CHAPTER 13

Hydrocarbons
Alkenes
Part 2
Prepared by: Cik Suhaila
For F5
1

Chemical Reaction Of Alkenes

Alkenes are more reactive compared to alkanes

Comparison between alkanes and alkenes

Alkanes
less reactive

Alkenes
more reactive

has C-C single

has C-C double
bond
bond
( bond) : more
( bond) : less
stable
undergoes free radicalstable
undergoes electrop
substitution reaction
2
addition reaction

Why alkenes are more reactive

3 Reasons
1 C-C double bond in alkenes consist of one and
one bond
bond is weaker than bond.
bond is easier to break, while bond
(in alkane) remains intact
2 bond in the double bond act as a source of
electrons.
alkenes is reactive towards electrophile
3

3 When bond is broken : provide side for new

covalent bond to form. One bond can form 2
bonds.
Breaking of bond is more favourable than
breaking of bond (because less energy
is needed for breaking bond)

Addition Rxn
Reaction in which an unsaturated system becomes
saturated by addition of molecules across the
multiple bond
Has 3 characteristics :
Breaking of bond, forming 2 bonds
Only one product is obtained at the end of rxn
The product is saturated organic compound

Electrophilic Reaction Mechanis

Of Alkenes
The mechanism take place in 2 steps
STEP 1 Formation of a carbocation
The rxn begins with an attack by the electrophile
(E+) on the electrons of the double bond which
acts as the nucleophile
C

+ + EY

slow

C
+

E
carbocation

+ :Y6

STEP 2 Rapid rxn with negative ion

The negative ion ( :Y- ) acts as the nucleophile and
attacks the positively charge carbon atom to give
the product of addition rxn.
C
E

C
+

carbocation

+ :Y-

fast

product

Reaction of
Alkenes

Hydrogenation of
alkenes
Halogenation of
alkenes
In inert solvent,
CCl4
In aqueous
solution
Hydrohalogenation of
alkenes
Addition of HBr in the presence
of peroxides
8

Continue

Hydration of alkenes
Oxidation of alkenes

Reaction of
Alkenes

With cold and dilute

KMnO4
With hot and conc.
KMnO4
Addition of sulphuric
acid
Ozonolys
is

Hydrogenation Of
Alkenes
Hydrogenation means addition of H atom to
multiple bonds to form saturated product

Alkene reacts with H2 (g) to form alkane, in the

presence of metal catalyst (Pt/Pd/Ni)
General rxn :

Alkene

+ H2

Pt/Pd/Ni

Alkane
10

 Example,
CH3-C=CH2 + H2

Pt/Pd/Ni

H
propene

CH3-CH2-CH3
propane

Example,
+ H2
cyclohexene

Pt/Pd/Ni

cyclohexane
11

Hydrogenation of alkene

Important process in food indus

Use to harden unsaturated fats
oils to make margarine

Presence of C = C in the oils low

the melting point makes them
too soft for commercial use
Therefore, they are hydrogenat
to produce margarine

12

Halogenation Of
Alkenes
(a) In inert
solvent, CCl4

in CCl4 at
room temperature, to form vicinal dihalides

Alkene reacts with chlorine and bromine

Vicinal DiHalide
2 substituents (in this case halogens)
are attached to the adjacent C atoms

13

 General rxn :
C

+ X2

CCl4

Alkene

CH3 H
2-methyl-2-butene

Vicinal dihalide

Example,
CH3-C = C-CH3 + Cl
2

Cl
CCl4

Cl

CH3-C - C-CH3

CH3 H
2,3-dichloro-2-methylbutane
14

Bromine test
of any alkene with bromine
ReactionHalogenation
:
water in presence of CCl4

Useful As
: a test for unsaturation (the presence
of double bond or triple bond)

ObservationWhen
: unsaturated compound presence
The colour of bromine changes from
reddish-brown colour to colourless
When saturated compound presence
The colour of bromine remain unchange
15

