strong base in comparison to CD3CH2I

Q.19
r t r ts
pe
x for dehydrohalogenation of x of pe
Q.20
E
The mechanism
ry
is E1cb while for dehydrohalogentaion
y E
i st i s tr
e m F
e m
Ch is E2 ,why? Ch
Cl

Q.21 2-chloro-3-methylbutane on treatment with alcoholic potash gives 2-methylbut-2-ene as major product.

Q.22 Out of the followings how many nucleophiles will give major product by E2 reaction on reaction

with
Br

O
    ||    
SH , OEt , O , O C  CH 3 , I , O Me , CN , SCH 3 , C  CH

t s t s
er er
E xp 
O
E xp
ry C  D + E ry
(i ) O3
  A 
alc.KOH
 B HBr

ist st
Q.23 

m
 ( ii ) H 2O / Zn
m i
e Br
e
Ch Ch
Q.24 Write major product of the the following reactions:
ClCH2CH2CH2Br + KCN  A
EtOH
(i)
(1eq .)

SF
(ii) PhCHO 
4 B

BrCH2CH = CHCO2Me  C

AgF
(iii)
DMF
(iv) EtOH + HI  D
(v) EtOH + HCN  E

Q.25 Explain why?

(a) Hydrogen atom of chloroform is definately acidic, but that of methane is not.
(b) A small amount of alcohol is added to chloroform bottles.
(c) RCl is hydrolysed to ROH slowly but reaction fastens on addition of KI.
(d) KCN reacts with R – I to give alkyl cyanide, whileAgCN results in isocyanide as major product.
r ts r ts
p e of benzyl chloride in 50% aqueous acetone proceeds byboth SN2 and SN1 mechanism,
Q.26 Alkaline hydrolysis
x x pe
y E is used as solvent, mechanism is now mainly SN1. Explain
but when water
r r yE
i st i st
h em h em
C C
Page # 7
 HALOGEN DERIVATIVES

IdentifyA,B,C,D,E andsF in the following series of reaction.

Q.27
r t r ts
Brx pe x pe
E A aq
. KOH
 B  E
y ry
2 Na
C
r h

i st i st
m m
alc.KOH
e e
Ch  E 
D   F
NBS C Ch
Q.28 Complete the following by providing the structure of (A), (B), (C) and (D):

3  (A)   (B) 

Alc.KOH NH 3
(i) CH3CH2CH2OH PBr
  (C) 
HBr
 (D)


H / H 2O
 (B) 2  (C)  (D)
SOCl
CH 3  CH 2  CH 3   (A)  
Alc.KOH H
(ii)
| LiAlH4
I

 (A)   (B)   (C) + (D)

Alc.KOH HBr (1eq.)
(iii) CH3CH2CH = CH2 NBS

Light

 (A)  (B) Alc

.  (C)
HBr KOH
(iv) CH3CH2MgBr CH CHO / H 2O
3  

H2SO4 NBS AgF/DMSO

Q.29
ts s
CH2 – OH 
A B C
t
er er
HBr

E xp E xp
r yE ry
Mg/ether B

ist st
D (SN 2 reaction)
F
i
h e mGive the major product (with proper explanation) when following halogen compounds
he
m
C
Q.30
sodium ethoxide.
C
are heated with

CH2Br
(a) CH 3  CH  CHCH 3 (b) (c) CH3
| | CH3
Br CH 3
Cl

Q.31 Carry out following conversions.

(a) CH3–CH2–CH2–Cl — CH 3  CH  CH 3 in two steps only
|
Br
Br

(b) Br — in two steps only

s s
e rt er
t
xp p
(c) — in three steps only
E E x
ry r y
i st i st
e m e m
Ch Ch
Page # 8
 HALOGEN DERIVATIVES

Q.32 Convert
r ts r ts
x pe x pe
(i)
ry
E CH2 — CH3  CH = CH 2
ry
E
(ii)i s t CH3CH2CH=CH2 CH3CH2CH2CH2NH2 i st
e m e m
Ch (iii) CH3CH2CH=CH2  CH2=CH—CH=CH2 Ch
Q.33 Carry out following conversions.
Cl
|
(a) CH 3  CH  CH 3 — CH3–CH2–CH2–Cl without using peroxide

O
||
(b) Ph – CH2 – Cl — Ph  CH 2  C  Cl

Q.34 Treatment of 2-bromobutane with hot alcoholic KOH gives a mixture of three isomeric butenes (A), (B)
and (C). Ozonolysis of the minor product (A), gives formaldehyde and another aldehyde in equimolar
amounts. What are the structural formulae of (A), (B) and (C)?

si) NBS
t ( t s
Q.35
e r 
,Benzoyl peroxide,CCl ,heat
         F
4
er
E xp (ii ) NaSCH
3
E xp
ry ry
i st i st
e m e m
Ch Ch

t s t s
p er p er
E x E x
r y r y
i st i st
e m e m
Ch Ch
Page # 9
 HALOGEN DERIVATIVES

s
EXERCISE-2 (Objective Questions)
ts
rt r
x pe x pe
r y E
[SINGLE CORRECT CHOICE TYPE]
ry
E
ist st
Q.1 Consider the given reaction:

mH C  CH  CH  CH  CH 3 S1 [P] HBr

m i
C he 3 | N
Ch
e
OH
In the given reaction the product [P] is :
Br
|
(A) H 3C  CH  CH  CH  CH 3 (B) CH 3  CH  CH  CH 2
|
Br Br
|
(C) CH2=CH–CH=CH2 (D) CH 3  CH  CH 2  CH 2  OH

Q.2 Which of the following is most reactive toward SN1.

CH2–Cl CH2–Cl CH2–Cl CH2–Cl

(A) (B) (C) (D)

H CH3 OCH3 NO2

ts t s
er
p following compounds will be most reactive for SN1 reactions: er
Q.3 Which one ofxthe
E E xp
ry ry
i st i st
e m e m
Ch (A) (B) (C) C(D)h

Q.4 In the given pair in which pair the first compound is more reactive than second for SN1 reaction.

(A) Cl CH2Cl

Cl
(B)
Cl

(C)
Cl Cl

s s
rt t
Cl
er
Cl
p e p
(D)
r y Ex r y E x

m ist m i st
e e
Ch Ch
Page # 10
 HALOGEN DERIVATIVES

Q.5 t scan not give SN1 reaction easily?

Which of the following
r r ts
x pe x pe
E E
Br
Br Br Br
ry ry
m ist
(A) (B) (C) (D)
m i st
e e
Ch Ch
Q.6 Among the bromides I–III given below, the order of reactivity in SN1 reaction is:

(I) (II) (III)

(A) III > I > II (B) III > II > I (C) II > III > I (D) II > I > III

Q.7 Arrange the following in the increasing order of reactivity towards SN1 reaction:
CH3–O–CH2–Cl (P) ; CH3–NH–CH2–Cl (Q);

Ph–CH2–Cl (R); Cl (S)

(A) P > Q > R > S (B) R > Q > P > S (C) Q > P > R > S (D) Q > P > S > R

Q.8 Consider the followingsgroups: s

(I) —OAc e r t (II) —OMe (III) —O—SO2—Me (IV) —O—SO2—CF3 er
t
The order of x p group nature is: xp
E leaving
(A) I >r IIy > III > IV (B) IV > III > I > II
E
r y> I
ist st
(C) III > II > I > IV (D) II > III > IV
i
Q.9 e mWhich of the following compounds is most rapidly hydrolysed by SN1 mechanism. m
Ch (A) C H Cl (B) Cl–CH –CH = CH
he C
6 5 2 2
(C) (C6H5)3CCl (D) C6H5CH2Cl

Q.10 Which compound undergoes hydrolysis by the SN1 mechanism at the fastest rate?
CH3 CH3 Br CH3 Br CH3

(A) (B) (C) (D)

Br Br

Q.11 Which one of the following compounds will give enantiomeric pair on treatment with HOH?

