ELECTROPHILIC ADDITION

Alkenes are more reactive than alkanes because:

i) the π electrons are located further away from carbon nuclei and therefore less
firmly bonded to them.
ii) The overlap of p-orbitals is not as effective as that in sigma bond. Thus pi bond is
a weaker bond and can be easily broken.

A reaction in which two molecules combine to yield a single molecule of product is called an
addition reaction. The C = C bond is electron rich (Lewis base). Therefore, it can react with
electrophilic reagents.

MECHANISM OF ELECTROPHILIC ADDITION

General Reaction

Mechanism:
Step 1:
The pi electrons attack the electrophile (the positive part of the reagent, usually the H+) and
form a carbocation.

Step 2:
The nucleophile (the negative part of the reagent, usually X-, OH- etc) attacks the carbocation
to form the addition product.

ORIENTATION OF ELECTROPHILIC ADDITIONS: MARKOVNIKOV’S RULE

The orientation of electrophilic addition is shown in the following example.

ADDITION OF HALOGEN ACIDS

Alkenes react with halogen acids (HCl, HBr, or HI) to form alkyl halides. HX can add to the
double bond of an unsymmetrical alkene to give two structural isomers.

Example:
Propene can react with HBr in two different ways. The hydrogen has a partial positive
charge in HBr and therefore is the electrophile.
 (n-Propyl bromide)
Experimentally, it is observed that 2-bromopropane is the major product. After studying a
large number of such reactions, Vladimir Markovnikov put forward the following rule:

In the addition of an acid to an unsymmetrical alkene, the hydrogen of the acid attaches itself
to the carbon atom that has greater number of hydrogens.

MECHANISM:
Step 1:
HBr ionises to give a proton (electrophile) and a bromide ion.

Step 2:
Proton (H+) can attack propene to give a primary carbocation or a secondary carbocation.
The order of stability of carbocations is:

Therefore, secondary carbocation is formed predominantly.

.
Modern Markovnikov’s Rule
Electrophilic addition to a C=C bond involves the intermediate formation of the most stable
carbocation.
Step 3:
Bromide ion attacks the more stable secondary carbocation to give 2-bromopropane.

(ACTUAL PRODUCT)
(MARKOVNIKOV PRODUCT)

RELATIVE REACTIVITY OF ALKENES

In addition reactions, a carbocation reactive intermediate is formed. Electron releasing

groups disperse the partial positive charge developing on carbon and stabilise the transition
state. Stabilisation of the transition state lowers Eact and makes the reaction faster.

Alkyl groups are electron releasing and stabilise carbocations. More stable carbocation is
formed faster.

Example:

Isobutylene forms a tertiary carbocation, hence reacts faster than 2-butene, which forms a
secondary carbocation. Similarly 2-butene reacts faster than ethene, which forms a primary
carbocation.

Alkenes generally show the following order of reactivity toward addition of acids:

Electron withdrawing groups (ex. Halogens) intensify the positive charge and destabilise the
carbocation. Thus, vinyl chloride (CH2=CHCl) is less reactive than ethene (CH2=CH2).
ELECTROPHILIC ADDITION: REARRANGEMENT

Rearrangement of carbocations can occur during electrophilic addition reactions. A

carbocation will undergo rearrangement if it produces a more stable carbocation.

In the above example, a 1, 2 shift of a methyl group converts the initially formed secondary
carbocation into a more stable tertiary carbocation.

ANTIMARKOVNIKOV ADDITION (PEROXIDE EFFECT)

When alkenes react with HBr in the presence of peroxides an anti markovnikov addition
occurs. Here, the hydrogen attaches to the carbon that holds lesser number of hydrogens.
The anti markovnikov addition of HBr to alkenes caused by the presence of peroxides is
known as peroxide effect.
MECHANISM:
(ANTI MARKOVNIKOV / FREE RADICAL MECHANISM / PEROXIDE EFFECT)

Step 1:
Peroxide dissociates by homolysis to give alkoxy free radical

Step 2:
The alkoxy free radical abstracts hydrogen atom from hydrogen bromide to give bromine
atom

Step 3:
Bromine atom (a free radical) can attack propene to give either a primary free radical or a
secondary free radical.

.
The order of stability of free radicals is : 30 > 20 > 10 > H3 C
Therefore, a secondary free radical is formed predominantly.

Step 4:
The more stable secondary free radical abstracts hydrogen atom from HBr to give
1-bromopropane and bromine atom. The Bromine atom goes back to step 3.
Note:
HCl and HI do not give anti-Markovnikov products in presence of peroxides. This is because,

a) H-Cl bond is stronger than H-Br bond. It is not broken by the alkoxy free radicals obtained
from peroxides.
b) The H-I bond is weaker than H-Br bond. It is broken by the alkoxy free radicals, but the
iodine atoms formed readily combine with each other to yield I2 molecules rather than attack
the double bond in alkenes.

ADDITION OF HYDROGENS TO ALKENES

Alkenes react with Hydrogen in the presence of a catalyst to give alkanes.

