Chapter 4:

Alkenes and Alkynes

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 Unsaturated Hydrocarbons
• Unsaturated hydrocarbon: contains one or more
carbon-carbon double or triple bonds
• alkene: contains a carbon-carbon double bond and has
the general formula CnH2n
• alkyne: contains a carbon-carbon triple bond and has
the general formula CnH2n-2
H H
C C H-C C-H
Ethyne
H H
(an alkyne)
Ethene
(an alkene)

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 Unsaturated Hydrocarbons
• Arenes:
Arenes benzene and its derivatives (Ch 9)

H C H
C C

C C
H C H

H
Benzene
(an arene)

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 Benzene and Phenyl Groups
• Alkenes
• widespread in nature( e.g., ripening agent)
• Ethylene and propene have enormous importance

• Ethylene is produced through thermal cracking of

ethane

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 Structure of Alkenes
• Bond angle about each carbon in a double bond
is approximately 120°

121.7° 124.7°
H H H CH3
C C C C
H H H H
Ethylene Propene

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 Structure of Alkenes
• a double bond consists of
• a  bond formed by overlap of sp2 hybrid orbitals

• a  bond formed by overlap of parallel 2p orbital

• No breaking of the pi bond(264kJ/mol) at room

temperature

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 Cis-Trans Isomerism
• restricted rotation about a C-C double bond
• groups on adjacent carbons are either cis or trans to
each other

H H H CH3
C C C C
H3 C CH3 H3 C H
cis-2-Butene trans-2-Butene
mp -139°C, bp 4°C mp -106°C, bp 1°C

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 Cis-Trans Isomerism
• trans alkenes are more stable than cis alkenes
• because of nonbonded interaction strain between alkyl
substituents on the same side of the double bond

trans-2-Butene cis-2-Butene

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 Structure of Alkynes
• The functional group of an alkyne is a carbon-
carbon triple bond

• A triple bond consists of

• one  bond formed by the overlap of sp hybrid orbitals
• two  bonds formed by the overlap of sets of parallel
2p orbitals

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 Nomenclature of Alkenes
• IUPAC Nomenclature
• use the infix -en-
en to show the presence of a carbon-
carbon double bond
• the parent chain is the longest chain containing the
double bond
• number the parent chain to give the 1st carbon of the
double bond the lower number
• follow IUPAC rules for numbering and naming
substituents
• for a cycloalkene, the double bond must be numbered
1,2

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 Nomenclature of Alkenes
• IUPAC nomenclature

5 3 1
6 4 2 6 4 2 4 2
5 3 1 5 3 1

1-Hexene 4-Methyl-1-hexene
2-Ethyl-3-methyl-
1-pentene

4 2
1 CH3
5
3 CH3 3

4
6 CH3
1 2 5
3-Methylcyclo- 1,6-Dimethylcyclo-
pentene hexene

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 Nomenclature of Alkenes
• Alkenes known by their common names
• low-molecular-weight ones
CH3
CH2=CH2 CH3CH=CH2 CH3C=CH2
IUPAC: Ethene Propene 2-Methylpropene
Common: Ethylene Propylene Isobutylene

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 Nomenclature of Alkynes
• IUPAC nomenclature
• use the infix -yn-
yn to show the presence of a carbon-
carbon triple bond
• number the parent chain to give the 1st carbon of the
triple bond the lower number
• follow IUPAC rules for numbering and naming
substituents
1
1
4
2 2 3 4 5
3 6 7

3-Methyl-1-butyne 6,6-Dimethyl-3-heptyne

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 Nomenclature of alkenes and alkynes
• More IUPAC rules

• If more than one double or triple bond is present,

use – diene, triene or diyne, -triyne.

