UNIT 16 ALKYL HALIDE :SUBSTITUTION AND

ELIMINATION REACTIONS

Structure
16.1 llitroduction
Objective
16.2 Classification of Halogen Derivatives
16.3 Nucleopliilic Substitution Reactions
16.4 SN2Reactions
Mechanism of SN2Reactions
Stereochemistry of S,2 Reactions
Reactivity of S,2 Reactions
16.5 SNl Reactions
Mechanism of S,1 Reactions
Stereochemistry of S, I Reactions
Reactivity of S, 1 Reactions
1 6.6 Elimination Reactions
16.7 E2 Reactions
Mechanism of E2 Reactions
Evidence of E2 Reactions
Orientation of E2 Reactions
Stereochemistry of E2 Reactions
16.8 E I Reactions
Mechanism E l Reactions
Evidence of E 1 Reactions
Orientation of E 1 Reactions
16.9 Surninary
16.10 Terrninal Questions

16.1 INTRODUCTION
I11 unit 15, we have discussed the Chemistry of aliphatic and aromatic hydrocarbons.
In tliis uriit we will ~nainlydiscuss the characteristic rections (i.e. substitutio~iand
elirniliatio~ireactions) of alkyl halides. Here we wit1 discuss the mechanism of
substiti~tionand eli~ni~iation reactions. We will also discuss the factors wli;ch affect
the rate of tliese reactions.
Objective
After studying tlie unit, you sliould be able to :
classify the halogen.derivativcs
explain the SN2and SN1 mechanisms
explain the effect of structure of an alkyl group, nucleophile, leaving group on
reactivity of S,1 and SN2reactions.
explain tlie ~~nl~nolecular(El) and bimolecular (E2) elimination reactions
explain stereoche~nistryand orientation pattern of EI and E2 reactions.
 Alkyl Halides :Substitution
16.2 CLASSIFICATION OF HALOGEN DERIVATIVES and Elimination Reactions
Compounds contairiing carbon, hydrogen and halogen atoms are generally known as
l~alogenderivati-vesof hydrocarbons. Tliese halogen derivative are divided into three
main classes :
Alkyl halide - Compound in wliicli halogen atom isattached to
carbon atom of the hydrocarbon chain.
Aryl halide - Compound in wliich the halogen atom is attached
to a carbon atom of aromatic ring .

Vinyl halide or - Co~npoundin which halogen atom is attached to

A1keriyl halide a vinyl group.

Alkvl halide

~hloro~i~ethane (Chloronietliyl) benzene

( U e n q l Cllloride)

I
Note : In benzyl chloride lialogen atom is attached to -CH, group not directly to
aromatic ring. Therefore it is alkyl lialide not aryl halide.

1 A w l halide

Vinyl halide or Alkenyl halide

Cliloroethaie
(Vinyl chloride)

The monolialogen derivatives, have a general formula CnH2n+IX. Where X stand for
halogen atom. Alkyl halide can also be classified as primary, secondary and tertiary
alkyl halide. In primary alkyl halide, halogen bearing carbon atom is attached to only
one other carbon atom. In secondary and tertiary alkyl halide, halogen bearing
carboll atom is attached to two and three carbon atoms res~ectivelv.For e x a m ~ l e

R I
R-CH2-X I R-C-X
Pr i~iinrynlkyl lialide ' R-CH-X
Secondary alkyl halide
; A
T n e i a m t alC.,l haliAn

The mail1 reactions of alkyl halides are substitution and elimination reactions. Let us
discuss them separately.
Chemistry of Carbon 16.3 NUCLEOPHILIC SUBSTITUTION REACTIONS
Compounds
Substitution reactions involve the reolacement of one atom or m o u bv
~ another atom
or group.

OH- + CH3CH2Br --+ CH3CH20H + Br-

nucleophik substrate product leaving group

In the above reaction, nucleophile (hydroxide ion) attacks the saturated carbon
substrate (bromoethane) giving ethanol and bromide ion as the products. You would
notice that the reaction involves heterolysis of carbon-bromine bond such that the
electron pair becomes associated with bromine which leaves as a bromide ion. Here
bromide ion acts p a leaving group.
Some important nucleophetic substitution reactions are given in Table 16.1.

..
-
Table16.1 :Some Nucleophilic Substitution Reactions

..- I
-
R -X + Nucleophile (name)
..: .
..
:X: + Product (name)

..
R -X:.. + :Y..: (another halide) X- + R -Y : (another alkyl halide)
!
+: N : (cyanide) ___) + R -c : N :(nitrile) I
-
+ :OR (akoxide) ..-R (ether)
+ R -o i
..
i
d

- .. -
..
+ N j (azide = :N =N = N :) ---, + R-N, (alkyl azide)

..

