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Chapter 7

Structure and Synthesis of


Alkenes

A. Alkene Stability
1. Basis of Comparison
The relative stability of alkenes is measured by
comparing their heats of hydrogenation

C C

H2

Pt

H C C H

H = heat of hydrogenation

Hydrogenation reactions of simple alkenes are always


exothermic so H is always a negative number

2. Substitution Effects

H2

Pt

H = -30.3 kcal/mol

1-butene (terminal, monosubstituted)

H2

Pt

H = -27.6 kcal/mol

2-butene (internal, disubstituted)

2-butene is more stable


by 2.7 kcal/mol

The more energy given off in hydrogenating a double


bond, the less stable the alkene
More highly substituted alkenes are more stable
because:
Alkyl groups are electron donating; they contribute
electron density via hyperconjugation.
Substitution of alkyl groups on a double bond makes
them farther apart (relative to if they were on alkane
carbons), reducing steric interactions
109.5

CH3 H
CH3

CH3

120

CH3

3. Geometric Isomers

H2

Pt

H = -28.6 kcal/mol

H2

Pt

H = -27.6 kcal/mol

cis-2-butene

trans-2-butene

trans-2-butene is more stable by 1.0 kcal/mol


In general, trans double bonds are more stable than cis
double bonds because steric interactions are reduced in
the trans isomer

Cis and trans nomenclature works for disubstituted


alkenes but what do we do for tri- and tetrasubstituted
alkenes?

cis or trans?

An unambiguous system, based on Cahn-Ingold-Prelog


priorities, is used to denote alkene stereochemistry as E
or Z

To assign E or Z
1. Use the C-I-P rules to determine which group
attached to each alkene carbon has a higher priority
2. If the two highest priority groups are on the same side
of the double bond (i.e. cis to each other) the alkene
is Z (from zusammen, German for together); if the
two highest priority groups are on opposite sides of
the double bond the alkene is E (from entgegen,
German for opposite)
2

Br

Cl

2
1
1

CH3O

OH

3. Cycloalkenes
Double bonds in rings behave like acyclic double
bonds (i.e. trans is more stable than cis) except:
a) 3- and 4-membered rings
Alkenes in 3- and 4-membered rings are very
strained (and therefore reactive) because bond
angles are limited to 60 and 90, respectively,
when ideal bond angles are 120
b) Trans double bonds in 3- to 9-membered rings
Trans double bonds are geometrically
impossible in 3- and 4-membered rings
In 5- to 7-membered rings, trans alkenes can
exist but they are very highly strained and
are therefore unstable

For 8- and 9-membered rings, trans alkenes are stable


but they are less stable than cis alkenes
These rules apply to bicyclic rings, as well; if trans
substituents are contained within one ring, the ring will
be unstable if it contains fewer than eight atoms
stable because the trans alkene substituents
are contained in different rings
trans substituents

trans substituents

not stable because the trans alkene substituents


are contained within a six-membered ring

A generalization of this is stated by Bredts Rule: A


bridged bicyclic compound cannot have a double bond
at a bridgehead position unless one of the rings
contains eight or more atoms
bridgehead
carbons

stable
2
5

4
2

unstable

4
5
6

unstable

B. Synthesis of Alkenes
1. Dehydrohalogenation
C C
H X

Base

C C

X:- + Base-H

Reactions may occur by either an E1 or E2


mechanism; for practical purposes E2 is the preferred
reaction because E1 is accompanied by SN1
Strong bulky bases are ideal
CH3

CH3
C O - K+
CH3

potassium tert-butoxide

N
H
diisopropylamine

triethylamine (Et3N)

E2 reactions generally give Zaitsev orientation, i.e. the


most substituted, most stable alkene product is usually
the major product
Reactions using very bulky bases and very hindered
substrates lead primarily to the less substituted product
(the Hoffmann product) because the base is sterically
hindered from abstracting the proton leading to the
Zaitsev product
too sterically hindered

H
Br

+ Et3N

+
major

minor

2. Dehydration of alcohols
When heated in strong acid, alcohols will dehydrate to
form alkenes

CH3

CH3
C OH
CH3

H3O+ +

H HSO4

CH3
CH3

C CH2

CH3

CH3 H
C O
CH3 H

CH3

CH3
C
CH2 H

HSO4-

OH2

The reaction is reversible but can be driven to the right


by boiling off the lower boiling alkene product

For a tertiary or secondary alcohol the reaction is E1


Competing SN1 is not a problem; potential nucleophiles
are water, which reforms the starting material, and
HSO4-, which is too weakly nucleophilic to add
reversibly
Dehydration is generally not a practical reaction for
primary alcohols since the necessary primary
carbocation intermediate is too unstable to form in
appreciable amounts