ELIMINATION REACTIONS

Elimination reactions involve the removal of two atoms or groups from a molecule and they
are not replaced by other atoms or groups.
The most common type of elimination reaction is 1,2-elimination (α β-elimination or simply
β-elimination), in which two groups are removed from adjacent atoms. In most of the cases one
group is a proton and the other one is a nucleophile. 1,2-elimination results in the formation of a
multiple bond.
Eg: Dehydrohalogenation of alkyl halides
a lc o h o l
C C + KOH C C + KX + H2O
H X

Dehydration of alcohols
a c id
C C C C + H2O
H OH

H2SO4 and H3PO4 are frequently used in alcohol dehydrations. KHSO4 is also used.
Dehalogenation of vicinal dihalides

C C + Zn C C + ZnX 2
X X

In an α elimination, both groups are lost from the same atom to give a carbene (or a nitrene).
-
-O H -
CHCl 3 CCl 3 CCl 2
-H +
- C l-

In a γ elimination, a three-membered ring is formed.

1,2-Elimination
β -Elimination reactions can occur by a variety of mechanisms of these E2 and E1 are the
most common. They are closely related to SN 2 and SN1 . Another mechanism is designated as E1 CB
mechanism elimination unimolecular of the conjugate base. In 1,2-eliminations, the C atom from
which nucleophile is removed is the 1-(α-) C and the C atom from which proton is removed is the 2-
(β-) C.

1. E2 mechanism
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 This is a concerted (one step) process. In this process both substrate and base participate in
the single step. The breaking of the C–H and C–Y bond takes place at the same time and proceeds
through a transition state. In the E2 mechanism (elimination, bimolecular), the two groups depart
simultaneously, with the proton being pulled off by a base:
The most common elimination reaction is the base induced removal of hydrogen halide from
alkyl halides (dehydrohalogenation).

E2 (Elimination bimolecular) mechanism follows second order kinetics. The rate of the
reaction depends on the concentration of the base and the substrate.
Rate = k[substrate][base]
2. E1 mechanism
This elimination takes place in two steps. The C-Y bond is broken firt to form a carbocation
and then C-H bond is broken. The formation of carbocation is slow and rate determining.

3. E1cB (Elimination, unimolecular, conjugate base) mechanism

In this mechanism, first step is the abstraction of proton by base leading to the formation of a
carbanion. This is a two step process and follows second order kinetics.

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 Rate of E1cB depends on the concentration of the substrate and the base. Among the three
mechanisms E2 is the most common and E1cB is the least common.
Factors affecting E2 Mechanism

The reaction rate increases with the strength of the base. The stronger the base, the more
favourable an E2 reaction will be. Thus the rate of E2 in the following bases will be in the order:
-NH > -OR > -OH
2

If the solvent is changed from polar-hydroxylic to polar aprotic, the strength of the base is greatly
enhanced. In polar aprotic solvents, there is no envelope of hydrogen bonded solvent molecules
around the base and it will be a more powerful base.
The rate also increases with a good leaving group. Anions of strong oxy-acids (e.g.:- tosylate) act as
good leaving groups and favour E2 mechanism. Among halide ions the relative rates of E2 will be in
the order:

I- > Br- > Cl- > F-

Structural features of the substrate also play an important role in E2 reactions. Structural
features that stabilize the product alkene or the transition state increase the rate of elimination. Thus
alkyl substitution at both α- and β-carbon atoms and introduction of a phenyl ring that can conjugate
with the developing double bond increase the rate of elimination.
Stereoselectivity in E2
The most important evidence for E2 mechanism is that it can be stereospecific. In E2

mechanism the five atoms involved in the transition state should be in one plane. If H, C α, Cβ and X
lie in one plane in the T.S, the p-orbitals of the developing double bond will be parallel to one
another and maximum overlap is possible. It will be energetically favourable for the base to lie in
this common plane. Thus E2 elimination will always takes place with a planar T.S. There are two
possibilities for this elimination. (A) H and X may be trans to one another, i.e. the dihedral angle is
180º. This conformation of H and X is known a antiperiplanar (B) H and X may be cis to one
another, i.e. the dihedral angle is 0º.