C2H5 CH 3 H C2 H5
| | | |
(A) C6 H 5  C  I (B) CH 3  C  Br (C) C 6 H 5  C  Br (D) C 2 H 5  C  Br
| | | |
C2H5 C2 H5 D CH 3

t s t s
p er p er
E x E x
r y r y
i st i st
e m e m
Ch Ch
Page # 11
 HALOGEN DERIVATIVES

Q.12 t s of the following halides in aqueous formic acid:

Consider the SN1 solvolysis
r r ts
pe pe
Ex E x
Br
ry ry
|
CH  CH  CH 3
i
(I)
st (II)
i st
e m e m
Ch Ch
(III) C 6 H 5  CH  C 6 H 5 (IV)
|
Br
Which one of the following is correct sequence of the halides given above in the decreasing order of their
reactivity?
(A) III > IV > II > I (B) II > IV > I > III (C) I > II > III > IV (D) III > I > II > IV

Q.13 Arrange the following compounds in decreasing order of their reactivity for hydrolysis reaction

(I) C6H5–CH2–Br (II) C 6 H 5  CH  C 2 H 5 (III) (IV)

|
Br
(A) I > II > III > IV (B) IV > II > I > III (C) III > IV > II > I (D) IV > III > II > I

Q.14 Arrange the following compounds in order of decreasing rate of hydrolysis for SN1 reaction:
s s
e rt er
t
Ex p xp
(I) CH –Br (II) H3C CH2–Br
E
2

t ry ry
s
i CH3–CH2 i st
e m(III) CH2–Br (IV) CH CHm
2–Br
e
Ch (A) II > III > IV > I (B) IV > III > II > I (C) III > IV > II > I
C(D)hI > II > III > I
Q.15 For the given reaction
R1 R1
| |
 R  C  OH
R  C  X HOH
| |
R2 R2
Which substrate will give maximum racemisation?
CH 3 CH 3
| |
(A) C6 H 5  C  Br (B) CH 2  CH  C  Br
| |
C2H 5 C2H 5

Br
Br
s
t OCH t s
er er
C6H5 C NO2
C6H5 C
p p
(C) 3 (D)
E x E x
r y r y
i st i st
e m CH3
NH3

e m
Ch Ch
Page # 12
 HALOGEN DERIVATIVES

Q.16 s withAgNO3?
Which will give whitet ppt. ts
r r
x pe x pe
(A)
ry
E (B) Cl (C) CH2Cl (D) Both A & C
ry
E
i st i st
m
Q.17e Which solvent is used for SN1 reaction ? e m
Ch (A) Dihydrogen oxide (B)Acetone Ch
(C) DMSO (D)Acetonitrite

Q.18 What will be product if aqueous KCN is added to 1-chloro-3-methylbutane

(dissolved in non polar solvent)

(A) (B)
CN CN

(C) (D) There will be no reaction

Q.19 Consider following reaction

I  + CH3–Br  CH3–I + Br 
s polarity on rate of reaction.
What will be effectroft solvent t s
e er
x p solvent polarity rate of reaction increases
E
(A) On increasing
E xp
y
(B) Onrdecreasing ry
s t solvent polarity rate of reaction decreases
i On increasing solvent polarity rate of reaction decreases i st
m(C)
m
C h e (D) No effect of solvent polarity on rate of reaction Ch
e

Q.20 Which compound should gives white turbidityimmediately on reaction with Luca's reagent?
OH

(A) (B)
OH

OH CH 3
|
(C) CH (D) H 3C  C  CH 2  CH 2  OH
|
CH 3

Q.21 The major product in the given reaction: + NH3 

t s t s
er
p2 p er
E xCH NH 2
CH2NH2 CH2Br
Ex
r y (D)All of theser y
ist st
(A) (B) (C)
m
Br NH2 NH2
m i
e e
Ch Ch
Page # 13
 HALOGEN DERIVATIVES

Q.22 For CH3Br + OH– 

r t s CH3OH + Br– r ts
p e is given by the expression:
the rate of reaction
x x pe
y E
(A) rate = k [CH3Br] (B) rate = k[OH–]
ry
E
s t r = k [CH3Br][OH–]
(C) rate (D) rate = k[CH3Br]° [OH–]°
st
e mi m i
h
CQ.23 Non-occurence of the following reaction he C
Br– + CH3OH  BrCH3 + OH–, is due to
(A)Attacking nucleophile is stronger one (B) Leaving group is a strong base
(C) Alcohols are not good substrate (D) Hydroxide ions are weak bases

Q.24 Which of the following is having highest extent of SN2 mechanism.

Cl Cl CH2–Cl CH2–Cl

(A) (B) (C) (D)

CH3 H

Q.25 Arrange these compounds in order of increasing SN2 reaction rate:

t s t s
(A) III < I <xIIp< IV
er er
E (B) III < II < I < IV (C) IV < III < I < II (D) III <IV < I < II
E xp
ry ry
Q.26 i
Thes treactivity of 2-bromo-2-methylbutane (I), 1-bromopentane (II) and 2bromopentane
i s t (III) towards
m N2 displacement is such that: em
C h e S(A) I > II > III (B) I > III > II (C) II > III > I
h C
(D) II > I > III

Q.27 Which reaction proceeds faster with NaI in DMSO.

CH2Cl Cl CH2Cl
Cl
(A) CH3 (B) (C) (D)

S 2
Q.28 + OH– 
 A
N

Ais:

(A) (B)

(C) Both (D) None

ts t s
p er p er
E x E x
r y r y
i st i st
e m e m
Ch Ch
Page # 14
 HALOGEN DERIVATIVES

Q.29
ts
In the given reaction
r r ts
CH 3  CH  CH e
p 2  CH 2  CH  CH 3 pe
|y E
x E x
ry
|
r
i st OTs OTs
i st
em e m
Ch Ch
[X]
[X] will be:


OTs S
| |
(A) CH 3  CH  CH 2  CH 2  CH  CH 3 (B) CH 3  CH  CH 2  CH 2  CH  CH 3
| |
S S
 

(C) (D)

Q.30 In which of the following, replacement of Cl– is most difficult?

t s(B) t s
er er
(A) (C) (D)

E xp E xp
Q.31 Whichrofythe following nucleophile will show minimum reactivitytowards S 2 reaction: r y
st s t
N

m i  
m i
e (C) Et–O e 2CHO
Ch Ch
(A) Me 3 C O (B) MeO (D) Me

Q.32 When ethyl bromide is treated with dryAg2O, main product is:
(A) Ethyl methyl ether (B) Ethanol (C) Ethoxy ethane (D)All of the above

Q.33 In the given reaction:

