CHAPTER

3
Alkenes

 Alkenes are unsaturated

hydrocarbons that contain one or
more carbon-carbon double
bonds.

H H
H C C CH3

H H H
H C C C CH2

 Molecular formula of alkenes with

one double bond is CnH2n and the
name ends with "-ene".
example: 3 carbons is propene
5 carbons is pentene
7 carbons is heptene
The double bond is more reactive
than a single bond making the
alkenes chemically more reactive.

 The different between alkanes and

alkenes is they have the same number of
carbon atoms but differs in the number of
hydrogen atoms.
Structural formula

H H
H

C C

H
H

H H
ethane

ethene

Molecular formula

C2H 6

C2H4

H
H

 Example: Propane would become a

propene with molecular formula C3H6.

CH3CH

CH2

H H

C C

Naming Alkenes
Find the longest continuous carbon
chain containing the double bond.
Start numbering from the end
closest to the double bond.
Name the parents compound and
indicates the position of the double
bond.

 Indicate the position of the

substituent and list in
alphabetical order.
Example:
6

CH3CH2CH2CH
Start
numbering
Parent name
Position of
the =

CHCH3

The name is 2-hexene

NOT 4-hexene OR 3hexene

 Halogens group are treated

equally like alkyl groups.

Cl
CH3CHCH2CH

CHCH3

5-chloro-2-hexene

Naming Alkenes with More

than One Double Bond
Alkenes with two double bonds are
called dienes, three are trienes
and four are tetraenes.
Name the following alkene.

H2C

CH

CH3

CH2

H2C

CH

CH2

CH3
Start numbering from the blue carbon
to give the substituent, methyl group
the lowest position number.

The name is 2-methyl-1,3butadiene

Naming Cycloalkenes
There is no chain end for
cycloalkenes to start the
numbering.

 Therefore, the carbon atom in

the double bond is assigned as
C1 and C2.
If substituent is exists, the ring is
numbered clockwise or
counterclockwise to give the first
substituent the lowest position
number.

Example 1: Choose the correct

name for the following compound.

CH3CH2
A) 1-ethylcyclopentene
B) 2-ethylcyclopentene

C=C is assigned as C1 and C2,

therefore the numbering system for
A and B are correct. But, since the
ethyl group is attached to the C
double bond, the priority (C1) is
goes to the substituent.
1

2
1

CH3CH 2
1-ethylcyclopentene

CH3CH2

2-ethylcyclopentene

1) Which one shows the correct

numbering system?
2) Name the compound.
1
6

2
3

H3C

CH3

H3C

A
The name of the
5
compound
is 3,54
6
dimethylcyclohexene

H3C

CH3

H3C

CH3

B
3
2

4
5

CH3

Example 3:

CH3
1

4
3

CH3

1,6-dimethylcyclohexene

Geometric Isomers (Cisand Trans-)

Geometric isomers are isomers
that differ from each other based
on the position of the attached
groups relative to the double bond
Geometric isomers are called cisand trans- isomers.

Cis Two substituents

that are on the
same side of the
double bond.

H
CH3

H
CH3

cis-2-butene

Trans Two substituents

that are on the
opposite side of
the double bond.

CH3
H

H
CH3

trans-2-butene

Preparation or
Synthesis of
Alkenes

 Preparation of alkenes is carried

out by elimination reactions.
Four types of elimination
reactions for the preparation of
alkenes:
Remove Ha) dehydration
of alcohols
OH

Remove
b) dehydrohalogenation
of
HX
haloalkanes

c) dehalogenation of alkyl halides

Remove XX

d) Reduction of alkynes to alkenes

Dehydration of Alcohols
General reaction:

C C
H OH
alcohol

H2SO 4
heat

Double
bond is
formed

C C

+ H2O

alkene

H2O is
removed

Atoms from two adjacent carbon

atoms are removed from the organic

Example:

CH3CH
OH

CH2
H

2-propanol

H2SO4

CH3CH

CH2 + H2O

propene

CH3CH
OH

CH2
H

H+

CH3CH

CH2

H O+

Step 1:
Protonation of the alcoholic oxygen
to make a better leaving group.

