Alkenes

Hydrocarbons
Hydrocarbons

Aliphatic
Aliphatic

Alkenes are
hydrocarbons that
contain a carboncarbon double
bond. H
H
C

Alkenes
Alkenes
H

C
H

Alkenes
Unsaturated hydrocarbon
Contain carbon carbon double bonds
Alkenes
General formula
Aliphatic hydrocarbons
Two simplest alkenes; ethene (ethylene) and propene
(propylene) are major raw materials for the chemical
industry.

Naming the alkenes (IUPAC

Nomenclature)

Longest carbon must contain the double bond.

The C=C functional and position of substituent must be
at lower number.
However, position of C=C is of higher priority (LOWER
NUMBER) than substituent.
1

CH3-CH2-CH=CH-CH2-CH2-CH3

CH3

3-heptene
H

1
2
3 4 5
CH3-C=C-C-CH3
H

H CH3

4-methyl-2-pentene

Br-CH2-CH2-CH-CH-CH2-CH3
2

CH=CH2

5-bromo-3-sec-butyl-1-pentene

For alkenes which show cis-trans isomerism,

prefix cis or trans is written before the IUPAC
name.

H
C

H3C
C

H3C

CH3
cis-2-butene

C
CH3

trans-2-butene

 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
5

CH3-CH=CH-CH=CH2
1,3-pentadiene
CH3-CH-CH2-CH=CH-CH2-CH=CH2
8

CH3
7-methyl-1,4-octadiene

Lets name the structural formulae

CH3CH2

C=C
H

CH2CH3

trans-3-hexene

CH2CH3

CH3CH2

C=C
H

CH2CH2CH3

cis-4- ethyl 3-heptene

Physical Properties
Similar to alkanes
Solubility
Soluble in non polar solvent
Not soluble in water
Low density, boiling point and melting point
Properties vary based on chain size.
Alkenes have week Van der Waals forces between
molecules; for example the lower carbon alkenes exist as
gases at room conditions.
Interesting physical properties
Alkenes with several double bonds will have a color
associated with them

Table below shows some physical

properties of alkenes and cycloalkenes

Name

Structural
Formula

Melting
Point
(C)

Boiling
Point
(C)

Ethene

CH2=CH2

-169

-104

Propene

CH2=CH-CH3

-185

-48

1-butene

CH2=CH-CH2-CH3 -185

-6.3

Cyclopentene

-135

44

Stability of Alkenes
There are 3 factors that influence the
stability of alkenes:
Degree of substitution : more highly
alkylated alkenes are more stables, so
tetra> tri > di > mono-substituted
Stereochemistry : trans > cis due to
reduced steric interactions when R groups
are on opposite sides of the double bond.
Conjugated alkenes are more stable than
isolated alkenes.

Synthesis of alkenes

Synthesis of alkenes: elimination reactions

a) Dehydration of alcohols:
X = H; Y = OH
b) Dehydrohalogenation of alkyl halides:
X = H; Y = Br, Cl
c) Dehalogenation of dihalides
d) Hydrogenation @ Reduction of alky
X

C
Y

A)

Dehydration of alcohol
Loss of H and OH from adjacent carbons.
Acid catalyst is necessary.
C

OH

H 2O

Example
H

H C

H2SO4

OH
ethanol

160C

H
C

C
H

ethene (ethylene)

H 2O

i)

More example on dehydration

of alcohols:H

ii)
H

OH

conc. H2SO4

1700C

CH3-CH=CH2

170 C
H

iii)

OH

OH

conc. H2SO4

H2O

170 C

iv)

CH3-CH-CH2-CH3
OH

conc. H2SO4
0

In dehydration reaction,
i) excess H2SO4 is
heated at 170C or

H2O

ethene

conc. H2SO4

170 C

H2O

ii) excess H3PO4 heated

at 225C or
iii) alcohol vapor is
passed over alumina at
350C.

CH2=CH-CH2-CH3

CH3-CH=CH-CH3

(minor)

(major)

Saytzeffs Rule; in elimination reactions, the major reaction

product is the alkene with the more highly substituted
(more stable).

