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UNIT 8: ALKENE
Contents
1.0 Introduction
2.0 Objectives
3.0 Main Content
3.1 Classification of Alkenes
3.2 Physical Properties
3.3 Preparation of Alkenes
3.3.1 Dehydrohalogenation of Alkyl Halides
3.3.2 Dehydration of Alcohols
3.3.3 Wittig Reaction
3.3.4 Preparation of Dienes
3.4 Reactions of Alkenes
3.4.1 Addition of Halogens
3.4.2 Hydrohalogenation
3.4.3 Addition of Water
3.4.4 Hydroboration
3.4.5 Ozonolysis
3.4.6 Hydroxylation

1.0 Introduction
Ethene, the simplest alkene, was known to chemists in the eighteenth century and was
obtained in pure form in 1794. Alkenes, 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. Many alkenes are
biologically active compounds. For example, ethene induces ripening in fruit.

2.0 Objectives
After studying this unit, you should be able to:
• classify the types of alkenes
• explain the structure of monoenes and dienes
• list their physical properties
• list the different methods for their preparation, and
• write down the important chemical, reactions of alkenes.

3.0 Main content

3.1 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 monenes. 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
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and tetraenes have four double bonds. The term polyene is used for hydrocarbons containing
more than four double bonds.

Skeletal, Positional, and Functional Isomerism in Alkenes and Alkynes

Alkenes and alkynes exhibit skeletal isomerism in which the carbon chain is varied and
positional isomerism where the position of the multiple bond is different. Functional isomers
differ in the class of compounds to which they belong. For example, functional isomers of an
alkyne could be a diene, cycloalkene, or bicyclic alkane.

Geometric Isomerism in Alkenes

A. Cis-Trans Isomerism
Alkenes in which there are two different groups on each of the double bonded carbons
are capable of exhibiting geometric isomerism. In the cis isomer, two identical or
comparable groups are on the same side of the double bond and in the trans isomer they
are on opposite sides. The pi-bond restricts rotation around the carbon-carbon double
bond and prevents interconversion of the two isomeric forms.
B. The E-Z System for Designating Configuration of Geometric Isomers
In the E-Z system,(E-trans- whereas Z-cis-)the two groups on each of the two carbons are
assigned a priority: higher priority, lower priority. If the two higher priority groups are
on opposite sides of the double bond being considered, the isomer is E; if they are on the
same side it is Z.

Geometric Isomerism
For geometric isomerism, each carbon in the double bond must have two different
attached groups.
• In 2-butene, each carbon has a hydrogen and methyl.

Cis- Trans-

• In 1-butene, the first carbon has two identical groups, hydrogens, and thus cis-
trans isomers do not exist.

• 1-bromopropene has two different groups on each carbon involved in the double
bond and exhibits geometric isomerism.

• 2-bromopropene and 3-bromopropene each have two identical groups on one of

the carbons and do not exhibit geometric isomerism.
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• 1-pentene has two hydrogens on one of the double bond carbons but 2-pentene
has two different groups on each of these carbons.

• In 2-methyl-2-pentene, there are two methyl groups on one of the double bond
carbons and geometric isomerism is not possible. In 3-methyl-2-pentene, each
carbon of the double bond has two different bonded groups. Notice that the cis
and trans designations are made on the basis of the longest chain of carbon and
whether it crosses the double bond in a cis or trans fashion.

3.2 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 20-30K per CH2
group except for the very 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 temperature. Alkenes are slightly more soluble in water
than the corresponding alkanes.

Structure of Monoenes and Dienes

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 and learnt that the carbon atoms involved in
double bond formation are sp2 hybridised. The bond angle around the sp2 hybridised carbon
atoms is 1200.

3.3 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.
Y
│ │ │
‒C‒C‒ -XY → ‒C=C‒ elimination
│
X
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Alkenes can be prepared from alkyl halides, alcohol and ketones and through cleavage reactions.
Some important methods for the preparation of alkenes are summarized in Table.

Preparation of alkenes
• Dehydrohalogenation of alkyl halides

│ │ │ │
‒C‒C‒ + KOH Alcohol → ‒C=C‒ + HX + H2O
│ │
H X

• Hydration of Alcohols
│ │ │ │
‒C‒C‒ Acid → ‒C=C‒ + HX + H2O
│ │
H OH

• Wittig reaction
│ │ │
‒C=O + Witting reagent → ‒C=C‒

3.3.1 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.
Thus, bromoethane yields ethene when treated with potassium hydroxide in alcoholic
solution.

CH3CH2Br + KOH/EtOH → CH2=CH2 + HBr + H2O

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.

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 nonterminal carbon atom and both
adjacent position have hydrogen atoms yield a mixture of alkenes.

