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Subject Chemistry

Paper No and Title Paper-9, Organic Chemistry-III (Reaction Mechanism-2)

Module No and Title Module-22, Elimination Reactions: E1 and E2 mechanisms-

Part-I
Module Tag CHE_P9_M22

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-22:Elimination Reactions: E1 and E2 mechanisms-Part-I
____________________________________________________________________________________________________

TABLE OF CONTENTS
1. Learning Outcomes
2. Introduction

3. Mechanisms of Elimination Reactions

3.1 The E1 mechanism
3.2 The E2 mechanism

4. Comparison between the E1 and E2 Elimination Mechanisms

5. Elimination vs Substitution

6. Summary

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-22:Elimination Reactions: E1 and E2 mechanisms-Part-I
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1. Learning Outcomes
After studying this module, you shall be able to

• Know what is meant by elimination reactions

• Learn about the types of elimination reactions
• Differentiate between the E1 and E2 mechanism
• Perceive factors favouring elimination over substitution
• Identify set of conditions responsible for E1 or E2 mechanism

2. Introduction
As is evident from the term “Elimination reactions”, these are organic chemical reactions in
which a pair of atoms or groups of atoms (leaving group) are removed (eliminated) from a
molecule, usually through the action of acids, bases, or metals and, in some cases, by heating to a
high temperature. In most organic elimination reactions, at least one hydrogen is lost to form the
unsaturated bond and it is one of the main methods used for the formation of unsaturated
compounds (alkene or alkyne) from substrates containing single carbon-carbon bonds (saturated
compounds). Elimination may be considered the reverse of an addition reaction.

Based on the position of the leaving group, these may be α-eliminations, β-eliminations or
1,3/1,n-eliminations, but most commonly encountered are the β-eliminations(1,2-elimination) in
which a leaving group from α-carbon and a proton from the β-carbon are eliminated, as shown
below. α-eliminations generate carbenes, which are unstable divalent carbon species useful for
many other reactions and not discussed here.

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-22:Elimination Reactions: E1 and E2 mechanisms-Part-I
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Note that a ring is equivalent to a double bond.

Common organic substrates that undergo β-elimination reaction are alkyl halides and alcohols.
These elimination reactions are represented below:

At least one hydrogen atom on the β-carbon is a pre-requisite for these types of
eliminations to occur. Further, two factors that provide an impetus for successful elimination
reactions are: (i) stability of the unsaturated product formed, and (ii) relief from the steric strain in
the substrate. To demonstrate this, consider a substrate that has more branching at β-carbon (and
may be substituted at α-carbon as well). This substrate will produce a substituted olefin which in
turn, is stabilized by hyperconjugation and hence favours elimination. Similarly, 3o halides favour
elimination than 2o and 1o with the following order: 3o > 2o > 1o. This can also be explained in
terms of bond-angles of the substrate (109.5o, sp3-hybridized) and that of the product i.e. olefin
(120o, sp2-hybridized).

3. Mechanisms of Elimination Reactions

Like the nucleophilic substitution reactions, elimination reactions can also proceed by either
unimolecular or bimolecular mechanisms and have been designated as E1 or E2 like the SN1 and
SN2 reaction mechanisms respectively. These are discussed as follows:

3.1 The E1 mechanism

In this type of elimination, the rate of reaction is first order and is dependent solely on the
concentration of the substrate.

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-22:Elimination Reactions: E1 and E2 mechanisms-Part-I
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rate of reaction = k [R],

where k is the rate-constant and R is the substrate

For elimination to occur by the E1 mechanism, the reactant first undergoes unimolecular
ionization and forms a carbocation intermediate without the involvement of any base. This step is
slow and rate-determining and is analogous to the rate-determining step in the SN1 mechanism.
The leaving group leaves in this step, and the elimination is then completed by rapid removal of a
β-proton.

For example, tert-butylbromide undergoes E1 elimination to form 2-methylprop-1-ene in basic

medium via the formation of tert-butyl cation and the rate of elimination is found to be
proportional to its formation.

Similarly, tert-butanol undergoes acid-catalyzed dehydration following the E1 mechanism as

shown below. The alcohol is first protonated, weakening the C—O bond and leading to loss of a
water molecule generating the tert-butyl carbocation. The latter then expels a proton as in the
previous case forming a stable alkene.

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-22:Elimination Reactions: E1 and E2 mechanisms-Part-I
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For tertiary alcohols, dilute acid and even lower temperatures are sufficient to effect dehydration.
However, secondary alcohols and primary alcohols require higher temperature and concentration
of acid which can be explained on the basis of stability of the generated carbocation.

The intermediate carbonium ion may not only eliminate but may also add a nucleophile to give a
substitution on product (SN1). Further, the carbonium ion may rearrange.

3.2 The E2 mechanism

The E2 elimination mechanism, as the name suggests, has a bimolecular rate-determining step.
So, the rate of reaction is second-order and is dependent upon the substrate as well as base. It is
similar to SN2.

rate = k [R] [B], where k is the rate-constant, R is the reactant and B is the base
Example of E2 elimination of an alkyl halide is as shown below. The reaction occurs in a single
step in which both the groups (proton and leaving group) are eliminated simultaneously. The base
abstracts a proton from the β-carbon, and the leaving group departs at the same time from the α-
carbon. The C-X and β C-H bonds are coplanar in the transition state and the two leaving groups
must be in trans relationship for undergoing E2 elimination and subsequent C=C bond formation
(anti-periplaner transition state).

The energy diagram for E2 elimination can be visualized as below. The process is concerted and
the transition state is less well-defined than the corresponding SN2 transition state ans
concomitant bond-breaking and formation takes place.