-
+ :.SR' + R - S -R' (thioether)
. (alkanethiolate) d

+
+ :NR',(amine) .. (alky~ammoniumsalt)
R - N Rt3 :x-:

+ OH^ (water)

+ I
.u-n
(alcohol) R - O - R I : .~. : I
K-U--'+HA: . .
H
H
I (ether) 1
On the basis of the mechanism of substitution reactions, nucleophilic substitution
reaction can be divided into two types
i) SN2 reactions
ii) SN 1 reactions
Let us discuss them separately.
 -

I
3

16.4 S,2 REACTIONS ~ ~ rHalides

y l :Substitution
and Elimination Reactions
The reaction of bromoethane with sodiurnhydroxide to give methanol is a typic* .A

example of S,2 reaction '

CH,Br + NaOH +CH,OH'+ ~&r-

The reaction of chloromethane (a primary alkyl halide) with OH- give alcohol. This
reaction follows SN2mechanism. Actually.primary alkyl halide (and methyl alkyl
halide) follows SN2mechanism. Secondary alkyl halide may follows any of the two
mechanism (i.e. SN1or SN2mechanism). Tertiary alkyl halide do not undergo SN2
mechanism, but follows SN1mechanism.
How do we find out which pathway this reaction would take? Reaction kinetics can
help us here. You would recall from the previous studies that the experimentally
determined rate expression gives an idea of the number of species involved in the
rate determining step of a multistep reaction.
Now the rate of the above reaction can be determined by following either the rate of
disappearance of the base, OH- or appearance of the bromide ion, Br-. This rate is
found to be proportional to the concentrations of both bromoethane and hydroxide
ion. The experimental rate expression is,
rate = k[CH,Br][OH-]
Where k is the rate constant and [CH,Br] and [OH-] represent the concentration of
the alkyl halide and hydroxide ion respectively.
This means that in this reaction both the reactants take part in the transition state.
(Fig. 16.1) So it has to be a biomolecule mechanism. The mechanism is described by
the symbol SN2meaning substitution nucleophilic bimolecular. The 2 in the symbol
signifies bimolecularity of the reaction.
16.4.1 Mechanism of S,2 Reactions
To understand the mechanism of SN2reactions take an example of reaction of
chloromethane with OH-.

In general methyl and primary alkyl halide undergo S 2 reaction with relatively
N.
strong nucleophile e.g. OH-, OR-, CN- etc. This reaction has been found to follow
second order kinetics.
On the basis of reaction kinetics and stereo chemistry of SN2reaction, following one
step mechanism is proposed.

partial bonds
7

transition state

The hydroxide ion attacks from the rear, away from the negatively charged field of
the bromide ion. As the hydroxide ion begins to bond to the carbon atom from the
rear, the bromine begins to leave as the bromide ion from the front. SN2is a one step
reaction. Carbon atom is partially bonded to both the incoming and leaving groups.
Cleavage of bond between carbon and the leaving group is a companied by a
synchronous formation of bond between carbon and nucleophile. Therefore S,2
mechanism is also known as direct displacement process.
The potential energy diagram of the above reaction is given in Fig 16.1.

Reaction coordinate - - -

Fig 16.1 :Potential energy diagram for the hydrolysis of bromometh:.neby Sh2
-

mechanism.

16.4.2 Stereochemistry of SN2 Mechanism

There are two ways in which S,2 reactions of methyl chloride with hydroxide ion
can occur. The OH- can attack the methylchloride at the front side of the carbon
where chlorine is attached or the OH- group attacks the carbon atom from the
opp~siteside. In either case, the making of C-OH bond and breaking of C-C1 bond
occur simultaneously. The front side attack and displacement of leaving group would
not alter the configuration of the substrate whereas the opposite side attack would
lead to an inversion of configuration. In the case of back side attack the carbon and
hydrogens become planer in the transition state.

fronf-side appraach

L
.brick-side nppronch
 I
I
In case of back-side attack when nucleophile is 180' away from the departing p u p
cause the stereochemistry of the substrate to invert much like an umbrella turning
Alkyl Halides :Substitution
and Elimination Reactions
inside out in the wind (Fig.16.2). This inversion is called Walden inversion after
Paul Walden who first reported it in 1896.

-F - -4 strong wind

Fig. 16.2 :Inversion of configuration during SN2reaction

16.4.3 Reactivity of S,2 Reactions
The rates of reactions proceeding by SN2mechanism are mainly affected by the
following three factors :
structure of alkyl halide
nature of the nucleophile and
L
nature of the leaving group
Structure of Alkyl halide q

The relative reactivity of a molecule in a SN2mechanism depends on its structure.

