AlKENES

2.1 Structure of Alkenes.

Alkenes forms a homologous series with the general formula CnH2n. Alkenes (olefins) are isomeric with
cycloalkanes. They are more reactive than alkanes and the reactivity is due to the double bond.
The alkyl portion can undergo substitution reaction but most of the reactivity resides in the C=C which can undergo
rapid addition reaction in which atoms are added to the molecule to obtain a product containing more atoms than were
present in the original molecule.

The ethylenic double bond (C=C) contain two SP2 hybridized carbon atoms. Alkenes are said to be unsaturated
because unlike the alkanes they do not contain the maximum number of hydrogen atoms.
The simplest member of the alkenes is ethene (common name: ethylene) which has the formula C 2H4

H H

C C

H H

The structures of some simple alkenes.

H CH2CH3 H CH2CH2CH3
H3C H
C C C C
C C
H H H H
H H
Propene 1-butene 1-Pentene

2.2 Classification of alkenes

Alkenes may be classified are monoenes, dienes or polyenes. Monoenes are alkene containing only one c=c and
conforms to the generic formula CnH2n.

Dienes have two double bonds and the generics formula CnH2n-2 describes them. There are three types of dienes:

(i) Isolated dienes: These have at least one methylene group (-CH2-) between the two double bonds.

1,6-Heptadiene 1,4-Cyclohexadiene

(ii) Conjugated dienes: These are dienes containing alternating double and single bonds.

(Z,Z)-2,4-Hexadiene 1,3-Cyclohexadiene

(iii) Cumulated dienes: These alkenes contain two double bonds bonded to the same carbon
 H H

C C C

H3C H

1,2-Butadiene

Polyenes are alkenes with more than two double bond. Examples are trienes (3-double bonds) and tetraenes (four
double bonds)

CH2=CH-CH2-CH=CH-CH2CH=CH2

1,4,7-Octatriene

2.3 Nomenclature of Alkenes

The IUPAC Names of Alkenes.

The IUPAC rules are applied in the naming of alkenes. With our experience in the naming of alkanes it should be
easier for us to name the alkenes with slight modification.

i. The longest continuous chain containing the C=C bond is chosen as the parent hydrocarbon.

ii. The chain is then numbered from the end of the chain which will give the carbon-carbon double bond the
smallest possible number.
Numbering the structure above from left to right carbons gives the carbons involves in the double
bond 3 and 4 but when numbered from right to left they get the number 5 and 6.
Since the double bonded carbon should have the least possible numbers, the right direction
for the numbering should be from left to right

iii. The presence of the C=C is indicated by replacing the suffix –ane of the alkane containing the same number
of carbons as in the parent hydrocarbon selected by the suffix –ene.

CH2 = CH2 CH3 CH = CH2

Ethene Propene

iv. In writing the name of the compound, the position of the carbon – carbon double bond is indicated by
using the number of the lower numbered carbon atom of the double bonded carbon atoms.

The number is placed immediately before the parent hydrocarbon name.

(CH3)2C=CCHCH2CH2CH3
2-methyl-2-heptene

In the case of ethane and propane it is not necessary to indicate the position of the double.

This is because the double bond can take only one position.

v. If the chain contains substituent such as a halogen or alkyl, the position and name of them substituent is
indicated as in the case of the alkanes.
 4 5 6 7 8 4 3 2 1
CH3.CH2.CH2.CH.CH2.CH2.CH2.CH3 CH3.CH.CH CH2
Cl
HC CH.CH3
3 2 1

4-Propyl-2-octene 3-Chloro-1-butene

vi. If there is more than one substituent, they are named in alphabetical order if the groups are different. If
however one group appears more than once on the chain the prefix di-, tri, tetra, etc is placed before
the name of the substituent.

Cl

3,5-dimethyl-3-octene 2-chloro-4-methyl-1-pentene

7. When a molecule poses more than one carbon double bonds, the suffix-diene, triene, tetraene etc are use for two,
three and four double bonds respectively.

The positions of all the double bonds are indicated before the parent hydrocarbon name.

CH2=CH.CH2.CH2CH=CH.CH3

1,5-Heptadiene

8. Cycloalkenes are named by replacing the –ane of the name of the corresponding cycloalkane with –ene,-diene etc.
Numbering must proceed through the double bond.

