CHAPTER 2

Hydrocarbon Compounds: Alkene

OUTLINE
 Nomenclature
 Structure and physical properties (boiling point and solubility)
 Sources and uses
 Synthesis:
 Dehydration of alcohols
 Dehydrohalogenation of haloalkanes
 Reactions:
 Addition (Hydrogenation)
 Electrophilic addition (anti-Markovnikov's rule)
 Oxidation
Classes of Hydrocarbons

Hydrocarbons  Alkenes are hydrocarbons that

contain a carbon-carbon
double bond
Aliphatic

H H

Alkenes
C C
H H
Classes of Hydrocarbons

Hydrocarbons  Alkenes whose carbon

atoms are joined in rings

Aliphatic

Cycloalkenes
Alkenes
 Unsaturated hydrocarbon

 Contain carbon – carbon double bonds

 Alkenes: R-C=C-R

 General formula: CnH2n

 Aliphatic hydrocarbons

 Two simplest alkenes; ethene (ethylene) and propene

(propylene) are major raw materials for the chemical industry
Cycloalkenes
 Alkenes whose carbon atoms are joined in rings

 General formula CnH2n-2 where n =3,4,5…..

 Examples:

Cyclopropene, C3H4 Cyclopentene, C5H8 Cyclohexene, C6H10

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 2 3 4
CH3-CH2-CH=CH-CH2-CH2-CH3
3-heptene
H

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

H H CH3

4-methyl-2-
pentene
CH3

3 4 5 6
Br-CH2-CH2-CH-CH-CH2-CH3
2 1
CH=CH2
3-(2-bromoethyl)-4-methyl-1-
hexene
  For alkenes which show cis-trans isomerism, prefix cis or trans is

written before the IUPAC name.

H H H3C H

C C C C

H3C CH3 H CH3

cis-2- trans-2-butene
butene
Naming Cycloalkenes
3 2

4 CH3
1
6-ethyl-1-methylcyclohexene
5 6
CH2CH3

1. Replace the -ane ending of the cycloalkane having the same

number of carbons by –ene

2. Number through the double bond in the direction that gives

the lower number to the first-appearing substituent
3. Number substituted cycloalkenes in the way that gives the
carbon atoms of the double bond the 1 and 2 positions

4. Number substituted cycloalkenes in the way that gives the

substituent groups the lower numbers at the first point of
difference.

CH3 1
6 2

5 3
H3C CH3
4

1-methylcyclopentene 3,5-dimethylcyclohexene
 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 4 3 2 1
CH3-CH=CH-CH=CH 2
5 1
1,3-pentadiene
2
4
CH3-CH-CH2-CH=CH-CH2-CH=CH2
8 7 6 5 4 3 2 1 3 CH3

CH3 2-methyl-1,3-cyclohexadiene
7-methyl-1,4-octadiene
H3C CH2 H H3C CH2 CH2CH3

C C C C

H CH2CH3 H CH2CH2CH3

trans-3-hexene trans-4- ethyl –3-heptene

H3C CH2 CH2CH2CH3

C C

H CH3

cis-4-methyl-3-heptene
 1 CH3

5
4
2
CH3
3 1
3
CH3 2

3-methylcyclohexene 1,5-dimethylcyclopentene
Let’s name the structural formulae
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:

Structural Melting Point Boiling Point

Name
Formula (°C) (°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.

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
 Synthesis of alkenes: Elimination reactions
a) Dehydrogenation of alkanes: X = Y = H

b) Dehydration of alcohols: X = H; Y = OH

c) Dehydrohalogenation of alkyl halides: X = H; Y = Br, Cl

X C C Y C C + X Y
 
 a) Dehydrogenation of alkanes
 Elimination of molecule H2

 Limited to industrial synthesis of ethylene and propene

H C C H C C + H2

Example
H H H H
750°C
C C + H2
H C C H
H H
ethane
H H ethene (ethylene)
 b) Dehydration of alcohol
· Loss of H and OH from adjacent carbons.

· Acid catalyst is necessary.

H C C OH C C + H2 O

Example
H H H H
H2SO4
C C + H2 O
H C C OH 160°C
H H
H H ethanol ethene (ethylene)
 More example on dehydration of alcohols:
i) H H H H

conc. H2SO4
H C C H H C C H H2O
1700C
ethene In dehydration reaction:
H OH

i) excess H2SO4 is heated at

ii) H H H

conc. H2SO4
170°C or
H C C C H
CH3-CH=CH2 H2O
0
170 C ii) excess H3PO4 heated at
H OH H
225°C or
iii)
OH
iii) alcohol vapor is passed
conc. H2SO4
over alumina at 350°C.
H2O
1700C

conc. H2SO4
iv) CH3-CH-CH2-CH3 CH2=CH-CH2-CH3 CH3-CH=CH-CH3
1700C (major)
(minor)
OH
 c) 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