( 
 [X]
i ) NaN 3
( ii ) NH 4 Cl ( aq )

[X] will be:

N3

(A) (B) OH

(C) Mixture of (A) and (B) (D)

ts t s
p er p er
E x E x
r y r y
i st i st
e m e m
Ch Ch
Page # 15
 HALOGEN DERIVATIVES

Q.34 t s/ DMSO

H 3C  CHBrF KOH
  Product(s)
r r ts
( R  Isomer )
pe (1.eq )
pe
y isx/ are
E E x
ry
Product(s)
i tr
(A)sS-1-Fluoro-ethan-1-ol (B) R-1-Fluoro-ethan-1-ol
i st
e m(C) R-1-Fluoro-ethan-1-ol + enantiomer (D) R-1-Bromo-ethan-1-ol
e m
Ch Ch
CH3
Q.35 D CH2–Br KSH
 Q, Q is
DMSO
H

CH3 CH3
(A) HS CH2D (B) D H
H CH2SH

CH3 CH3
(C) D CH2–SH (D) HSH2C D
H H
ts t s
er er
E
Me
xp SOCl2
E xp
ry P
ry
Q.36
m ist
HO D
m i st
e e
Ch Ch
SOCl2
Q
H
N

P and Q are respectively

Me Me Me Me

(A) D Cl Cl D (B) Cl D D Cl

H H H H
Me Me Me Me

H H
(C) Cl D Cl (D) D Cl Cl

H D H D

t s t s
p er p er
E x E x
r y r y
i st i st
e m e m
Ch Ch
Page # 16
 HALOGEN DERIVATIVES

r ts O
r ts
Ph – CH2 – x
pe 18
x pe
Q.37
ry
E
OH + Cl – S CH3  OH

 M
ry
E
i st O i st
e m e m
Ch Ch
M is
O O
18 18  18 
(A) Ph  CH 2  OH (B) Ph–CH2O–S–O (C) Ph – CH2 – OH (D) Ph–CH 2–S–O
O O

CH3

18 O CH
OH   
3  R
PCl3
Q.38 H

D
R is
CH3 CH3
18
(A) H O–CH 3 (B) H3CO D
D
s H s
e3 rt er
t
Ex p xp
CH CH3
y
(C) Hr3CO
18
ry
E
ist st
H (D) H O–CH3
m m i
e e
Ch Ch
D D

Q.39 Benzyne intermediate is not observed in:

OCH3 Cl Cl +
F H3C CH3 N2
(A) (B) (C) (D)
COO

Q.40 In the reaction of p-chlorotoluene with KNH2 in liquid NH3, the major product is:
(A) o-Toluidine (B) m-Toluidine
(C) p-Toluidine (D) p-Chloroaniline

Q.41 Which chloroderivative of benzene among the following would undergo-hydrolysis most readily with
aq.NaOH to furnish the corresponding hydroxy derivative.
NO2
(A) O2N Cl (B) O2N Cl
NO2
t s t s
p er p er
(C) Me2N E x Cl (D) Cl E x
r y r y
i st i st
e m e m
Ch Ch
Page # 17
 HALOGEN DERIVATIVES

s ts
r* t
Q.42 In the given reaction:
e  e r
CH 3  CH 2 xpS  CH 2  CH 2  Br  [X] xp
HOH

y
r be:
[X] will E 

ry
E
is t s t
* i
e m(A) CH  CH  S 
*
C H  CH  OH (B) CH  CH  S  CH 2 e
 m
CH 2  OH
C h 3 2 2 2 3 2
C h
(C) 1 : 1 mixture of (A) and (B) (D) 2 : 1 mixture of (A) and (B)

Q.43 CH2=CH–CH2–CH2–CH2–CH2–SH Br

2  ?
CCl 4

Major product of this reaction is:

(A) Br2  CH 2  CH  CH 2  CH 2  CH 2  CH 2  SH
|
Br

(B) Br2  CH 2  CH  CH 2  CH 2  CH 2  CH 2  SH
|
CCl 3

(C) Br2  CH 2  CH  CH 2  CH 2  CH 2  CH 2  SH
|
Cl

t s t s
er er
(D)

E xp E xp
ry ry
i st OH
i st
m m
Che
Q.44 Br
2  
/ CCl 4
Ch
e
Which compound will be major product for the above reaction?
OH Br
(A) (B)
Br O

(C) O (D) O
Br Br
Br

Q.45 2-chloropentane on halogenation with chlorine gives 2,3-dichloropentane. What will be the structure of
free radical species formed in the reaction?
(A) Planar (B) Trigonal planar (C) Square planar (D) Pyramidal

t s t s
p er p er
E x E x
r y r y
i st i st
e m e m
Ch Ch
Page # 18
 HALOGEN DERIVATIVES

Correct order of rate ofsphotochlorination for following compounds is:

Q.46
rt r ts
e pe
xp
CH 3
E x
yE
|
y
r 3 CH 3  C  CH 3
r
CHs3t–CH st
m i CD3–CD3 |
m i
h e (I) he
CH 3
C (II) (III) C
(A) II < I < III (B) I < II < III (C) III < I < II (D) II < III < I

Q.47 What will be the major product, when 2-methyl butane undergoes bromination in presence of light?
(A) 1-bromo-2-methyl butane (B) 2-bromo-2-methyl butane
(C) 2-bromo-3-methyl butane (D) 1-bromo-3-methyl butane

Q.48 Select the incorrect statement about the product mixture in the following reaction :
Br
2  Products
CCl4
(A) it is optically active (B) it is racemic mixture
(C) it is a resolvable mixture (D) it is a mixture of erythro compounds

Q.49 The reaction of SOCl2 on alkanols to form alkyl chlorides gives good yields because
(A)Alkyl chlorides are immscible with SOCl2
(B) The other products of the reaction are gaseous and escape out
(C)Alcohol and SOCl2 are soluble in water
s s
r t not occurs via intermediate formation of an alkyl chloro sulphite
(D) The reaction does
er
t
x pe xp
r
E
Q.50 Find outythe correct order of rate of reaction towards allylic substitution.
ry
E
i s t i s t
e m CH 3
| e m
C h (I) CH –CH = CH (II) CH –CH –CH=CH (III) CH3  CHC hCH  CH 2
3 2 3 2 2

(A) I > II > III (B) II > I > III (C) III > II > I (D) III > I > II

Q.51 NBS
 Allylic brominated products
CCl4 , 

Find out the incorrect statement.

(A) It gives total 9 allylic brominated products (B)All allylic brominated products are optically active
(C) Substrate has 7 allylic hydrogens (D) NBS gives Br constantly to reaction mixture.

Q.52 What is the order of reactivity with HBr.

(a) (b) (c)

(A) a > b > c

s(B) b > a > c (C) c > b > a (D) b > c > a
s
e rt er
t
p p
r y Ex r y E x

m ist m i st
e e
Ch Ch
Page # 19
 HALOGEN DERIVATIVES

s ts
e rt r
x p HBr x pe
E E
C = CH 2

Q.53 r y D CCl  ry

i
H
st 4
i st
e m e m
Ch CH3

What is stereochemistry of product?

