5.

1
Alkene Nomenclature
characterized by molecular formula C
n
H
2n
have a C=C double bond
said to be "unsaturated or olefins
Chapter 5
Structure and Preparation of Alkenes:
Elimination Reactions
Chapter 5; Alkanes and Elimination Reactions
1. Nomenclature
2. Geometric Isomers
i. Cis/trans and E/Z
ii. Priority Rules
3. Physical Properties
4. Alkene Stability
5. Elimination Reactions
i. E1 and E2 Mechanisms
ii. :H and :R shifts
6. Dehydrohalogenation Reactions
1) Find the longest continuous chain that
includes the double bond.
2) Replace the -ane ending of the unbranched
alkane having the same number of carbons
by -ene.
3) Number the chain in the direction that gives
the lowest number to the doubly bonded
carbon.
H
2
C CHCH
2
CH
3
1-Butene
Alkene Nomenclature
4) If a substituent is present, identify its position
by number. The double bond takes
precedence over alkyl groups and halogens
when the chain is numbered.
The compound shown above is
4-bromo-3-methyl-1-butene.
H
2
C CHCHCH
2
Br
CH
3
Alkene Nomenclature
4) If a substituent is present, identify its position
by number. Hydroxyl groups take
precedence over the double bond when the
chain is numbered.
The compound shown above is
2-methyl-3-buten-1-ol.
H
2
C CHCHCH
2
OH
CH
3
Alkene Nomenclature
Alkene Nomenclature
5. If more than one double bond is present;
name as a diene or triene. Use numbers
to indicate multiple bond positions.
Cycloalkene Nomenclature
1) Replace the -ane ending of the cycloalkane
having the same number of carbons by -ene.
Cyclohexene

1) Replace the -ane ending of the cycloalkane
having the same number of carbons by -ene.
2) Number through the double bond in the
direction that gives the lower number to the
first-appearing substituent.
6-Ethyl-1-methylcyclohexene
CH
3
CH
2
CH
3

Cycloalkene Nomenclature
1
2 3
4
5
6
Planar
Restricted C-C Bond Rotation
Structure of Ethylene
C C
H
H
H
H
Isomers
Constitutional isomers Stereoisomers
different atom connectivity same atom connnectivity;
different arrangement
of atoms in space
Requirements for Geometric Isomers
(Type of Stereoisomer)

1. Restricted Bond Rotation
Cycloalkane
Multiple Bond
2. Two Different Carbon Atoms that Have Two
Different Substituents Attached to Them
2-Methylpropene 1-Butene
cis-2-Butene
C C
H
H
H
CH
2
CH
3
H
CH
3
C C
H
3
C
H
C C
H
H H
3
C
H
3
C
Constitutional Isomers
of C
4
H
8
cis-2-Butene
trans-2-Butene
H
3
C
C C
CH
3
H
H
H
CH
3
C C
H
3
C
H
Stereoisomers of C
4
H
8

Also known as Geometric isomers, cis/trans isomers, or
E/Z isomers
E, Z nomenclature is used when
cis/trans ranking is ambiguous
What is needed:

1) systematic body of rules for ranking
substituents
2) new set of stereochemical symbols other
than cis and trans
C C
H F
Cl Br
C C
E : higher ranked substituents on opposite sides
Z : higher ranked substituents on same side

Entgegen
higher
higher lower
lower
C C
Zusammen
lower
higher
lower
higher
The E-Z Notational System
(1) Higher atomic number outranks lower
atomic number
Br > F Cl > H
(Z )-1-Bromo-2-chloro-1-fluoroethene
higher
lower
Br
F
Cl
H
higher
lower
C C
Table 5.1 CIP Rules
(2) When two atoms are identical, compare the
atoms attached to them on the basis of their
atomic numbers. Precedence is established
at the first point of difference.

CH
2
CH
3
outranks CH
3
C(C,H,H)
Table 5.1 CIP Rules
C(H,H,H)
(3) Work outward from the point of attachment,
comparing all the atoms attached to a
particular atom before proceeding further
along the chain.
CH(CH
3
)
2
outranks CH
2
CH
2
OH
C(C,C,H) C(C,H,H)
Table 5.1 CIP Rules
(4) Evaluate substituents one by one.
Don't add atomic numbers within groups.
CH
2
OH outranks C(CH
3
)
3
C(O,H,H)
C(C,C,C)
Table 5.1 CIP Rules
(5) An atom that is multiply bonded to another
atom is considered to be replicated as a
substituent on that atom.
CH=O outranks CH
2
OH
C(O,O,H) C(O,H,H)
Table 5.1 CIP Rules
Alkene Polarity and Boiling Point
C C
Cl
H
Cl
H
C C
Cl
Cl
H
H
Dipoles cancel;
Trans isomer nonpolar
Lower boiling pt
Dipoles reinforce;
Cis isomer polar
Higher boiling pt
Double bonds are classified according to
the number of carbons attached to them.
H
C C
R
H
H
monosubstituted
R'
C C
R
H
H
disubstituted
H
C C
R
H
R'
disubstituted
H
C C
R H
R'
disubstituted
Double bonds are classified according to
the number of carbons attached to them.
R'
C C
R
H
R"
trisubstituted
R'
C C
R
R"'
R"
tetrasubstituted
In general; the more substituted the alkene is
the more stable it is.
Electronic (larger effect)
disubstituted alkenes are more stable
than monosubstituted alkenes
Steric (smaller effect)
For disubstituted alkenes;
trans alkenes are more stable than cis alkenes
Substituent Effects on Alkene Stability
+ 6O
2
4CO
2
+ 8H
2
O
2707 kJ/mol
2717 kJ/mol
2710 kJ/mol



Figure 5.4 Heats of
combustion of C
4
H
8

isomers.
cis-2-butene
trans-2-butene
van der Waals strain
due to crowding of
cis-methyl groups
Figure 5.5
cis and trans-2-Butene
Give the structure or make a molecular model of
the most stable C
6
H
12
alkene.

C C
H
3
C
H
3
C CH
3
CH
3
Problem 5.8