B)
Dehydrohalogenation of alkyl halides
Loss of H and halogen (X) from an alkyl halide
In the presence of strong base in solvent likewise
NaOCH3 in methanol, or KOH in ethanol
C

+ HX

Example
H
H

C
H

H
C
H

Cl

(Sodium ethoxide)
NaOCH2CH3
ethanol, 55C

Ethyl chlorides

H
C

+
H

ethene (ethylene)

HCl

Hydrogen
chloride

More examples on dehydrohalogenation

of alkyl halides
i)

H
H

ii)

Br

KCH3CH2O
CH3CH2OH

CH3CH=CH2

HBr

Cl

HCl

iii) CH -CH -CH-CH KOH, CH CH OH CH -CH -CH=CH

3
2
3
3
2
3
2
2
(minor)
Br

CH3-CH=CH-CH3
(major)

HBr

C) Dehalogenation of dihalides
C
Br

2 NaCl
acetone

Br

@
Zn
CH3COOH

+ Cl2

2 NaBr

ZnBr2

D) Hydrogenation @ Reduction of alkynes

Depending on the condition & catalyst that will

be used.
Catalyst
H2 / Pt
H2 / Ni2B @ P - 2

Product
CH3CCCH3 CH3CH=CHCH3

CH3CH2CCCH2CH3

H2, Pd / CaCO3 & Lindlars catalyst

CH3CH2

CH3CH2

C
Li @ Na in NH3
NH2C2H5 / low temp.

H
H
CH3(CH2)2CC(CH2)2CH3
CH3(CH2)2
C
H

Cis alkene

H
C
(CH2)2CH3

Trans alkene

Reaction of alkenes
Addition of symmetric reagents
a) Hydrogenation (H2)
b) Halogenation (X2)
Addition of unsymmetric reagents
c) Hydration (H2O)
d) Hydrohalogenation (HX)
Oxidation reactions
a) Ozonolysis
b) Hydroxylation with KMnO4 (room temp)
c) Oxidation cleavage of alkenes with acidic
KMnO4

 Primarily reactions involve the double bond

The key reaction of double bond is addition reaction
(Breaking the bond and adding something to each carbon)
The major alkene reactions include additions of hydrogen
(H2),halogen ( CI2 or Br2), water (HOH) or hydrogen
halides (HBr or HCI)

A- B
A B

 Alkenes are more reactive than alkane due to

the presence of bond. The bond has high
electron density and susceptible to be
attacked by electrophiles ( electron deficient
species and low electron density).
Alkenes undergo ELECTROPHILIC
ADDITION reactions which means the C=C (C
double bonds) are broken to form C-C bond
(single bonds).

a)

Hydrogenation Addition of H2

Addition of a molecule of H2
Results in the formation of an alkane

Usually requires heat, pressure and a catalyst like Pt, Pd or Ni

Examples on Hydrogenation
Can be carried out by using hydrogen gas in
the presence of catalysts such as Ni/ Pd/ Pt.
CH2=CH2

CH3-C

Ni / H2

C-CH2CH3

CH3-CH3
Ni / H2

CH3-C

CH CH2CH3

CH3 CH3

CH3 CH3
CH3

CH3

2H2

Ni

(2 mole C=C requires 2 mole of H2 gas)

b)

Halogenation: Addition of X2

The addition of halogen to an alkene

produces a haloalkane or alkyl halide

R C CR

X2

R C C R
X X

Simple laboratory test for unsaturation.

Examples on Halogenation
Using Cl2 or Br2 in inert solvents such as
tetrachloromethane, CCl4.
CH2=CH2

Cl2 / CCl

H2C
Cl

CH2
Cl

Br
CH3-CH2-CH=CH2

CH2

Br2 / CCl4

CH3-CH2-CH-CH2Br

Br

CH3

2Br2 / CCl4

CH2CH3

Br

Br
Br

This reaction can be used to detect the presence of C=C

(alkene). The observation is the reddish brown colour of
bromine solution decolourises to colourless.
Reaction mechanism (Electrophilic Addition)
H

H
Br

slow

Br

Br

Br

The Br2 molecule polarised by C=C undergo heterolytic

fission to form electrophile, (Br+) and nucleophile.
H
H
H

Br

fast

Br

The bromide ion, Br- (nucleophile) attacks the

on C as it is, electron deficient.

