CHAPTER 12.

2
ALKENES
HYDROCARBONS
 REACTION IN ALKENES

C=C is a site of high electron density (nucleophilic

site), becomes the site of electrophilic attack.

Reactions of alkenes are mainly electrophilic

addition reaction.

C C + A—B
C C

A B
 I) HYDROGENATION

 Addition of H2(g) in the presence of catalyst

(Pt /Pd /Ni)

Examples:
 EXERCISE – 01
CHAPTER 12.2.3

What alkane is formed when each alkene is

treated with H2 and a Pd catalyst?

(a) CH3 (b)

CH2CH(CH3)2
C C
CH3 H

(c) (d)
CH3
CH═CH2
 II) HALOGENATION OF ALKENES
IN INERT SOLVENT (CH2Cl2)

CH2Cl2
C C + X—X C C

X X
 Reactant: alkene and halogen (Cl2, Br2)
 Product: vicinal dihalide

vicinal (vic) = next to

another
 EXAMPLE:

CH2Cl2 Br
+ Br2

Br
1,2–dibromocyclohexane

CCl4 CH3CH—CHCH3
CH3CH═CHCH3 + Cl2
Cl Cl
2,3–dichlorobutane

6
 CHAPTER 12.2.3
EXERCISE 2

Predict the product of the following reaction:

(a) cyclooctene + Br2 in CH2Cl2

(b) 3–decene + Br2 in CCl4

(c)
+ Cl2 in CHCl3

(d)
+ 2Cl2 in CH2Cl2
 III) HALOGENATION OF
ALKENES IN WATER
C C
C C + X2 + H2O
X OH
 X adds to C that has greater halohydrin
number of H
EXAMPLE:

CH3 CH3
H2O
CH3–CH–CH═CH2 + Cl2 CH3–CH–CH–CH2
3–methyl–1–butene
OH Cl
1–chloro–3–methyl–2–butanol
 CHAPTER 12.2.3
EXERCISE 3

Draw the major product of each reaction.

(a) Br2
CH2 ?
CH2Cl2

(b) Br2
CH2 ?
H2O
 MARKOVNIKOV’S RULE
 In addition of HX to an alkene, H atom
adds to the C atom of the double bond
that already has the greater number of
H atoms
C with the greater
number of H

CH3 CH CH2 CH3 CH CH2

X H

X H
 IV) HYDROHALOGENATION

EXAMPLE:

ethene
bromoethane
H and X are added! It Follow
Markovnikov’s Rule and it is
Electrophilic Addition reaction!
EXAMPLE:

H H H H
C C + HBr H C C H
H H
H Br
ethylene
bromoethane

+ HCl

cyclohexene H Cl
chlorocyclohexane
 CHAPTER 12.2.3
EXERCISE 4

Draw the products formed when each

alkene is treated with HCl.
(a)
CH3

(b) CH3
C CH2
CH3

(c) CH3CH2CH2CH2C═CH2

CH
 V) HYDRATION

 Electrophilic addition of water

d+ d–
H3O+
C C + H—OH C C

H OH
alcohol

 Conditions: with Catalyst, dilute H2SO4 (aq)

 Follow Markovnikov Rule
 EXAMPLE

a) +

c)
CH3CH2CH═CH2 +

b) +
H OH
 CHAPTER 12.2.3
EXERCISE 5
Give the major product obtained from the
acid–catalyzed hydration of each of the
following alkenes

(a) (b)
1‒hexene
CH2

(c) (d) CH3

CH2═CCH2CHCH3

CH3
 MECHANISM OF HYDROHALOGENATION

STEP 1 Formation of carbocation and halide ion

H
X H + C C C C+ + x–
d d+
–
electrophile nucleophile carbocation
STEP 2

Halide ion donate electron pair to carbocation

H H X
–
C C+ + x C C

electrophile nucleophile
EXAMPLE:

d+ d– +
CH3—C═CH2 + H—Br CH3—C—CH3
CH3 CH3
2–methylpropene 3o carbocation

Br–

Br

CH3—C—CH3
CH3
2–bromo–2–methylpropane
 CHAPTER 12.2.3
EXERCISE 6

Outline mechanism for the electrophilic

addition of HCl to 2–methyl–2–butene.
 MECHANISM OF HYDRATION

STEP 1: Formation of carbocation

CH2 CH3

C + H C+
H3C CH3 H3C CH3
3o carbocation

O H
+
H
 STEP 2:

 Formation of protonated alcohol

CH3 CH3
+●●
C+ + O H
CH3 C O H
H3C CH3 CH3 H
H
protonated alcohol
 STEP 3:

 Elimination of H+

O H
CH3 H CH3
CH3
+●● ●● +
C O H CH3 C O–H + H3O
●●

CH3 H CH3
2–methyl–2–propanol
 CHAPTER 12.2.3
EXERCISE 7

Write the mechanism of the acid–catalyzed

hydration of 1–butene.
 ANTI–MARKOVNIKOV
ADDITION
Occurs only when HBr is used in the presence of
peroxide (R–O–O–R)- Examples: H2O2, CH3OCH3

