5

H2C

CH2

Br2

Br
H2C
Br

CH2
Br

HC
Br

Br

2 Br2

CH

HC

CH

Br

Reactions of
Alkenes and Alkynes

CHAPTER SUMMARY

Addition is the characteristic reaction of alkenes and alkynes.

Since the carbons of a double or triple bond do not have the maximum number
of attached atoms, they can add additional groups or atoms. Double bonds
undergo addition once and triple bonds can undergo addition twice. The
reactivity of alkenes and alkynes is due to the presence of pi-bonds. Unlike
sigma bonds, pi-bonds are directed away from the carbons; the electrons are
loosely held, very accessible, and quite attractive electron-deficient species
(electrophiles) seeking an electron source.

105

Chapter 5

Reactions of Alkenes and Alkynes

5.1 Addition Reactions of Alkenes

A. General Reaction Equation for Addition to Alkenes
Alkenes add hydrogen halides, halogens (chlorine and
bromine), water (sulfuric acid catalyst), and hydrogen (metal catalyst).
One part of the adding reagent adds to each carbon of the double bond;
the double bond becomes a single bond during the process.
B. Mechanism of Electrophilic Addition
With the exception of hydrogenation, the addition reactions of alkenes
presented in this text occur by an electrophilic addition mechanism.
The electrophile (H+ or X+) attacks the electron-rich pi-bond of the
double bond. The pi electrons are used to form a single bond between the
carbon and attacking species; the other carbon becomes a carbocation.
The carbocation is then neutralized by halide ion or water; the addition is
complete. In bromination reactions, the bromine adds in a trans
fashion.
C. Orientation of Addition
When an unsymmetrical reagent adds to an unsymmetrical
alkene, two addition products are possible. When the electrophile bonds,
it can bond to either carbon of the carbon-carbon double bond to form two
different carbocations. The more stable carbocation is favored and the
addition product resulting from the more stable carbocation intermediate is
the predominant product.
The order of carbocation stability: 3 o > 2 o > 1 o > methyl. A
tertiary carbocation has three bonded alkyl groups. Secondary
carbocations have two alkyl groups bonded directly to the carbocation
carbon and in primary carbocations there is only one. Since alkyl
groups are electron-releasing groups they stabilize the positive
carbocation. Tertiary carbocations have the greatest number of alkyl
groups and are the most stable.
Reactions in which one product predominates are termed
regioselective and those in which one is formed exclusively are
regiospecific. The electrophilic addition reactions in this chapter are

106

Reactions of Alkenes and Alkynes

Chapter 5

usually regioselective and the rule for predicting the predominant product
is known as Markovnikov's rule.
5.2 Addition Reactions of Alkynes
A. General Reaction Equation for Addition to Alkynes
Alkynes add hydrogen, hydrogen halides, and halogens (chlorine
and bromine). They can add one mole of reagent to produce a double
bond or two moles to form a single bond.
B. Mechanism of Catalytic Hydrogenation
of Alkenes and Alkynes
Hydrogenation of alkenes and alkynes is accomplished in the
presence of a metal catalyst which attracts both the hydrogen and
hydrocarbon to its surface. As a result of the reactants being adsorbed
onto the same surface, the reaction occurs with cis addition.
C. Electrophilic Addition Mechanism for Alkynes
The mechanism of electrophilic addition to alkynes is the same as
with alkenes. Orientation of addition of unsymmetrical reagents to
unsymmetrical alkynes is determined by the stability of the intermediate
carbocation.
D. Addition of Water to Alkynes
Alkynes add water to form aldehydes and ketones.
5.3 Addition Polymers
A polymer is a giant molecule composed of a repeating structural unit
called a monomer. Addition polymers result from the addition of alkene
molecules to one another. The polymerization occurs by cationic, freeradical, and anionic reaction mechanisms. Examples of addition polymers
include polyethylene, polystyrene, PVC, and Teflon.

