FIITJEE - THE FUNDAMENTAL APPROACH . . .

HALOGEN DERIVATIVE

Q.5
Reactant SN1 SN2
X
(1) Cl X
X X
(2) CH2 = CH — Cl
~
~
(3) CH2 — Cl
~
~
(4) CH2 = CH — CH2 — Cl

X
(5) *

Cl
-

-
- -
(6) CH3 — O — CH2 — Cl
-

-
(7)
-

~
CH—N — CH— Cl2

E
3

CH3 X
X
(8) -
CH3 — F
CH3 X
(9)

(10)
CH—
3 C — Cl
CH3
Br
JE ~

*
X
IT
-
(11) CH3— C — Et -
Cl
Oh
CH—Cl
2
, X ~
(12)
FI

Cl X
~
(13)

C
CH3
X
X
(14) CH3 —C — CH2 — Cl
CH3
E
(15) — CH—
2 Cl ~ X

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 FIITJEE - THE FUNDAMENTAL APPROACH . . . HALOGEN DERIVATIVE

Q.1 Compare the rate of SN1 reaction:- EtOH

(3) Ph — CH2 — Br 
(a) Ph — CH2 — Cl Ph — CH — Cl O
||
H—C—OH
Ph (4) Ph — CH2 — Br 
(i) (ii)
PhOH
Ph (5) Ph — CH2 — Br 
Ph — C — Cl Ans: (1) Ph — CH2 — OH
(2) Ph — CH2 — OCH3
Ph (3) Ph — CH2 — OEt
(iii) O
I I I ||
(4) Ph — CH2 — O — C — H
(b) (5) Ph — CH2 — OPh

(i) (ii) (iii) Q.3 Which SN1 reaction is expected to occur

I I I rapidly.
O

E
1. (a) (CH3)3 CCl + H H (CH3)3 C OH+ HCl
(c) O
(b) (CH3)3 CBr + H H  (CH3)3 C OH + HBr
O
(i) (ii) (iii)
(d)

(e)
CH3 — O — CH2 — Cl
(i)
CH3 — O — CH2 — CH2 — Cl
(ii)
CH—Cl
2
CH—Cl
2
JE 2. (a)

(b)
Cl + EtO— 

1.0 M 1.0 M
Cl + tO— 
O — Et + Cl—

O — Et + Cl—
2.0 M 1.0 M
IT
3. (a) Cl + EtO—  O — Et + Cl—
CH3
Ans: (a) (iii) > (ii) > (i) (b) (ii) > (iii) > (i) 1.0 M 1.0 M
(c) (i) > (ii) > (iii) (d) (i) > (ii)
(e) (i) > (ii) (b) Cl + EtO—  O — Et + Cl—
FI

1.0 M 1.0 M 1.0 M 2.0 M

Ans. (1) b > a (2) a < b (3) a = b

Q.4 Compare rate of SN1 reaction

O
1. (a) Cl + H H 
1
Q.2 SN reactions are also known as solvolysis as O
.. Θ (b) Br + H H 
solvent molecules behave as Nu . Write
the product in each case. O
2. (a) Cl + H H 
H2O
(1) Ph — CH2 — Br  
O
CH3OH Cl + CH3 H 
(2) Ph — CH2 — Br   (b)

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 FIITJEE - THE FUNDAMENTAL APPROACH . . . HALOGEN DERIVATIVE

O
3. (a) Cl + H H  6.
O
Cl + H H Me
(b) 
Br CH—Br
2

(a) (b)
Br (better leaving group) Ans. (1) a > b (2) b > a (3) a > c > b > d
Ans. (1) (b) (4) a < b (5) a < b (6) b > a
O
(2) (b) H H better solvation
8
* Q.6 These substrates cannot give SN1. Explain
(3) (a) Cl
(double bond character) 1. 2. CH2 = CH — Cl 3.

Q.5 Compare rate of SN1 Cl

Me Cl
Me CH3
1.

E
Me Me 4. CH— C — F 5. CH3 — CH2 — F
3

CH3
Me
OTS CH3
Me OTS 6. CH— C — CH— Br 7.

2.
t–Bu
(a)

t–Bu
JE (b) 32

CH3

( O , F & CH3 – O cannot be substituted

strong bars & weak leaving groups)

SN2 reaction nucleophilic substitution

Cl

SN2 — Reaction
Nucleophilic Substitution 2nd order
IT
Cl Cl
(a) (b) . .
Nu + R—L  Nu – – R – – L
I Cl Br Cl
. .
O O O Nu — R + L
3.
FI

O Characteristics:-
x x

(a) (b) (c) (d) 1. Nu + C—L Nu - - - C - - - L 

y z
y z
H OTS H OTS x

4. Nu — C +L
y
z
(a) (b) 1
2. rate of reaction  .
Bulkiness in x, y & z
5. Br . .
3. rate  strength of Nu
Br . .
(a) (b) 4. rate  Leaving group ability of L
5. Inversion of configuration takes place. ‘

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 FIITJEE - THE FUNDAMENTAL APPROACH . . . HALOGEN DERIVATIVE

(ii) Br + CH3O— 
Characteristics
Q.1 Compare rate of SN2 reaction:– 1.0 M  2.0 M
1. CH3 — CH2 — CH2 — Br & CH—CH—Br Ans. (A) i > ii (B) I < ii (C) ii > i (D) ii > i
3

CH3 Q.3 1– Bromobicyclo [2.2.1] heptane is extremely

(i) (ii) unreactive in either SN1 or SN2 reaction.
Explain:
2. CH3 — CH2 — CH2 — CH2 — Cl SN1 X
(i)
(Bridge Head position)
CH3 — CH2 — CH2 — CH2 — I
(ii)

3. CH3 — CH — CH2 — Cl Br
(i) SN2 X
CH3 — CH2 — CH2 — CH2 — Cl (Walden unreason not possible)
|
CH3

E
(ii) Q.4 Write the products of SN2 reaction:–
1. H KSH 
H 
4. Br
Cl Cl Br
(i) (ii) Br
5.

Ans. (1) 1 > 2

(4) 1 < 2
(i)
Cl

(2) 2 > 1
(5) 1 > 2
JE (ii)
(3) 1 > 2
Cl 2. D
H
CH3
CH3
D
ACO— 
H 

KSH 
2
3. H Cl 
Q.2 Compare rate of SN reaction:–
IT
—
(A)(i) Cl + CH3 — CH2 — O  Et
CH3
or KSH 
(ii) Cl+ CH3 — CH2 — OH  4. Cl — CH—
2 C — CH—
2 CH 2— Cl 
CH3
(B)(i) Cl + CH3 — CH2 — O  — NaCN (1 eq)
FI

Cl
Cl + CH3 — CH2 — S—  CH2 I
(ii)
NaCN  6. KSH(1eq)
(C)(i) Br + (C6H5)3N  5.   

(ii) Br+ (C6H5)3P  I

Br
(D) (i) Br + CH3O—  7. KSH 
Br — CH2 — CH = CH — Br 
(1eq)
1.0 M 1.0 M

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