Section (A) : Phenol: Aromatic Compounds

Aromatic Compounds
Introduction :
All organic compounds classify into two broad classes, aliphatic compounds and aromatic compounds.
Aromatic compounds are those that resemble with benzene in chemical behaviour.
Proposed structure of benzene :
H
H
C
H–C C–H H H
H–C C–H H H
C
H
H Dewar's benzene
Kekule benzene
* Benzene mostly represents by Kekule structure.
Huckel's (4n + 2) rule for aromaticity :
An aromatic compound must have cyclic clouds of delocalised (4n + 2) electrons above and below the
plane of the molecule or in other words a compound which is cyclic, planar and have complete cyclic
delocalisation of 2,6,10...... electrons is an aromatic compound, according to Huckel's rule.
The following three rules are useful in predicting whether a particular compound is aromatic or non-
aromatic.
(i) Aromatic compounds are cyclic and planar.
(ii) Each atom in an aromatic ring is sp2 or sp hybridised.
(iii) The cyclic  molecular orbital (formed by overlap of p-orbitals) must contain (4n + 2) electrons, i.e., 2,
6, 10, 14 ........  electrons. Where n = an whole number 0, 1, 2, 3,..............
Characteristic reaction of aromatic compounds :
* Aromatic compounds prefer electrophilic substitution rather than electrophilic addition reaction.
* In aromatic electrophilic substitution reaction benzene ring serve as source of electrons that is as a
base or nucleophile.
* Electrophilic aromatic substitution includes a wide variety of reactions :
e.g. Halogenation, Nitration, Sulphonation, Friedel Crafts alkylation & acylation but reactions like
Nitrosation and Diazocoupling undergoes only by rings of high reactivity.
Section (A) : Phenol

Phenol, also known as carbolic acid, was first isolated in the early nineteenth century from
coaltar. Nowadays, phenol is commercially produced synthetically. In the laboratory, phenols are
prepared from benzene derivatives.
Some common examples are :
(i) OH CH3 CH3 CH3
OH
OH
OH
Common name : Phenol o-Cresol m-Cresol p-Cresol
IUPAC name : phenol 2-methylphenol 3-methylphenol 4-methylphenol
Reg. & Corp. Office : CG Tower, A-46 & 52, IPIA, Near City Mall, Jhalawar Road, Kota (Raj.) – 324005
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ADVAC - 1
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Aromatic Compounds
(ii) OH OH OH
OH
OH
OH
Common name : Catechol Resorcinol Hydroquinone or quinol
IUPAC name : Benzene-1,2-diol Benzene-1,3-diol Benzene-1,4-diol
Dihydroxy derivatives of benzene are known as 1,2-, 1,3- and 1,4-benzenediol.
(a) Preparation of phenol
NaOH, 
(1)  

HCl
Fusion
H O/ (i) O
(2) 
2
 (3) 
2

(ii) H3 O
KOH/ 
(4) soda lime/
 (5)  
HCl
 Ph–OH
high pressure
high temperature
Mechanism (Cumene hydroperoxide method) :
(i) O / 

2

 +
(ii) H3 O
(b) Properties of phenol :

Phenol is a colourless crystalline solid, m.p. 43ºC, b.p. 182ºC, which turns pink on exposure to air and
light.
Phenol is used as an antiseptic and disinfectant and in the preparation of dyes, drugs, bakelite, etc.
ADVAC - 2
Aromatic Compounds
(c) Chemical reactions of phenol :
Phenol generally gives electrophilic substitution with electrophilic reagents.
OH
Br , water
(1) 
2

OH
Br , CS
(2) 
2 2
 +
273 K
OH
dil. HNO
(3) 
3

OH
HNO /H SO
(4) 
3 2 4
 (Major is oxidative cleavage of ring) + Picric acid (small amount)
(5)
(6) Reimer-Tiemann formylation reaction :
Mechanism :
Step (I) : CHCl3 + NaOH : CCl2
Step (II) :
ADVAC - 3
Aromatic Compounds
(7) Reimer-Tiemann carboxylation reaction :
(8) Kolbe carboxylation reaction :
Preparation of aspirin :
COOH COOH
OH OCOCH3
Pyridine
+ (CH3CO)2O + CH3COOH
Salicylic acid Acetylsalicylic acid

(Aspirin)
(9) (polymer)
(10)
(11) (12)
(13) Williamson ether synthesis
(14) Protection of –OH and –NH2 group.