Table 16.2 shows the effect of the structure of alkyl halides over the reaction rate.
In this table we have given average reaction rates (taking the reaction rate for ethyl
halides as one) of SN2reaction of some alkyl halides.
Table 16.2 : Effect of branching in alkyl halide on rate of SN2reaction
Alkyl halide Rate of reaction
CH,-X 30

.
Among the alkyl halides, a typical sequence for S,2 reactivity is thus,
CH3X > CH3CH2X > (CH3),CHX > (CH3)3CX

pri-halide > sec-halide > tert-halide

Similarly,among simple primary halides the reactivity is,

Primary halides which have an unsaturated group attached to the carbon react much
faster than brornomethane. Thus,
C,H,CH,Br > CH, =CHCH,Br aCH3Br r.
Two distinct effects appear to be responsible for the wide variations in the foregoing
table. Electronic effects apparently are responsible, but steric effects also have a
major role. As hydrogen atoms ofmethyl group are gradually replaced by bulkier
alkyl groups, the nucleophile finds it Inore and more difficult to push in through the
three carbon substituents in order to forin the transition stat:. If the substituents are
bulky, the transition state will be heavily crowded and the nonbonded interactions
bemeen various substituents would raise its energy and make it unstable. he steric
Chemistry of Carbon effect is also noticed, when the carbon next to the reaction site is highly branched,
Compounds there is a severe hinderance to the approach of the attacking group. This effect is
responsible for the very low,reactivityof I -bromo-2,2-dimethylpropane(neopentyl)
substrate inspite of its being primary in nature. The back-side attack of the
nucleophile is hindered by three P-methyl groups.
Nature of the nucleophile
We have seen that the rate of a SN2reaction depends upon the concentration of .
both the substrate and the nucleophile. Therefore, nucleophilicity of the reagent is
also important in S,2 reactions. The order of nucleophilicity in some oxygen
nucleophiles is,
C,H;O- > OH- > C,H,O- > CH,COO- > H,O
'
Nucleophiles with atoms of the same period in the periodic table show a decrease in
nucleophilicitieswith an increase in electronegativity. For example, oxygen is less
electronegativethan fluorine and holds the electrons around it less firmly than
flourine does. Therefore, the hydroxide ion is better able to donate its electrons and
consequently is more nucleophilic than F- ion. A nucleophile with a charge is more
powerful than its conjugate acid.
This is because in a neutral molecule, the electrons are held tightly by the atom,
whereas the electrons on an atom bewing a negative charge are more loosely held,
and therefore, can be easily donated to a positive centre.
In larger atoms, the outer electrons are less tightly bound to the nucleus and hence
are more polarisable. This would lead to a certain amount of distortion of the outer
electrons, and consequently equip them better to attack the carbon atom of the
substrate.Thus, necleophilicity is dependent on polarisability. For example, the
increasing order of nucleophilicity in the following is as given :

SAQ 1
Arrange the following in the increasing order of nucleophilicity.

a) R3C-, RO', F-, R2N-

--------------------------------------------------------------------------------------------------
SAQ 2
Which member of the following pair would undergo the faster SN2reaction and why?
a. C6H5CH2CI or C6HllCI
 Nature of the leaving group Alkyl Halides :Substitution
The rate of a reaction also dependents on the type of leaving group. We would and Elimination Reactions
expect that weak bases would be good leaving groups. Good leaving groups are
conjugate bases of acids with pKa value below 3. Strong bases, s~ichas OH-, are
never good leaving groups in substitution reactions. Other strong bases which are
poor leaving groups are OH-, RO-, H2N-, R2N-.

16.5 S , 1 REACTIONS
We saw in the previous section that tert-alkyl halides either have a very slow rate of
reaction or do not undergo SN2reactions. Now, the question arises, if tertiary alkyl
halides cannot undergo SN2reaction, how are the substitution products formed? The
answer is that tertiary alkyl halides undergo substitution by a different mechanism,
"
called the S,1 reaction (substitution nucleophilic unimolecular). An example of
such a reaction is the hydrolysis of 2-chloro-2-methylpropanewith water. This type
of reaction is also known as solvolysis reaction.
Hydrolysis (CH~)~C-OH
(CH,),C-CI
16.5.1 Mechanism of SN1 Reactions
This is a two step mechanism. In the first step the leaving group departand the
intermediate carbocation is formed. In the second step nucleophile attacks the
carbocation to give the substituted product. Carbocation, being very reactive, reacts
rapidly with the nucleophile and hence the second step is very fast. Thus the first
step-is slow and is the rate determining step (RDS). The two steps of S 1
mechanism can be shown as follows :
r
Step I :

L J
Transition State I

CH3- G+
CH3
I

I
CH3
Fast
H20
)
CH3;C
CH3
I
I
CH3
6+
- - - - - "2 ] -.' 'cH3-c
CH3
I
I
CH3
- OH Because ofthe lack of
stabilization, methyl and
primary halides do not normally
Transition State 11 form carbocation.

