REACTIONS

OF ALKENES

6-1

REACTIVITY OF ALKANE
C=C has more reactivity than C-C)

This because C=C has bonds, while C-C has only bond.

2px

2py

2pz

sp2

2s
6-2

ADDITION REACTIONS
1. For alkenes and alkynes, the most characteristic reaction is the
addition of groups of atoms to the carbons of the double or triple
bond.
2. Many different kinds of reactants can be added to double and triple
bonds to form more stable products.
3. Some addition reactions require a catalyst but others do not.

The general equation for the addition reaction

6-3

ELECTROFILIC ADDITION OF ALKENES

D escrip tive N ame(s )

React ion

C C

HCl
( HX)

C C

H2 O

C C

Br2
( X2 )

C C

Br2
( X2 )

H
C C
Cl (X)
H
C C
OH
(X) Br
C C
Br (X)
H2 O

HO
C C
Br (X)

Hydrochlorin ation
(hydrohalogen ation )
Hydration

Bromin ation
(h alogenation)

Bromo(halo)hydrin
formation

6-4

Hg(OAc) 2

C C

C C

BH3

C C

OsO4

C C

H2

H2 O

HgOAc
Oxymercuration
C C
HO
C C
H BH2

Hydrob oration

C C
HO OH

D iol formation
(oxidation)

C C
H H

Hydrogenation
(reduction )

6-5

Markovnikovs rule

based on Markovnikov's experimental observations on the addition of

hydrogen halides to alkenes
The Rule states:
when an unsymmetrical alkene reacts with a hydrogen halide to give
an alkyl halide, the hydrogen adds to the carbon of the alkene that
has the greater number of hydrogen substituents, and the halogen to
the carbon of the alkene with the fewer number of hydrogen
substituents

Although Markovnikov's rule is specifically applied to the addition of

hydrogen halides to alkenes, many additions are also described as
Markovnikov or anti-Markovnikov depending on the regioselectivity of the
addition reaction.

6-6

Example
What is the product of this reaction?

a.

cyclohexane

b.

cyclohexyne

c.

hexane

d.

hexene

Answer: a. This is a hydrogenation reaction. The

double bond is converted to a single bond.
6-7

What is the product of this reaction?

a.

b.

c.

Answer: b. Markovnikov's rule

says that the carbon with the most
hydrogens gets the hydrogen in
addition reactions.

d.

6-8

Question
What is the product of this reaction?

a.

b.

c.

d.

Answer: a. Hydration reactions add a hydrogen atom and an -OH group

to the double bond.
6-9

Question
What is the equation for the hydrogenation of 2-methyl-2-butene?
a.
b.
c.
d.

Answer: b.
6-10

Reactivity of Alkenes
based on their enthalpy of hydrogenation

6-11

Heats of Hydrogenation - cis & trans

Are the entaphy these two reaction same ?

H3C

CH3
C

H2

H3C

H
C

C
CH3

H2

H H H H
H
C
C
C
C H H
H H
H

H H H H
H
C
C
C
C H H
H H
H

6-12

H0 COMPARISON OF CIS & TRANS

Reduction of an alkene to an alkane is exothermic
there is net conversion of one pi bond to one sigma bond
H0 for a trans alkene is lower than
that of an isomeric cis alkene

H3C

CH3
C

H2

H2

H
C

+
H

H3C

-115

-120

a trans alkene is more stable than a

cis alkene

C
CH3

H H H H
H
C
C
C
C H H
H H
H

Reaction Coordinate
6-13

STABILITY/REACTIVITY OF SUSTITUTED ALKENE

mono

C
H

di

H
C

tri

H
C

tetra

R
C

C
R

The more subtituents that are present,

the more opportunities exist for
hyperconjugation, and the more stable
the alkene.