Ch
(A) Racemic mixture (B) Opticallyinactive (C) Diastereomers (D) Meso product

Q.54 Addition of CCl3Br in presence of Peroxide is example of :

(A) ElectrophillicAddition (B) Free Radical substitution
(C) Free RadicalAddition (D) Electrophillic substitution

Me
|
Q.55 Me  C  CH 2  OH HBr
 Major product.
|
Me

Me
Me Me |
(A) C=C (B) Me  C  CH 2  Br
Me H |
t s Me
t s
er er
Brx p
E E xp
t r y C|  CH  Me ry
i
(C)s Me (D) Me  CH  CH  Me i st
m m
2

he he
| | |
C Me Me Me C
CH3

/ h
Q.56 Cl
2  Monochloroderivatives

Total number of monochloroderivatives formed in above reaction are

(A) 8 (B) 12 (C) 10 (D) 6

Q.57 HBr
 
(1eq.)
40C
Which statement is incorrect about this reaction.
(A) Major product is formed by 1,2-addition.
(B) 1,4- addition product is KCP (Kinetically controlled product)
(C) TCP (Thermodynamically controlled product) is formed by 1,4-addition
t s product. t s
er er
(D) TCP forms as major
x p x p
r y E r y E
i st i st
e m e m
Ch Ch
Page # 20
 HALOGEN DERIVATIVES

CH3 r ts r ts
Dx pe x pe
Q.58
H
y
r H
E HBr
 M, M is ry
E
D
i st i st
e m e m
Ch Ch
OH

CH3 CH3 CH3 CH3

H D D H H D H D
(A) D H (B) H D (C) H D (D) H Br
Br Br Br D

14

Q.59 SOCl
2  Product(s)
OH

Product(s) is / are

14
Cl
14
14 Cl
(A) only (B) only (C) Both (A) and (B) (D)
Cl
t s t s
er er
E xp E xp
ry ry
i s t CH i st
e m 3
e m
h
CQ.60 C NaI
  P,,
/ acetone
P is Ch
H
F
D

CH3 CH3 CH3

C C
(A) I (B) (C) No reaction (D) C + en
H H I I
D D H
D

t s t s
p er p er
E x E x
r y r y
i st i st
e m e m
Ch Ch
Page # 21
 HALOGEN DERIVATIVES

CH3
r ts r ts
H e
OHp HBr pe
Q.61
H
ry
EBrx  Product(s) ry
E x
i s t CH3 i st
e m e m
Ch C h
Product(s) formed in above reaction is / are
CH3 CH3 CH 3
H Br H Br Br H
(A) (B) &
H Br H Br H Br
CH3 CH3 CH3

CH3 CH3 CH3 CH3

H Br H Br Br H H Br
+ en + +
(C) Br H (D) H Br H Br Br H
CH3 CH3 CH3 CH3

A  CHBr3
KOBr
Q.62
Reactant Ais :
(A) Isopropyl alcohol (B) Methanol
(C) Ethanoic acid (D) n-Butyl alcohol

Q.63 Which product is obtained when bleaching powder is distilled with acetone:
(A) CCl4 s(B) CHCl3
t (C) CH2Cl2 (D) CH3Cl
t s
er er
E xp E xp
Q.64 H C rCy R  
 CHX OH / X 2
ry
st st
3 3

m i ||
m i
e O
e
Ch Which halogen should not be used in above reaction? Ch
(A) Cl2 (B) F2 (C) Br2 (D) I2

CHCl3  A    B (major)

Ag HCl ( excess )
Q.65

B is
Cl
(A) H 2C  CH 2 (B) H3C – CH (C) H 3C  C  Cl (D) H  C  CH 2  Cl
| | Cl || ||
Cl Cl O O
Q.66 Which of the following compound can not show haloform reaction?
(A) H 3C  CH  C  OH (B) Ph  C  CH 2  C  Ph
| || || ||
OH O O O
t s t s
(C) H 3C  C  CerOH (D) H 3C  C  O  CH 3 er
| | p|| p
Ox O
E E x
||
ry y
O
r
i st i st
e m e m
Ch Ch
Page # 22
 HALOGEN DERIVATIVES

Q.67 ts
The product of therreaction r ts
pe
x CH Br  P x pe
r y E
CH
Alc.KOH

ry
E
t 
st
2 2

m is
Pis:
m i
e e
Ch (A) OH (B) C hOH
O–CH –CH
2 2

O
(C) (D) CH=CH2

Q.68 In the given pairs, which pair represent correct order of rate dehydrohalogenation reaction.
(A) < (B) <

(C) < (D) CH3–CH2–Cl < CD3 – CD2 – Cl

I Br

Q.69 Consider the reaction.

CH 3
r ts | t s
p e
CH 2  CH     CH 3 Alc
.KOH

 Product Major.. er
xp
CH CH CH
x
2

y E |
ry
E
tr
Cl
i s i st
e mThe major product is e m
Ch CH 3
|
ChCH 3
|
(A) CH 2  CH  CH  CH  CH  CH 3 (B) CH 2  CH  CH  CH 2  CH  CH 3

CH 3 CH 2
| ||
(C) CH 2  CH  CH 2  CH  CH  CH 3 (D) CH 2  CH  CH 2  CH 2  C  CH 3

C H O
Q.70   ? Major product is:
2 5
C 2 H5OH

(A) (B)

t s t s
p er p er
Ex x
(C) (D)

r y r y E
m ist m i st
e e
Ch Ch
Page # 23
 HALOGEN DERIVATIVES

s of dehalogenation of (2R, 3S)-dibromobutane? ts

rt
Q.71 What will be the product
e CHp e
r
p CH
Ex Ex
CH3 3 Br CH3 CH3 H CH3 3

(A)
t r y C=C (B) C=C (C) C=C (D) C =r Cy
t
m i s Br H CH3 H H CH3
m H is H
he
CQ.72 C he
In which of the following reaction alkene is obtained?
Br Br
Br

(A) Zn (B) OH–

 

OH Me
N
(C) H+ (D) OH¯
 

–
OH
Q.73 Major product.

NMe3
t s t s
er er
E xp E xp
ry ry
ist st
(A) (B) (C) (D)

m m i
he
CQ.74 In the given reaction: Ch
e
Br
 C CNa / 
CH
3  

the products are:

(A) and

(B) +

(C)

t s t s
p er p er
(D)
E x E x
r y r y
i st i st
e m e m
Ch Ch
Page # 24
 HALOGEN DERIVATIVES

R1 Zn
dust

 r ts r ts
pe pe
Q.75

E x E x
rZnydust ry
s t 
R2   st
e mi e m i
Ch Compound R1 & R2 respectively.
Me Me Me
CMeh
Br H Br H Br H Br H
(A) , (B) ,
H Br Br H Br H H Br
Me Me Me Me
Me Me Br
Br Br
(C) H Br , Br H (D) ,
Br
Et Et

Br
Q.76 KI
/   Product
acetone

Br

isr ts t s
Formed product e er
E xp E xp
ry ry
ist st
I

m(A) m i
e e reaction
Ch Ch
(B) (C) (D) No
I

Br

/
Q.77 EtOH
  

Which statement is correct.