H C C X C C + HX

Example
H H (Sodium ethoxide) H H
NaOCH2CH3
C C C C + HCl
H Cl ethanol, 55°C Hydrogen
H H chloride
H H Ethyl chlorides ethene (ethylene)
 More examples on dehydrohalogenation of
alkyl halides:
i) H H H
KCH3CH2O
CH3CH=CH2 HBr
H C C C H
CH3CH2OH
H Br H

ii) Cl

HCl

iii) CH -CH -CH-CH KOH, CH CH OH CH3-CH2-CH=CH2 CH3-CH=CH-CH3 HBr

3 2 3 3 2
(minor) (major)
Br
Reactions of alkenes
 Addition reactions
 Hydrogenation
 Hydration
 Hydrohalogenation
 Halogenation

 Oxidation reactions
 Ozonolysis
 Hydroxylation with KMnO4 (room temp)
 Oxidation cleavage of alkenes with acidic KMnO4
 Combustion

 Polymerization
Reactions of alkenes
 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
Reactions of alkenes
 Alkenes are more reactive than alkane due to the presence of π

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).
Addition Reactions
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 Ni / H2 CH3-CH3

CH3-C C-CH2CH3 Ni / H2 CH3-C CH CH2CH3

CH3 CH3 CH3 CH3

CH3 CH3
Ni
2H2

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

b) 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
c) 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 Markonikov’s 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 HCl CH3-CH2Cl
(one product)

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

Br
(one product)

CH3-CH2-CH=CH2 HCl CH3-CH2-CH-CH3 CH3-CH2-CH2-CH2-Cl

Cl (minor)
(major)
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.

HBr
CH3-CH2-CH=CH2 CH3-CH2-CH2-CH2Br
Peroxide
or (major)
ROOR

CH3 HBr CH3

Peroxide
or
ROOR
Br
(major)
d) Halogenation: Addition of X2
 The addition of halogen to an alkene

 Produces a haloalkane or alkyl halide

H H H H
R C CR X2 R C C R
X X
Simple laboratory test for unsaturation
 Examples on Halogenation
i) Using Cl2 or Br2 in inert solvents such as tetrachloromethane, CCl4.

CH2=CH2 Cl2 / CCl

H2C CH2

Cl Cl
Br

CH3-CH2-CH=CH2 Br2 / CCl4 CH3-CH2-CH-CH2Br

CH2 CH3 Br

CH2CH3
Br
2Br2 / CCl4

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 H H
The Br2 molecule
polarised by C=C slow
H C C H H C C H Br
undergo heterolytic
fission to form Br
Br Br
electrophile, (Brδ+) and
nucleophile

H H H H

f ast
H C C H Br H C C H

Br Br Br

The bromide ion, Br- (nucleophile) attacks the

charge on C as it is, electron deficient.
ii) Addition of halogen in aqueous or halohydrin formation:

 Using X2 (X= halogen) in aqueous(H2O). The reaction follows

Markovnikov’s Rule whereby the X (halogen) atom is added to the

carbon double bond bonded directly to more hydrogen atoms.
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 C
C C + O3
O O
H R” ozonide
R R’
H2O, Zn
C O + O C

H aldehyde ketone R”
Examples on Ozonolysis
H H O O
O3 , Zn
H C C H C C H
+
H2O / H
H H
H

O3 , Zn O O
H3C C C CH3

H2O / H+ H3C C H H3C C CH3

H CH3

H
O
H3C
O3 , Zn C-CH2-C
H2C
H2O / H+ CH3
H
C O

H
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 H H
+
KMnO4 / H
H C C H H C C H
cold

OH OH

CH3 CH3

CH3
CH3 +
KMnO4 / H
cold 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 O O
+
conc. KMnO4/ H
H2C C CH3 H C H + H C CH3
(methanal) aldehyde

HCOOH
O

HO C CH3
CO2 & H2O 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.
 d) Reaction with oxygen
(combustion)
 Alkenes burn in air with soothy flame. The unburnt carbon is left

behind as soot. Hence, alkenes are not used as fuels.

CH2=CH2 + 3O2 2CO2 + 2H2O

 In the presence of silver catalyst at 180ºC, ethene reacts with O2 to

produce epoxyethane.

H2C=CH2 + 1 O2 H2C CH2

2
O
 Epoxyethane is unstable because of the ring strain, hence it will

react rapidly with water to produce 1,2-diol. This is industrial

method to prepare ethane-1,2-diol which is used to
manufacture antifreeze and polyesters.

H2C CH2 + H2 O H2C CH2

O OH OH
Polymerization
Polymerization
 A polymer is a very large molecule consisting of repeating units

of simpler molecules, formed by polymerization

 Alkenes react with radical catalysts to undergo radical

polymerization
 Ethylene is polymerized to poyethylene, for example:
Exercises
1. Based on the reaction below, draw the structure of the organic products
formed:
2. 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.