(less energy, less reactivity)

6-14

H0 of Hydrogenation
Eth yle ne

S tru ct ural
Formu la
CH 2 =CH 2

Prop en e

CH 3 CH=CH2

N ame

H
[k J (k cal)/m ol]
-137 (-32.8)
-126 (-30.1)

1-Bu te ne

-127 (-30.3)

cis -2- Bu ten e

-120 (-28.6)

t rans -2-Bu te ne

-115 (-27.6)

2-M eth yl-2-b ut en e

-113 (-26.9)

2,3-D ime th yl-2-b ute n e

-111 (-26.6)

H0 depends on the degree of substitution

the greater the substitution, the lower the value of H

6-15

STEREO SELECTIVITY OF HYDROGENATION

Composition (cis and trans )
even though addition syn stereoselectivity, some
product may appear to result from trans addition
CH3
CH3
1,2-D imethylcyclohexene

H2 / Pt

CH3

CH3
+

CH3
70% to 85%
cis-1,2-D imethylcyclohexan e

CH3
30% to15%
t rans -1,2-D imethylcyclohexane
(racemic)

6-16

Syn SELECTIVITY OF Hydrogenation

Hydrogenation is sensitive to steric hindrance

explaining the selectivity for reaction

hydrogen addition occurs with "syn addition", with

hydrogen entering from the least hindered side.[

6-17

Hydrogenation for Manufacturing of margarine

commonly used catalysts are transition metals (Pt, Pd, Ru, and Ni)
the process is called catalytic reduction or, alternatively, catalytic
hydrogenation

6-18

HALOGENATION

6-19

HALOGENATION
In the halogenation reactions of alkenes or alkynes, halogen atoms such as
chlorine or bromine are added to the double or triple bonds.
The reaction occurs readily, without the use of any catalyst, and adds halogen
atoms to yield a di- or tetrahaloalkane product.
In the general equation for halogenation, the symbol XX or X2 is used for
Cl2 or Br2.

X
C==C

+ XX

CC

6-20

BROMINATION

(a) When bromine is added to an alkane in the first test tube, the
red color of bromine remains because the alkane does not react
or react slowly. (b) when bromine is added to an alkene in the
second test tube, the red color immediately disappears as
bromine atoms add to the double bond.
6-21

Addition of Cl2 and Br2

carried out with either the pure reagents or in an inert
solvent such as CH2Cl2
Br Br
CH3 CH=CHCH3
2-Buten e

Br2

CH2 Cl2

CH3 CH-CHCH3
2,3-Dib romob utane

addition of bromine or chlorine to a cycloalkene gives

a trans-dihalocycloalkane
Br
+

Br2

Cyclohexen e

CH2 Cl2

Br
+

Br
Br
trans-1,2-D ibromocyclohexane
(a racemic mixture)

addition occurs with anti stereoselectivity; halogen

atoms add from the opposite face of the double bond
we will discuss this selectivity in detail in Section 6.7

6-22

Addition of Cl2 and Br2

Step 1: formation of a bridged bromonium ion
intermediate
Br
Br
C

Br

Br
C

Br
C

Thes e carbocation s are major

contribu ting s tru ctures

+ Br

The bridged bromoniu m

ion retains the geometry

6-23

Addition of Cl2 and Br2

Step 2: attack of halide ion (a nucleophile) from the
opposite side of the bromonium ion (an electrophile)
opens the three-membered ring to give the product
Br

Br
C

Br
Br

A nti (cop lan ar) orie ntation

of ad ded b romine atoms

C
Br

Br

Br
N ew man p roje ction
of the p rodu ct
Br

Br

Br

Br

A nti (cop lan ar) orie ntation

of ad ded b romine atoms

Br
N ew man projection
of th e p rod uct

6-24

Addition of Cl2 and Br2

for a cyclohexene, anti coplanar addition corresponds
to trans diaxial addition
the initial trans diaxial conformation is in equilibrium
with the more stable trans diequatorial conformation
because the bromonium ion can form on either face of
the alkene with equal probability, both trans
enantiomers are formed as a racemic mixture
Br

+ Br
2

Br

Br

Br
(1S,2S)-1,2-D ibromocyclohexan e

Br

Br

Br
Br
(1R,2R)-1,2-D ibromocyclohexane
6-25

HYDROHALOGENATION

6-26

HBr + 2-Butene
A two-step mechanism

Step 1:
proton transfer from HBr to the alkene gives a carbocation
intermediate

CH3 CH=CHCH3 + H Br

slow , rate
determining

H
CH3 CH-CHCH3 + Br
s ec-Butyl cation
(a 2 carbocation
intermediate)

Carbocations
6-27

HBr + 2-Butene
Step 2:
reaction of the sec-butyl cation (an electrophile) with
bromide ion (a nucleophile) completes the reaction

