Week 4:

Unsaturated
Hydrocarbons
(Part I)
Course Content Outline:
• Characteristics of alkenes and cycloalkenes
• Names for alkenes and cycloalkenes
• Isomerism in alkenes
• Physical properties of alkenes
• Chemical reactions of alkenes
• Polymerization of alkenes: addition polymers
• Alkynes
• Aromatic hydrocarbons
• Names for aromatic hydrocarbons
• Aromatic hydrocarbons: physical properties and
sources
• Chemical reactions of aromatic hydrocarbons
• Fused-ring aromatic compounds
 Characteristics of Alkenes and Cycloalkenes

• Organic compounds containing one or more carbon–carbon multiple bonds

have fewer hydrogen atoms than structurally related alkanes or
cycloalkanes.

• For this reason, these compounds are said to be unsaturated and denoted
as alkenes.

• An alkene must contain at least one carbon–carbon double bond.

• A double bond contains both a carbon–carbon 𝜎 bond and a 𝜋 bond that

forms from 2p orbitals on adjacent carbon atoms overlapping “side by side.”
• Alkenes and their chemical
cousins, the cycloalkenes, are
very common in nature.

• Alkenes have many commercial

applications and biological
functions.

• They occur in fats, oils, some

vitamins and others.

• Ethene is the simplest hormone.

• Ethene is produced in small
amounts in many fruits and
stimulates ripening.
Ethene has an important commercial application in
the food industry.

Ripened fruit does not travel well, so growers pick

their fruit while it is still green.

Unripened fruit is shipped to a warehouse, where it

is exposed to ethene.

To avoid ripening during transport, the fruit is stored

in ventilated containers.

This decreases the concentration of ethene and

retards ripening.

Some fruits can be ripened in the home by placing

them in a partially enclosed container that allows
some buildup of ethene in the air around the fruit.
Fruit that has started to ripen helps to ripen the
remaining fruit.
 overlapping “side by side.” We also recall that the carbon atoms in a bond of an alkene are sp
hybridized (Section 1.15).
• A more complex alkene, called muscalure,
Alkenes and is a chemical
their pheromone cousins, secreted by the
the cycloalkenes, common
are very common in nature. Alken
housefly (Musca domestica).have many commercial applications and biological functions. They occur in fats and oils, some vitamin
some are hormones, and others act as pheromones. Ethene is the simplest hormone. It is produced
• Muscalure, an unbranched alkene containing
small amounts 23and
in many fruits carbon atoms,
stimulates ripening.is released
Ethene by thecommercial applicatio
has an important
female to attract males. in the food industry. Ripened fruit does not travel well, so growers pick their fruit while it is still gree
Unripened fruit is shipped to a warehouse, where it is exposed to ethene. To avoid ripening during tran
• Muscalure has been synthesized
port, thein the
fruit laboratory
is stored and
in ventilated can be
containers. used
This to the
decreases lure male flies
concentration to and retard
of ethene
traps. ripening. Some fruits can be ripened in the home by placing them in a partially enclosed container th
allows some buildup of ethene in the air around the fruit. Fruit that has started to ripen helps to ripen th
remaining fruit.
A more complex alkene, called muscalure, is a pheromone secreted by the common housefl
(Musca domestica). Muscalure, an unbranched alkene containing 23 carbon atoms, is released by th
female to attract males. Muscalure has been synthesized in the laboratory and can be used to lu
male flies to traps.
H H
C C
CH3(CH2)11CH2 CH2(CH2)6CH3

muscalure
• Some alkenes, called polyenes, contain two or more carbon–carbon
double bonds.

• Alkenes with two, three, and four double bonds are called dienes, trienes,
and tetraenes, respectively.

• Multiple double bonds are present in polyunsaturated compounds called

oils.

• These substances are esters that contain several carbon–carbon double

bonds.

• Polyunsaturated compounds are common, naturally occurring

compounds.
nds are present in polyunsaturated compounds called oils. These substances are esters that cont
eral carbon–carbon double bonds. Polyunsaturated compounds are common, naturally occurr
mpounds. For example, linolenic acid is a triene that is present as an ester in some polyunsatura
• For example,
. Arachidonic linolenic
acid, a tetraene, is acid is a triene
a precursor that is presentactive
to physiologically as anmolecules
ester in some
called prostagl
s. polyunsaturated oils.

CH3CH2CH CHCH2CH CHCH2CH CHCH2CH2CH2CO2H

Linolenic Acid

78-0-12-812838-1.50005-0 Copyright © 2018 Elsevier Inc. All rights reserved. 1

• Arachidonic acid, a tetraene, is a precursor to physiologically active molecules
called prostaglandins.

CH3(CH2)4CH CHCH2CH CHCH2CH CHCH CHCH2(CH2)3CO2H

Arachidonic Acid
• 𝛽-Carotene and vitamin A contain double bonds separated from one another by
one single bond.

• The single and double bonds are “alternating.”

• The alternation of single and double bonds is called conjugation.

• Therefore, both 𝛽-carotene3 andCHCH

CH (CH ) CH
2 4 vitamin
2 A are
CH CHCH conjugated
CH CHCH
2 polyenes.
CHCH (CH ) CO
2 2 3
H 2
Arachidonic Acid

-Carotene

OH

Vitamin A
ne and vitamin A contain double bonds separated from one another by one single
• Some industrial products are derived from conjugated dienes.
he single and double bonds are “alternating.” The alternation of single and dou
• NaturalTherefore,
onjugation. rubber is aboth
polymer-carotene and vitamin A are conjugated polye
of isoprene.
products are derived from conjugated dienes. Natural rubber is a polymer of iso
• The
rubbers synthetic
called rubbers
neoprenes are called neoprenes
produced are produced from chloroprene.
from chloroprene.