CH3 CH2 CH2CH2Cl + KOH/EtOH → CH3CH2CH=CH2

In the first reaction, chlorobutane can lose hydrogen only from C2; therefore, it gives only
one product, i.e. 1-butene.
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CH3 CH2 CH(Cl)CH3 + KOH/EtOH → CH3CH=CH CH3 + CH3CH2CH=CH2 (Mixture)

2-butene 1-butene
(major) (minor)
However, in the second reaction, 2-chlorobutene 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.
In an alkene, a beta carbon atom(ᵦ) is the second carbon atom in a chain, following the
carbon atom directly attached to a fuctional group - alpha(ὰ)

3.3.2 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 475 K.
Dethydration is also brought about by passing the alcohol vapour over alumina (Al2O3) at
625-675 K, e.g., (Convert K to C is K-273.15)

CH3 CH2OH + 95%H2SO4/2000C → CH2=CH2

In the 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-butanol, hydrogen
elimination can occur either from C1 or C2. The direction and the rate of reaction again
follow the Saytzeff rule and hence 2-butenes, the more substituted alkene, is the major
product and 1-butene the minor one.

CH3 CH2 CHCH3 + H/H2O → CH3CH=CH CH3 + CH3CH2CH=CH2 (Mixture)

│ 2-butene 1-butene
OH (major) (minor)

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

3.3.3 Wittig Reaction

In 1954, George Witting reported a method of synthesising alkenes from carbonyl compounds.
This reaction is applicable to aldehyde and ketones and leads to replacement of carbonyl oxygen
by the group=CRR’ (where R and R’ are hydrogen or alkyl group).

This phosphonium salt further reacts with a strong base, which abstracts a weakly acidic α -
hydrogen to give alkylidenetriphenylphosphorane (the phosphorous ylide) commonly known as
the Wittig reagent.
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The phosphosrous ylide has a hybrid structure and it is the negative charge on carbon that is
responsible for their characteristic reactions.

The resulting phosphorous ylide attacks the carbonyl carbon to form betaine which often
undergoes elimination spontaneously to yield alkene.
Betain: A molecule having non-ajacent charges opposite.

Preparation of Dienes:
For example, 1, 4-dihydroxybutane on treatment with sulphuric acid gives 1, 3-butadiene.

HOCH2 CH2 CH2CH2OH + H2SO4 → CH2 =CHCH =CH2

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

CH3 CH2 CHCH3 + Heat/Cat. → CH3CH=CH CH3

+ Heat/Cat. → CH2 =CHCH =CH2
CH3CH2CH=CH2

3.4 Reactions of Alkenes

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.

│ │ │ │
‒C = C ‒ + XY → ‒C ‒ C ‒
│ │
X Y

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 hybridized carbon atoms are re-hybridized to
sp3 carbons. Compounds containing π bonds are usually of higher energy than those having σ
bonds.

3.4.1 Addition of Halogens

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

CH3CH2CH=CH2 + Br2 → CH3CH2CH(Br)‒CH2Br

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.
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3.4.2 Hydrohalogenation
An alkene is converted by hydrogen halide (halogen acid) into the corresponding alkyl halide.

CH3CH2CH=CH2 + HBr → CH3CH2CH(Br)CH3

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 propene should give two products, i.e, 1-bromopropane and 2-bromopropane.

CH3CH=CH2 + HBr → CH3CH2‒CH2Br ……..1

Unsymmetrical

CH3CH=CH2 + HBr → CH3CH(Br)CH3 ………2

However, only one product, 2-bromopropane, is produced. Such reactions are called
regiospecific reactions.
Regiospecific: Only one of the two directions of addition is observed. To explain the exclusive
formation of the product, the Russian chemist Markovnikoff formulated a rule know after him as
Markovnikoffs 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.

Peroxide Effect
You must be under the impression that addition to alkene always give Markovnikoffs 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 Markovnikoffs rule but it was contrary to the Markovnikoffs rule. Such additions
are sometimes referred to as anti-Markovnikoff additions. Since the reversal of the addition
reaction is brought about in the presence of peroxide, it is known as the peroxide effect. For
example, the addition of hydrogen bromide to propene in the presence of peroxides give 1-
bromopropane rather than 2-bromopropane.

3.4.3 Addition of Water

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

>C=C< + H2O → ‒C‒C‒

│ │
H OH
Like hydrogenation, addition of H2O to unsymmetrical alkene follows Markovnikoffs rule.

CH3CH=CH2 + H2O/cat. H2SO4 → CH3CH(OH)CH3

2-propanol

Another method used to accomplish Markovnikoffs hydration of an alkene is oxymercuration-

demercuration. Alkene reacts with mercuric acetate in the presence of water to give hydroxyl-
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mercurial compounds which on reduction accomplishes demercuration and produces an alcohol.

The products 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 .

CH3CH2CH=CH2 + H2O + Hg(OOCCH3)2 → CH3CH2CH(OH)CH2‒HgOOCCH3

CH3CH2CH(OH)CH2‒HgOOCCH3 + NaBH4 → CH3CH2CH(OH)CH3

2-butanol

3.4.4 Hydroboration
When an alkene reacts with borane, addition to the carbon-carbon double bond takes place to
yield an organoborane – a compound with a carbon-boron bond. The reaction is known as
hydroboration. Borane (BH3) itself is unknown but its dimmer, diborane (B2H6) behaves as if it
were the hypothetical monomer (BH3)2. This reaction is very facile and requires only few
seconds for completion at 272 K and gives organoboranes in very high yield.