(A) Major product is formed by E2 reaction.
(B) Minor product is formed by E1 reaction.
(C) Major product is formed by dehydrohalogenation by E1 mechanism
(D) Major product is formed by E1CB

t s t s
p er p er
E x E x
r y r y
i st i st
e m e m
Ch Ch
Page # 25
 HALOGEN DERIVATIVES

CH3 r ts r ts
x   pe x pe
Q.78
r y E  
alc.KOH

I Cl

ry
E
i st Br i st
e m e m
Ch Ch
H
Major products of above reaction are
CH3 CH3 CH3 CH3
(A) (B)

I I Cl Cl
Cl Cl I I

CH3 CH3

(C) Cl + en (D) I + en
I Cl

Br
Ph H
Br NaI
 s  P,, s
Q.79 H / acetone
t t
Ph er er
P is : E xp E xp
ry ry
i st Ph Ph Ph Br Ph H Ph
i s Ht
e m C=C e m
Ch ChH
(A) (B) (C) (D)
H Br H H Ph H Ph


Q.80 OEt  A (Major product),
/ EtOH

Br
A is :

(A) (B) (C) (D)

OEt OEt

Q.81 NBS
 NaI   Q
/ acetone

Q on reaction with Na/ether gives

(A) (B) (C) (D)

t s t s
p er p er
E x E x
r y r y
i st i st
e m e m
Ch Ch
Page # 26
 HALOGEN DERIVATIVES

r ts r ts
x pe x pe
E E
conc.H2SO4 DBr
Q.82
r y OH

ry
t
i s major product is : i st
e mFinal e m
Ch D Ch
D Br
(A) (B)
Br

(C) (D)
D Br Br

Q.83 On heating glycerol with excess amount to HI, the product formed is–
(A)Allyl iodide (B) Isopropyl iodide (C) Propylene (D) 1,2,3–tri–iodopropane

 

ts OH
 s
OH
t
er er
Q.84 II I

x p xp
B
y E A
ry
E
s
Steps
i t rI and II are i st
e m(A) I can't be SN1 (B) II can't be SN1 (C) I SN1 & II SN2 (D) I Sm
e N2 & II SN1
h
CQ.85 Ch
The given compound CH –O–CH –Br gives which one of the following reactions:
3 2
(A) Only SN1 (B) Only SN2
(C) SN1 as well as SN2 (D) E1

Q.86 Which of the following compound can not decolourise bromine water-

(A) (B) (C) (D) H3C – C  C – CH3

Q.87 Rate of which reaction increases on increasing polarity of solvent?

(A) Br  + CH3 – OTs  (B) (H3C)3N + CH3 – I 
CH 3
| 
(C) CH 3  S CH 3  O H  (D) CH3Cl + NaOH 


t s t s
p er p er
E x E x
r y r y
i st i st
e m e m
Ch Ch
Page # 27
 HALOGEN DERIVATIVES

r ts r ts
e
p    K,
I
pe
x  x
TsCl
(
E E
Q.88 i ) BH .THF
3

ry ry
( ii ) H O / OH
2 2

is
K is t
:
i st
e m CH CH2I CH3 e m
h Ch
CH3
C
3

I H H H
(A) H (B) OH (C) H (D) I
OH H I H

Q.89 Br
2   P,,
/ CCl 4
P is

Br

(A) (B) + enantiomer

Br
Br
Br
(C) (D) No reaction
Br
Br
r ts r ts
x p e iodine containing Harmone whose deficiency leads to goiter, the hormonexis:p e
yE yE
Q.90 Our body produces
(A) Thyroxine (B)Arenine
t r r
(C)sGrowth
i Harmone (D) Renin
i st
e m e m
h h
CQ.91 Which Halogen containing antibiotic drug is very effective for treatment ofCtyphoid fever-
(A) Chlorine (B) Iodine (C) Flarine (D) Bromine

Q.92 Which of these compounds is used as solvent as a paint remover-

(A) Methylene chloride (B) Chloroform
(C) Iodoform (D) Carbon tetrachloride

Q.93 Which compound releases poisonous gas on exposure to air under light-
(A) Freons (B) Chloroform
(C) Carbon Tetrachloride (D) Methylene chloride

Q.94 Which compound helps in the production of Freon refrigerant 22 ?

(A) Chloroform (B) Methylene chloride
(C) Carbon tetrachloride (D) Iodoform

Q.95 Which compound widely used as anaesthetic in surgery

(A) Iodoform
t s (B) Carbon tetrachloride
t s
per
(C) Methylene chloride (D) Chloroform
p er
E x is widely used in production of drugs E x
Q.96
r y
Which compound
r y
i st
(A ) M ethylenechloride (B) Triiodomethane
i st
e m(C) Trichloro methane (D) Carbon tetrachloride
e m
Ch Ch
Page # 28
 HALOGEN DERIVATIVES

Q.97
t s
Which compound has antiseptic properties
ts
r r
pe
(A) Methylene chloride
(C) Trichloroxmethane
(B) Freons
x pe
ry
E (D) Iodoform
ry
E
t
i s compound is used as a decreasing agent, as spot remover & as fire extinguisher
is ? t
Q.98
mWhich
m
C h e (A) Carbon tetrachloride (B) Methylene chloride h e
C
(C) Chloroform (D) Freons

Q.99 Breathing about 900 parts this substance per million parts of air for a short time cause dizziness headache
& fatigue, headache is-
(A) Methylene chloride (B) Chloroform
(C) Iodoform (D) Tetra chloromethane

Q.100 Exposure to this substance can make heart beat irregularly or stop.
(A) Methylene chloride (B) Tetrachloro methane
(C) Freons (D) DDT

Q.101 Which gas depletes the ozone layer ?

(A) DDT (B) Iodoform
(C) Methylene chloride (D) Carbon Tetrachloride

Q.102 Extremely stable, non toxic, non-corrosive substance is-

(A) DDT s(B) Iodoform (C) Freons (D) Methylene chloride s
e rt er
t
x pinitiate radical chain reaction in stratosphere that can upset ozone layer substance
Q.103 This substance
E x p is
E
t r y tetrachloride
(A) Carbon (B) Freons
t ry
s
i Chloroform
(C) (D) Methylene chloride i s
h em h em
CQ.104 This organic compound is 1st chlorinated organic insecticides. Which is effective
C against mosquito that
spread malaria & lice that carry typhus compound is-
(A) Chloroform (B) Methylene chloride
(C) DDT (D) Carbon Tetrachloride
Cl

Cl
Q.105
Cl Cl
Cl H
Compound is
(A) Freons-2 (B) DDT (C) Urea (D) None of these

Q.106 Which reagent is not used in Swartz reaction ?

(A) AgF s(B) Hg2F2
t (C) CoF2 (D) NaF
t s
p er p er
E x E x
r y r y
i st i st
e m e m
Ch Ch
Page # 29
 HALOGEN DERIVATIVES

t s for enantiomers-
Q.107 Which properties is same
ts
(A) Melting pointe r r
x pRefractive index
(B) Boiling point
x pe
ry
E
(C) Solubility& (D)All of these
ry
E
t
i s Freon is most common among the following in industrial use? i st
m
Q.108 Which
m
Ch e (A) C2F4Cl2 (B) C2F2Cl4 (C) CCl2F2 e
C(D)hCFCl 3

Q.109 Freon-12 is manufactured generally by which reaction

(A) From CCl4 by Swartz reaction
(B) From CCl4 by Finkelstein reaction
(C) From acetone on reaction with OH¯/F2
(D) From formic acid on reaction with SnCl2 / HCl & H3O+

Q.110 Which substance is widely used after world war II for minimising the causes of malaria.
(A) Dichloro diphenyl trichloroethane (B) Methylene chloride
(C) Iodoform (D) Tetrachloro methane

Q.111 Among the following option which has highest boiling point?
(A) Bromomethane (B) Bromoform
(C) Chloromethane (D) Dibromomethane

[PARAGRAPH TYPE]
t s Paragraph for question nos. 112 & 113
t s
er er
r Ex p
y 
 Mono chloro derivatives
Cl2
ry
E xp
st st
h

m i m i
Ch e (A)
Q.112
4 (B) 6 (C) 3
e
(D)h2
How many dextrorotatory monochloro derivatives will form in above reaction?
C
Q.113 How many fractions will be obtained by fractional distillation of mixture of products?
(A) 4 (B) 6 (C) 8 (D) 5

Paragraph for question nos. 114 & 115

For the following compound.