Cl

isoprene chloroprene
 reactions of alkenes.
Structure and Bonding of Alkenes
The IUPAC names of alkenes use the suffix -ene. Alkynes, which are also unsatur
cause they contain one or more carbon–carbon triple bonds, will be discussed in Chapter 7.
• Therated compounds
simplest alkene, Cthat contain a benzene ring or structural units that resemble a benzene
2H4, commonly called ethylene, has the IUPAC name ethene.
aromatic hydrocarbons. They will be discussed in Chapter 13.
• Alkenes contain trigonal planar sp2-hybridized carbon atoms.

• Therefore, the bond

The simplest angles
alkene, C2around the sp2-hybridized
H4, commonly carbon has
called ethylene, atoms
theshould
IUPAC ideally
namebeethene. Fi
120°.
shows how it is bonded. Alkenes contain trigonal planar sp²-hybridized carbon atoms. Th
• The the bond
bond angles
angles of around the
alkenes are sp²-hybridized
typically within carbon
a few atoms should
degrees of this ideally
value. be 120°. The bond
NES alkenes are typically within a few degrees of this value. For example, the H—C—C bond
• For ethene is 121.7°.
example, The C—C=C
the H—C—C bond
bond angle in angle
etheneofispropene
121.7°.isThe
124.8°.
C—C=C bond angle of
propene is 124.8°.
121.7o H 124.8o CH
H H 3

C C C C
H H H H
ethene propene
• The length of a bond between carbon and another atom is shorter for a
carbon atom with sp2 hybrid orbitals than for a carbon atom with sp3 hybrid
orbitals.
• For example, the C—H bond lengths in ethene and ethane are 107 pm and
109 pm, respectively.
• The C—H bond energies of ethene and ethane are 451 kJ mole-1 and 410 kJ
mole–1, respectively.
• The carbon–carbon bond lengths of ethene and ethane are 133 pm and 154
pm, respectively.
• The C=C bond energy of ethene is 605 kJ mole–1. The C—C bond energy of
ethane is 368 kJ mole–1.
 Classification of Alkenes
• Alkyl groups bonded to the sp2-hybridized carbon atoms of alkenes
affect the stability of the double bond.

• The chemical reactivity of alkenes also is often affected by the number

of alkyl groups bonded to the sp2-hybridized carbon atoms.

• Thus, it is useful to classify alkenes by the number of alkyl groups

attached to the C=C structural unit.

• This feature is called the degree of substitution.

 CH2=CH—H 107 452

Classification
• An alkeneof Alkenes
that has a single alkyl group attached to one of the sp2-hybridized
carbon atoms of the double bond is monosubstituted.
Alkyl groups bonded to the sp²-hybridized carbon atoms of alkenes affect the stability of the double
bond. The chemical reactivity of alkenes also is often affected by the number of alkyl groups bonded to
• An alkene whose double bond is at the end of a chain of carbon atoms is
the sp²-hybridized carbon atoms. Thus, it is useful to classify alkenes by the number of alkyl groups at-
also sometimes called a terminal alkene.
tached to the C=C structural unit. This feature is called the degree of substitution. An alkene that has
a single alkyl group attached to one of the sp²-hybridized carbon atoms of the double bond is mono-
• Alkenes that have two, three, and four alkyl groups bonded to the carbon
substituted. An alkene whose double bond is at the end of a chain of carbon atoms is also sometimes
atoms of the double bond are disubstituted, trisubstituted, and
called a terminal alkene. Alkenes that have two, three, and four alkyl groups bonded to the carbon
atoms of tetrasubstituted, respectively. trisubstituted, and tetrasubstituted, respectively.
the double bond are disubstituted,
monosubstituted: RCH CH2
disubstituted: R2C CH2 or RCH CHR
trisubstituted: R2C CHR

tetrasubstituted: R2C CR2

 Practice Exercise
Farnesene contains a terminal double bond on the right with two hydrogen atoms bonded to it. Thus, it is monosu
Classify
bond in eachisof
the “middle” double bond
disubstituted, in the
and the following
double bond on isomeric dienes. Which compounds
the left is trisubstituted.
contain conjugated double bonds?
5.4 Classify each of double bond in the following isomeric dienes. Which compounds contain conjugated double b

(a) (b) (c) (d)

(a) Two conjugated trisubstituted double bonds. (b) The double bond on the left is disubstituted; the one in the c
substituted. They are conjugated. (c) The double bond on the left is disubstituted; the one on the center is tetra
They are not conjugated. (d) The double bond on the left is disubstituted; the one on the center is trisubstitute
not conjugated.

5.6 Based on its location in the periodic table, how should sulfur be treated in the calculation of the degree of unsa
 lem 5.4 Classify
farnesene,
he C—Cl ineach
a compound
bond of double bond
found in
chloroethane. the in the coating
waxy following
ofisomeric
apples. dienes. Which compounds contain conjugated double b
a terminal double bond on the 3right with two hydrogen atoms bonded to it. Thus, it is monosubstituted.
nd stronger bonds than the sp -hybridized carbon atom of
le” is disubstituted, and the double bond on the left is trisubstituted.
175 pm. (a) (b) (c) (d)

double bond in the following isomeric dienes. Which compounds contain conjugated double bonds?
found in the
the right withwaxy
twocoating
hydrogenof apples.
atoms bonded to it. Thus, it is monosubstituted.
wers: (a) Two
he double bondconjugated
on the lefttrisubstituted double bonds. (b) The double bond on the left is disubstituted; the one in the c
is trisubstituted.
substituted.
(b) They are conjugated.(c) (c) The double bond
(d)on the left is disubstituted; the one on the center is tetra
They are not conjugated. (d) The double bond on the left is disubstituted; the one on the center is trisubstitute
wing isomeric dienes. Which compounds contain conjugated double bonds?
not conjugated.

