Reaction

Mechanisms
Substitutions in
LECTURE 8 Alcohols
#JEELiveDaily Anupam Gupta
B.Tech & M.Tech - IIT Delhi

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 Reaction
Mechanisms
Substitutions in
LECTURE 8 Alcohols
 General Terms for Reaction

solvent
Reactant (substrate) + Reagent Product
 Type of nucleophilic substitution reaction:

Type of nucleophilic substitution reaction:

● SN1
● SN2
● SNi
● SN2Ar
● SN2Th
Substitution of Alcohols
 Reaction with hydrogen halides

● A common method is to treat the alcohol with acids like HI or HBr

● These acids are used to convert alcohols into the corresponding alkyl halides.
 Reaction with hydrogen halides

i. In acidic solution, an alcohol is in equilibrium with its protonated form.

i. Protonation converts the hydroxyl group from a poor leaving group (OH)- into a good
leaving group (H2O)
 SN1 Reaction of Alcohols

Mechanism : H+ + RDS + X-, Fast

R - OH R - OH2 R R-X
-OH2

Reactivity of HX : HI > HBr > HCl

Reactivity of ROH : 30 > 20 > 10

 SN1 Reaction of Alcohols

Conc. HBr
CH3CHCH3
or NaBr, H2SO4
I
OH

Isopropyl alcohol
Example Which describes the best stereochemical aspects of the following reaction?

CH3

H - Br
Et Product
Ph OH

A. Inversion of configuration occurs at the carbon undergoing substitution

B. Retention of configuration occurs at the carbon undergoing substitution
C. Racemization occurs at the carbon undergoing substitution
D. The carbon undergoing substitution is not stereogenic
 Lucas Reagent

HCI (Hydrochloric acid) reacts with alcohols in much the same way that as the hydrobromic
acid.

Chloride ion is a weaker nucleophile than bromide ion because it is smaller and less
polarizable.
 Lucas Reagent

Lewis acid, such as ZnCl2, is sometimes necessary to promote the reaction of HCl with
primary and secondary alcohols.
 Lucas Reagent

SN1 reaction with the Lucas reagent (fast)

CH3 CH3
I ZnCl2 I ZnCl2 CH3

:
H-C-O-H H - C - O+ H - C+
I I

:
H CH3
CH3 CH3

Alcohol-zinc chloride complex carbocation

 Lucas Reagent

SN1 reaction with the Lucas reagent (fast)

CH3
CH3 I
Cl-

:
H- C+ H - C - Cl + HO - ZnCl2
I

:
CH3
CH3
 Lucas Reagent

CH2CH2CH3
CH3CH2CH2 ZnCl2 I
:

: Cl : C - O+ Cl- C O+ - ZnCl2
H I
:

H H H
H H

transition state

CH2CH2CH3 ZnCl2
Cl - C :O:

H
H H
Example CH3 - CH2 - CH - CH3 Conc HCl / ZnCl2
I [X]
OH

Identify product X and the mechanism of the reaction.

A. CH3 - CH2 - CH2 - CH2 - Cl and SN1 B. CH3 - CH2 - CH2 - CH2 - Cl and SN2

C. CH3 - CH - CH2 - CH3 and SN1 D. CH3 - CH - CH2 - CH3 and SN2
I I
Cl Cl
Example Conc.HCl + Anhydrous ZnCl2
Ph - CH2 - CH - CH3 X (Major product) X is :
I
OH

A. Ph - CH2 - CH - CH3 B. Ph - CH - CH2 - CH3

I I
Cl Cl

Cl
I
C. Ph - CH2 - CH2 - CH2 D. Ph - C - CH3
I I
Cl CH3
Example What is the correct order of reactivity of alcohols in the following reaction?

R - OH + HCl + ZnCl2 R - Cl + H2O

A. Ethanol > Propan - 1 - ol > Butan - 2 - ol

B. Butan - 1 - ol > Propan - 1 - ol > Butan - 2 - ol
C. Neopentyl alcohol > t-Butyl alcohol > Methanol
D. T-Butyl alcohol > Butan - 2 - ol > Propan - 1 - ol
 SN2 Reaction of Alcohols

Reaction with HX :
The protonated unbranched primary alcohol is well suited for the SN2 reaction.

Mechanism :

H+ + X-
R - OH R - OH2 R - X + H2O
 SN2 Reaction of Alcohols

Reaction with phosphorus trihalides

● Several phosphorus halides are useful for converting alcohols to alkyl halides.
● PBr3, PCl3, and PCl5 work well and are commercially available.
 SN2 Reaction of Alcohols

Reaction with phosphorus trihalides

● Phosphorus halides produce good yields of most primary and secondary alkyl halides, but
none works well with tertiary alcohols.
● The two phosphorus halides used most often are PBr3 and the P4/I2 combination.
 SN2 Reaction of Alcohols

Reaction with phosphorus trihalides

(PX3 = PCl3, PBr3, PI3)

3R - OH + PX3 3R - X + H3PO3
 SN2 Reaction of Alcohols

Mechanism :

Step : 1

Protonated alkyl
dithiophosphate
 SN2 Reaction of Alcohols

Mechanism :

Step : 2
Example
 SN2 Reaction of Alcohols

Reaction with PCl5

Example
 SN2 Reaction of Alcohols

Reaction with thionyl chloride in presence of pyridine

Example
Example HO OH
SOCl2
Product is :
Pyridine

Cl
HO
Cl Cl
A. B.

Cl Cl Cl
HO
C. D.
Example

Product, Identify the product

A. B.

C. D.
Example
C3H7 C 3H7

K CH3OTs
C 2H 5 OH C 2H 5 OK Product

H H

C3H7 C 3H7

TsCl CH3OK
C 2H 5 OH C 2H 5 OTs Product

H H

a. Pick up the nucleophile in both reactions.

b. Write the structure of the product in the two reactions
c. Is there any relation between the two products, if yes
then mention it.
Example
C3H7 C 3H7

K CH3OTs
C 2H 5 OH C 2H 5 OK Product

H H
Example

C3H7 C 3H7

TsCl CH3OK
C2H5 OH C2H5 OTs Product

H H
SN2Th
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