Chapter 5
Elimination Reaction
• The elimination reaction is the second of the
fundamental heterolytic organic processes.
• In an elimination reaction, a small fragment is
ejected from a molecule, and unsaturation
(multiple bonding) is introduced.
Dehydration (H2O) of alcohols
H OH
Conc. H2SO4 H H
H C C H C C + H2O
Heat
H H H H
Ethyl alcohol Ethylene
Dehydrohalogenation (HX) of alkyl halides
H Cl H H
Alcoholic KOH
H C C H C C + HCl
Heat
H H H H
Ethyl chloride Ethylene
• Depending on the relative timing of the bond
breaking and bond formation, different
pathways are possible:
E1 reaction or unimolecular elimination and
E2 reaction or bimolecular elimination
E1 and E2 Mechanism
E1 reaction mechanism
• E1 reaction is first order elimination.
• results from the loss of a leaving group to form a
carbocation intermediate
• This reaction is most common with good leaving groups,
stable carbocations and weak bases (strong acids).
Slow Fast
C C C C + L: C C + BH + L:
H L H
B
Rate = K[RX]
Cont’d
• the rate-determining step involves one molecule, and
it is the slow ionization to generate a carbocation.
• The second step is the fast removal of a proton by the
base (solvent) to form the C=C bond.
CH3 CH3
H3C CH3
CH3OH
H C C C2H5 C C + HBr + CH3OH
Heat
H Br H C2H5
3-Bromo-3-methyl pentane 3-Methyl-2-pentene
E2 reaction mechanism
• it is a second order elimination
• the removal of a proton and simultaneous loss of a
leaving group to form the C=C bond.
• is most common with high concentration of strong
bases, poor leaving groups and less stable carbocations.
L L
C C C C C C + L: + BH
H B H
B:
Transition State
Rate = K[RX][B]
• The bromide and the proton are lost
simultaneously to form the alkene.
• The E2 reaction is the most effective for the
synthesis of alkenes from primary alkyl halides.
CH3 CH3
H3C CH3
CH3ONa + CH3OH +
H C C C2H5 C C NaCl
CH3OH, Heat
H Cl H C2H5
3-Chloro-3-methyl pentane 3-Methyl-2-pentene
• The E2 mechanism similar to the SN2 mechanism follows
a concerted mechanism, where removal of the proton
and formation of the double bond occur at the same
time
• When the hydrogen and leaving group eclipse each other
(0°), this is known as the syn-coplanar conformation.
• When the leaving group and hydrogen atom are anti to
each other (180°), this is called the anti-coplanar
conformation.
B:
H
H :B
X H X H
X
syn-Coplanar (0) syn-Elimination anti-Coplanar (180) anti-Elimination
• The E2 reaction is stereospecific, since it prefers the
anti-coplanar transition state for elimination.
• The (R,R) diastereomer gives a cis-alkene, and the
(S,R) diastereomer gives a trans-alkene.
B:
H C2H5 C2H5 C2H5
H + BH + Br:
C2H5
H3C Br H3C H
cis-configuration
(R,R)
Elimination versus Substitution
Zaistev’s and Hoffman Rules
• When an elimination reaction produces the more
highly substituted alkene, for example, 2-butene
from 2-bromobutene, the reaction is said to follow
the Zaistev’s rule.
• If the elimination reaction forms the less substituted
alkene, for example, 1-butene from 2-bromobutene,
theBr reaction is said to follow the Hofmann
H H
rule.
H CH3
CH3CH2O +
CH3CH2CHCH3 CH3CH2CH=CH2 +
CH3CH2OH
2-Bromobutane H3C CH3 H3C H
1-Butene
19 cis-2-Butene trans-2-Butene
22 59
• When the pathway of an elimination reaction
proceeds along the E1 mechanism, the direction of
elimination usually follows the Zaistev’s orientation.
• An E2 reaction mechanism shows less discrimination
between the Zaistev’s and Hofmann products.
• If the leaving group is large, then the Hofmann
product predominates.
N(CH3)3 OH
CH3CH2CHCH3 CH3CH2CH=CH2 + CH3CH=CHCH3
N,N,N-Trimethyl-2-butyl- 1-Butene 2-Butene
ammonium hydroxide 95 5
• the amount of Hofmann elimination product
increases with increasing base size.
Br
CH3CH2O
CH3CH2CHCH3 CH3CH2CH=CH2 + CH3CH=CHCH3
CH3CH2OH
19 81
Br
(CH3)3CO
CH3CH2CHCH3 CH3CH2CH=CH2 + CH3CH=CHCH3
(CH3)3COH
77 23
Other Elimination Reactions
E2 elimination of X2: Preparation of alkenes
X
CC NaI
Acetone
X X = Cl or Br
Alkene
Hofmann Elimination
HO
H
CC
CH3I
RNH2 RN(CH3)3 I N(CH3)3
Alkene