107

Chapter 5

Reactions of Alkenes and Alkynes

A. Cationic Polymerization by Electrophilic Addition

In cationic polymerization, an electrophile (such as H +) adds to the
carbon-carbon double bond of a monomer to form the more stable
carbocation. The reaction conditions are such that there is relatively little
electrophile and corresponding carbocation neutralizing species. As a
result, the carbocation attacks the double bond of another monomer
molecule producing another carbocation that carries on the process until
the growing chain is eventually neutralized.
B. Polymerization by a Free-Radical Chain Reaction
In this mechanism of polymerization, a small amount of free radicals is
generated. These attack the carbon-carbon double bonds of monomer
molecules, bond to one carbon, and produce the more stable free radical;
this is the initiation step. Since few chains are initiated, the free radical
attacks yet another monomer, adds to the double bond, and forms another
free radical that, in turn, continues the process; this is propagation.
Eventually two developing free radical chains may bond together and
terminate the chain reaction.
CONNECTIONS 5.1 Serendipity in the Discovery of Polymers
CONNECTIONS 5.2 Recycling Plastics
5.4 Electrophilic Addition to Conjugated Dienes
Conjugated dienes are compounds in which two carbon-carbon double
bonds are separated by a single bond. Upon treatment with adding reagents,
conjugated dienes undergo 1,2-addition, in which the reagent adds to one of
the double bonds and 1,4-addition in which the reagent adds to the first and
fourth carbons with the remaining double bond shifting between carbons 2 and
3. This is caused by the formation of an allylic intermediate such as an allylic
carbocation. An allylic carbocation is one in which the carbocation carbon is
attached directly to a carbon-carbon double bond. Such a carbocation
engages in resonance allowing neutralization at the second and fourth carbons
of the original conjugated diene.

108

Reactions of Alkenes and Alkynes

Chapter 5

Resonance forms are classical structures used to describe a more

complex system; they do not actually exist. The species is more accurately
described by a resonance hybrid which can be imagined as an average of
the resonance forms. Resonance always stabilizes a system. Each atom in a
resonance stabilized system has a p-orbital. Allylic carbocations are stabilized
by delocalization of the positive charge.
5.5 Resonance Stabilization of Reactive Intermediates
Allylic carbocations, free radicals, and carbanions are resonance
stabilized. In each case the stabilization is the result of delocalization of the
positive or negative charge or the free radical. Resonance forms differ in the
position of electrons and charge but not atoms. Every atom in an allylic
carbocation, free radical, or carbanion possesses a p-orbital and the pielectrons and charges or unpaired electrons are delocalized throughout these
orbitals.
5.6 Natural and Synthetic Rubber
Natural rubber is produced from a milky-white colloidal latex found in the
rubber tree. It is a polymeric terpene with isoprene being the recurring
polymeric unit. Polyisoprene rubber can also be produced synthetically by the
addition polymerization of isoprene by 1,4-addition. Other synthetic rubbers
include SBR (styrene-butadiene rubber), polybutadiene, and neoprene.
Rubber is strengthened, hardened, and made more elastic by a process called
vulcanization in which sulfur bridges form links within the polymeric chains.
These links become strained when the rubber is stretched and when released
the rubber assumes its original conformation.
CONNECTIONS 5.3 Terpenes
5.7 Oxidation of Alkenes
A. Hydroxylation with Potassium Permanganate
Treatment of alkenes with potassium permanganate produces 1,2diols in a cis configuration.
109

Chapter 5

Reactions of Alkenes and Alkynes

B. Ozonolysis
Ozonolysis cleaves the carbon-carbon double bond of an alkene to
form aldehydes and ketones.
5.8 Acidity of Terminal Alkynes
Terminal alkynes have weakly acidic hydrogens that can be abstracted by
strong bases such as sodium amide.
CONNECTIONS 5.4 The Treatment of Atherosclerosis