Bromine test
A

PLACE A SOLUTION OF
BROMINE IN A TEST TUBE

ADD THE HYDROCARBON

TO BE TESTED AND SHAKE

IF THE BROWN COLOUR

DISAPPEARS THEN THE
HYDROCARBON IS AN
ALKENE

colourless

+ Br2
reddish
brown

CCl4

Br Br
colourless

16

Bromine test

This test is used to distinguish alkenes fr

CH3-CH

CH2 + Br2

propene

CCl4

dark

CH3-CH-CH2
Br Br
1,2-dibromopropane

Observation : The colour change from reddish-brown

to colourless
CH3-CH2-CH3
propane

+ Br2

CCl4
dark

No Reaction

Observation : The colour of bromine remain unchange

17

Halogenation Of
Alkenes

(b) In aqueous
solution

Halogenation of alkene in aqueous solution,

formed haloalcohol (halohydrin)

General rxn :

Alkene

+ X2

H 2O

OH-

OH

halohydrin
18

 Example,
H
H

H
H

+ Br2

H2O

Br OH

ethene

bromoethanol

NOTE !

If the alkenes is unsymmetrical, the halogen ends up

on the carbon atom with the greater number of
hydrogen atoms.
19

 Example,
OHCH3

CH2

CH3

+ Br2

2-methyl-1-propane

OH Br
H2O

CH3

CH2

CH3

1-bromo-2-methyl-2-propanol

Example,

CH3

+ Cl2

1-methylcyclohexene

H2O

OH
Cl H

CH3

20
2-chloro-1-methyl-1-cyclohexenol

Hydrohalogenation Of
Alkenes

Alkenes react with hydrogen halides (HX) to form

haloalkanes
Hydrogen and halogen atoms are added across the
double bond
General rxn :

Alkene

+ HX

X H
haloalkanes

21

 Example,
H and halogen atoms can be added to the
C = C in 2 different ways :
MAJOR
PRODUCT

CH3
3

CH3

Br H
2-bromopropane
H + HBr

propene
MINOR
PRODUCT

CH3

H Br
1-bromopropane

22

How to predict the

MAJOR and MINOR PRODUCT ?

t Can Be Explain In Term Of

MARKOVNIKOVs RULE

23

Markovnikovs Rule

addition of HX, the more electropositi

reagent (usually H atom) is added to
e double bond Carbon which has great
number of Hydrogen atoms

24

 Example, Propene
MAJOR
PRODUCT

CH3

+ H + HBr

MINOR
PRODUCT

CH3

Br H
2-bromopropane

CH3

H Br
1-bromopropane

25

 Example, 2-methylpropene
CH3
CH3

CH2

2-methylpropene

+ + HCl

CH3
CH3

CH2

Cl H
2-chloro-2-methylpropene
MAJOR PRODUCT
CH3
CH3

CH2

H Cl
1-chloro-2-methylpropene
MINOR PRODUCT
26

4 Addition Of HBr In The

Presence
Of
Peroxides

When alkene reacts with HBr in the presence of

peroxide (e.g. H2O2), addition occurs in an

Anti-Markovnikov manner
Whereby that the hydrogen atom of HBr attach to
the double bond carbon with fewer hydrogen atoms.
C

Alkene

+ HBr

ROOR

Br H
haloalkanes

27

 Example,

CH3

propene

+ H + HBr

H2O2

CH3

H Br
1-bromopropane
MAJOR PRODUCT

28

Hydration Of
Alkenes
Hydration is addition of water
Addition of water to the C=C of alkene follows the
Markovnikovs rule and alcohol is formed.
The rxn is catalysed by strong acids, which protonate
water molecules, to give the electrophile, H 3O+

Alkene

+ H2O Diluted
acid

OH H
alcohol
29

 Example,
H+

CH3
CH3

CH2

+ H2O

OH2-methylpropene

CH3
H+ @
H3O+

CH3

CH2

OH H
2-methyl-2-propenol
MAJOR PRODUCT
CH3
CH3

CH2

H OH
2-methyl-1-propenol
30
MINOR PRODUCT

Oxidation Of
Alkenes

(a) With cold and diluted

KMnO4

Pottasium permanganete, KMnO4 in basic can be

used to oxidised elkene to

1,2-diol (glycol)