Br

Br

charge

c)

Hydration: Addition of H2O

The addition of water to an alkene

One carbon get an H, the other an OH
produces an alcohol

Reagents used are concentrated sulphuric acid followed

by addition of water and high temperature or dilute warm
aqueous acids such as H2SO4.

d)

Hydrohalogenation

Addition of HX to an alkene
HX HF, HCI, HBr, HI
HX in the gaseous state or dissolved in organic solvent. (i.e:
CCl4)

It follows Markonikovs rule where the H ends up on the

carbon with the most hydrogen to start with

Examples on Hydrohalogenation
Using HX (X=Cl/ Br/ I) to attack the (double bond (C=C)
whereby the HX molecule is the electrophile.
CH2=CH2

CH3-CH2Cl
(one product)

HCl

CH3-CH=CH-CH3

HBr

CH3-CH-CH2-CH3
Br
(one product)

CH3-CH2-CH=CH2

HCl

CH3-CH2-CH-CH3
Cl
(major)

CH3-CH2-CH2-CH2-Cl
(minor)

However, with HBr peroxide/ ROOR (not HCl or HI),

the major product is ANTI-MARKOVNIKOV. The H
from HBr will be bonded to carbon double bond is
bonded directly to less hydrogens atoms.
CH3-CH2-CH=CH2

CH3

HBr
Peroxide
or
ROOR

CH3-CH2-CH2-CH2Br
(major)

HBr

CH3

Peroxide
or
ROOR

Br

(major)

Oxidation reactions

a) Ozonolysis of alkenes
1st step - reaction of alkene with ozone to form
ozonide.
2nd step - hydrolysis of ozonide to form aldehyde
and ketone.
R
R
O
C

H
R

+ O3

O
O
ozonide

R
R
C

H aldehyde

ketone R

H2O, Zn

Examples on Ozonolysis
H

O3 , Zn
H

H3C

C
H

C
CH3

CH3

H2O / H

H2 O / H+

O3 , Zn
H3C

H
H3C

O3 , Zn
H 2O / H +

H3C

C-CH2-C
H2C
C

CH3
H

H
O

CH3

b) Hydroxylation With Potassium Manganate (VII)

(Baeyer test)
Reaction with potassium manganate (VII) solution either acidic
or alkaline at room temperature will result addition of 2-OH
groups at the carbon double bonds.
H

H
+

KMnO4 / H
H

cold

OH

OH

CH3

CH3
CH3

KMnO4 / H+
cold

CH3
OH
OH

This test can be used as a chemical test to detect the presence of

C=C (alkene) functional group. The purple color of potassium
manganate (VII) solution will turn colourless.

c) Reaction with hot, conc acidified KMnO4

H
H2C

O
CH3

conc. KMnO4/ H+

O
H

(methanal)

CH3

aldehyde
O

HCOOH

CO2 & H2O

O
HO

CH3

carboxylic acid

If the product is methanal, it will oxidised to HCOOH and then form

carbon dioxide and water. If the product is other aldehyde containing
more than one carbon atom, it will oxidised to carboxylic acid.
However, if ketones is formed, as ketone DOES NOT undergo
oxidation, it will remain as ketone.

Base on the reaction below, draw the structure of the

organic products formed.

 An alkene X, containing 8 carbon

atoms reacts with hot acidified
potassium manganate (VII) solution
to form propanoic acid and pentanoic
acid. Draw the two forms of which
exist as cis-trans isomers.

Uses of alkenes
The most important use of alkene are:
Manufacture of plastics
Ethene is used to produce plastics such as
polyethene, polychloroethene and polyester
(textile).
Manufacture of ethane-1,2-diol
Ethane-1,2-diol is used as antifreeze in car
radiators and for making detergents.
Manufacture of ethanol
Ethanol is used as a solvent for vanishes,
cosmetic and toilet preparations and also in
manufacture of ethanal.