lem 5.6
rogen Based
atoms on itstolocation
bonded it. Thus,in itthe
is periodic table, how should sulfur be treated in the calculation of the degree of unsa
monosubstituted.
d trisubstituted double bonds. (b) The double bond on the left is disubstituted; the one in the center is tetra
eft sulfur-containing organic compound?
ey is
aretrisubstituted.
(c) (c) The double bond (d)
conjugated. on the left is disubstituted; the one on the center is tetrasubstituted.
njugated. (d) The double bond on the left is disubstituted; the one on the center is trisubstituted. They are
wer: Sulfur is in the same group as oxygen. Thus, there is no effect on the degree of unsaturation calculation.
.
hich compounds contain conjugated double bonds?
lem
ation5.7 Calculate
in the periodicthe unsaturation
table, how shouldnumber fortreated
sulfur be each ofinthethefollowing.
calculation of the degree of unsaturation of a
nds. (b) Thecompound?
ng organic double bond on the left is disubstituted; the one in the center is tetra
double bond(a) C on
(d)
10
Hthe
16
left
(b) is
C8disubstituted;
H10Br2 (c)the
C6HoneOon the center
6 3
(d) C5is
H6tetrasubstituted.
N2
bond
e grouponasthe left isThus,
oxygen. disubstituted;
there is nothe oneononthe
effect the center
degree of isunsaturation
trisubstituted. They are
calculation.
wer: (a) 3 (b) 3 (c) 4 (d) 4
nsaturation number for each of the following.
 lem 5.4 Classify
farnesene,
he C—Cl ineach
a compound
bond of double bond
found in
chloroethane. the in the coating
waxy following
ofisomeric
apples. dienes. Which compounds contain conjugated double b
a terminal double bond on the 3right with two •hydrogen
Two atoms bonded todouble
trisubstituted it. Thus,bonds.
it is monosubstituted.
nd stronger bonds than the sp -hybridized carbon atom of
le” is disubstituted, and the double bond on the
• left
Theyis trisubstituted.
are conjugated.
175 pm. (a) (b) (c) (d)

double bond in the following isomeric dienes. Which compounds contain conjugated double bonds?
found in the
the right withwaxy
twocoating
hydrogenof apples.
atoms bonded to it. Thus, it is monosubstituted.
wers: (a) Two
he double bondconjugated
on the lefttrisubstituted double bonds. (b) The double bond on the left is disubstituted; the one in the c
is trisubstituted.
substituted.
(b) They are conjugated.(c) (c) The double bond
(d)on the left is disubstituted; the one on the center is tetra
They are not conjugated. (d) The double bond on the left is disubstituted; the one on the center is trisubstitute
wing isomeric dienes. Which compounds contain conjugated double bonds?
not conjugated.

lem 5.6
rogen Based
atoms on itstolocation
bonded it. Thus,in itthe
is periodic table, how should sulfur be treated in the calculation of the degree of unsa
monosubstituted.
d trisubstituted double bonds. (b) The double bond on the left is disubstituted; the one in the center is tetra
eft sulfur-containing organic compound?
ey is
aretrisubstituted.
(c) (c) The double bond (d)
conjugated. on the left is disubstituted; the one on the center is tetrasubstituted.
njugated. (d) The double bond on the left is disubstituted; the one on the center is trisubstituted. They are
wer: Sulfur is in the same group as oxygen. Thus, there is no effect on the degree of unsaturation calculation.
.
hich compounds contain conjugated double bonds?
lem
ation5.7 Calculate
in the periodicthe unsaturation
table, how shouldnumber fortreated
sulfur be each ofinthethefollowing.
calculation of the degree of unsaturation of a
nds. (b) Thecompound?
ng organic double bond on the left is disubstituted; the one in the center is tetra
double bond(a) C on
(d)
10
Hthe
16
left
(b) is
C8disubstituted;
H10Br2 (c)the
C6HoneOon the center
6 3
(d) C5is
H6tetrasubstituted.
N2
bond
e grouponasthe left isThus,
oxygen. disubstituted;
there is nothe oneononthe
effect the center
degree of isunsaturation
trisubstituted. They are
calculation.
wer: (a) 3 (b) 3 (c) 4 (d) 4
nsaturation number for each of the following.
 lem 5.4 Classify
farnesene,
he C—Cl ineach
a compound
bond of double bond
found in
chloroethane. the in the coating
waxy following
ofisomeric
apples. dienes. Which compounds contain conjugated double b
a terminal double bond on the 3right with two •hydrogen
Two atoms bonded todouble
trisubstituted it. Thus,bonds.
it is monosubstituted.
nd stronger bonds than the sp -hybridized carbon atom of
le” is disubstituted, and the double bond on the
• left
Theyis trisubstituted.
are conjugated.
175 pm. (a) (b) (c) (d)

double bond in the following isomeric dienes. Which compounds contain conjugated double bonds?
found in the
the right withwaxy
twocoating
hydrogenof apples.
atoms bonded to it. Thus, it is monosubstituted.
wers: (a) Two
he double bondconjugated
on the lefttrisubstituted
• bonds.
double
is trisubstituted.
The double
(b) Thebond
doubleon theon
bond left
theis left
disubstituted; thetheone
is disubstituted; oneinin the c
substituted.
(b) They are conjugated. thedouble
(c) (c) The centerbond
is(d)tetrasubstituted.
on the left is disubstituted; the one on the center is tetra
They are not conjugated. (d) The double• They
bondare
on conjugated.
the left is disubstituted; the one on the center is trisubstitute
wing isomeric dienes. Which compounds contain conjugated double bonds?
not conjugated.

