VIDEO1

Describe alkenes as unsaturated

hydrocarbons with the general formula
CnH2n , n 2
Draw the structures and name the
compounds according to the IUPAC
nomenclature for:
i. Straight chain and branched alkenes
(parent chain C10)
ii. Cyclic alkenes (parent cyclic C3 C6)
iii. Simple dienes (C4 C6)
 General formula: CnH2n , n 2.
Functional group: C=C double bond
Unsaturated hydrocarbon
Each carbon atom ( C=C ) is sp2 hybridized.
Restricted rotation of carbon-carbon double
bond causes cis-trans isomerism
i. Straight chain and branched alkenes
(parent chain C10)

Determine the parent name by selecting

the longest chain that contains the
double bond and change the ending
-ane in alkane to -ene.
 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)

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)
 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 CHCH CH2
1,3-butadiene

1 2 3 4 5 6 7
H2C CHCH CHCH CHCH3
1,3,5-heptatriene
ii. Cyclic alkenes (parent cyclic C3 C6)

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)

VIDEO2
Two frequently encountered alkenyl
groups are vinyl group and allyl group.

RCH=CHR -H RCH=CH-
alkene alkenyl

CH2=CH- CH2=CHCH2-
vinyl group allyl group
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.
VIDEO 3
 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
a) Dehydration of alcohols
b) Dehydrohalogenation of alkyl halide

VIDEO 1
 Describe the preparation of alkenes
through:
i. Dehydration of alcohols
ii. Dehydrohalogenation of haloalkenes
Write the mechanisms for dehydration
of alcohols
State Saytzeffs rule
Deduce the major product of the
elimination reaction.
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

VIDEO 2
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
Saytzeffs rule.
 Saytzeffs Rule

An elimination usually gives the most

stable alkene product, commonly the most
highly substituted alkene.
*** The major product is the most stable alkenes.
*** The most stable is the alkene that has greater
number of alkyl group.
 H2SO4 (conc.)
(1) CH3CH2OH
H2C CH2

+ H2O

H2SO4 (conc.)
(2) H3C CH CH3 H2C CH CH3

OH + H2O
 Mechanism for the dehydration
of alcohol
C H3CH CH2CH3 H SO (conc.) CH 3 CH=CHCH 3
2 4

OH (major product)
+ CH 2 =CHCH 2 CH 3
(minor product)
+ H 2O

VIDEO 3
 H H
H C C CH CH + +
:O H
3 2 3
:OH H
..

H H
H 3C C C H 2C H 3 + :O H
+ ..
: OH
H
 H H
H 3C C C H 2 C H 3 H3 C +
C CH 2CH3
+:OH
carbocation
H
H
+ :O H
..
 H H H H
+
H C C C CH3 :O H
+ ..
H H

a
Root a : major product
Root b : minor product
 H H H H
+
H C C C CH3 + :O H
..
H H

Root a : major product (red line)

Root b : minor product (blue line)
 H H H
C C + +
: O H
H3C CH3 H
stable alkenes
(major product)
+ CH 2 =CHCH 2 CH 3
(minor product)
Example 1:

CH3 H
H2 SO4 (conc.)
H3C C C CH3

CH3OH
 CH3
H 3C C C CH 3
CH3
(major product)

CH
3
+ H C C CH CH
2 3
CH
3
(minor product)
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
rearrangement
CH H CH H
3 3

2o carbocation 3o carbocation
(less stable) (more stable)

VIDEO 4
 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, this kind of
rearrangement is often called a 1,2 shift.
 CH
(a) 3
HC C CH C H
(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
(b) 3
(major product)
more stable alkene
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 Saytzeffs
rule.
 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)
 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
Saytzeffs rule is used to determine the
major product
VIDEO5
 (1)
Cl
alcohol
H3C 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
HC + alcohol CH
KOH
CH reflux CH
3 3
(minor product)

CH
+ 2
CH
3

(major product)
(4) CH3 H

CH3 C C CH3 + KOH alcohol

reflux
CH3 Cl

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
 Mechanism of dehydrochlorination of
3-chloro-2,2-dimethylbutane

