ALKENES

List of Topic
1. Unsturated hydrocarbons
2. Test for unsaturation
3. Alkenes
4. IUPAC nomenclature of Alkenes
5. Isomerism in Alkenes
6. Preparation of alkenes
7. Properties of alkenes
8. IMP points.

1)Unsaturated hydrocarbons:-

Unsaturated hydrocarbons are hydrocarbons have multiple bonding i.e. double or triple
covalent bonds, between adjacent carbon atoms.

Unsaturated hydrocarbons having double bonds are called alkenes while those having triple
bonds are known as alkynes.

2)Test for unsaturation:-

By Br2 in CCI4 : The decolorization of 5% Br2 in CCI4 by a compound confirms the presence
of unsaturation in molecule.

By Baeyers reagent : The decolorization of pink colour of 1% cold alkaline KMnO by

a compound confirms the presence of unsaturation in molecule.

Note :
1. Alkenes without any hydrogen atom on olefinic bond do not show these tests.
2. Aldehydes, primary and secondary alcohols which are readily oxidized by alk. KMnO4
and thus decolorize alk.KMnO4.

3)Alkenes:-

Alkene is an unsaturated chemical compound containing at least one carbon-to-carbon

double bond.
It is also called Olefin or Olefine.
The simplest alkene is ethylene (C2H4), which has IUPAC name ethene.

Alkenes (olefins) contains the structural unit >C=C< and have the general formula CnH2n.
These unsaturated hydrocarbons are isomeric with the saturated cycloalkanes.

Carbon atoms of alkenes involved in double bond are sp2 hybridized having trigonal planar
structure with an angle of 120o. The coplannar structure of ethene is shown in the below picture.

Alkenes have the following characteristic bond lengths and bond energy.

C=C =C-H

Bond length 1.34 A 1.108 A

Bond energy 143.1 kcal mol-1 98.69 kcal mol-1

4)IUPAC nomenclature of Alkenes:-

The IUPAC name is derived from the IUPAC name of alkanes by replacing ending 'ane' by
'ene' alongwith the position of double bonds.(e.g. alkane - ane + ene = alkene)

In case of two double or three double bonds, the ending 'ne' of alkanes is suitably replaced
by diene or triene accordingly.
Examples:-
CH3CH=C=CH2 : buta-1, 2-diene
CH2=CH-CH=CH2: buta-1, 3-diene
Alkenyl groups : Residual part left after the removal of one H atom from alkene is known as
alkenyl group. According to IUPAC nomenclature, these groups are named by replacing terminal 'e'
of alkene by 'yl'.
Examples:-

Group Trivial name IUPAC name

CH2=CH- Vinyl Ethenyl

CH2=CH-CH2- Allyl prop-2-enyl

-CH=CH-CH3 - prop-1-enyl

The numbering in alkenyl group is started from the carbon with free valencies.

5)Isomerism in Alkenes:-

The cis - trans system for alkenes:-

The C=C consists of a bond and a bond, in a plane at right angles to the plane
of the single bonds to each C. The bond is weaker and more reactive than the bond. The
reactivity of the bond imparts the property of unsaturation to alkenes; alkenes therefore readily
undergo addition reactions. The bond prevents free rotation about the C=C and therefore an
alkene having two different substituents on each doubly bonded C has geometric isomers. For
example, there are two 2- butenes (cis butene & trans butene).
The carbon-carbon double bond doesn't allow any rotation about it. That means that
it is possible to have the CH3 groups on either end of the molecule locked either on one side of the
molecule or opposite each other.
These are called cis-but-2-ene (where the groups are on the same side) or trans-
but-2-ene (where they are on opposite sides).

6)Preparation of alkenes:-

1. Dehydrohalogenation of vic-Dihalides or gem-Dihalides:-

2. Dehalogenation of vic-Tetrahalogen Compounds:-

3. Dehydration of alcohols:-

Heating most alcohols is a general method of preoarationof alkenes. Heating

alcohols with a strong acid causes them to lose a molecule of water (to
dehydrate) and form an alkene.

4. Kolbes electrolysis :

Electrolysis of aqueous solutions of sodium or potassium salts of saturated

dicarboxylic acids gives alkene.

5. Partial hydrogenation of alkynes:-

Hydrogenation of alkynes in presence of Lindlar catalyst gives alkenes.

CHCH CH2=CH2

RCCH RCH=CH2

7)properties of alkenes:-

a)Physical properties of alkenes:

All are colourless & have no characteristic odour. Ethene has pleasant smell
Lower members (C2 to C4) are gases, middle one (C3 to C17) are liquids, higher
are solids.
The boiling points, melting points, and specific gravities show a regular increase
with increase in molecular weight, however less volatile than corresponding alkanes.
A cis isomer has high boiling and melting point than trans isomer because of more
polar nature.
Like alkanes, these too are soluble in non polar solvents.
Alkenes are weak polar. The polarity of cis isomer is more than trans which are
either non polar or less polar. (e.g. Trans 2- butene is non polar; trans 2- pentene is
weak polar).

b)Chemical properties of alkenes:

Alkenes are more reactive than alkanes due to the presence of a double bond. The
carbon-carbon double bond consists of a strong bond and a weak () bond.The typical
reactions of alkenes involve the breaking of this weaker () bond,viz., and formation of two
sigma () bonds.

