Markownikoffs Rule

Markownikoffs Rule

When a hydrogen halide reacts with an unsymmetrical alkene

the hydrogen of the hydrogen halide attaches itself to the carbon
of the alkene bearing the larger number of hydrogens and
smaller number of carbons"

Addition reactions of unsymmetrical alkenes

Addition of HBr to propene CH3CH=CH2:

HBr can add in two different ways

Two products are possible:

CH3CH=CH2
HBr

Contains more
H atoms
CH3CH=CH2
BrH

CH3CH2CH2Br

CH3CHBrCH3

Minor product

Major product

Its all controlled by carbocations

H

Primary carbocation
One C joined to C+

C H
C

H
C

C H

Br
3

Secondary carbocation
Two C joined to C+

H
H

C H

C
H

Br

Br

Br

Minor product

Br

Major product

Types of carbocation
Primary carbocation

Least
stable

One carbon chains attached to C+

Secondary carbocation:

Two carbon chains attached to C+

Tertiary carbocation:

Three carbon chains attached to C+

Most
stable

Reasons for carbocation stability

Least
stable

Electron-donating ability of alkyl groups.

Each alkyl group pushes electrons towards

C+ charge of carbocation.

Primary

Positive charge is spread over alkyl groups

The more alkyl groups attached to the C+

The more the positive charge is spread out

The greater the stability of the carbocation

Secondary

Most
stable
Tertiary