Elimination Reactions

By
Dr Rina Shah
M G Science Institute
ELIMINATION REACTIONS
Definition: Elimination reaction defined as the reaction in which atom
or groups are eliminated to form a new bond.

Every elimination reactions under goes two common steps

•Departure of leaving groups with its electron pair
•Removal of proton by base(leaving behind electrons to form a
new bond)
Types of elimination reactions
α-Elimination where atoms or groups are eliminated from the same
atom
CHCl3→:CCl2 + HCl

β-Elimination where atoms or groups are eliminated from the adjacent

positions
RCH2-CH2Cl→ CH2=CH2 + HCl

√-Elimination where atoms or groups are eliminated from the alternate

atoms/positions
RCH2CH2CH2Cl→ R
Alkyl halides
Alkyl halides undergo elimination of HX when treated with base. The
products are Alkenes.

Elimination reactions usually require forcing conditions, i.e. heat and

strong base. The elimination reactions which alkyl halides undergo are
known as 1,2-eliminations or -eliminations.

CH3 CH3
 KOH, EtOH 
CH3 C Br C + HBr
heat CH3
CH2
CH3 
B-Elimination reaction

• The elements of HX are lost from neighboring carbon atoms and a

C=C is formed. The head carbon of the alkyl halide is termed 
(“alpha”) and the carbon atom or atoms next to it are designated 
(“beta”). The halogen atom is lost from the  carbon, and the
hydrogen from one of the  carbons.
• important mechanisms by which alkyl halides undergo elimination
reactions are:
• The E1 mechanism (unimolecular);
• The E2 mechanism (bimolecular)
The unimolecular mechanism (E1)
• The slow, rate determining step entails one species – the alkyl
halide.
• The rate of the reaction = k[alkyl halide], and the carbocation
intermediate
R R R
slow, r.d.s. R
(a)    
R C C X R C C + X
H R H R

R
R
R
  fast C + B-H
(b) R C C R
C R
B H R
R
E1 mechanism
A carbocation intermediate is formed when alkyl halides undergo
elimination via the E1 (unimolecular) mechanism.3o alkyl halides are
likely to lose HX via this mechanism. For t‐butyl bromide in aqueous
alcoholic KOH:
H CH3 H
slow, r.d.s. CH3
(a)    
H C C Br H C C + Br
H CH3 H CH3

H
H
CH3
  fast C
(b) H C C H
C CH3
HO H CH3
CH3
+ H-O-H
Evidences for E1 mechanism
• It follows first order kinetics as rate of reaction depends only on
concentration of substrate and is unimolecular
• Not accompanied by H‐isotope effect, which is not expected in E1 as
proton is removed in fast second step, whose rate is negligible
• Rate of reaction depends on the stability of carbo cation30>20>10)
• When substrate structure permits it undergo rearrangement by
hydride or alkyl shift e.g. neo pentyl bromide
• E1 reactions are nonstereospecific
• Ease of formation of alkene is R2C=CR2>CR2=CHR> RCH=CHR>
CR2=CH2> RCH=CH2> CH2=CH2
• Potential energy diagram of PE vs Reaction progress
E1Cb mechanism:
In E1cb mechanism in a fast first step base abstracts the proton in a
forming carban ion i.e. conjugate base of a substrate, which is under
equilibrium with substrate. Rate of reaction depends on the
concentration of carban ion, therefore the name given Unimolecular
Elimination via Conjugate base.
Step 1

:B H
f ast
RCH CH2Cl RCH CH2Cl

carban ion, cb of substrate

E1cb
We can establish Keq=[anion]/[base][substrate]----1
In the second slow step leaving group departs with its electron pair to
form a new bond slow
RCH CH2Cl RCH CH2 RCH=CH2

Now rate α [anion]‐‐‐‐‐‐2

So rate=K1[anion]‐‐‐‐‐‐‐‐3
And [anion]=Keq[base][substrate]‐‐‐4
From 1 and 4 we have Rate = K1.Keq[base][substrate]
Establishing new constant K for K1.Keq we have
Rate = K[base][substrate]
E1cb

