Lecture - VII

Mechanism Of Organic Reactions….

• Introduction to Elimination Reactions

Date : 2079 – 03 - 21
• Types of Elimination Reactions
• Bimolecular Elimination Reaction (E2 )
• Mechanism of (E2 )
• Important Points of (E2 )
• Bimolecular Elimination Reaction (E1 )
• Mechanism of (E1 )
• Important Points of (E1 )
• Saytzeff’s Rule
• Factors governing E1 & (E2 ) 1
 Elimination Reactions
Elimination Reactions
The reactions which involve the removal of two atoms or
groups from a molecule are called elimination reactions.
The elimination of two atoms or groups may occur from
same atom or different atoms in molecules. On the basis of
mode of removal of atoms or groups the reactions may be
classified as
1.α-Elimination or 1,1-elimination: When two atoms are
removed from the same carbon atom the reaction is called
α-Elimination or 1,1-elimination. For example, formation of
dichlorocarbene from chloroform in presence of base.

The atoms removed are

dichlorocarbene
encircled by red borders 2
 Elimination Reactions…
2.β- Elimination or 1, 2- elimination: When two atoms or
groups are eliminated from two adjacent (α and β) carbon
atoms of a molecule the reaction is called β - Elimination.
This results in the formation of π bonded system. For
example, dehydrohalogenation of alkyl halide.
Removal of halogen from alpha carbon and
elimination of H-atom from beta carbon

Or 1- bromopropane Or propene
It involves breaking or two sigma bonds and formation of
one pi bond.
This type of elimination is the most common and is classified into
two types. Alcoholic KOH – As a base , so it abstracts
from proton (H+) from beta-carbon 3
 Elimination Reactions…
Like SN2
& SN1
Bimolecular Elimination Reaction or E2 Reaction: When the rate
of elimination is dependent on the concentration of a substrate
and a base, the reaction is second order and is designated as E2.

Rate α [Substrate] [base]

Example of E2 reaction: Dehydrohalogenation of 10 or primary

alkyl halide by alcoholic KOH. For this reaction the alkyl halide
should contain β-carbon.

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Bimolecular Elimination (E2)

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 Bimolecular Elimination (E2)…
Mechanism of E2 Reaction: Like SN2 reaction, E2
reaction involves one step in which abstraction of a
proton (H+) by a base from β-carbon and
elimination of halide ion from α-carbon occurs
simultaneously. This is rate determining step which
involves both alkyl halide and base.

Base : From Alcoholic KOH or NaOH

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7
 Unimolecular Elimination (E1)
Unimolecular Elimination Reaction or E1 Reaction: When
the rate of elimination is dependent on the concentration
of substrate and independent of a base, the reaction is
first order and is designated as E1.
Rate α [Substrate]
Example of E1 Reaction: Dehydrohalogenation of 3 0 or
tertiary alkyl halide by alcoholic KOH.
Acts a base

Alcoholic
A base abstracts one H + from
one beta carbon atom
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 Unimolecular Elimination (E1)
Unimolecular Elimination Reaction or E1 Reaction: When
the rate of elimination is dependent on the concentration
of substrate and independent of a base, the reaction is
first order and is designated as E1.
Rate α [Substrate]
Example of E1 Reaction: Dehydrohalogenation of 3 0 or
tertiary alkyl halide by alcoholic KOH ( Acts as a base).

Alc.
Base abstracts one H+ from one
of the - carbon atoms of the
alkyl halide.
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 Unimolecular Elimination (E1)…
Mechanism of E1 Reaction: Like SN1 reaction, E1
reaction involves two steps.
Step I: Ionization of the alkyl halide to form carbonium
ion or carbocation. This step is slow so called the rate
determining step which involves only the haloalkane. The
carbonium ion formed is planar since the central carbon
is sp2 hybridized.

Tertiary butyl bromide Tertiary or 3 o

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or 3 o Alkyl halide carbonium ion
 Unimolecular Elimination (E1)…
Step II: The base abstracts β- proton (the H-atom attached
to β-carbon) of the carbonium ion to form alkene (2-methyl
propene).This step is fast

t Base

β- proton

β-carbon

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 Two -step

in more than
one step.