SOLUTIONS TO PROBLEMS
5.1 Addition and Elimination Reactions
(a) H2C
Br
H2C

CH 2 + KOH

H2C

H2C

CH 2 + HBr

OH

CH 2

H2SO 4

CH 2

CH 2 + H 2O

H2C

H2C
OH

110

Addition

CH 2

Elimination

+ H 2O

H
H2SO 4

H2C

Elimination

+ KBr + H 2O

Br
(b) H2C

CH 2

CH 2
H

Addition

Reactions of Alkenes and Alkynes

Chapter 5

5.2 Addition Reactions of Alkenes

a) CH3CH

CHCH3 + H2

b) CH3CH

CHCH3 + Cl2

Pt

CH 3CH 2CH 2CH 3

CH3CH

CHCH3
Cl

Cl
c) CH3CH
d) CH3CH

CHCH3 + HBr

CH3CH

CHCH3 + H2O

H2SO 4

CHCH3

Br
H
CH3CH
HO

CHCH3
H

5.3 Addition Reactions

(a)

HCl
Cl

(b) CH 3CH 2CH

CH 2 + HBr

H
CH 3CH 2CH
Br

CH 2

or

H
CH 2

CH 3CH 2CH
H

Br

5.4 Electrophilic Addition Mechanism

H+

CH 3CH 2CH

CH 2

Br -

CH 3CH 2CH
Br

H
CH 3CH 2CH

CH 2
H

CH 2
CH 3CH 2CH
H

CH 2

Br -

CH 3CH 2CH

CH 2

Br

111

Chapter 5

Reactions of Alkenes and Alkynes

5.5 Halogenation of Alkenes

(a)

CH 3CH

CH 2

CH 3CH

Cl2

CH 2

Cl
(b)

H3C

Br2

Br

CH 3

Cl

CH 3

H3C

Br

5.6 Halogenation: Electrophilic Addition

(a) CH 3CH

CH 2

Cl

CH 3CH

CH 2

Cl

CH 3CH
Cl

Cl
(b)

CH 2
Cl

Br

H3C

CH 3

5.7 Hydration of Alkenes

(a)

CH 3CH

CHCH 3 + H2O

H2SO 4

CH 3CH
OH

(b) CH 3CH

CHCH 3

H+

CH 3CH

CHCH 3

CHCH 3
H

H2O

H
CH 3CH
OH
H

112

CHCH 3
H

- H+

CH 3CH
OH

CHCH 3
H

Reactions of Alkenes and Alkynes

Chapter 5

5.8 Carbocations
Arranged most to least stable:
CH 3

CH 3

CH 3CCH 3 > CH 3CHCH 2CH 3 > CH 3CHCH 2 and CH3CH 2CH 2CH 2
3O

2O

1O

1O

most stable
5.9 Orientation of Addition
(a)
CH3

H+

CH3CH 2C
+

Cl

CH3CH 2C

CH3
CH3CH 2C

CH2

CH3

Cl H
predominant
product

more stable
3 carbocation

CH2

CH3
CH3CH 2C

H+

CH2
+

CH2

Cl

CH3

CH3CH 2C
H

CH2
Cl

less stable
1 carbocation

(b)
H+

CH3 H2O

- H+

CH3
OH

CH3

predominant
product

more stable
3 carbocation

CH3

H2O

- H+

CH3
H
OH

less stable
2 carbocation

113

Chapter 5

Reactions of Alkenes and Alkynes

5.10 Addition Reactions of Alkynes

(a) CH3C

CCH3 +

1Br2

CH3C

CCH3

Br Br
Br
(b) CH3C

CCH3

2Br2

Br

CH3C

CCH3

Br Br
(c) CH3C

CCH3 +

1Cl2

CH3C

CCH3

Cl Cl
H
(d) CH3C

CCH3

Ni

2H2

CH3C

CCH3

5.11 Hydrogenation of Alkynes

1H 2
Pt
CH3CH 2C

CH3CH 2

CH3
C

CH 3CH 2CH 2CH 2CH 3

5.12 Hydrogenation of Alkenes

Pt
H2

Pt
+
H3C

114

CH 3

cis
addition

CCH3
2H 2
Pt

H2

H3C

CH 3

Reactions of Alkenes and Alkynes

Chapter 5

5.13 Electrophilic Addition to Alkynes

Br
CH3CH 2CH2C

CH

2HBr

CH3CH 2CH2C

H
CH

Br

Reaction Mechanism

.. _
:Br
.. :

H+
CH3CH 2CH2C

CH3CH2CH2C

CH

HBr adds to
triple bond
and then to
Br
the resulting
double bond.
CH3CH2CH2C
In each case
the more stable
Br
carbocation is formed.