I
In the first step, which is the rate determining step, only one molecule i.e. alkylhalide,
, is involved. That means the rate of reactiofi is proportional to the concentration of
I
t
I
the one reacting species, which is the alkyl halide and is independent of the
nucleophile.
Rate a (CH,),CCI
or Rate = k [(CH,),CCI]
The potentialgnergy diagram for a SN1reaction is given in Fig. 16.3 Step 1 has high
energy of activation and is, therefore, the slow step. Also potential energy of the
transition state, where bond breaking (I) and bond making I1 actually occur, is a high
point on the potential energy curve, e.g., I and 11(Fig. 16.3).As shown in this figure,
an intermediate has lower energy than the transition state. However, the
intermediate has higher energy than the final products.
i

I
Chemistry of Carbon

Reaction coordinate -----*

Fig. 16.3 :Potential energy diagram for a S,1 mechanism

16.5.2 Stereochemistry of S,1 Reactions

In the S N I reaction we have just seen that in the first step carbocation intermediate
is formed. The stereochemistry of the product would therefore, depends on the
stereochemistry of the carbocation. As we all know that carbocations are planar
and the carbon atom is sp2 hybridized that means the groups attached to it are in
the same plane and the angles between bonds are 120'. Therefore in the second
step the nucleophile can attack the carbocation from either side with equal
probability i.e.

-
Or

CH3
I
OH-C-CH,
I
CH3

Thus the product should be a 50 : 50 mixture of (+) and (-) isomers i.e. a racemic
mixture. In practice, however, it is found the complete recemisation is not there and
that inversion almost always exceeds retention. The reason for this is that the
nucleophile attacks the carbocation before the leaving group has completely
departed. In such situation the leaving group to certain extent, shields the
carbocation from its side. As a result, more of a product with inverted configuration
would be formed.
16.5.3. Reactivity in S,1 reactions
-
Alkyl
Like SN2reaction, S, 1reaction is also influenced by following factors. and Elimination Reactions
StructureofAlkyl halide
Structure of Leaving group
Sincein SN1reaction the nucleophile comes in picture only after rate determining
step, it cannot effect the rate of reaction. Let us discuss the two factor in little detail.
Structure of the Alkyl halide
The structure of alkyl halide effects the rate of S,l reaction. The rate of a reaction
proceeding by S,1 mechanism is fast when the intermediate carbocation is stable.
You may recall that the carbocation is stabilised by inductive effect, resonance
effect andhyperconjugation. The order of stability of carbacation is
tertiary > secondary > primary
In other words, among alkyl halide the order of relative rate is:
tert. RX > sec RX >pri RX > CH,X
Carbocations are also stabilised by resonance by phenyl and allyl groups.

R-C R-C R-C R-C R-C,.

The order of stability of cations as a result of resonance effect is as follows :

+ + + +
(C6H5)3C>(C6H5), C H > C 6 H 5 C H 2 >CH2 = C H - C H 2
mphehnyl benzhydryl benzyl ally1
methyl

We are giving the relative rates of reaction of some alkyl bromides under typical SN1
conditions in Table 16.3.
Table 16.3 :Relative reaction rates of hydrolysis of some alkyl bromides under typical S,1
conditions.
Alkvl bromide Relative rate

(CH3)2CH-B' 11.6
(CH3),C-Br 1 . 2 lo6
~

Thus, the electronic effects; inductive and resonance effects play a major role in
S,1 mechanism whereas the steric effects are more important in SN2mechanism.
From the above discussion it is clear that primary alkyl halide undergo SN2reaction
at a faster rate than the secondary and tertiary alkyl halide. Tertiary alky1.halides
undergo S, 1 reaction at a faster rate than the secondary and primary alkyl halides.
Now the question arises what would be the mechanism in the case of secondary
halides? In this case some reactions proceed both by SN1and S,2 mechanisms,
These are borderline cases. Either both operate simultaneously or in some cases a
common mechanism - an in between type can be given. These complications will be
dealt with in an advanced course.
As we have just learned that carbocation is formed in the rate determining step of
SN1mechanism arid we know that rearrangement is one of the characteristics of
~,,,mistryof Carbon carbocation. A carbocation formed often undergo rearrangement to give more stable
Compounds carbocation to give more stable substituted products, e.g.

I 1 '

CH3 -C-CH2Br 'low ,CH3 - C-CH2 ---4

1 RDS I
CH3 CH3

Effects of the leaving group

Effect of the leaving group is relatively simple as in SN2reactions. The more easily
the bond to theTeaving group is broken, the more reactive the substance will be.
In many substitution reactions, the nucleophile can also act as a base. In these
cases, elimination becomes a competitive reaction along with substitution. This we
will discuss in the next section.
SAQ 3
Which of the following pair would undergo a faster SN1 reaction and why?

16.6 ELIMINATION REACTIONS

...Aside reaction that occurs during substitution reactions of alkyl halides is the.
elimination of HX (dehydrohalogenation)to produce an alkene.

(L = living group e.g. halogen, PR,, OH, OCOR etc.)

