CHAPTER HETEROCYCLIC

1 COMPOUNDS

INTRODUCTION

Cyclic compounds, which have at least one hetero atom along with carbon in the
formation of ring are called Heterocyclic Compounds. Example-

N
N

N N
H O S N N H

Pyrrole Furan Thiophene Pyridine Pyrimidine Imidazole

Heterocyclic compounds may or may not be aromatic.

CLASSIFICATION

A. Classification based on their structure

1. Five membered ring

N N N
H O S H H

Pyrrole Furan Thiophene Imidazole Pyrazole

2. Six membered ring

N N O S

Pyridine Pyrimidine Pyron Thiopyron

 3. Condensed heterocyclic

N N

N
N N N
H H N H

Indole Carbazole Quinoline Purine

B. Classification based on their nature

1. Aromatic Heterocyclic Compounds

N
H O N

Pyrrole Furan Pyridine

2. Non-aromatic Heterocyclic Compounds

N N
H O O H

Piperidine 1, 4-dioxane THF Pyrrolidine

NOMENCLATURE

Systematic names for monocyclic compounds are given by using prefixes for the
nature of heteroatom present. E.g.
Compound Prefix
Oxygen oxo
Sulphur thia
Nitrogen aza
Silicon silo
Phosphorus phospha
NOTE: If heteroatoms are different, the order for citation starts from heteroatom of the
highest group in the periodic table and as low an atomic number when in the same
group.
Priority Order- O > S > N > P > Si
E.g. oxazo (O then N)

The size of the monocyclines is indicated by suffix –ole for five membered and –ine
for six membered.
Numbering is given in such a way that the heteroatom gets the lowest number and it
proceeds anticlockwise around the ring.
In common names Greek letters denote the position of substituents. E.g.

(
4
(') 5 CH3 (') 4 3 (
3 (
( ') 6 ( ') 5 .. 2 ( )
2 ( )
N O
1 ..
1 N

Pyridine (azine) β-methyl pyridine Furan (oxole)

4 N3 4 N3
5 .. 2 1
5 .. 2
N1 O
H ..

Imidazole (1, 3-diazole) Oxazole (1, 3-oxazole)

NOTE: N does not give the lowest no. in isoquinoline.

5 4 5 4
6 3 6 3

7 2 7 N2
8 N 8
1 1

Quinoline Isoquinoline
Systematic names are written in italic form I in bracket.
 ..
N
PYRROLE H C4H5N
Azacyclopenta-2,4-diene

Pyrrole is numbered as-

4 3 ( ') 
or

5 2 (') 

N1 N
H H

The position 2, 5 and (α and αʹ) are equivalent while position 3, 4 and (β and βʹ) are
equivalent.
If monosubstituted is carried out → 2 isomer possible. e.g.
a. 2 or α
b. 3 or β
If disubstituted is carried out → 4 isomer are possible. e.g.
a. 2,3 (α, β)
b. 2,4 (α, βʹ)
c. 2,5 (α, αʹ)
d. 3,4 (β, βʹ)

PREPARATION

1. From acetylene :-

H H
CH O CH2 NH
OH
+ OH
NH
CH O CH2

Acetylene Formaldehyde Pyrrole

 2. By distillation of succinimide with Zn dust :-

2+
Zn

O N O N
H H

Succinimide Pyrrole

3. By treatment of furan with ammonia :-

NH3

O N
H

Furan Pyrrole

4. Paal Knorr synthesis :-

NH3

O O
OH
HO N
Succinaldehyde H

(keto) (enol) Pyrrole

5. Knorr Pyrrole synthesis :-

CH3
O
O
CH3

O
O O
O CH3 H3C
H + H3C
H3C _-
O O
H
H3C
+ O

O CH3 O
NH2 O + + O
CH3 CH3
O N
_ N
H3C H
H3C

α-amino ketone β-keto ester Pyrrole denvative

CHEMICAL PROPERTIES

Pyrrole is aromatic in nature as it follows Helickel’s rule i.e., (4n+2) π electrons.