+ CH3 CHCH2 CH3

Br
Bromide ion
sec-Butyl cation
(a nu cleophile) (an electrophile)

fast

Br
CH3 CHCH2 CH3
2-Bromobu tane

6-28

Electrophilic Addition symmetric

H3C
H3C

CH3

+
H

CH3
H

Br

H
H3C

nucleophile
(Lewis base)

electrophile
(Lewis acid)

2o carbocation

or

Br-

CH3

2o carbocation

H H

Br

H3C

+
H

CH3
H
H

electrophile
(Lewis acid)

nucleophile
(Lewis base)

H3C
H

CH3
H
Br H

only one product !!!!

6-29

HBr + 2-Butene

An energy diagram for the two-step addition of HBr to 2-butene

the reaction is exergonic

6-30

regioselectivity in Addition of HX
one of two or more possible products is formed IN
PREFERENCE TO all others that might be formed
H adds to the carbon of the double bond having
the greater number of hydrogens

Br H
CH3 CH=CH2
Propene

+ HBr

Br

CH3 CH-CH2 + CH3 CH-CH2

2-Bromoprop ane 1-Bromopropane
(not obs erved)

Why to follow Markovnikovs rule ?

6-31

regioselectivity in Addition of asymetric alkenes

H3C

H3C

CH3

+
H3C

nucleophile
(Lewis base)

H3C

(Lewis acid)

H3C

H3C

Br

CH3

H H

electrophile
(Lewis acid)

H3C

electrophile
(Lewis acid)

CH3
H electrophile

H3C

H3C

CH3
H

Br-

nucleophile
(Lewis base)

H3C
H3C

CH3
H
Br

(Major)

H3C
H3C

CH3
Br

H H

H3C

3o carbocation

or

Br-

CH3
2o carbocation

H H

Markonikovs
Rule

regiospecific

(Minor)

6-32

Look at
Stability Carbocations
that formed 1st step of
electrofilic addition

6-33

Carbocations

has only six electrons in its valence shell and bears

positive charge (electrophiles);

that is, they are electron-loving (Lewis acids)

are classified as 1, 2, or 3 depending on the

number of carbons bonded to the carbon
bearing the positive charge

6-34

Stereo of Carbocations

bond angles about a positively charged carbon are approximately 120

carbon uses sp2 hybrid orbitals to form sigma bonds to the three
attached groups
the unhybridized 2p orbital lies perpendicular to the sigma bond
framework and contains no electrons

6-35

Carbocation Stability
relative stability
H

H
C+

H
Methyl
cation
(meth yl)

H
CH3 C+
H
Ethyl
cation
(1)

CH3

CH3

CH3 C+

CH3 C+

H
Isopropyl
cation
(2)

CH3
t ert-Bu tyl
cation
(3)

Increasin g carbocation s tability

a 3 carbocation is more stable than a 2 carbocation, and

requires a lower activation energy for its formation
a 2 carbocation is, in turn, more stable than a 1 carbocation,
methyl and 1 carbocations are so unstable that they are never
observed in solution

6-36

Carbocation Stability
we can account for the relative stability of
carbocations if we assume that alkyl groups bonded to
the positively charged carbon are electron releasing
and thereby delocalize the positive charge of the
cation
we account for this electron-releasing ability of alkyl
groups by (1) the inductive effect, and (2)
hyperconjugation

6-37

The Inductive Effect

the positively charged carbon polarizes electrons of
adjacent sigma bonds toward it
the positive charge on the cation is thus localized over
nearby atoms
the larger the volume over which the positive charge is
delocalized, the greater the stability of the cation

6-38

Hyperconjugation
partial overlap of the -bonding orbital of an adjacent C-H or C-C
bond with the vacant 2p orbital of the cationic carbon
the result is delocalization of the positive charge

6-39

Check with bonding energy

H
R

C+
H

Bond

D(kJ/mol)

(CH3)3CH

390

(CH3)2CHH

401

Ease of breaking:

CH3CH2H

420

3o > 2o > 1o

H
R

C+
R

Stability

R
R

C
R

C
H

H
H

R
H

Reactivity

6-40

Predict major product

Markonikovs Rule

CH3
CH3CH2CH

CCH2CH3

HCl

ether

6-41

Predict major product:

Br
ether

6-42

Predict major product:

Markonikovs Rule
regiospecific

CH3

CH3CH2C

H3PO4

CHC(CH3)3
KI

6-43

Predict major product:

Markonikovs Rule
regiospecific

CH2

CH2

CHCH2CH2CH2CH

CHCH2CH2CH2CH

CH2

CH2

HCl

2HCl

ether

ether

6-44

Predict major product:

Markonikovs Rule
regiospecific

CH2

HBr

ether

6-45

Predict major product:

Markonikovs Rule
regiospecific

HBr

ether

6-46

CARBOCATION REARRANGEMENTS

In

electrophilic addition to alkenes, there is the

possibility for rearrangement
Rearrangement: a change in connectivity of the
atoms in a product compared with the
connectivity of the same atoms in the starting
material

6-47

Evidence of Carbocation

H3C

H H

CH3

HCl

H3C

H H
H

Cl

Cl
H3C

CH3

H
H

CH3

minor

major

H H
H3C

+
CH3

H-shift

6-48

Carbocation Rearrangements
the driving force is rearrangement of a less stable
carbocation to a more stable one
+

CH3 C- CHCH3 + : Cl :

Cl :

CH3

:
CH3 CCH= CH2 + H
H
3-Methyl-1-butene

slow, rate
determining

CH3

H
A 2 carbocation
intermediate

the less stable 2 carbocation rearranges to a more

stable 3 one by 1,2-shift of a hydride ion
CH3
CH3 C- CHCH3
+

fast

CH3
CH3 C- CHCH3
+

H
A 3 carbocation

6-49

Carbocation Rearrangements
reaction of the more stable carbocation (an
electrophile) with chloride ion (a nucleophile)
completes the reaction
CH 3

C H 3 C- CH 2 CH 3 + : Cl :
+

fast

CH 3

CH 3 C- C H 2 CH 3
: Cl :

2-Chloro-2-methylbutane

6-50

Predict all products:

CH3

HBr

6-51

CH3

CH3

Br

+H

CH3

+
+

CH3

Br

CH3

CH3
E&Z
Br

CH3

CH3
Br-

Br

CH3

E&Z

CH3

6-52

Explain this Carbocation Rearrangements

Cl
+ HCl
3,3-Dimethyl1-butene

Cl

2-Chloro-3,3-dimethylbutane 2-Chloro-2,3-dimethylbutane
(the expected product; 17%)
(the major product; 83%)

6-53

Explain this Carbocation Rearrangements

in acid-catalyzed hydration of an alkene

+ H2 O
3-Methyl-1-buten e

H2 SO4

OH
2-Methyl-2-butan ol

6-54

ANTI-MARKOVNIKOV PRODUCT

6-55

anti-Markovnikov product
is formed when HBr is added in the presence of peroxides

Example:
CH 3

CH

ROOR
CH2

Br

CH3

CH

CH2

Br

The reason for the change in regiochemistry is

that the reaction proceeds via a free radical
mechanism rather than a carbocation
mechanism. The production of free radicals is
initiated by the presence of the peroxide.
6-56

Mechanism:
RO

CH 3

heat

OR

CH

Br

CH 2

Br

OH + Br

CH 3

CH

CH 2
Br

CH 3

CH

CH 2
Br

Br

CH 3

CH

CH 2 + Br

Br

Note that reaction proceeds to form the most stable

radical.
6-57

ALKENES Oxidation with O3

Treatment

of an alkene with ozone followed by a

weak reducing agent cleaves the C=C and forms
two carbonyl groups in its place
CH3
CH3 C= CHCH2 CH 3

2-Methyl-2-pentene

O
1 . O3
CH3 CCH3
2 . ( CH3 ) 2 S
Propanone
(a ketone)

O
+ HCCH 2 CH3
Propanal
(an aldehyde)

6-58

Oxidation with O3
the initial product is a molozonide which rearranges to
an isomeric ozonide
CH 3 CH = CH CH 3
2-Butene

O3

O OO
C H 3 CH - C H CH 3
A molozonide
H

O
C H 3 CH

C
C
( CH 3 ) 2 S
CH 3
O O
Acetaldehyde
An ozonide

H3 C

6-59