CHEM 130: ORGANIC CHEMISTRY I

Dr. Alex Mugwiria Muthengi

CHAPTER 3 ALKENES

3.1 INTRODUCTION
Ethene, the simplest alkene, was known to chemists in the eighteenth century and was obtained
in pure form in 1795. A1kenes, also called olefins, are hydrocarbons which contain one or more
carbon-carbon double bond(s). Since alkenes evidently contain less than the maximum number
of hydrogen atoms, they are referred to as unsaturated hydrocarbons.
Alkenes are often found as plant products and in petroleum. Alkenes play many important roles
in biological systems. For example, hormones. A hormone is a compound that controls growth
and other changes in tissues. It is found in animals and plants. Ethene is a plant hormone which
plays an important role in seed germination, flower maturation, and fruit ripening.
Insects communicate by releasing pheromones. Pheromones are chemical substances that other
insects of the same species detect with their antennae. There are sex, alarm, and trail
pheromones, and many of these are alkenes.
Many of the flavours and fragrances produced by certain plants also belong to the alkene family.
In industries, many alkene containing monomers are used to prepare polymers. Alkenes are also
used as solvents.

In this unit, we will discuss structure of alkenes, their nomenclature, physical properties,
different methods for their preparation and finally, we will study their important chemical
reactions.

3.2 CLASSIFICATION OF ALKENES

Alkenes can be classified on the basis of the number of double bonds present in the molecule.
Hydrocarbons containing one carbon-carbon double bond are called monoenes. The monoenes
have the general formula CnH2n.
Hydrocarbons containing two double bonds are called diolefins or alkadienes or dienes. They
have the general formula CnH2n-2 and are isomeric with alkynes. Trienes have three double bonds
and tetraenes have four double bonds. The term polyene is used for hydrocarbons containing
more than four double bonds.

Dienes are divided into three main classes depending on the relative positions of the two double
bonds in the molecule: isolated or non-conjugated dienes, conjugated dienes and cumulated
dienes. In conjugated dienes, the two double bonds are separated by a single bond. A typical
conjugated diene skeleton is given below:
─C=C─C=C─
conjugated diene

1
In isoiated dienes, the two double bonds are separated by more than one single bond for which
two typical skeletons are given below:

─C=C-C─C=C─ ─C=C─C─C─C=C─
isolated diene isolated diene
(two single bonds between (three single bonds between
two double bonds) two double bonds)
In cumulated dienes, there are two double bonds around the same carbon atom; a typical skeleton
is given below:

─C=C=C─
cumulated diene (allene)
Compounds that contain cumulated double bonds are known but are not common. The
conjugated dienes are the most important among the dienes. They show certain reactions that are
not shown by monoenes or other dienes. Thus, in this unit, we shall concentrate our attention on
monoenes and conjugated dienes.

3.2.1 Structure of Monoene

The carbon-carbon double bond is both an important structural unit and an important functional
group in organic chemistry. The shape of the organic molecule is influenced by the presence of
the double bond which is also the site of most of the chemical reactions that alkenes undergo. So
it is necessary to understand the structure of these molecules.

Carbon-carbon double bond is the distinguishing feature of the monoenes and dienes. You have
already studied about the bonding of monoenes in Unit 1 of this course and learnt that the carbon
atoms involved in double bond formation are sp2 hybridised. The bond angle around the sp2
hybridised carbon atoms is 120˚ (Figure 4.1). Bonding in dienes with isolated double bonds is
similar to monoenes.

sp2

sp2
C

120o
sp2

Figure 4.1 sp2 hybridisation.

2
SAQ1

Fill in the blank in the spaces given below:

(i) Polyenes contain more than …………. double bonds.

(ii) Double bonds that alternate with single bond are ……………. dienes.

(iii) In allene the central atom is ……………. hybridised and the terminal atoms are
…………………. hybridised.

3.3.1 NOMENCLATURE OF ALKENES

The nomenclature of alkenes follows the same rules as those followed in the nomenclature of
alkanes.

