TOPIC: CARBOCATION AND CARBANION

Presented by : Muttu B Mugali

Department of Pharmaceutical chemistry
M Pharm 1st SEM

Submitted to: Dr. S. B. Biradar

Professor Department of Pharmaceutical Chemistry
HSK college of Pharmacy Bagalkot
 CONTENTS

• Reactive intermediates
• Definition
• Formation of carbocation
• Structure of carbocation
• Reactions of carbocation
• Stability of carbocation
• Application of carbocation
• References
 Reactive intermediates

These are the intermediate of the organic reactions occurs during reaction are
called reactive intermediates. Main carbon reactive intermediates are:

1) Carbocations
2) Carbanions
3) Carbenes
4) Free radicals
5) Nitrenes
6) Enamines
 CARBOCATIONS
• Carbocation is organic compound in which carbon atom having a positive charge and
three bonds is called as carbocation.
• It is also known as carbenium ion.
• The carbocation formed by the formation of heterocyclic cleavage of covalent bond.

Ex:
CH3 CH3
Heterolytic
Fission H3C C + Cl
H3C Cl
chloride
CH3 CH3

2-chloro-2-methylpropane
2-methylpropan-2-ylium
• The SN1 and SN2 Mechanism are involved in the formation of carcboaction.
• SN1 is a unimolecular reaction and SN2 is a bimolecular reaction.
• SN1 involved weak nucleophile attack and SN2 involved Strong nucleophile attack.

SN1 reaction SN2 reaction

It is a unimolecular reaction It is a bimolecular reaction.

Nucleophile not involved in the rate determining Nucleophile is involoved in the rate determining
step step.

Weak nucleophile required Strong nucleophile required

It is a two-step mechanism It is only a one-step mechanism

 SN1 Mechanism

The carbocation is formed from the removal of the leaving group.

Then nucleophile will attack to the carbocation to give the product.

Rate = k [R-X]

STEP 1
CH3 CH3
Slow
H3C C + Cl
H3C Cl

CH3 CH3

STEP 2
CH3 CH3
Fast
OH + H3C C H3C OH

CH3 CH3
 SN2 Mechanism

• It is a nucleophilic substitution reaction where a bond is broken and another is formed
synchronously.

• The rate of reaction is dependent on the concentration of both reactant and nucleophile.

• Rate = k [Nu][R-X]

CH3 CH3
H H
Br Cl
C Cl Br C Cl Br CH

H H
CH3 H
 Formation of carbocation

The carbocation will formed by,

• From alkenes
• From alcohols
• From amines
• From alkylhalides
• From diazonium ions
From alkenes
• The carbocation will be formed by reaction of alkenes with the hydrogen halides.

H
C Br
Br +
+ H bromide
propan-2-ylium
hydrogen bromide
prop-1-ene
• From alcohols:

Alcohols on treatment with concentrated acids get protonated and protonated carbocations.

R OH + HCl R + H 2O + Cl
Mechanism: H H

H OH H O

+ HCl Cl
ClH

H C C H H C C H +

H H H H

H H

H H O

H2O H C C H H C C H
+

H H H H
 From amines
• The carbocation will be formed by reaction of primary amines with the nitrous acid.

NH2

N HCl
+ HO O N N
propan-2-amine nitrous acid propane-2-diazonium

N N CH + N

propane-2-diazonium dinitrogen
propan-2-ylium
 From Alkyl halides

• Ionization of alkyl halides gives carbocation.

Cl Cl
CH2
+
propan-1-ylium chloride
1-chloropropane
 From Diazonium ions
• The diazonium ions are unstable at room temperature and get decomposition to form
carbocations.

Cl
CH2 +
N N
-N2 chloride
propan-1-ylium
propane-1-diazonium
Structure of Carbocation
• It is SP2 hybridized and it used it’s a 3 bonds to form bonds with others.
• The remaining SPz orbital is perpendicular to the plane of other 3 bond.
• It is planar in nature (trigonal planar).
• It’s bond angle is 120º.

empty p orbital
C R
 Stability of carbocation

• Inductive effect:
The alkyl group has electron withdrawing group (+I effect), hence the stability of
carbocation will increases as the EDG will attached to the carbocation.
hence, the order of stability of the carbocation is as follows.