This is same as bimolecular rate law for E2 reaction, which is evident

by following reaction, Deuteriated product is only possible if it follows
second order kinetics.
NaOD
Cl2C CHCl CCl2=CDCl

Increasing acidity of B-proton leading to the spectrum towards E1cb

reaction.
High electro withdrawing nature of leaving group increases the acidity
of B-proton.
Use of stronger base and base concentration also increase E1cb reaction
to occur.
E1cb

This much likely to occur when triple bond is formed, since the H of
SP3 is less acidic H of SP2, so triple bond is more readily formed.
e.g.

EtO- H
f ast slow
Cl2CH CF3 Cl2C CF2F CCl2=CF2
carban ion
The bimolecular mechanism (E2)
This is a concerted reaction. Bond formation and bond breaking take
place simultaneously.the rate determining step entails the base and
the alkyl halide.
B R
H R
  C
R C C R R
C R
R X
R
+ B-H + X

Where rate = k[alkyl halide][base]

Evidences for E2 mechanism
• It follows second order kinetics as rate of reaction depends only on
concentration of substrate and base i.e. bimolecular
Rate=[substrate][base]
• Accompanied by H‐isotope effect, which expected in E2as proton is
removed in the same step
• If H is replaced by D, rate of reaction is slower down as breaking of C‐
H bond is faster than C‐D bond
• Not accompanied by rearrangement
• E1 reactions are stereospecific
• Ease of formation of alkene is R2C=CR2>CR2=CHR> RCH=CHR>
CR2=CH2> RCH=CH2> CH2=CH2
• Potential energy diagram of PE vs Reaction progress
Stereochemistry of E2 mechanism:
• Syn and Anti elimination in E2 mechanism:
• In the case of bimolecular elimination reaction the eliminating groups
eliminate either from the same side or from the opposite sides. If
they eliminate from the opposite sides i.e. anti in position the
elimination is known as anti elimination.
• If they eliminate from the same side i.e. syn in position the
elimination is known as syn elimination.
• In anti E substrate has staggered conformation while that of in syn is
eclipsed. In staggered conformation C‐X, C‐C and C‐H bonds are in the
same plane making an angle of 1800, therefore electron pair to B‐
carbon is made easily available for the formation of new bond.
Sterechemistry of E2
E2 reactions are highly stereospecific and anti elimination is preferred
over syn elimination as substrate has to adopt an eclipsed
conformation, which is higher in energy, eliminating groups are
eclipsing in position making 00 angle.
X

antiE

H
staggered antiE product

H Br
syn

Eclipsed synE product

Anti elimination in E2
A very important feature for an alkyl halide to undergo
elimination via the E2 mechanism, the H and X groups must
be anti to each other and be in the same plane with each other
and the carbon atoms to which they are attached. The elements
of H‐X must be antiperiplanar.
Evidences for anti elimination in E2:
1,2‐Diphenyl‐1‐bromopropane undergoes elimination to form Z and E‐1,2‐
diphenylprop‐2‐ene.
H3C
H3C
Ph CH CH Ph
Br Ph
CH 3 Ph
H and
Ph

Ph
H
Z-isomer E-isomer

Ph‐C(Br)‐CH(CH3)‐Ph. It can exist as erythro and threo isomers. In

addition each erythro
Ph
and threo isomers exists as enantiomers.
Ph Ph Ph

H 3C H H CH 3 H 3C H H CH 3

Br H H Br H Br Br H

Ph Ph Ph Ph
Erythreo I Erythreo II threo II
threo I
a pair of enantiomers dlpair 1 a pair of enantiomers dl pair 2
Stereochemistry of E2
In anti elimination atoms or groups are removed from opposite sides.
Erythro isomer undergoes elimination to give Z‐isomer and threo
isomer gives E‐isomer as a product.
H
Ph H 3C H

