Chapter 6

Reactions of Alkenes:
Addition Reactions
The characteristic reaction of alkenes is
addition to the double bond.

Chem 207

AB

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6.1. Hydrogenation of Alkenes

Hydrogenation of Ethylene
H
C
H

HH

Exothermic H = 136 kJ/mol.

Catalyzed by finely divided Pt, Pd, Rh, Ni.
The metals are insoluble in solvents used in this reaction:
heteregeneous reactions. Reaction occurs at the interface
of the two phases.
Chem 207

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Example
CH2

H3C
H3C

H2, Pt

CH3

H3C
H3C
Chem 207

H
(73%)
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Problem 6.1
What three alkenes yield 2-methylbutane on
catalytic hydrogenation?

H2, Pt

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Mechanism of Catalytic
Hydrogenation: Mechanism 6.1

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6.2. Heats of Hydrogenation

Can be used to measure relative stability
of isomeric alkenes.
Correlation with structure is same
when heats of combustion are measured.

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as

Heats of Hydrogenation of Isomers

126
119
115
CH3CH2CH2CH3
Chem 207

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Heats of Hydrogenation (KJ/mol)

Chem 207

Ethylene

136

Monosubstituted

125-126

cis-Disubstituted

117-119

trans-Disubstituted

114-115

Terminally disubstituted

116-117

Trisubstituted

112

Tetrasubstituted

110
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Problem 6.2
Match each alkene of Problem 6.1 with its correct
heat of hydrogenation.
highest heat of
hydrogenation;
least stable isomer

126 kJ/mol

118 kJ/mol
lowest heat of
hydrogenation;
most stable isomer

112 kJ/mol

Chem 207

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6.3. Stereochemistry of Alkene Hydrogenation

Two
spatial
(stereochemical)
alkene hydrogenation:

aspects

of

(1) Syn addition of both H atoms to double bond.

(2) Hydrogenation is stereoselective, corresponding
to addition to less crowded face of double bond.
A reaction in which a single starting material can give
two or more stereoisomeric products but yields one of
them in greater amounts than the other (or even to the
exclusion of the other) is said to be stereoselective.
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10

syn-Additon versus anti-Addition

syn addition

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anti addition

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11

Example of Syn Addition

H
CO2CH3

H2, Pt

CO2CH3

CO2CH3
CO2CH3

(100%)

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12

H3C

CH3

H
H3C

H3C
H
D
H3C
D

D2, cat
H3C
D

CH3
Both products
correspond to
syn addition
of H2.

But only this one if formed!

Chem 207

Example of
Stereoselective
Reaction

B. R. Kaafarani

CH3

H
D
CH3
13

H3C

CH3

H
H3C

Example of
Stereoselective
Reaction

H2, cat

Top face of double

bond blocked by
group
H3C this methyl
CH3

H
H
H3C

H
Chem 207

H2 adds to
bottom face of
double bond.
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14

6.4. Electrophilic Addition of Hydrogen

Halides to Alkenes
General equation for electrophilic addition

Chem 207

+ EY

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15

When E+ is a hydrogen halide:

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+ HY

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16

Example
CH2CH3

CH3CH2
C
H

HBr
CHCl3, -30C

C
H

CH3CH2CH2CHCH2CH3
Br
(76%)
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17

Mechanism
Electrophilic addition of
hydrogen halides to alkenes
proceeds by rate-determining
formation of a carbocation
intermediate.
Electrons flow from the
system of the alkene (electron
rich) toward the positively
polarized proton of the
hydrogen halide.
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18

Mechanism
+C

H
..
:X
.. :

C
Chem 207

..
X:
..
..
:X
..

C
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H
19

Reactivity of Hydrogen Halide

HF << HCl < HBr < HI

least acidic

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most acidic

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20

6.5. Regioselectivity of Hydrogen Halide

Addition: Markovnikov's Rule
When an unsymmetrically substituted alkene
reacts with a hydrogen halide, the hydrogen
adds to the carbon that has the greater number
of hydrogen substituents, and the halogen adds
to the carbon that has the fewer hydrogen
substituents.