CH3 H CH3 H
CH3 C C CH3 CH3 C C CH3
+
CH3 Cl CH3

+ Cl-
 CH3 H CH3 H
CH3 C C CH3 1,2 shift CH3 C C CH3
+ +
CH3 CH3

20 carbonium ion 3o carbonium ion

 CH3
CH3 C C CH3

CH3
CH3 H major product
CH2 C C CH3
+
H
CH3 CH3 H
CH2 C C CH3

CH3
minor product
 Explain the addition reaction of alkenes
with:
i. Hydrogen in the presence of catalyst
ii. Halogen (Cl2 or Br2) in inert solvent
(CH2Cl2)
iii. Halogen (Cl2 or Br2) in water
 Comparison of The Reactivity Between
Alkanes and Alkenes
Alkenes are more reactive compared to
alkanes.

Alkanes have carbon-carbon single bonds

( bonds) while alkenes have carbon-carbon
double bonds ( bonds).

The double bond is a site of high electron

density (nucleophilic).

Therefore most alkenes reactions are

electrophilic additions.
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
H3C CH3
slow
C C + H Cl
H3C CH3
CH3CH3
+ -
H3C C C CH3 + Cl
CH3
 CH3CH3
Cl- fast
H3C C
+
C CH3 +
CH3
CH3CH3
H3 C C C CH3
CH3Cl
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
VIDEO 1 VIDEO 2
 (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
 C H3
CH2Cl2
H3 C C C C H3 + Cl 2
H
Cl Cl
H3C C C C H3
CH3H
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
VIDEO 3
H H H H
C C + Br2 + H2O H C C H
H H Br OH
2-bromoethanol

If the alkenes is unsymmetrical, the

halogen ends up on the carbon atom with
the greater number of hydrogen atoms.
H3C C C H2 + Br 2 + H2O
C H3
CH3H
H3 C C C H
OH Br
1-bromo-2-methyl-2-propanol
Complete the following reaction:

+ Br 2 + H2 O
CH3
 Explain and write the mechanism of
electrophilic addition reaction of alkenes
with:
iv. Hydrogen halides (HCl or HBr)
v. Acidified water
Explain the formation of the product
according to the Markovnikovs rule
Determine the product of the reaction
between alkene and hydrogen bromide in the
presence of hydrogen peroxide/acid peroxide
according to anti-Markovnikovs rule.
3)(i) Hydrohalogenation : Markovnikovs rule

Hydrogen halides ( HBr or HCl ) 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, follows Markovnikovs rule.

VIDEO1
 Markovnikovs 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.

VIDEO2
i. The addition of HBr to propene, could
conceivably lead to either -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 Markovnikovs rule.
 Mechanism
CH 3

CH 3 C CH CH 3 + H Br
slow

CH3

CH3 C CH CH3 + Br -
+
30 Carbocation
 CH3

CH3 C CH CH3 + Br - fast

+

CH3

CH3 C CH CH3

Br H
3)(ii) Hydrohalogenation : Anti
Markovnikovs rule (Addition of HBr to
Alkenes in The Presence of Peroxides)

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.

VIDEO3
 ROOR
H2C CH CH3 + HBr

Br CH2CH2CH3

VIDEO4
 Complete the following reactions:

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

CH2 H2 O2
+ HBr
4) 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 Markovnikovs rule.

+
H3O
C C + H2O C C
H OH
 +
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
i) An alkenes with hydrogen halides(HX)
* H+ ion reacts as an electrophile

C=C + H+ C C+ + X- C C

H H X
H H H H H H

C=C + H+ H C C+ + Cl - C C H
H
H H
H H H Cl
 + +
CH3CH=CH 2 + H+ CH3 CH CH2 @ CH3 CH CH2
H H
 +
CH3 CH CH2 + X - CH3 CH CH2
H
X H
2-halopropane

+
CH3 CH CH2 + X- CH3CH CH2
H
H X
1-halopropane
Video 1
 Example: 3-methylbutene react with HX