Under appropriate conditions suchas the use of a strong base (OH- or OR-), and
high temperature, elimination can be the principal reaction and thus become a
method for preparing alkenes.
Elimination reactions like nucleop.hilic substitytion reaction can proceed by either a
first or a second order mechanism. The first order elimination reaction is symbolised
as El and the second order elimination reaction as E2. El and E2 mechanisms are
clolsely related to SN1and SN2mechanisms respectively. E l and E2 mechanisms are .
different from each other at the time of breaking C-H and C-L bonds and
consequently in their kinetics. Now let us discuss them separately.
Like substitution reactions rate of elimination reactions are also affected by many
factors, which we have already studied in b i t 13.

16.7 E2 REACTIONS
The most useful elimination reaction of alkyl lnlides is the E2 reaction (bimol~cular
elimination). The E2 reactions of alkyl halides are favoured by the use of strong
bases, such as OH- or OR- and high temperature. Typically the E2 neaction is
carried out by heating the alkyl halide with KOH or C2H50-Na+in ethanol.
 Alkyl Halides : Substitution
Br
I and Elimination Reactions
CH3CHCH3 + CH3CH20- CH3CH20H
CH3CH = CH2 + CH3CH20H + BF
2-bromopropme ethoxide ion heat propene

16.7.1 Mechanism of E2 Reactions

E2 meclianis~iiinvolves breaking of C-L and C-H bonds simultaneously. The base
pulls away hydrogen, as a proton, from carbon atom; simultaneously the leaving
group departs and a double bond is formed. Tlie leaving group takes its electrons
pair with it and hydrogen leaves its electrons pair behind to form the double bond.
This is a one step mechanism involving a transition state with a partial double bond
character,

7 .

lransition stale

Since it is a one step reaction, both reactants are involved in the transition state and
the rate of overall reaction depends on tlie concentration of the substrate as well as
concentration of tlie base, i.e.
Rate a [substrate] [base]
This reaction is known as bi~nolecularelim,ination or E2 reaction. Reaction kinetics is
typically second order : first order in base and first order in the substrate.
Another mechanism tliat is consistent with tlie above kinetic requirements is called
tlie carbanion or ElcB ~nechariisrnin which hydrogen leaves first. This is a two steps
mechanism. Tlie base removes tlie hydrogen in tlie first step to form an intermediate
carbanion, which then can react rapidly, in the second step, either to give substituted
product or lose L- to forin the alkene.

ElcB mechanism is tlie least common of the elimination pathways. The carbanion
meclianism has been shown to be a special case and occurs only where the
carbanion from tlie si~bstrateis strongly stabilised and where the leaving group is a
poor leaving group and would not be lost from the developing anion. An example of
a reaction, wliicli follows ElcB mechanisms, is the formation of 1,l-dichloro-2,2-
difluoroethene from I, I -dicliloro-2,2,2-trifluoroethanein the presence of
I - +
I
I
C2Hj O N a . You may note that the carbanion is strongly stabilised due to -I effect
of halogens. further F is a poor leaving group.
)

Tlie name ElcB comes from tlie fact that it is the conjugate base of the substrate
tliat is giving up tlie leaving group. The process usually, shows second order kinetic
but is designated as ElcB (elimination, uni~nole~ular, of aconjugated base) to indicate
tliat departure of the leaving group from tlie initially formed carbanion leads to the
prodi~ct.
Chemistry of Carbon SAQ 4
Compounds Fill in the blanks in the following statements.
a) E2 elimination is ..................................... step reaction.,
b) Rate of E2 elimination depends on concentration of .....................................
and ......................................
c) Reaction kinetics of ElcB elimination is .....................................order.
d) Reaction kinetics of E? elimination is ..................................... order.
16.7.2 Evidence of E2 Reaction
'The most important evidence supporting this mechanism is the reaction kinetics,
whicl~you have just studied. The other evidence that supp~ttE2 mechanism are:
i) Absence of rearrangement
ii) Isotope effect
iii) Absence of hydrogen exchange
i) Absence of Rearrangement
Rearrangement is characteristic of carbocations. Since E2 is a single step
mechanism, it does not i~ivolveintermediate carbocation and therefore, it doe not
give rearranged product (compare with El reaction given later in this unit).
ii) Isotope Effect
A second and more compelling piece of evidence that supports ou~understandingof
E2 mechanism is isotope effect.
Let us consider dehydrohalogenation of labelled (deuterated) and unlabeled
I -bromopropanes.