H3C
Cyclohexene 3-Chloro-cyclopentene 5-methyl-1,3-cyclohexadiene

2.4 Isomerism in alkenes.

Isomerism occurs when two or more compounds have the same molecular formula but differ in the way the atoms
are linked together.
There are two types of isomerism in alkenes, structural and stereoisomerism

Structural isomers in alkenes differ in the position of substituent and in the position of the double bonds.
Examples of structural isomers
Cl
CH3-CH=C-CH3
CH3-CH=CH-CH2-Cl

(1) 2-Chloro-2-butene (2)

1-Chloro-2-butene

1and 2 are structural isomers.

CH3CH2CH=CH2 CH3CH=CH-CH3
1-butene 2-butene
 Structural isomers

Stereoisomers are isomeric compounds that have identical structures but differ in the arrangement of atoms in three
dimensional space.

Geometric isomerism also known as the cis-trans isomerism is a type of isomerism exhibited by some alkenes. Not
all alkenes display geometric isomerism. For this type of stereoisomerism to occur to exist each of the two double
bonded carbons must have two different groups attached to them and must have the general structures show below.

a a a b a a

b b b a b d
cis-isomer trans-isomer cis-isomer

A cis- alkene (on the same side) is an alkene that has two identical groups on the same side of the molecule.

H3C CH3
C C
H H
A trans-alkene is an alkene that has two identical groups on opposite side of molecule.
Example
H Cl H H

Cl H Cl Cl

trans-1,2-dichloroethene cis-1,2-dichloroethene

The Zusammen-Entgegen system.

Cis-trans applies to only substituted alkenes but not tri, tetra, etc
The zusammen-Entgegen ( (Z)-(E) ) method is applied to alkenes with four different groups attached to the double
bonded carbons. The four groups are ranked based on a system called priority rankings.
The rules for the priority ranking are as follows

1. For two different atoms directly attached to a carbon of the double bond, the atom of direct attachment to
the double bonded carbon with the higher atomic number shows the higher priority. Example

CH3

C C NH2

The –NH2 group shows the higher priority than the CH 3-group because the atomic number of nitrogen (7)
is higher than that of a carbon (6)

2. When two atoms directly attached to the carbon of the double bond are the same, the atomic numbers of the
next atom(s) further away from the double bond determine the priority. Example;
 H2C H

C C CH2-CH3

The –CH2CH3 group shows the higher priority because the carbon of the methyl group is bonded to three hydrogens
each with an atomic number of 1, while the methylene carbon of the ethyl group is bonded to two hydrogens and a
carbon, with an atomic number of 6.
Once group priorities are established the following rules are used.

1 When two groups of higher priority, each on different carbons of the double bond are on the same side of
the molecule, the name of the molecule is prefixed with(Z)-(from the German zusammen, together).

2 When the groups of higher priority are on opposite side of the molecule, the designation (E)- (from German
Entgegen, across) is used.

Thus
1 1 1 2
C C C C
2 2 1
2
(Z)- isomer (E)- isomer

Example

Br CH3 Cl CH3
1 1 2 1
C C C C
H Br H
Cl 2
2 2 1

(Z)- 1-bromo-1-chloropropene (E)-1-bromo-1-chloropropene

2.5 Physical properties of alkenes

1. Alkenes are non polar molecules and are insoluble in water but soluble in non polar solvents such as pentane and
carbon tetrachloride.

2 Like alkanes boiling points of alkenes increases with increasing molecular weight and decrease with increasing
branching of the molecule.

3 Internally double-bonded alkenes have higher boiling points than the corresponding 1-alkenes. This is because
internally double-bonded alkenes are more symmetrical, stock up better in the liquid state and have greater
intermolecular London forces between molecule than the 1-alkenes

4. Density of alkenes increases with increasing molecular weight. The more symmetrical the alkene the more they
can be placed in a set volume resulting in a higher density. Alkenes are generally denser than water.

