UNIT-7

Lesson Structure

7.0 Objective
7.1 Introduction
7.2 The E2 (Elimination Bimolecular)Reaction
7.3 Effects of the structure of the substrate, strength and
concentration of the base, and effect of the leaving group
on the rate of the E2 Reaction
7.4 E1 (Unimolecular Elimination) Reaction
7.5 Effects of the structure of substrate, strength of base, nature
of leaving group and solvent on the rate of E1 reaction
7.6 E1cb Reaction
7.7 Solved Examples
7.8 Model Question

7.9 References

7.0 Objective
Objective of this unit is to study the removal of two atoms or two groups or one atom
and one group from the molecule.

7.1 Introduction
Few organic reactions give a 100% yield of a single product. The reason for this is
that it is uncommon to find a set of reaction conditions which will permit one reaction to
occur to the total exclusion of another. Nucleophilic substitution reaction are no exception.
They complete for starting material with elimination reactions. Indeed proper selection of
reagents and the reaction conditions may actually result in more starting material undergoing
elimination than substitution.

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 AROMATIC NUCLEOPHILIC SUBSTITUTION REACTION

The most common type of elimination reaction is one in which two fragments are
removed from a substrate to produce a modified substrate and two small units. One of these
fragments is usually the leaving group of the substrate. Eliminations usually produce a new
pi-bond in the modified substrate.

CH 3  C H  CH 2  L  CH 3  CH  CH 2  H   L
 
|
H
leaving -bond in
group the product

7.2 The E2 (Elimination Bimolecular) Reaction

The reaction of ethyl bromide with ethoxide ion is an example of an E2 reaction. It is

a second order reaction because the rate of reaction depends on the concentration of both
alkyl halide and base. It is called E2 reaction : E for elimination and 2 for bimolecular.

CH 3  CH 2  Br  C 2 H 5 O 
 CH 2  CH 2  C 2 H 5OH  Br

Rate = K [alkyl halide] [base]

The rate law tells us that ethyl bromide and ethoxide ion are both involved in the
transition state of the rate determining step of the reaction. The following mechanism agree
with the observed second order kinetics.

OC2H5
OC2H5
H H
Slow step
CH2 – CH2 CH2 CH2
X X

CH2 = CH2 + C2H5OH + X

Scheme 7.1 Mechanism of E2 reaction.

The E2 reaction is a concerted, one step reaction, the proton and the bromide ion are
removed in the same step. i.e., in the rate determining step.

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 AROMATIC NUCLEOPHILIC SUBSTITUTION REACTION

An energy profile for the reaction is given in figure 7.1

T.S.
(I)
Energy

CH2 = CH2 + C2H5OH + X

CH3 – CH2 – X + C2H5O

Progress of the reaction

Fig. 7.1 The E2 reaction. The reaction of ethyl halide with ethoxide ion.

An experimental evidence that is helpful in determining the mechanism of a reaction

via a kinetic isotope effect, can be used to demonstrate that a carbon-hydrogen bond is broken
in the rate determining step.

When the rate constant (KH) for elimination of H and Br from 1-bromo-2 phenylethane

at 40°C is compared with the rate constant (KD) for climination of D and Br from 1-bromo-
2,2- dideuterio-2 phenyl ethane determined at the same temperature, KH is found to be 7
times KD. so the deuterium kinetic isotope effect 7.1 which is primary kinetic isotope effect.
The fact that the hydrogen containing compound undergoes elimination faster than the
deuterium containing compound tells us that the carbon-hydrogen (or C-D) bond is broken in
the rate determining step agrees with the mechanism proposed for an E2 reaction.

C6 H 5CH 2 CH 2  Br  C 2 H 5 O  KH
  C 6 H 5 CH  CH 2  Br + C2H5OH

KD
C6H5 – CD2 – CH2Br + C2H5 O   C6H5 – CD = CH2 + C2H5 OH + Br

KH
 7 .1
KD

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 AROMATIC NUCLEOPHILIC SUBSTITUTION REACTION

7.2.1 Direction of Elimination

When only one type of -hydrogen is present the direction of elimination is certain.
For example, all of the hydrogens adjacent to the carbon bearing bromine in isopropyl bromide
are equivalent. Therefore, the loss of HBr from isopropyl bromide can produce only one
compound, propene.

