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Heterocyclic Compounds

The document discusses heterocyclic compounds and provides details about pyrrole including its structure, properties, aromaticity, methods of preparation and chemical reactions. It defines heterocyclic compounds and discusses various nomenclature methods. Tables provide prefixes for heteroatoms and stems for ring sizes. Examples of heterocyclic compounds and their systematic nomenclature are also given.

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0% found this document useful (0 votes)
1K views62 pages

Heterocyclic Compounds

The document discusses heterocyclic compounds and provides details about pyrrole including its structure, properties, aromaticity, methods of preparation and chemical reactions. It defines heterocyclic compounds and discusses various nomenclature methods. Tables provide prefixes for heteroatoms and stems for ring sizes. Examples of heterocyclic compounds and their systematic nomenclature are also given.

Uploaded by

jatinkshitij8005
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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HETEROCYCLIC

COMPOUNDS
Dr. RASHMY NAIR
DEPARTMENT OF CHEMISTRY
S S JAIN SUBODH P G (AUTONOMOUS) COLLEGE, JAIPUR

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
DEFINITION OF HETEROCYCLIC COMPOUNDS:
Heterocyclic compound is the class of cyclic organic compounds those having at least one hetero atom (i.e. atom other
than carbon) in the cyclic ring system. The most common heteroatoms are nitrogen (N), oxygen (O) and sulphur (S).

NOMENCLATURE OF HETEROCYCLIC COMPOUNDS

TRIVIAL METHOD OF NOMENCLATUTRE:


During the early days of organic chemistry, names of the heterocyclic organic compounds were given based on their
occurrence, their first preparation and some characteristic properties.

For example
picoline; picoline Name “Pyrrole” given on the basis of their
is derived from characteristic properties. For example, pyrrole;
coal tar. This is which is basic in nature; the name of pyrrole was
based on Lattin originated from the Greek word for fiery red because
word pictus means of characteristic colour which the compound gives
tarry. with pine splint dipped in hydrochloric acid.

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
Some heterocyclic compounds with recognized trivial names

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
SYSTEMATIC METHOD OF NOMENCLATUTRE:
Hantzch-Widmann system specifies the nature, position, ring size, number, and types of heteroatoms present in any
heterocyclic compounds. This systematic method generally derived the nomenclature using the following syntax;
Name: Prefix + Stem + Suffix
Following are the important points to be remembered during the systematic nomenclature of heterocyclic compounds.

1. In this nomenclature the nomenclature of heterocyclic compounds are assigned by combining ‘prefix’ (that indicate
the heteroatom present) with ‘stem’ (that indicate the ring size as well as the saturation and unsaturation in the ring)
and ‘suffixes’. The common prefixes are shown in Table 1. It should be noted that final ‘a’ is dropped when prefix is
followed by vowel.
2. Nomenclature of heterocyclic compound starts with the heteroatom appears first in the table 1.
3. If more than two different heteroatoms are present in any heterocyclic compound the prefixes are listed in order in
which they are appear in above table (Table 1).
4. If there are two or more than two hetero atoms of same types are present in a heterocyclic compound they are indicated
by di-, tri- etc.
5. The position of saturated atom is numerically indicated with prefix ‘H-’ as a part of the name of the ring system. It
should be noted that where, there is a choice of numbering, the indicated position is given the lowest possible number.
6. The size of a monocyclic ring (three to ten membered rings) is indicated by stem. The common ‘stem’ nomenclature is
given in Table 2.
Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
Table 1: Common Prefix for Heteroatoms (arranged in the preferential order)

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
Table 2: Common Prefix for Heteroatoms (arranged in the preferential order)

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
Some examples of heterocyclic compounds with systematic nomenclature

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
STRUCTURE AND AROMATICITY OF PYRROLE, FURAN, THIOPHENE AND PYRIDINE

The structure of pyrrole, furan and thiophene is the resonance hybrid of all resonating structures.