Resonance-

_ _

_
_ .. ..
.. + +
N N N N N N N
H H + + H H

I II III IV V

Resonance energy => 87.8-130 KJ/mole

Loan pair of electron involve in resonance. Hence, they are not involved in
hybridization.
sp2-sp2
(C-C bond)

H H

sp2-s
(C-H bond)
H
H
N
sp2-sp2
sp2-s
(C-N bond) H
(N-H bond)

Each ring atom in pyrrole also has an unhybridised p-orbital and these are
perpendicular to the plane of δ-bond.
The p-orbital on carbon contain one electron each and p-orbital on nitrogen contain 2
electrons.
The lateral overlap of these p-orbital produce a molecular orbital containing 6
electrons i.e., 4n+2=6 (n=1). Thus, pyrrole shows aromatic character.
Why pyrrole give electrophilic attack at 2nd position rather than the 3rd position?

Pyrrole undergoes electrophilic substitution at the 2nd position.

Attack of the electrophile at 3-position in pyrrole leads to an intermediate with only
two resonance structure.
Three resonance structure are possible for the intermediate product by attack at 2nd
position. i.e., the intermediate produced by attack at 2nd position is more stable.
This is the reason that electrophilic attack occurs at 2nd position rather than at 3rd
position.
Attack at 3rd position-
E
H H

E E
+ _ +
E H
+
.. .. + ..
N N N N
H H H

Resonance stabilised = Carbocation

(Fewer resonating structure = less stable)

Attack at 2nd position-

+
H
+ H H _ +
E H

.. + +
.. .. E
N N E N E N N
H E H
H H

(more stable)

Intermediate carbocation is stabilized by the accommodation of the positive charge on

the heteroatom.

O Furan

N Pyrrole
X
..
X
S Thiophene
 A. Electrophilic substitution reactions
I. Halogenation
Br Br

Br Br

N N Br
Br H
H

Pyrrole 2,3,4,5-tetrabromopyrrole

II. Nitration

_
+
CH3COO/NO2
N N NO 2
Acetyl nitrate H
H

Pyrrole 2-nitropyrrole
III. Sulphonation

SO3
N N SO 3H
H
Pyridine H

Pyrrole 2-pyrrole sulphonic acid

IV. Friedal-craft acylation

O O Anhyd.AlCl 3
CH3
N
+ H3C O CH3
N
H H
O

V. Diazotization

_
+ HCl
N
+ C6H5N2Cl
N N N C6 H5
H H

Pyrrole 2-phenyl azo-pyrrole

VI. Reimer-Tiemann reaction

KOH
N
+ CHCl 3
N CHO
H H
Pyrrole
2-formyl pyrrole

VII. Gatterman Koch synthesis

HCl
N
+ HCN
N CHO
H H

B. Reduction

Ni/H Zn/CH 3COOH HI/RedP

N N N N
H H H H

Pyrrolidine Pyrrole Pyrroline Pyrrolidine

C. Oxydation

O
.. CrO 3/CH 3COOH
N N O
H O H

Pyrrole Maleinimide
 ..
O:
C4H4O
FURAN
Oxacyclopenta-2,4-diene

PREPARATION

1. From pentosans (C5 polysaccharides) –

CHO
+
H3 O 
(CHOH) 3 
(C 5H8O4)n -CO
H2SO4
O ZnO/Cr 2O3
CHO O
H2C OH
Furfural Furan
Aldopentose

2. By the oxidation of furfural –

[O]

O -CO 2
O O O
CHO
OH Furan
Furfural
Furoic acid

3. Paal-Knorr synthesis –
P 2O 5

CH3 -H 2O H3C
H3C O CH3
H3C CH3
O O
2,5-dimethylfuran
OH OH
Acetonyl acetone
 ..
THIOPHENE S
..
C4H4S
Thiocyclopenta-2,4-diene

PREPARATION

1. By treatment of furan with P4S7 –

P 4S 7

O S

Furan Thiophene

2. By acetylene –

CH 0
400 C
2 + H2S
Al 2O3
CH ..
S

Acetylene Thiophene
3. By sodium succinate –

H2C CH2

+ P 4S 7
COONaCOONa ..
S
..
Sod. succinate Tetraphosphorus Thiophene
heptasulphide

4. From n-butane –

H2C CH2

+ 4S + 3H 2S
CH3 CH3
S
n-Butane Thiophene
 FURAN THIOPHENE

1. Electrophilic substitution reactions

Bromination Bromination
Br2 Br Br2
O Br S Br
2-bromofuran
2,5-dibromothiophene
Nitration
CH 3COONO 2 NO 2
Nitration
O
2-nitrofuran CH 3COONO 2
Sulphonation NO 2
S
SO3/Pyridine
O SO3H 2-nitrothiophene (70%)
Furan 2-sulphonic acid
O Sulphonation