The base name is determined by selecting the longest continuous chain that contains the double
bond. The ending of the base name is –ene. Some examples are:

CH3CH=CH2 propene

CH3CH2CH=CH2 butene

CH3CH2CH2CH2CH=CH2 hexene

The longest chain is numbered such that the smallest number possible is given to the carbons of
the double bond. The numbers of the first carbon of the double bond is used as a prefix in the
name to indicate the position of the double bond in the molecule. Some examples are:

1 2 3 4
CH2=CHCH2CH3
1-butene or but-1-ene

1 2 3 4 5 6
CH3CH=CHCH2CH2CH3
2-hexene or hex-2-ene

1 2 3 4 5 6
CH3CH2CH=CHCH2CH3
3-hexene or hex-3-ene

The locations of substituent groups are indicated by the number of the carbon atoms to which
they are attached. Some examples are:

CH3

3
 │
CH3C=CHCH3
1 2 3 4
2-methyl-2-butene or 2-methylbut-2-ene

CH3
│
CH3C=CHCH2CHCH3
1 2 3 4 │5 6
CH3
2,5-dimethyl-2-hexene or 2,5-dimethylhex-2-ene

CH3
│
CH3CH=CHCH2CHCH3
1 2 3 4 │5 6
CH3
5,5-dimethyl-2-hexene or 5,5-dimethylhex-2-ene

The numbering of the carbon of the double bond takes precedence over the
numbering of alkyl groups or halogen substituents.

Substituted cycloalkenes are numbered such that the carbon atoms of the double bond are given
the 1- and 2-positions and also giving the carbon atoms with substituent groups the lower
numbers at the first point of difference. Some examples are:

CH3 1
1 6 2
2 3
H3C 5 CH3
4

1-methylcyclopentene 3,5-dimethylcyclohexene
Not 2-methylcyclopentene

The position of the first carbon atom of the double bond is taken to be always
number one, this is not indicated in the name.

3.3.1 Geometrical Isomers

For disubstituted alkenes, the prefixes cis- and trans- are used.

4
cis- is used when the substituents are on the same side of the double bond and trans- is used
when they are on opposite sides of the double bond. Some examples are:

H3C CH3 H3C H

H H H CH3
cis-2-butene trans-2-butene

Cl Cl Cl H
C C
H H H Cl
cis-1,2-dichloroethene trans-1,2-dichloroethene

For tri- and tetrasubstituted alkenes, the Cahn-Ingold-Prelog convention (sequence rule) is used.

This is done by assigning priorities based on the atomic numbers of the atoms bonded to each
carbon of the double bond. The rules for a branched chain require that we follow the chain with
the highest priority atoms. If the same numbers are on the same side of the double bond, then
(Z)- is used otherwise (E)- is used. Some examples are:

1 Cl 2 1 2
H Cl H
C C

C C
1 Br H 2 2 H Br 1

(Z)-1-bromo-2-chloroethene (E)-1-bromo-2-chloroethene

1 2
Cl Cl
(E)-1-bromo-1,2-dichloroethene
H Br
2 1

5
 1
Br H 2
1
2 1
1

H H
2 2

3-bromo-(3Z,5E)-octadiene

3.4 PHYSICAL PROPERTIES

In general, the physical properties of alkenes are similar to those of the corresponding alkanes.
Like alkanes, the boiling points of a homologous series of alkenes increase 20-30˚C per CH2
group except for the very small homologues. Like alkanes, branching in an alkene also lowers
the boiling point. Lower alkenes, from ethene to butene, are colourless gases, higher ones, from
C5-C15, are liquids and the rest are solids at room temperature.

Alkenes are slightly more soluble in water than the corresponding alkanes because the π-
electrons are attracted to the partially positive hydrogen of the water molecules.

3.5 PREPARATION OF ALKENES

Synthetically, alkenes are prepared by introducing a double bond in saturated hydrocarbons

through elimination of atoms or groups from two adjacent carbon atoms. The result is the
formation of a double bond between these two carbon atoms.

Alkenes can be prepared from alkyl halides, alcohols and ketones and through cleavage
reactions. Some important methods for the preparation of alkenes include:

1. Dehydrohalogenation of alkyl halides

2. Dehydration of alcohols

Let us discuss each method in detail.

