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Organic Reactions & Mechanisms

Module 3.1: Elimination Reactions

Elimination is the reverse of addition reaction. In this type of reactions two


atoms or groups of the same molecule are removed. The two atoms or
groups are generally on the adjacent carbon atoms of the reactant
molecule. As a consequence of the elimination reaction, a multiple bond is
created.

Some of the common elimination reactions are cited below.

i) Dehydrohalogenation of alkyl halides with alcoholic potassium hydroxide

(2 - bromo butane) (2 - butene)

ii) Ethyl alcohol, on dehydration with a strong Lewis acid, gives ethylene

(Ethanol) (Ethylene)

In these elimination reactions (in elimination, second order reaction) (E 2


reactions), the two groups to be eliminated (for example H and X in an alkyl
halide) are trans to each other and hence E2 reactions are generally trans
elimination reactions. These reactions are divided into three types. They
are
i) Elimination reactions
ii) Elimination reactions
iii) Elimination reactions

i) Elimination reactions: Groups are eliminated from the same atom.

Ex: Formation of a carbene from chloroform in the presence of a base

(Chloroform) (dichloro carbene)

ReimerTiemann reaction involves the formation of a carbene. In this


reaction, phenol reacts with CHCl3 in the presence of a base to produce
a mixture of ortho and para substituted phenol.
Mechanism:

(chloroform) (dichloro carbene)

ii) Elimination reactions: The two groups that are eliminated are on
adjacent atoms. An atom or group from -carbon atom and a proton
from the -carbon are eliminated. In all these reactions the presence of
one hydrogen on the -carbon atom is necessary.
These -elimination reactions are also known as E2 reactions or 1,2-
elimination reactions. In such elimination reactions (i.e. E2 reactions) the
two groups being eliminated (Ex: H and X atoms) are trans to each
other. Hence E2 reactions are generally trans elimination reactions. In
such elimination reactions, the more stable trans alkene is formed as a
major product.
Ex 1: Tertiary butyl bromide, when treated with alcoholic potash, gives 2
-methyl 1-butene

(2 - bromo 2 - methyl propane) (2-methyl 1-propene)

Ex 2: Hofmann Elimination:
Pyrolysis of a quaternary ammonium hydroxide salts, derived from an
amine having an alkyl group that is larger than the methyl group gives
an olefin and a 30 amine. This type of elimination is known as
Hofmann elimination reaction.
OHion acts as a strong base and it abstracts the -hydrogen of the larger
alkyl group (n-propyl group in the above example) forming a -bond.
Trimethyl amine in the given example is expelled by E2 elimination. The
Hofmann elimination reaction products are generally the least substituted
alkenes. This principle is known as Hofmann rule. When two acidic -
hydrogens are present (let us call them as Ha and Hb atoms), Ha is removed
such that the least substituted alkene is predominantly formed in the
products.

In these Elimination reactions, the more stable trans alkene is the major
product.

The Hofmann elimination is useful in

(a) the determination of the structure of naturally occurring amines like


alkaloids.

Ex: Structure of Piperidine


(b) for opening the rings in nitrogen containing compounds

Ex:

Ex 3: Saytzeff elimination:
In dehydrohalogenation and dehydration reactions, when two acidic -
hydrogens are present (Ha and Hb atoms), Hb is removed such that the
most substituted alkene is formed as a major product. This is known as
Saytzeff elimination rule.

-Elimination reactions are classified into

(a) E1 reactions and

(b) E2 reactions

(a) E1 reactions: These are non concerted reactions in which the


mechanism involves 2 steps. (a) step i) involves the formation of the
carbocation (b) step ii) formation of a multiple bond or conversion of the
carbocation into an alkene or an unsaturated compound.
Ex: t-butyl bromide gives 2-methyl propene on treatment with
alcoholic potash

(b) E2 reactions: E2 reaction is a one step reaction. It proceeds


through the transition state formation.

Ex: s-butyl bromide gives 2-butene on dehydrohalogenation.

iii) Elimination reactions: In these reactions, the first leaving group


from the -atom and the second leaving group from the -atom are
eliminated together. A three membered ring compounds result due to
cyclization.
In these eliminations, the intermediate species formed is the carbanion.

The elimination of acidic -H atom is promoted by the presence of a


positively charged substituent on the -carbon atom.

Aldol condensation is an example for the elimination of water molecule


from the aldol or -hydroxy carbonyl compounds. The formation of
aldol and the elimination of water molecule to form , -unsaturated
aldehyde is given below.
Another important application of the elimination reaction is the
preparation of coumarin.

Coumarin is a natural perfume and also used as an artificial flavouring


agent.

Assignment questions:

1. Write a note on Elimination reactions.


2. Explain E1 reactions with an example.
3. Give a short note on E2 reactions.
4. How are elimination reactions useful in chemistry? Give few
applications.