Cl
Cl Cl
Cl

Cl Cl
(A) (B) (C)

s Boiling point?
Q.114 Which is correct order of
t t s
(A) A > B > C er (B) A > C > B (C) C > B > A (D) A > B  C er
p p
Ex
Q.115 Whichrisycorrect order of Melting point ? r y E x

m i s Ct > A > B
(A) (B) C > B > A (C) B > A > C (D) B > Ci s>tA
m
e e
Ch Ch
Page # 30
 HALOGEN DERIVATIVES

s
[MULTIPLE CORRECT CHOICE TYPE]
ts
e rt r
x p can show faster SN1 reaction than x pe
ry
E
Q.116 Which compound
Cl
ry
E
is t Cl i st
e m e m
C h (A) Br
(B) I (C) C(D)hH C = CH – Br
2

Me

Q.117 OH + SOCl2 ( 

or   Product
C 2H 5 )3 N

Et N
Product possible is / are
Me Me

(A) Cl (B) Cl

Et Et
 
(C) (C 2 H 5 )3 NH Cl s s
rt t
(D) SO2

p e er
Q.118 Rate of SNE x E xp
r yof2 Nucleophile
depends on
ry
i t
(A) Conc
sNature
(B) Conc of substrate
i st
e m(C) of leaving group (D) Nature of solvent
e m
Ch
Q.119 SN2 reaction will be negligible in Ch
Br

(A) (B) (C) (D)

Q.120 In the given pair in which pair the first compound is more reactive than second to SN2 reaction.

Cl
(A) Cl CH2Cl (B)
Cl

Cl Cl

(C) (D)
Cl Cl

t s t s
p er p er
E x E x
r y r y
i st i st
e m e m
Ch Ch
Page # 31
 HALOGEN DERIVATIVES

t s case configuration about chiral C) is retained:

Q.121 In which of the following
r r ts
x pe pe
(A)
ry
E 
Na
3
CH Br
(B)
SOCl
y
2  3
CH ONa
r
Ex
i st i st
e m e m
Ch (C) 
PCl
3  3
CH ONa
(D) H
C h
1. TsCl
 

2.MeONa

Q.122 Select correct statement about the product (P) of the reaction:

Br
2 / P
CCl 4

(A) P is optically inactive due to internal compensation

(B) P is optically inactive due to the presence of plane of symmetry in the molecule
(C) The structure of P can have three optical isomers possible.
(D) P can have four possible optical isomers.

Q.123 Which of following reaction product are diastereomer of each other ?

Me
Br2
(A) CH 3  (B) D H HBr

ts
CCl 4
t s
er er
E xp E xp
ry ry
Ph
i st i st
e m 
 HBr
m HCl
ePh peroxide
(D) CH 3  CH  CH  CH  
Ch h
(C) CCl 4
| C
Et
Q.124 Products formed when HCl adds to 2,4- hexadiene is:
(A) 4-chloro-2-hexene (B) 2-chloro-3-hexene
(C) 2-chloro-4-hexene (D) 1-chloro-2-hexene

Q.125 HCl
  Possible products
/ ZnCl 2

OH

Cl

(A) (B) (C) (D)All of these

t s Cl t s
er er
Cl
x p x p
r y E r y E
i st i st
e m e m
Ch Ch
Page # 32
 HALOGEN DERIVATIVES

s is / are:
Q.126 Incorrect about alkylthalides ts
e r r
x p on exposure to sunlight
(A) Tertiary alkyl halides undergo SN2 substitutions
x pe
y E
(B)Alkyl iodides
r
gradually darken
ry
E
i s t chloridessubstitution
(C)Alkyl do not give beilstein test
i st
m
e
(D)Anucleophilic is most difficult in alkyl iodides
e m
h
CQ.127 Ch
In the given reaction

C7H12 (A) HBr



(A) can be

(A) (B) (C) (D)

Q.128 A gem dichloride is formed in the reaction :

(A) CH3CHO and PCl5 (B) CH3COCH3 and PCl5
(C) CH2 = CH2 and Cl2 (D) CH2 = CHCl and HCl

Q.129 Which reaction(s) is represents correct major product.

O
t s Cl
t s
(A) er5 
PCl
er
xp xp
Cl

ry
E ry
E
t – O – Et PCl
(B)sMe 5  Et – Cl + Me – Cl st
e mi 5  H3C – Cl + Et  C  Cl
(C) H 3C  C  OEt PCl e m i
Ch ||
O
||
O
Ch
Cl
(D) OH 
PCl5

Q.130 In which product formation takes place according to Hoffmann's rule

 
t B u O K CH3CH 2 O K
(A) CH 3CH 2  CH  CH 3   (B) CH 3CH 2  CH  CH 3   
 
| |
Br Br

 
(C) O
H
 (D) CH 3CH 2CH  CH 3 O
H

 
|

S(CH 3 ) 2

t s t s
p er p er
E x E x
r y r y
i st i st
e m e m
Ch Ch
Page # 33
 HALOGEN DERIVATIVES

t sgive syn-elimination
Q.131 Which of followingwill
r r ts
p e2–OCOCH (B) CH 3CH 2CH  CH 3 pe
E
(A) CH3CH2CH
x 3
E x
r y |
ry
i st Cl
i st
em e m
Ch |  h
CH 3

(C) CH 3CH 2CH 2  O  C  S  CH 3 (D) CH 3CH 2CH 2 N  O

C
|| |
S CH 3
Q.132 Which of the following is/are  – elimination reaction?
CH3
(A) CH3 – C – Br + KOH(alc.) 