3.5.1 Dehydrohalogenation of Alkyl Halides

Alkyl halides are converted into alkenes by dehydrohalogenation. Dehydrohalogenation

involves elimination of the halogen atom together with a hydrogen atom from an adjacent carbon
atom. The elimination is brought about by treating the alkyl halide with a strong base. For
example, bromoethane yields ethene when treated with potassium hydroxide in alcoholic
solution.
KOH
6
 CH3CH2Br CH2CH2 + HBr + H2O
bromoethane C2H5OH ethane
The function of hydroxide ion is to abstract hydrogen from the carbon atom next to the halogen
bearing carbon. The carbon halogen bond then cleaves resulting in double bond formation.
- X -

C C C C + X + H2O
H

OH

Ease of dehydrohalogenation of alkyl halides is: tert > sec > pr

The alkyl halides, in which halogen is attached to a terminal carbon, yield a single alkene but
alkyl halides in which the halogen atom is attached to a non-terminal carbon atom and both
adjacent position have hydrogen atoms yield a mixture of alkenes. For example:
KOH (alc)
CH3CH2CH2Cl CH3CH=CH2
chloropropane propene

Cl
| KOH (alc)
CH3CH2CHCH3 CH3CH=CHCH3 + CH3CH2CH=CH2
2-chlorobutane 2-butene 1-butene
(major) (minor)

In the first reaction, chloropropane can lose hydrogen only from C2; therefore, it gives only one
product, i.e., propene. However, in the second reaction, 2-chlorobutane can lose hydrogen from
any of the two-β-carbon atoms and, hence, it gives a mixture of 2-butene (80%) and 1-butene
(20%). Now you may ask why 2-butene is the major product? Dehydrohalogenation follows
Saytzeff rule which says that the more highly substituted alkene is the dominant product.

3.5.1.1 Stability of alkenes

The stability of alkenes follows the following sequence:

R R R R R H R H

> > >

R R R H R H H R

R R R H H H

> > >

H H H H H H

7
3.5.2 Dehydration of Alcohols

An alcohol is converted into an alkene by dehydration, i.e., elimination of a molecule of water.

Dehydration requires the presence of an acid and the application of heat. The alcohol is heated
with sulphuric or phosphoric acid to a temperature as high as 200°C. Dehydration is also
brought about by passing the alcohol vapour over alumina (Al2O3) at 350-400°C. For example:

95% H2SO4
CH3CH2OH CH2=CH2
ethanol ethene

In case of secondary and tertiary alcohols other than 2-propanol, there exists the possibility of the
formation of more than one alkenes. For example, in 2-pentanol, hydrogen elimination can occur
either from C1 or C3. The direction and the rate of reaction again follows the Saytzeff rule and
hence 2-pentene, the more substituted alkene, is the major product and 1-pentene the minor one.

OH
│
CH3CH2CH2CHCH3 CH3CH2CH=CHCH3 + CH3CH2CH2CH=CH2
2-pentanol 2-pentene (major) 1-pentene (minor)

The ease of dehydration of various alcohols has been found to follow the order:
tert > sec > pr

This will be delt with later when dealing with the reactions of alcohols

3.5.3 Preparation of Dienes

Methods for Preparation of Dienes: Dienes are usually prepared by adaptation of the method
used to make simple alkenes. For example, 1,4-dihydroxybutane on treatment with sulphuric
acid gives 1,3-butadiene.

H2SO4
HOCH2CH2CH2CH2OH CH2=CHCH=CH2
1,4-dihydroxybutane 1,3-butadiene

1,3-Butadiene can also be prepared from butane by the cracking process using Cr2O3.

SAQ2

Write equations for the preparation of alkene from the following starting material(s). If there is
more than one product indicate the major one.

8
 Br
|
a) CH3CH2CHCH3
…………………………………………………………………….

CH3
│
b) CH3─C─CH2─CH3
│
OH

3.6 REACTIONS OF ALKENES

Let us first look at some terms which are used in organic reactions before we look at the
reactions of alkenes. Organic ionic reactions involve the reaction of an electron rich reagent and
an electron deficient reagent so as to form a sigma bond. The electron rich reagent is known as a
nuclephile. A nucleophile is a nucleus loving reagent and has either a negative charge or a lone
pair of electrons. An electron deficient reagent is known as an electrophile. An electrophile is an
electron loving reagent and has either a positive charge or an electron deficient system within it.
Nuclephiles are also termed as bases and electrophiles are termed as acids.

When writing a reaction mechanism involving electrophiles and nuclephiles, a curley arrow (
) is used to indicate the movement of a pair of electrons. In this case, the arrow should
always be drawn moving from the nucleophile (where the electron pair is) towards the
electrophile (where the electron pair is needed). When this is done, a bond is either broken or is
formed.