2.6 Relatives Stabilities Of alkenes

Trans-alkenes are more stable than cis- alkene. The two alkyl groups placed on the same side in the cis –alkenes cause
crowding making the molecule less stable
 crowding

R
R R H
C C C C
H R
H H

Generally the greater the number of alkyl group attached to the double bonded carbon atoms the greater the stabilities
is as follows
R R R R R H R H R R R H H H
C C > C C > C C > C C > C C > C C > C C
R R R H H R H H H H
R H H H

2.7 Synthesis of alkenes

Two principal methods are used in the synthesis of alkenes and they are all involved in elimination: the dehydration
of alcohols and the dehydrohalogenation of alkyhalides.

(i) Synthesis of alkenes: dehydration of alcohols

When alcohols are treated with hot concentrated H2SO4 alkenes are produced.

Conc. H2SO4
C C

H OH
An H and an OH bonded to adjacent carbons are eliminated as water and thus the reaction is referred to as dehydration.
The ease of dehydration of alcohols is as shown below.

(tertiary (3° ) alcohols > Secondary (2° ) alcohol > primary (1° ) alcohols

This trend of the ease of dehydration is shown by the acid concentration and the reaction temperature required in the
following reactions.

95% H2SO4 + H2O

CH3CH2-OH H2C CH2
180oC
H 50% H2SO4
H3C C CH2CH2CH3 CH3CH CHCH2CH3 + H2O
170oC
OH
CH3 CH3
H3C C CH2CH3 33% H2SO4 + H2O
H3C C CHCH3
60oC
OH

Mechanism Of dehydration

Three steps are involved in the mechanisms of dehydration. For secondary (2 o) and tertiary(3o) alcohols this follows
what is called the elimination one (E1) mechanism

Step1: Protonation of the OH of the alcohol

 H
H H
..
.. H3C C O
.. H
H3C C O
..
H H+ HSO4- +
CH3
CH3
Protonated alcohol
or oxonium

Step 2: Release of H2O molecule.

H H H
H
..
+
H3C C O
.. H H3C C+ O H
+
CH3 CH3
ethylium ion
carbonium ion

Step 3: Deprotonation from the β-carbon.

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

The step 2 is the slowest step and therefore the rate determining step. The stability of the intermediate carbonium
determines how fast the reaction will be. The more stable the carbonium the faster and easier the dehydration of the
alcohol.

For primary alcohol the mechanism of dehydration follow that of elimination two mechanism (E2) which avoid the
formation of primary carbocation. The primary carbocation is very unstable and therefore difficult to form.

H H
..
H
..
+
H3C C O
.. H H HSO4- H3C C O
.. H
+
H H
Protonated alcohol
or oxonium

H H
H2O +
H2C C O H H2C CH2 + H2O + H3O+
H H

Relative Stabilities Of carbonium ions

We have earlier discussed that the ease of dehydration of alcohols is in the order 3°>2°>1°. This can be explained by
the stability of the intermediate carbonium ion in step 2 of the mechanism. 1°, 2° and 3° carbonium ions are obtained
from 1°, 2° and 3° alcohols respectively.
 H H H
..
H3C C OH H C C+ 1o carbonium
..

H H H
1o alcohol

CH3 H CH3
.. 2o carbonium
H3C C OH H C C+
..

H H H
2o alcohol

CH3 H CH3
..
H3C C OH
.. H C C+ 3o carbonium
CH3 H CH3
o
3 alcohol

The stability of charged system is increased by dispersal of the charge. In 3° carbonium the positive charge is dispersed
over three alkyl groups attached to the carbonium respectively. Thus the charge density on 3° carbonium is less than
the charge density on 2° carbonium and than on the 1° carbonium. The lesser the charge density the more stable the
carbonium and the greater the ease of its formation.

R
R

R C+
R CH2+ R CH+

Area of charge dispersal on Area of charge dispersal on R

primary carbonium secondarycarbonium
Area of charge dispersal on
tertiary carbonium

Saytzeff’s Rule

Saytzeff’s rule states that in an elimination reaction, the major product will be that which involves loss of hydrogen
from the carbon that possesses the smallest number of hydrogens

Example

H H H H H H H H H H H H
1 2 3 4 H2SO4
H C C C C H H C C C C H + H C C C C H
H OH H H H H H H

2-butanol 1-butene (minor product) 2-butene (major product)

C1 bears hydrogens and C3 bears 2 hydrogens and so according to Sayzeff’s rule the elimination of hydrogen from C3
gives major product while elimination of hydrogen from C 1 will give minor product.