H
.. _
:Br
.. :

CH3CH2CH2C

CH

CH

Br H

CH3CH 2CH2C

CH

H+

CH

Br H

5.14 Hydration of Alkynes

CH 3C

CH +

H2O

H2SO 4

CH 3C

HgSO 4

CH 2

CH 3CCH 3

OH
enol

ketone

5.15 Cationic Polymerization of Propene

H+

CH2

.. CH

H .. CH2

CH3
H .. CH2

CH
CH3

CH2

CH+

CH2

.. CH

CH3
CH+ etc. etc.
CH3

.. A -

CH3
H

CH2

CH

CH3

115

Chapter 5

Reactions of Alkenes and Alkynes

5.16 Free Radical Polymerization of 1,1-Dichloroethene

RO. + RO.

ROOR
Cl

RO.

CH 2

.. C

RO..CH 2

Cl
RO.. CH2

Cl

CH 2

Cl

Cl

Cl

C. CH2

C.

Cl

Cl

Cl

.. C

Cl
Cl

etc. etc.

RO

CH2

OR

Cl

5.17 1,2 and 1,4 Addition

CH 2 CH

(a)

CH

CH 2

Br
H
1,2 addition
CH 2 CH

CH

CH 2

+ 1HBr
CH 2 CH

CH

CH 2
H

Br

1,4 addition

(b)

Br
+ Br2

Br

Br

+
Br
1,2 addition

116

1,4 addition

Reactions of Alkenes and Alkynes

Chapter 5

5.18 Electrophilic Addition Mechanism: 1,2 and 1,4 Addition

(a)

Reaction Mechanism

STEP 1: Electrophile, H+
is attracted to pi-cloud and uses
two pi-electrons to bond. More
stable allylic carbocation results.

CH 2 CH

CH 2 CH

CH 2

H+

CH
+

CH 2

CH 2 CH
+

CH 2
H

Br-

CH

CH 2

Br

CH 2 CH

CH

Br

1,2 addition

(b)

CH

Resonance Forms

STEP 2: The allylic carbocation

is resonance stabilized. Resonance
forms show the two places it can be
neutralized by bromide ion.

CH 2 CH

CH

CH 2
H

1,4 addition

Reaction Mechanism

STEP 1: Electrophile, Br+

is attracted to pi-cloud and uses
two pi-electrons to bond. More
stable allylic carbocation results.

Br+
Br

Br

STEP 2: The allylic carbocation

is resonance stabilized. Resonance
forms show the two places it can be
neutralized by bromide ion.

Resonance Forms

Br-

Br
+

Br

Br

Br
1,2 addition

1,4 addition

117

Chapter 5

Reactions of Alkenes and Alkynes

5.19 Resonance Forms, Hybrids, and Bonding Pictures

(a)

CH 3CH

CHCH 2

CH 3CH

CH

CH 3CHCH

CH 2

+
CH 3CH

(b)

CH 3CH

CHCH 2

CH 3CH

CH

CH

CH 3CHCH

CH 2

CH 2

CH 2
CH 3CH

(c)

CH 2

CH 3CH

CHCH 2

CH 3CH

CH

CH

CH 3CHCH

CH 2

CH 2

CH 2
CH 3CH

CH

CH 2

(d)
CH 3

CH 3

CH 3

5.20 Terpenes
(a) monocyclic monoterpene

(b) acyclic monoterpene

(c) bicyclic sesquiterpene

(d) acyclic tetraterpene

(e) tricyclic diterpene

(g) acyclic monoterpene

118

(f) monocyclic monoterpene

CH 3

Reactions of Alkenes and Alkynes

Chapter 5

5.21 Reaction of Alkenes with Potassium Permanganate

(a)

