UNIT - I|

AROMATICACIDS
Points to be covered in this topic
1. INTRODUCTION

2. NOMENCLATURE

3. METHODS OF PREPARATION

4. CHEMICAL REACTIONS

OINTRODUCTION
The aromatic acids are the derivatives of aromatic hydrocarbons in
which one or more hydrogen atoms have been replaced by the
carboxylicgroups.
The carboxylic group may be directly attached to the aromatic
nucleus and is known as benzoic acid or its derivatives
Sometimes carboxylic group is present in the side chain of the
aromatic nucleus for e.g.

COOH COOH CH,COOH

.CHa

Benzoicacid o-Toluic acid Phenyl acetic

acid
 DNOMENCLATURE
1. Common system:
According to this system the aromaticacids are generally known as
derivatives of benzoicacid. For e.g.
C

OOH
p-Chlorobenzoic acid

And some aromatic acids have special names. For e.g. Methyl benzoic
acidis also known as Toluicacid
COOH

CH3

Methyl benzoic acid

(Toluic acid)

2. IUPACsystem:
The simplest aromatic acid is Benzoic acid.
The other aromaticacids are named as derivatives of benzoic acid.
The saltsof aromatic acids are named by writing the name of cation
followed by the name of the acid in which the ending "icacid" has been
replaced by "ate".For e.g.
COOH
CH,CH,COOH coON.

H,
3-phenylpropanolc acid p-Methyl benzoic acid Sodium benzoate
 OMETHODS OF PREPARATION
1. Friedel-Craft's reaction:
When benzene is reacted with carbonyl chloride in the presence of
anhydrous aluminium chloride, an acid chloride is obtained which on
further treatment with water gives the corresponding acid
AlCl, HCI
CçH6 CoCl, CçH-COCI
Benzene Carbonyl Benzoyl
chloride chloride

CçHsCoCI + H,0 CçH-C0OH + HCI

Benzoic acid

2.Sandmeyer's reaction:
Aniline on diazotization (HNO,/HCI) give benzene diazonium chloride
which on reaction with CuCN product Benzonitrile further benzonitrile
gives benzoic acid on treatment with water.

HNO,/HCI CuCN HOH

CçH,NH, CGH,N,ClI CçHsCN CH,COOH
Aniline Benzene diazonium Benzonitrile Benzoicacid
chloride

3. From Phthalicacid:
An aromatic acid is obtained by passing vapours of phthalic acid either
by partial decarboxylation with soda lime or mixed with steam over
heated catalyst.
CoOH
Steam
COOH
Nisalt

COOH
COOH Ca0
Phthalicacid NaOH
Benzoic acid
4. By oxidation of alkyl benzenes:
Alkyl benzenes are oxidized by dil. nitric acid or alkaline potassium
permanganate or dichromate and H,SO, or chromium trioxide in glacial
acetic acid.

CGHsCH, 3[0] CçH;C0OH H,0

Toluene Benzoic acid

5. From benzotrichloride:
OH
Fe/Ca(0H), CçH;C-OH
C,H,CCl, 3H,0
Benzotrichloride OH
Unstable

-H,0

C,HsCOOH
Benzoic acid

6. From sulphonicacid:
When the potassium salt of an aromatic sulphonic acid is fused with
potassium cyanide, we get a nitrile, which on hydrolysis, gives an
aromatic acid.

KCN H,0
C,H,SO,K CçH,CN CçHsCOOH
Potassium Benzo-nitrile Benzoic acid
benzene sulphonate

7.From Primary alcohol:

Aromatic acid can be prepared by oxidation of primary alcohol with
acidified potassium dichromate, alkaline KMnO, or HN0,

K,Cr,0,
C,HCH,0H CGHCOOH
H,So4
Benzyl alcohol Benzoic acid
8. By hydrolysis of nitriles:
Nitriles on hydroxy by dilute acids or alkalies gives aromatic acid

H"
CH,CEN 2H,0 CH,cOOH + NH,

Phenyl acetonitrile Phenylacetic acid

9. Baeyer-Villiger Oxidation:
In this reaction, carboxylic acids are formed when aldehydes (both
aliphatic and aromatic) are treated with a peracid in the presence of acid
catalysts.
o=o
0
CgHs-C-0-OH, H*
H,C-CH,-C-H H3C-CH,-C-OH CçHs-C-OH
Propanal CH,C1,, reflux Propanoic acid Benzoic acid

0
H ||
R-C--0-0H, H* OH
R-C-OH
CH,Cl,, reflux
Phenol Benzoic acid (R=CH,)
 DCHEMICAL REACTIONS
1.Salt Formation:
Aromatic carboxylic acids show asimilar behaviour to aliphatic acids.
They react with NaHCO, and NaOH to form salts; with alcohols they form
sOCl, esters; with PCI, they form acid chlorides; and with ammonia they
form amides. When heated, aromatic carboxylic acids form anhydrides.
0 0

soCI, HCI

0
-t-OH NH3
H.0

H',A
-i-oH CH,0H -i-oCH, H,0

2. Reduction:
" Just like ester functional groups, the carbonyl group undergoes
reduction with LiAlH,to form a primary alcohol

()LiAlHL,
-C-OH -CH,
-CH,-OH
() H*

(0) LLAH,
H,C -C-OH H,C CH,-0H
()H*
p-Toluic acid p-Methylbenzyl alcohol

3. Decarboxylation:
When carboxylic acids are treated with sodium bicarbonate, carbon
dioxide isevolved. On heating the sodium salt of the acid with soda lime,
ahydrocarbon is formed with the loss of carbon dioxide.
 0
+
-0 Na
Sodalime 4
Na,CHO

C-0
CH3
Soda lime
Na,CO3
H,C
Sodium toluate

4. Ring Substitution:
Carboxyl group is the electron-withdrawing group and thus is meta
directing. Metaisomer is produced by the nitration of benzoicacid.