lem 5.6
rogen Based
atoms on itstolocation
bonded it. Thus,in itthe
is periodic table, how should sulfur be treated in the calculation of the degree of unsa
monosubstituted.
d trisubstituted double bonds. (b) The double bond on the left is disubstituted; the one in the center is tetra
eft sulfur-containing organic compound?
ey is
aretrisubstituted.
(c) (c) The double bond (d)
conjugated. on the left is disubstituted; the one on the center is tetrasubstituted.
njugated. (d) The double bond on the left is disubstituted; the one on the center is trisubstituted. They are
wer: Sulfur is in the same group as oxygen. Thus, there is no effect on the degree of unsaturation calculation.
.
hich compounds contain conjugated double bonds?
lem
ation5.7 Calculate
in the periodicthe unsaturation
table, how shouldnumber fortreated
sulfur be each ofinthethefollowing.
calculation of the degree of unsaturation of a
nds. (b) Thecompound?
ng organic double bond on the left is disubstituted; the one in the center is tetra
double bond(a) C on
(d)
10
Hthe
16
left
(b) is
C8disubstituted;
H10Br2 (c)the
C6HoneOon the center
6 3
(d) C5is
H6tetrasubstituted.
N2
bond
e grouponasthe left isThus,
oxygen. disubstituted;
there is nothe oneononthe
effect the center
degree of isunsaturation
trisubstituted. They are
calculation.
wer: (a) 3 (b) 3 (c) 4 (d) 4
nsaturation number for each of the following.
 lem 5.4 Classify
farnesene,
he C—Cl ineach
a compound
bond of double bond
found in
chloroethane. the in the coating
waxy following
ofisomeric
apples. dienes. Which compounds contain conjugated double b
a terminal double bond on the 3right with two •hydrogen
Two atoms bonded todouble
trisubstituted it. Thus,bonds.
it is monosubstituted.
nd stronger bonds than the sp -hybridized carbon atom of
le” is disubstituted, and the double bond on the
• left
Theyis trisubstituted.
are conjugated.
175 pm. (a) (b) (c) (d)

double bond in the following isomeric dienes. Which compounds contain conjugated double bonds?
found in the
the right withwaxy
twocoating
hydrogenof apples.
atoms bonded to it. Thus, it is monosubstituted.
wers: (a) Two
he double bondconjugated
on the lefttrisubstituted
• bonds.
double
is trisubstituted.
The double
(b) Thebond
doubleon theon
bond left
theis left
disubstituted; thetheone
is disubstituted; oneinin the c
substituted.
(b) They are conjugated. thedouble
(c) (c) The centerbond
is(d)tetrasubstituted.
on the left is disubstituted; the one on the center is tetra
They are not conjugated. (d) The double• They
bondare
on conjugated.
the left is disubstituted; the one on the center is trisubstitute
wing isomeric dienes. Which compounds contain conjugated double bonds?
not conjugated.

lem 5.6 Based on itstolocation

it. Thus,in itthe
is periodic table, how should sulfuron
bethe
treated in
is the calculation of the
the degree of unsa
d trisubstituted double bonds. (b) The double •bond Theon double
the left isbond left disubstituted; one on
rogen atoms bonded monosubstituted. disubstituted; the one in the center is tetra
eft sulfur-containing organic compound? the center is tetrasubstituted.
ey is
aretrisubstituted.
(c) (c) The double bond (d)
conjugated. on the left is disubstituted; the one on the center is tetrasubstituted.
• They arethenot
njugated. (d) The double bond on the left is disubstituted; oneconjugated.
on the center is trisubstituted. They are
wer: Sulfur is in the same group as oxygen. Thus, there is no effect on the degree of unsaturation calculation.
.
hich compounds contain conjugated double bonds?
lem
ation5.7 Calculate
in the periodicthe unsaturation
table, how shouldnumber fortreated
sulfur be each ofinthethefollowing.
calculation of the degree of unsaturation of a
nds. (b) Thecompound?
ng organic double bond on the left is disubstituted; the one in the center is tetra
double bond(a) C on
(d)
10
Hthe
16
left
(b) is
C8disubstituted;
H10Br2 (c)the
C6HoneOon the center
6 3
(d) C5is
H6tetrasubstituted.
N2
bond
e grouponasthe left isThus,
oxygen. disubstituted;
there is nothe oneononthe
effect the center
degree of isunsaturation
trisubstituted. They are
calculation.
wer: (a) 3 (b) 3 (c) 4 (d) 4
nsaturation number for each of the following.
 lem 5.4 Classify
farnesene,
he C—Cl ineach
a compound
bond of double bond
found in
chloroethane. the in the coating
waxy following
ofisomeric
apples. dienes. Which compounds contain conjugated double b
a terminal double bond on the 3right with two •hydrogen
Two atoms bonded todouble
trisubstituted it. Thus,bonds.
it is monosubstituted.
nd stronger bonds than the sp -hybridized carbon atom of
le” is disubstituted, and the double bond on the
• left
Theyis trisubstituted.
are conjugated.
175 pm. (a) (b) (c) (d)

double bond in the following isomeric dienes. Which compounds contain conjugated double bonds?
found in the
the right withwaxy
twocoating
hydrogenof apples.
atoms bonded to it. Thus, it is monosubstituted.
wers: (a) Two
he double bondconjugated
on the lefttrisubstituted
• bonds.
double
is trisubstituted.
The double
(b) Thebond
doubleon theon
bond left
theis left
disubstituted; thetheone
is disubstituted; oneinin the c
substituted.
(b) They are conjugated. thedouble
(c) (c) The centerbond
is(d)tetrasubstituted.
on the left is disubstituted; the one on the center is tetra
They are not conjugated. (d) The double• They
bondare
on conjugated.
the left is disubstituted; the one on the center is trisubstitute
wing isomeric dienes. Which compounds contain conjugated double bonds?
not conjugated.