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21

Markovnikov's Rule
Example 1
CH3CH2CH

CH2

HBr
acetic acid

CH3CH2CHCH3
Br
(80%)

Example 2
CH3

H
C

CH3

C
H

CH3
HBr
acetic acid

CH3

CH3

Br
(90%)

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22

Markovnikov's Rule
Example 3
CH3

HCl

CH3

0C

Cl
(100%)

Protonation of double bond occurs in direction

that gives more stable carbocation.

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23

6.6. Mechanistic Basis for

Markovnikov's Rule: Example 1
+
CH3CH2CH2CH2
primary carbocation is less stable: not formed
+
CH3CH2CHCH3 + Br
HBr
CH3CH2CH

CH2

CH3CH2CHCH3
Br

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24

H
secondary
carbocation is
less stable:
not formed

CH3
H

Mechanistic Basis
for Markovnikov's
Rule: Example 3

H H
+

CH3

Cl

HCl
H
CH3

CH3
Chem 207

Cl
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25

6.7. Carbocation Rearrangements in Hydrogen

Halide Addition to Alkenes
H2C

Rearrangements
sometimes occur!

CHCH(CH3)2
HCl, 0C

+
CH3CHCH(CH3)2

+
CH3CHC(CH3)2

CH3CHCH(CH3)2

CH3CH2C(CH3)2

Chem 207

Cl

(40%)

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(60%)

Cl

26

6.8. Addition of Sulfuric Acid (H2SO4)

to Alkenes
CH3CH

CH2

HOSO2OH

CH3CHCH3
OSO2OH
Isopropyl
hydrogen sulfate

- Follows Markovnikov's rule

- Yields an alkyl hydrogen sulfate
Chem 207

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27

Mechanism
CH3CH

CH2 + H

..
O
..

SO2OH

slow

+
CH3CH

CH3

..
+ :O
..

SO2OH

fast

CH3CHCH3
OH
: OSO
2
..

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28

Alkyl hydrogen sulfates undergo

hydrolysis in hot water
+

CH3CHCH3
O

HOH

SO2OH
heat

CH3CHCH3
O
Chem 207

HOSO2OH

H
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29

Application: Conversion of
alkenes to alcohols

OH

1. H2SO4
2. H2O, heat
(75%)

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30

But...
Not all alkenes yield alkyl hydrogen sulfates
on reaction with sulfuric acid
These do:
H2C=CH2, RCH=CH2, and RCH=CHR'
These don't:
R2C=CH2, R2C=CHR, and R2C=CR2

Chem 207

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6.9. Acid-Catalyzed Hydration of

Alkenes
C

HOH

OH

Reaction is acid catalyzed; typical hydration medium

is 50% H2SO4-50% H2O.

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32

Follows Markovnikov's Rule

H3C

H
C

H3C

C
CH3

50% H2SO4
50% H2O

CH3
CH3

CH2CH3

OH
(90%)

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33

Follows Markovnikov's Rule

CH2

50% H2SO4

CH3

50% H2O

OH
(80%)

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34

Mechanism
Involves a carbocation intermediate.
Is the reverse of acid-catalyzed dehydration of
alcohols to alkenes.

H3C
C

CH2 + H2O

H+

H3C

Chem 207

CH3
CH3

CH3

OH

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35

Mechanism
Step (1): Protonation of double bond

H3C
C

CH2

+
O:

H3C

H
slow

H3C

H
+
C

CH3 +

H3C
Chem 207

:O:
H

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36

Mechanism
Step (2): Capture of carbocation by water

H3C

H
+
C

CH3 +

H3C

:O:
fast

CH3
CH3

H
+
O:

CH3
Chem 207

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H
37

Mechanism
Step (3): Deprotonation of oxonium ion

CH3
CH3

H
+

C +O :
CH3

H
:O:
H

H
fast

CH3
CH3

C
CH3

Chem 207

..
O:

H
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+
O:
H
38

Relative Rates
Acid-catalyzed hydration
Ethylene

CH2=CH2

1.0

Propene

CH3CH=CH2

1.6 x 106

2-Methylpropene

(CH3)2C=CH2

2.5 x 1011

The more stable the carbocation, the faster it is

formed, and the faster the reaction rate.
Chem 207

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39

Principle of Microscopic Reversibility

H3C
C

CH2 + H2O

H+

H3C

CH3
CH3

CH3

OH

In an equilibrium process, the same intermediates

and transition states are encountered in the forward
direction and the reverse, but in the opposite order.

