INTRODUCTION

FREE RADICALS:Reaction which involved intermediates

formed by the homolytic fission of the covalent bonds

These intermediates having an unpaired electron &

are know as free radicals
These are species having one or more unpaired
electrons (odd no.)
Free radical is an atom or group of atom which an
unpaired electron in its valance shell

TYPEA OF FREE RADICAL:I) stable free radicals or free radicals of long life
II) Short lived free radicals or transient free radicals
most of the common free radical are extremely
reactive species and could not be isolated by traditional
method. Such radicals are know as short lived free radicals
in contras to stable radicals which are not very reactive and
have been found to exist in equilibrium with the normal
compound
I) stable free radicals or free radicals of long life :Gomberg in 1900 discovered the first free radicals i.e.
Triarylmethyl, Actually, he was trying to prepare
Hexphenylethane by condensing Triphenylmethyl chloride
with zinc dust in Benzene as solvent in the absence of air

The product obtained by him was colourless, crystalline

solid. This compound showed the following unexpected
characteristic
i) it is very reactive towards many substance such as
oxygen, halogens, hydrogen, nitric oxide etc, forming
addition products
ii) it developed yellow color in organic solvent which
disappeared in air
iii) as the solution was paramagnetic, it indicated the
presence of odd electrons in the product
iv) it reacted with iodine
Triphenyliodomathane,
nitric oxide
Triphenylnitrosomethane
Oxygen
Triphenyl methyl peroxide
v) the molecular weight of the product was 243 while the
molecular weight of Hexaphenylethane was 486

Reaction of Triarylmethyl free radicals:1) Addition reaction

a) Addition of hydrogen:- Triphenylmethyl radicals gets
reduced with platinum / hydrogen producing
Triphenylmethane

b) Addition of Oxygen :- Triphenylmethyl radicals on

absorbing atmospheric oxygen form colourless oxide
very rapidly

c) Addition of halogen:- Triphenylmethyl radicals reacts

rapidly with halogen at room temp.

d) Addition of Nitric oxide & Nitrogen peroxide:On passing nitric oxide into Triphenylmethyl
solution the bluish green nitroaotriphenyl methane
formed which gets further polymerized to a colourless
product of unknown structure

e) Addition of metals :- When solution of Triphenylmethyl

radicals are treated with metals such as sodium, potassium
& magnesium, they form the organomerallic derivatives

f) Addition of Olefinic compound:- Two molecules of

triphenylmethyl radicals have been found to add on various
unsaturated compounds on their double bonds in the
following way

g) Addition of p-benzoquinone :- Triphenylmethyl

radicals adds to p-benzoquinone to produce
ditriphenylmethyl ether of hydrocarbon

2) disproportionation :- Triphenylmethyl radical is

disproportionate in which one molecule of the radical gets
reduced at the expense of the phenyl group of another
molecule which thus gets oxidized

This reaction is enhanced by light

3) Irreversible dimerisation :- In the presence of mineral

acids, triphenylmethyl radicals undergo irreversible
dimerisation.

II) Short lived or transient free radicals :- They are short

lived free radicals and some example under this category
are methyl, ethyl, acetyl, benzoate, phenyl, etc.
1) Thermal decomposition :- compound having weak
bonds produce free radicals on heating
a) Paneths method :- It was the first method for
producing shot lived free radicals.
# vapors of tetra methyl lead + H/N2
# Quartz tube pressure 1-2 mm by using
high speed vacuum pump

# Tube strongly heated (600-8000)at point X

# Lead mirror deposited at the point X formed from
tetramethyl lead
# Free radicals carried by H2 gas
# The mirror of metallic lead is deposited at another point Y
to detect the methyl radicals
# Methyl radical with h2/n2 gas combine with metallic lead
at Y forming tetramethyl lead
# Thus the lead mirror at Y disappears

# If the distance between X&Y greater than 32cm

- the mirror does not disappear
- bcoz methyl radical have shot life
- and combine readily in absence of lead mirror to
for Ethane

half life period for Methyl radical is found as 0.006

second

b) Thermal or pyrolytic decomposition of other

compound :- Thermal method of producing free radicals is
applicable to compounds having weak covalent bonds.
Organic peroxides (R-O-OH) or per acids. Which have low
O-O bond energy (30-440 Kcal/mole) undergo
decomposition readily at quite low temp. into free radicals

Similarly, thermal decomposition of aliphatic Azo

compound

2) Photochemical decomposition or photolysis :- Some

molecules undergo homolysis by absorbing radiation in
UV/Visible range. It is know as photolysis

It is also possible that a free radicals may produce a new

free radical by further cleavage or by reacting with another
free radical

3) Redox reaction by inorganic ions :- The free radicals

are prepared in solution by redox reaction involving one
electron transfer. The diazonium sails on heating with
cuprous salts get reduced to aryl radicals. It is a transient
intermediate in Sand-Meyer reaction.

Similarly, Fentons reagent (mixture of H2O2 & ferrous

salt) the H2O2 gets oxidized into hydroxyl radicals. They
generate new free radical by abstracting hydrogen atoms

Radicals are also produced by the reduction of inorganic

ions

Electrolytic method is used to generate free radical In

Kolbe electrolytic synthesis of hydrocarbon, the carboxylate
ions get oxidized at the anode giving free radicals. Then
they dimerise to form hydrocarbons.

