Elimination Reactions

Three Major Mechanism is Involved

1) E1: Elimination, unimolecular
closely related to SN1, via carbocation intermediate
rate = [R2CHCH2X]
2) E1cB: Elimination from conjugated base
via carbanion intermediate/anionic intermediate
rate = [R2CHCH2X][Base]

3) E2: Elimination, bimolecular

closely related to SN2, concerted
rate = [R2CHCH2X][Base]

E1 Mechanism: Like SN1, first a carbocation form

The elimination reaction favored at higher temperatures.

Primary alkyl halides do not form carbocations; therefore

they cannot undergo SN1 and E1 reactions.

the E1cB mechanism

1)

.. _
O:
..

..
O
..

H
C

fast

C
Br

_
..
C

C
Br

O
O

2)

C
O

_
..
C

C
C

slow

Br

Elimination from conjugated base: via carbanion intermediate

rate = [R2CHCH2X][Base]

_
Br

The E2 Reaction

Hydroxide cannot act as a nucleophile in this reaction because of

the bulky tertiary halide. Rather, hydroxide acts as a base and
abstracts a proton.

In addition to E2 reaction some SN2 product can form

The removal of a proton and a halide ion is called

dehydrohalogenation:

An E2 reaction is also called a b-elimination or a

1,2-elimination reaction:

The weaker the base, the better it is as a leaving group

E2 eliminations have anti-periplanar transition states

In E2 eliminations, the new bond

is formed by overlap of the C-H
bond with the C-X * antibonding
orbital

Another view of the E2 reaction mechanism

The best overlap of the interacting orbitals is achieved

through back-side attack

Anti elimination avoids repulsion of the electron-rich

base

Torsional strain
In TS, a negative charge is develop at -carbon it undergo overlapping with *

i) anti-periplanar, in transition state developing electron

cloud undergo easy overlapping with empty *
ii) Base and leaving group are in maximum distance
hence minimum steric interaction
iii) staggered conformation is least energetic than eclipsed

staggered
anti-periplanar arrangement
Stabilizing interaction between filled
C-H bond and empty C-X *
antibonding bonding orbital

Conclusion: when possible think about elimination (E2)

from anti-periplanar arrangement

eclipsed
syn-periplanar
arrangement

Why is the eclipsed conformation higher in energy

than the staggered conformation?

The H-atoms are too small to get in each others

way-steric factors make up < 10% of the rotational
barrier in ethane

Torsional strain
Caused by repulsion of the bonding electrons of one substituent with the bonding
electrons of a nearby substituent

filled orbitals repel

Stabilizing interaction between filled

C-H bond and empty C-H *
antibonding bonding orbital

The real picture is probably a mixture of all 3 effects

The rotational barrier is (12 kJ/mol) small enough to allow the conformational isomers
to interconvert million of times per second

When only one hydrogen is bonded to the b-carbon, the

major product of an E2 reaction depends on the structure
of the alkene

Elimination from Cyclic Compounds

In an E2 reaction, groups to be eliminated must be in
axial positions

Q.

CH3

CH3

CH3

NaOEt
Cl

(faster
reaction)

1:3
CH3

CH3
NaOEt

(250 times

Cl slower)

Me

OEt
H
Me

Cl

Cl
Me

Cl
Cl

(slower reaction)

Me
H
OEt

The hydrogen that is removed and the leaving group

both have to be in the axial position, therefore

H3C

Br
C6H5
C6H5

C6H5

OH

(faster)
CH3

C6H5

H3C

Br
C6H5
C6H5

C6H5

OH

(slower)
CH3

C6H5

H
Br

Br
H3C

Ph

Ph

CH3

Ph
Ph

OH

OH

faster

slower

Br
CO2H

C6H5
H

CO2H

C6H5

C5H5N

COC6H5

COC6H5
H

Whereas

Br
C6H5

HO2C
H

C5H5N

COC6H5

C6H5

COC6H5

Br
H

C6H5
H

COC6H5
CO2H

C5H5N

C6H5

COC6H5

C6H5

CO2H

COC6H5

Predict the product of following reaction

OMe

HO2C
HO
NH2

HNO2

It is more difficult to form an acetal of compound A than of B.

Why?
O
O
HO

OH

H+

A
O
O
HO

OH

H+