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 Conformation (A) is called anti-periplanar. Elimination from this conformation in which H
and XY depart in opposite directions is called anti elimination. Conformation (B) is syn-periplanar.
Elimination from this conformation in which H and X depart in the same direction is called syn
elimination. In the absence of special features anti elimination is favoured over syn elimination.
The possible reasons for this are
(a) In anti elimination lower energy staggered conformation is involved while in syn elimination
higher energy eclipsed conformation is involved.
(b) In anti elimination, the base and the leaving group are as far apart as possible.
(c) During double bond formation, the electron pair of the C–H bond is attacking the α-C atom from
the opposite side of C–X bond in anti elimination.

This is similar to the backside attack in SN2 mechanism. If both Cα and Cβ are chiral, syn

elimination and anti elimination will lead to different products.

Some examples for the predominant anti elimination is given below.

1. Elimination of HBr from meso-1,2-dibromo-1,2-diphenylethane gave cis-2-bromostilbene. The
(+) or (-) isomer gave the trans bromo stilbene. In this case elimination is exclusively anti.

(2) In the case of cyclohexyl substrates both the leaving group and H should be at axial positions.
Only in this arrangement C–H bond is anti-periplanar to C–X bond. Syn elimination is not at all
possible with cyclohexyl systems. For monosubstituted cyclohexyl substrates, axial conformer is less
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stable. But a considerable amount of this conformer will be present and elimination will takes place
from this conformer. The equatorial conformer is anti-periplanar only to C–C bonds and elimination
from this conformer is not possible.

Consider the following two diastereomeric cyclohexyl derivatives. On reaction with Na

ethoxide both eliminate HCl, but (A) reacts rapidly and gives a mixture of products while (B) gives a
single product slowly.

Both (A) and (B) will adopt chair conformations. Normally the largest substituent is in
equatorial position. In this case the largest substituent is isopropyl group. In (A) isopropyl group is
equatorial which means that methyl group is also equatorial. The Cl should be axial. Thus in the
most favoured conformation of (A), Cl atom is in axial position and have two axial H atoms on
adjacent C atoms. Since the conditions required for E2 elimination is already present in the preferred
conformation (A) undergoes elimination readily. Because of the presence of two H atoms in axial
positions on adjacent C atoms two products are formed. In (B) again isopropyl group and hence
methyl group are in equatorial position. But in this case Cl atom should be in equatorial position.
From this conformer elimination is not possible since there are no anti-periplanar protons. Therefore
it should undergo ring flip first. Ring flip gives a conformer in which all three substituents are in
axial positions which is very much less stable. This is the reason for the slow reaction of (B). Also in
this conformer (i.e. with three axial groups) only one anti-periplanar proton is present and hence only
one product is formed.

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 Adjacent trans groups on a six-membered ring can be diaxial or diequatorial and the molecule
is generally free to adopt either conformation, although one may have a higher energy than the other.
Anti-periplanarity of the leaving groups requires that they be diaxial, even if this is the conformation
of higher energy. The results with menthyl and neomenthyl chlorides are easily interpretable on this
basis.

Menthyl chloride has two chair conformations, 2 and 3. Compound 3, in which the three
substituents are all equatorial, is the more stable. The more stable chair conformation of neomenthyl
chloride is 4, in which the chlorine is axial; there are axial hydrogens on both C-2 and C-4. The
results are: neomenthyl chloride gives rapid E2 elimination and the alkene produced is

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predominantly 6 (6/5 ratio is 3:1) in accord with Zaitsev’s rule. Since an axial hydrogen is available
on both sides, this factor does not control the direction of elimination and Zaitsev’s rule is free to
operate. However, for menthyl chloride, elimination is much slower and the product is entirely the
anti-Zaitsev, 5. It is slow because the unfavorable conformation 2 has to be achieved before
elimination can take place, and the product is 5 because only on this side is there an axial hydrogen.
Syn Elimination
Syn-elimination have been found in molecules where H and X cannot achieve an anti-
periplanar conformation. Eg: The deuterated norbornylbromide gave 94% of the product not
containing deuterium during elimination. In this case the exo Br cannot achieve anti-periplanar
conformation with the β-H atom because of rigidity of molecule. Thus syn elimination is preferred
and deuterium which is syn to Br is eliminated.