CH3

Br
:

(B) Et3N


(C) CHBr3 + Me3CO–K+  :CBr2

t s t s
r
eOH + NaOH  er
(D)
Br
E xp O E xp
ry ry
i st i st
e m e m
h Which of following are correct for given reaction
CQ.133 Ch



(A) Major product of reaction is (B) Major product is

(C) The reaction is thermal elimination reaction (D) The reaction is E2 reaction

CH3
H Br 
Q.134 OEt  Possible products
/ EtOH
D H 

CH3
s s
e rt er
t
CH3 CHp3 CH3 H CH3 CH3 p
Ex x
CH3 H

r y r y E
i s tD s tCH3
(A) (B) (C) (D)
m H D CH3 H H H
m i
e e
Ch Ch
Page # 34
 HALOGEN DERIVATIVES

ts ts
erreaction
Q.135 Consider the given
p pe
r
E x E x
r y CH 3
ry
i s t | i st
m   OTs m
he e
H C NaCN
 CH3CH 2 CH  CN
C |
C 2 H 5 (S) | Ch
CH 3
which of following statements are correct for above reaction.
(A) Product formation takes place due to the breaking of O–Ts
(B) The reaction is S 2
N
(C) The reaction is S
N1
(D) Configuration of product is (R)

Q.136 SN1 & SN2 is not favourable in

(A) H2C = CH–Cl (B) Ph–CH2–Cl (C) Ph–Cl (D) H2C=CH–CH2–Cl

Q.137 SN1 & SN2 product are same in (excluding stereoisomer)

(A) (B) (C) (D) Ph  CH  CH  CH 3

ts ts
er r
| |
xp
CH 3 Cl pe x
ry
E ry
E
i s t are possible products in following
Q.138 Which
m m i st
e e
Ch Ag


/ H 2O / 
 Ch

(A) (B) (C) (D)

Q.139 Which statement(s) is / are incorrect.

(A) S-Butan-2-ol gives S-2-chlorobutane on reaction with SOCl2 / Pyridine
Cl

(B) gives white precipitate ofAgCl on reaction with alc.AgNO3.


(C) CH3–CH2–Cl on reaction with KCN / DMSO gives CH3 – CH2 – N  C¯ as major product.
s
(D) Acetone gives 2,t2-dichloropropane on reaction with PCl5. t s
p er p er
E x E x
r y r y
i st i st
e m e m
Ch Ch
Page # 35
 HALOGEN DERIVATIVES

s
t not represents correct major product.
Q.140 Which reaction(s) rdo(es) ts
r
x pe x pe
ry
E ry
E
(A)s t st
mi i
OH 
HBr
Br
e e m
Ch Cl CN Ch
(B) KCN


CH3 CH3 CH3

H OH H Br Br H
(C)
H 

HBr +
Br H Br H Br
CH3 CH3 CH3


  
OCH
3
(D)
Cl OCH3 + Cl

Q.141 Which of the following characteristics are follows in Finkelstein reaction-

(A) Reaction of alkyl chlorides/bromides with NaI
s
(B) Reaction of alkyl chlorides/bromides with NaI in dry acetone
tchloride/bromide ts
e r
(C) Heating an alkyl
e r
in presence of a metallic fluoride such as AgF, HgF2, CoF2 etc.
xp
(D)All of these
E xp E
t rofythe following,Alkyl halide are in gaseous state tr
y
i s
Q.142 Which is
m
e Methyl chloride (B) Ethyl chlorides (C) Methyl bromide
(A) e m bromides
(D) Ethyl
C h Ch
Q.143 Boiling point of isomeric haloalkanes-
(A) is inverselyproportional to branching (B) is directlyproportional to branching
(C) have no relationship with branching (D) Cannot say with structure

Q.144 Which halogen derivatives are denser than water-

(A) Bromo derivatives of hydrocarbon
(B) Fluoro derivatives of hydrocarbon
(C) Iodo derivatives of hydrocarbon
(D) Polychloro derivatives of hydrocarbon

Q.145 In which compound H-bonding is strong-

(A) R – Cl – – – R – Cl (B) H  O    H  O
| |
H H

(C) R  Cl    H  O (D) None of these

t Hs s
|
r t
p e act asAmbident Nucleophile
Q.146 Which of thexfollowing p er
E x
y (D) RCOO¯ y E
(A) Cyanides
r (B) Nitrites (C) LiAlH4(H¯)
r
i st i st
e m e m
Ch Ch
Page # 36
 HALOGEN DERIVATIVES

t s s
rt
[MATRIX TYPE]
r
Q.147 Match List I witheList II and select the correct answer from the codes given below: e
E xp
List-I List-II
E xp
y
r CH ry
is
(A) t –O–SO CH + C H O

(1) CH –CH –PH is t
m m
3 2 3 2 5 3 2 2
e e
Ch Ch
(B) CH 3 –CH 2 –I + PH 3 (2) CH 3 –O–C H
2 5
 
(C) HC  C Na + CH3–CH2–Br (3) CH3–O–CH3

(D) CH3–Cl + CH3– O (4) CHC–CH2–CH3

Q.148 Match List-I with List-II for given S reaction & select the correct answer from the codes given below
N2
 
Z–CH 2Br + CH3 O  Z–CH2–OCH3 + Br
List-I List-II (relative reactivity)
(A) H– (P) 0.1
(B) CH3– (Q) 3
(C) C2H5– (R) 1

(D) (S) 100

Q.149 Column I Column II

s
talc.-KOH t s
(A) CHCl2–CF3
er (P) Carbanion / Carbanionic character
er
E xp 
E xp
ry ry
Br
 
alc.KOH

ist st
(B) (Q) Two step process
m

m i
e Cl e
Ch (C) CH3–CH2–O

(R) Carbocation Ch
F
(D) alc-KOH (S) Transition state


Q.150 Ethers on acidic hydrolysis (H+/H2O) give alcohols / mixture of alcohols.

Ethers Mechanism followed

(A) O (P) SN1

(B) O (Q) SN2

(C) CH2–O–CH3 (R) No reaction

(D) s2 s
rt t
CH3 – CH – CH
O
p e p er
r y Ex r y E x

m ist m i st
e e
Ch Ch
Page # 37
 HALOGEN DERIVATIVES

s ts
rt
Q.151 Column I Column II
e r
CH2x
p
(Haloalkanes) (Density)
x pe
(A)
y 3
(B) r CHCl
E
Cl2 (P) 1.489
ry
E
t
i s CCl4
(Q) 1.336
i st
e m(C) (R) 1.595
e m
Ch Ch
Q.152 ColumnI Column II
(Boiling point)
(A) 1-Chloropropene (P) 46.6°C
(B) Isopropyl chloride (Q) 78°C
(C) 1-Chlorobutene (R) 35.7°C

t s t s
er er
E xp E xp
ry ry
i st i st
e m e m
Ch Ch

t s t s
p er p er
E x E x
r y r y
i st i st
e m e m
Ch Ch
Page # 38
 HALOGEN DERIVATIVES

s ANSWER KEY
ts
rt r
pe pe
Ex x
EXERCISE-1
Q.1 tert-Butyly chloride, sec butyl chloride and Butyl chloride with alc. silver nitrate
r ry
E
i st i st
e m e m
Ch Ch
Me3C – Cl > CHCl > CH3– CH2– CH2– CH2– Cl

Me
Q.3 (A) , (B) Pr OEt Q.4 8 Q.5 4
H

Q.6 OCH3 Q.8 Q.10 9

N CN

Q.11 (a) Ph  CH  Et , (b) Me2C(I)–Et, (c) , (d)

|
Br
Q.12 8 products Q.14 6 Q.15 1,2,3,4,5,6,7,9,10,11,12
Q.16
t s than C–Cl bond and thus on heating heterolytic cleavage of C –I form It– s
C–I bond being less stable
erprecipitate withAgNO3 er
xp xp
which gives yellow
Q.18 7
ry
E ry
E
Q.19 The
t
i s elimination of HI (or DI) in presence of strong base shows E2 elimination. The t
i s determining step
rate
m m
C h e involves breaking up of C – H (or C–D) bond. The C–D bond being stronger
elimination is faster in case of CH3 – CH2I.
h e than C–H and thus
C
Q.21 H 3C  CH  CH  CH 3 KOH
 ( alc
)  CH3  C  CH  CH3  CH3  CH  CH  CH 2
| | | |
CH 3 Cl CH3 CH 3
major minor
Elinination occurs according to saytzeff rule. The major product is one which involves elimination of H
from less hydrogenated carbon.
Q.22 4

