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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
2. Substitution Effects
H2
Pt
H = -30.3 kcal/mol
H2
Pt
H = -27.6 kcal/mol
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
cis or trans?
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
trans substituents
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
CH3
C O - K+
CH3
potassium tert-butoxide
N
H
diisopropylamine
triethylamine (Et3N)
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