Hydrogenation is of two types:

i) Heterogenous: the catalyst is finely divided metal e.g., Platinum, Palladium,
Nickel etc.

A catalyst lowers Eact by permitting the reaction to take place in a different

mechanism. In this case, the reactants are adsorbed on the surface of the
finely divided metal, where reaction occurs.

ii) Homogenous (one phase) : the catalysts are organic complexes of transition
metals like rhodium or iridium. They are soluble in organic solvents and thus
hydrogenation takes place throughout the solution.
Example: Wilkinson’s catalyst- tris (triphenylphosphine)chlororhodium.
HEAT OF HYDROGENATION AND STABILITY OF ALKENES

Hydrogenation is an exothermic reaction. The quantity of heat evolved when one mole of
unsaturated compound is hydrogenated is called as the heat of hydrogenation.

Heat of hydrogenation can give valuable information about the relative stabilities of
unsaturated compounds.

For example;
Cis-2-butene has heat of hydrogenation of 28.6kcal.
Trans-2-butene has a heat of hydrogenation of 27.6 kcal.

Both reactions consume one mole of hydrogen and yield the same product, n-butane.
Therefore, the trans isomer is more stable than the cis isomer by 1 kcal.

In case of simple alkenes usually the trans-isomer is more stable than the cis-isomer. The cis-
isomer is comparitively unstable due to the strain caused by the crowding of two alkyl groups
on same side of the double bond.

cis-isomer trans-isomer
ADDITION OF HALOGENS

Chlorine and bromine react with alkenes in the presence of an inert solvent (CCl4) to form
vicinal dihalides. Halogens add with complete stereoselectivity and by anti-addition.

Addition of bromine is used detection of unsaturation. A solution of bromine is red but the
dihalide is colourless. Rapid decolourisation of a bromine solution is characteristic of
compounds containing the C=C bond.

Mechanism:

Step 1:
The alkene polarises the bromine molecule. The more positive bromine atom is transferred
from bromine molecule to the alkene forming a cyclic bromonium ion.

Step 2:
Bromonium ion reacts with bromide ion to give the product.

ADDITION OF HYPOHALOUS ACID

Addition of chlorine or bromine in presence of water yields halohydrins. The net result is
addition of hypohalous acid. Orientation follows Markovnikov’s rule.
ADDITION OF WATER

Water adds to the more reactive alkenes in the presence of acids to give alcohols. This
addition follows Markovnikov’s rule.

ADDITION OF SULPHURIC ACID

Alkenes react with cold concentrated sulphuric acid to form alkyl hydrogen sulphates.
Addition of sulphuric acid follows Markovnikov’s rule. Since alkyl hydrogen sulphates are
soluble in sulphuric acid a clear solution is obtained. If it is diluted with water and heated an
alcohol is obtained. This is an excellent method for the large scale manufacture of alcohols.

Example:

HYDROXYLATION. GLYCOL FORMATION

Certain oxidising agents convert alkenes into 1,2-diols (also known as Glycols). Most
commonly used oxidising agents are:
1) cold alkaline potassium permanganate (KMnO4)
2) Peroxyformic acid (HCOOOH)

GLYCOL

Examples:

Since the purple colour of KMnO4 disappears during the reaction; it is used as a test for the
presence of a double bond (known as the Baeyer test).
OXYMERCURATION – DEMERCURATION

Alkenes react with mercuric acetate in the presence of water to give hydroxy mercurial
compounds which on reduction yield alcohols.

Oxymercuration involves electrophilic addition of –OH and –HgOAc with the C=C bond.
Mercuric ion acts as the electrophile. In Demercuration, the –HgOAc is replaced by –H,
using sodium borohydride (NaBH4).

Oxymercuration-demercuration process gives alcohols corresponding to Markovnikov’s

addition of water.

Example:

HYDROBORATION-OXIDATION

Alkenes undergo hydroboration reaction with Diborane (BH3)2, to yield alkylboranes.

Alkylboranes on oxidation give alcohols. In this reaction diborane acts as though it is borane.
(BH3). Boron has only six valence electrons and is the electrophile. It reacts with the double
bonds in a one step mechanism. Rearrangement does not occur in hydroboration because
carbocations are not intermediates. Hydroboration-oxidation process give alcohols
corresponding to anti-Markovnikov’s addition of water.

Example:

Borane itself is unstable, and exists either as a dimer or as a complex with tetrahydrofuran.
DIMERISATION AND POLYMERISATION OF ALKENES

Alkenes in the presence of strong acids can be made to polymerise. Depending on the
reaction conditions, either lower molecular weight products (dimers, trimers etc.) or high
molecular weight products (polymers) are formed.

Mechanism:

Step 1:
Proton adds to the double bond forming a carbocation

Step 2:
The carbocation adds to another molecule of alkene to form a larger carbocation.

