FREE RADICAL

CHP 3
AN ATOM or group of atoms carrying any charge obtained by the loss or gain of electron
during a reaction called radical .
FREE RADICAL
They donot possess any charge on it or we can say that they are neutral species .they are
neither positively charged nor negatively charged they are electrically neutral.
An atom or group of atm ,which contain one or more unpaired electron is called a free
radical .it is denoted by putting a dot (.) for example cl.
Free radical are small group or single atoms that have unbounded electron.
Free radical are produced when covalent bond split in half with each atom receiving an
equal share of electron pair .
Homolytic cleavage fish hock arrow
Photolysis
Thermolysis
Redox reaction
Stability of free radical
Inductive effect
Polar covalent bond
Hyperconjugation
Alkyl or aryl radical
Stability order
Benzylic
Alkylic
3 alkyl radical
2 alkyl radical
1 alkyl radical
FORMATION OF FREE RADICAL
Photolysis
Carbonyl containing compound
Homolytic cleavage
Uv and visible light
Reaction of free radical
Addition reaction
Reaction in which two or more molecules combine to form a single molecule of product is called
addition reaction .
Example alkene
2)Peroxides gives free radical with the help of photolysis or thermolysis
Peroxides are unstable compound and 0-0 bonding
peroxides compound gives a addition reaction ?
Peroxides compound are react with hydrochloric acid and hydrogen iodide but hydrogen
hydrochloric acid having a strong bonding and its cannot dissociate easily .
Hydrogen iodide bond is weaker than hydrogen bromide bond because lower bond dissociation
energy ,but in iodine molecules because of high atomic weight.
A) Alkoxy free radical is generated
B) Alkoxy free radical attack ,HBR to form bromine radical and alcohol
C) Bromine radical attack alkene to form more stable alkyl free radical .
D) The alkyl free radical react with hydrobromide to form antimarkonive addition reaction .
Substitution reaction
Halogenation reaction
The substitution reaction in which one or more hydrogen atoms of alkane is replaced by same
numbers of halogens in the presences of sunlight is known as halogenation
Mechanism of halogenation
Halogenation of methane ,promoted by sunlight is an example of free radical chain reaction of
photochemical type
3stages
1 initiation step
The ignition step consists of photochemical dissociation of chlorine molecules inn to 2
chlorine atoms which has an add electron called chlorine free radical the breaking and cleavage
is homolysis.
2.Propagation step

3.Termination step
ADDITION OF PLOYMERIZATION
Polymerization is a process in which the simple molecules unite together to form large
molecules the simple compound from which polymer is obtained is called or
monomers.
INITIATION PROCESS
PROPAGATION PROCESS
TERMINATION PROCESS
CHAIN INTITION
CHAIN PROPAGATION
CHAIN TERMINATION
HETEROCYLIC COMPOUND
A heterocyclic compound or ring structure is a
cyclic compound that has atoms of at least two
different elements as members of its
ring(s). Heterocyclic chemistry is the branch of
organic chemistry dealing with the synthesis,
properties, and applications of these heterocycles.
CARBON

NITROGEN

SULPHUR

CLASSIFICATION OF HETEROCYLIC COMPOUND

5 MEMBERED COMPOUND

6 MEMBERED COMPOUND
5 Membered heterocyclic compound

Pyrrole ,furan ,thiophene

6 Membered heterocyclic compound

Pyridine , pyran

Benzo fused ring

Quinolones
Five membered compound
Those compound in which four carbon atom and one other atom in cyclic structure is called five
membered heterocyclic compound
pyrrole
Furan
Thiophene
It is also known as azole found in many natural product like chlorophyll
Preparation of pyrrole
1)By succinimide
By this process simple pyrrole is formed .in this process two steps are
involved
Dry distillation
Zinc dust
2) By alpha amino keto and b di keto
In this process alpha amino keto and di keto amine are react with each other
to form pyrrole by this process substituted pyrrole is prepared .(substituted)
3) With furan
In this process prepared by steam distillation in industries pyrrole is
obtained by passing a mixture of furan and ammonia over alumina at 400
centigrade.
FURAN
Furan is obtained or synthesized from furfural
obtained by acid hydrolysis of pentose
Pentose ---------- aldopentose ----------- furfural
------------ furan
2) Mucic acid is react with furoic acid in the presence off dry distillation make a furan .

PREPARATION OF THIOPHENE

1)Butane react with Sulphur at 600 centigrade and make thiophene

2) Ethylene is react with aluminum oxide and Sulphur in 400 centigrade and make thiophene
Reactions of electrophilic compounds
Mostly attack position is carbon 2
NITRATION
Pyrrole give a nitropyrene in the presences of acetic anhydride and HNO3
Furan give nitrofuran in the presences of acetyl nitrile and CH3COONA
Thiophene give nitro thiophene in the presences of fuming HNO3.
Sulphonation
Furan give a sulphofuran in the presences of SO3 and pyridine

Thiophene give a sulphothiophene in the presences of cold suplhuric acid

Pyrole give a sulphopyrole in the presences of pyriline and so3.

Acetylation

Pyrrole is converted to 2 acetyl pyrrole in the presences of BF3 and

acetic anhydride

Thiophene is converted to 2 acetyl thiophene is prepared by BF3 and

acetic acid

furan is converted to 2 acetyl furan in the presences of BF3 and acetic

anhydride
FORMYLATION
Formylation occur in presences of dimethyl formamide and
phosphooxy chloride ( pyrole and furan )
SIX MEMBERED NITROCYCLIC RING
PYRIDINE

Pyridine is react with hydrochloric acid and prepared a pyridinium SALT

Pyridine react with LIALH4 prepared a 1,2 DIHYDROPYRIDINE

Pyridine heated on 300 centigrade make pentane (REDUCTION

PROCESS)
FUSED RING
Contain a benzene ring fused with pyridine ring quinolones and iso
quinolones
Are common in plant kingdom such as Morphine ,heroin ,codeine

SKRRAUP SYNTHESIS
Useful method for preparing quinolones
1) Determination of glycerol by hot Sulphuric acid produced
unsaturated aldehyde acrolein (1 propenal)
2) Nucleophilic addition of aniline to acrolein produced beta phenyl
amino propenal aldehyde.