.. SO3/Pyridine
S S SO3H
..
Friedal-craft alkylation Thiophene 2-sulphonic acid
C2H5OH/SnCl 4
O C2H5
2-ethyl Furan Friedal-craft alkylation
Diazotization C2H5OH/SnCl 4
N
S C2H5
Cl N 2 Cl
N Cl
O 2-ethyl Thiophene
Azo dye
Gatterman-Koch Reaction
HgCl 2
HCN/HCl Mercuration
O CHO S HgCl
2-formyl Furan (Furfural) 2-mercuric chloride thiophene

2. Oxidation reactions

+
nC4H9-Li CO 2/H
O2 OO
.. Li S COOH
S S
O O ..
2-Lithothiophene Thiophene
Furan Furan2,5-peroxide 2-carboxylic acid

3. Reduction reactions

H H
Excess Pd/H2 H H
H H H
H
Raney-Ni H H H
H S
2H 2 H H
.. Tetrahydrothiophene
O H S
H O ..
Desulphonation
T.H.F. H3C CH2 CH2 CH3
H2/Ni
 SIX MEMBER HETEROCYCLIC COMPOUND


' 
PYRIDINE ' 
N
.. or C5H5N or AZINE

C-C  bond
(sp2-sp2)
H H

H NH : :
C-H  bond
(sp2-s)
C-N  bond
H H (sp2-sp2)

Each ring in pyridine also has an unhybridised p-orbital containing one electron.
These p-orbital are perpendicular to the plane containing δ-bond.
The lateral overlap of the p-orbital produces a delocalized π molecular orbital
containing 6 electron.
Pyridine shows aromatic property or aromaticity because the resulting π molecular
orbital satisfies the huckel’s rule. i.e., 4n+2 π electron.

RESONANCE –

+ +
:N :N : N- :N
- -
:N
I II III IV

NOTE 1:- Pyperidine is stronger base than pyridine because of sp3 hybridized nitrogen
in piperidine.
HH H H
[H]
H H
Reduction H
H ..
N N
.. H H
H
Pyridine Piperidine
sp2 sp3
NOTE 2 –

monosubstituted pyridine Picoline

N CH3
..
CH3

disubstituted pyridine Lutidine

N CH3
..

CH3

trisubstituted pyridine Collidine

H3C N CH3
..

NOTE 3 – 2,3 and 4 pyridine carboxylic acid are generally referred to as picolinic,
nicotinic and isonicotinic acid.
COOH

COOH

N COOH N N
.. .. ..
Picolinic acid Nicotinic acid Isonicotinic acid
(pyridine-2-carboxylic acid) (pyridine-3-carboxylic acid) (pyridine-4-carboxylic acid)

PREPARATION

1. From acetylene

1. NH 3 CH
HCN
2
2. CH 2(OCH 3)2
N N
CH
Formaldehyde
dimethyl acetal

2. From acrylene
CH3 COOH
NH3 [O]

2 H2C CH CHO
K2Cr2O7 CaO
N -CO2 N
N
3-methylpyridine
 3. From tetra hydro furfuryl alcohol
NH3

CH2 N
O
HO

4. From nicotinic acid

COOH
CaO + NaOH
+ Na 2CO3 + H2 O
DH
N N

BASIC CHARACTER

..
.. N
R NH2 H
N
.. sp2 because loan pair are not free
sp3 sp2 but free loan pair of electron & involved in resonance

Primary amine > Pyridine > Pyrrole

CHEMICAL PROPERTY
1. Electrophilic substitution reaction –
The attack of the electrophile at 2nd position (4th position) in pyridine leads to
an intermediate with only two important resonance contributing structure whereas 3
resonance structure are possible for intermediate produced by attack at 3-position.
Attack at position 2 -
4
5 3 + + +
E + -H
H H
6 .. 2
N N N E
1 .. E N
.. E

Attack at position 3 –
H
4 H
+ H E
5 3 + +
E -H

6 .. 2 + E + E E
N N N
1 .. N N
.. ..
a. Nitration

NO 2

+ KNO 3

N N
Pyridine 3-nitropyridine

b. Sulphonation

SO3H
0
250 C
+ H2SO4

N N
Pyridine 3-pyridine sulphuric acid

c. Bromination

Br
0
300 C
+ Br2

N N
Pyridine 3-bromopyridine

d. Friedal-craft alkylation
It does not react with pyridine because
reagent AlCl3 itself react with pyridine
+
to form complex. N
_
AlCl 3