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40

6.11
Hydroboration-Oxidation of Alkenes

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41

Synthesis
Suppose you wanted to prepare 1-decanol from
1-decene?

OH
Needed: a method for hydration of alkenes with a
regioselectivity opposite to Markovnikov's rule.
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42

Synthesis
Two-step reaction sequence called hydroborationoxidation converts alkenes to alcohols with a
regiochemistry opposite to Markovnikov's rule.

1. Hydroboration
2. Oxidation
OH

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43

Hydroboration Step

+ HBH2

BH2

Hydroboration can be viewed as the addition of

borane (BH3) to the double bond. But BH3 is not
the reagent actually used.

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44

Hydroboration Step
C

Hydroboration reagents:

H
H2B

HBH2

BH2
H

BH2

Diborane (B2H6)
normally used in an
ether- like solvent
called "diglyme"
O

O
O

2-Methoxyethyl ether or diglyme

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45

Hydroboration Step

HBH2

BH2

Hydroboration reagents:
Borane-tetrahydrofuran
complex (H3B-THF)

+O
BH

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46

Oxidation Step

BH2

H2O2, HO

OH

Organoborane formed in the hydroboration

step is oxidized with hydrogen peroxide.

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47

Example

1. B2H6, diglyme
2. H2O2, HO
OH
(93%)

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48

Example
H3C

CH3
C

H3C

C
H

H
1. H3B-THF
2. H2O2, HO

CH3 C

OH
C

CH3

CH3 H
(98%)

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49

Features of Hydroboration-Oxidation
Hydration of alkenes.
Regioselectivity opposite to Markovnikov's rule.
No rearrangement.
Stereospecific syn addition.

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50

6.14. Addition of Halogens to Alkenes

General features

+ X2

Electrophilic addition to double bond.

Forms a vicinal dihalide.

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51

Example

CH3CH

CHCH(CH3)2

Br2
CHCl3
0C

CH3CHCHCH(CH3)2
Br Br
(100%)

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52

Scope
- Limited to Cl2 and Br2.
- F2 addition proceeds with explosive violence.
- I2 addition is endothermic: vicinal diiodides
dissociate to an alkene and I2.

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53

6.15. Stereochemistry of Halogen Addition

anti addition
Example
H

Br2

Br
Br

trans-1,2-Dibromocyclopentane
80% yield; only product
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54

Example
H
H

Cl

Cl2

H
Cl
trans-1,2-Dichlorocyclooctane
73% yield; only product

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55

6.16. Mechanism of Halogen Addition to

Alkenes: Halonium Ions
Mechanism is electrophilic addition
Br2 is not polar, but it is polarizable.
Two steps:
(1)
Formation of bromonium ion.
(2)
Nucleophilic attack on bromonium
ion by bromide.
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56

Table 6.3. Relative Rates of Bromination

Ethylene

H2C=CH2

Propene

CH3CH=CH2

2-Methylpropene

(CH3)2C=CH2

2,3-Dimethyl-2-butene

(CH3)2C=C(CH3)2

1
61
5400
920,000

More highly substituted double bonds react faster.

Alkyl groups on the double bond make it more electron
rich.

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57

Mechanism?
H2C

CH2 +

Br2

BrCH2CH2Br

+
C

..
+ : Br :
..

: Br :
..
No obvious explanation for anti addition provided
by this mechanism.
Chem 207

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58

Mechanism
H2C

CH2 +

Br2

BrCH2CH2Br

..
+ : Br :
..