OH OCOCH3
CH3COCl or (CH3CO)2O
Pyridine
ADVAC - 4
Aromatic Compounds
AlCl3/ 
O Fries Rearrangement
O–C–CH3
O–CO–CH3 O–CO–CH3
HNO3 NO2
H2SO4
Phenyl ester NO2
O–CO–CH3 O–CO–CH3
R-X
R
AlCl3
R
(15) Fries rearrangement :
(16) Oxidation of phenol :

OH O
II
Na2Cr2O7
H2SO4, H2O
II
O
(d) Test of phenol :
(1) Phenols turn blue litmus red. Phenols behave as acid and ionise in aqueous solution to give H+ ions.
(2) Reaction with ferric chloride : Phenol gives a violet-coloured water soluble complex with
neutral ferric chloride.
6C6 H5 OH + FeCl3 [Fe(OC6 H5)6]–3 + 3H+ + 3HCl
Violet complex
(3) Libermann’s test : When a sodium nitrite (NaNO2) is added to a phenol dissoved in conc.
sulphuric acid, red or brown colour is produced and changes to blue by the addition of a strong alkali.
This test can be used to distinguish between phenols from alcohols.
2NaNO2 + H2SO42HNO2 + Na2SO4
Sodium nitrite Nitrous acid
OH
+
/H
HNO2


ADVAC - 5
Aromatic Compounds
Section (B) : Nitrogen containing compounds (Nitrobenzene & Aniline)
(a) Preparation of nitrobenzene :
Conc.H SO
+ HNO3 2 4

333K
(conc.)
NO2
Conc.H SO
+ HNO3 2 4
 + H2O
373K
(conc.)
NO2
(b) Chemical reactions of nitrobenzene :
NO2 NH2
Ni / Pd
(1)
NO2 NH2
(2)
NO2
(3)
+ 4H
NO2
(4)
(+8H)
NO2
(5)
NO2 NH2
(6)
NO2
(7)
(8)
(9)
ADVAC - 6
Aromatic Compounds
(10)
(c) Test of nitrobenzene : (Mulliken- Barker’s test)
AgNO NH OH
+ Zn + NH4Cl  
3 4
 
(d) Test of benzaldehyde (Aromatic aldehyde)
 
 PhCOO NH4 
(e) Prepartion of aniline
(1)
(2)
(3)
(4) Hofmann bromamide degradation reaction :

Hofmann developed a method for preparation of primary amines by treating an amide with bromine in
an aqueous or ethanolic solution of sodium hydroxide. In this degradation reaction, migration of an alkyl
or aryl group takes place from carbonyl carbon of the amide to the nitrogen atom. The amine so formed
contains one carbon less than that present in the amide.
O
C H2O
R–NH2 + 2NaBr + Na2CO3 + 2H2O
R NH2 + Br2 + 4 NaOH
Mechanism :
ADVAC - 7
Aromatic Compounds
(5) Gabriel phthalimide synthesis :

Gabriel synthesis is used for the preparation of aliphatic primary amines. Phthalimide on treatment
with ethanolic potassium hydroxide forms potassium salt of phthalimide which on heating with alkyl
halide followed by alkaline hydrolysis produces the corresponding primary amine. Aromatic primary
amines cannot be prepared by this method because aryl halides do not undergo nucleophilic
substitution with the anion formed by phthalimide.
(f) Chemical reactions of aniline
(1) (2)
(3)
(4)
(5)
ADVAC - 8
Aromatic Compounds
(6)
(7)
(8)
NH2 NH2
(9) (oxidation) (10)
(11) Schotten Bauman reaction.
(g) Test of aniline :