2. Nucleophilic substitution reaction –

Attack at 2nd position :- (more stable than 3rd)

_
:Nu _ H _H -
H - :H
-
N N N N
.. .. Nu .. Nu .. Nu N Nu
 a) Reaction with sodium amide
0
100 C
+ NaNH 2 + NaH

N N NH2
Pyridine 2-aminopyridine

b) Reaction with phenyl lithium

0
+ - 100 C
+ C6H5 Li
N N C6 H5
Pyridine 2-phenylpyridine

c) Reaction with Grignard reagent

-
+ C6H5CH 2 /MgCl
N N CH 2C6H5
Pyridine 4-benzylpyridine

3. Reduction reaction


H2/Ni
N N
H
Pyridine Piperidine

4. Oxidation reaction

peracid

N N

O
Pyridine Pyridine N-oxide

USES

It is used as a basic solvent in the organic reactions.

It is used to denature the alcohol.
It is used for preparing sulphapyridine.
 4
5
N
3
PYRIMIDINE 6 2
N
1

It is a six membered heterocyclic compound present in many natural products

(Nucleic acid) and synthetic drugs e.g. Barbiturates.

SYNTHESIS

O
H
C N
COOC 2H5 H2N
C2H5ONa
C O
H2C + O
-C 2H5OH
H2C

COOC 2H5 H2N C N

H
O

Malonic ester Urea (keto form)

OH

.. Cl C N
N N
POCl 3
 OH
Cl HC
Zn
N N
.. Cl C N

OH
Pyrimidine (enol form)

PROPERTIES -

1. Physical properties
Colour – Colorless compound
M.P. – 230C
It follows Huckle’s rule i.e. (4n+2) π electron. Hence, it is an aromatic compound and
its resonating energy is 109 KJ/mole.
2. Chemical properties
a) Basic character – It is a weaker base than pyridine.
b) Alkylation – In electrophile of weak alkylating agent, only one nitrogen undergoes to
the alkylation while in electrophile of strong alkylating agent (triethyloxonium
 fluoroborate), both nitrogen undergo alkylation.
+ - + - ..
N C2H5]BF4 [C2H5] 3O BF 4 N CH 3I N:

+ +
N N N
- ..
C2H5]BF4 -
CH 3]I

c) Electrophilic substitution reaction – The presence of one additional nitrogen in

pyrimidine ring deactivate it still further to electrophilic aromatic substitution
reaction. However its monoprotonated pyrimidine undergoes bromination at position
5.
4 Br
5 Br 2
N N
3 + HBr
6 + 2
N N
H
1
Protonated pyrimidine 5-bromopyrimidine

NOTE-
+

N: N: N: N

.. + - - - +
N N N N
.. .. ..

In above resonating structure, the position 5 of the pyrimidine ring is comparatively rich in electron density.
Thus, if electrophilic substitution occurs, it will occur at position 5 and if nucleophilic attack occurs, it will
occurs at position 2, 4 and 6.

d) Nucleophilic substitution reaction –

a) Nucleophilic substitution of halogenated pyrimidine – Cl atom at 2, 4 and 6
position can readily be replaced by –OH or –NH2 gro

aq. NaOH N
2-hydroxypyrimidine
N OH
N:

NH3
N N
.. Cl 2-aminopyrimidine
2-chloropyrimidine N
NH2

b) Reaction with aryl lithium –

C6H5
H C6H5
- +
N: C6H5 Li - N + KMnO 4 N
Li + LiH

N N N
..
4-phenylpyrimidine
 4
N
3

IMIDAZOLE 5 2

N
H
1 C3H4N2

It occurs in purine and in histidine.

PREPARTION
1.

O R
R C O N
+ 2NH 3 + R'' CH + 3H 2O
R' C O
N R''
R'
dicarbonyl H
compound

2.