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 Saytzeff ‘s Rule

More substituted double bond product – the product having alkyl

groups on both sides of double bond. 13
 Saytzeff ‘s Rule…

CH3

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 Factors Affecting E2 and E1 Reactions
• Nature of base: Strong base & its higher concentration
favors E2 reaction mechanism because the rate of E2 is
dependent upon the concentration of substrate and the
base which abstracts proton from substrate molecule.
Low concentrated and even weaker base favors E1
reaction because the rate of E1reaction does not depend
upon the concentration the base since it does not directly
abstract the proton from the substrate.
• Nature of solvent: Highly polar solvent favors E1 reaction
because it proceeds by ionization whereas non polar
solvent favors E2 reaction because it does not involve
ionization . 15
 Factors Affecting E2 and E1 Reactions…
Nature of substrate: Dehydrohalogenation of primary or
1 o alkyl halide favors E2 reaction mechanism but
dehydrohalogenation of tertiary alkyl or 3 o favors E1.
Dehydrohalogenation of secondary alkyl halide may occur
either by E2 or E1.
Nature of leaving group : All leaving groups favor E2 and
E1 reaction mechanism but good leaving group favors E1
since at the first step of E1 reaction mechanism, ionization
occurs so the leaving group will be kicked out from the
substrate carbon .
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 Differences Between E2 & E1 Reactions
E 1 Reaction E 2 Reaction
• Unimolecular reaction with • Bimolecular reaction with
first order kinetics order second order kinetics
Kinetics. • One- step mechanism.
• Two -step mechanism. • No reactive intermediate is
• Reaction proceeds - the formed.
formation of carbocation. • Increasing the polarity of
• Increasing the polarity of solvent slightly decreases the
solvent increases the rate of rate of E2 reaction. However,
E1 reaction. Polar protic the polar aprotic solvents
solvent increases the rate of increase the rate of E2reaction.
E1 reaction. • Strong bases increase the rate
• Strength of base does not of E2 reaction.
affect the rate of E1 reaction. • Rate α [Substrate][base]
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• Rate α [Substrate]
 Questions on Elimination Reactions
• Write the mechanism of unimolecular elimination
reaction. How does it differ from bimolecular elimination
reaction? 2067 [3+2]
• Explain the reaction mechanism involved when primary
alkyl halide react with alcoholic alkali and aqueous alkali.
2067 [5]
• What do you mean by Elimination reactions? Explain the
reaction mechanism for the reaction between primary
alkyl halide and alcoholic NaOH. 2070 [2+3]
• What is elimination reaction? Explain the reaction
mechanism for the dehydrohalogenation of primary alkyl
halide. 2074 [1+4]

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 Questions on Elimination Reactions…
• Explain reaction mechanism for dehydrohalogenation of
tertiary butyl bromide. What solvent favors the reaction
mechanism? 2073 [3+2]
• What do you mean by Elimination reactions? Explain the
reaction mechanism for the dehydrohalogenation of
tertiary alkyl halide. 2072 [2+3]
• Explain E2 and E1 reactions with reference to
dehydrohalogenation of haloalkane and point out the
factors affecting these mechanism. 2072 [1.5+1.5+2]
• What is elimination reaction? Mention the differences
between E2 and E1 mechanism with examples. 2076 [1+4]

•
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 Questions on Reaction & Isomerism-078
Explain E1 reaction with reference to dehydrohalogenation of
haloalkane and give an account of Saytzeff’s rule [3+2]
Why does SN1 reaction give both retention and inversion isomers?
Explain SN2 reaction mechanism with reference to hydrolysis of alkyl
halide [ 2+3]
Isomerism -078
Draw all the possible stereoisomers of 3-bromobutane-2-ol and
specify whether they are optically active or not. Identify all the
possible enantiomers and diastereomers. Does the presence of two
chiral carbons atoms always make the molecule optically active ?
Explain giving examples. [3+2]
Assessment questions-079
Explain SN2 reaction mechanism with a suitable example. Give
possible isomers of 2,3-dichloropentane. Specify the enantiomers
and diastereomers with reasons. [2+3]
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