lem 5.6 Based on itstolocation

it. Thus,in itthe
is periodic table, how should sulfuron
bethe
treated in
is the calculation of the
the degree of unsa
d trisubstituted double bonds. (b) The double •bond Theon double
the left isbond left disubstituted; one on
rogen atoms bonded monosubstituted. disubstituted; the one in the center is tetra
eft sulfur-containing organic compound? the center is tetrasubstituted.
ey is
aretrisubstituted.
(c) (c) The double bond (d)
conjugated. on the left is disubstituted; the one on the center is tetrasubstituted.
• They arethenot
njugated. (d) The double bond on the left is disubstituted; oneconjugated.
on the center is trisubstituted. They are
wer: Sulfur is in the same group as oxygen. Thus, there is no effect on the degree of unsaturation calculation.
.
hich compounds contain conjugated double bonds?
lem
ation5.7 Calculate
in the periodicthe unsaturation
table, how should number forThe
sulfur •be each double
ofinthe
treated thefollowing.
calculation
bond on of theleft
the degree of unsaturation of
is disubstituted; thea one on
nds. (b) Thecompound?
ng organic double bond on the left is disubstituted; the one in the center is tetra
the center is trisubstituted.
double bond(a) C on
(d)H the left
(b) is
C disubstituted;
H Br the
(c) C one
H Oon the center
(d) C5is
H6tetrasubstituted.
N2
10 16 8 10 2
• 6 They
6 3
are not conjugated.
bond
e grouponasthe left isThus,
oxygen. disubstituted;
there is nothe oneononthe
effect the center
degree of isunsaturation
trisubstituted. They are
calculation.
wer: (a) 3 (b) 3 (c) 4 (d) 4
nsaturation number for each of the following.
 D OCH3 D OCH3 F OCH3
Names for Alkenes and Cycloalkenes
• The IUPAC rules for naming alkenes are similar to those for alkanes, but the
position of the double bond in the chain and the geometric arrangement of
mon Names of Alkenyl
substituents Groups
around the double bond must be indicated.

• As in the case
the nomenclature of somemany
of alkanes, simple alkyl derived
groups groups, from
a few alkenes
commonhave
names are names. Th
common
allowed as part of an IUPAC name, including vinyl, allyl, and isopropenyl.
ost often encountered are the vinyl, allyl, and isopropenyl groups.

