1. Elimination Reactions
Organic Chemistry
4th Edition
Paula Yurkanis Bruice
Chapter 11
Elimination Reactions
of Alkyl Halides
Competition Between
Substitution and
Elimination
Irene Lee
Case Western Reserve University
Cleveland, OH
©2004, Prentice Hall

2. In addition to substitution, an alkyl halide can undergo an elimination reaction

3. The E2 Reaction

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

6. The Regioselectivity of the E2 Reaction
The major product of an E2 reaction is the most stable
alkene
The greater the number of substituents, the more stable
is the alkene

7. Reaction coordinate diagram for the E2 reaction of
2-bromobutane and methoxide ion

9. The Zaitsev Rule
The more substituted alkene product is obtained when a
proton is removed from the b-carbon that is bonded
to the fewest hydrogens
The most stable alkene is generally (but not always) the
most substituted alkene

11. Conjugated alkene products are preferred over the
more substituted alkene product
Do not use Zaitsev’s rule to predict the major product
in these cases

12. Steric hindrance also affects the product distribution

14. Another exception to Zaitsev’s rule

15. Consider the elimination of 2-fluoropentane …

16. A carbanion-like transition state

17. Relative stabilities of carbanions
tertiary
carbanion
secondary
carbanion
primary
carbanion
methyl
anion
least
stable
most
stable

18. The E1 Reaction

19. Reaction coordinate diagram for the E1 reaction of
2-chloro-2-methylbutane

22. Because the E1 reaction forms a carbocation
intermediate, we need to consider carbocation
rearrangement

24. Competition Between E2 and E1 Reactions

25. Stereochemistry of the E2 Reaction
The bonds to the eliminated groups (H and X) must be
in the same plane H X H X
the more stable conformation
The anti elimination is favored over the syn elimination

26. 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

27. Consider the regioselectivity of the E2 reaction
The alkene with the bulkiest groups on opposite sides of
the double bond will be formed in greater yield, because
it is the more stable alkene

29. Reaction coordinate diagram for the E2 reaction of
2-bromopentane and ethoxide ion

30. The particular alkene isomer that is formed depends on
the configuration of the reactant

31. Stereochemistry of the E1 Reaction

32. Elimination from Cyclic Compounds
In an E2 reaction, groups to be eliminated must be trans
to one another

36. E1 Elimination from Cyclic Compounds
An E1 reaction involves both syn and anti elimination

39. Utilization of kinetic isotope effect to study a reaction mechanismkH kD
A carbon deuterium bond (C–D) is stronger than a carbon hydrogen bond (C–H)
The deterium isotope is 7.1, indicating that C–H (or C–D)
bond must be broken in the rate-determining step

40. Competition Between Substitution and Elimination
Alkyl halides can undergo SN2, SN1, E2 and E1
1) decide whether the reaction conditions favor SN2/E2 or SN1/E1
SN2/E2 reactions are favored by a high
concentration of nucleophile/strong base
SN1/E1 reactions are favored by a poor
nucleophile/weak base
2) decide how much of the product will be the substitution product
and how much of the product will be the elimination product

41. Consider the SN2/E2 conditions

42. A bulky base encourages elimination over substitution

43. A weak base encourages substitution over elimination
strong
base
weak
base

44. Consider SN1/E1 conditions

45. Substitution and Elimination Reactions in Synthesis

46. In synthesizing an ether, the less hindered group should
be provided by the alkyl halide

47. However, the most hindered alkyl halide
should be used if you want to synthesize an alkene

48. Consecutive E2 Elimination Reactions

49. Intermolecular Versus Intramolecular Reactions
A low concentration of reactant favors an intramolecular
reaction
The intramolecular reaction is also favored when a five-
or six-membered ring is formed

50. Three- and four-membered rings are less easily formed
Three-membered ring compounds are formed more
easily than four-membered ring compounds
The likelihood of the reacting groups finding each other
decreases sharply when the groups are in compounds
that would form seven-membered and larger rings.

51. Now we can design a synthesis …