(1) Carbylamine reaction
Primary amines (alphatic as well as aromatic) react with chloroform (CHCl 3) on heating in the presence
of ethanolic solution of KOH to form isocyanides (also called carbylamines) which are foul smelling
substances. Secondary and tertiary amines do not undergo this reaction, therefore this reaction is used
as a test for Primary amines (alphatic as well as aromatic).
(2) Reaction with nitrous acid

Amines of different classes react with nitrous acid (unstable acid). HNO2 is prepared by the reaction of
sodium nitrite (NaNO2) and dilute hydrochloric acid.
Primary aromatic amines react with nitrous acid at low temperature (273-278 K) to give aromatic
diazonium salts. This reaction is known as diazotisation.
Primary aliphatic amines also react with nitrous acid to form diazonium salt, however, the aliphatic
diazonium salts being unstable, decompose to yield mixture of alcohols, alkenes along with nitrogen
gas.So this reaction is used to distinguish between aromatic and aliphatic 1º amines.
NaNO2 / HCl H2O
C2H5NH2     C2H5 OH + CH2 = CH2 + N2 + H2O
(Major)
ADVAC - 9
Aromatic Compounds
Secondary aliphatic and aromatic amines react with nitrous acid to produce nitroso-amines that are
insoluble in the aqueous solution and separate out as a yellow oily layer.
(C2H5)2 NH + HNO2  (C2H5)2 NH—NO + H2O

Diethyl amine N-Nitrosodiethylamine
Tertiary aliphatic amines react with nitrous acid to form salts, which decompose on warming to
nitrosoamine and alcohol while tertiary aromatic amines undergo electrophilic substitution at the ring.

R3N + HNO2  R3N.HNO2   R2N  N  O + ROH
Nitrite salt Nitrosoa min e
(3) Hofmann mustard oil reaction
 HgCl
CH3CH2NH2 + S=C=S   
2
 CH3CH2–N=C=S + HgS + 2HCl

(1º amine) Ethyl isothiocyanate
(4) The Hinsberg test :
The hinsberg test can be used to demonstrate whether an amine is primary, secondary or tertiary
Primary amine :
O O O O O O
R H S – S S
N OH R' KOH R'
+ Cl N N
H –HCl H
Base soluble salt
Acidic hydrogen (Clear solution)
Secondary amine :
O O O O
R H S – S
N OH R' KOH
+ Cl N No reaction.
R –HCl R
Insoluble in base
(Precipitate)
Tertiary amine :
If the amine is tertiary amine and it is water insoluble no apparent change will take place in the mixture
as we shake it with benzene sufonyl chloride and aqueous KOH. When we acidify the mixture, the
tertiary amine dissolves because it forms a water soluble salt.
Section (C) : Benzenediazonium salt and its reaction

(a) Preparation of benzenediazonium salt
+ –
N2 Cl
Benzene
diazonium chloride
ADVAC - 10
Aromatic Compounds
(b) Chemical reactions of benzenediazonium chloride
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
ADVAC - 11
Aromatic Compounds
(11)
(12)
(13)
(14)
(15)
(16)
(17)
ADVAC - 12

Section (A) : Phenol: Aromatic Compounds

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Aromatic Compounds

Section (A) : Phenol

(a) Preparation of phenol

Mechanism (Cumene hydroperoxide method) :

(b) Properties of phenol :

(6) Reimer-Tiemann formylation reaction :

(8) Kolbe carboxylation reaction :

Salicylic acid Acetylsalicylic acid

(13) Williamson ether synthesis

(14) Protection of –OH and –NH2 group.

(16) Oxidation of phenol :

(c) Test of nitrobenzene : (Mulliken- Barker’s test)

(d) Test of benzaldehyde (Aromatic aldehyde)

(e) Prepartion of aniline

(4) Hofmann bromamide degradation reaction :

(5) Gabriel phthalimide synthesis :

(f) Chemical reactions of aniline

(9) (oxidation) (10)

(11) Schotten Bauman reaction.

(g) Test of aniline :

(2) Reaction with nitrous acid

(C2H5)2 NH + HNO2  (C2H5)2 NH—NO + H2O

(3) Hofmann mustard oil reaction

Section (C) : Benzenediazonium salt and its reaction

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