: Br :
+
Cyclic bromonium ion
Chem 207

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59

Formation of Bromonium Ion

Br

Br

Br

Br
+

Mutual polarization of
electron distributions of
Br2 and alkene
Chem 207

Electrons flow from

alkene toward Br2
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60

Formation of Bromonium Ion

Br
electrons of
alkene displace
Br from Br.

Chem 207

+
Br

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61

Stereochemistry
..
: Br :
..

..
Br +
..
..
: Br :
..

Attack of Br from side opposite

CBr bond of bromonium ion gives
anti addition.
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..
Br :
..
62

Example

Br2

Br
Br

trans-1,2-Dibromocyclopentane
80% yield; only product.

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63

Cyclopentene +Br2

Bromonium ion

Chem 207

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64

Bromide ion attacks the

bromonium ion from side
opposite carbon-bromine bond.
Chem 207

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trans-Stereochemistry
in vicinal dibromide
65

6.17. Conversion of Alkenes to Vicinal Halohydrins

C

+ X2

Alkenes react with X2 to form vicinal dihalides.

Alkenes react with X2 in water to give vicinal
halohydrins.

C + X2 + H2O

OH

+ HX
Chem 207

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66

Examples
H2C

CH2 +

Br2

H2O

BrCH2CH2OH
(70%)

Cl2

OH

H2O
Cl

anti addition: only product

Chem 207

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67

Mechanism
O:
..

..
Br +
..
O
..

Bromonium ion is intermediate.

Water is nucleophile that attacks
bromonium ion.
Chem 207

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..
Br :
..
68

Regioselectivity
H3C
C
H3C

CH2

Br2
H2O

CH3
CH3

CH2Br

OH
(77%)

Markovnikov's rule applied to halohydrin formation:

the halogen adds to the carbon having the greater
number of hydrogens.
Chem 207

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69

Explanation
H
H

..
O
H3C
H3C

SN2 Stereochemistry
SN1 Regiochemistry

CH2

H3C
H3C

: Br :

..
O

CH2

: Br :

Transition state for attack of water on bromonium ion has

carbocation character; more stable transition state (left) has
positive charge on more highly substituted carbon
Chem 207

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70

Few alkenes are soluble in water

HO
NBS

Br

H2O/DMSO
O
N

Br

N-Bromosuccinimide (NBS)

NBS is a source of Br2 in low concentration:

radical addition. Works for allylic susbstitution.
Chem 207

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71

6.18. Free-radical Addition

of HBr to Alkenes
The "peroxide effect"

Chem 207

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72

Markovnikov's Rule

CH3CH2CH

CH2

HBr
acetic acid

CH3CH2CHCH3
Br
(90%)

Chem 207

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73

Addition of HBr to 1-Butene

CH2

CH3CH2CH

HBr

CH3CH2CHCH3

CH3CH2CH2CH2Br

Br
only product in
absence of peroxides
Chem 207

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only product when

peroxides added to
reaction mixture
74

Addition of HBr to 1-Butene

CH2

CH3CH2CH

HBr
Addition opposite to
Markovnikov's rule
occurs with HBr (not
HCl or HI)

CH3CH2CH2CH2Br
only product when
peroxides added to
reaction mixture

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75

Photochemical Addition of HBr

CH2 + HBr

CH2Br
H
(60%)

Addition of HBr with a regiochemistry opposite

to Markovnikov's rule can also occur when
initiated with light with or without added peroxides.

Chem 207

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76

Mechanism
Addition of HBr opposite to Markovnikov's rule
proceeds by a free-radical chain mechanism.
Initiation steps:

Chem 207

..
O
..

..
O
..

..
. + H
O
..

..
:
Br
..

B. R. Kaafarani

..
..
. + .O
O
..
..

..
..
.
+
:
O
H
Br
..
..

77

Mechanism

Propagation steps:

..
CH2 + . Br :
..

CH3CH2CH

CH3CH2CH
.

Chem 207

CH2

.
CH3CH2CH

..
Br:
..

CH2

..
Br:
..