H+ + +
CH3CHCH=CH 2 CH3CHCHCH 3 CH3CHCH 2CH2
+
CH3 CH3 CH3

less stable

X
+ +
CH3CHCHCH 3 CH3CCH2CH3 X-
CH3CCH2CH3

CH3 CH3 CH3

2o carbocation 3o carbocation

Video 2
 H+ + OH -
CH3CH=CH2 CH3CHCH 3 CH3CHCH 3
H3O+ H3O+

propene OH
2-propanol

When an alkene reacts with acidified water

formed an alcohol followed Markovnikovs
rule. An acid reacts as a catalyst.
Video 3
 Explain the unsaturation test for alkenes:
i. Baeyers test using dilute alkaline
KMnO4
ii. Bromine in CH2Cl2
iii. Bromine water
Determine the position of double bond
through:
i. Ozonolysis (O3 followed by Zn,H2O)
ii. Reaction with hot, acidified KMnO4
 Unsaturation test for alkenes

There are two chemical test to

differentiate between an alkanes and
alkenes:

i. Baeyers Test using cold, dilute,

alkaline solution KMnO4 at room
temperature
ii. Reaction with bromine in CH2Cl2 and
bromine water (bromine test)
i) Reaction of alkenes with cold, dilute
KMnO4 (Baeyers test)

The reaction known as hydroxylation. It

involves the addition of the two OH
groups to the double bond
Potassium permanganate in alkaline
solution can be used to oxidise alkenes
to 1,2-diols (glycols).
This test is used to distinguish alkenes.
 Unsaturated hydrocarbon

dilute, cold
C C KMnO4
+ (purple)

C C + MnO2
(brown precipitate)
OH OH
Observation: Purple colour of KMnO4
decolourised and brown precipitate formed.
 Saturated hydrocarbon

dilute, cold
CH3CH2CH3 + KMnO4 No reaction

Observation: the purple color of KMnO4

remains
 This reaction is called Baeyers 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.
 -
OH ,H2 O
H2C CH2 + KMnO4
cold

H H
H C C H + MnO2
OH OH
 C C + Br2 CH2Cl2
Room temperature
(colourless) (reddish brown)

C C
Br Br
( a colourless compound)
 When bromine is used for this reaction,
it can serve as a test for the presence of
the carbon-carbon double 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
Example:

Give observation and write the equation

for the following experiment:

2-butene is bubbled through a cold,

dilute and basic solution of potassium
manganate (VII)
 KMnO4, OH-
CH3 CH CH CH3 CH 3CH CHCH 3
cold
OH OH
(glicols)

+ MnO2
(brown precipitate)

Observation:

a) Purple colour of KMnO4 solution turned

to colorless
b) Brown precipitate formed
 Oxidation of Alkenes
Alkenesundergo a number of reactions
in which the C=C is oxidized

KMnO4 ozonolysis
basic,cold,dilute
acidic,hot,concentrated
VIDEO1
 Reactions of alkenes with hot, concentrated
KMnO4

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, the
two carbonyl-containing products are
ketones

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

CH3
O O

H3C
C
C H3
+ H3C
C
CH3
 If a hydrogen is present at double bond,
one of the carbonyl-containing products
is a carboxylic acid;

If two hydrogens are present on one

carbon, CO2 is formed.
 -
(i)
H+,OH
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
acidic potasium permanganate solution
to form propanoic acid and butanoic
acid. What is the structure of this alkene?
 (i)
H+, -,heat
OH
C 7 H14 + KMnO4
(ii) H3 O
+

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

H H
H3C CH2C C CH2CH2CH3
3-heptene
 An unknown alkene undergoes oxidation
in hot acidic KMnO4 to give the following
product:

O O
CH3CCH2CH2CH2CH2C OH

Deduce the structural formula for the

unknown alkene.
 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, which rearrange
spontaneously to form compounds called
ozonides.

VIDEO2
 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
 CH3 (i) O3
+
H3C C CH CH3 (ii) Zn,H2O/H

CH3 CH3

H3C
C
O
+ H
C
O
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. 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
3. 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.