CH3

CH2 CH CH2 CH CH2 CH2 CH

vinyl allyl isopropenyl
Rule 1

IUPAC
The
Rule Names
longest of Alkenes
continuous chain of carbon atoms that contains the double bond is Remarks
Structure the parent alkene.
The IUPAC rules for naming alkenes are similar to those for alkanes, but the position of the double
1 in the chain and the geometric arrangement
bond 7 8 • The around
of substituents longest thecontinuous chain
double bond must be of carbon
CH3CH
indicated. As in the case of some simple alkyl groups,
3 atoms names
a few common that contains
are allowed the double
as part of an bond is
5
IUPAC name, including vinyl, allyl, and isopropenyl. There are
CH3 CH2 CH CH3 theeight
parent alkene.
carbons in this
6 chain. It is an octene.
3C C4
Rule 1 • There are eight carbons in this chain. It
CH3CH2 CH3 is an octene.
The longest continuous
1 2 chain of carbon atoms that contains the double bond is the parent alkene.
Rule 2
2 7 8 • The parent chain has the same name
CH3CH3 asbut
thethecorresponding alkane, but the
The parent chain has the same name5 as the corresponding alkane, suffiex -ene replaces the suffix
-ane. The parent nameCHfor3 the structure
CH2 shownCH above, There
CH3 for are
example,eight
suffix carbonsreplaces
-ene
is octene. in this the suffix -ane.
6 chain. It is an octene.
Rule 3 3C C4
• The parent name for this structure is
Number the carbon atoms in the
CH3CH 2
CH 3
octene.
longest continuous chain starting from the end of the chain nearer
the first branch. 1 2
Rule 2 5 6 7
This is a substituted 3-heptene,
CH3 CH2 CH2 CH3
not a substituted 4-heptene.
 Rule 3
Rulethe carbon atoms in
Number Structure Remarks
the longest continuous chain starting from the end of the chain nearer
the first
3 branch. • Number the carbon atoms in the longest
5 6 7
continuous chain starting from the end of
CH3 CH2 CH2 CH3 This is a substituted 3-heptene,
not athe chain nearer
substituted the first branch.
4-heptene.
3C C4
ule 4 • This is a substituted 3-heptene, not a
CH3CH2 CH3 substituted 4-heptene.
1 2
kyl groups and other substituents are named, and their positions on the chain are identified, ac-
ording to the numbering established by rule 3. Names and numbers are prefixed to the parent name.
145
4 • Alkyl groups and other substituents are
named, and their positions on the chain
1
CH3 CH3 are identified, according to the numbering
This is 2,3-dimethyl-2-pentene
established by Rule 3. Names and
3C C2 not 3,4-dimethyl-3-pentene.
numbers are prefixed to the parent name.
CH3CH2 CH3
5 4 • This is 2,3-dimethyl-2-pentene not 3,4-
dimethyl-3-pentene.
ule 5
 he compound can exist as an E or Z isomer, the appropriate prefix followed by a hyphen is
5 Rule
ced within parentheses inStructure
front of the name. Remarks
• If
5 can exist as an E or Z isomer, the appropriate prefix followed
compound by the compound
a hyphen is can exist as an E or Z
within parentheses in front of the name. 5 6 isomer, the appropriate prefix followed by
CH3 CH2 CH3 a hyphen is placed within parentheses in
5 6
CH3 CH2 CH3 front of the name.
3C C4 This is (E)-3-methyl-3-hexene.
3C C4 This is (E)-3-methyl-3-hexene.
CH3CH2 CH3CH
H 2 H • This is (E)-3-methyl-3-hexene.
1 2 1 2
6
le 6 6 • If the compound contains more than one
double
ompound contains more than one double bond, specify the location of each double bond,
bond by specify the location of each
ber. A prefix to -ene indicates the number of double bonds. double bond by a number.
he compound contains more than one double bond, specify the location of each double bond by
1 2 3 4 5 6 7
umber. A prefix
CH2 toCH
-ene CH
indicates
CH theCH
number
CH of
CHdouble
3 • Abonds.
prefix to -ene indicates the number of
1,3,5-heptatriene
double bonds.
1 2 3 4 5 6 7
7 CH2 CH CH CH CH CH CH3
• This is 1,3,5-heptatriene.
1,3,5-heptatriene
cycloalkenes by numbering the ring to give the double-bonded carbon atoms the numbers 1
Choose the direction of numbering so that the first substituent on the ring receives the lower
 and 2.the
ndicates Choose theofdirection
number of numbering so that the first substituent on the ring receives the lower
double bonds.
number. The position of the double bond is not given because it is known to be between C-1 and
Rule
C-2.
2
CH CH CH
3 4 5Structure
6
CH CH CH3
7 Remarks
7 1,3,5-heptatriene 2 • 2Name cycloalkenes by numbering the ring
CH 1 CH3
1 3 3 3
to give the double-bonded carbon atoms
the numbers 1 and 2.
4 6
5 4
bering the ring to give the double-bonded carbon atoms the numbers• 5Choose
1 the direction of numbering so that
of numbering so that the first substituent on the ring receives
3-methylcyclopentene the first substituent on the ring receives
the lower
1-methylcyclohexene
e double bond is not given because it is known to be between C-1the andlower number.
Rule 8
2 2 • The position of the double bond is not
Compounds
3 CHwith
3 1 CH
a carbon–carbon double bond
3 positioned between
givena because
ring carbonit atom and a sub-
is known to be between
3
stituent on the ring are named using -ylidene to name the group as a substituent.
C-1 and C-2. However, the
(=CH2) group is named methylene
4 rather
6
than methylidene.
5 4
5 CH2
ethylcyclopentene 1-methylcyclohexene
CH CH3
 3 CH3 1
3
stituent on the ring are named using -ylidene to name the group as a substituent. However, the
(=CHRule
2
) group is named methylene rather than methylidene.
Structure Remarks
4 6
4
8 5
• Compounds
CH2 with a carbon–carbon double
bond positioned between a ring carbon
ylcyclopentene 1-methylcyclohexene
CH CH3 atom and a substituent on the ring are
named using -ylidene to name the group
as a substituent.
ethylidinecyclopropane methylenecyclohexane
bon double bond positioned between a ring carbon atom and a sub-
• However,
using -ylidene to name the group as a substituent. However, the the (=CH2) group is named
ene rather than methylidene. methylene rather than methylidene.

CH2

CH CH3

ecyclopropane methylenecyclohexane
Practice Exercise
Draw the structures of the following compounds.
(a) 1-methyl-1,4-cyclohexadiene
(b) 3-methyl-1,4-cyclohexadiene
(c) 1-methyl-1,3-cyclohexadiene
1-methyl-1,4-cyclohexadiene

3-methyl-1,4-cyclohexadiene

1-methyl-1,3-cyclohexadiene
 CH
CH3
1-methyl-1,4-cyclohexadiene (a) (b)

CH3

3-methyl-1,4-cyclohexadiene
(d) (e)

1102

1-methyl-1,3-cyclohexadiene
 CH
Problem 5.14 Draw the structures of the following isomeric compounds.
CH3
(a) 1-methyl-1,4-cyclohexadiene (b) 3-methyl-1,4-cyclohexadien
1-methyl-1,4-cyclohexadiene (a) (b)
(c) 1-methyl-1,3-cyclohexadiene (d) 2-methyl-1,3-cyclohexadien
(e) 5-methyl-1,3-cyclohexadiene

Answers: CH3
CH3
CH3
3-methyl-1,4-cyclohexadiene
(a) (b) (c)
(d) (e)

1102
CH3

1-methyl-1,3-cyclohexadiene CH3
(d) (e)
 CH
Problem 5.14 Draw the structures of the following isomeric compounds.
CH3
er: (Z )-2,3-dibromo-2-hexene Br Br
(a) 1-methyl-1,4-cyclohexadiene (b) 3-methyl-1,4-cyclohexadien
1-methyl-1,4-cyclohexadiene (a) (b)
(c)
C C 1-methyl-1,3-cyclohexadiene (d) 2-methyl-1,3-cyclohexadien
(e) 5-methyl-1,3-cyclohexadiene
CH3 CH2CH2CH3
Answers: CH3
em 5.14 Draw the structures of the following isomeric compounds. CH3
CH3
3-methyl-1,4-cyclohexadiene
(a) 1-methyl-1,4-cyclohexadiene (b) 3-methyl-1,4-cyclohexadiene
(a) (b) (c)
(c) 1-methyl-1,3-cyclohexadiene (d) 2-methyl-1,3-cyclohexadiene
(d) (e)
(e) 5-methyl-1,3-cyclohexadiene

ers: CH31102 CH3

CH3
CH3
1-methyl-1,3-cyclohexadiene CH3
(a) (b) (c)
(d) (e)
 Isomerisme in Alkenes
• Free rotation around carbon—carbon single bonds is fast at room temperature.