O
CHO N
+ 2NH 3 + H C H
+ 3H 2O
CHO N
H
Glyoxal Formaldehyde Imidazole

3.
+
R'' NH2
R C O R O -
Br
+ HN C NH2
R'
R' CH Br NH R''

-bromoketone Amidine H2 HBr

R
N

R' N R''
H
PROPERTIES

1. Imidazole have comparatively higher boiling point than pyrazole is due to linear
association of molecule via intermolecular hydrogen bonding.
2. Imidazole is isomeric with pyrazole.
N
N
N N
H H
Imidazole Pyrazole
3. Reaction with methyl iodide –
N CH 3I N  N
KOH Isomerised
N N N CH3
H H
CH3
Imidazole 1-methyl
imidazole

4. Oxidation and reduction – Not occurs.

5. Reaction with H2O2 –
O

N H2O 2 C NH2

C NH2
N
H O

Imidazole Oxamide

6. Reaction with benzoyl chloride in basic medium –

O

N HC NH C C6H5

+ 2C 6H5COCl + 3NaOH + HCOONa + 2NaCl

N HC NH C C6H5
H O
Imidazole Dibenzoyl diamino ethylene

7. Nitration –
O 2N
N N N
HNO 3
+
N N O 2N N
H H H

Imidazole 4-nitro 5-nitro

imidazole imidazole
 8. Sulphonation –
HO 3S
N
N N
H2SO4
N
+
N HO 3S N
H
H H
Imidazole Imidazole Imidazole
4-sulphonic acid 5-sulphonic acid

9. Bromination –
Br
N
N N
Br2
N
+
N Br N
H
H H
Imidazole 4-bromoImidazole 5-bromoImidazole

If 4 and 5 position is occupied then 2-substitution occurs.

R R
N N
Br2

R' N R' N
H H Br

Imidazole 2-bromoImidazole

Thus on bromination it form tribromo derivative.

USES

It is found in many biologically active compounds like purine, alkaloid, histidine etc.
It is found in many pharmaceutical products.
E.g. Naphazoline
Tetrahydrozoline
Oxymetazoline
N
CH2 .HCl
N
H

Naphazoline

They are used as vasoconstrictor in the treatment of upper respiratory tract.

 H H
4 3

N
PYRAZOLE H 5 N
H
2

1 C3H4N2

It is isomeric with Imidazole.

PREPARATION

1. From acetylene –
HC CH
Acetylene
+ -
+ N N N
H2C N N
N H
Diazomethane Pyrazole

2. From 1 , 1, 3, 3-tetraethoxypropane –
CH(OC 2H5)2 HN

HCl
H2C + HCl
N
N + 2C 2H5OH + 2HCl

CH(OC 2H5)2 HN H
Pyrazole
1,1,3,3-tetraethoxy Hydrazine
propane dihydrochloride

3. By decarboxylation of pyrazole tricarboxylic acid –

COOH
HOOC
0
300 C
N -3CO 2 N
N N
HOOC H
H
Pyrazole-3,4,5-tri Pyrazole
carboxylic acid
PROPERTIES

Physical properties:-

Colorless solid
M.P. = 700C
It exists in dimer due to intermolecular hydrogen bonding.
It is aromatic in nature and undergoes electrophilic substitution reaction at position 4.

Chemical properties:-

A. Electrophilic substitution reaction –

Cl

Cl 2
N
N
H
4-chloropyrazole

Cl

HNO 3
N N
N N
H H
Pyrazole 4-nitropyrazole
HO 3S

H2SO4
N
N
H
Pyrazole
4-sulphonic acid

B. Salt formation –

N + HCl N
N N
H H .HCl
Pyrazole Pyrazole
hydrochloride
 C. Oxidation –
It is resistant to oxidation but its alkylated form undergoes oxidation to form
pyrazole 5-carboxylic acid.

KMnO 4
N N
H3C N HOOC N
H H
5-methyl Pyrazole Pyrazole
5-carboxilic acid

D. Reduction –

N [H] [H]
N NH
N Catalyst N N
H H H
Pyrazole Pyrazoline Pirazolidine

USES

Pyrazole, an isomer of imidazole is found to be present in the following compounds:

OH

N
N
N N
H
Allopurinol

I. Allopurinol – used in gout

II. Oxyphenbutazone – used in gout & rheumatoid arthritis
III. Phenylbutazone – used in gout & rheumatoid arthritis.
 4 3
N
THIAZOLE 5 ..
S1
2
.. or C3H3SN

PREPARATION

1.

NH2
CHO 0
N
130 C
+ CH
+ H2O + HCl
H2C Cl S
S
Chloroacetaldehyde Thiazole

2. By diazotization of 2-aminothiazole –

N NaNO 2 N C2H5OH N

HCl BOIL
S S S
NH2 N2Cl
2-aminothiazole Thiazole

3.