(ii) Synthesis Of Alkenes: Dehydrohalogenation Of alkylhalides

Dehydrohalogenation is the loss or removal of H and a halide from adjacent carbons of alkyl halide.
Dehydrohalogenation is carried out by treating the alkyl halide with a basic reagent, usually in alcoholic or aqueous –
alcoholic solution. Typical bases used are the alkali (NaOH, KOH) and alkali metal salt of weak acids eg. RONa

Example
 alcoholic
CH3CH2Cl + KOH CH2=CH2 + KCl + H2O

Mechanism

The strong base, in this case the OH, removes the hydrogen. Simultaneously the Cl detaches from the molecules as
a Cl-ion and the pair of electrons that bonded the H before it left as a proton is used to form a double bond.

H H H
- + Cl- + H2O
H O C C Cl C C

H H H H
One step reaction

2.8 Reactions of alkenes

1. Additional Reactions
The π-bond is less stable than the sigma bond. The π-bond is thus weaker than the sigma bond and it is broken during
chemical reaction.

pie bond
H H
C C A B C C
H H
sigma bond A B

Since A-B is added across the double bond, this type of reaction is known as addition reactions. Because of the π-
electrons most of the addition reactions of alkenes are initiated by eletrophilic attack. Examples of electrophiles are
H+, CH3+, BF3,BH3 etc. An electrophile is an electron-pair seeking reagent that is electron- deficient, a lewis acid.

Addition of symmetrical reagents to alkenes

Symmetrical reagents that can be added to alkenes include H2 and the halogen molecules (Cl2, Br2 etc)

Addition of hydrogen: This requires catalysts such as Pt, Pd or Ni

catalyst
C C
+ H2 C C
200oC
H H

Halogenations:

The halogens, Cl2 and Br2 add to the C=C to give vicinal dihalide. A vicinal dihalide (Vic-) is a halide where the two
halogens are bonded to two adjacent carbon atoms in the molecule.

H3C H H H
CCl4
C C
+ Br2 H3C C C H
20oC
H H Br Br
1,2-dibromopropane
Mechanism of halogenations
 Step 1

C C C+ C

Br
Br

Br
Step 2

C+ C

Br Br+
cyclic bromonium ion
Step 3
Br-
Br
C C
C C
Br+
Br
vicinal dibromide

Addition of Unsymmetrical Regents to ethylenic Double Bond

Addition of hydrogen halides (HX) - HCl, HBr, HF, HI

The addition of HX to a symmetrically substituted alkene yields the monohalide derivative.

H H
R-CH=CH-R + HX R C C R

H X

The addition of the H to either of the two ethylenic carbon of the symmetrical alkene , followed by the addition of the
halide to the other carbon leads to the same haloalkane.

When the HX is added to an unsymmetrical alkene, however, two products are possible. For example

H
CH3CH2 CH=CH2 + HCl CH3CH2CH2CH2Cl + CH3CH2 C CH3

Cl
1-chlorobutane 2-chlorobutane
(not obtained) (obtained)

Experimental results show that 2-chlorobutane is formed almost exclusively.

Mechanism:

Step 1 Eletrophilic attacks on the C=C by H+

H H
+ +
CH3CH2 CH3CH2CH-CH3 + CH3CH2CH2-CH2
C C H + H Cl
2o carbonium 1o carbonium
more stable unstable
The secondary carbonium is more stable and it is the intermediate formed. The mechanism of addition of
unsymmetrical reagents to an unsymmetrical alkene is therefore as follows.

Step 1
+
CH3CH2CH CH2 + H Cl CH3CH2CH CH2 (slow)
H
-
Step 2 Cl
+
CH3CH2CH CH2
CH3CH2CH CH2 (fast)
H
Cl H

All ionic addition to the ethylenic double bond follow this mechanism under normal condition.