When a carbon atom in a neutral molecule loses a pair of electrons, it forms a species with a
positive charge on that carbon. Such a species is referred to as a carbocation. For example:

CH3 CH3

H3C C CH2 + H+ H3C C CH3

nucleophile electrophile carbocation

A species with a negative charge on a carbon atom is referred to as a carbanion. A carbocation

acts as an electrophile and a carbanion acts as a nuclephile.

The double bond consists of a strong σ bond and a weak π bond; so most of the reactions of
alkenes would involve the breaking of this weaker bond.

+ X-Y

X Y
9
In addition reactions of alkene, the π-bond is broken and the electron pair comprising it, is used
in the formation of two new σ bonds. Thus, two sp2 hybridised carbon atoms are rehybridised to
sp3carbons. Compounds containing π bonds are usually of higher energy than those having σ
bonds. Consequently, addition reactions are usually exothermic processes.

In the region of the double bond, there is a cloud of electrons above and below the plane of
bonded atoms. The π electrons are loosely held by the nuclei and are thus easily available to
electron-seeking reagent. Such reagents are called electrophilic reagents or electrophiles and the
typical reaction of an alkene is the electrophilic addition. Some of the important reactions of
alkenes are:

(i) Catalytic Hydrogenation

(ii) Addition of Halogens
(iii) Hydrohalogenation
(iv) Addition of Water
(v) Addition of Concentrated Sulphuric Acid
(vi) Ozonolysis
(vii) Hydroxylation
(viii) Halohydrin Formation

3.6.1 Catalytic Hydrogenation

Hydrogen adds to alkenes in the presence of a metal catalyst such as nickel, palladium or
platinum to form alkanes.

catalyst
+ H2

H H
The process is called catalytic hydrogenation. Both the hydrogen and alkene are adsorbed on the
surface of the catalyst, and they are added on the same side (face) of the double bond. The kind
of addition is called a syn-addition. An example is:

catalyst
H3C CH3 Catalytic
H2 hydrogenation
is used H C CH3 commercially to
3 H H hydrogenate
double cis-1,2-dimethylcyclopentane bonds in
vegetable oils
to convert them to margarine and other cooking fats.

3.6.2 Addition of Halogens

10
Halogens are quite reactive towards alkenes. Treatment of alkenes with halogens gives
1,2-dihalogenated alkanes. For example:

CCl4
CH3CH=CHCH3 + Cl2 CH3CH─CHCH3
│ │
Cl Cl
2-butene 2,3-dichlorobutane

Bromine and chlorine are particularly effective electrophilic addition reagents. Fluorine tends to
be too reactive and difficult to control for most laboratory procedures and iodine does not react
with alkenes.

Mechanism

Although bromine is non-polar, it is nevertheless highly polarisable and, in the vicinity of the
nucleophilic double bond, the bromine molecule becomes polarised and hence a partial positive
charge (δ+) develops on one bromine atom and a partial negative charge (δ-) on the other. The π
electrons of alkene attack the positive end of the plarised bromine molecule, displacing bromine
ion and forming a cyclic bromonium ion.

-
 
C   + Br
Br-Br
Br
C +

The cyclic structure shields one side of the molecule and, for this reason, Br- attacks from the
opposite side of the already added bromine atom to give trans product. This process is known as
trans addition. This steric course of the reaction is important in case of alkenes which can give
rise to different isomeric products.

Br
-
+ Br C C

Br Br
Addition + of bromine is
extremely useful
for detection of carbon-carbon double bond. Rapid decolourisation of bromine solution serves as
a test for the presence of the carbon-carbon double bond in a compound.

11
 Br
CCl4
+ Br2 C C

Br
The red-brown colour of bromine disappears almost instantly if the alkene is in excess.
The reaction is carried out at room temperature in the absence of light to avoid
production of free radicals by the halogen.

3.6.3 Hydrohalogenation

An alkene is converted by hydrogen halide (halogen acid) into the corresponding alkyl halide.
For example:

+ HX
X H
As long as the alkene is symmetrical, we get only one product. In case of unsymmetrical
alkene, the position of attachment of nucleophile is governed by the nature of substituents.
Addition of HBr to 1-butene should give two products, i.e., 1-bromobutane and 2-bromobutane.