CH 3CH

KMnO 4

CH 2

CH 3CH

H2O

OH

KMnO 4

(b)

CH 2
OH

H CH
3

H2O
HO

CH 3

OH

5.22 Ozonolysis
Each double bond is cleaved; the carbons become carbon-oxygen double
bonds.
CH3
(a) CH3C=CHCH2CH 3

O3

H2O

O
+

CH 3CCH3

CH 3CH 2CH

Zn
CH 3

CH 3

(b) CH2=CHC=CHCH 2CH=CCH 3

O3

H2O

O CH 3

O
+

HCH

HC

Zn
O

O
+

HCCH 2CH

c)

O3

H2O
Zn

CH 3CCH 3

HCCH2CH 2CH 2CH 2CH

5.23 Ozonolysis
Whereever you see a carbon-oxygen double bond, there was originally a
carbon-carbon double bond. Since there are only two carbon-oxygen double
bonds, they must have been involved in the carbon-carbon double bond.
CH 3 CH=CHCH2 CH 3
5.24 Acidity of Terminal Alkynes
CH3CH 2C CH + NaNH 2

CH3CH 2C

CNa + NH3

119

Chapter 5

Reactions of Alkenes and Alkynes

5.25 Addition Reactions of Alkenes: Section 5.1

(a) CH 3(CH 2)3CH
Br
CH 3
(d)

CH 3

CH 2

(b)

CH 3

CH 3
(e)

CH 3C

Cl

Cl

Br

Br

CH 3CH 2CCH 3

(g) CH 2

(c)

CH 2CH 3

CH 3

(f) CH 3CHCH 2CCH 3

CH

CH

CH 2

Cl

Cl

Cl

OH
CH 2CH 3

(h)

OH

5.26 Addition Reactions of Alkynes: Section 5.2

Br Br
a) CH3CH 2C

CH

Cl

b) CH3CH 2C

CCH3

c) CH3CH 2CH2CH2CH

CH2

Br Br

Cl

(d) CH 3CH 2CH 2CH 2CH 2CH 3

Br
(e)

CH 3CH 2CH 2C

CH 2

(f) CH 3CH 2CH 2CCH 3

Br

Br

5.27 Reaction Mechanisms - Electrophilic Addition to Alkenes:

Section 5.1B
Br

Br
(a) CH 3CH

CH 2

CH 3CH

CH 2

CH 3CH

Br
The carbocation in this case is actually a bromonium ion.
CH 3
(b)

CH 3C

CHCH 3

H+

CH 3
CH 3C

CHCH 3
H

120

Cl

CH 2

Br

Br

CH 3
CH 3C

CHCH 3

Cl H

Reactions of Alkenes and Alkynes

CH 3

(c)

Chapter 5

+ CH 3

Br
CH 3

Br

CH 3
(d)

CH 3C

CH 2

CH 3

H+

CH 3C

CH 3

H2O

CH 2

CH 3C

CH 2

+ OH

-H

CH 3

CH 3C

CH 2

OH H

5.28 Reaction Mechanisms - Electrophilic Addition to Alkynes

Section 5.2C

CH 3C

CCH 3

H+

Cl
CH 3C

CCH 3

CH 3C

H
Cl
CH 3C
Cl

CCH 3

Cl

Cl

+
CH 3C

CCH 3

H
CCH 3

Cl

H
H+

5.29 Bromination: Section 5.1B2

Bromination involves cis addition due to an intermediate bromonium ion.
Br
+ Br2
Br
5.30 Hydrogenation: Section 5.2B
CH3
CH3
(a)

CH3CHC

CCH3

(b)