Such reactions are called addition reactions and are initiated by an electrophile,
proceeding through ionic mechanism. However, some addition reactions proceed through
free-radical mechanism.

Combustion:-
Alkenes, like alkanes, are highly combustible. Alkenes burn with a luminous
flame to give carbon dioxide and water. The flame becomes luminous because of
the higher carbon content of alkenes than alkanes. Their combustion reactions are
exothermic.

Addition reactions:-
The electrons of the carbon-carbon-double bond are available to an
electrophile (any species seeking electrons). Thus, the addition reactions
shown by alkenes are in fact electrophilic addition reactions.
Addition of Hydrogen:-
Alkenes add hydrogen in the presence of platinum or nickel catalyst, to form
alkanes. The reaction termed as hydrogenation, is an exothermic reaction.
CnH2n+ H2 CnH2n+2+ heat

This is known as Sabatier-Senderens reduction.

CH2=CH2+ H2 CH3-CH3+ 132.2 kJ

Addition of halogens:-
Alkenes react with halogens to form dihaloalkanes. The order of reactivity is,
chlorine > bromine > iodine. Simply mixing together the two reactants, usually in
an inert solvent like carbon tetrachloride, best carries out the reaction.

Addition of halogen acid:-

Alkenes with concentrated aqueous solution of halogen acids give

haloalkanes. The order of reactivity is,HI > HBr > HCl
For example:

Markownikoff's rule:- According to this rule negative part of the addendum

(adding molecule) gets attached to that carbon atom which possesses lesser
number of hydrogen atoms.

Peroxide effect:-When addition of halogen acid reaction is proceed under

the presence of peroxide ion the reaction gives the product perfectly opposite
product of Markownikoff's .Hence this effect is also called anti-Markownikoff rule.

8)IMP Points
Open chain, Unsaturated hydrocarbons with general formula (CnH2n).

At least one >c=c< (double bond) group i.e. sp2 hybridisation, is present throughout the chain.

Allene: alkene molecule in which at least one C has double bonds with each of the adjacent
carbon i.e. -c=c=c- group.

Isomeric with saturated cycloalkanes.

Geometric Isomers:
Z is used if the higher - priority substituents on each C are on the same side of the double
bond.letter E is used if they are on opposite sides

Heats of Hydrogenation: Heat of hydrogenation increases with increase in stability of alkene.

Order of heat of hydrogenation:1-Butene> cis-2-Butene > trans-2-Butene
Order of stability:1-Butene> cis-2-Butene > trans-2-Butene
Preparation:-

Cracking of petroleum:
Dehydrohalogenation of alkyl halides:RCH2CH2X + alc.KOH RCH = CH2
Dehydration of Alcohols :
Saytzeff Rule: In dehydration and dehydrohalogenation the preferential order for
removal of an H is 3 > 2 > 1
Reduction of alkynes:

Chemical Properties:
1. Electrophilic Polar Addition Reactions

Reagent Product
Name Structure Name Structure
Halogens Ethylene
X:X CH2XCH2X
(Cl2, Br2 only) dihalide
Hydrohalic acids H:X Ethyl halide CH3CH2X

Ethylene
Hypohalous acids X:OH CH2XCH2OH
halohydrin

Sulfuric acid (cold) H:OSO2OH Ethyl bisulfate CH3CH2OSO3H

Water (dil. H3O+) H:OH Ethyl alcohol CH3CH2OH

Borane
H2B:H Ethyl borane (CH3CH2BH2) (CH3CH2)3B

Peroxyformic acid H:O-OCH=O Ethylene

CH2OHCH2OH
(HCO3H) glycol
2.Addition of Hydrogen Halides to Alkenes: Markovnikovs Addition:

R - CH= CH2+ HBr R CHBr CH3

Mechanism:

R - CH= CH2+ HBr R CH+- CH3+Br-

R CH+- CH3+ Br- R CHBr- CH3

Anti - Markovnikovs Addition (Peroxide Effect):

R - CH= CH2+ HBr + (C6H5CO)2O2 R CHBr CH3

Mechanism:-

Initiation:

R - O - O - R 2RO.

RO.+HBr Br. +ROH

Propagation

CH3CH = CH2 + Br. CH3CH - CH2Br

CH3CHCH2Br + HBr CH3CH2CH2Br + Br.

Termination:

2RO. R - O - O - R

Br.+ Br.Br2

3.Addition of Water to Alkenes: Acid Catalyzed Hydration:

4. Oxymercuration-Demercuration:

Examples:

5. Hydroboration-Oxidation:

6. Halogen Addition in Non-polar Solvent:

7. Halogen Addition in Aqueous Medium:

8. Syn Hydroxylation: Formation of di-oles.

9. Ozonolysis of Alkenes: