ALKENE

General Characteristic

The alkenes have at least one double bond consisting of a

sigma and a pi-bond between two adjacent carbons in the
molecule.

The two carbons are sp2 hybridized. The geometrical

shape of the two sp2 carbons is ‘trigonal planer’.

The Pi bond is much weaker than the sigma bond.

The alkenes are more reactive than alkanes.

In a molecule that has pi-bonds and sigma bond, the pi-

bond breaks without disturbing the sigma bond, during
chemical reactions.

The general formula for alkenes with only one double bond
in the molecule is CnH2n where n is the number of carbon
atoms in the molecule.

The alkenes are more reactive than alkanes.

The pi-bond is electron deficient hence alkenes are more

acidic in nature.

Structures of Alkenes

Few structure of alkene are shown below:

Physical Properties

• They follow the same trend as alkanes.

• Physical state depends on molecular mass.
• The ethene to butene are gases and pentene onwards are
liquids.
• The simplest alkenes, ethylene, propylene and butylene
are gases.
 • Linear alkenes of approximately five to sixteen carbons are
liquids.
• The higher alkenes are waxy solids.
• The boiling point increases with molecular mass.
• The branching reduces the boiling point.
• The alkenes are slightly soluble in water.
• Their density is lower than water.

Physical properties of Alkynes

Alkynes are compounds containing at least one carbon to

carbon triple bond. The trend in physical properties is similar to
alkanes and alkenes. They are slightly more reactive, more polar,
more acidic and more soluble than alkenes.

Stability of alkenes

• The order of stability is opposite to the order of reactivity.

It means that “less stable is more reactive” and vice versa.
• The stability pattern is related to the number of alkyl
groups attached to carbon of double bond.
• Higher the number of attached alkyl groups greater is the
stability of alkenes. It means that the more highly
substituted the carbon atom of the double bond greater is
the stability of alkenes.
• The following trends are noticed.
 However the rule of ‘less stability more reactivity ‘is not followed in
certain addition reactions of alkenes.(Discussed in later section)
The most stable alkenes are most reactive when mixed with
electrophile. The above order is nearly reversed when alkenes reacts
with an electrophile.
Synthesis of Alkenes

The preparation of alkenes is dominated by elimination

reactions. The two most common alkene formation reactions
are dehydrohalogenation of alkyl halide and dehydration of
alcohols. Some of these reactions follow Saytzeff rule.

Elimination reaction

Elimination reaction is the reaction in which one or two

function groups are removed and the electrons left behind combined
to form a double bond.

Saytzeff rule

The rule states that in dehydrohalogenation the preferred

product is the alkenes that has the greater number of alkyl group
attached to the doubly bonded carbon atoms.

Dehydrohalogenation of Alkyl halide

• The reaction is classified as elimination reaction.

• It may follow either E1 or E2 mechanism.
• E1 mechanism is a two step process and no strong base is
needed.
• E2 mechanism requires a strong and bulky base and
completes in one step.

Dehydrohalogenation: E1 Mechanism

• The reaction is completed in two steps

• The first step is a slow and rate determining step.
• Conversion of tert-butyl chloride to 2-Methylpropene is
explained as an example.
 • tert-butyl chloride is treated with 80% aqueous ethanol at
250C to give the product
• Over all reaction is

Initial step is formation of tert butyl cation. This is a slow step

1) Aided by polar solvent, chlorine leaves carbon with its bonded

electron pair.
2) The step also produces stable 30 carbocation and a chlorine ion.
3) The ions are solvated and stabilized by surrounding water
molecules.
4) The reaction is unimolecular.
5) In the 2nd step solvent molecule acts as base and pulls a B-
hydrogen as proton.

The electron pair moves in to form a double bond between α and β

carbon. The step produces the alkenes and a hydronium ion.

Dehydrohalogenation E2 mechanism

• It is a single step reaction.

• It is bimolecular reaction.
• It needs a strong base.
• Concentration of reactant is an important rate determining
factor.
• Synthesis of propene from isopropyl bromide follows E2
mechanism and is taken as example to explain the
mechanism.
• Isopropyl bromide is heated with sodium ethoxide in
ethanol to obtain propene.
Sodium ethoxide is prepared by using sodium hydride with excess of
alcohol which becomes solvent for the reaction.

Basic ethoxide ion starts removing a proton (by forming a

bond) from β-carbon
• It uses its electron pair to form a bond to proton.
• At the same time the electron pair of β-carbon and
hydrogen starts moving.
 • The bond which starts moving becomes pi-bond of the
double bond.
• The bromine begins to depart with bonded electron.
• In transition state partial bond exists between oxygen and
β-hydrogen.
• Another partial bond exists between α-carbon and
bromine.
• At this stage carbon – carbon bond is developing double
bond character.
• The double bond of alkenes is fully formed.
• The other products are ethanol and bromide ion.
• It has been noticed that if the base is very bulky the
reaction does not follow Saytzeff rule and a least
substituted alkene is formed.

Synthesis of alkenes by dehydration of alcohol

• Dehydration means elimination of a water molecule.

• In this reaction a water molecules is removed from alcohol
• The relative ease off dehydration of alcohol is
30 > 20 > 10 > methyl.
• The dehydration is done using a strong acid at high
temperature.
• The temperature and acid concentration depends upon
type of alcohol. ( primary secondary or tertiary )
• The mechanism of reaction is Elimination type E1.
• The rate of reaction depends upon the concentration of
alcohol.
• The reaction is completed in three steps.
• The dehydration of tert-butyl alcohol is explained as an
example.
• The first step is an acid base reaction.
• A proton is transferred from an acid to one of the
unshared electron pair of oxygen of alcohol group.
• The proton produces a positive charge on oxygen of
protonated alcohol.
• Presence of positive charge weakens all bond from oxygen
including C – H bond.
• The 2nd step is slowest step and rate determining step.
• In this step carbon and oxygen bond breaks leaving
behind a water molecule.
 Carbon-oxygen bond undergoes heterolytic cleavage.
• This leaves a carbocation which is highly reactive.
• The ease of formation of carbocation is 30 > 20 > 10>
methyl.
• In 3rd step carbocation transfers a proton to water
molecule.

• Step three is also an acid base reaction and any one of the
nine hydrogen atoms can be transferred to water molecule.
• The double bond is formed by the electron pair left behind
by proton.

Hydrogenation of Alkenes

Hydrogenation is a reaction in which hydrogen is added

to alkenes and a saturated hydrocarbon is formed. The reaction
becomes faster if carried in presence of catalyst. The reaction which
takes place in presence of catalysts is called catalytic hydrogenation.

Catalytic hydrogenation

Catalyst used for catalytic hydrogenation is

heterogeneous catalyst. A catalyst is called heterogeneous when its
physical phase is different from the reactant or the product. The
catalyst used for catalytic hydrogenation is finely divided platinum,
nickel or palladium. The hydrogen atom is added to the same side of
alkene molecules. This mode of addition is called syn addition.

Characteristic of hydrogenation

It is an exothermic reaction. It has high energy of

activation. The energy of activation is reduced in presence of a
catalyst. The reaction can be highly selective in choosing a double
bond. It can be made to choose one particular double bond out of two
present in order to convert into a single bond.
Heat of hydrogenation

It is the quantity of heat evolved when one mole of

unsaturated (alkenes or alkynes) compound is hydrogenated. The
lower the heat of hydrogenation higher is the stability. Hence it can
be used to compare the relative stability of alkenes

Syn addition of alkynes produces alkene

Oxidation of Alkenes

Some of the oxidizing agents convert alkenes into 1,2-diol

which is also known as glycol. Two hydroxyl groups get attached to
adjacent carbon bearing a double bond. The location of hydroxyl
group is always at two carbons bearing the double bond. This
property can therefore be utilized to detect location of double bond in
alkenes.
Ozonolysis of Alkene

It is a reaction in which a double bond is cleaved and

alkene molecule is completely broken into two smaller molecules.
The reagent used in the reaction is ozone hence the name Ozonolysis.

Ozonolysis is carried in two stages. In first stage ozone is

added to alkene to produce an intermediate known as ozonide. In the
second stage hydrolysis of ozonide produces the two products.
Ozonolysis of Alkynes produces carboxylic acid

Electrophilic Addition of Alkenes

A reaction in which two molecules combined to give a

single molecule of the product is called addition reaction.

Electrophile

Electrophile is a species which are electron loving so that

they will be attracted towards negative charge and they might carry a
positive charge however small it may be.

Positive charge may be even temporary due to any other

reagent or a temporary induced dipole. Double bond of alkenes is
electron rich species which will attract electrophile.
 In all electrophilic addition reactions, rate of formation of
carbocation depends upon its stability. It is because the higher
stability leads to faster formation, i.e. more stable carbocation is
formed faster in comparison to less stable. Thus the rate of addition
of hydrogen ion to double bond depends upon the stability of
carbocation being formed.

Addition of hydrogen halide to alkynes follows nearly the same

steps as in alkene

Markovnikokv’s rule

The rule is generally applicable to addition reaction

between halogen acid and unsymmetrical alkenes. The rule says that
if an unsymmetrical alkene reacts with hydrogen halide (HX) the
hydrogen of the acid will attach itself to the carbon of double bond
which has highest number of hydrogens.

The addition reaction takes places in two steps and it is an

electrophilic addition reaction. Mechanism is explained taking
addition of HBr to 2-Methylpropene forming tert-butyl bromide.
¾ The first is the slow and rate determining step.
¾ In the first step, hydrogen of acid is transferred as a proton
to alkene.
¾ Proton acts as an electrophile donated by the acid (HBr)
 ¾ Pi-electron of alkene forms a bond with proton and a 30
carbocation is formed.
¾ Note that a primary carbocation is not formed because
tertiary carbocation is more stable than a primary
carbocation.
In other words hydrogen attaches itself to the carbon which
has higher number of hydrogen.
¾ As proton leaves acid a bromide ion is formed.
¾ In the 2nd step carbocation reacts with bromide ion in which
carbocation acts as an electrophile.
¾ The final product tert-butyl bromide is also formed in 2nd
step.

Anti Markovnikov Rule

¾ The rule is applicable only to addition of hydrogen

bromine to alkene following the path of electrophilic
addition.
¾ The rule is applicable only in the presence of
peroxides.(the compound containing—O—O— linkage)
¾ In the presence of peroxide hydrogen does not follow
Markovnikiov rule.
¾ Hydrogen attaches itself to the carbon with less number
of hydrogen.
¾ The rule is not applicable to other halogens.

Hydration of alkene

The reaction takes place when water is added to alkenes in

presence of an acid. It follows Markovnikove rule and it is
electrophilic addition reaction. The product formed is an
alcohol.
 The reaction is reverse of dehydration of alcohols (discussed in
later section)
In dehydration the equilibrium is shifted to alkene by removal
of alkene from reaction mixture and in case of hydration it is
shifted to alcohols by high concentration of water. Low
temperature and dilute acid drive the reaction toward alcohols
whereas high temperature and concentrated acid drive toward
alkene formation.

Oxymercuration – demercuration

Alkenes react with mercuric acetate in presence of water

forming hydroxy-mercurial compound which on reduction gives
alcohol. The reaction is electrophilic addition reaction which follows
Marcovnicove rule.
The reagent is called mercuric acetate Hg(OAc)2 in solution it ionizes
into acetate ion and a positively charge mercuric species which is
very electrophilic.

Oxymercuration

Oxymercuration is the electrophilic attack of these spices

on a double bond, giving a three membered ring compound called
mercuriniumion.
Water molecule attacks the carbon with most positive charge (most
electrophilic carbon)

Nucleophilic oxygen present in water opens the mercurinium ring

and generates an organomercurial alcohol.
The electrophilic HgOAc+ gets attached to less highly
substituted carbon and –OH attaches itself to other carbon.
Demercuration

It is the removal of the mercury containing species, which is

achieved by reaction with Sodium borohydride, a powerful reducing
agent, which replaces the mercury species with a hydrogen atom –
giving the desired alcohol.

The new H and OH groups are on the opposite sides of the

double bond. This is called anti addition.

Alkoxymercuration-Demercuration

This is an extension of the previous reaction, where the

reaction is performed in the presence of an alcohol rather than water.

Hydroboration of Alkenes

Hydrboration is a reaction in which -OH group is added

to alkene. The reaction takes place in presence of paraoxide. It follows
anti Markovnikove rule.

Borane is added to alkenes with anti-Markovnikov orientation, and

these alkylboranes can then be oxidized to alcohols
Halogenation of Alkene

Halogens add to alkenes to give vicinal dihalides. Normally it

occurs with anti addition the halogen molecule (X2) which is
electrophilic - a nucleophile will attack one end, and displace a halide
ion.

Typically, a π bond will attack the bromine molecule kicking out

bromide ion and generating a bromonium ion. (3 membered
positively charged ring containing bromine).

This bromonium ring is then opened by back side attack of a

nucleophile (often the halide) to give the final product.
Halohydrin formation

Halogenation reaction in presence of water forms a

halohydrin. It is a compound containing halogen and hydroxyl on
adjacent carbon atom. Halogen attaches itself to the carbon with
higher number of carbon as per Markovnikove rule and it is also an
electrophilic addition reaction.

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