The labelled 1-bromopropane contains two deuterium atoms at P-carbon, from

which one deuterium atom must be lost in the elimination reaction. We have seen
that breaking of the C-H bond is an integral part of the rate determining step of an
E2 reaction. The stronger C-D bond requires more energy to be broken. Therefore
rate of elimination in deuterated 1-bromopropane should be slower. In fact, it has
been observed that the unlabelled alkyl halide reacts seven time faster than the
labelled alkyl halide.
What is significant about the existence of isotope effect here? This shows the
breaking of C-H bond takes place in rate-determining step. Let us compare the rate
of this reaction if it was proceeding according to El mechanism. In E l elimination,
too, C-D and C-H bonds would be broken but from the carbocation, in the second
step, which is not the rate determining step. Thus it has no effect on the overall rate
of reaction. .
iii)Absence of Hydrogen Exchange
E2 elimination reactions are not accompanied by hydrogen exchange. A distinction
between the E2 and ElcB mechanisms can be made by means of tracer
experiments to test for hydrogen exchange. T& reaction of l-bromo-2-
phenylethane with sodium ethoxide, was run in deuterated ethanol, C2H50D.
C2H50Dand the unchanged
1-bromo-2-phenylethane was recovered. If the carbanioh mechanism had operated,
deuterium would have been found in the recovered 1-bromo-2;phenyleihane i.e.
%
 Alkyl Halides :Substitution
and Elimination Reactions

The recovered I -bromo-2-phenylethane did not contain any deuterium, so the

carbanion ~nechaiiis~n does not operate in this case.
16.7.3 Orientation in E2 Reactions
-
As unsymmetrical substrate with at least two hydrogen-bearing b-carbons can
afford a mixture of alkenes. For example, 2-bromobutane on 1,2-elimination can give
either I -butene or 2-butene.

Similarly,deconipositio~iofsec. butyl tri-methyl ammonium hydroxide also gives a

mixture of I -tn~teneand 2-butene.

Now the question arises, which isomer will predominate? It is observed that in first
reaction 2-bukne formed as a major product and in second reaction I-butene as the
major product. The direction of orientation is governed by Hofmann rule or Saytzeff
rule. Therefore, let us first discuss these rules.
Hofmann Rule
Hofmann rulegoverns the direction of orientation in elimination reactions in which
the a carbon atom is attached to a positively charged atom. It states that during the
elimination reactionsofpositively charged species, the least substituted alkene will
be the major product. Although originally applied to quarternary ammonium
compounds, this rule has since been applied to other substrates also, in which the a-
carbon is attached to a positively charged atom, e.g.,

I
. C2H50-
CH3CH2-CH-CH3 > CH3CH2CH2= CH2+ CH3CH =CHCH3
I-Butene (Major) 2-Butene (Minor)

CH3CH2- C H - CH3 +CH3CH2CM= CH2 + CH3CH = CHCH3

I-Butene (Major) 2-Butene (Minor)
+L(CH,~
Saytzeff Rule
Saytzeff rule governs the direction of orientation in elimination reactions involving
neutral substrates. Itstates that a neutral substrate, such as an alkyl halide, is *

converted preferably to the more substituted alkene. Thus in the following reactions
2:butene and 2 methyl3 butene will be the major product i.e.
Chemistry ofcarbon The elimination reactions covered by these orientation rules are base-induced
Compounds reactions which is a characteristic of E2 reactions. But why is there such a variation
in the nature of obtained from quarternary ammonium compounds on the
one hand and alkyl halides on the other? The following reasoning may best explain
these differences.
Let us first consider the transition states (T.S.) for the formation of the two alkenes
i.e. less substituted and more substituted alkene from an alkyl halide. Both the
transition states for the E2 elimination reaction have partial double bond character
as shown below.

T.S. of less T.S. of more

substituted alkene substituted alkene
Since both the transition states have double character, the transition state leading to
more stable alkene is itself more stabilised and is of lower energy.

L
RX + base more substituted ulkene
1 predom inunf product

Progress of reaction -
Fig. 16.4 :Energy diagram for a typical E2 reaction.
Therefore the inore stable alkene is formed as a major product. The more the
number of alkyl substituents on either side of the double bond, the greater the
stability of the resulting alkene. Thus, another way of stating Saytzeff rule is to say
that the more stable alkene is formed preferentially. This is also an instance of
relative rates of formation of products. However, Hofmann rule contradicts the
"thermodynamic control" as the product composition reflects the preferential
formation of the less-substituted (i.e. the less stable) alkene. How does one account
for this?
The rule can be understood by considering the mechanism of elimination reaction of
quarternary ammoilium hydroxide. In this reaction, base abstracts, a proton from the
P-carbon atom with simultaneous expulsion of a tertiary base from.the a-carbon
atom.giving rise to the formation of a double bond, i.e.,

CH3 =CH2 - CH - C H2 CH3CH2CH= CH2

I *I
*(;~3)3'N3 I4 Less substituted alkcne

There is one more possibility,

 - -
CH3 - -
.- & CH3CH =CHCH,

More substituted alkene

I11 the preserlc:e of strong elec wit1ldra wing group, positive charge i induced o
all the surrourlding atoms, ca the loosening of a P-hydrogen wkic gets easily
abstracted by the base. But if an electron releasing group, say an alkyl is
attached to this carbon, it tends to neutralise the induced positive charge and thus
abstractiori of (3-hydrogen becomes difficult. It is understandable that if the
alnlno~~iu~vl salt has an ethyl as well as a propyl group attached to the positively
charged nitrogen, ethyl group would be lost more readily to form ethene.
Dehydrohalogenation of 2-bromobi~taneusing a bulky base leads to the formation of
I-butene (less substituted alkene) as a major prociuct (steric effect). An example of
this type of el in~iriationis :