CH3CH

CH2

H O

CH3CH

CH2 + H2O
H

Step 2:
Cleavage of the C-O bond allows the
loss of the good leaving group, a
neutral water molecule, to give a

CH3CH

CH2 + H2O

CH3CH

CH2 + H3O+

Step 3:
Deprotonation by a base (a water
molecule) from a C atom adjacent to
the carbocation center leads to the

 There can be more than one

elimination product if an alcohol
with more than three atoms is
used in the reaction.
According to Zaitsevs Rule, the
major product is obtained when a
proton is removed from the carbon
that is bonded to the least
hydrogen.

Exercise
Write the complete structural
equations on dehydration of the
following compounds:
a) 2-methyl-2-butanol
b) 2-methyl-cyclohexanol

Dehydrohalogenation of Alkyl Halides

General reaction:

C C
H

H 2SO4
heat

haloalkane

X = Br, Cl or I

Double
bond is
formed

C C

+ HX

alkene

Hydrogen
halide is
removed

Example:

CH3CH
Br

CH2
H

2-bromopropane

H 2SO4

CH3CH

CH2 + HBr

propene

 There can be more than one

elimination product if an alkyl
halide with more than three
atoms is used in the reaction.
The major product usually follow
the Zaitsevs Rule to yield more
stable alkene.

Exercise
Write the complete structural
equations on the reaction of the
following compounds with
sulphuric acid:
a) 2-chloro-2-methylpentane
b) 1-bromo-2-methylcyclohexane

Dehalogenation of
Dihalides
Dihalides compound reacts with
zinc in alcohol to form alkene and
X2 is eliminated in this reaction.
H H

H H
H C C H
X

Zn
alcohol

H C C H + ZnX2

Reduction of Alkynes to
Alkenes
There are two methods for
reduction of alkynes to alkenes:
a) Catalytic hydrogenation using a
poisoned catalyst to produce
cis- alkene.
b) Dissolving metal reduction to
produce trans- alkene.

 Alkynes reacts with H2 in the

presence of metal catalyst such as
palladium; Pd to yield alkanes.
This is a complete reduction from
alkyne to alkane.

H H
H C C H

2H2/Pd

H C C H
H H

 However, the reduction can be

stopped to yield alkene by using
Lindlar catalyst to produce cisalkene.

H3C C C CH3

H2
Lindlar catalyst

H3C
H

C C

CH3
H

Lindlar Catalyst
It consists of palladium deposited
on calcium carbonate and treated
with various forms of lead (Pb) such
as lead acetate, (Pb(CH3COO)2);
and lead oxide, PbO.
The function of lead additive is to
deactivate the palladium sites.

 Alkynes reacts with Na metal in

ammonia to yield trans- alkene.
Na metal in ammonia is reacts as a
reducing agent.

H3C C C CH3

Na/NH3
H3C
H

H
C C
CH3

Reactions of
Alkenes

 Alkenes undergo an addition reaction.

An addition reaction is a conversion of
unsaturated compound to saturated
by the addition of a molecule/reagent
across the double bond.
Only one product is produced at the
end of the reaction.

pi-bond is
broken

C C

+ X-Y

addition
reaction

unsaturated

C C
X

saturated

Two new
single/sigma
bonds are formed

Hydrogenation Reaction
Addition of the H2 molecule to a
carbon-carbon double bond to
give an alkane.
Usually the reaction requires heat
and catalyst like Pt, Pd or Ni.

CH3CH

CHCH3

H2/Pt
heat

2-butene

CH3CH
H

CHCH3
H

butane

Mechanism of the reaction:

H H/Pt

H Pt
H Pt

Step 1: Hydrogen molecules react

with the metal atoms. H-H bond is
broken and replaced with two metalH bonds.

CH3CH

CHCH3 + Pt H
Pt H

CH3CH

CHCH3

CH3CH
Pt
H

CHCH3
Pt
H

Step 2: The pi bond interacts with the

metal catalyst and breaks to two
sigma bonds.

CH3CH
Pt
H

CHCH3
Pt
H

CH3CH
H

CHCH3
H

Step 3: The hydrogen atoms are

transferred from the catalyst to the
carbon of the double bond.

H2/Pd
heat
cyclohexane

cyclohexene

H C
H C
H

H
C

C
H

C
C

H
H
H

H2/Pd

H C

heat

H C
H

H
C

C
H

H
C H
H

Hydration Reaction
Hydration is the addition of water in
the presence of acid (i.e. H2SO4 or
HCl) to an alkene to form an alcohol.
There is NO reaction takes place
when only H2O is added to an alkene
because the O-H bonds of water
are too strong.