H 3C H H 3C
Ph
Ph antiE
Br
Br H H H 3C
H
Ph
Ph
Ph Ph
Erythreo I
Br
H

Ph
H 3C Ph
H CH3 antiE Ph
H CH 3

Br H Z-1,2-diphenylpropene
H Br Ph
H
Ph
Br H Ph
Erythreo II
Ph
Threo isomer gives E‐olefin
H
Ph H 3C H

H 3C H H 3C
Ph
Ph antiE
H
H Br Ph H 3C
Br
H
Ph
Ph Ph
threo I
Br
Ph

Ph
H 3C Ph
H
H CH3 antiE
H CH 3

Br H E-1,2-diphenylpropene
Br H Ph
Br
Ph
H Ph H
threo II
Ph

This results are only obtained if anti elimination occurs.

 2) Reaction of meso‐2,3‐dibromobutane in presence of iodide ion gives
trans‐2‐butene, where as d/l 2,3‐dibromobutane gives cis‐2‐butene
H CH3
Br H CH3
H CH3 antiE
Br Br
I-
H3C H
H3C H
Br
meso H3C H Trans-2-butene
threo
H3C H H H
Br antiE
H3C H
I-
Br Br
H3C H H3C CH3
Br cis-2-butene
d/l H3C H
erythro

Reaction of meso‐2,3‐dibromobutane in presence of iodide ion as base gives trans‐2‐

butene, where iodide ion abstracts the bromonium ion(Br+) as base abstracts the proton,
and bromanium ion(Br‐) departs as a leaving group with its electron pair. d/l 2,3‐
Dibromobutane under same condition gives cis‐2‐butene. Meso compound undergoes
reaction at the double rate than dl pair as bulky methyl groups are in opposite sides(threo),
while that of dl pair are in the same side(erythro) lowering the rate of reaction.
Eclipsing effect in E2
• Lowering the rate of reaction in E2 reactionsdue to steric effect is
known as eclipsing effect in E2.
• If CH3 groups are replaced by Phenyl groups, rate of reaction
decreases 100 times. Steric effect lowering the rate of E2 is known as
eclipsing effect in E2.
3) Reaction of 2-bromo-1-phenylprapane in presence of alkoxide as
base gives styrene. Threo isomer gives trans product whereas erythro
gives cis product. Among threo undergo reaction at a faster rate.
H Ph
Br H Ph
H Ph antiE
H Br
I-
H3C H
H3 C H
H
H3C H Trans-styrene

Ph H H H
Br
antiE
Ph H
I-
H Br
H3C H H 3C Ph
H cis-styrene
d/l H3C H

In threo isomer they are on the opposite side. While in erythreo isomer bulky Ph
and Me groups are on the same side, that causes steric effect leading to the partial
eclipsing conformation, which is less stable conformer and undergoes reaction at a
lower rate than threo isomer. In this case eclipsing effect plays important role.
Cis‐tert‐butylcyclohexylbromide under goes elimination reaction to give Cis‐tert‐
butylcyclohexene, where as its trans isomer does not undergo reaction at all‐justify
Br

Me 3C Me3C

Cis ea

Br
1,2‐
Me 3C
no reaction dimethylcyclohexane trans aa ee
trans-1,4 ee sterically unf avourable cis ea ae
CMe 3 1,3‐dimethyl trans ea ae
cis aa ee
1,4‐dimethyl trans aa ee
trans-1,4 aa Br
cis ea ae
For Cis-tert-butylcyclohexylbromide ea or ae conformations are possible.
E2 elimination in six membered ring proceeds best when adjacent trans
group can adopt antiperiplanar conformation, even if this is higher energy
conformation.
The stable conformation having bulky tert-butyl in equatorial position and
bromide in axial position, in which Br-C, C-C and C-H bonds have
antiperiplanar relationship and can easily undergo E2 reaction to give Cis-
tert-butylcyclohexene.
Whereas, in case of trans-tert-butylcyclohexylbromide aa or ee conformations
are possible. The stable conformation having bulky tert-butyl and bromide
both in equatorial position.
To adopt antiperiplanar relationship for Br-C, C-C and C-H bonds, ee
conformation to be converted aa conformation, where tert-butyl group has
to be equatorial, that is sterically unfavourable, therefore it can not undergo
E2 elimination at all.
Neomenthyl bromide when undergoes E2 elimination reaction to
give 1-menthene(more stable, major prod 75%) and 2menthene(less
stable minor prod 25%), while menthyl bromide under goes E2
elimination reaction to give only 2-menthene as a product-justify.
Br
anti E +