Orientation in E2
The following rules have been suggested to predict the major product of elimination.
1. Bredt’s rule: The rule suggests that double bond is not formed at a bridgehead carbon
unless the sizes of the rings are large.

Br

A B
X

The β-elimination of X forms B not A.

2. When the substrate is already having a double bond, second double bond formed on
elimination should be conjugated with the double bond already present.
CH3 CH2
H2C B ase H2C

Br
x CH3
H2C

3. Saytzeff Rule
This rule suggests that the most substituted alkene is formed as the major product.

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 CH3
H
H3C
H3C H3C
CH3 CH3

Br m a jo r
Br
H

H2C

CH3 CH3
m in o r

Br

The greater stability of the more substituted alkene can be explained on the basis of
hyperconjugation.

The number of resonating structures tends to increase with the increase in the no: of alkyl
substituents and this in turn increases the stabilization.
If the leaving group is neutral (when it is attached to the C atom), the predominant product is
the satyzeff product.. Thus when Y = Br, OTs etc, the predominant product is the more stable, more
heavily substituted alkene. In such cases, the T.S is more alkene like. If the number of alkyl
substituents is more, the T.S. will be more stable. Therefore, the more substituted alkene will be the
predominant product. An example is the elimination reaction of MeCH2CHBrMe.

4. Hofmann Rule
Exceptions to Sayzeff rule are observed from base induced eliminations from
quarternary ammonium salts and from sulphonium salts which give predominantly the
less substituted alkene.

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 If Y is positively charged (i.e. groups like Me 3N+, Me2S+ etc), the predominant product is

the Hofmann product.. Groups like +NMe3 will exert powerful –I effect/field effect on both β-C

atoms. Thus the Hs attached to the β-C atoms will be highly acidic and the removal of such H atoms
will be enhanced.

In other words, +vely charged leaving groups enhance the formation of carbanion. These

groups also stabilize the carbanion by e- withdrawal. Therefore, whenever groups like +NMe3 is

involved, the T.S is more carbanion like (E1cB like T.S). A carbanion like T.S is stable with the least
number of alkyl substituents. Thus Hofmann product is favoured.

An example is shown below.

Normally during E2 elimination, Saytzeff rule predicts the formation of a more substituted
alkene and the exceptions are when the leaving group is poor. In this case, the negative charge will

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build up on the carbon from the proton is lost and therefore, the carbanion stability determines the
major alkene product. Moreover in several eliminations, the less stable alkene predominates when
the base is bulky and sterically hindered.

If F is the leaving group, even though it is not positively charged, Hofmann product will be
the predominant product. The reason is that F is an extremely powerful electron withdrawing group
and it is an extremely poor leaving group. Thus the C–F bond breaking is delayed and the T.S will be
more carbanion like.
Steric factors may also important in elimination reactions. Normally positively charged
leaving groups are larger than neutral leaving groups. Since the positively charged leaving groups are
large enough to hinder the attack of base on protons, the base will attack the least hindered proton
leading to Hofmann elimination. Also bulky substrates favour Hofmann elimination. Bulky bases
prefer Hofmann elimination, while small bases prefer Saytzev elimination.
E1 Mechanism
Consider the E1 elimination reaction of MeCH2CMe2Br in EtOH. The reaction follows a

first order kinetics. First step is the formation of carbocation, which is slow and rate limiting. In the
second step, an H+ is removed from the carbocation by a base. In this case, the solvent acts as the
base. Thus the E1 rate equation is indistinguishable from E2 rate equation. If the solvent itself is the
base, then E2 rate equation also will follow pseudo 1 st order kinetics. But these two mechanisms can
be distinguished by adding a small amount of the conjugate base of the solvent. E1 reactions are
unaffected by the conc. and nature of the base. Increase in conc. of the base increases the rate of E2
mechanism. Also E2 is faster with strong bases than with weak bases.
Since a carbocation intermediate is involved, there will be always competition between S N1