+
CH3

CH3

1H2

1H2

Pd

CH3

CH3CH
C

H
Pd

H
CH3

CH3

H
121

Chapter 5

Reactions of Alkenes and Alkynes

5.31 Reaction of Alkenes with Potassium Permanganate

+

OH OH

KMnO 4/H2O

H3C

H3C

5.32 Hydration of Alkynes: Section 5.2D

O
CH

(a) CH3CH 2C

H2SO 4
H2O HgSO
4

CH 3CH 2CCH3
O

(b) CH3C

CCH3

H2SO 4
H2O HgSO
4

CH 3CH 2CCH3

5.33 Electrophilic Addition to Conjugated Dienes: Section 5.4

CH 3
(a)

CH 2

CH

CH 2

H+
CH 3

CH 3
H2C

CH

H2C

CH 2

CH

CH 2

resonance forms

H2 O
- H+

CH 3
H2C
H

CH

OH

1,2 addition

122

CH 3
CH 2

H2C

CH

H
1,4 addition

CH 2
OH

Reactions of Alkenes and Alkynes

Chapter 5

Cl +

(b)

Cl

Cl

+
resonance forms

The electrophile
attacks one of the
double bonds to
form an allylic
carbocation that
is described by
two resonance
forms. Neutralization forms two
products.

Cl
Cl

Cl

Cl

+
Cl
1,2 addition

1,4 addition

5.34 Resonance Forms and Resonance Hybrids: Section 5.5

Resonance forms

(a) CH3CH

CH CH
. 2

Resonance hybrid

CH3CH CH

(c)

CH 2
..
_

CH

..

O:

..

CH 2
H

CH3

CH2

CH 2
H

CH3

CH3CH

.. _
:O:

..

O:
(b)

CH2

C
H

CH3

CH3

+
+

(d)
O

123

Chapter 5

Reactions of Alkenes and Alkynes

5.35 Resonance Forms and Resonance Hybrids: Section 5.5

-. ..

. .O.

.. .
O.
C

... ..O.

. ..O

.. ..O

.O..

2-

O
O

-. ..

.. .O. ..-

.. ..O..C

...
..O. -

5.36 Addition Polymers: Section 5.3

a)

CH2

CF2

b)

CH2

CH

Br

5.37 Oxidation of Alkenes: Section 5.7A

(a) CH3CH=CH2

KMnO4

CH 3CHCH2
OHOH

(b)

KMnO4

OHOH
5.38 Ozonolysis: Section 5.7B
Each place there is a carbon-carbon double bond it cleaves and each carbon
becomes a carbon-oxygen double bond.

124

Reactions of Alkenes and Alkynes

O

a) CH 3CCH3

O
c) CH3C

HCCH2CH2C

CCH2CHCH2CH

Chapter 5
CH3
C

2 HCH

CH
O
O

CH3

b)

CH3

HCH

CH2CH
O

CCH3
O

5.39 Ozonolysis: Section 5.7B

Since all of the examples are hydrocarbons, each place you see a carbonoxygen double bond, you are looking at a carbon that originally was involved in
a carbon-carbon double bond.
(a)

CH 3CH 2C

(b)

CCH 2CH 3

CH 3CH 2CH 2CH

CH 3 CH 3

CCH 3
CH 3
CH 3

(c)

CH 3C

CHCH 2CH 2CH CCH 3

CH 3

(d)

CH 3

CH 3

5.40 Acidity of Terminal Alkynes: Section 5.8

+
NaNH2
(a) CH3C CH
CH3C CNa + NH3
(b) CH3CH2CH2C CH +
NaNH2
CH3CH 2CH2C CNa +
No Reaction
(c) CH3CH 2C CCH3
+
NaNH2
Not a terminal alkyne
5.41 Synthesis: Sections 4.5, 5.1, 5.2
a) A = CH3CH 2CH2CH CH2 or CH3CH 2CH

NH3

CHCH3
CH3

b) B = CH 3CH 2CHX 2 (X = Cl, Br, I)