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-22:Elimination Reactions: E1 and E2 mechanisms-Part-I
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4. Comparison Between the E1 and E2 Elimination Mechanisms

An elimination reaction may follow E1 or E2 mechanism depending upon several factors. Often,
a reaction may proceed in either of the two pathways subject to the reaction conditions employed.
These factors are listed as follows:

1. Base

From the rate equation for E2 mechanism, it becomes clear that as the concentration of
the base is increased, the rate of E2 elimination will also increase. On the contrary, for E1
elimination, there is no effect of any weak or strong base or its concentration. Thus, E2
elimination is favoured over E1 by stronger and more concentrated base. However, one
needs to understand that though E1 reaction has no effect of base (as shown by its rate
equation), it still requires a stronger base (but weaker nucleophile) to evade the SN1 path.

2. Nature of substrate

Since E1 elimination requires the formation of a stable carbocation, hence presence of

electron releasing groups that stabilize the positive charge in the carbocation intermediate
lead the reaction to the E1 route and tertiary substrates are the most favourable for E1
reaction. For example, secondary alkyl halides may eliminate by E1, while primary alkyl
halides may eliminate only by E2 because the primary carbocation required for E1 would
be too unstable.

3. Solvent

E1 elimination requires an ionizing solvent which eventually aids in formation and

stabilization of the formed carbocation intermediate. Hence, polar protic solvents (water,
methanol etc.) favour elimination via E1 route. On the other hand, E2 elimination can
occur in less polar solvents but their rate is increased by use of polar aprotic solvents
(DMSO, DMF etc.).

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-22:Elimination Reactions: E1 and E2 mechanisms-Part-I
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4. Leaving group

Both E1 and E2 are possible in substrates possessing a good leaving group, but other
factors as discussed above, actually shape the way in which a given elimination will
proceed. For example, consider the following two Hofmann eliminations as depicted in
equations A) and B). In the first case, a strong base (such as NaOCH3) is used to effect
elimination and since a stabilized cation cannot be formed, hence the reaction takes place
by the E2 mechanism. However, in the second case, formation of a tertiary cation is
possible through removal of the leaving group and as base is not present, it definitely
involves the E1 mechanism.

5. Elimination vs Substitution
For many combinations of substrates and nucleophiles (base), substitution reactions may compete
with elimination, and may sometimes be the major reaction path. This is because the same
substrates also undergo substitution reactions. One may wonder that what factors are responsible
for a reaction to proceed in either of these pathways.

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-22:Elimination Reactions: E1 and E2 mechanisms-Part-I
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Careful observations have led to the conclusion that following conditions are mainly responsible
for effecting elimination over substitution in a substrate:

1. Temperature:

From thermodynamics, we know that

ΔG = ΔH – TΔS  

Thus, for a favorable reaction, ΔG must be negative. As the entropy change (ΔS) is more
for elimination than for substitution (in an elimination, two molecules become three
while in a substitution, two molecules lead to only two new molecules), so higher
temperatures (T) will definitely favour elimination reaction.

2. Basicity of the nucleophile

The basicity of the nucleophile is also pivotal to realize which path a reaction will
proceed. If the nucleophile attacks at carbon, it will lead to substitution whereas attack at
hydrogen (proton abstraction) leads to elimination. Since strong bases are good at
extracting protons, so it means that the more basic the nucleophile, the more likely that
elimination is going to replace substitution reaction path.

3. Bulkiness of the nucleophile

It is harder for it a bulky nucleophile (steric hindrance) to attack at a carbon as it has to

squeeze past other substituents. On the other hand, there is no such difficulty for it to
attack a proton. So, bulkier bases such as potassium tert-butoxide are among the best to
induce elimination on a substrate. The general principle is sterically hindered bases are
good proton abstractors but poor nucleophiles.

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-22:Elimination Reactions: E1 and E2 mechanisms-Part-I
____________________________________________________________________________________________________

4. Nature of substrate

In general, elimination is favoured with an increase in branching of the carbon-chain.

This can be explained on the basis of stability of the resultant alkene due to
hyperconjugation. Also, presence of appropriate stabilizing groups such as -Ph, -vinyl
etc. favour elimination reaction over substitution because the stabilisation energy due to
conjugation in the product.

5. Nature of solvent

A less polar solvent favours elimination (by E2 mechanism, as we will see in the
proceeding section) over SN2. Also, use of aprotic solvents allows an increase in the base
strength as any solvent layer around the base is absent because of no hydrogen-bonding.

6. Summary

• In an elimination reaction a pair of atoms or groups of atoms (leaving group) are removed
(eliminated) from a molecule, usually leading to an unsaturated product.
• A 1, 2-elimination, or β-elimination is the most common, and involves the loss of a
leaving group and an electrophile from adjacent atoms in a substrate. This loss results in
the formation of a π bond.
• Usually there is a competition between elimination and substitution reaction-pathways
since the substrate-requirement is the same for both the competing reactions.
• Higher temperatures, bulky and strong base (having less nucleophilicity) and a non-polar
solvent favor elimination over substitution.
• The E1 mechanism is a two step reaction, the first is the ionization of the leaving group to
give rise to a carbocation and the second elimination of the hydrogen from the β-position.
The E2 mechanism is a concerted single step reaction.
• An E2 mechanism requires that the leaving group and the hydrogen be in the same plane
and anti-periplanar to each other.
• Whether a substrate will follow E1 or E2 mechanism is dependent upon the nature of
substrate and the prevailing reaction conditions.

CHEMISTRY PAPER No. 9 : Organic Chemistry-III (Reaction Mechanism-2)

Module-22:Elimination Reactions: E1 and E2 mechanisms-Part-I