REACTION INTERMEDIATES

Carbocations

H
Heteolytic

H
X
fission

C H

C H

H
H e t e o l y t i c X R C f i s s i o n

H X R C + H

R C R

R 120 o

C R R

R R C R > R

R C H > R

H C H

CH2

CH2

CH2

CH2

H C C C H C C C H 2 2 H 2 2 H H

Stability order Tropylium cation > (C6H5)3C+ > C6H5CH2+ > Allyl carbocation
Triphenyl methyl Benzyl

(CH3)3C+ >
Tertiary butyl carbocation

(CH3)2CH+
Isopropyl carbocation

> CH3CH2+ > CH3+

ethyl carbocation methyl carbocation

 Stability of the carbocation is greater when the positive charge is in conjugation with double bond

C C R C R R

C C R C R R

C C R C R R

 Carbocation stability is also increased due to the presence of hetero atom having an unshared pair of electrons adjacent to the cationic centre

R R C O Me R

R C O Me

 Presence of cyclopropyl group increases the stability of carbocation, this is because of the conjugation between the bent orbitals of cyclopropyl ring and the vacant p orbitals of cationic carbon.

C H C C H

<
3

H C

<

Generation of Carbocations
From alkyl halides

s o l v e n t + R + X R X
X = I, Br, Cl

From diazonium ions

+ R + N R N N 2

 From alcohols

H + + R O R R O H + H
H O 2

From acyl halides

C l A l C l R C O C l R C O R C O + A l C l 3 4

A l C l 3

 Reactions of Carbocations Addition to nucleophiles

C H C H C H B r C H C H C H + B r 3 2 2 3 2 2
Addition to unsaturated compounds

CH3 H3C C CH2

CH3

CH3 CH3 H3C C H2 C

CH3 C CH3 CH3

C CH3

 Molecular rearrangements
CH3 H3C C CH3 H C +
Rearrangement

CH3 CH3 H3C C +

CH3 C H CH3

Carbanions
H
Heteolytic

H
X
fission

C H

C H

C R R R

C H 2

C H 2

C H 2

C H 2

Generation of Carbanions

Abstraction of H by base

C H 3 B a s e

C H 2

O N 2

O N 2

From unsaturated compounds

R C C H 2 N u H+

H H 2 R N u C C

From alkyl halides

E t h e r + M g R M g X R X

Reactions of Carbanions Addition reactions

O O H H C 3 C H O H C 2 H C C H 3 C H O H C 3

O C H C H C H O 2

H O 2

O H H C 3 C H C H C H O 2

Elimination reactions
O E t H P h CC H 2 H B r P h CC H 2 H B r P h CC H 2 H

Displacement reactions
O C H O C 2 5 C H 2 C H O C 2 5 O
O E t

O C H O C 2 5 C H C H O C 2 5 O

O C H O C 2 5 R B r R C H

C H O C 2 5 O