..
CH3CH2CH2CH2 Br:
..
+

..
Br
.. :

..
. Br :
..
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78

6.19. Epoxidation of Alkenes

Epoxides are examples of heterocyclic compounds
three-membered rings that contain oxygen.

CH2

H2C

O
Ethylene oxide

Chem 207

CHCH3

H2C

Propylene oxide

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79

Epoxide Nomenclature
Substitutive nomenclature: named as epoxysubstituted alkanes.
epoxy precedes name of alkane.
1

H3C

O
1,2-epoxypropane
Chem 207

H3C

CHCH3

CHCH3

H2C

2-methyl-2,3-epoxybutane
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80

Problem 6.22. Give the IUPAC name,

including stereochemistry, for disparlure

cis-2-Methyl-7,8-epoxyoctadecane

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81

Epoxidation of Alkenes
O
C

RCOOH
peroxy acid

O
C

RCOH

O
Chem 207

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82

Example
O
+ CH3COOH
O
O

Chem 207

+ CH3COH
(52%)

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83

Stereochemistry of Epoxidation
O
C

RCOOH

syn addition

O
C

RCOH

O
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84

Problem 6.23.
Give the structure of the alkene,
including stereochemistry, that you would choose as
the starting material in a preparation of synthetic
disparlure.

H
peroxy acid

H
Chem 207

H
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85

Relative Rates of Epoxidation

Ethylene

H2C=CH2

Propene

CH3CH=CH2

22

2-Methylpropene

(CH3)2C=CH2

484

2-Methyl-2-butene

(CH3)2C=CHCH3

6526

More highly substituted double bonds react faster.

Alkyl groups on the double bond make it more electron
rich.
Chem 207

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86

6.20. Ozonolysis of Alkenes

Ozonolysis has both synthetic and analytical
applications.
- Synthesis of aldehydes and ketones.
- Identification of substituents on the double bond of
an alkene.

+ O3

C
O

O
C
O

First step is the reaction of the alkene with ozone.

The product is an ozonide.
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87

Ozonolysis of Alkenes
Second step is hydrolysis of the ozonide.
Two aldehydes, two ketones, or an aldehyde
and a ketone are formed.

+ O3

C
O

C
O
H2O, Zn

C
Chem 207

C
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88

Ozonolysis of Alkenes
As an alternative to hydrolysis, the ozonide can
be treated with dimethyl sulfide.

+ O3

C
O

C
O
(CH3)2S

C
Chem 207

C
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89

Example
CH2CH3

CH3
C

CH2CH3
1. O3
2. H2O, Zn
CH2CH3

CH3
C

CH2CH3
(57%)

(38%)
Chem 207

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90

C=C bond cleavage

H3C

KMnO4
Acetone

CO2H

HO2C

H3C

NaIO4

OH

OsO4

OH

OH

O
H

O
O

Cyclic periodate intermediate

2RCHO

KMnO4: Potassium permanganate

NaIO4: Sodium periodate
OsO4: Osmium tetroxide
Chem 207

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91

Introduction to Organic
Chemical Synthesis:
RETROSYNTHESIS

Chem 207

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92

Prepare cyclohexane from cyclohexanol

OH

Devise a synthetic plan:

- Reason backward from the target molecule.
- Always use reactions that you are sure of.

Chem 207

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93

Prepare cyclohexane from cyclohexanol

Ask yourself the key question:

"Starting with anything, how can I make
cyclohexane in a single step by a reaction that
will work?"
Chem 207

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94

Prepare cyclohexane from cyclohexanol

H2
Pt
The only reaction covered so far for preparing
alkanes is catalytic hydrogenation of alkenes.
This leads to a new question. "Starting with
anything, how can I prepare cyclohexene in a single
step by a reaction I am sure will work?"
Chem 207

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95

Prepare cyclohexane from cyclohexanol

OH

H2SO4

H2

heat

Pt

Alkenes can be prepared by dehydration of

alcohols.
The synthesis is complete.

