ELECTROPHILIC ADDITION

REACTIONS
Types of alkene addition reactions
 ELECTROPHILIC ADDITION
What does the term "electrophilic addition"
imply ?

An electrophile, E+, is an electron poor

species that will react with an electron rich
species such as C=C.

An addition implies that two systems

combine to give a single entity.
An electrophilic addition reaction is an
addition reaction which happens because
what we think of as the "important"
molecule is attacked by an electrophile.
The "important" molecule has a region of
high electron density which is attacked by
something carrying some degree of
positive charge.
Generalized mechanism for electrophilic addition
Addition of HX to Alkenes

+ H X H X
Mechanism for HX addition to alkenes
Reactivity of Alkenes towards Acidic
Reagents

CH3
|
CH2 = C – CH3 > CH3CH = CHCH3 ,
CH3CH2–CH=CH2 , CH3CH=CH2 >
CH2=CH2 > CH2=CHCl
 Evidence for the Mechanism
Rate of reaction depends upon the concentration
of both the alkene and the reagent.

Reaction requires an acidic reagent.

Products obtained are unexpected ones,

wherever structure permits rearrangements.

Orientation of addition as well as reactivity of

alkenes are consistent with the mechanism i.e.
formation of carbocations as an intermediate.
REGIOSELECTIVITY
WHY THIS REGIOSELECTIVITY?
 MARKOVNIKOV RULE
The addition of HX and other acidic reagents to
carbon-carbon double bond is found to form
major products in which the electrophile (proton)
is found to add to that doubly bonded carbon to
which more hydrogens are bonded.
These observations were first made by Markovnikov.
Addition of HBr to Isobutene and Markovnikov Rule
Protonation of double bond yields the most
stable carbocation
 CH3 CH3 H H3C CH3
HCl
H3C CH CH2 ? H3C Cl + Cl C CH3
H
CH3 CH3 CH3 H3C
3-Chloro-2,2-dimethylbutane 2-Chloro-2,3-dimethylbutane

H3C CH3
CH3 CH3 H
+ 1,2-methyl shift
H
H3C CH CH2 H3C C CH3
H
CH3 CH3 CH3
H3C
Cl-
Cl-

H3C CH3
CH3 H
H3C Cl Cl C CH3
H
CH3 CH3 H3C
 STEREOCHEMISTRY OF THE IONIC
ADDITION TO AN ALKENE

Achiral reactants produce achiral products.

Orientation of addition :Stereochemistry of
H-Br addition.
Br H

H Br H
H C C Br +
H 3C CH3+
H
No Control of
Stereochemistry
Br H
Br- adds to H Br
either side
of carbocation.
Regiochemistry is perfect.
Only the product from secondary
carbocation is formed.

But stereochemistry is not controlled

Addition of HBr in Presence of peroxide

H-Br

Anti-Markovnikov product
 Free - Radical addition to alkenes
Mechanism
Essence of the mechanism is that hydrogen
and bromine add to the double bond
homolytically rather than heterolytically.
The intermediate is a free radical rather than
a carbocation.
Like halogenation of alkanes, this is a chain
reaction, this time involving addition rather
than substitution.
 Free - Radical addition to alkenes
Mechanism
FACTS SUPPORTING THE MECHANISM
• A few molecules of peroxide can change
the orientation of addition of many
molecules of HBr.
• This strongly indicates a chain reaction.
• So, too, does the fact that a few molecules
of inhibitor (such as hydroquinone) are
able to prevent this change in orientation.
• The anti - Markovnikov addition is caused
not only by the presence of peroxides but
also by irradiation
• This is done with irradiation using light of
a wavelength known to dissociate HBr
into hydrogen and bromine free radicals.
You can now predict the product of the reactions
given below:
Br

Br Br
+ HBr ?

Br Peroxide Br
+ HBr ? Br
 HX addition to alkenes
The order of reactivity of the HX is
HI > HBr > HCl >HF, and unless the alkene is highly
substituted, HCl reacts so slowly that the reaction is
not useful as a preparative method.
The addition of HX to an unsymmetrical alkene can
occur in two ways.
In practice, however, one product only predominates
When a reaction, potentially can yield two or more
constitutional isomers, but yields only one of them as
the major product, then such a reaction is known as
regioselective reaction.
 Markovnikov vs Anti- Markovnikov
Addition of HBr to Alkenes

In the absence of peroxides, the reagent that

attacks the double bond first is a proton.
Because proton is small, steric effects are
unimportant.
It attacks carbon atom by ionic mechanism
so as to form the more stable carbocation.
The result is Markovnikov addition.
In the presence of peroxides, the reagent that
attacks the double bond first is the larger
bromine atom.
It attaches itself to the less hindered carbon
atom by a radical mechanism, so as to form
the more stable radical intermediate.
The result is anti-Markovnikov addition.
Addition of ICl to alkenes