OH

OH

CH3
d) D = CH3CHCH

c) C = CH 3CHCH2CHCH3

CH2

e) E =

F=

125

Chapter 5

Reactions of Alkenes and Alkynes

f) G = CH 3CHCH3 or CH 3CH 2CH 2X

H = CH3CH

CH2

X = Cl, Br, I

X
g) I = CH 3CH

CHCH 3

K =CH 3CH

CHCH 3

J = CH 3CH 2CHCH 3
Br

5.42 Hydration: Section 5.1

Pay attention to orientation of addition as explained in Section 5.1C.
CH 3
(a) CH3CH 2CH 2CH=CH 2
(b)
5.43 Reaction Mechanism: Section 5.1
CH3

..
:OH

CH3

CH3

CH2

CH3

+ :..
OH

CH3

..+

-H

OH

CH3

:O :

5.44 Hydrogenation: Section 5.2B

Cis addition occurs.
(a)

CH3CH 2C CCH3

1H2

Pt

CH3CH 2

CH3
C C

H
CH3
(b)

CH3CH 2CHC CCH3

1H2

Pt

CH3
CH3CH 2CH
H

CH3
C C

5.45 Reactions of Alkynes: Section 5.2

Br
(a) CH3CH 2CH2C CH

2HBr

CH 3CH 2CH 2CCH3

Br

126

CH3

Reactions of Alkenes and Alkynes

Chapter 5
Cl

(b) CH3CH 2C CCH3

(c) CH3CH 2C CCH3

2HCl

2Cl2

CH 3CH 2CCH2CH 3
Cl
Cl Cl
CH3CH 2C CCH3
Cl Cl

5.46 Units of Unsaturation: Sections 3.6, 5.1A.2, 5.2A

1-Buten-3-yne has one triple bond and one double bond. This represents three
units of unsaturation. One mole of the compound will add three moles of
bromine, one mole to the double bond and two to the triple bond.
5.47 Units of Unsaturation: Sections 3.6, 5.1A.4, 5.2A-B
Since the compound is non-cyclic all the units of unsaturation must be in the
form of carbon-carbon double bonds or triple bonds. Four mole-equivalents of
hydrogen are consumed so there must be four units of unsaturation: four double
bonds, two triple bonds, or one triple and two double bonds.
starting material

C8H10

4H2

C8H18

hydrogenation product

5.48 1,4 Addition: Section 5.4

5.49 Allylic Carbocations: Section 5.4-5.5

The three resonance forms show where this resonance stabilized carbocation
can be neutralized.

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Reactions of Alkenes and Alkynes

resonance forms

products

CH 3CH=CH-CH=CH-CHCH2CH 3

CH 3CH=CH-CH=CH-CHCH2CH 3

Br
CH 3CH=CH-CH-CH=CHCH2CH 3

Br CH 3CH=CH-CH-CH=CHCH2CH 3
Br

CH 3CH-CH=CH-CH=CHCH2CH 3

CH 3CH-CH=CH-CH=CHCH2CH 3
Br

ACTIVITIES WITH MOLECULAR MODELS

1. Make molecular models of ethene and ethyne. Now convert these to the
products formed when bromine (Br2) adds to the double bonds and triple
bonds to form single bonds. How many bromines are needed to convert a
double bond to a single bond and a triple bond to a single bond? How
many bromines are in your products and to which carbons did they add?

+ Br 2

2Br2

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Reactions of Alkenes and Alkynes

Chapter 5

2. Make molecular models of 1-butene and 2-butene (cis or trans). Make

models of the one product formed from the addition of HBr to 2-butene and the
two products formed from 1-butene. Why is there a difference in the number of
addition products. Which product predominates in the addition to 1-butene?

HBr

HBr

major
product
3. Make a model of 2-butyne and the product of cis addition of hydrogen.

H2
Pt

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Chapter 5

Reactions of Alkenes and Alkynes

4. Make a model of cyclopentene and the product of trans addition of bromine.

Br2

130