CH3CH2CH=CH2 + HBr CH3CH2CH2CH2Br + CH3CH2CHCH3

│
Br
1-butene 1-bromobutane 2-bromobutane

However, only one product, 2-bromobutane, is produced. Such reactions are called regiospecific
reactions. To explain the exclusive formation of the product, the Russian chemist Markownikoff
formulated a rule known after him as Markownikoff’s rule, which states that addition of a
hydrogen halide to an unsymmetrical alkene takes place in such a way that the negative part of
the reagent goes to that carbon atom of the alkene which carries the lesser number of hydrogen
atoms.

Regiospecific: Only one of the two directions of addition is observed.

Markownikoff’s rule can be explained on the basis of the relative stabilities of carbocations
which are of the order of tertiary > secondary > primary. Accordingly, the more substituted
carbocation is formed as an intermediate in preference to the less substituted one. For example,
in the addition of H+ to 1-butene, there exists the possibility of the formation of either a primary
or a secondary carbocation. Since, the secondary carbocation is more stable, addition of H+ gives
exclusively 2-bromobutane via the more stable intermediate.

12
   Br-
CH3CH2CH=CH2 + H─Br CH3CH2CH─CH2 CH3CH2CH─CH2
(2º carbocation, more stable) │
  Br
H─Br

Br-
CH3CH2CH2─CH2 CH3CH2CH2CH2Br
(1º carbocation, less stable)

Peroxide effect

You must be under the impression that addition to alkene always give Markownikoff’s product.
But it is not so. After an extensive study of the mechanism of addition of HBr to alkene,
Kharasch and Mayo found that in the presence of peroxide the product obtained was not the one
predicted by Markownikoff’s rule but it was contrary to the Markownikoff’s rule. Such additions
are sometimes referred to as anti-Markownikoff additions. Since the reversal of the addition
reaction is brought about in the presence of peroxides, it is known as the peroxide effect. For
example, the addition of hydrogen bromide to 1-butene in the presence of peroxides give 1-
brombutane rather than 2-bromobutane.

peroxide
CH3CH2CH=CH2 + HBr CH3CH2CH2CH2Br
1-butene ∆ or UV 1-bromobutane

The reaction intermediate in such additions is a free radical rather than a carbocation. The
mechanism is somewhat similar to that of halogenation of an alkane.

In the presence of peroxide, the reaction goes via the most stable free radical. The peroxide is
broken into free radicals by either heat or UV light. The generated free radical then reacts with
HBr to give ROH and Br.. The Br. radical then reacts with the alkene.

∆ or UV
(i) R─O─O─R 2 RO.

(ii) RO. + HBr ROH + Br.

(iii) Br. + CH3CH2CH=CH2 CH3CH2CHCH2Br (2˚ free radical is

more stable than 1˚ free radical)

(iv) CH3CH2CHCH2Br + HBr CH3CH2CH2CH2Br + Br.

SAQ3
Complete the following reactions:

13
 (a)
H H2

CH3 Pd

CCl4
(b) CH3CH2C=CHCH3 + HBr
│ r.t.
CH3

peroxide
(b) CH3CH2C=CHCH3 + HBr
│
CH3

3.6.4 Addition of Water

Addition of H2O to alkene is known as hydration of alkene. This reaction occurs when H2O adds
to alkenes in the presence of an acid catalyst to yield an alcohol.

H+
+ H2O
HO H

Like hydrohalogenation, addition of H2O to unsymmetrica1 a1kene follows Markownikoff’s

rule. For example:
H3C H3C
H+
CH2 H3C C OH
H2O
H3C H3C

Mechanism:

CH3
+
slow │
(i) CH3─C=CH2 + H─O─H CH3─C+ + H2O
│ │ │
CH3 H CH3

CH3 CH3
│ fast │ +
(ii) CH3─C+ + O CH3─C─OH2
│ │

14
 CH3 H H CH3

CH3 CH3
│ + fast │
(iii) CH3─C─O─H O CH3─C─OH + H3O+
│ │ │
H3C H H H CH3

Sometimes the intermediate carbocation may rearrange if it can form a more

stable carbocation. For example:

H H
│ │ +
CH3─C─CH=CH2 + H+ CH3─C─CH─CH3 (2º carbocation)
│ │
CH3 CH3

rearranges by migration of H-

H
+
│
CH3─C─CH─CH3 (3º carbocation,
│ more stable)
CH3
This 3º carbocation forms an unexpected alcohol.

