12.

ALKENES
2
• General formula CnH2n , n ≥ 2.

• Functional group → double bond C=C

• Unsaturated hydrocarbon

• Each carbon atom ( C=C ) is sp2 hybridized.

hybridized

• Restricted rotation of carbon-carbon

double bond causes cis-trans isomerism
IUPAC Nomenclature
Step 1
Determine the parent name by
selecting the longest chain that
contains the double bond and
change the ending ‘-ane’ in alkane
to ‘-ene’.
 Step 2

When the chain contains more

than three carbon atoms, a
number is need to indicate the
location of the double bond.
The chain is numbered starting
from the end closest to the
double bond..
1 2 3 4 5 6 7 8
CH3CH2CH CH CH2CH2CH2CH3
3-octene (not 5-
octene)
 Step 3
Indicate the position of the substituent
by the number of the carbon atoms to
which they are attached.

CH3
H3C C CH CH3
1 2 3 4
2-methyl-2-butene
(not 3-methyl-2-butene)
 1 2 3 4 5 6
H3C C CH CH2 CH CH3
CH3 CH3
2,5-dimethyl-2-hexene
(not 2,5-dimethyl-4-
hexene)
 Step 4

The ending of the alkenes with more

than one double bond should be
change from - ene to

• diene – if there are two double bonds

• triene – if there are three double bonds
 1 2 3 4
H2C CH CH CH2
1,3-butadiene

1 2 3 4 5 6 7
H2C CHCH CHCH CHCH3
1,3,5-heptatriene

MORE
 Step 5

In cycloalkenes :
Number the carbon atoms with a
double bond as 1 and 2, in the
direction that gives the substituent
encountered first with a small
number.
 CH3
1
5 2

4 3

1-methylcyclopentene
(not 2-methylcyclopentene)
 1

6 2

5 3
CH3 CH3
4

3,5-dimethylcyclohexene
(not 4,6-dimethylcyclohexene)

MORE
 Step 6

Two frequently encountered alkenyl

groups are vinyl group and allyl
group.

-H
RCH=CHR RCH=CH-
alkene alkenyl

CH2=CH- CH2=CHCH2-
vinyl group allyl group
 Step 7

When two identical groups are

attached:
a) on the same side of the double
bond, the compound is cis
b) on the opposite sides of double
bond, it is trans.

cis / trans
 Cl Cl Cl H
C C C C
H H H Cl

cis-1,2-dichloroethene trans-1,2-dichloroethene
Give IUPAC names for the following alkenes

1)

2) CH3

CH3
3)

4) CH2CH3

CH3

5) CH3CH=CHCH2C(CH3)2CH3
 Preparation of alkenes

a) Dehydration of alcohols
b) Dehydrohalogenation of alkyl halide
 Dehydration of alcohols
• Alcohols react with strong acids in the
presence of heat to form alkenes and
water.

H2SO4 (conc.)
C C
∆
C C + H2 O
H OH
• Concentrated sulphuric acid (H2SO4) or
phosphoric acid (H3PO4) : as acidic
catalysts and dehydrating agents.

• The major product is the most stable

alkene, which has greater number of
alkyl group attach to C=C is follow
Saytzeff’s rule.
 Saytzeff’s Rule

An elimination usually gives the most

stable alkene product, commonly the
most highly substituted alkene.
 Examples
H2SO4 (conc.)
(1) CH3CH2OH H2C CH2
∆
+ H2O

( H2SO4 (conc.)
H3C CH CH3 H2C CH CH3
2)
∆
OH + H2O
 Mechanism for the
dehydration of alcohol
H C CH CH CH H SO (conc.) CH CH=CHCH
3 2 3 2 4 3 3
OH ∆ (major product)

+ CH =CHCH CH
2 2 3
(minor product)

+ H 2O
 Step 1:
Protonation of alcohol.
alcohol
H H
H C C CH CH + +
:O H
3 2 3
:OH H
..

