CARBOCATIONS, CARBANIONS,

AND CARBORADICALS

N U R R A H M I H A N D AYA N I

CARBOCATIONS
Why are different products formed?

CARBOCATION STRUCTURE
Bond angles about the positively
charged carbon are 120
Carbon uses sp2 hybrid orbitals
to form sigma bonds to the
three attached groups

+
C

R
R

CARBOCATION STABILITY
H

H
H C+

CH3

H
Methyl
cation
(methyl)

C+

Ethyl
cation
(1)

CH3
CH3 C +
H
Isopropyl
cation
(2)

CH3
CH3 C +
CH3
tert-Butyl
cation
(3)

Increasing carbocation stability

Inductive effect :

H3 C

Hyperconjugation :

+
+
C CH
3

H3 C

CARBOCATION REARRANGEMENT
In electrophilic addition to alkenes, there is the
possibility for rearrangement
Rearrangement: any change in connectivity of
the atoms in a product compared with the
connectivity of the same atoms in the starting
material

HYDRIDE SHIFT
CH3

1.

CH3 CCH=CH2

+ H

Cl

slow, ratelimiting step

CH3

3-Methyl-1butene

CH3 C-CHCH3
H

Cl

A 2 carbocation
intermediate

CH3

2.

CH3

fast

CH3 C-CHCH3

CH3 C-CHCH3

3.

H
A 3 carbocation
intermediate

CH3
CH3 C-CH2 CH3
+

Cl

fast

CH3
CH3 C-CH2 CH3
Cl

2-Chloro-2-methylbutane

METHYL SHIFT

RING OPENING REARRANGEMENT

CARBANION

CARBANIONS
Alpha halogenations of ketones
O

O
+ Cl2,

cyclohexanone

O
C CH3

acetophenone

Cl

H+

+ HCl
2-chlorocyclohexanone

+ Br2, NaOH

O
C CH2Br + NaBr

-bromoacetophenone
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ENOLATES
Hydrogens that are alpha to a carbonyl are weakly
acidic due to resonance stabilization of the carbanion.

O
C

CH2

O
C

CH2

"enolate" anion
The enolate anion is a strong base and a good nucleophile
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CARBANION STABILITY

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CARBANION REACTIONS
Grignard reaction

O
C

OMgX
C
R

+ RMgX

Aldol condensation
dil. NaOH

CH3CH=O
acetaldehyde

OH
CH3CHCH2CH O
3-hydroxybutanal
+ H2O

OH
CH2CH=O + CH3CH O

+ H2O

O
CH3CHCH2CH O

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CARBANION REACTION
Wittig reaction
O + Ph3PCHCH=CH2

CHCH CH2 + Ph3PO

Claisen condensation
CH3COOEt

NaOEt

O
CH3CCH2COOEt + EtOH

OEt

CH2COOEt

CH3

O
C
OEt

CH3

O
C OEt
CH2COOEt

nucleophilic acyl substitution by enolate anion

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CARBORADICALS
Carbon radicals are classified as 1, 2 or 3.
A carbon radical is sp2 hybridized and trigonal planar,
like sp2 hybridized carbocations.
The unhybridized p orbital contains the unpaired
electron and extends above and below the trigonal
planar carbon.

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CARBORADICALS

The relative stability of 1 and 2 carbon radicals

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RADICAL REACTIONS
Reaction of a Radical X with a C-H Bond:
A radical X abstracts a hydrogen atom from a CH bond to from HX and a
carbon radical.

Reaction of a Radical X with a C=C Bond:

A radical X also adds to the bond of a carboncarbon double bond.

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MECHANISM OF RADICAL REACTION

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RADICAL REACTION

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RADICAL REACTIONS

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RADICAL REACTIONS

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