Similarly, free radicals are also formed during the

electrolysis of ketones to pinacols

DETECTION OF FREE RADICALS :- The free radical

have been detected by the following methods
a) Mirror method :- when free radicals are carried in a
current of inert gas over a metallic Mirror of Lead , bismuth
etc. Then metal coating disappears. This occurs because
free radicals attacks on the metal coating. The highly
reactive alkyl free radicals in gaseous phase have been
detected by this method.

b) Polymerisation reaction method :- The free radical

initiated the polymerisation reaction & can there for be
detected. A mixture of equal amount of styrene & methyl
methacrylate get polymerised into a copolymer by a free
radical

c) Colour reaction method :- The free radicals can be

readily detected by the following colour reaction. A Nitrogen
radical called 1,1-diphenyl-2-picryl hydrazyl is extremely
stable & even forms Violet coloured crystals.

In, solution it react with other free radical to form colourless

compounds. Therefore, it can also be used as a trap for
free radicals

d) Magnetic moment method :- The free radicals have a

net magnetic moment due to the unpaired electron. Hence,
they are paramagnetic. Therefore, they can be detected by
their values of magnetic susceptibility. This method is not
reliable because only the FR of large concentration can be
detected by this method.
e) ESR method :- It is the most powerful tool for the study
of FR . It is based on the fact that when FR kept in
magnetic field, its odd electron spin gets oriented
preferentially in the more stable position. However, with the
absorption of light energy, the spin can turn over to the
unstable orientation .
Transition between stable & less stable level produces a
line in the ESR spectrum.

The number of lines in the ESR spectrum is always n+1

where n is the number of coupling protons,
e.g.- Methyl radical shows 3+1 or 4 lines

on the other hand, the 1,3,5-cycloheptatriene radical shows

7+1 or 8 resonance lines
This method is very sensitive & can be applied to detect
FR even at the conc. Of 10-7 M.

STABILITY OF FREE RADICALS:- Generally, free radical

are very reactive the alkyl radical are very unstable while
many other FR such as triarylmethyl radical are relatively
more stable
Stability of alkyl free radical :- Like the carbonium ions,
the simple alkyl FR have following order of stability

In general, smaller the amount of energy required for bondbreaking the more stable is the radical.

Bond dissociation energy of some compound :-

Hyperconjugation (resonance)
canonical structure of the primary ethyl free radical

canonical structure of the secondary isopropyl free radical

canonical structure of the tertiary butyl free radical

Other factor that increase stability of tertiary radical may be

Steric factor

In (I) allylic & (II) benzylic radical, the p-orbital having the
unpaired electron overlaps with TT molecular orbital & the
unpaired electron gets delocalized

Stability of Triarylmethyl radical:Resonance effect:-

Hyperconjugation stability e. g. p-alkyl substituent

Electron withdrawing substituents

Steric effect
Three phenyl group in a triphenylmethyl radical occupy
large volume, it is difficult for two radicals to come closer
for a bond formation

CONFIGURATION OF FREE RADICALS :- It was found

by Brown, Kharasch & chao that free radical chlorination of
(+)-1-chloro-2-methylbutane results in the formation
racemic 1,2-dichloro-2-methylbutane.

Racemisation of the (+)- isomer during FR chlorination has

been explained on the basis of the following two probable
configurations of FR
a) Planar configuration :b) Pyrimidal configuration:-

a) Planar configuration :- Here, the FR is considered to

be a planar species in which the carbon atom having
the odd electron is sp2 hybridised & the odd electron
is present in the p orbital But the intermediate (FR) is
planar. Therefore, attachment of chlorine atom to
either face is equally probable. Hence, both the
optical isomers of the product will be obtained i.e.
racemisation will occur

b) Pyrimidal configuration :- Here, the FR is assumed to

have a shape which resembles a shallow pyramid & the
orbital having unpaired electron is more or less a hybrid
between sp2 & sp3 orbital , the formation of racemic
product in such cases has been explained on the basis of
assumption that the inversion of such a pyramid is faster
than the transfer reaction with chlorine molecule there by
resulting in the formation of racemic product.

From the evidence, it follows that in radicals which are

stabilised by the unpaired electron , the three bonds of the
carbon are coplanar.
On other hand, if the unpaired electron lies at a bridge
head of bicyclic system, an sp2 configuration is completely
ruled out by the geometric requirements & a pyrimidal
configuration becomes more or less mandatory
e.g. :- Apocamphoyl peroxide which readily undergoes
dissociation in cabrontetrachloride to form the apocamphyl
radical.

REACTION OF SHORT LIVED FREE RADICALS :- The

FR are very reactive due to the presence of the
unpaired electron. The F R are chain reaction
involving three steps:a) Initiation :- In which free radicals is generated.
b) Propagation :- In which these radicals react to give
new free radicals.
c) Termination :- In which radicals combine to give
stable molecules.
1) Polymerisation
2) Halogenation
3) Autoxidation
4) Aromatic substitution
5) Rearrangement of radical

1) Polymerisation :initiation

propagation

termination

when we need to control mol. Wt. of polymer chain

terminator are added to reaction mixture

2) Halogenation :a) Chlorination:initiation

propagation

termination

b) Bromination
c) Iodination
d) Fluorination

3) Autoxidation :- slow oxidation of organic substances by

atmospheric oxygen is termed as autoxidation

4) Aromatic substitution :-

5) Rearrangement of radical:-

ADDITION TO CARBON-CARBON MULTIPLE BONDS :Addition of hydrogen bromide to olefins

This type of reaction are called Non-stereospecific & some

time it may be stereoselective

REFERANCE:1)
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