ALKENES

Alkenes are unsaturated hydrocarbons containing at

least one double bond.

general formula for alkenes is CnH2n.

Alkenes are also known as olefins (oil forming) since the first member, ethylene or
ethene (C2H4 ) was found to form an oily liquid on reaction with chlorine.
 Structure of alkenes

Carbon-carbon double bond in alkenes consists of one strong sigma (σ)

bond due to head-on overlapping of sp 2 hybridised orbitals and one
weak pi (π) bond obtained by lateral or sideways overlapping of the two
2p orbitals of the two carbon atoms.

The pi (π) bond is a weaker bond due to poor

sideways overlapping between the two 2p
orbitals. Thus, the presence of the pi (π) bond
makes alkenes behave as sources of loosely
held mobile electrons. Therefore, alkenes are
easily attacked by electrophilic reagents.
Nomenclature
Isomerism
Alkenes show both structural isomerism and geometrical isomerism.

Structural isomerism : As in alkanes, ethene (C2H4 ) and propene (C3H6 ) can have only one structure but alkenes
higher than propene have different structures
 Geometrical isomerism: ( a type of stereoisomerism)
the restricted rotation of atoms or groups around the doubly bonded carbon
atoms gives rise to different geometries of such compounds. The stereoisomers
of this type are called geometrical isomers.

The isomer, in which two identical atoms or groups lie on the same side of the
double bond is called cis isomer

the other isomer , in which identical atoms or groups lie on the opposite sides of
the double bond is called trans isomer
the cis isomer less symmetrical and the electron cloud distribution is more unequal. Therefore the cis isomer
is more polar than the trans isomer and has a slight permanent dipole - permanent dipole attraction between
molecules.

in the trans-but-2-ene, the two methyl groups are in opposite directions, Therefore, dipole moments of C-CH3
bonds cancel, thus making the trans form non-polar.

Thus the cis isomer has a higher boiling point than the trans isomer.

In the case of solids, it is observed that the trans isomer has higher melting point than
the cis form due to the symmetrical structure of trans isomer.
Preparation

1. From alkynes

2. From alkyl halides

3. From vicinal dihalides:

4. From alcohols by acidic dehydration:

1. From alkynes

partial reduction using Lindlar’s

catalyst – alkenes with cis geometry

Lindlar’s catalyst - Partially

deactivated palladised charcoal-
deactivated with poisons like sulphur
compounds or quinoline.

alkynes on reduction with sodium in

liquid ammonia form trans alkenes.
 2. From alkyl halides: - By dehydrohalogenation
Alkyl halides (R-X) on heating with alcoholic potash eliminate one molecule of halogen
acid to form alkenes
since hydrogen atom is eliminated from the β carbon atom , also called β-elimination reaction.

β carbon atom (carbon atom next to the carbon to which halogen is attached)

Nature of halogen atom and the alkyl group

determine rate of the reaction.
for halogens, the rate is: iodine > bromine >
chlorine,
for alkyl groups it is : tert > secondary >
primary.
3. From vicinal dihalides –by dehalogenation.

Vicinal dihalides on treatment with zinc metal lose a molecule of ZnX2 to form
an alkene. This reaction is known as dehalogenation.
Dihalides in which two halogen atoms are attached to two adjacent carbon atoms are
known as vicinal dihalides.
4. From alcohols by acidic dehydration:

Alcohols on heating with concentrated sulphuric acid form alkenes with the
elimination of one water molecule.

This is an eg. Of β-elimination reaction since –OH group takes out one hydrogen
atom from the β-carbon atom.
Physical properties

soluble in nonpolar solvents

regular increase in boiling point with increase in size

straight chain alkenes have higher boiling point than isomeric branched chain compounds.
 Chemical properties
Alkenes are the rich source of loosely held pi (π) electrons, due to which they show addition reactions in
which the electrophiles add on to the carbon-carbon double bond to form the addition products.

1. Addition of dihydrogen – Hydrogenation

2. Addition of halogens - Halogenation

Halogens like bromine or chlorine add up to alkene to form vicinal dihalides.

The reddish orange colour of bromine solution in carbon tetrachloride is discharged when bromine
adds up to an unsaturation site. This reaction is used as a test for unsaturation.

Addition of halogens to alkenes is an example of electrophilic addition reaction involving cyclic halonium
ion formation.
3. Addition of hydrogen halides - Hydrohalogenation

• Hydrogen halides (HCl, HBr,HI) add up to alkenes to form alkyl halides.

• The order of reactivity of the hydrogen halides is HI > HBr > HCl
• addition of hydrogen halides is also an example of electrophilic addition reaction.

Addition reaction of HBr to symmetrical alkenes by electrophilic addition

reaction.
Addition reaction of HBr to unsymmetrical alkenes (Markovnikov Rule)

The major product formed is determined by Markovnikov rule

- The rule states that negative part of the addendum (adding molecule) gets attached
to that carbon atom which possesses lesser number of hydrogen atoms.
 Mechanism

Step 1 : Formation of carbocation

Hydrogen bromide provides an electrophile, H+ , which attacks the double bond to form carbocation

More stable carbocation is formed at a faster rate

Step 2 : The carbocation (b) is attacked by Br– ion to form the product
Addition of HBr to unsymmetrical alkenes in the presence of peroxide - Anti Markovnikov addition or
peroxide effect or Kharash effect

(takes place contrary to the Markovnikov rule)

Mechanism : Peroxide effect proceeds via free radical chain mechanism

The peroxide effect is not observed in addition of HCl and HI. This may
be due to the fact that the H–Cl bond being stronge than H–Br bond, is
not cleaved by the free radical.

H–I bond is weaker and iodine free radicals combine to form iodine
molecules instead of adding to the double bond.
4. Addition of sulphuric acid
5. Addition of water

in accordance with the Markovnikov rule

 6. Oxidation

a) with cold, dilute, aqueous solution of potassium permanganate (Baeyer’s reagent) produce vicinal glycols.

Decolorisation of KMnO4 solution is used as a test for unsaturation.

b) Acidic potassium permanganate or acidic potassium dichromate oxidises alkenes to ketones and/or acids.
7. Ozonolysis :

Ozonolysis of alkenes involves the addition of ozone molecule to alkene to form ozonide, and then cleavage of
the ozonide by Zn-H2O to smaller molecules
8. Polymerisation:

The reaction by which large molecules are formed by the combination of simple compounds at high
temperature, high pressure and in the presence of a catalyst is known as polymerisation.

simple compounds from which polymers are made are called monomers

The large molecules thus obtained are called polymers