CH2=CH2 + (BH3)2 → CH3CH2 ‒ BH2

Since BH3 has three hydrogen, addition occurs three times to produce triakylborane product e.g.
CH2=CH2 + CH3CH2 ‒ BH2 → (CH3CH2)2BH
CH2=CH2 + (CH3CH2)2 ‒ BH2 →(CH3CH2)3B

Organoborane are generally not isolated but are instead used directly as reactive intermediates
for further synthetic reaction. For example, oxidation of organoborane by alkaline H2O2 gives
corresponding alcohol.

3.4.5 Ozonolysis
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.

RR1 ‒C=CHR11 + O3 → RR1COOOCHR11 → RR1C=O + O=CHR11

Ozonide Ketone Aldehyde

Take note of the Branched which yields aldehydes and ketone and unbranched alkenes yields
both two aldehydes compounds.

3.4.6 Hydroxylation
Alkenes 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 of potassium permanganate or osmium tetroxide (OsO4).

CH2=CH2 + H2O/KMnO4(aq) →CH2‒CH2

│ │
OH OH
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3.4.7 Oxymercuration-demecuration
Alkenes react with mercuric acetate in presence of water to give hydroxymercurial compounds
which on reduction yields alcohols.

CH2=CH2 + H2O/Hg(OAc)2 → CH2 ‒ CH2 + NaBH4 → CH2 ‒ CH2

│ │ │ │
OH HgOAc OH H
-OAc = CH3COO-

The first stage, oxymecuration, involves addition to the carbon-carbon double bond of –OH and
–HgOAc. Then in demecuration, the –HgOAc is replaced by –H. The reaction sequence amounts
to hydration of alkene, but is much more widely applicable than direct hydration.

The two stage process of oxymercuration-demercuration is fast and convenient, takes place
under mild conditions, and gives excellent yields – often over 90%

The alkene is added at room temperature to an aqueous solution of mercuric acetate diluted with
the solvent tetrahydrofuran (THF). The organomercurial compound is not isolated but is simply
reduced in situ by sodium borohydride, NaBH4.

Oxymercuration-demercuration is highly regiospecific, and gives alcohols corresponding to

Markovnikov addition of water to the C-C double bond.

CH3(CH2)3CH=CH2 + 1. Hg(OAc)2/H2O/2. NaBH4 → CH3(CH2)3CH(OH) CH3

1-methylcyclopentene → 1-methylcyclopentanol

3.4.8 Polymerization of Alkenes

When ethylene is heated under pressure with oxygen, there is obtained a compound of high
molecular weight, which is essentially an alkane with a very long chain.

nCH2=CH2 + O2/∆/pressure → ‒CH2‒CH2‒CH2‒CH2‒ OR (‒CH2‒CH2‒)n

This compound is made up of many ethylene units and hence called polyethylene. The formation
of polyethylene is a simple example of the process called polymerization: the joining together
of many small molecules to make very large molecules – polymer. The simple compounds from
which polymers are made are called monomers.
Examples of organic peroxides:
• Peroxyacetic acid (PAA)
• Methyl ethyl ketone peroxide
• Benzoyl peroxide*

nCH2=CH + Peroxide → ‒CH2‒CH‒CH2‒CH‒ CH2‒CH‒ OR (‒CH2‒CH‒)n

│ │ │ │ │
Cl Cl Cl Cl Cl
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Analysis of Alkenes
1. In organic chemistry, the most common laboratory analysis method to identify alkenes is
the bromine water test, where an orange bromine water solution becomes colourless
when mixed with an alkene due to the addition reaction occurring at the double bond,
essentially “decolorizing” the bromine water; this is a qualitative test indicating the
presence of carbon-carbon double bond, characteristic of alkenes.

R‒C=C‒R + Br2/CCl4 → R‒CBr ‒CBr‒R

Alkene Red Colourless

Observation: When an alkene is added to bromine water, the orange color fades rapidly,
turning colorless.
Mechanism: The bromine molecule Br2 readily adds across the double bond of the alkene,
forming a colorless dibromoalkane.
Note: Alkanes do note react with bromine water, so the solution remains orange.

2. A cold, dilute, neutral permanganate solution (Baeyer’s test)

R‒C=C‒R + MnO4- → MnO2 + R‒COH ‒COH‒R

Alkene Purple Brown ppt Colorless
• In Baeyer’s test, an alkaline solution of potassium permanganate is added to a compound.
• If the compound contains an alkene, the solution’s color changes from purple to brown.
• This color change indicates the presence of unsaturated C-C bond.
• The alkene is oxidized to cis-1,2-diol and the permanganate is reduced to manganese
dioxide.