H H
H C C CH CH + :O H
3 + 2 3 ..
: OH
H
 Step 2:
Formation of carbocation
H H
H C C CH CH +
HC C CH CH
3 +:OH 2 3 3 2 3

carbocation
H
H
+ :O H
..
 Step 3:
Formation of alkenes
H H H H

H C C+ C CH :O H
b 3 + ..
H H

a
Root a : major product
Root b : minor product
 H H H
C C + +
: O H
H C CH H
3 3
stable alkenes
+ CH =CHCH CH
2 2 3
(minor product)
 Rearrangement During
Dehydration of Alcohol
Example 1:

CH H
3 H SO (conc.)
HC C C CH 2 4
3 3 ∆
CH OH
3
 CH3
H 3C C C CH3
CH3
(major product)

CH
3
+ H C C CH CH
2 3
CH
3
(minor product)
Step 1 and Step 2 are similar to
the previous example.
Step 3:
• Now the rearrangement occurs.
• The less stable, secondary carbocation
rearrange to form more stable tertiary
carbocation.
 CH CH
3 3

+ +
H C C C CH H C C C CH
3 3 3 3

CH H rearrangement CH H
3 3

2o carbocation 3o carbocation
(less stable) (more stable)
• The rearrangement occurs through the
migration of an alkyl group (methyl)
from the carbon atom adjacent to the
one with the positive charge.

• Because a group migrates from the one

carbon to the next,
next this kind of
rearrangement is often called a 1,2
shift.
 (a) CH
3
HC C CH CH
(a) 2 3
CH
3
H + CH3 H
(minor product)
H C C C CH3 + :O H
..
less stable alkene
H CH H
3

CH
3
(b) HC C C CH
3 3
CH
3
(b) (major product)
more stable alkene
The final step can occur in two
ways:

Path (a): leads to less stable,

disubstituted alkene and produces
the minor product of the reaction.
Path (b): leads to highly stable
tetrasubstituted alkene and produces
the major product according to the
Saytzeff’s rule.
 Try this!

CH H CH
3 H2SO4 (conc) 3
H C C C CH H C C CH CH
3 3 ∆ 3 3
H OH (major product)

CH
3
+ H C C CH CH
2 2 3
(minor product)
(2) Dehydrohalogenation of Alkyl Halides
• The elimination of a hydrogen and a
halogen from an alkyl halide to form an
alkene.

alcohol
C C + KOH
reflux
C C
H X
+ HX

• Saytzeff’s rule is used to determine the

major product
 Examples:
(1)
Cl
alcohol
H3 C CH CH2CH2CH3 + KOH
reflux

H3C CH CH CH2CH3 + H2C CH CH2CH2CH3

(major product) (minor product)
 (2)
alcohol
H3C CH CH3 + KOH
reflux
H2C CH CH3
Br
(3)
Br
CH + alcohol CH
KOH
CH reflux CH
3 3
(minor product)

CH2
+
CH3

(major product)
(4)
CH3 H
CH3 C C CH3 + KOH alcohol
CH3 Cl reflux

CH3 H CH3
CH2 C C CH3 CH3 C C CH3
CH3 CH3
2,3-dimethyl-1-butene 2,3-dimethyl-2-butene
(minor product) ( major product)
2 alkyl groups 4 alkyl groups
Chemical Reaction of Alkenes
Comparison of The Reactivity Between
Alkanes and Alkenes
• Alkenes are more reactive compared to alkanes.
• Alkanes have carbon-carbon single bonds (σ
bonds) while alkenes have carbon-carbon
double bonds (π bonds).
• The double bond is a site of high electron
density (nucleophilic).
nucleophilic
• Therefore most alkenes reactions are
electrophilic additions.
 Electrophilic Additions
Mechanism

H H H
slow +
C C + X Y H C C H
H H X H
-
+ Y
 H H H
+ - fast
H C C H + Y H C C H
X H X Y
 Example:
i.

H3C CH3
slow
C C + H Cl
H3C CH3
CH3CH3
H3C C C
+
CH3 + -
Cl
H
 CH3CH3
fast
H3C C C CH3 + Cl-
+
H
CH3CH3
H3 C C C CH3
H Cl
 Addition Reaction of Alkenes
(1) Hydrogenation
• The reaction of an alkene with hydrogen in
the presence of catalyst such as platinum,
nickel and palladium to form alkane.

Pt or Ni or Pd
C C + H2 C C
H H
 Examples:
(
1)
Pt /Ni / Pd
H3C C CH2 + H2 H3C CH CH3
CH3 CH3

( Pt /Ni / Pd
2) + H2
(2) Halogenation of Alkenes

(i) In inert solvent (CH2Cl2)

• Alkenes react rapidly with chlorine or
bromine in CH2Cl2 at room temperature to
form vicinal dihalides.

CH2Cl2
C C + X2 C C
X X
 Example:

CH3
CH2Cl2
H3C C C CH3 + Cl 2
H
Cl Cl
H3C C C CH3
CH3H
• When bromine is used for this reaction, it
can serve as a test for the presence of
carbon-carbon double bonds.
bonds

• If bromine is added to alkene, the reddish

brown color of the bromine disappears
almost instantly as long as the alkene is
present in excess.
 Unsaturation test
CH2Cl2
C C + Br2
room temperature

C C
Br Br
Observation: The reddish brown bromine decolourised
(3) Hydrohalogenation : Markovnikov’s
rule
• Hydrogen halides (HI, HBr, HCl and HF) add to the
double bond of alkenes to form haloalkanes.

