CARBOCATIONS

VAMSI RAJASEKHARA REDDY

M.PHARMACY 1st year
(Pharmaceutical Chemistry)
CONTENTS

INTRODUCTION

CARBOCATIONS
 DEFINITION

 STABILITY

 GENERATION

 REACTIONS

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CARBOCATIONS
In Heterolytic Fission Of A C-x Bond In An Organic Molecule
The Positively Charged Carbon Species Is Called Carbocation
H
H
R C+ -
:X
R X
H H

A carbon atom which is trivalent, contains an even number

of electrons and carries a positive charge is known as
carbocation.

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STABILITY OF CARBOCATIONS
Tertiary carbocation is more than secondary carbocation
which in turn more stable than a primary carbocation.

R R H
+ + +
R C > R C > R C
R H
H
tertiary secondary primary
carbocation carbocation carbocation

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STABILITY OF CARBOCATIONS

Increase in the number of electron releasing groups

increases carbocation stability.
The more the canonical structures for carbocation, thae
more stable it will be.

+
CH2 CH2 CH2 CH2

+ +

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ORDER OF STABILITY
tropylium cation >trimethyl carbocation>benzyl carbocation> allyl
carbocation> tertiary butyl carbocation> isopropyl carbocation> ethyl
carbocation> methyl carbocation

+ CH3

+ > +
> +
CH2 > H2C CH CH2 > H3C C+
C
CH3

H3C CH
+ +
H3C CH2
+
CH3
> >
H3C

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GENETRATION OF CARBOCATIONS
• FROM ALKENES
CH3 CH3 CH3 CH3
+
+ H +
H2C CH3 H3C CH3

• FROM ALKYLHALIDES _
+

(X=I,Cl,Br)
R X R + X

• FROM DIAZONIUM IONSR N

+
N
+
R + N2

• FROM ALCHOLS + + - H2 O +
R OH + H [ROH2] R

• FROM ACYL
RCOCl
HALIDES
+
RCO ...
_
ClAlCl 3
+
RCO +
_
AlCl 4
Carbocation
(acylium ion)
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REACTIONS OF CARBOCATIONS
ELIMINATION OF A PROTON

NaNO2 + +
CH3CH2CH2NH2 CH3CH2CH2N N CH3CH2CH2 CH3HC CH2
HCl
1 Propylcation propene
1 Aminopropane Rearrangement
Propyldiazonium cation
(primary cation)

+
CH3CHCH3
Secondary cation

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REACTION WITH NUCLEOPHILES

+ .. _
H3C CH2 CH2 + :Br:
..
H3C CH2 CH2Br
n-Propyl bromide
Propyl carbocation
+ .._
H3C CH
CH2 +
:Cl:
..
H3C HC CH3
Secondary propyl carbocation Cl
isopropyl chloride

H3C CH3 + CH3

.. -H
+ +
H3C C
+ O H H3C C O H H3C C OH

H3C H CH3 H CH3

Tertiary butyl water

t-butyl alcohol
carbocation (neutral nucleophile)

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ADDITION TO UNSATURATED COMPOUNDS

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

2-methylpropene

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MOLECULAR REARRANGEMENT
+ +
Rearrangement
CH3CH2CH2 H3C CH CH3
(primary carbocation) (secondary carbocation)

CH3 H3C CH3

+ Rearrangement
H3C C CH CH3 H3C C C CH3
+
CH3 H
3,3-Dimethyl-2-butyl
2,3-Dimethyl-2-butyl
carbocation carbocation
(secondary carbocation) (tertiary carbocation)

+ + + O
.. OH
HO CH2NH2 HO CH2N2 HO CH2
.. +
NaNO2/HCl -N2 -H
0 to 5

1Aminomethyl
cyclohexanol cycloheptanone

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Stereochemistry of rearrangements

R
H
H3C R
H3C H H H
Y _ +
R CH3
: Z
H H CH3 H3C Z
H3C

H3C
H
R

H3C Z

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Friedel-craft reaction
It carried out by treating aromatic with the alkyl
halide in the presence of Lewis acid.
H CH2 R
H CH2 R H CH2 R
+ - + +
+ R CH2 Cl AlCl 3

R
H2C
H CH2 R

+
-
AlCl 4 + HCl + AlCl 3

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Wagner-meerwein rearrangement
In these rearrangements the change in the carbon skeleton
occurs through the rearrangement of carbocation
intermediate.
H3C CH3
H2SO 4 + +
1,2methylshift
H3C CH2OH H3C CH2 H3C C C2H5
-H2O
H3C CH3 CH3
+
H3C C C2H 5 H3C C C 2H 5

H3C CH3
major

+
H2C C C 2H 5

CH3
minor

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REFERENCES

ADVANCE ORGANIC CHEMISTRY REACTIONS, MECHANISMS AND

STRUCTURE BY JERRY MARCH , PG NO:165-185.

Organic name reactions and molecular rearrangements by Gurdeep raj

pgno: A-158,A332.

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