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
Arranged according to their resonance energies:
Benzene >Thiophene> Pyrrole > Furan
144.4 117 87.8 71.1 KJ/mol

Order of reactivity:

Benzene < Thiophene < Furan < Pyrrole

All these heterocyclic compounds are aromatic and are more reactive than benzene and hence are termed
as Super aromatic compounds. (अति aromatic yogik)
Reason: Furan is less reactive than pyrrole because Oxygen has lesser capacity to hold the positive charge
as it is more electronegative than nitrogen.
Thiophene is less reactive than furan because sulphur atom is larger in size than oxygen and hence +M
effect caused by thiophene is lesser than caused by furan.

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
METHOD OF PREPARATION OF PYRROLE

1. From bone oil:

2. From succinimide:

Dr. Rashmy Nair,


Department of Chemistry,
S. S. Jain Subodh P. G. (Autonomous)
College, Jaipur
3. From Furan:

4. Paul-Knorr synthesis:

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
5. Knorr Pyrrole Synthesis

As α-aminoketone is unstable compound so it can be prepared in situ (within the reaction)

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
6. Hantzsch Pyrrole Synthesis

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
7. From Acetylene:

8. From ammonium mucate

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
PHYSICAL PROPERTIES (भौतिक गुण)

1. Colourless liquid, b.p. 131°C रं गहीन िरल, b.p. 131°C

2. It is highly sensitive to air, when pyrrole is exposed to air it turns brown and gradually resinifies.

हवा के प्रति अत्यधिक संवेदनशील, जब हवा के संपकक में पाइरोल होिा है िो यह भूरा और िीरे -िीरे resin me बदल
जािा है

3. Pyrrole is slightly soluble in water but completely miscible in ether and ethanol.

4. When a pine splint dipped in HCl is brought in contact with vapours of pyrrole, it turms red.
Hence the name PYRROLE came from the Greek word: Pyrros: fiery red and in Latin language: oleum means oil.

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
CHEMICAL PROPERTIES (रासायतिक गण
ु )
1. Pyrrole is an aromatic compound and more reactive than benzene. Because of the aromatic nature pyrrole gives all
characteristic reactions (electrophilic substitution reactions) of aromatic compounds such as halogenation,
nitration, sulphonation, Friedel-Crafts reactions etc.
पायरोल एक सुगंधिि यौधगक है और बेंजीन की िुलना में अधिक प्रतिक्रियाशील है
2. Pyrrole undergoes electrophilic
substitution at the position C-2.
Approach of the electrophile at
position C-2 leads the formation of
three resonating structures; however,
only two resonating structures are
obtained when the electrophile
approaches at position C-3. Thus the
intermediate obtained by the approach
of electrophile at position C-2 is more
stable than the intermediate obtained
by the approach of electrophile at
position C-3. This is the reason that
electrophilic attack occurs at position
C-2. Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur

All the electrophilic substitution reactions of pyrrole occur at position C-2 and follow the similar mechanism as shown above.
1) Electrophilic Substitution Reactions
i. Halogenation: Pyrrole reacts with halogens [X2 (X2 = Cl2, Br2 and I2)] to give tetrahalopyrrole. For example, Reaction
of bromine with pyrrole gives tetrabromopyrrole.

ii. Nitration: Nitration of pyrrole is achieved by reacting it with HNO3 in acetic anhydride. The reaction of HNO3 and
acetic anhydride resulted acetyl nitrate in which –NO2 acts as an electrophile.

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
iii. Sulphonation: Sulphonation of pyrrole is achieved by reacting it with sulfur trioxide (SO3) – pyridine mixture in
ethylene chloride.

iv. Friedel-Crafts Acylation: Reaction of pyrrole with acetic anhydride under heating condition gives 2-acetylpyrrole.

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
v. Diazotization (Coupling reaction): Pyrrole reacts with benzene diazonium chloride in acidic medium to give 2-
phenylazopyrrole.

vi. Reimer-Tiemann Reaction: Pyrrole reacts with Chloroform in presence of KOH to give 2-Formylpyrrole. This
reaction is known as Reimer-Tiemann reaction. It also takes place through electrophilic substitution reaction mechanism.

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
vii) Kolbe’s reaction

viii) Gattermann reaction

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
ix) Houben-Hoesch reaction

2. Reduction

Dr. Rashmy Nair, Department of Chemistry,


S. S. Jain Subodh P. G. (Autonomous) College,
Jaipur
3. Oxidation

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
4. Ring Opening reaction
When pyrrole is treated with hot ethanolic hydroxylamine then dioxime of succindialdehyde is formed.