H H H H
H H 1-menthene, more stable 2-menthene, lessstable
major prod, 75% minorprod, 25%
H at C1 and C3 are anti to Br

anti E

Br H H

H H
menthylbromide 2-menthene, only prod minorprod as only H at C3 is anti to Br
E2 in menthylchloride and neomenthylchloride
• E2 elimination in six membered ring proceeds best when
adjacent trans group can adopt antiperiplanar conformation,
even if this is higher energy conformation.
• In neomenthyl bromide bulky iso‐propyl group tends to remain
equatorial, Br is axial and two axial H atoms on neighboring
carbon are axial and anti to Br for E2 anti elimination.
• Where as in menthylchloride bulky iso‐propyl group tends to
remain equatorial, Br is also equatorial. For Br, To become axial it
has to convert iso‐prop group from equatorial to axial which is
sterically unfavourable, and can have only one axial H atom on
neighboring carbon anti to Br for E2 anti elimination.
• In addition 1‐menthene is obtained as a major product according
to Sayzeff’s orientation rule.
Syn elimination in E2:
• In certain rigid system eliminating groups do not contain
antiperiplanar arrangement, then the elimination follows
different path. When eliminating groups are on the same
side making an angle of 00 having syn periplanar
arrangement they follow syn elimination.
1. Deuteriated norbordyl tosylate when undergoes E2
elimination reaction syn product is obtained without D
(major) and anti product with retention of D (minor). Ion
pairing in ionizing solvent promotes syn E.
OTs H
H
H
D RO
+

H D
H
synE product antiE product

D and OTs are H and OTs are

removed removed, no 180
but 120
70% in presence of 30% in presence
18-C-6 of 18-C-6
2. When cyclobutyltrimethylammonium hydroxide
undergoes E2 elimination, following syn and anti products
are obtained.

OH-
H N+Me3 D

D +

H
SynE antiE
product product
Major Minor
 Other aspects of E1 and E2 reactions
• The distinction between the E1 and E2 mechanisms is not as clear as
the distinction between the SN1 and SN2 mechanisms.
• 3o and 2o alkyl halides will eliminate H‐X via both the E1 and E2
mechanisms, the elimination of H‐X from 1o alkyl halides takes place
via the E2 mechanism only.
• For both E1 and E2 mechanisms, the rates follow the trend:
• 3o R‐X > 2o R‐X > 1o R‐X (do not react via E1)
For many alkyl halides, there are two possible
elimination products.
The 3o alkyl halide below has three  carbons;
two are identical methyl (Me) groups, and the 3rd
CH3 H
H
H C C C CH3

H Br H
e.g.the elimination of HBr from this compound via the E1 mechanism.

The proportion of the less substituted alkene (Hofmann product)

can be increased by using a very bulky base. Two examples of
bulky bases are shown
Bulky bases increase the proportion of the less
substituted alkene (Hofmann product) formed in
elimination reactions.
CH3

H3C C O K potassium t-butoxide

CH3 K t-BuO

CH2CH3

CH3CH2 C O K potassium 3-ethyl-3-pentoxid

Et
CH2CH3 O K
Et C
Et
The H’s on the less substituted  carbon are more
sterically accessible to the base than are the H’s on
the more substituted  carbon. When the base is
very bulky, then the H’s on the less substituted 
carbon are almost exclusively removed, and the less
substituted (Hofmann) alkene product predominates.