H
CH3 H

H3C C
H3C C > H C CH3
> >
CH3
CH3 CH3
tertiory carbocation methyl
Seconadry carbocationA ethylium carbocation
Resonance effect:
Carbocation is +vely charged carbon atom is attached to a double bond or triple bond
or a benzene ring are stabilized by resonance.

CH2 CH2 CH2

CH2 CH2

As the no. of phenyl group attached to the carbocation there is increase in the no. of
resonance structures and also increases the stability.
 Reactions of carbocations:
• Elimination of a proton: A carbocation may remove of a proton from the adjacent
atom forming a double bond.
H H

H C O H H C + H
O
• Reaction with nucleophiles:
A carbocation may combine with a nucleophile to form a new bond.Propyl
carbocation on reaction with Br- forms n-propyl bromide.

H2 H2
H3C C CH2 + Br H3 C C CH2Br

Propyl carbocation n-propyl bromide

Addition reaction:

A carbocation may react with an alkene to produce another carbocation.

CH3 CH3 CH3 CH3

H2
H3C C CH2 + C CH3 H3C C C C CH3

CH3 CH3
2-Methylpropene
2-methylpropan-2-ylium 2,4,4-trimethylpentan-2-ylium
• Addition to unsaturated compounds:
A carbocation may react with an alkene to produce another carbocation.

CH3 CH3 CH3 CH3

H2
H3C C CH2 + C CH3 H3C C C C CH3

2-Methylpropene CH3 CH3

• Molecular rearrangements:
A carbocation undergoes molecular rearrangement to produce a more stable carbocation.

1. A primary carbocation on rearrangement gives a more stable carbocation(secondary or

tertiary carbocation).

Rearrangement H
CH3CH2CH2 H3C C CH3
1- Carbocation 2-Carbocation
2.A secondary carbocation on rearrangement gives a tertiary carbocation.

CH3 CH3 CH3

H Rearrangement
H3C C C CH3 H3 C C C CH3

CH3 H
3,3-Dimethyl-2-butyl carbocation 2,3-Dimethyl-2-butyl carbocation
2- carbocation 3- carbocation

The above rearrangements take place either by migration of a hydrogen with its pair of
bonding electrons or by migration of an alkyl group with its pair of bonding electrons. The
former is called hydride shift and later is called alkyl shift. The rearrangements in which the
migrating group migrates from One atom to very next atom is called 1,2-shift.
 Applications
• Markownikoff's rule

The rule state that with the addition of a H-X to an asymmetric alkenes, the hydrogen gets
attached to the carbon with the more number of hydrogen and the halide group get attached
to the carbon with more alkyl substituent.
• Friedel crafts reaction:

Benzene will reacts with acid chloride in presence of AlCl3 to form substituted benzene
along with HCl.

C CH3
O
AlCl3
+ + HCl
H3C C Cl

Benzene Acetophenone
Baeyer-villiger oxidation:

• Ketones react with peracids to give esters by insertion of oxygen.

O
R
C6H5COOOH + C6H5COOH
C O R C OR

Mechanism:
O
R
R
C O C6H5 C O O
C OH
R R

O
O O OC6H5
R
+ C6H5COO + H
C R C OR
O H
R
 CARBANIONS
• Negatively charged ion in which a carbon atom exhibits trivalence and contains –ve
charge.
• Due to the presence of unshared paired electron it is acts as neucleophile.
• Carbanions are formed when a carbon atom loses electrons.
• This can happen when a carbon atom bonds with a more electronegative atom such
as oxygen or nitrogen.
• The carbon atom will have a partial negative charge and the other atoms will have
partial positive charges.

H H

heterolytic
H C H H C H
fission
H H

Methane Carboanion
• Structure of Carbocation

 Carbanions are trigonal pyramidal around carbon bearing the –ve charge.

 Carbon with –ve charge is in sp3 hybridization with 3 hybrid orbital forming bonds
and fourth hybrid orbital containing lone pair of electrons.

H3C CH3
CH3

Carbanion
 FORMATION OF CARBANION

Carbanions have been generally as intermediates in a large number of organic

reaction

a) Abstraction of H by base
An appropriate organic substrate having a C - H bond on treatment with suitable
base result in abstraction of hydrogen to generate a carbanion.

O O

H2 NH3
H3C C C CH3 NH2 H3C C CH CH3

Butane-2-one Carboanion
 Stability of carbanion

• Before we discuss the stability of carbanions , we need classify

them on the basis of saturation.
• The first is alkyl carbanion which are give below.