H atom attached to C atom with fewer H atoms

C with fewer H atoms

H2O2
CH3 CH CH2 CH3 CH CH2
H Br
H Br
EXAMPLE:

ANTI-MARKOVNIKOV
H2O2
CH3CH═CH2 + HBr CH3CH2CH2Br
1–bromopropane

MARKOVNIKOV

CH3CH═CH2 + HBr CH3CHBrCH3

2–bromopropane
 EXERCISE 8 CHAPTER 12.2.3

Predict the major products of the following

reactions.
(a)
HBr
CH3CH2CH═CH2
ROOR

(b)
HBr
CH2CH═CH2
ROOR

27
 UNSATURATED TEST

 To test the presence of C=C

 To distinguish alkene and alkane

BROMINE TEST BAEYER TEST

 I) BAEYER TEST

 At room temperature

Dilute, OH ‒
C C + KMnO 4 C C + MnO2
cold
OH OH Brown
diol precepitate

 Observation:
Purple color of KMnO4 decolourised

 Brown Precipitate formed

EXAMPLE:
CH3CH—CH2
CH3CH═CH2 KMnO4 Dilute, OH‒ OH OH
+
cold
propene 1,2–propanediol

+ MnO2

OH
+ KMnO4 Dilute, OH‒
cold
OH
cyclohexene
1,2–cyclohexanediol
+ MnO2
 II) BROMINE TEST (Br2 in CH2Cl2)

CH2Cl2
C C + Br2 C C

Br Br

 Observation:
Reddish-brown color of Br2 decolourised
EXAMPLE:
Br
Br2
CH2Cl2
Br
cyclohexene 1,2–dibromocyclohexane

Observation:
The reddish-brown color of
bromine decolourised
 III) TEST WITH BROMINE WATER

H2O
C C + Br2 C C

Br OH

 Observation:
Reddish–brown color of Br2 decolourised
EXAMPLE:
Br
Br2
H2O
OH
cyclohexene 2–bromocyclohexanol

Observation:
The reddish-brown color of
bromine decolourised
 OXIDATIVE CLEVAGE OF C=C

i) Ozonolysis

ii) Reaction of Alkene with hot,

acidified KMnO4
 I) OZONOLYSIS

 Reactant: alkene

 Product: aldehyde and / or ketone

 Conditions: O3 followed by Zn , H2O

R R R’
R’ [i] O3
C C C O + O C
R H [ii] Zn, H2O R H
ketone aldehyde
EXAMPLE: CH3
CH3C═O
CH3 acetone
[i] O3
CH3C═CHCH3 +
[ii] Zn, H2O
O
CH3CH
acetaldehyde

CH3 O

CH3 CH3CH–CH
[i] O3
CH3CH–CH═CH2 isobutyraldehyde
[ii] Zn, H2O
O
+ formalde
HCH
hyde
 EXERCISE 9
Draw the products formed when each alkene
is treated with O3 followed by Zn, H2O.
(a) (CH3)2C═CHCH2CH2CH2CH3

(b) 3–heptene

(c) CH3
 EXERCISE 10
Draw the products formed when each diene
is treated with O3 followed by Zn, H2O.

(a)

(b)
 Ozonolysis can be used to determine the
structure of an unknown alkene

EXAMPLE: working
backwards

H3C CH2CH2CH3 CH3

C O + O C CH3C═CHCH2CH2CH3
H3C H
acetone butanal 2–methyl–2–hexene

ozonolysis products alkene that

underwent ozonolysis
40
 ii) REACTION WITH HOT,
ACIDIFIED KMnO4
 Reagent:

 KMnO4, H+,Heat OR  i)KMnO4, OH‒, Heat

ii) H3O+

Product: ketone and / or carboxylic acid

or CO2 and H2O

R R’ R R’
KMnO4 , H+
C C C O + O C
R H ∆ R OH
ketone
carboxylic acid
EXAMPLE:

O
KMnO4 , H+
CH3CH═CHCH3 CH3COH
∆

CH3 CH3
KMnO4 , H+ CH3CH2C═O
CH3CH2C═CH2
∆
+ CO2
Terminal C=C

+ H2O
EXAMPLE:

KMnO4 , H+
∆ +

OH
C
 EXERCISE 11
Draw the products formed for the following
reactions

(a) [i] KMnO4, OH– , heat

[ii] H3O+

CH3 KMnO4 , H+

(b) ∆
 Valuable tool for structure determination
of unknown compounds (alkenes)

EXAMPLE:

Oxidation products:

O O

CH3CH2C–OH + HO–CCH2CH2CH2CH3
propanoic acid pentanoic acid

join these two C to deduce the starting material

CH3CH2CH═CHCH2CH2CH2CH3
3–octene
 EXERCISE 12

Show the structures of alkenes that give the

following products on oxidative cleavage with
hot concentrated KMnO4 solution:

(a) CH3CH2CO2H + CO2

(b) (CH3)2C═O + CH3CH2CH2CO2H

(c) ═O + (CH3)2C═O
 VERSATILITY OF ALKENES
Wide variety of compounds can be made from
alkenes:

alcohol alkane

halohydrin

diol

dihalolalkane
alkene carbonyl
compound

Carboxylic acid
alkyl halide