Q.23 (A) (B) (C) (D) CH 2

Br ||
O O

ts s
(E)
r t
ClCH2p e 2CH2CN p er
Q.24 (i)
x CH (ii) PhCHF2
x
(iii) y Ereaction
FCH
r no 2CH = CHCO2Me (iv) EtI
r y E
(v)
i st i st
e m e m
Ch Ch
Page # 39
 HALOGEN DERIVATIVES
Q.25
s chlorine atoms present on carbon, the latter acquires a partial positivet s
(a) rt
Due to three electronegative
e r
charge due tox –I pe
p effect of chlorine. As a result, it tends to attract electrons of the C–H bondxtowards
r
itself. Hence E
y the removal of hydrogen atom as proton becomes easier. E
r y diethyl
(b)
is t
Alcohol acts as inhibitor for oxidation of chloroform.Also it reacts with COCl to
is
givetharmless
m m
2
e carbonate.
h egive ROH because alkyl
(c)h KI reacts with RCl to form RI. This RI molecule now hydrolysed easily to
C C
iodide are more reactive than alkyl chloride.
RCl + K I  RI HOH
 ROH (faster)
(d) KCN is an ionic compound [K+(:C N:)–] in which both C and N carrya lone pairelectron. Carbon carrying
lone pair of electrons is more reactive and thus alkyl attacks carbon to give alkyl cyanide. AgCN being
covalent hasAg– CN : structure with lone pair on N thus N atom attacks on R and R–N   C is formed.

Q.26 The dielectric constant of water is greater than that of aqueous acetone, and so ionisation of benzyl
chloride is facilitated.

 
Br OH O Na

Br2 aq. KOH Na

h
(A) (B) (C)
alc. KOH
t s t s
er er
Ex p xp
NBS (C)
Q.27
ry Br ry
E
ist st
(D) (E) (F)
m O m i
e e
Ch Ch

Q.28 (i)A, CH3CH2CH2Br ; B, CH3CH = CH2 ; C, CH3CHBrCH3; D, CH3CHNH2CH3

(ii) A, CH3CH = CH2; B, CH3CHOHCH3; C, CH3CHClCH3; D, CH3CH2CH2
(iii) A, CH3CHBrCH = CH2; B, CH2=CH–CH=CH2; C, CH3CHBrCH=CH2& CH3CH = CH–CH2Br
(iv) A, CH3CH2CHOHCH3; B, CH3CH2CHBrCH3; C, CH3CH = CH – CH3
F

Q.29 A B C D

MgBr
E F

t s t s
p er p er
E x CH2OCH2CH3
E x
Q.30 (a)
r y (b) (c)
r y
i st i st
e m e m
Ch Ch
Page # 40
 HALOGEN DERIVATIVES

s Cl
ts
rt r
p e —CH —Cl pe
AlCl3 |
Q.31 (a)
E x
CH —CH
3 2 2

CH3—CH—CH 3
E x
ry
(b)s t (i) ry
i

O  (ii) HBr / H2O2
i st
e m(c) (iii) PCl3 or SOCl2h e
m
Ch (i) Mg/ether (ii) HCHO/ H2O
C
CH2—CH 3 NBS alc KOH
Q.32 (i) CH—CH3 CH = CH2

Br
(ii) (i) B2H6/NH2—Cl
CH3—CH2—CH = CH2 CH3—CH2—CH2—CH2—NH2

(iii) CH3—CH2—CH = CH2 NBS CH3—CH—CH = CH2 alc KOH CH2 = CH—CH = CH2

Br
Br

Q.34 (A) (B) (C) Q.35 CH2 OCH3

CH3S

t s t s
er er
E xp E xp
ry ry
i st i st
e m e m
Ch Ch

t s t s
p er p er
E x E x
r y r y
i st i st
e m e m
Ch Ch
Page # 41
 HALOGEN DERIVATIVES

s EXERCISE-2
s
Q.1 A Q.2 Cer t Q.3 A Q.4 C Q.5 C Q.6 A Q.7 Cer t
E x pC p
Q.14x A E
Q.8 B
Q.15 C s t
y D
Q.9
r Q.16
Q.10 B Q.11 C Q.12 A Q.13 B
y
Q.20 C s t r Q.21 A
i Q.17 A Q.18 D Q.19 C
i
Q.22e mC Q.23 B Q.24 C Q.25 A Q.26 C Q.27e m
B Q.28 B
Ch
Q.29 C Q.30 D Q.31 A Q.32 C Q.33 C C h
Q.34 B Q.35 C
Q.36 B Q.37 A Q.38 A Q.39 B Q.40 B Q.41 A Q.42 C
Q.43 D Q.44 C Q.45 B Q.46 A Q.47 B Q.48 A Q.49 B
Q.50 C Q.51 A Q.52 B Q.53 C Q.54 C Q.55 C Q.56 B
Q.57 C Q.58 C Q.59 C Q.60 C Q.61 A Q.62 A Q.63 B
Q.64 B Q.65 B Q.66 D Q.67 D Q.68 A Q.69 A Q.70 C
Q.71 C Q.72 D Q.73 A Q.74 B Q.75 A Q.76 D Q.77 C
Q.78 C Q.79 D Q.80 D Q.81 D Q.82 C Q.83 B Q.84 C
Q.85 C Q.86 B Q.87 B Q.88 D Q.89 D Q.90 A Q.91 A
Q.92 A Q.93 B Q.94 A Q.95 D Q.96 D Q.97 D Q.98 A
Q.99 B Q.100 B Q.101 D Q.102 C Q.103 B Q.104 C Q.105 B
Q.106 D Q.107 D Q.108 C Q.109 A Q.110 A Q.111 B Q.112 A
Q.113 B Q.114 D Q.115 A Q.116 AB Q.117 BCD Q.118 ABCD Q.119 ABC
Q.120 BD
r t sQ.122
Q.121 AC ABC Q.123 ABD Q.124 AB Q.125 AB Q.126 ACD
t s
Q.127 ABC Q.128pABD e Q.129 er
Q.133 pAC
x AB Q.130 ACD Q.131 ACD Q.132 AB
x
y E BD Q.136
Q.134 BC r Q.135 AC Q.137 BC Q.138 AB Q.139 ABC r y E
i s t Q.141 B Q.144 ACD Q.145 Bi s
t
e m
Q.140 ABCD Q.142 ABC Q.143 A
em
Q.146 B
h (A) 2 ; (B) 1 ; (C) 4 ; (D) 3
CQ.147 Q.148 (A) S ; (B) Q ; (C)hR ; (D) P
C
Q.149 (A) PQS (B) S (C) S (D) PS Q.150 (A) R (B) P (C) P,Q (D) Q
Q.151 (A) Q (B) P (C) R Q.152 (A) P (B) R (C) Q

t s t s
p er p er
E x E x
r y r y
i st i st
e m e m
Ch Ch
Page # 42