Br
|
CH 3  CH  CH 3 
 CH 3  CH  CH 2
'  propene

When all -hydrogens cannot be equal, the alkene normally produced is the most highly
substituted one, i.e,. the one with the largest number of alkyl groups bonded to the double
bond, this statement is known as saytzeff rule. Saytzeff pointed out that the most substituted
alkene product is obtained when a proton is removed from the -carbon that is bonded to the
fewest hydrogens. Most dehydrohalogenations follow this rule, thus, an E2 reaction is
regioselective, more of one constitutional isomer is formed than the other.

Br
C H OH
CH 3  CH 2  CH  CH 3  C 2 H 5 O 2 5  CH 3 CH 2 CH  CH 2 
|

1 Butene 20%
CH 3 CH  CH  CH 3
2 Butene 80%
Formation of major product of the reaction can be explained by the mechanism as
follows we know that 2-butene is more stable than 1-butene. In the transition state leading to
an alkene the C-H bond and C-Br bonds are partially broken and the double bond is partially
formed, giving the transition state an alkene like structure. Because the transition state has
an alkene like structure, the transition state leading to 2-butene is more stable than the
transition state leading to 1-butene for the same reason that 2-butene is more stable than 1-
butene. The more stable transition state allows 2-butene to be formed faster than 1-butene.
 
Br Br
CH3 = CH CH – CH3 CH3 = CH2 – CH – CH2
H H

OC2H5 OC2H5
 
Transition state leading to Transition state leading to
2-butene (more stable) 1-butene (less stable)

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 AROMATIC NUCLEOPHILIC SUBSTITUTION REACTION

Alkyl halides have the following relative reactivities in an E2 reaction, because

elimination from a tertiary alkyl halide typically leads to a more highly substituted alkene
than elimination from a secondary and elimination from a secondary alkyl halide leads to a
more highly substituted alkene than elimination from a primary alkyl halide.
Relative reactivities of alkyl halides in an E2 reaction.
tertiary alkyl halides > Sec alkyl halides > primary alkyl halides.
In most of the dehydrohalogenation reactions, the major products are the saytzeff product.
But the most substituted alkene is not always the major product. In some cases the major alkene
product is the least substituted alkene. Elimination in which least substituted alkene is the major
product is known as Hofmann elimination and the rule is known as Hofmann rule. Thus if a reaction
produces more of the less highly substituted alkene it is following Hofmann rule.
Hofmann elimination reaction takes place in the following four cases :
(i) When the base is bulky.  
(ii) When the leaving group is a poor leaving group such as F, R 3 and S R 2
N
(iii) Steric hindrance at -carbon, and
(iv) When the alkyl halide contains one or more double bonds.
Example.
F
|
1. CH 3  CH 2  C H  CH 3  CH 3 O 
 CH 3CH  CH  CH 3 + CH3CH2CH = CH2
(poor leaving group) 30% 70%
CH3 CH3
| |
2. CH 3  C  CH 2  CH 3  CH 3  C  O 

| |
Br CH 3
(bulky base)
CH 2  C  CH 2  CH 3  CH 3  C  CH  CH 3
| |
CH3 CH3
78% 20%
CH3 CH3
CH 3  C  CH 2  C  CH 3  C 2 H 5 O 

| |
3.
| |
CH3 Br
(Steric hindrance at -carbon)
CH3 CH3 CH3
CH 3  C  CH  C  CH 3  C  CH 2  C  CH 2
| | |

| | | |
CH3 CH3 CH3 CH3
12% 88%

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 AROMATIC NUCLEOPHILIC SUBSTITUTION REACTION

CH3
4. CH 2  CH  CH 2  CH  CH + CH3 O 

|
CH3
Br
(Alkyl halide contains a double bond)
CH3 CH3
CH2 = CH – CH = CH – CH + CH2 = CH – CH2 – CH = C
CH3 CH3
80% 20%

7.3 Effects of the structure of substrate,strength and concentration of

the base, and effect of leaving group on the rate of the E2 reaction
Structure of substrate :
It has been found that branching at  and -carbons increases the rate of the E2 reaction.
This is because as the number of substituents increases on the carbon atoms of the developing
double bond, the stability of transition state increases (table 7.1).
Table 7.1 Substrate structure and rate of E2 reactions.
Substrate % yield Rate of 25°C
CH3CH2Br 0.9 1.0 × 10 5


CH 3  CH  Br
|
CH 3
(branching at -carbon) 80.3 2.3 × 105

CH 3
|
CH 3  C  Br 97 4.7 × 105
|
CH 3
(branching at -carbon)

CH 3 C H 2 CH 2  Br 8.9 5.3 × 105

(branching at -carbon)