Chem 207

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96

Prepare 1-bromo-2-methyl-2propanol from tert-butyl alcohol

(CH3)3COH

(CH3)2CCH2Br
OH

"Starting with anything, how can I make the

desired compound in a single step by a reaction that
will work?"
The desired compound is a vicinal bromohydrin.
How are vicinal bromohydrins prepared?
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97

Prepare 1-bromo-2-methyl-2propanol from tert-butyl alcohol

(CH3)2C

CH2

Br2
H2O

(CH3)2CCH2Br
OH

Vicinal bromohydrins are prepared by treatment

of alkenes with Br2 in water.
How is the necessary alkene prepared?

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98

Prepare 1-bromo-2-methyl-2propanol from tert-butyl alcohol

(CH3)3COH
H2SO4
heat
(CH3)2C

CH2

Br2
H2O

(CH3)2CCH2Br
OH

2-Methylpropene is prepared from tert-butyl alcohol

by acid-catalyzed dehydration.
The synthesis is complete.
Chem 207

B. R. Kaafarani

99

6.21. Reactions of Alkenes with

Alkenes: Polymerization

Cationic polymerization
Free-radical polymerization
Coordination polymerization

Chem 207

B. R. Kaafarani

100

Dimerization
Dimerization of 2-methylpropene
monomer
(C4H8)

(CH3)2C

CH2
H2SO4

two dimers
(C8H16)

CH3
CH3CCH

CH3
C(CH3)2 + CH3CCH2C

CH3
Chem 207

CH2

CH3 CH3
B. R. Kaafarani

101

Mechanism of Dimerization
CH3
CH3C +

CH3
+

H2C

C
CH3

CH3

CH3

+
CH3CCH2C

CH3

CH3 CH3
Chem 207

B. R. Kaafarani

102

Mechanism of Dimerization
CH3

+
CH3CCH2C

CH3

CH3 CH3
CH3

CH3
CH3CCH

C(CH3)2

CH2

CH3 CH3

CH3
Chem 207

CH3CCH2C

B. R. Kaafarani

103

Cationic Polymerization
AlCl4- CH

CH3
H3C

Cl

+ AlCl3

H3C

CH3

CH3
AlCl4- CH3
+
H3C

CH3
H3C

CH3

Ar

H3C

CH3
H3C

AlCl4+

Ar

Ar

AlCl4-

H3C
Ar

Ar
Ar

Chem 207

B. R. Kaafarani

104

Free-Radical Polymerization of
Ethylene
H2C

CH2

200 C
2000 atm

CH2

CH2

CH2

O2 or
peroxides

CH2

CH2

CH2

CH2

polyethylene
Chem 207

B. R. Kaafarani

105

Mechanism
OR

H2C

RO

H2C

OR

OR

CH2
H2C

CH2

H2C

CH2

CH2

H2C
H2C

H2C

H2C

CH2
H2C

OR

H2C

CH2
H2C

CH2

CH2

CH2
H2C

CH2
H2C

H2C

CH2

OR

OR

OR

CH2

H2C

CH2
H2C

B. R. Kaafarani

CH2
H2C

CH2

CH2
H2C

H2C

Chem 207

CH2

CH2

CH2
H2C

CH2

106

Free-Radical Polymerization of Propene

H2C

CH
CH3

CH2 CH

CHCH3

CH2

CH3

CH
CH3

CH2 CH
CH3

polypropylene
Chem 207

B. R. Kaafarani

107

Mechanism
OR

H2C

RO

H2C

OR

OR

CHCH3

H2C

H2C

CHCH3

CHCH3

H2C
H2C

H2C

H2C

CHCH3
H2C

CHCH3

CHCH3

H2C

H2C

CHCH3

OR

CHCH3

H2C

CHCH3

CHCH3
H2C

Chem 207

H2C

H2C

CHCH3

OR

OR

OR

CHCH3

H2C

CHCH3

CHCH3
H2C

CHCH3

CHCH3
H2C

CHCH3

H2C

B. R. Kaafarani

CHCH3

CHCH3
H2C

CHCH3

108

Likewise...
H2C=CHCl
H2C=CHC6H5
F2C=CF2

Chem 207

polyvinyl chloride
polystyrene
Teflon

B. R. Kaafarani

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