Two OH groups are added to the C-C double bond

Alkene

OH
+ KMnO4
(purple) cold

OH OH
gylcol

+ MnO2
(brown)
31

 This rxn is also known as Beayers Test

It can be used to test the presence the C-C double
bond in the compound
Observation :
The purple colour of the KMnO4 decolourised,
and brown precipitate of MnO2 is formed
Example,
CH2

CH2 + KMnO4

ethene

H2O, OHcold

CH2

CH2

OH

OH

+ MnO2

ethane-1,2-diol
32

Oxidation Of
Alkenes

(b) With hot and

concentrated KMnO4

When oxidation of alkene is carried out in

hot, concentrated and acidic KMnO4 ,

it involved the cleavage of C-C double bond

The products are containing

C

Alkene

+
conc
/
H
+ KMnO4
hot

C = O group
C=O + O=C

2 carbonyl compound
33

 Example,
CH3

CH3
CH3

CH3 + KMnO4

CH3
2,3-dimethyl-2-butene

conc / H+
hot

CH3

+
O

CH3

CH3
propanone
(ketone)

34

Notes !
If the double bond is

2 carbonyl produc

tetrasubstituted

(ketones) are obtaine

If 1 H present on

carboxylic acid

the double bond

is obtained

If 2 Hs present on

CO2 and H2O

1C

is obtained

35

 Example,
1 H on the
C double bond
CH2

CH-CH3

propene
2 H on the
C double bond

+ KMnO4

conc / H+
hot

O
OH-C-CH3
ethanoic acid
(carboxylic acid)
+ CO2
+ H2O
36

The Rxn is used to establish the location of

the double bond

Example
An alkene with the molecular formula C 6H12 is
oxidised with hot KMnO4 solution. The carboxylic
acid, butanoic acid (CH3CH2CH2COOH) and
ethanoic acid (CH3COOH) are produced. Identify
Solution
the structural formula of the alkene.

Product -

1) Butanoic acid (CH3CH2CH2COOH)

2) Ethanoic acid (CH3COOH)

37

Solution - continue
- 2 oxygen

CH3-CH2-CH2-C OO H

CH3-CH2-CH2-CH -

Butanoic acid

CH3-C OO H
Ethanoic acid

CH3-CH - 2 oxygen

CH3-CH2-CH2-CH = CH-CH3
Alkene used in the rxn is :

2-hexene

38

7 Addition Of Sulphuric Acid To

Alkenes

Alkenes dissolve in concentrated H2SO4 :

to form alkyl hydrogen sulphates

Alkyl hydrogen sulphates is then hydrolysed (by
heating with water :

to form alcohol

The rxn follow Markovnikovs rule

39

 General Rxn
C

Alkene

H2SO4
(conc)

Hydrolysis
C

OSO3H

H-OH

Alkyl hydrogen
sulphate
H2SO4 +

OH

Alcohol
40

H
C

H H
+

CH3
propene

H2SO4
(conc)

Hydrolysis
CH3

OSO3H

H-OH

Alkyl hydrogen
sulphate
H H
H

OH

CH3

propanol
41

Ozonolysis Of
Alkenes

More widely used method for

bond

locating the doub

of an alkene involves the use of ozone (O 3)

Ozone reacts vigorously with alkenes to form

unstable compounds called

molozonides.

Molozonides then rearrange spontaneously to

form

ozonides.

Ozonides involves the cleavage of the C-C double

bond, in presence of

Zn/H+ and H2O.

The products is the carbonyl compounds (aldehydes

or ketones

42

 General Rxn
H
R

R
Alkene

O3

H
R

O
C

R
R

Ozonide
(i) Zn/H+
(ii) H2O
HC=O
R

O=CR
R
43

 Example
CH3
CH3

O3

CH3

CH3
CH3

2-methyl-2-butene

O
C

H
CH3

Ozonide
(i) Zn/H+
(ii) H2O

CH3 C = O
CH3
propanone

O=CH
CH3
ethanal

44

END

OF ALKENES

45