Hydration Reaction
(symmetrical alkenes)

CH2

CH2

ethene

H2O/H+

CH2

CH2

OH
ethanol

Mechanism of the reaction:

CH2

CH3 + H O H
H
CH2

CH2

+ H2O

Alkene donates a pair of electrons to

a proton of hydronium ion and form a
carbocation.

CH2
H

CH3 +

O H
H

H
CH2

C O H

H H

protonated alcohol

Step 1: The carbocation reacts with a

molecule of water to form a
protonated alcohol.

H
CH2

C O H +

O H

H H

protonated alcohol

CH2

CH2 + H3O+

OH
ethanol

Step 2: The protonated alcohol

transfer a proton to a molecule of
water and the product is formed.

Hydration Reaction
(unsymmetrical alkenes-Markovnikovs Rule)

The addition of water and

hydrogen halide to
unsymmetrical alkenes is always
follows the Markovnikovs Rule.

Definition of
Markovnikovs Rule
The rule states that when the
reagent is added to the
unsymmetrical alkenes, the hydrogen
of the reagent adds to the double
bond carbon which has the greater
number of hydrogen and the nonhydrogen part of the reagent adsd to
the carbon with fewer hydrogen.

 The simple definition is The rich

get richer meaning that the
carbon with the most hydrogen
bonds will receive the new one.

Example:

CH3CH

H2O/H+

CH2

propene

CH3C H

CH2
OH

CH3C H
OH

CH2
H

1-propanol

2-propanol

mino
r

majo
r

Hydrohalogenation Reaction

Addition of hydrogen halides (HX)

to an alkene to form alkyl halide.
X is any halogens group such as
fluorine, chlorine, bromine or
iodine

Hydrohalogenation Reaction (symmetrical alkenes)

CH3C H

CHCH 3

HCl/CCl4

2-butene

CH 3CH
H

CHCH 3
Cl

2-chlorobutane

Mechanism of the reaction:

CH3CH

CHCH3 + H Cl
CH3CH

CHCH3 + Cl-

Step 1: Proton is transferred to the

double bond of alkene and form a
carbocation.

CH3CH
H

CHCH3 + ClCH3CH
H

CHCH3
Cl

Step 2: The nucleophile (bromide

ion) attacks the carbocation and
form the product.

Hydrohalogenation Reaction
(unsymmetrical alkenesMarkovnikovs Rule)
CH3
CH3C

CHCH3

HBr/CCl4

2-methyl-2-butene

CH3
CH3C
H

CHCH3
Br

2-bromo-3-methylbutane

mino

CH3
+

CH3C

CHCH3

Br H
2-bromo-2-methylbutane

majo

Anti Markovnikovs
Addition
It is an addition of hydrogen
bromide (HBr) to alkenes in the
presence of peroxide (ROOR).
Contradictory with Markovnikovs
Rule, hydrogen is attached to the
carbon with fewer hydrogen
atoms.

Example 1: This reaction only occurs

if HBr is used with peroxide. It is not
occur with HF, HI or HCl.

CH3CH

CH 2

HBr/ROOR'

propene

CH3CH
H

CH 2
Br

1-bromopropane

Example 2:

CH3
CH3C

CHCH3

HBr/ROOR'

2-methyl-2-butene

CH3
CH3C
H

CHCH3
Br

2-bromo-3-methylbutane

majo

CH3
+

CH3C

CHCH3

Br H
2-bromo-2-methylbutane

mino

Halogenation Reaction

Addition of halogen X2 to an alkene.

Reactions of alkenes with Br2 or Cl2 in
an inert solvent like dichloromethane
or carbon tetrachloride will produce a
vicinal dihalide.
The solvents will dissolve both
reactants but does not participate in
the reaction.

 Only Cl2 and Br2 are useful for

halogenation reaction because the
addition of I2 is too slow and
unstable at room temperature.
The addition of F2 is too explosive.

Example: The Formation of

Vicinal Dihalide

CH3CH
propene

CH 2

Cl2/CCl4
CH3CH
Cl

CH 2
Cl

1,2-dichloropropane

Mechanism of the reaction:

CH3CH

CH 2 + Cl Cl
CH3CH

CH 2

+ Cl-

Cl
Step 1: Cl atom attacks the C-C pibond and leaves behind one of its
electrons with the other chlorine.
Now it become chloride anion.