Markownikoff’s Rule

Markownikoff’s rule is an empirical rule that predicts the product of addition of unsymmetrical reagents such as the
hydrogen halides to unsymmetrical alkenes.
The Markownikoff’s rule states that in an electrophilic addition reactions a proton (the electrophile) will bond to the
carbon in a double bond that already is bonded to the greater number of hydrogen atoms.
Electrophiles other than the proton can also react with alkenes and bond the carbon atom containing the most hydrogen.
Thus
Br-
Br
+
CH3CH=CH2 + H-Br CH3CH-CH3 CH3-CH-CH3

carbon with more Hs

This can be explained interms of the stability of the carbonium that is formed. The more stable the carbonium ion the
more it will be formed. The stability of the carbonium ion is found to be in the order tertiary (3°) > secondary (2°) >
primary (1°)
So if the two possible carbonium ions from an electrophilic attack are 1° and 2° then the more stable 2° carbonium
will be preferred.
Why is the trend of stability of carbonium in the order 3° > 2° > 1°? This can be explained by the phenomenom of
inductive effect.
Alkyl groups are electron-donating and give a positive inductive effect. The more the alkyl groups attached to the
carbonium carbon (carbon bearing the positive charge) the more stable the carbonium since the electron donating
effect reduces the positive charge and leads to a stable carbonium.
R
>

H
R > CH2+ R > C < R R > C < R
+ +
1o carnonium o
2 carbonium o
3 carbonium
least stable most stable
The charge density on the carbonium is thus reduced from 1° to 2° to 3° and the lower the charge density the more
stable the carbonium.

R
>

H
R > CH2+ R > C < R R > C < R
+ +
o
1 carnonium o
2 carbonium
charge density high 3o carbonium
least stable lowest charge density
most stable
Anti-Markownikoff’s rule
In the presence of perioxides,e.g. benzylperioxide, the addition of unsymmetrical reagents like the hydrogen halides
to alkenes do not follow the Markownikoff’rule and there is said to be anti –Markownikoff’s addition.

perioxide
CH3CH=CH2 + H-Br CH3CH2CH2Br

Addition of H2SO4: Hydration of Alkenes

Concentrated H2SO4 will add to alkenes to give alkyl hydrogen sulphate in the Markownikoff’s

fashion. Example

H
H3C C CH3
CH3CH=CH2 + H-OSO3H
OSO3H
Propene sulphuric acid isopropylhydrogen sulphate

The alkyl sulphonates are soluble in sulphuric acid solution. Dilution of the H2SO4 with water and then heating or
boiling hydrolyses the HSO4 yeilding alcohols.

H hydrolysis H
H3C C CH3 + H2O H3C C CH3

OSO3H OH
isopropylhydrogen sulphate isopropyl alcohol
(2-propanol)

Another reagent that can also end add to the ethylenic double bond is HCN

Hydroboration-oxidation

Alkenes react with diborane (B2H6) to yield trialkylborane. The trialkylborane can be oxidized with H 2O2 to give and
alcohol with water (H and OH) added in anti Markownikoff’s orientation. Diborane can be represented as BH3.

H3C H H
H
3 C C + BH3 H3C C C .B
H 3
H H H

H H
H H
H3C C C .B
+ H2O2 3 H3C C C H + BO33-
3
H H H OH

Addition of Carbene to Alkenes

Singlet methylene prepared by photolysis (cleavage by light) of diazomethane

(CH2N2) is a very reactive intermediate and react easily with the C=C to yield cyclopropane
 - + hv
H2C N N :CH2 + N2

H2
C
CH3CH=CH2 + :CH2 H3C C CH2
H
methylene singlet methylcyclopropane

Oxidation of Alkenes

Oxidation agents are electron deficient, hence seek to gain electrons. The C=C is rich in electrons, nucleophilic and it
is attacked readily by oxidizing agents

(1) Oxidation With Cold Dilute KMnO4

Oxidation with cold dilute, neutral aqueous KMnO4 yield vicinal diols.

H H
CH3CH=CHCH3 + KMnO4 H3C C C CH3

OH OH
a vicinal diol

This reaction is can be used as a test for c=c bond. The purple colour of the KMnO 4 is discharged when a drop of
KMnO4 is added to a solution of an alkene.

Oxidation Of Alkenes With Hot Concentrated KMnO4

Oxidation of alkenes with hot concentrated KMnO4 causes the clearage of the molecule at the C=C into fragments
(Drastic oxidation). The oxidation product yields depend on the nature or structure of the alkene.