• Therefore, alkanes can exist in many conformations.

• Free rotation does not occur around the carbon–carbon double bond of an
alkene at room temperature because of its 𝜋 bond, which forms by side-by-
side overlap of two 2p orbitals.

Figure 5.2
• About 240Rotation
kJ mole–1 is required to
About the Bond
break a bond.
For rotation to occur about a
carbon–carbon double bond,
the bond must break. Loss
of overlap between parallel 2p
orbitals requires about 240 kJ
mole–1.
 to occur about a
on double bond,
• Alkenes
must break. Loss with the same molecular formula and the same connectivity of atoms
can exist
etween parallel 2p as stereoisomers.
ires about 240 kJ
• These isomers differ because groups bonded to the double bond have
different spatial arrangements with respect to each other.

• We call these Alkenes

compoundswith the same molecular
geometric formula and the same connectivity of atoms can
isomers.
mers. These isomers differ because groups bonded to the double bond have differen
ments with respect to each other. We call these compounds geometric isomers. G
• Geometric isomers have different configurations.
have different configurations.
Consider an alkene whose formula is CXY=CXY. We can draw the structu
• Consider an alkene whose formula is CXY=CXY. The structural formula can
ways.
be drawn in two ways.
Y Y X Y
C C and C C
X X Y X
 C C
Cl“side” of theCl
• In the structure on the left, two X groups are on the same
molecule. This is the cis isomer.
ne 1,2-dichloroethene
• In the structure on the right, the X groups are on opposite “sides” of the
molecule. It is called the trans isomer.
c
Y Y Y X
mearound
on plane. In no rotation
C Catoms coplanar
all C C
d “Y” groups
ond double bon
the double X X X Y
mer, “X” and
cis geometric isomer
e sides of the trans geometric isomer
interconvert
These two • Cis and trans
structures isomers
represent are possible
different only(Figure
molecules if an alkene
5.3). Inhasthetwo different
structure onatoms
the left, two
oups are oron groups
the sameof“side”
atomsofattached to each
the molecule. Thisdouble-bonded
is the cis isomer.carbon
In the atom.
structure on the right, th
groups are on opposite “sides” of the molecule. It is called the trans isomer.
• For example, in 1,2-dichloroethene, each unsaturated carbon atom has a
Cis and trans isomers are possible only if an alkene has two different atoms or groups of atom
chlorine atom and a hydrogen atom attached to it.
ached to each double-bonded carbon atom. For example, in 1,2-dichloroethene, each unsaturate
rbon atom has agroups
• These chlorineare
atom and a hydrogen
different, and bothatom
cis andattached
trans to it. These
isomers aregroups are different, an
possible.
th cis and trans isomers are possible.

H H
different groups C C different groups

Cl Cl
1,2-dichloroethene
• If one of the unsaturated carbon atoms is attached to two identical groups, cis–
trans isomerism is not possible.

• For example, neither chloroethene nor 1,1-dichloroethene can exist as cis and
trans geometric isomers.

Cl H
identical groups C C identical groups

Cl H
1,1-dichloroethene
H H
different groups C C identical groups

Cl H
chloroethene
 H H
H
E, Z Nomenclature of Geometrical Isomers
H C C
C C CH2 C
C H
• In the previous CH
section,
3CH2CH2
the terms cis
H and trans are applied to describe the
relationship of two substituents in the disubstituted alkene 1,2-
HOCH2CH2
dichloroethene.

• This type of nomenclature can easily be used for any disubstituted alkenes.
In the previous section, we applied the terms cis and trans to describe the relationship of two substitu-
ents
• inTwo
the disubstituted
examples are alkene 1,2-dichloroethene.
cis-2-butene This type of nomenclature can easily be used for
and trans-2-butene.
any disubstituted alkenes. Two examples are cis-2-butene and trans-2-butene.

H H H CH3
C C C C
CH3 CH3 CH3 H
cis-2-butene trans-2-butene
 • However, the cis and trans notation does not describe isomeric trisubstituted
and tetrasubstituted alkenes because there is no longer a simple reference
giving the relationship of groups to one another.
, the cis and trans notation does not describe isomeric trisubstituted and tetrasubstitut
• For example, even the following relatively simple compounds cannot be
cause there is no longer a simple reference giving the relationship of groups to one anothe
designated as cis and trans isomers.
even the following relatively simple compounds cannot be designated as cis and trans iso

Br H Cl H
C C C C
Cl F Br F

distinguish the above isomers and all other tri- and tetrasubstituted alkenes by the E,Z s
• Isomers and all other tri- andBrtetrasubstituted
H alkenesCl H
can be distinguished by the E,Z
system of configurational nomenclature.
C C C C
• The E,Z system uses sequenceCl rules toF assign priorities
Br to the groups
F bonded to the atoms
of the double bond of any alkene.