CH3CH
Cl

CH3

+ ClCH 3CH
Cl

Step 2: Chloride anion (Cl-) is

attracted to the slight positive
charge on the carbon atoms and
attack on the other side of the

CH2
Cl

 If water is used as solvent, the

major product of the reaction will
be a vicinal halohydrin.
A halohydrin is an organic
molecule that contains both a
halogen and an OH group.

Example: The Formation of

Vicinal Halohydrin
CH3
CHCH3

CH3C

Cl2/H2O

2-methyl-2-butene

CH3

CH3
CH3 C

CHCH3

OH Cl
2-methyl-3-chloro-2-butanol
(a chlorohydrin as a major product)

CH3C

CHCH3

Cl Cl
2,3-dichloro-2-methylbutane

General Mechanism of the reaction:

CH2

CH2 + Cl H 2O
CH2

CH2 + H2O

Cl

Step 1: Cl atom attacks the C-C pibond and leaves behind one of its
electrons with the other chlorine.
Now it become chloride anion.

CH2
Cl

CH2 +

O H
H
CH2

CH2

Cl

O H
H

Step 2: Water molecule attacks one

of the carbon of halonium ion. The CH bond breaks and protonated
halohydrin is formed.

CH2

CH2 +

Cl

O H
H

O H
H
CH2

CH3 + H3O+

Cl

O H
H

Step 3: The protonated halohydrin

loss a proton and form a vicinal
halohydrin.

Rememb
er!
For unsymmetrical alkenes, a
compound with halogen atom
bonded to carbon atom with
greater number of hydrogen atom.
Water molecule always attack the
carbon atom with more alkyl
substituents.

Oxidation Reactions of
Alkenes (Epoxidation)

Organic compounds containing

the following group are known as
epoxy compounds.

O
C

 Ethene reacts with oxygen to form

epoxyethane in the form of silver
catalyst at high temperature.

CH2

CH2

ethene

O2
Ag/2000C

2
CH2

O
CH2

epoxyethane

 Epoxyethane goes for hydrolysis

when reacts with dilute aqueous
mineral acid at room temperature
to form 1,2-ethanediol.

O
CH2

H2O/H2SO4
CH2

epoxyethane

CH2

CH2

OH

OH

1,2-ethanediol
(ethylene glycol)

Ozonolysis
Ozonolysis is a method to prepare
compounds with carbonyl functional
groups.
It is a process of treating alkenes
with ozone, O3 in methylene
chloride; followed by zinc and acetic
acid to produce molozonide and
then reduced to ketone or aldehyde.

Example:

CH3
CH3C

CHCH3

O 3/CH2Cl2
Zn/CH 3COOH

2-methyl-2-butene

CH3
CH3C

O + O

propanone

CHCH3
ethanal

Mechanism of Ozonolysis
C C
-

C C
O

O
O
+

C
O

O
initial ozonide

+
-O

C
O+

The initial ozonide

fragments

Step 1: Alkene reacts with ozone, O3; to

form
separate
unstable
ozonide
fragments.

O
C

C
-O

O+

ozonide fragments
recombined

O
C

C
O

ozonide

Step 2: Under vigorous condition, the

initial
ozonide
fragments
spontaneously
rearrange
the
structures to form ozonides.

O
C

C
O

ozonide

Zn/acetic acid

C O + O C
carbonyl groups

+ Zn + O + acetic acid

Step 3: Ozonide reacts with Zn in

acetic acid to form two carbonyl
groups.

Test for
Unsaturated
Compounds

Reaction of Alkenes with KMnO 4

(Hydroxylation/Baeyer Test)

Hydroxylation is the introduction of a

hydroxyl group (-OH) into an organic
compound.
Alkenes are oxidized by alkaline
potassium manganate (VII) solution
that acts as an oxidizing agent.

 Alkene decolorizes the purple color

of KMnO4 and forms brown
precipitates.

This is a test for the carbon-carbon

double bond.

 The product is called diol because

it contains two hydroxyl groups.

CH2

CH2

ethene

KMnO4/H2O

CH2

CH2

OH

OH

1,2-ethanediol or
ethylene glycol
a diol

Reaction of Alkene with

Bromine Water
Alkene decolorizes the red brown
color of bromine.

 The reactions equation:

H H
H2C CH2
alkene

Br 2/CCl4
(reddish-brown)

H C C H
Br Br
colorless solution

Uses of Alkanes/Alkenes

Methane/propan
e - Natural gas
for heating and
cooking

Petroleum jelly

Lubricating oil
Paraffin wax

A solvent
in paint
thinner

Fuel/diesel