NH2
CHO N N
+ S C

H2C Cl NH2 S NH2 S

Chloroacetaldehyde Thiourea 2-aminothiazole Thiazole

PROPERTIES

Odour - pyridine like odour

B.P. - 1170C
Liquid state
CHEMICAL PROPERTIES:-

1. It is stable towards the reducing agent but ring cleaves by Na/C2H50H.

H3C
CH3
N
Na/C 2H5OH
H 5 C6 CH2 CH NH CH3 + H2S
H5C6 S

2. It is resistant towards the substitution reaction but if –NH2 or –OH group is present on
position 2, electrophilic attack occurs at position 5.

H3C H3C
N CHCl 3 N
+ Br2
-HBr
S OH S OH
Br
2-hydroxy
4-methylthiazole 5-bromo2-hydroxy
4-methyl thiazole

3. Sulphonation –
N H2SO4 N

S S
OH HO 3S OH
2-hydroxy Thiazole 2-hydroxy Thiazole
5-sulphonic acid

4. Nitration –
N Conc.HNO 3 N

+H2SO4
S S
OH O 2N OH
2-hydroxy Thiazole 2-hydroxy5-nitroThiazole

USES

The thiazole ring is present in various compounds which are used in treatment of
various types of diseases. E.g. Thiobendazole – Anthelmentic agent.
 4
5
N
BENZIMIDAZOLE 3
6 2
N
7
H
1 or C7H5N2

The benzimidazole ring is found in the vitamin B12.

PREPARATION
O
NH2 NH
-H 2O -H 2O N
+ C OH OHC

NH2 H NH2 N
H
O-phenylene diamine Formic acid Benzimidazole

PROPERTIES

1. It undergoes electrophilic substitution reaction like nitration, sulphonation and

halogenations at position 5.
HO 3S
H2SO 4 N
Sulphonation
N
H
Benzimidazole
5-sulphonic acid
O 2N
N N
Conc.HNO 3

N Nitration N
H H
Benzimidazole 5-nitro
Benzimidazole

Cl
N
Cl 2
Chlorination N
H
5-chloro
Benzimidazole

2. Nucleophilic substitution reaction takes place at 2nd position.

N

aq.NaOH
N OH
N H

N
NH3 N
H
Benzimidazole
N NH2
H
2-amino
Benzimidazole
 4
5 3

INDOLE 6
N
2
7
H
2,3-benzopyrrole 1 or C8H17N

PREPARATION

1. Fischer Indole synthesis-

H3C COOH
ZnCl2/  250oC
N
N
-NH3 N -CO2
COOH N
H
H H

Phenylhydrazole of Indole
Pyruvic acid

2. Madelling synthesis-
CH3 O
C2H50Na
CH
NH NaNH2 N
H

N-O-tolylFormamide Indole

3. By heating O-amine-ω-chlorostyrene with sodium ethoxide-

CH CH
C2H50Na
Cl
NH2  N
H

O-amino chlorostyrene Indole

PROPERTIES

1. Electrophilic substitution reaction-

Attack at 3rd position – stable product
Attack at 2nd position – less stable product
 If both position i.e. 2nd and 3rd are occupied, then substitution takes place at 6th
position.

SO 3H NO 2

Sulphonation Nitration

fumingH2SO4 N Conc.HNO3
N H N
H H
Indole3-sulphonic acid Indole
3-nitro Indole

X2 Halogenation

N
H
3-haloIndole

Friedal-craft acylation-
COCH 3
(CH3CO)2O Rearrangement

N N N
H H
COCH 3
Indole N-acetyl Indole 3-acetyl Indole

Reimer-tieman reaction-
CHO
CHCl3

N NaOH N
H H

Indole Indole 3-carbaldehyde

Mannich reaction-
CHO
CHCl3

N (CH3)2NH N
H H

Indole Indole 3-carbaldehyde

 2. Reduction

Sn/HCl

N
H
2,3-dihydro Indole
N
H
Indole
[H]
Raney Ni
N
H
Octahydro Indole

3. Oxidation
O
H
N
O3

N |O|
H N
H
Indole
O
Indigotin

USES

The indole ring is present in various compounds such as:

Indomethacin- Anti-inflammatory
Analgesic
Used in rheumatoid arthritis.
 9 H 1
N
PHENOTHIAZINE 8 10 2

7 3
S
6 5 4 or C12H9NS

PREPARATION

1. By heating O-amino thiophenol with catechol-

H
NH2 HO N

+ + H2O
SH S
HO
O-amino Catechol Phenothiazine
Thiophenol

2. By fusion & biphenyl amine with sulphur-

H
H
N N

+ 2S
+ H2S
S
Phenothiazine