5. Ring expansion reaction

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
MECHANISM

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
6. Sensitivity of Pyrrole towards acids

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
7. Acidic Properties of Pyrrole

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
STRUCTURE AND AROMATICITY OF PYRROLE, FURAN AND THIOPHENE

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
Continued….

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
EVIDENCES IN FAVOR OF AROMATIC CHARACTER OF PYRROLE

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
FURAN
Also known as Furfuran. Rice bran on distillation with dilute sulphuric acid led to aldehyde, furfural. In Latin,
Bran is also called Furfur and hence the name ‘Furfuran’ and later the name ‘Furan’ was given.

METHOD OF PREPARATION

i. From Mucic acid: Dry distillation of mucic acid first gives Furoic acid which on decarboxylation by heating gives
Furan.

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
ii. From Furfural: Furan is synthesized from furfural which is obtained by acid-hydrolysis of pentose sugars.

iii. Paal-Knorr Synthesis: Dehydration of 1,4-diketone with P2O5 (phosphorous pentaoxide) gives derivatives of Furan.

Dr. Rashmy Nair,


Department of Chemistry,
S. S. Jain Subodh P. G.
(Autonomous) College, Jaipur
Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
PROPERTIES OF FURAN:
Physical Properties
• Furan is colorless liquid.
• Its boiling point is 31.4° C.
• Dipole moment: 0.7D
• It has an odor similar to Chloroform.
• It is insoluble in ether but soluble in most of the organic solvents.
Chemical Properties
1) Electrophilic Substitution reactions

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
i. Halogenation: Furan reacts with halogens [X2 (X2 = Cl2, Br2 and I2)] to give 2-halofuran. For example, reaction of
bromine with Furan gives 2-bromofuran.

ii. Nitration: Nitration of furan is achieved by reacting it with HNO3 in acetic anhydride. The reaction of HNO3 and
acetic anhydride resulted acetyl nitrate in which –NO2 acts as an electrophile.

Dr. Rashmy Nair,


Department of
Chemistry, S. S. Jain
Subodh P. G. (Auto)
College, Jaipur
iii. Sulphonation: Sulphonation of Furan is achieved by reacting it with sulfur trioxide (SO3) – pyridine mixture in
ethylene chloride at 100° C.

iv. Friedel-Crafts Acylation: Reaction of furan with acetic anhydride in presence of BF3 gives 2-acetylfuran.

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
v. Mannich Reaction

vi. Gattermann Koch Synthesis: When furan is treated with a mixture of HCN and HCl in the presence of Lewis acid
catalyst AlCl3, furfural is obtained as final product.

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
Furfural on heating with ammonia forms hydrofuramide.

vii. Furan on reaction with n-butyllithium forms 2-lithium derivative, which on further reaction with
carbon dioxide forms furoic acid.

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
viii. Gomberg reaction: Just like benzene the furan will react with the diazonium salt in the presence of alkali to form an
adduct of homolytic arylation.

ix. Mercuration: When furan is treated with mercuric chloride in aqueous sodium acetate then mercuration occurs at
position 2, which is readily substituted by halogen or acyl group.

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
2) Reduction: On catalytic hydrogenation of furan, the tetrehydrofuran (THF) is obtained. THF is used as a solvent in
place of ether in the Grignard reactions.

3) Diels-Alder Reaction: Furan is the only heterocyclic compound which undergoes Diels-Alder reaction. Diels-Alder
reaction is a cycloaddition reaction of 4π-system to 2π- system.

Dr. Rashmy Nair, Department


of Chemistry, S. S. Jain
Subodh P. G. (Autonomous)
College, Jaipur
4) Reaction with oxygen or air

Furan-2,5-peroxide

5) Reaction of Furan with acetic acid and bromine

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
6) Synthesis of thiophene and pyrrole from furan

7) Ring opening reaction

1,4-dioxo compounds
Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
THIOPHENE

General methods of preparation


i. From n-Butane: Thiophene is obtained when n-butane is heated with elemental sulphur at very high temperature
(923K).

ii. Laboratory Method: When sodium succinate is heated with phosphorous sulphide, thiophene is obtained.