• If both double and triple bonds are present,

-Use -enyne as suffix
-Number from side with nearest multiple bond (either
double or triple)
-If a double and triple bond is equidistant, make the
double bond the lower number

1-octen-7-yne
4-methyl-7-nonen-1-yne
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p.4.1 4-14
 Configuration: Cis-Trans
• The cis,trans system:
• used for the configuration of disubstituted alkenes
• configuration is determined by the orientation of atoms
of the main chain

H CH2 CH3 H CH3

2 3
C C C C
1 4
CH3 CH2 H H3 C CH(CH3 ) 2
trans
-3-Hexene cis-3,4-Dimethyl-2-pentene

wrong example

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p.4.2
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 Configuration: E,Z
• must be used for tri- and tetrasubstituted alkenes
• assign a priority to the substituents on each carbon of
the double bond
• if the groups of higher priority are on the same side of
the double bond, the configuration is Z
• if the groups of higher priority are on opposite sides of
the double bond, the configuration is E

higher higher higher lower

C C C C
lower lower lower higher
Z (zusammen) E (entgegen)

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 Configuration: E,Z
• Priority rules
1. the higher the atomic number, the higher the priority
(1) (6) (7) (8) (16) (17) (35) (53)
-H -CH3 -NH2 -OH -SH -Cl -Br -I
Increasing priority

2. If priority of the atoms bonded directly to the double

bond is same, look to the next set of atoms
(1) (6) (7) (8)
-CH2 -H -CH2 -CH3 -CH2 -NH2 -CH2 -OH
Increasing priority

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 Configuration - E,Z
3. Atoms in a double or triple bond are considered to be
bonded to an equivalent number of similar atoms by
single bonds
C C
is treated as
-CH=CH2 -CH-CH2

O O C
is treated as
-CH C O
H

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 Configuration - E,Z
• Example: name each alkene and specify its configuration
by the E,Z system
Cl
Cl
(a) (b) (c)

Cl
(d) (e)
Br

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 Cis-Trans Isomerism in cycloalkenes
• the configuration in cyclopropene through
cycloheptene must be cis due to smaller ring size
H CH3

H C H3

• cyclooctene is the smallest cycloalkene that can

accommodate a trans double bond

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 Cis-Trans Isomerism
• Dienes, trienes, and polyenes
• for an alkene with n carbon-carbon double bonds, each
of which can show cis-trans isomerism, 2n cis-trans
isomers are possible
• consider 2,4-heptadiene; it has four cis-trans isomers,
two of which are drawn here

Double bond 2 2
C2 -C3 C4 -C5 4 4
trans trans
trans cis
trans,trans-2,4- trans,cis-2,4-
cis trans
heptadiene heptadiene
cis cis

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 Cis-Trans Isomerism
• vitamin A has five double bonds
• four of the five can show cis-trans isomerism
• vitamin A is the all-trans isomer

enzyme-
catalyzed
oxidation
OH

Vitamin A (retinol)
O

Vitamin A aldehyde (retinal)

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 Physical Properties
• Alkenes and alkynes
• nonpolar compounds
• the only attractive forces between their molecules are
dispersion forces
• Physical properties
• similar to those of alkanes of similar carbon skeletons
• liquids at room temperature are less dense than water
• dissolve in each other and in nonpolar organic
solvents
• insoluble in water

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 Terpenes
• Terpene:
a compound whose carbon skeleton can be divided into
two or more units identical with the carbon skeleton of
isoprene

head 2 4 tail
1 3
2-Methyl-1,3-butadiene
(Isoprene)

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 Terpenes
• myrcene, C10H16, a
component of bayberry
wax and oils of bay and
verbena

• menthol, from
peppermint

OH

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 Terpenes
• Vitamin A (retinol)
• the four isoprene units in vitamin A
• they are linked head to tail, and cross linked at one
point (the blue bond) to give the six-membered ring

OH

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 Acidity of alkane, alkene, and alkyne

• Alkane < Alkene < Alkyne

Why?
electronegativity of hybrid orbitals for anions

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 The Acidity of Terminal Alkynes
• Unlike alkanes and alkenes, terminal alkynes are acidic
enough to go through an acid-base reaction

• Acidity of Alkanes, Alkenes, and Alkynes.

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 Alkenes and Alkynes

End Chapter 4
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