CH3

CH3 CH3 CH2 CH3 CH

H3C C
CH2
CH3

Methylcarbation Ethyl tert-butyl

Isopropyl
carbation 1 carbation(3)
carbation 2
• The carbanion being electron rich are very reactive intermediates and are readily
attacked electrophile
• The stability of carbanion is increased if electron attacking group is present in the
molecule
• The stability of carbanion is decreased if electron releasing
group is present in the molecule.

 Factors effect on stability

i. On the basis of hybridisation.

ii. Stability of carbanions with electron –withdrawing group.
 Stability of carbocation

• Inductive effect:

The alkyl group has electron withdrawing group (+I effect), hence the stability of
carbanaion will increases as the EWG will attached to the carbon atom. Hence the order
of stability of the carbocation is as follows.

CH3

CH3 CH3 CH2 CH3 CH

H3C C
> > >
CH3
CH3

Methylcarbation Ethyl tert-butyl

Isopropyl
carbation 1 carbation(3)
carbation 2
• Hybridization.

 Hence we can say that as the character of carbon bearing negative charge increases, the
lone pair gets better stabilization and therefore overall carbanion stability also increases.

HC C > H2C CH > H3C CH

sp sp2 sp3
 REACTIONS

1) Addition reaction
The carbanion being electron rich behaves like nucleophile these add to the carbonyl
group of aldehyde (or) ketone .

O
O H O
H3C C H
CH3 C H CH2 C O H3C C CH2CHO
H
Carbanion
Acetyldehyde
H2O

OH

H3C C CH2CHO
H
3 Hydroxy butanal
2)Elimination reaction

Phenylethyl bromide on the treatment with a suitable base like (NaOEt) result in the
formation of styrene. The reaction proceeds the formation of carbanion intermediate.

OEt
H
Slow
C6H5 C CH2 C6H6 CH CH2

H Br Br
Phenyl ethyl bromide Crbanion

C6H 5 C CH2
H
Styrene
3) Rearrangement Reaction

Like carbocations, the carbanion can also undergo rearrangement reaction although it is
not very common.

C6H5 C6H5
H2
C6H5 C CH2 C6H5 C C C6H5

C6H5
• Application of carbanion

1. Perkin Reaction
The condensation of aromatic aldehyde with anhydrides is called as Perkin
reaction.
In this reaction formation of α,β -unsaturated acid

H
(CH3CO)2O
CH3COONa COOH
Benzyl dehyde a,ß unsaturated acid
Mechanism of Perkin reaction.

Step 1)

H
O O
C CH2 C CH2
CH3COONa
O O CH3COOH
175 c
C CH3 C CH3
O O

Acetic anhydride
Step2)

O H

C CH2
H-OH
O

C CH3
O

Acetic anhydride Benzyldehyde

OH
O O
H
C C C
C C C -H2O
H H
O O H H

C CH3 CH3
O
O

H2O

HOOC C C CH3COOH
H

Cinnamic acid
3) Aldol condensation reaction

Two molecule of acetaldehyde combine with each other in the presence of dilute NaOH
to form 3 – Hydroxybutanal

OH O
O
OH H2
2 CH3 H3C C C C H
C H H

2 Acetyl dehyde Hydroxy butanal

4) Cannizaro reaction.

Aldehyde which lack an alpha hydrogen, when heated with concentrated NaOH
undergo a disproportionation reaction . One half of the aldehyde molecule are oxidized to
a carboxylic acid one half are reduced to an alcohol this reaction is known as Cannizaro
reaction.

H O

2 NaOH CH3OH H C O Na
H C H
Formyldehyde Methnol
Sodium formate
 References

1. V K Ahuluwalia and R K Parashar. Organic reaction mechanisms. 2nd –ed. Daryaganj,

New Delhi: N.K. Mehra for Narosa Publishing house; 2005, Pg no.12-18 and 78-86.
2. Jerry March. Advanced organic chemistry: reactions, mechanisms and structures. 4th –ed.
Daryaganj, Ansari road, New Delhi: Willey India Pvt.Ltd.2010, Pg no. 165-174.
3. John M. Beale,Jr. And John H. Block. Organic medicinal and pharmaceutical chemistry.
12th –ed.
T HA N K Y O U