CH 3  CH  CH 2  Br 59.5 8.5 × 105
|
CH 3

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 AROMATIC NUCLEOPHILIC SUBSTITUTION REACTION

Table 7.1 shows that branching at  or  carbon increases the yield as well as rate of
the E2 reaction. This table also shows that 30- halides are more reactive than secondary alkyl
halides which are more than the primary alkyl halide.
30 > 20 > 10
Since the transition state of an SN2 reaction involves high steric strain, the  and 
branches slow down the SN2 reaction rate while they speed up the E2 reaction rate. Thus,
with increasing branching at  and  carbons, the E2/ SN1 ratio increaeses.
It has also been found that the electron withdrawing groups on the -carbon increase
the rate of E2 reaction. This is because the -I group on -carbon increases the acidity of the
-hydrogens and stabilises the carbanion character of the transition state.
The nature of the leaving group
In general, the better the leaving group, the higher is the rate of the E2 reaction. Thus,
when -phenylhalides are treated with sodium ethoxide in ethyl alcohol, the rate of E2 reaction
increases with the leaving power of the halogen atom.
Table 7.2 Leaving groups and rate of chemical reaction.
Substrate Rate at 25°C
C6 H5 CH2 – CH2 – Cl 0.007 × 103
C6 H5 CH2 CH2 Br 4.2 ×103
C6 H5 CH2 – I 27 × 103
It has also been found that with the increasing size of the halogen atom E2/SN2 ratio
increases but to a minimum extent.
Strength of the base :
With the increasing basicity of the added base, the rates of the E2 reactions have been
found to increase. The order of basicity among OH , C2H5 O and NH2 is :

N H2 > C2H5 O > OH

The rate of E2 reactions on a given substrate with the above bases under identical
conditions is also found to be :

NH2 > O C2H5 > O H

Thus, the order of basicity is also the order of the rate.

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 AROMATIC NUCLEOPHILIC SUBSTITUTION REACTION

When the base is weak but strongly nucleophilic toward carbon, E2/SN2 ratio is low
but in the presence of a strong base the E2/SN2 ratio increases.
The effect of temperature :
As the temperature of reaction increases the rate of reaction increases.
The nature of the Slovent :
The field of the product in E2 reaction increases with the decrease in solvent polarity
because this favours the formation of the transition state of the reaction. Thus, the E2/SN2
ratio in the reaction of 2-bromo propane at 50°C with sodium hydroxide has been found to
increase as the solvent polarity decreases.

Solvent E2/SN2 ratio

60% C2H5OH and 40% HOH 1.17

80% C2 H5OH and 20% HOH 1.44

100% C2H5 OH 2.45

7.4 E1 Unimolecular Elimination Reaction

The reaction of tert-butyl bromide with sodium hydroxide is a first order elimination
reaction because the rate of reaction depends only on the concentration of the alkylhalide. It
is called an E1 elimination :E for elimination and 1 for unimolecular.

 CH3
|
CH 3  C  Br  O H 
 CH 3  C  CH 2  Br + HOH
| |
CH3 CH 3

Rate = K [alkyl halide]

Since reaction is unimolecular reaction, the reaction must be at least two step reaction.
An E1 reaction is a two step reaction. In the first step the alkylhalide dissociates
heterolytically. This step is the rate determining step of the reaction. In the second step of
the reaction, the base forms an elimination product by removing a proton from a carbon adjacent
to the positively charged carbon. Because the first step of the reaction is the rate determining
step, increasing the concentration of the base which comes into play only in the second step
of the reaction has no effect on the rate of the reaction. Thus, the following mechanism
agrees with the observed first order kinetics.

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 AROMATIC NUCLEOPHILIC SUBSTITUTION REACTION

CH3 CH3 CH3

| slow
CH 3  C  Br CH3 – C Br CH3 – C
|
CH3 CH3 CH3

T.S.1

+ –
CH3 – C – CH2 – H CH3 – C CH2 H B
CH3 B CH3 T.S.2
Fast

CH3 – C = CH2 + BH
CH3

Scheme : Mechanism of E1 reaction

7.4.1 Regioselectivity :
When two elimination product can be formed, the major product is always the one
which is obtained according to the saytzeff rule.(The hydrogen is removed from the -carbon
bonded to the lowest hydrogens).

