Target : JEE (IITs)

CHEMISTRY
COURSE : VISHWAAS (JF)

TOPIC : HALOALKANES, ALCOHOLS, ETHERS & GRIGNARD REAGENT

SOLUTION OF ADVANCED LEVEL PROBLEMS
3.

CN and NH3 are nucleophile

4.

Conjugate base of weak acid is strong & across the period basicity & nucleophilicity order will be same. In the
period left to right nucleophilicity decreases.

5.

Nucleophilicity Size (in group)

7.

(a) Rate of SN1 reaction [(CH3)3CBr]

(b) Rate of SN1 reaction [(CH3)3CBr]

9.

10.

(a)

(b)

RESONANCE

H2O

Acetone
25C

H O

CH OH

Haloalkanes, Alcohols, Ethers & Grignard Reagent - 1

12.

CH

KOH

(a)

3
K

1 eq.

(b)

PhCH2Cl

PhCH2OCH2CH3

is present in excess and is stronger nucleophile than

PhCH2OCH2CH3
13.

so product is

SN1

% SN1 = S 2 S 1 100
N
N
=

0.24 10 5 [RX]
4.7 10 5 [RX] [5] 0.24 10 5 [RX]

100

0.24

= 4.7 5 0.24 100 = 1.01%

15.

17.

Say after completion (100%) of reaction, there will be 66.66% SN1 product (Racemic mixture) and 33.33% SN2
product (inverted product)
So enantiomeric excess = 33.33 %
Pure (S) -2-butanol has + 13.5 sp.rotation
So observed rotation =

19.

33.33 13.5
= 4.5
100

PI3
NaSH
PhCH2I
CH2OH

PhCH2SH
S 2
N

SH
SN 2

PhCH2SCH2Ph

RESONANCE

Haloalkanes, Alcohols, Ethers & Grignard Reagent - 2

22.

H2O
CH3 CH CH2 CH3
CH3CH=CHCH3 + CH2=CHCH2CH3
|
(cis & trans)
OH

CH3 C H CH2 CH3

|
Cl
(d + )

Y = 3, Z = 2

HBr
excess

24.

CH3 CH2 CH2 CH2 Br

HBr
excess

CH2OCH2

HBr
excess

HBr
excess

CH 3
|
+
SN 1

CH 3 C CH 2
( Br )
|
CH 3

28.

P-carbonium ion
(less stable)

29.

(a)

(b)

(c)

RESONANCE

H shift

methyl shift

Haloalkanes, Alcohols, Ethers & Grignard Reagent - 3

(d)

ring contraction

30.

31.

alcoholic KOH,

E2

37.

39.

40.

Hshift

(a)

HCOOH

(b)

(c)

aq. AgNO

ring exp ansion

H O

It is SN1 reaction

RESONANCE

Haloalkanes, Alcohols, Ethers & Grignard Reagent - 4

41.

Ph C C Ph ( = Elimination)

43.

(a) It is an E2 reaction (Anti elimination)

(c) It is SN1 reaction

44.

(a)

(b)

(b) It is an E2 reaction (Anti elimination)

(d) It is SN2 reaction

E2

E1

Meshift

Mg / ether, CH Br

45.

3
Isopentane
(a) sec. butyl bromide

46.

2
2
3
(a) CH3 CH3 CH3CH2Br CH3 CH2 CH3

Br / h

CH MgBr

Br / h

(b)

49.

(i) Boiling point increase with the size of the halogen atom and number of halogen atom.
(ii) For the same halogen, boiling point increases as the size of the alkyl group increases and the boiling
point decreases as the branching increases.

RESONANCE

Haloalkanes, Alcohols, Ethers & Grignard Reagent - 5