Another method used to accomplish Markownikoff’s hydration of an alkene is oxymercuration-

demercuration. Alkene reacts with mercuric acetate in the presence of water to give hydroxy-
mercurial compounds that on reduction accomplishes demercuration and produces an alcohol.
The product of oxymercuration is usually reduced with sodium borohydride (NaBH4).
Oxymercuration-demercuration reaction usually gives better yield of alcohols than the addition
of water with H2SO4. In this method, rearrangement of carbocation does not take place and the
required alcohol is obtained. For example:
H2O
CH3─CH─CH=CH2 + Hg(OCOCH3)2 CH3─CH─CH─CH2
│ │ │ │
CH3 CH3 OH HgOCOCH3

CH3
NaBH4 │
CH3─CH─CH─CH3
OH- │
OH

15
3.6.5 Addition of Concentrated Sulphuric Acid

Cold concentrated sulhuric acid adds to an alkene to give an alkyl hydrogen sulphate which upon
hydrolysis yields an alcohol. For example:

H2O
CH3CH=CH2 + HOSO2OH CH3CHCH3 CH3CHCH3
│ ∆ │
OSO3H OH

The Markownikoff’s rule is followed.

3.6.6 Ozonolysis

In all the reactions of alkenes studied so far, the carbon skeleton of the starting material was left
intact. We have seen the conversion of the carbon-carbon double bond into new functional
groups (halide, alcohol, etc.) by adding different reagents, but the carbon skeleton was not
broken or rearranged. Ozonolysis is a cleavage reaction, i.e. a reaction in which the double bond
is completely broken and alkene molecule is converted into two smaller molecules.

Ozonolysis consists of two separate reactions, the first is oxidation of alkene by ozone to give an
ozonide; and the second is reduction of the ozonide to yield cleavage product.

O
C C Zn
+ O3 O+ O + Zn(OH)2
H3O+
O O

Some examples of ozonolysis are given below:

CH3 1. O3 CH3
CH3CH2CH=C CH3CH2CHO + O=C
CH3 2. Zn/H2O CH3
(an aldehyde) (a ketone)

1. O3
CH2=CHCH2CH3 CH2=O + O=CHCH2CH3
2. Zn/H2O
(an aldehyde) (an aldehyde)

16
 1. O3
CH3CH=CHCH3 2 CH3CHO
2. Zn/H2O
(an aldehyde)

The reaction is used to locate the position of the double bond in an alkene.
Dimethyl sulphide, (CH3)2S or Zn in acetic acid can also be used in the last step.

3.6.7 Hydroxylation
A1kenes are readily hydroxylated (addition of hydroxyl groups) to form a dihydroxy compound
(diol) known as glycols. The most popular reagent used to convert an alkene to diol is cold
alkaline aqueous solution of potassium permanganate or osmium tetroxide. For example:
H2O
(CH3)2C=C(CH3)2 + MnO4- (CH3)2C─C(CH3)2 + MnO2
cold │ │
HO OH

H3C CH3
C C
H3C
NaHSO3
CH3
(CH3)2C=C(CH3)2 + OsO4 O O
Os H2O
O O

CH3 CH3
│ │
CH3─C──C─CH3
│ │
OH OH

This addition reaction goes via five member rings. The addition takes place on the same side of
the ring and the end product has the –OH group cis. For example:

O H2O, OH-
+ MnO4- OH
O Mn O-
OH

17
 O NaHSO3
+ OsO4 OH
O H2O
O Os OH

O
osmate ester

The bonds of O-metal are the ones broken in the last step.
Osmium tetroxide is highly toxic and also expensive although it gives higher
yields.

If the reaction with KMnO4 is carried at high temperature, oxidative cleavage of the double bond
takes place. Some examples are:

KMnO4, OH- H+
CH3CH=CHCH3 2 CH3CO2- 2 CH3CO2H
∆

Terminal CH2 of an alkene is completely oxidized to CO2 and H2O. For example:

1. KMnO4, OH-, ∆
CH3CH2C=CH2 CH3CH2C=O + CO2 + H2O
│ 2. H+ │
CH3 CH3

CH3
O O
1. KMnO4, OH-, ∆ ║ ║
CH3─C─CH2CH2CH2CH2─C─OH
2. H+

This reaction can be used to locate the position of the double bond in an
alkene.