CH3 CH3
| |
CH 3  CH 2  CH 2  C  CH 3  NaOH 
 CH 3  CH 2  CH 2  C  CH 2
|
Br
(Minor product)
CH 3  CH 2  CH  C  CH 3
|
CH 3
(Major product)
7.4.2 Relative reactivities of alkyl halides
The rate of E1 reaction depends upon both the case with which the leaving group leaves
and the stability of the carbocation that is formed because the first step is the rate determining
step. Thus, the relative reactivities of a series of alkyl halides with the same leaving group
parallel the relative stabilities of carbocations.
Ralative reactivities of alkyl halides in E1 reaction 30 benzyl halide > 30 allyl haliede > 20
benzyl halide > 20 allyl halide  30 alkyl halide > 10 benzyl halide  10 allyl halide > 10 alkyl
halide > vinyl halide.

Decreasing reactivity

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 AROMATIC NUCLEOPHILIC SUBSTITUTION REACTION

7.4.3 Rearrangement
Because the E1 reaction involves the formation of a carbocation intermediate,
rearrangement of the carbon skeleton can occur before the proton is lost. Saytzeff rule is
generally followed in E1 reactions.
For example, 3-bromo-2-methyl-2-Phenyl butane gives mixture of two alkenes. One
alkene is normal and other is rearranged product.

CH3 CH3
| | 
C6 H 5  C  CH  CH 3 
 C6 H 5  C  C H  CH 3 


H
| | |
CH3 Br CH3
(1, 2-methyl shift)
CH3
|
C6 H 5  C  CH  CH 2
|
CH3
(minor product)
 CH3
C 6 H 5  C  CH
|
CH3
CH3
 –H
CH3
C6 H5  C  C
|
CH3
CH3
(Major product)
rearranged product
The E1 reaction of 2-Chloro-2,4,4- trimethyl pentane is interesting because it produces
an excess of the less substituted alkene. However, this still goes through the more stable
activated complex (TS). In this case the steric repulsions are greatest in the transition state
leading to the most highly substituted product. This is an example of steric effect which
leads to Hofmann- elimination in E1 reaction.

CH3 CH3 CH3

| |
– Cl 
CH 3  C  CH 2  C  Cl
|
CH 3  C  CH 2  C  CH 3
| | | |
CH3 CH3 CH3 CH3

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 AROMATIC NUCLEOPHILIC SUBSTITUTION REACTION

CH3 CH3 CH3

CH3 – C – CH2 – C = CH2 CH3 – C – CH = C
CH3
CH3 CH3 CH3
81% 19%

Scheme : Formation of Hofmann product

7.5 Effects of the structure of the substrate strength of bases, nature of

leaving group and solvent on the rate of the E1 reaction.
Structure of substrate :
E1 reaction takes place by the formation of carbocation as reaction intermediate. Thus,
the rate of E1 reaction depends on the stability of the carbocation. Since +I effect,
hyperconjugation and congujative effect stabilise carbocation, any structure which forms stable
carbocation will be reactive. Steric strain around leaving group also favours the formation of
carbocation thus, the order of reactivity in decreasing order is as follows:
30 > 20 >10 alkyl halide.
Thus, alkyl and aryl substitutions on  and - carbons with respect to the leaving group
increase the rate of E1 reactions. As the strain increases the field of the E1 product increase.
Strength and concentration of base.
Since E1 reactions do not usually require any base (the solvent molecules serve the
purpose which themselves behave as base) the strength and concentration of the base have
nothing to do with the rate of E1 reactions.
Nature of Leaving Group
Reactivity of the substrate depends mainly on the nature of the leaving group. The best
leaving group are those which are least basic and more polarisable. Thus, the decreasing
order of the leaving group reactivity is :

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 AROMATIC NUCLEOPHILIC SUBSTITUTION REACTION

I > Br > Cl >F

Nature of Solvents :
Since, E1 reactions involve ionic intermediate, the carbocations, the rate of E1 reaction
increases with increasing polarity of the solvent.

7.6 E1cb Reaction

This is a third mechanism for -eliminations. This one begins with a rapid loss of
proton to base. Loss of proton leads to a stabilised carbanion. The carbanion is then converted
to an alkene, conversion of carbanion to an alkene is the rate determining step. This elimination,
since it proceeds through the conjugate base of the starting material, is known as E1cb. The
E1cb reaction competes with the E2 reactions. However, E1cb reactions are much less common
then are E2 reactions because of the greater instability of carbanions. Indeed, only a very
small percentage of eliminations follow this path way.

