(4) Addition of HBr to Alkenes in The

Presence of Peroxides
(Anti Markovnikov’s rule)
• When alkenes are treated with HBr in the presence
of peroxides, ROOR (eg: H2O2) the addition occurs
in an anti-Markovnikov manner

• The hydrogen atom of HBr attached to the doubly

bonded carbon with fewer hydrogen atoms.
Example:

ROOR
H2C CH CH3 + HBr

Br CH2CH2CH3
Complete the following reactions:

(1)
H2 O2
H3C CH2C CH2 + HBr
CH3
(2)

CH2 H2 O2
+ HBr
(5) Hydration of Alkene
• The acid-catalyzed addition of water to the
double bond of an alkene (hydration of an
alkene) is a method for the preparation of
low molecular weight alcohols.

• The acid most commonly used to catalyze

the hydration of alkenes are dilute solution
of sulphuric acid and phosphoric acid.
• The addition of water to the double bond
follows Markovnikov’s rule.

+
H3O
C C + H2O C C
H OH
Example:
+
H3 O
H3C C CH2 + H2 O
CH3
OH
H3C C CH3
CH3
Complete the following reactions:

(1)
+
CH2 H3 O
+ H2 O

(2)
+
H3 O
H2C CH CH3 + H2 O
(6) Addition of Sulphuric Acid to
Alkenes
• Alkenes dissolve in concentrated sulphuric
acid to form alkyl hydrogen sulphates.
sulphates
• Alkyl hydrogen sulfates can be easily
hydrolyzed to alcohols by heating them
with water.
• The overall result of the addition of
sulphuric acid to alkenes followed by
hydrolysis is the Markovnikov addition of
-H and -OH.
CH3CH3
H3 C CH3
conc. H2 SO 4 H3 C C C CH3
C C
H3 C CH3 H OSO 3 H
alkyl hydrogen sulphate

CH3CH3
H2 O H3 C C C CH3
heat
H OH
• Example:

OSO H
conc.H SO 3
H C CH CH 2 4
H C CH CH
2 3 3 2

OH
H O
2
HC CH CH
heat 3 2

H
6 ) Oxidation of Alkenes
Alkenes undergo a number of reactions
in which the carbon-carbon double
bond is oxidized

KMnO4 ozonolysis
 cold & dilute KMnO4
 hot , OH- or H+
i) With cold and dilute potassium
permanganate, KMnO4

• Potassium permanganate in base can

be used to oxidize alkenes to 1,2-diols
(glycols).
-
OH ,cold
C C + KMnO4
(purple)

C C + MnO2
OH OH (brown precipitate)
• This reaction is called Baeyer’s test.
test

• It can serve as a test for the presence of

carbon-carbon double bonds where the
purple colour of the KMnO4 decolourised,
and brown precipitate of MnO2 is formed.
Example:
-
OH ,H2 O
H2C CH2 + KMnO4
cold

H H
H C C H + MnO2
OH OH
ii) With hot potassium permanganate
solutions to alkenes (oxidative
cleavage of alkenes)

 When oxidation of the alkene is carried out

with KMnO4, in acidic rather than basic
solution,
solution cleavage of the double bond occurs
and carbonyl-containing products are
obtained.
 If the double bond is tetrasubstituted,
tetrasubstituted
the two carbonyl-containing products
are ketones;
ketones

 If a hydrogen is present on the double

bond,
bond one of the carbonyl-containing
products is a carboxylic acid;
acid

 If two hydrogens are present on one

carbon, CO2 and H2O are formed.
Example:
1)

CH3 -
(i) OH ,heat
H3C C C CH3 + KMnO4
(ii) H3O
+

CH3
O O

H3C
C
CH3
+ H3C
C
CH3
2)
-
(i) OH ,heat
H2C CH CH3 + KMnO4
(ii) H3O
+

HO
C
CH3
+ CO2 + H2 O
• The oxidative cleavage of alkenes can
be used to establish the location of the
double bond in an unknown alkene.
Example:
• An unknown alkene with the formula C7H14
was found on oxidation with hot basic
permanganate, to form a three-carbon
carboxylic acid (propanoic acid) and four-
carbon carboxylic acid (butanoic acid).
What is the structure of this alkene?
(i) OH-,heat
C 7 H14 + KMnO4
(ii) H3 O
+

O O
H3C
CH2
C
OH
+ H3C
CH2 C
CH2 OH
Answer:
O O
H3C C CH2 C
CH2 OH H3C CH2 OH
propanoic acid butanoic acid

H H
H3C CH2C C CH2CH2CH3
3-heptene
Example
• An unknown alkene undergoes oxidation
by hot basic KMnO4, after acidification,
gives the following product:

O O
CH3CCH2CH2CH2CH2C OH

Deduce the structural formula for the

unknown alkene.
iii) Ozonolysis of Alkenes
(Oxidative Cleavage of Alkenes)

• A more widely used method for locating

the double bond of an alkene involves
the use of ozone (O3).
• Ozone reacts vigorously with alkenes to
form unstable compounds called
molozonides,
molozonides which rearrange
spontaneously to form compounds as
ozonides.
O
C C
C C + O3

O O

ozonide
• Ozonides:
• very unstable compounds

• can easily explode violently

• they are not usually isolated but are

reduced directly by treatment with
water and in the presence of zinc and
acid (normally acetic acid) to give
carbonyl compounds (either
aldehydes or ketones).
O H
+
H2 O,H
C C
+ Zn

R
O O

ozonide
H
C=O + O=C
R
Example:
CH3 (i)O3
+
H3C C CH CH3 (ii)Zn,H2 O/H

CH3 CH3

H3C
C
O
+ H
C
O
Example
• Deduce the structural formula of an
alkene that gives the following compound
when it reacts with ozone in the presence
of Zn / H+.

O=CH-CH2-CH2-CH(CH3)CH=O
Exercise
1. Write the structure of alkene that
would produce the following products
when treated with ozone followed by
water, zinc and acid
CH3COCH3 and CH3CH(CH3)CHO
2. Acid-catalyzed dehydration of
neopentyl alcohol, (CH3)3CCH2OH,
yields 2-methyl-2-butene as the major
product. Outline a mechanism
showing all steps in its formation.
Exercise
• Compounds A, B, C and D are isomers
with the molecular formula C4H8. A and B
give a positive Baeyer test,
test while C and D
do not. A exist as cis- and trans- isomers,
isomers
while B does not have geometrical
isomers. C has only secondary hydrogen,
hydrogen
while D has primary, secondary and
tertiary hydrogen.
hydrogen Give the IUPAC names
for A, B, C, and D.