6.

4
Electrophilic Addition of
Hydrogen Halides to
Alkenes
General equation for electrophilic addition

 –
C C + E—Y E C C Y
 When EY is a hydrogen halide

 –
C C + H—X H C C X
 Example

CH3CH2 CH2CH3
HBr
C C
CHCl3, -30°C
H H

CH3CH2CH2CHCH2CH3

Br

(76%)
Mechanism

Electrophilic addition of hydrogen halides

to alkenes proceeds by rate-determining
formation of a carbocation intermediate.
 Mechanism

Electrons flow from

the  system of the
alkene (electron rich)
toward the positively
polarized proton of
the hydrogen halide.
Mechanism

+C C H

.. –
:X
.. :

..
H X:
..

C C
Mechanism

+C C H

.. –
:X
.. :

..
H X:
..

..
C C :X
.. C C H
 6.5
Regioselectivity of
Hydrogen Halide Addition:
Markovnikov's Rule
 Markovnikov's Rule

When an unsymmetrically substituted

alkene reacts with a hydrogen halide,
the hydrogen adds to the carbon that
has the greater number of hydrogen
substituents, and the halogen adds to
the carbon that has the fewer hydrogen
substituents.
 Markovnikov's Rule

HBr
CH3CH2CH CH2 CH3CH2CHCH3
acetic acid
Br
(80%)

Example 1
 Markovnikov's Rule

CH3 H CH3
HBr
C C CH3 C CH3
acetic acid
CH3 H Br
(90%)

Example 2
 Markovnikov's Rule

CH3
HCl
CH3
0°C Cl

(100%)

Example 3
 6.6
Mechanistic Basis
for
Markovnikov's Rule

Protonation of double bond occurs in

direction that gives more stable of two
possible carbocations.
 Mechanistic Basis for Markovnikov's Rule:
Example 1

HBr
CH3CH2CH CH2 CH3CH2CHCH3
acetic acid
Br
 Mechanistic Basis for Markovnikov's Rule:
Example 1

+
CH3CH2CH—CH3 + Br –

HBr

CH3CH2CH CH2 CH3CH2CHCH3

Br
 Mechanistic Basis for Markovnikov's Rule:
Example 1
+
CH3CH2CH2—CH2
primary carbocation is less stable: not formed
+
CH3CH2CH—CH3 + Br –

HBr

CH3CH2CH CH2 CH3CH2CHCH3

Br
 Mechanistic Basis for
Markovnikov's Rule:
Example 3

H
CH3
HCl
CH3
0°C Cl
 Mechanistic Basis for
Markovnikov's Rule:
Example 3

H H

+ CH3 Cl –
HCl
H
CH3
CH3
Cl
 H Mechanistic Basis for
secondary H Markovnikov's Rule:
+
carbocation is Example 3
less stable:
not formed CH3
H H

+ CH3 Cl –
HCl
H
CH3
CH3
Cl
 6.7
Carbocation Rearrangements in
Hydrogen Halide Addition
to Alkenes
 Rearrangements sometimes occur

H2C CHCH(CH3)2

HCl, 0°C
H
+ +
CH3CHCH(CH3)2 CH3CHC(CH3)2

CH3CHCH(CH3)2 CH3CH2C(CH3)2

Cl (40%) (60%) Cl
 Cationic polymerization

Initiation and Propagation

The mechanism of cationic polymerization is a kind of
repetitive alkylation reaction

Electron donating groups are needed as the R groups

because these can stabilize the propagating species
by resonance. Examples:
Example:

Propagation is usually very fast. Therefore, cationic vinyl polymerizations must often
be run at low temperatures. Unfortunately, cooling large reactors is difficult and
expensive. Also, the reaction can be inhibited by water if present in more than trace
amounts, so careful drying of ingredients is necessary (another expense).
Chain Transfer Reactions
Cationic vinyl polymerization is plagued by numerous side reactions, most of which lead to
chain transfer. It is difficult to achieve high MW because each initiator can give rise to many
separate chains because of chain transfer. These side reactions can be minimized but not
eliminated by running the reaction at low temperature. Here are a few examples:
examples of commercial cationic polymers
 Cationic Polymers
Commercial and Technological Significance
Chemical Name Trade Name Formula

• Polyisobutylen Vistanex, Oppanol

• Isobutylene-isoprene copolymer
and chlorinated copolymer
~98% ~2%
Butyl Rubber
and Chlorobutyl

•Polyoxymethylene Delrin
Trioxane-epoxide copolymer Celcon
~2%
 Cationic Polymers
Commercial and Technological Significance
Chemical Name Trade Name Formula
•Polyepichlorohydrin Hydrin Rubber
Lycra or Spandex
•Poly(THF) or Poly(tetramethylene oxide)

•Polybischloromethyl Oxetane
Penton
Cationic Polymerization

the alkene monomer

reacts with an electrophile
The carbocation intermediates formed during
polymerization can undergo rearrangement
Monomers that are best able to undergo cationic
polymerization are those with electron-donating
substituents