H
B slow
–C–C–X –C–C–X >C=C<

conjugate base
of the substrate

Kinetics : The E1cb reaction is first order in base and first order in substrate just like
the E2 reaction.
Rate = K [alkyl halide] [Base]
Thus, the reaction is second order reaction, first order with respect to alkyl halide and
first order with the base. But the reaction is unimolecular reaction because reaction velocity
depends only on the concentration of the conjugate base of the substrate.
The use of deuterium labelling can help to distinguish the E1cb reaction from the E2
path-way. If an E2 reaction is carried out in a solvent which could act as deuterium source,
and the reaction is interrupted before it has gone to completion, recovered starting material
is free from any deuterium. This happens because there is no way by which deuterium could
become incorporated into the starting material.
E2 Pathway :

H D
KOD
–C–C–X –C–C–X
C2H5OD

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 AROMATIC NUCLEOPHILIC SUBSTITUTION REACTION

Any reaction which involves a carbanion as an intermediate, on the other hand, should
produce recovered starting material labelled with deuterium. It is precisely such deuterium
incorporation which occurs in those reactions presumed to be E1cb.
E1cb Pathway :

H D
KOD D2O
–C–C–X –C–C–X –C–C–X
D2O

This incorporation also confirmed that the first step is reversible step.
The reaction of 1,1-dichloro-1-deutero-2,2,2 trifluoroethane illustrates a -elimination
which follows the E1cb mechanism. It also shows how, by starting with a deuterated substrate,
the carbanion cab be trapped using OH /HOH rather than OD /D2O.

OD
DCCl2 – CF3 Cl – C – CF3
D2O
Cl
Stabilised by vacant
d-orbitals of Cl and
Cl – C – CF3 strong-I group CF3
Cl
HOH
HCCl2 – CF3 CCl2 = CF2 + F

Thus,
(1) E1cb mechanism is limited to substrates which can stabilise the carbanion intermediate
i.e., -carbon should contain carbonyl, nitro, cyano, sulphonyl or other carbanion
stabilising group.
(ii) Product formation generally takes place by Hofmann rule.
(iii) Leaving group of the substrate is generally poor leaving group.
(iv) -Hydrogen should be highly acidic so that the carbanion formation may take place
easily.
(v) Reaction takes place in the presence of a strong base.

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 AROMATIC NUCLEOPHILIC SUBSTITUTION REACTION

7.7 Solved Examples

Q.1. Give the mechanism of the given reaction.

CH3
CH3
H/
CHOH – CH3
CH3
Solution : mechanism of the reaction is as follows:

CH3 CH3
H
CH – CH3 CH – O – H

OH CH3 H

CH3
CH3 CH3
–H
CH
CH3 CH3
CH3

Q.2. Acid catalysed dehydration of neopentyl alcohol yields 2- methyl -2- butene as the
major product. Outline a mechanism showing all steps in its formation.
Solution :
Neopentyl alcohol is primary alcohol even then it does not give E2 reaction because
(i) there is steric hindrance around - carbon and (ii) -carbon has no hydrogen, it gives E1
reaction in which product formation takes place by formation of carbocation as an reaction
intermediate.

CH3 CH3
| 
CH 3  C  CH 2  O  H
|
CH 3  C  CH 2 OH  H 
| | |
CH3 CH3 H

CH3
1, 2  methyl shift
CH 3  C  CH 2 CH 3       CH 3  C  C H 2
 | 

| |
CH3 CH3

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 AROMATIC NUCLEOPHILIC SUBSTITUTION REACTION


–H

CH 3  C  CH  CH 3
|
CH3
2-methyl-2-butene

7.8 Model Questions

1. When cis 2- dichlorocyclohexanol is treated with base, the product is cyclohexanone

Explain.
2. Why does trans-I-bromo-4- tert-butylcyclohexane undergo E2 reaction in the presence
of ethoxide ion much more slowly than corresponding cis isomer. Explain.
3. Predict the product (s) in the following reactions. Give mechanisms.

Br
(CH ) COK
CH 3  CH  CH  CH 2  CH 3  33 

|
(a)
| 
CH3

CH3
+ OH
(b) CH 3  CH 2  N CH2 – CH2 – CH3
CH3


CH3
OH
(c) CH 3  CH 2  N CH3

CH3

4. What are the conditions that favour E1cb mechanism in an elimination reaction ?
Illustrate with two examples.

7.9 References

1. Advanced Organic Chemistry by Dr. Jagdamba Singh and Dr. L.D.S.Yadav.

2. Advanced Organic Chemistry by Jerry March.
3. Reaction Mechanism in Organic Chemistry by S.M. Mukherji and S.P. Singh.
l

118