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
iii. Industrial Method: Industrially, thiophene is prepared by passing a mixture of acetylene and hydrogen sulphide
through a tube containing alumina (Al2O3) at 673K.

iv. Paul-Knorr synthesis of thiophene derivatives: In this method, dehydration of 1,4-diketone with P2S5 (phosphorous
pentasulphide) gives derivatives of thiophene.

Dr. Rashmy Nair,


Department of Chemistry,
S. S. Jain Subodh P. G.
(Autonomous) College, Jaipur
PROPERTIES OF THIOPHENE:
i. Physical Properties of thiophene:
Thiophene is colorless liquid.
Boiling point of thiophene is 357 K.
It smells like benzene.
It is soluble in alcohol and ether but insoluble in water.
ii. Chemical Properties of thiophene:
1) Electrophilic Substitution Reactions

Dr. Rashmy Nair, Department of Chemistry,


S. S. Jain Subodh P. G. (Autonomous) College,
Jaipur
i. Halogenation: Thiophene reacts with halogens [X2 (X2 = Cl2, Br2 and I2)] to give 2- halofuran. For example, reaction
of bromine with Thiophene in absence of any halogen carrier gives 2,5-dibromothiophene.

However, Iodination of thiophene in presence of yellow mercuric oxide gives 2-iodothiophene.

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
ii. Nitration: 2-Nitrothiophene is obtained when nitration of thiophene is performed by reacting it with fuming HNO3 in
acetic anhydride. The reaction of HNO3 and acetic anhydride resulted acetyl nitrate in which –NO2 acts as an electrophile.

iii. Sulphonation: Sulphonation of thiophene is achieved by reacting it with cold concentrated H2SO4. Thiophene-2-
sulphonic acid is obtained as product.

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
iv. Friedel-Crafts Acylation: Reaction of thiophene with acetic anhydride in presence of H3PO4 gives 2-acetyl
thiophene.

v. Chloromethylation

vi. Formylation: Dimethyl formamide on reaction with furan in presence of phosphorus oxychloride forms thiophene-2-
carbaldehyde.
Dr. Rashmy Nair,
Department of Chemistry,
S. S. Jain Subodh P. G.
(Autonomous) College,
Jaipur
vii. Mercuration:

viii. Reaction with butyllithium

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
Pyridine can be obtained from coal tar
PYRIDINE and bone oil and is also decomposition
product of alkaloids.
Method of Preparation
1) On passing a mixture of acetylene and hydrogen cyanide through a red hot tube, pyridine is formed.

2) Pentamethylene diamine hydrochloride on heating forms piperidine which on oxidation with sulphuric acid at 300°C
forms pyridine.

Dr. Rashmy Nair,


Department of Chemistry,
S. S. Jain Subodh P. G.
(Autonomous) College, Jaipur
3) Acetylene, formaldehyde hemimethyl and ammonia is passed through alumina-silica at 500°C to obtain pyridine.

4) Industrial Method:

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
5) From acrolein: Pyridine can be prepared by the reaction of acrolein and ammonia according to following reaction
steps.

6) Hantzsch Synthesis (1882):

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
PROPERTIES OF PYRIDINE:
Physical Properties of Pyridine:
Pyridine is a colourless liquid. Its boiling point is 115.5° C. It has a characteristic unpleasant odor. It is soluble in water
and most organic solvents.
Chemical properties of Pyridine:
a. Basic character of pyridine: Pyridine is basic in nature. Its pKb is 8.75. It reacts with strong acids to form salts.

Dr. Rashmy Nair,


Department of Chemistry,
S. S. Jain Subodh P. G.
(Autonomous) College, Jaipur

The basic nature of pyridine is due to the freely available lone pair of electrons in sp2 hybridized orbital pyridine, which
does not participate in the formation of delocalized π -molecular orbital. Pyridine is less basic in comparison to aliphatic
amines whereas, it is more basic than aniline and pyrrole. This is because the lone pair of electrons in aliphatic amines
exists in sp3 hybridized orbital, however, in case of pyridine the lone pairs of electrons exists in sp2 hybridized orbital.
Electrons are held more tightly by the nucleus in a sp2 hybridized orbital than an sp3 hybridized orbital. Hence the lone pair
of electrons in pyridine is less available for protonation. The less basicity of pyrrole and aniline can be explained in terms
of non-availability of these lone pair of electrons on nitrogen atom. These lone pair of electrons is involved in the
formation of delocalized π -molecular orbital.
b. Reduction: Under catalytic hydrogenation of pyridine, hexahydropyridine is formed. It is also known as Piperidine.