C C + HX C C
H X

• The addition of HX to an unsymmetrical alkenes,

alkenes
follows Markovnikov’s rule.
rule
• Markovnikov’s Rule:

– In the addition of HX to an alkenes, the

hydrogen atom adds to the carbon atom
of the double bond that already has the
greater number of hydrogen atoms.
 i. The addition of HBr to propene, could
conceivably lead to either 1-
bromopropane or 2-bromopropane.
The main product, however, is 2-
bromopropane
H H
H2C CH CH3 + HBr H C C CH3
H Br
ii. When 2-methylpropane reacts with HBr,
the main product is tert-butyl bromide,
not isobutyl bromide.
Br
H3C C CH2 + HBr H3C C CH3
CH3 CH3

• The addition of HX to an unsymmetrical

alkenes, yield the main product according
to the Markovnikov’s rule.
 Mechanism

CH 3
+
slow
CH 3 H Br
C CH CH 3

CH3

CH3 C CH CH3 + Br -
+
30 Carbocation
 CH3
fast
CH3 C CH CH3 + Br -
+

CH3

CH3 C CH CH3

Br H
(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
(ii) In aqueous (Halohydrin Formation)

• If the halogenation of an alkene is carried

out in aqueous solution, the major product
of the overall reaction is a haloalcohol
called a halohydrin.

C C + X2 + H2O C C
X OH
X2 = Cl or Br halohydrin
 Example:
H H H H
C C + Br2 + H2O H C C H
H H Br OH
2-bromobutanol
Unsaturated test
Observation : the reddish brown bromine decolourised
• If the alkenes is unsymmetrical,
unsymmetrical the
halogen ends up on the carbon atom with
the greater number of hydrogen atoms.
 Example:

H3C C CH2 + Br 2 + H2O

CH3
CH3H
H3 C C C H
OH Br
1-bromo-2-methyl-2-propane
Complete the following reaction:

+ Br2 + H2 O
CH3
(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 catalyse

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
 Mechanism
STEP 1

CH3 H
..
CH3 C CH CH3 + H O+ H

CH3

CH3 C CH CH3
+
H
STEP 2

CH3

CH3 C CH CH3 + H2O

..
+ ..

H
CH3

CH3 C CH CH3

H O+ H

..
H
STEP 3
CH3

CH3 C CH CH3

H O+ H
CH3
..

H CH3 C CH CH3 + H3O.. +

H2O
..
..

OH H
(6) Addition of Sulphuric Acid to
Alkenes
• Alkenes dissolve in concentrated sulphuric
acid to form alkyl hydrogen sulphates.
sulphates
• Alkyl hydrogen sulphates can be easily
hydrolysed 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
 7 ) Oxidation of Alkenes
Alkenes undergo a number of reactions
in which the C=C is oxidized

KMnO4 ozonolysis
 basic,cold,dilute
 acidic,hot,concentrated
i) With cold and dilute potassium
permanganate, KMnO4

• Potassium permanganate in alkaline

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

C C + MnO2
OH OH (brown precipitate)

Observation: Purple colour of KMnO4 decolourised and

brown precipitate formed.
• This reaction is called Baeyer’s test.
test

• It is a test for the presence of C=C 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

 When oxidation of the alkene is carried out

in acidic solution of KMnO4, 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

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

CH3
O O

H3C
C
CH3
+ H3C
C
CH3
 If a hydrogen is present at double
bond,
bond one of the carbonyl-containing
products is a carboxylic acid;
acid

 If two hydrogens are present on one

carbon,
carbon CO2 is formed.
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
undergoes oxidation with hot basic
potasium permanganate solution to form
propanoic acid and 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
in hot basic KMnO4 followed by acidific to
give the following product:

O O
CH3CCH2CH2CH2CH2C OH

Deduce the structural formula for the

unknown alkene.
iii) Ozonolysis of Alkenes

• A more widely used method for locating

the double bond of an alkene is the use
of ozone (O3).
• Ozone reacts vigorously with alkenes to
form unstable compounds called
molozonides,
molozonides which rearrange
spontaneously to form compounds
called 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,H2O/H

CH3 CH3

H3C
C
O
+ H
C
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
 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
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 exists 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.