• The two groups bonded to each sp 2-hybridized carbon atom are designated low priority and
We can distinguish the above isomers and all other tri- and tetrasubstituted alkenes by the E,Z system
high priority.
of configurational nomenclature. The E,Z system uses sequence rules to assign priorities to the groups
bonded to the atoms of the double bond of any alkene. The two groups bonded to each sp2-hybridized
• If the higher priority groups on each carbon atom are on the same side of the double bond,
carbon atom are designated low priority and high priority. If the higher priority groups on each car-
the alkene is the Z isomer (German zusammen, together).
bon atom are on the same side of the double bond, the alkene is the Z isomer (German zusammen,
together). If the higher priority groups on each carbon atom are on opposite sides of the double bond,
• If the higher priority groups on each carbon atom are on opposite sides of the double bond,
thealkene
the alkene is
is the
theEEisomer
isomer(German
(German entgegen, opposite).
entgegen, opposite).

high high low high

C C C C
low low high low
Z isomer E isomer
 Sequence Rules
Rule 1:
• If two atoms with different atomic numbers are directly bonded to a double bond,
the atom with the higher atomic number receives a higher priority.

• The priority order of some common elements is Br > Cl > F > O > N > C> 2H > H.

• Applying these priorities to the following alkene, which contains several halogen
atoms, to make the E, Z assignment.

• The priority 2H > H tells us that if two isotopes are possible, the one with the
higher mass has the higher priority.
 higher priority.

high priority Br CH2CH2Br low priority

C C
low priority Cl F high priority
E isomer

• The atomic
The number of bromine
atomic number of bromine is greater
is greater than than
that of that of chlorine.
chlorine. Therefore, bromine has a higher
priority than chlorine. A fluorine atom has a higher priority than a CH2CH2Br group, although the
• Therefore,reason for this assignment
bromine may not be
has a higher immediately
priority thanobvious. The priority of a group depends on the
chlorine.
atomic number of the atom directly bonded to the carbon atom of the double bond. In this case, we
have to compare carbon to fluorine. Because fluorine has a higher atomic number than carbon, it has
• A fluorinethe
atom
higherhas a higher priority than a CH2CH2Br group.
priority.

• The priority
2. of a atoms
If the group depends
directly on
attached to thethe atomic
carbon number
atom of the of the
double bond atom
have the same directly
atomic num-bonded
to the carbonber,atom
consider
ofthe
thesecond, third, and
double bond.farther atoms until a difference is found. Then apply rule 1.

The difference between an ethyl and a methyl group illustrates this rule. They are equivalent at the
• In this case, we have
first directly bondedto compare
atom: carbon
a carbon atom in eachto fluorine.
case. The carbon atom of a methyl group is bonded
to three hydrogen atoms. The carbon of the ethyl group is bonded to another carbon atom and two
• Because hydrogen
fluorineatoms.hasThus, the ethyl atomic
a higher group has anumber
higher priority
thanthancarbon,
a methyl group because
it has theChigher
> H.
priority. 143
Rule 2:

• If the atoms directly attached to the carbon atom of the double bond have the
same atomic number, consider the second, third, and farther atoms until a
difference is found.

• The difference between an ethyl and a methyl group illustrates this rule.

• They are equivalent at the first directly bonded atom: a carbon atom in each
case. The carbon atom of a methyl group is bonded to three hydrogen atoms.
The carbon of the ethyl group is bonded to another carbon atom and two
hydrogen atoms. Thus, the ethyl group has a higher priority than a methyl
group because C > H.

• If the first point of difference is not the type of atom, but rather the number of
those atoms, then the group with the greater number of high-priority atoms is
assigned the higher priority. Based on this consideration, the order of alkyl
groups is tert-butyl > isopropyl > ethyl > methyl.
 of chlorine. Therefore, bromine has a higher priority than chlorine. A fluorine a
priority than a CH2CH2Br group, although the reason for this assignment may n
Rule 3: obvious. The priority of a group depends on the atomic number of the atom dire
carbon atom of the double bond. In this case, we have to compare carbon to fluor
• The third rule of rine has priorities
assigning a higher atomicof number than carbon,
groups deals it has the higher
with priority.
multiple
If the first point of difference is not the type of atom, but rather the number of
bonded atoms. the group with the greater number of high-priority atoms is assigned the higher
this consideration, the order of alkyl groups is tert-butyl > isopropyl > ethyl > met
• A double or triple bond is considered equivalent to the same
number of single bonds3. to
The like atoms.
third rule of assigning priorities of groups deals with multiple bonded at
triple bond is considered equivalent to the same number of single bonds to li
double bond is counted as two single bonds for both of the atoms in the doubl
• Thus, a double bond is counted as two single bonds for both of
principle is used for a triple bond.
the atoms in the double bond. C C

• The same principle is used C C is treated as C C

for a triple bond.
C C

C C is treated as C C

C C
 C C is treated as C C
• Multiple bonds to atoms other than carbon are also “doubled” or “tripled.”
C C
• For example, a carbonyl
C C
group isistreated
considered
as a Ccarbon
C atom with two single
bonds to oxygen atoms, but also an oxygen atom bonded to two carbon
atoms. C C
Multiple bonds to atoms other than carbon are also “doubled” or “tripled.” For example, a carbonyl
• A cyano group isa considered
group is considered carbon atom with a two
carbon atomto with
single bonds oxygenthree
atoms, single bonds
but also an oxygen to a
atom
bonded toatom
nitrogen two carbon
and atoms.
also Aascyano group is considered
a nitrogen a carbon atom
atom bonded with three
to three single bonds
carbon atoms.to
a nitrogen atom and also as a nitrogen atom bonded to three carbon atoms.

is treated as C O
C O
O C

N C

C N is treated as C N

N C