Pyridine:

There are different methods for the synthesis of pyridine

i) From acrolein

In the first step, two molecules of acrolein are involved. There is formation of 3-methyl pyridine.
In the second step process of oxidation takes place in the presence of potassium dichromate and
sulphuric acid which act as oxidizing agents. There is the formation of pyridine 3-carboxylic
acid. In the third step process of decarboxylation occurs and pyridine is formed.

O CH3
NH3 , COOH
K2Cr2O7/H2SO4
2 H2C C C H
H -2H2O
N
N
2-propenal
3-methylpyridine Pyridine-3-carboxylic acid
or acrolein
CaO/
-CO2

ii) Second method:

By heating pentamethylene diamine hydrochloride, there is formation of piperidine. One

molecule of ammonium chloride and hydrochloric acid are removed. The piperidine is oxidized
with concentrate sulphuric acid to produce pyridine.

NH2 HCl

H2C CH2
-NH4Cl H2SO4
H2C
-HCl N 300 oC N
H
H2C CH2
Piperidine Pyridine
NH2 HCl
pentane-1,5-diamine
dihydrochloride

You can see starting material has two different names. So its not problem, you can use which is
easy.
Physical properties

Pyridine is a colourless liquid. Boiling point is 115oC. It has unpleasant odour.

It is soluble in water and also in organic solvents.

Hybridization:

Pyrdine is six membered heterocyclic ring and each ring atom is Sp2 hybridized. Each ring atom
has an unhybridized p orbital containing one electron. As you can see in diagram, Sp2 orbital of
nitrogen contains two electrons. This electron pair is not delocalized on the ring and therefore
pyridine is basic in nature. It is more basic than pyrrole.

Resonance forms of pyridine

N + +
N N N N

In resonance forms, an extra electron pair comes on the nitrogen atom and positive charge is
delocalized on the ring.

Electrophilic substitution reaction

Pyridine undergoes electrophilic substitution reactions under vigorous condition at position

number 3. The vigorous conditions are necessary because in the resonance forms there is positive
charge on ring carbon atoms. And electrophile is also positively charged. Therefore attack of
electrophile is difficult. Electrophilic substitution reaction takes place at position number 3
because the intermediate product is more stable and three resonance forms are possible. If
electrophile attacks at position number 2 then the intermediate product is less stable because only
two resonance forms are possible.

Attack atposition numer 2

+ +
E E

N N H N H

Attack at position number 3

E E + E

H H H
+ +
N N N N

Electrophilic substation becomes easier if there is presence of electron-donating groups in the

ring.

Nitration

NO2
Conc. H2SO4
+ KNO3
N N
3-Nitropyridine

Sulphonation

SO3H
HgSO4
+ Conc. H2SO4
N 220oC
N
Pyridine-3-sulphonic acid

Halogenation
 Cl
AlCl3
+ Cl2
N 100oC N
3-Chloropyridine