"Kinetic versus Thermodynamic

Control of Addition Reactions to

Conjugated Dienes"
Sean Boson, Ph.D.
City College of New York

Classes of Dienes

Isolated diene
1 ,4 - P e n ta d ie n e

Conjugated diene
1 ,3 - B u ta d ie n e

Cumulated diene

H 2C = C = C H

1 ,2 - P r o p a d ie n e

Addition of Hydrogen Halides to Conjugated Dienes

Conjugated dienes add same electrophiles as simple alkenes do. Although
isolated dienes undergo addition reactions in the same manner as individual
alkenes do, the reaction of conjugated dienes is somewhat different.
H B r
ro o m te m p e ra tu re

Br

1 -B u te n e

2 -B ro m o b u ta n e

H B r
ro o m te m p e ra tu re

Br

1 ,4 - P e n ta d ie n e

4 -B ro m o -1 -p e n te n e

H B r
ro o m te m p e ra tu re
1 ,3 - B u ta d ie n e

Br

Br
3 -B ro m o -1 -b u te n e

1 -B ro m o -2 -b u te n e
3

Other electrophiles, such as HCl, or Br2 react with conjugated dienes similarly.

This unusual behavior of 1,3-butadiene can be attributed to the stability and

delocalized nature of the intermediate allylic carbocation. Lets look at the
mechanism for the reaction of 1,3-butadiene with HBr,
Step 1

..
B. .r

..
..

..

..

..
.B . r

A n a lly lic c a r b o c a tio n

e q u iv a le n t to

Step 2
_

..
..

..
.B. r

Simple addition

Br
Br

Conjugate addition
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Kinetic vs Thermodynamic Control

Not only does a conjugated diene give a mixture of two different reaction
products, namely, the 1,2- addition product (or simple addition) and 1,4addition product (or conjugate addition), the relative proportion of the two
products depends on the temperature at which the reaction is carried out.
1,2-addition

1,4-addition

When the product mixture formed at the lower temperature is brought to

the higher temperature, the relative amounts of the two products change.
This new reaction mixture eventually contains the same proportion of
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products given by the reaction carried out at the higher temperature.

It can be shown that at the higher temperature the 1,2addition product rearranges to the 1,4-addition
product and that an equilibrium exists between them.

Because this equilibrium favors the 1,4-addition

product, that product must be more stable.
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At elevated temperatures, the mechanism for this

inter-conversion at equilibrium can be shown as:

1 ,2 - a d d itio n p r o d u c t
fo r m e d fa s te r

1 ,4 - a d d itio n p r o d u c t
m o r e s ta b le

This step determines the

regioselectivity of the reaction.

Energy diagram showing relationship of kinetic control to

thermodynamic control in addition of HBr to 1,3-butadiene.

The summary of Explanation

In the competing reaction pathways, the relative amount of reaction products
(1,2-addition product and 1,4-addition product) is determined in one instance
by the relative rates of reactions, and in another instance by the relative
stabilities of the final products.
At the lower temperatures,
the relative amounts of the products of the addition are determined by

the relative rates at which the two additions occur; 1,2 addition occurs
faster so the 1,2-addition product is the major product.
this is because at low temperature, a larger fraction of collisions

between the intermediate ions has enough energy to cross lower

barrier (leading to the 1,2 product), and only a very small fraction of
collisions has enough energy to cross the higher barrier (leading to the
product).

1,4

in either case (1,2 or 1,4), whichever barrier is crossed, the product

formation is irreversible because there is not enough energy available

either product out of its deep potential energy valley.

to lift

Since 1,2-addition occurs faster, the 1,2 product predominates and the

reaction is said to be under kinetic control.

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At the higher temperatures,

the intermediate ions have sufficient energy to cross both
barriers with relative ease.
both reactions are reversible. Sufficient energy is also available
to take the products back over their energy barriers to the
intermediate level of allylic cations and bromide ions.
the 1,2 product is still formed faster, but, being less stable than
the 1,4 product, it also reverts to the allylic cation faster.
the relative proportion of the products reflect the relative
stabilities of the products themselves.
since the 1,4 product is more stable, it is formed at the expense
of the 1,2 product, the change from 1,2 product to 1,4 product is
energetically favored.
such a reaction is said to be under thermodynamic control.

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Overall Relative Stabilities of Alkenes

Studies of numerous alkenes reveal a pattern of stabilities that is
related to the number of alkyl groups attached to the carbon
atoms of the double bond. The greater the number of attached
alkyl groups (i.e., the more highly substituted the carbon atoms of
the double bond), the greater the stability. The general order is:

>

>

R
R

H
H

>

R
H

H
R

>

>

>

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Before leaving this I should point out that the numbers in the terms
1,2- and 1,4-addition refer to carbons within the C = C C = C
structural unit wherever it may be in the molecule and not to the
IUPAC numbering. For example, 1,2- and 1,4-addition to 2,4hexadiene would involve the carbons shown below.

1 ,2 - a d d itio n

HCl

Cl

ro o m
te m p e ra tu re

1 , 4 - a d d it io n

Cl

4 - C h lo r o - 2 - h e x e n e

2 - C h lo r o - 3 - h e x e n e

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Conjugated trienes often show 1,6-addition. For example,

the addition of HBr to 1,3,5-cyclooctatriene.

H Br

4 0 oC
Br

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End

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The End
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Regioselective Reaction
Regio comes from the Latin word regionem meaning direction. When
a reaction that can potentially yield two or more constitutional
isomers actually produces only one (or a predominance of one), the
reaction is said to be regioselective.
For example, the Markovnikov additions of hydrogen halides to
alkenes.

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Markovnikovs Rule
Original statement of the Markovnikovs rule is:
In the addition of an reagent like, HX to an alkene, the
hydrogen atom adds to the carbon atom of the double bond
that already has the greater number of hydrogen atoms.

Modern statement of the Markovnikovs rule is:

In the addition of an unsymmetrical reagent to a double
bond, the positive portion of the adding reagent attaches
itself to a carbon atom of the double bond so as to yield
the more stable carbocation as an intermediate.
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Mechanism for Markovnikov Addition Reaction

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Energy diagram for the addition of HBr to propene.

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