(substitution) and E1 (elimination). In a solvent with high dielectric constant, the ratio of substitution
to elimination products is independent of the leaving group. For example, in 80% aq. ethanol t-butyl
iodide solvolyses 100 times faster than t-butyl chloride, but the ratio of elimination to substitution
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products is the same for the Cl- and the I-. This shows that, SN1 and E1 have the same r.d.s, i.e. they

proceed through the same carbocation intermediate. Formation of carbocation is followed by either
addition of a nucleophile (SN1) or removal of a proton (E1).

E1 is favoured by a polar protic solvent and when no good base or nucleophile is present.
Consider the reaction of MeCH2CMe2Br in EtOH. First step is the formation of carbocation,

followed either by addition of a solvent molecule (SN1) or removal of a proton (E1).

In solvents of low ionizing power, the ratio of substitution to elimination depends on the
nature of the leaving group. This is because in such solvents formation of ion-pairs will take place
and the leaving group itself acts as the base.
Factors favouring SN1, also favours E1. An alkyl group in the substrate that can give rise to a

relatively stable carbocation and a good ionizing, ion solvating medium promote E1. The reactivity
of alkyl halides under E1 conditions will be the order,
tertiary > secondary > primary
Branching at β-carbon atom also favours E1 mechanism. Branching at β-carbon leads to the
formation of more heavily substituted and hence more thermodynamically stable alkene during E1
elimination. If there is the possibility of formation of two different alkenes, the more substituted
alkene will be the predominant product. During E1 elimination of MeCH2CMe2Br, two products are
possible.

In this reaction B is the major product. E1 may lead to unusual products due to the
rearrangement of the initial carbocation formed.

Elimination versus Substitution

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 E1 reactions are often accompanied by SN1. Also E2 reactions are often accompanied by

SN2, even though they do not have a common T.S. The ratio of products of elimination to those of

substitution is affected by several factors.

(a) Basicity and size of the nucleophile: - Attack of the nucleophile on carbon atom leads to
substitution while attack on H leads to elimination. Nucleophilic substitution reactions and
elimination reactions often compete with each other. Since bases attack protons, more basic
nucleophile favours elimination over substitution. If the size of the nucleophile is large, the
elimination is favoured. For a large nucleophile it is often difficult to approach a C atom because of
the presence of substituents. But it is easier to approach a H atom which is always less hindered.
Therefore bulky bases like t-butoxide favour elimination.
(b) Substrate structure: - Elimination reactions will become more favourable in the order, primary <
secondary < tertiary. An increase in number of substituents will favour the transition state leading to
the formation of alkene. Bulky substrate favour elimination due to the relief from steric strain.
Double bonds or aryl groups present in the substrate which can stabilize the developing double bond
through conjugation also favours elimination.
(c) Nature of Leaving group: - The ratio of E1 to SN1 is unaffected by the nature of the leaving

group. But nature of leaving group affects E2 to SN2 ratio. But in both these cases C–Y bond

breaking is involved and hence correlation is difficult.

(d) Temperature: - During elimination two molecules react to give three molecules while in
substitution, two molecules give two molecules. Therefore entropy change is favourable for
elimination. According to the equation ΔG = ΔH-TΔS, for elimination with increase in temp., the
term -TΔS will become more and more negative and hence ΔG will become more and more negative.
Thus high temperatures favour elimination.

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The structure III gains importance when L is a poor leaving group or if (-) chargely carbon is
adjacent to group with -I effect.
The structure IV gains importance when on the other hand L(-) is a good leaving group while B is a
weak base.
Structure II becomes significant when L is a good leaving group and Bis a strong base.
The transition state III will have considerable carbanion character when the leaving group is poor eg:
NMe3 in Hofmann elimination

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The negative charge is destabilized by CH3 group..

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