Birch Reduction

Reduction does not disturb the conjugation

On treating with strong reducing


agents like HI, the ring is broken.

Dr. Rashmy Nair,


Department of Chemistry,
S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
Electrophilic substitution Reactions: Pyridine is also an aromatic compound. It is less aromatic than benzene and
pyrrole. Pyridine usually considered a highly deactivated aromatic nucleus towards electrophilic substitution reactions.
Therefore highly vigorous reaction conditions should be used for these reactions to take place. The low reactivity of
pyridine towards the electrophilic substitution reactions is due to the following reasons:
• The higher electro negativity of nitrogen atom reduces electron density on the ring, thus deactivate the ring.
• Pyridine is highly sensitive to acidic medium; it readily forms pyridinium cation with a positive charge on nitrogen
atom. Similarly, electrophile itself may also react with pyridine to form corresponding pyridinium ion. This positive
charge on nitrogen atom decreases electron density on nitrogen atom, consequently, the electron density on ring also
decreases.
However, the effect of such deactivation is comparatively lower at position C-3. The position C-3 is thus, comparatively,
the position of highest electron density in pyridine.

Dr. Rashmy Nair,


Department of Chemistry,
S. S. Jain Subodh P. G.
This is the reason that the pyridine undergoes electrophilic substitution at position C-3. (Autonomous) College, Jaipur
Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
i. Sulphonation: Sulphonation of pyridine is achieved by reacting it with fuming H2SO4 at 250oC. Pyridine-3-sulphonic
acid is obtained as product.

ii. Nitration: 3-Nitropyridine is obtained when nitration of pyridine is performed by reacting it with KNO3 in
concentrated H2SO4 at 300oC. The reaction of KNO3 and concentrated H2SO4 resulted–NO2 which acts as an electrophile.

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
(iii) Halogenation

Free radical mechanism

(iv) Mercuration

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
Nucleophilic Substitution Reactions:
As we have discussed that pyridine generally deactivated the aromatic ring towards electrophilic substitution reaction. The
deactivation of aromatic ring towards electrophilic substitution resulted due to the electron withdrawing nature of nitrogen
atom. Due to such deactivation, pyridine also gives nucleophilic substitution reaction. Nucleophilic substitution in pyridine
ring occurs at position C-2. Approach of the nucleophilic at position C-2 leads the formation of three resonating structures
(I, II and III); similarly, approach of nucleophilic at position C-3 also leads the formation of three resonating structures (IV,
V and VI). The resonating structures for intermediate resulting from the attack of nucleophile at position C-2 are
more stable than those of position C-3, since more electronegative nitrogen atom hold – ve charge in one of the resonating
structure (III) obtained from the attack of nucleophile at position C-2. Hence, the nucleophilic substitution in pyridine at
position C-2 is always favored. Following mechanism is suggested for the electrophilic attack at position C-2.

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
(i) Amination (Chichibabin Reaction)

Dr. Rashmy Nair, Department of Chemistry,


S. S. Jain Subodh P. G. (Autonomous) College, Jaipur

(ii) Reaction with organolithium compounds (iii) Reaction with Grignard reagent
(iv) Reaction with potassium hydroxide

(v) Pyridine substituted at position 2- or 4- positions are readily substituted by nucleophilic substitution
reaction as halogen is a good leaving group.

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
Oxidation

On treating pyridine with sodium, it forms a disodium derivative, which on leaving in air forms 4,4’-dipyridyl.

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur
Structure and Aromaticity of Pyridine
Molecular Orbital Theory

Dr. Rashmy Nair, Department of Chemistry, S. S. Jain Subodh P. G. (Autonomous) College, Jaipur

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