(a) Terminal alkenes gives CO2 and H2O and a carboxylic acid

CH3CH=CH2 + KMnO4 H3C + H2CO3 CO2 + H2O

OH

(b) Non terminal alkenes give only carboxylic acid

O O
[O]
CH3CH2CH=CHCH3 H3CH2C C OH + HO C CH3
drastic

(c) Alkenes with an alkyl or aryl substituent on the double bonded c will give a ketone.

O
[O] +
CH3CH2 C CH2CH3 CH3CH2C=O HO C CH3

CH3 CH3

(d) Dienes, trienes etc may yield dicarboxylic acid in addition to the other products

CH3CH2CH=CHCH2CH2CH=CHCH3 CH3CH2COOH + HOOCCH2CH2COOH + HOOCCH3

Oxidation With Ozone (ozonolysis)

Ozonolysis also results in the cleavage of the double bond. But the extent of oxidation is less than oxidation with
KMnO4. Oxidation with ozone yields aldehydes instead of carboxylic acids and terminal alkenes do not produce CO 2
and H2O.

O O
O
H3C 2[H]
CH3CH=CH2 + O3 CH CH2 H3C C H + H C H
Zn/acetic acid
O O
ozonide ethanal methanal

O O O
2[H]
H3C C CHCH2CH=CH2
O3
ozonide
H3C C O + H C H2
C C H
+ H C H
Zn/acetic acid CH3
CH3
propanone a dial methanal
malonaldehyde

Polymerization Of Alkenes

Polymerization is the whereby many small molecules link themselves up to form giant molecules consisting of many
repeating units of the original molecule. The original molecule is known as a monomer while the giant molecule is
called a polymer.

n C C * C C *
n

A number of alkenes undergo polymerization. monomer polymer

A typical example of alkene polymer is polyethene.

H H H H

n C C * C C *
n
H H
H H
ethene polyethene

Example of alkenes are listed in the table below.

 Monomer Repeating unit Polymer name Uses
film, toys, bottles
-CH2-CH2-
polyethene
CH2=CH2

H2 H polyvinylchloride phonograph records, vinylplastics

H2C CH C C flooring
Cl Cl

lubricating oils, sealants

H2 H poly(isobutylene)
H2C C CH3 C C CH3
CH3 CH3

H2 H rugs, blankets, yarn, apparel

H2C CH C C polyacrilonitrile simulated fur
orlon, acrilan
CN CN

F2 F2 poly(tetrafluoroethylene) nonsticking surfaces, liners,

CF2=CF2 C C Teflon cable insulations
H2 H
H2C CH C C
polystyrene packaging, toys, appliances, disposable
food containers

poly(vinylacetate) latex paints, adhesives

CH H2 H
H2C C C
OCOCH3
OCOCH3

H2C C CH3 CH3 poly(methylmethacrilate) lighting fixtures, signs,

H2
C C plexiglas, lucile solar panels, skylights
OCOCH3
OCOCH3

Mechanism of polymerization
Polymerization of alkenes involves three steps, initiation, propagation and termination steps.

Step (1) : Initiation step

For peroxide catalysed polymerization, the initial free radicals are formed by the homolytic bond fission of the O-O
bond in a peroxide molecule.

R O O R R O + O R

Step (2) : Chain propagation step

The 'alkoxy radical' adds onto an alkene molecule. If you split open half the alkene double bond (i.e. one bond pair),
one electron pairs up with the unpaired electron of the 'alkoxy radical' to form a C-O bond. The other electron remains
unpaired at the end of the radical, so that one active free radical is replaced by another.

R O H2C CH2 R O CH-CH2

Step (3): Subsequent chain propagation

Illustrates all the further subsequent chain propagation steps in which the polymer free radical adds onto another
monomer alkene molecule to make the chain longer and longer.
R O CH-CH2 H2C CH2 R O CH-CH2-CH2-CH2

R O CH2-CH2-CH2-CH2 + n H2C CH2 R O CH2-CH2-CH2-CH2 [CH2-CH2]n-1-CH2-CH2

Step (4) chain termination step

Here the electrons of two free radicals pair up to form a covalent C-C bond.

R O CH-CH2 [CH2-CH2]n-CH2-CH2 + CH2-CH2 [CH2-CH2]m CH-CH2 O R

R O CH2CH2-[CH2CH2]n-CH2-CH2-CH2-CH2-[CH2-CH2]m-CH2-CH2 O R