Another type of "orientation" effect may be mentioned here briefly. When a 1,2-
dis~rbstit~rtedor inore highly substituted alkene is formed, cis-trans isomerism is
possible. Tliirs, 2-bromobutane actually yields three products rather tha'n the two
indicated PI-eviously.Two of these are geometrical isomers, the third a structural
isomer,

CH3CH,CHCH, ----+C H 3 \ C , C /CH3+ H=C<?'+CH,CH,CH

l ~ =CH,
I H' H' CH',
Br cis trans

As you woirld expect, tlie more stable of the isomeric 2-butenes is the trans isomer,
since tlie two ~netliylgroups are as far from each other as possible. In general, the ,
geometric isomer of an alkene, which has the two largest groups trans to each other
is the more stable isomer.

SAQ 5
Give tlie major product ofthe following

OH-
C) CH3CH2CH2CHCH3
I

Stereochemistry of E2 Reactions
A kriowledge of the stereochemistry of E2 eliminations is important for a compIete
understanding of their mechanism. An elimination react'ion can occur in two
stereoche~nicallydifferent ways, viz., syn eliminqtion and antielimination. In syn
elimination H and L leave the alkyl halide from the same side, while in anti
elimination H arid L leave from the opposite sides, i.e. ,
Experimentally, it is found thatE2 elimination is an anti-elimination. The interesting
feature of an anti-elimination is that the groups that are lost in the formation of the
product determine the stereochemistry of that product.
The, E2 reaction seems to be easier when hydrogen and the leaving group are trans
and the four atoms involved (H, Cg, Ca, L) are in the same plane (trans coplanar).
Let us consider another example, dehydrohalogenation of 1-bromo-l,2-diphenyl- .
propane.

CH3
I
.
-+C6H5CH = C C6H5
I,Z-Diphenyl propane

,
Tliis compund. contaii~sto chiral centres and hence it has four stereoisomers.
(Two pairs uf eiantiomds .e. erythro and threo.)

C,H, C,H,
I TI
1 I
Erthro
Since there is only one P-hydrogen present in the molecule, all the four isomers yield Alkyl Halides :Substitution
the same product, i.k. 1,2-diphenyl-1-propene. But this product too, exists as a pair and Elimination Reactions
of stereoisomer : the Z and E geometrical isomers.
TIie eli~ninationof HBr from erythro halide (1 or 11), which follows anti elimination
gives only 2-alkene. Since the reaction yields only one diastereomer,Z, of a possible
pair, it is stereoselective.

Similarly, elimination of HBr from threo halide (DI or IV) gives only the E-alkene,
which also follows anti-elimination.

(E)1,2-Diphenylpropene

CH,

A reaction in which different stereoisomers of the reactant yield stereochemically

different products is said to be stereospecific reaction. Our studies have s50wn that
E2 elimination is both stereoselective and stereospecific.
These discussions show that E2 is an anti-elimination. Now, the question arises why
is anti-elimination preferred? This is because anti-elimination occurs through a
Chemistry of Carbon transition state in which the molecule assumes a staggered conformation and syn-
Compounds elimination occurs through a transition state that has an eclipsed conformation. Since
staggered conformation is more stable, the transition state of anti-elimination is also
more stable. Hence anti-elimination is faster and preferred over syn-elimination.
This can also be explained on the basis of steric factor. In anti-elimination the
attacking species, a base and the leaving group are on opposite side of the molecule
and cannot interfere with each other's way. However, in syn-elimination both, base
and leaving group are on the same side and therefore, they can interfere sterically
with each other's way. Therefore, anti-elimination is preferred over iyn-elimination.
The rate of the following reactions support an anti-elimination E2 reactions. The
isomeric cliloromaleic acid (Hand CI cis) and chlorofumaric acid (H and C1 trans)
both give butynedioic (acetylene dicarboxylic) acid on treatment with a base; but
chlorofurnaric acid reacts about 50 times faster.

H COOH
'P'

Slow
C COOH
/ \
C1 COOH I
Chlormalic acid

I
H
\
C
'
COOH
-
COOH

-II . OH- 1 Butynadioic

C acid
/ \ Fast
HOOC CI
Chlorofumeric acid

SAQ 6
Which compound in each ofthe following pairs undergoes E2 reaction more rapidly
and why?