Step 3:
The larger carbocation can lose a hydrogen atom in two different ways to form the products.
ADDITION OF ALKANES: ALKYLATION

Alkanes can also add to alkenes. For example, when Isobutylene and isobutane react in the
presence of an acidic catalyst, they form 2,2,4-trimethylpentane.

Mechanism:

Step 1:
Proton adds to the double bond forming a carbocation

Step 2:
The carbocation adds to another molecule of alkene to form a larger carbocation.

Step 3:
The carbocation abstracts a hydrogen atom from the alkane. This yields a new alkane and a
new carbocation to continue the chain. Abstraction occurs in such a way that yields the more
stable 30 carbocation rather than the less stable 10 carbocation.

then again step2, step3, step2, step3 etc.

FREE RADICAL POLYMERISATION OF ALKENES

Polymerisation is the joining together of many small molecules to form very large molecules.
Polymerisation requires the presence of a small amount of an initiator like peroxide.
When ethylene is heated under pressure with oxygen, a polymer called polyethylene is
produced. It is used in packaging films.

Similarly, vinyl chloride undergoes polymerisation to produce poly(vinyl chloride). It is used

to make phonograph records, plastic pipe, raincoats etc.

Mechanism:

EPOXIDATION

Alkenes react with peroxy acids to form epoxides. An epoxide is a three membered ring
containing an oxygen.
ADDITION OF CARBENES

Carbenes are neutral reactive intermediates having two single bonds and a pair of non-
bonding electrons. Carbenes are electrophiles because they must acquire a pair of electrons
to complete a stable octet. Example: Methylene ( :CH2)

Carbenes react with alkenes to form cyclopropanes. This kind of addition, in which a ring is
generated, is called cycloaddition.

Generation of carbenes:

1) Photolysis of Diazomethane or ketene:

Example:

2) Alpha elimination from Haloforms

Example:
 OZONOLYSIS

When an alkene reacts with ozone (O3), the double bond is broken and a carbon-oxygen
double bond is formed on each fragment of the molecule. This is called ozonolysis (cleavage
by ozone).

Ozone is an electrophile. It adds to an alkene to give an unstable cyclic compound called

molozonide. The molozonide later gives ozonide. Ozonides are unstable. They break up in
water in presence of a reducing agent like zinc or dimethyl sulfide to give carbonyl
compounds (aldehydes and ketones).

Example;

APPLICATION OF OZONOLYSIS

Ozonolysis is a degradation reaction. Degradation reactions involve breaking down of an

unknown compound into a number of smaller, more easily identifiable fragments.

By finding the structure of the aldehydes and ketones produced in ozonolysis reaction, it is
possible to determine the position of the double bond in the original alkene.

Therefore, the original alkene must be:

 DIELS ALDER REACTION

Otto Diels and Kurt Alder won the nobel prize for developing this reaction.

The Diels-Alder reaction is a cycloaddition reaction of a conjugated diene with a double bond
or triple bond. Since the reaction involves a system of 4π electrons (the diene) and a system
of 2π electrons (the dienophile), it is known as (4+2) cycloaddition.

Diels-Alder reaction is a pericyclic reaction. Pericyclic reactions are concerted reactions that
take place in a single step without any intermediates, and involve a cyclic redistribution of
bonding electrons. No catalyst is required.

The alkene or alkyne used in Diels-Alder reaction is called as dienophile. The product of
Diels-Alder reaction is called the adduct. The net result is the formation of two new sigma
bonds and one new pi bond in place of three original pi bonds. It takes place readily for a
wide variety of reactants.

Electron withdrawing groups such as –CN, CHO, COOH and COOR in the dienophile
increase the reaction rate.

STEREOCHEMISTRY OF DIELS-ALDER REACTION

Diels-Alder reaction is stereospecific. The stereochemistry of the dienophile is retained in

the product.

Diels-Alder reaction is a syn addition reaction with respect to both the diene and the
dienophile. Therefore, if the substituents in the dienophile are cis, they will be cis in the
product; if the substituents in the dienophile are trans, they will be trans in the product.
The substituents in the diene will also maintain their relative configurations in the products.

A diene can react only if it adopts the S-cis conformation.

A conjugated diene can exist in two different conformations, S-cis and S-trans. The ‘s’
stands for single bond or sigma bond. In the Diels-Alder reaction, the conjugated diene has
to be in S-cis conformation. A conjugated diene that is permanently in s-trans conformation
cannot undergo this reaction.

When endo and exo products are possible, the endo product is preferred.
There are two possible configurations, endo and exo, for bridged bicyclic compounds
obtained from the reaction of a cyclic diene and cyclic dienophile. Diels-Alder reaction
produces the endo product preferrentially.

Example: When cyclopentadiene reacts with a substituted alkene as the dienophile

(CH2=CHZ), the substituent Z can be oriented in two different ways in the product. The
terms endo and exo are used to indicate the position of Z.

A substituent is endo if it is closer to the longer bridge that joins the two carbons common to both rings.
A substituent is exo if it is closer to the shorter bridge that joins the carbons common to both rings.