a type of organic reaction in

which two substituents are

removed from a molecule in
either a one or two-step
mechanism
a-elimination
b-elimination
g-elimination
C C
H
X
C C
H
X
C C
H
X
B:
C C
C C
H
+
C C
X
C C
C C
B:
B:
E2
E1
E1cb
concerted
halogen
first
proton
second
proton
first
halogen
second
carbocation
carbanion
1,2-elimination (b-elimination) indicates that
the atoms that are lost come from adjacent
C atoms.

The two most important methods are:
1. Dehydration (-H
2
O) of alcohols
2. Dehydrohalogenation (-HX) of alkyl
halides
In the 1920,
Christopher Ingold
and Hughes
elimination
bimolecular
the base-induced
elimination of
"HX" of an alkyl
halide gives rise to
an alkene.
rate =
k [B][RLG ]
second-order kinetics
( two molecules must
come together for the
reaction to occur)
a one-step process
of elimination with
a single transition
state
Reaction often
present with
strong base
Hybridization of
carbons need to
be lowered from
sp3 to sp2
Must have one or
more b-hydrogens
H and the leaving group must be
anti to one another and must be in
the same plane as the two carbons
to which they are attached
If two or more alkenes are produced, the
one having the greater or greatest
number of carbon-containing
substituents attached to the C=C bond is
usually the major product.
Stereochemical E2 reactions always occur via
periplanar", geometry, that is, the atoms of the H-C-C-X
group involved in the reaction must all lie in the same
plane. This gives rise to two possible orientations

R-X
Methyl and
1
o
SN
2

2
o
SN
2
and
E
2
E
2
if strong
bases are
used
3
o
E
2
if
strong bases
are used
LG
The C-LG bond
is broken
during the rate
determining
step, so the
rate does
depend on the
nature of the
leaving group.
However, if a
leaving group
is too good,
then an E
1

reaction may
result
Base
More
reactive
bases will
favour an
E
2
reaction.
Weak bases
will favour
an E
1

reaction
Temperature
& Solvent
T >
Elimination
was occur
rather then
substitution
Solvent
E
2
/SN
2
polar
aprotic
Cl
H
EtO
Me
i
Pr
i
Pr
Me
100%
Cl
Cl
i
Pr
Me
H
EtO
Because conformer B has two different axial b
hydrogens, labeled H
a
and H
b
, E2 reaction occurs in
two different directions to afford two alkenes.
The major product contains the more stable
trisubstituted double bond, as predicted by the
Zaitsev rule.
Because conformer D has only one axial b H, E2
reaction occurs only in one direction to afford a
single product. This is not predicted by the Zaitzev
rule.
unimolecular elimination
Reactions involving carbocations
rate = k [R-LG ]
The reaction rate is influenced only by the concentration of
the alkyl halide because carbocation formation is the slowest
rate-determining step. Therefore first order kinetics reaction
a two-step proces of elimination : ionization (carbon-halogen
breaks to give a carbocation intermediate) and deprotonation.
of the carbocation
Reaction mostly occurs in complete absence of base or presence
of only a weak base
Typical of tertiary and some secondary substituted alkyl
halides
E
1
reactions are in competition with SN
1
reactions because they
share a common carbocationic intermediate
R
Reactivity
order: carbocation
stability
the rate
determining step is
the loss of the
leaving group to
form the
intermediate
carbocation.
there is always the
possibility of
rearrangements to
generate a more
stable carbocation.
This is indicated by
a change in the
position of the
alkene or a change
in the carbon
skeleton of the
product when
compared to the
starting material.
LG
The only event in
the rate
determining step is
breaking the C-LG
bond
There is a very
strong dependence
on the nature of the
leaving group (the
better the leaving
group, the faster the
E1 reaction will be)
In the acid
catalysed reactions
of alcohols, the -OH
is protonated first
to give an oxonium
ion, providing the
much better leaving
group, a water
molecule
B
Since the base is not
involved in the rate
determining step,
the nature of the
base is unimportant
in an E1 reaction.
However, the more
reactive the base,
the more likely an
E2 reaction
becomes
MEDIUM
reactions are most
favorable in protic
solvents, such as
carboxylic acids or
alcohols.
Neutral or acidic
conditions are most
common, but
sometimes the
media are slightly
basic.


E
1
reactions usually favour the more stable
alkene as the major product :
more highly substituted
trans- > cis-








CH
3
Br
CH
3 CH
2
+
major minor
0.001 M
KOH / EtOH
tertiary trisubstituted disubstituted
very dilute base
Zaitsev
Strong base is needed for E
2
but not for E
1
E
2
is stereospecific, E
1
is not
E
1
gives Zaitsev orientation
[RX] constant, [B] increasing
Rate
rate = k
1
[RX]
E1
rate = k
2
[RX] [B]
E2
BEHAVIOR OF THE RATE
WITH INCREASING BASE CONCENTRATION
second order
first order
E1 dominates
at low base
concentration
E2 dominates
at higher base
concentration
EXAMPLES
N a O E t
E t O H
E t O H
6M
K O H
0.01 M
C H
B r
C H
3
C H
B r
C H
3
C H C H
2
C H C H
3
+
E2
E1
rate = k [RBr]
rate = k [RBr] [OEt]
..
:O E t
..
[RX] constant, [Base] increasing
Rate
EFFECT OF BASE CONCENTRATION ON E1/E2 REACTIONS
secondary RX, k
tertiary RX, k
primary RX, k
k
1
[RX]
E1
For E1 elimination : k (tertiary) > k (secondary) > k (primary).
k
2
[RX] [B]
E2 At high base concentration
E1 never has a chance.
At low base concentration
E2 is nonexistent
1
1
1
secondary RX, k
tertiary RX, k
primary RX, k
[RX] constant, [B]
Rate
k
1
[RX]
E1
EFFECT OF BASE CONCENTRATION ON E1/E2 REACTIONS
k
2
[RX] [B]
E2
For E2 elimination : line slopes k
2
differ for 1
o
,2
o
,3
o
.
Different substrates react at different rates,
primary
secondary
tertiary
1
1
2
k
2
k
k
2
E2 mechanism E1 mechanism
strong base
high base conc.
weak base
low base conc.
ALKYL HALIDE + BASE
solvolysis
must be able to make
good carbocation
or
anti-coplanar
requirement
stereospecific not stereospecific
(solvent is base)
regioselective regioselective
CH
3
CH
3
CH
3
Br
H
H
H
H
H
Zaitsev
Anti-Zaitsev
NaOEt
EtOH / D
E2
stereospecific
anti
not
stereospecific
E1
EtOH / D
anti
syn
major product
E1 doesnt require
anti-coplanarity
CH
3
Cl
Et OH
D
CH
3
+
CH
3
OEt
CH
3
H
H
+
O Et
H
MANY E1 REACTIONS ARE SOLVOLYSIS REACTIONS
SOLVOLYSIS
SOLVOLYSIS = THE SOLVENT IS THE REAGENT (BASE)
E1
competing product
EtOH adds to the
carbocation
O Et
H
+
CH
3
H
H
EtOH solvent
acts as base -
no other base
is present
H
H
H
H
OH
H
concd H
2
SO
4
180
o
C
H
H H
H
+ H
2
O
OH
H
85% H
3
PO
4
165-170
o
C
+ H
2
O
20% H
2
SO
4
85
o
C
+ H
2
O
H
3
C OH
CH
3
CH
2
H
CH
2
CH
3
H
3
C
3 Alcohols
Exceptionally
Easy to
Dehydrate
Can Use
Dilute Acid,
Lower
Temperatures
Relative Ease
of Reaction:
3 > 2 > 1
H
3
C OH
CH
3
CH
2
H
H
+
H
3
C OH
2
CH
3
CH
2
H
CH
3
CH
3
C
H
2
H
+ H
2
O
CH
2
CH
3
H
3
C
-H
+
-H
2
O
Base
H
3
C
CH
3
H H
H
OH H A
H
3
C
CH
3
H H
H
OH
2
A
H
3
C
H
3
C H
H
+ H
2
O + H-A
Step One Fast

Step Two Slow

Weak Bases, Substitution more likely
Strong Bases, Elimination more likely
Base strength
of Nucleophile
Sterically Unhindered, Primary haloalkanes, Substitution
more likely
Sterically Hindered, Branched primary, secondary, tertiary
haloalkanes, Elimination more likely
Steric
Hindrance
around the
reacting carbon
Sterically Unhindered, Substitution may occur with 1
Sterically Hindered, Elimination more likely
Steric
hindrance of
strong bases
This elimination gives the less substituted
alkene.
Its the less sterically hindered b hydrogen that
is removed by the base
Hoffman elimination is opposite to the Zaitsevs
rule
N(CH
3
)
3
H CH
2
CH
3
H
H
H
OH
-H
2
O
-N(CH
3
)
3
H H
H CH
2
CH
3
1-Butene
(major product)
N(CH
3
)
3
H CH
3
H
H
3
C
H
OH
-H
2
O
-N(CH
3
)
3
H CH
3
H
3
C H
trans-2-Butene
(minor product)
these two groups
crowd each other
Bulky Base Favors Least Substituted Product, Due to Steric
Crowding in Transition State (2 Hydrogens)
H
Br
CH
3
H
3
C
H
CH
2
CH
3
H
3
C
H
H
H
Br
CH
3
H
3
C
H
CH
3 CH
3
CH
3
H
3
C
H
72.5%
27.5%
OK
OK