16.8 E l REACTIONS
In the absence of a strong base, tertiary alkyl halides, and to some extent secondary
alkyl halides, dehydrohalogenate via the El mechanism.
16.8,l Mechanism of E l Reactions
El mechanism involves first the breaking of C-L bond which is then followed by
breaking of C-H bond and formation of a new x bond between the two carbon
atoms. In this mechanism, the bond broken and bond-made are the same as iq E2
mechanism; however, bond breaking and bond making here are taking place not
simultaneously,but one after the other. So, whereas E2 is a one step process, El is
a two step process.
The first step in an El mechanism is identical to the first step of the SN1mechanism
i.e., the substrate undergoes heterolysis to form a carbocation.
 Alkyl Halides :Substitution
and EliminationReactions

I I I I
H H
Carbocaticn

In the second step, the carbocation rapidly loses a P-proton to the base, which is
generally the solvent itself, and forms the alkene.

The first step of E l mechanism is slow and therefore, is the rate determining step.
As shown above, only the substrate is involved in the rate determining step that
means the rate of reaction is dependent only on the concentration of the substrate
and is independent of the concentration of base.
Rate a [substrate]
Therefore, it is knowr~as unimolecular elimination or El elimination and the reaction
kinetic is of first order.
16.8.2 Evidence of E l Reaction
Like in E2 reaction, here too, the reaction kinetics is the most important evidence
supporting El mechanism. The other evidences are :
Absence of isotope effect
Rearrangement
i) Absence of Isotope Effect
El mechanisni does not show isotope effect. We have seen that isotope effect
occur in elimination only ifthe P-carbon-hydrogen bond is broken in the rate
deter~niningstep. In El mechanism rupture of the C-H (or C-D) bond occurs in the
second step which is not the rate determining step, so there is no difference in the
rate of reaction in an unlabelled and isotopically (D),Jabelled compound.
ii) Rearrangement
We know that reactivity of El reaction is determined by the rate of formation of
carbocation and this depends upon the stability of wrbocation.
The first step of an El reaction gives a carbocation. Since rearrangement is
characteristic of carbocations, E 1 reaction should be susceptible to rearrangements.
This, too, is confirmed by experiment. For example,

I
,
(CH ), C C HCH3
I
C2H50H ) (CH3)3CCH= CH2+CH3C = CCH3
Normal product 1
Br '333
Re arranged
product

16.8.3 Orientation in E l Reactions

We have studied that the orientation of\E2reactions is governed by the Hofmann
and Saytzeff rules. Do El eliminations follow these rules? In the El reaction,
hydrogen is not lost until the carbocation is formed and therefore, the loss should not
depend on the nature of the departing group. So, the distinction of a positively
charged leaving group and a neutral one cannot be invoked here. Since the same
carbocation would arise from ionization of halide or a quarternary ammonium group
~hcniistryofcarbon the same orientation should be observed. Tliis hypothesis has been validated by
Comlw~~ntls showing that E I reactions of both halides and quarternary ammouium salts give the
same product - the Saytzeff product i.e., tlie more substit~~ted alkene. Since tlie
most stable alke~iearises from tlie most stable transition state one should expect tlie
Saytzeff product to predominate regardless of tlie substrate or mechanism.

SAQ 7
Why El mechanism does not show isotope effect.
..........................................................................................

16.9 SUMMARY
In this unit you have studied :
reactions mostly following SN1 or SN2 mechanis~n.
Substit~~tion
In S,2 reaction nucleophile attacks tlie substrate fro111tlie side opposite to the
leaving group. Tlie rate of resctioli depends upon tlie co~icentratio~i
~iucleopliileand substrate.
111SN1 carbacatio~iformed in tlie first step and tlie rate of reaction depends
only on co~icentrationof tlie substrate.
Elimination reaction take place either by E2 or El ~neclia~iism.
In E I reaction leaving group departs first to produce carbocation and in E2
reaction botli groups depart sim~~ltaneously.
In E2 reaction botli reactants are involved in rate determining step and
tlierefore its reaction kinetic is of second order.
In El reaction only substrate is involved in tlie rate determining step and
tlierefore reactiou kinetic is first order.
When Inore substit~~ted
alkene is the product it is said to follow Saytzeff
orientation. For~natio~i
of less Stibstituted alke~ieis result of tlie Hofiiiann
orientation.
 QUESTION
Wliat is signilicance of "hydrogen exchange" in E l reaction and "isotope
cffect" in E2 reaction?
What is the difference between E l and ElcB mechanism.
Arrange the followi~ig: CH,ClI,CH,OCH,, CH3CH2CH20Tarid
- - in increasinb order of SN2reactivity and justify your answer
CI-I.CH,CH,Br
.)

Whal is LIII/~ arld ,SJ>II elimination? Explai~lwith specific examples.

Wliat are the factors which control the product forrnatiorl under eo~npetirlg
co~iditionsof biomolecular substitution and elimination reactions? Explain any
two l'actors.

Predict the dehydrol~alogenatio~~

products, including their stereochemistry of
the following
a) 1!1espdi broniosti bene