3.6.9 Halohydrin Formation

Alkenes react with halogens in the presence of water to give halohydrins. For example:

H2O
+ Br2
18 H3C Br

H3C HO H
 The reaction is anti-addition (see reactions with halogens) ie H2O and Br2 add
from opposite side of the double bond. The reaction follows Morkownikoff’s rule
(the halogen adds to the carbon atom with greater number of hydrogen atoms).

SAQ 3

Predict the products of the following reactions:

CH3
H2
(i)
Pt CH3
CH3 Br2
(ii)
H2O
CH3 CH3
Br2
(iii)
CCl4, r.t.
CH3
HCl
(iv)

CH3

HCl
(v)
peroxide
H2O CH3
(vi)
H+
CH3
CH3
1. O3
(ix)
2. Zn, H2O
CH3

3.7 SUMMARY

 Hydrocarbons containing one carbon-carbon double bond are known as monoene or

olefins. Hydrocarbons containing two double bonds are known as alkadienes or dienes:

19
 Dienes are divided into three classes, i.e., conjugated dienes, isolated dienes and
cumulated dienes.

 In general, the physical properties of alkenes are similar to the corresponding alkanes.

 Alkenes are generally prepared by the elimination of atoms or groups from the adjacent
carbon atoms. Two such reactions are dehydrohalogenation of alkyl halides and
dehydration of alcohols. The ease of dehydrohalogenation of alkyl halide or dehydration
of alcohol is:
tert > sec > pr

 The main reactions of alkenes are electrophilic addition reactions. These reactions
include addition of halogen, addition of alkyl halide, addition of water, etc.

 Alkenes can be oxidised by ozone, permanganate and osmium tetroxide. Alkenes on

ozonolysis give aldehydes or ketones and on oxidation give 1,2-diols.

3.8 TERMINAL QUESTIONS

1. Give a structural formula for the carbocation intermediate that leads to the principle product in
the following reaction:

CH3 OH CH3
+
│ H │ │
CH3─C─CH=CH2 + H2O CH3─C──CH─CH3
│ │
CH3 CH3

2. Identify the major alkene obtained on dehydration/dehydrohalogenation of each of the

following compounds:

CH3
│
(i) CH3─C──CHCH3 (iii) CH3CH2CHBrCH3
│ │
CH3 OH

CH3
│
(ii) CH3─CH2─C─CH3 (iv) CH3CH2CHCH2OH
│ │
Br CH3

3. Give the product formed when HBr reacts with 2-methyl-2-butene in presence of peroxide and

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in absence of peroxide.

4. Arrange the following alkenes in order of decreasing stability.

R2C=CR2; R2C=CH2; CH2=CH2; R2C=CHR; RHC=CHR; RCH=CH2.

3.9 ANSWERS

Self Assessment Questions

1. (i) and (ii) Refer to section 4.2

(iii) sp ; sp2

Br
│ alc. KOH
2. (a) CH3CH2CHCH3 CH3CH=CHCH3 + CH3CH2CH=CH2
∆ major

CH3 CH3
│ H+ │
(b) CH3C─CH2CH3 CH2=C─CH2CH3 + CH3─C=CHCH3 + H2O
│ │
OH CH3
Major

(c) H3 C CH3
C C
H3 C CH3

Br
H
│
3. (a) H (b) CH3CH2C─CH2CH3
H │
CH3
CH3

H Br
│ │
(c) CH3CH2C─CHCH3
│
CH3

H Br Br
(i) CH3 (ii) CH3 CH3
4. (iii)
H CH3 CH3
CH3 OH Br
21
 Cl
(iv) (v) (vi)
Cl OH
CH3 CH3
CH3
H
(vii) (viii) OH
OH
CH3
CH3 H

O
(ix) H C CH3
3
O

Terminal Questions

1. CH3C───CHCH3
│ │
CH3 CH3

H3 C CH3
2. (i) C C
H3 C CH3

(ii) CH3─C=CHCH3
│
CH3

(iii) CH3CH=CHCH3

(iv) CH3─C=CHCH3
│
CH3

3. Presence of peroxide: CH3CH─CHBrCH3

│
CH3

Br
│
absence of peroxide: CH3C─CH2CH3
│
CH3
4. Refer to sub-Section 4.5.1.1.

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