Et
H CH3 Et C O K H  CH
H 3

H3C C C C H Et H3C C C
 C H
CH3 Cl H CH3 
H

97% less substituted alkene

HOFMANN PRODUCT
Elimination products: Hofmann vs. Saytzeff
Steric accessibility of the  h affects the outcome of elimination reactions. If the h on
the  carbon whose elimination leads to the more substituted alkene is very
crowded, then the proportion of the less substituted alkene product will be high.
CH 3H  CH
3

H 3C C C C C H MAJOR

CH 3 H H
CH 3H  CH
3 H
  less substituted alkene
H 3C C C C C H Et O Na HOFMANN PRODUCT
 +
CH 3 H Br H
 CH
CH 3 3

H 3C C  C H
very more C C H MINOR
accessible 
crowded CH 3 H
H
more substituted alkene
SAYTZEFF PRODUCT
When Me2CHCH(Me)S+(Me)2 undergoes elimination under E1
condition it favors Saytzeff’s product, where as under E2 condition it
favors Hoffmann product formation.
CH-CHS i.e. HC(H3C)2 CH(CH3)S(CH3)2

E1

H3C C H
CHCH3
H3C C C CH2
H
CH3
CH3
Saytzeff product 91% Hoffmann product 9%

CH-CHS i.e. HC(H3C)2 CH(CH3)S(CH3)2

E2

H3C C H
CHCH3
H3 C C C CH2
H
CH3
CH3
Saytzeff product 9% Hoffmann product 91%
Substitution versus elimination: SN1 vs E1
When substitution reactions are carried out on 3o alkyl halides (SN1
reactions), products of elimination (alkenes) are almost inevitably
formed. Let us consider the following reaction.
CH2CH3 CH2CH3
CH3CH2 C CH2CH3 + H2O CH3CH2 C CH2CH3 + HBr
Br OH

CH2CH3 CH2CH3
CH3CH2 C CH2CH3 + H2O CH3CH2 C CH2CH3 + HBr
Br OH
In this reaction the carbocation intermediate, once it is formed, can lose
a proton by reaction with a weak a base as H2O to give appreciable
quantities of the alkene (elimination) product.

CH3
H2O H3C H
H C H C

C C
CH3CH2 CH2CH3 CH3CH2 CH2CH3
Substitution versus elimination: E2 vs SN2
• It is easier to create conditions which favor the E2 mechanism over
the SN2 mechanism, or vice versa.
• very strong base (ethoxide as opposed to hydroxide)
• Relatively non‐polar solvents
• (e.g. ethanol in preference to water)
• Higher temperature
• will favor the E2 mechanism over the SN2 mechanism.
Organometallic compounds
 
C M

Compounds in which a metal is directly bonded to carbon are known as

organometallic compounds. The metal-carbon bond is polarized as shown.metals
are less electronegative than carbon; larger differences in electronegativity between
the metal and carbon increase the ionic character of the metal-carbon bond. Ionic
character of metal carbon bonds follows the trend is
Na > Li > Mg > Al > Rn > Cd > Hg
Alkyl derivatives of almost all metals have been prepared.these are named as
“alkylmetals”
(Me)2Hg dimethylmercury
(liquid; bp 92 oc; neurotoxin; environmental contaminant)
(Et)4Pb tetraethyllead (liquid; bp ~ 220 oc; toxic; formerly used as a gasoline
additive)
Grignard reagents
Alkylmagnesium halides, R-Mg-X, are known as grignard reagents.
Grignard reagents are prepared by reacting alkyl halides with excess
magnesium metal in dry alcohol-free diethyl ether or tetrahydrofuran
(THF). Diethyl ether and THF are solvents.
Et
R O Et
CH3CH2 O CH2CH3 Mg
O
diethyl ether tetrahydrofuran X
O Et
(THF), a cyclic ether Et

R-X + Mg  R-Mg-X (radical mechanism)

Ease of formation follows the trends shown below
R-I > R-Br > R-Cl.
CH3X > C2H5X >C3H7X
Grignard reagents are usually closely associated with two molecules
of the ethereal solvent in which they have been prepared.