OH OH

HNO, H,S04

NO,
m-Nitrobenzoic acid (80%)

5.Acids Halide Formation:

Reaction between aromatic acids and phosphorushalides or thionyl
chloride yields acid halides. Thisreaction occurs with more difficulty
with aromatic acidsas compared to the aliphatic acids.

CçHsCOOH PCls CGH,COCl POCl, + HCI

ArC0OH
sOcl; ArCoCl HCI So,
6. Esterification:
The unsubstituted aromatic acids can undergo esterification with
alcohols inthe presence of a mineral acid. However in the presence of
an ortho- substituent, steric hindrance is observed which greatly
reduces the esterification rate. Therefore, such aromaticacids are
esterified by the action of alkyl halides on their silver salts.

+ H,0
CçH;C00H CzHs0H CçHsC00CzHs
Benzoic acid Ethylbenzoate

7.Acid Amide Formation:

Reaction between aromaticacids and ammoniayields an ammonium
salt which on heating forms amide by losing a water molecule.

NH3
Ar.C0OH Ar.COONH,
- H,0
Ar.CO.NH2
Ammonium salt Acid amide

8. Schmidt Reaction:

On treating aromaticacids with hydrazoic acid in the presence of

sulphuricacid, an amine is yielded. Acyl azide is formed as an
intermediate which decomposes into amine.

H,s04
CH4(CH,).cOOH NzH CH,(CH,)NH, N,
p-Toluic acid p-Toluidine

H,S0,
CeH,CH,coOH NgH CGH,CH,NH, N, CO2
Phenylacetic acid Benzylamine
 9. Reactions of the Benzene Nucleus:

The aromatic acids undergo common electrophilic substitution

reactions like nitration,sulphonation, and halogenation

Since the -C0OH groupis a deactivating and m-directing group, the

new group attaches at the m-position with respect to -COOH group.
They do not give Friedel-Crafts reaction.

COOH COOH COOH

Br;/FeBr, HNO;/H,SO,
Bromination
Br NO,
m-Ntrobenzoic
m-Bromobenzoic acid
acid So,/H,s0,
Sulphonation

COOH

so,H
m-Sulphobenzoic acid

10. Side Chain Substitution:

On treating aromatic acids having -C0OH group in the side chain with
halogen and phosphorus,side chain halogenation occurs. This reaction is
also known as Hell-Volhard- Zelinsky method.

Cl,/P
Ar.CH,COOH Ar.CHCI.COOH
 UNIT - II
AROMATICACIDS

Points to be covered in this topic

1. ACIDITY

2. EFFECT OF SUBSTITUENTS ON ACIDITY

3. BENZOICACID
4. USES OF BENZOIC ACID

5. PHYSICAL PROPERTIES OF BENZOIC ACID

6. IMPORTANT REACTIONSOF BENZOIC ACID

OACIDITY
The acidity of aromatic carboxylic acids is slightly more than that of
aliphatic acids.
Thisis because the electronegativity of sp²-hybridised carbon atom of
the benzene ring is more than that of the sp³ hybridised carbon atom in
an aliphatic chain
Thus, the phenyl group acts as an electron-withdrawing group.
In the phenoxide ion, due to resonance a partial charge resides on the
benzene ring.
Therefore, acidity of phenol is more than that of ethanol. Similarly, it is
assumed that direct attachment of -COOH group on benzene ring
increases the acidity of benzoic acid more than that of acetic acid.
However, difference between the acidity of both the acids is less.
The K, value for benzoic acid is 6.5 x105 and for acetic acid is 1.8 x 105
because the acid itself is stabilised by resonance
 OH OH
"0OH

etc.

This type of conjugation is less effective in benzoate ion than in

phenoxide ion so the aromaticring contributes less to increase the
acidity than in phenol as there is a charge separation.
In benzoate ion,direct resonance of the carboxylate ion with the ring
does not exist.

DEFFECT OF SUBSTITUENTS ON ACIDITY

If electron-withdrawing groups are present on the benzene ring of
benzoicacid,the benzoate ion stabilises and acidity thus increases.
Thisis attributed to inductive and resonance effects
In case of p-nitrobenzoic acid and its m-isomer, based on the
inductive effect alone the m-isomer would be assumed to be stronger
than the p-isomer but the reverse is also true.
No direct resonance of the carboxylate ion with the ring exists; but the
esonance structures for each isomer shown below can be
considered:

CO0 -coo

-coo -Coo

62
 Apparenty the resonance in p-isomer places the positive charge on the
carbon atom carrying the -CO0 ion
Therefore,the ion stabilises due to strong inductive effect
In m-isomer, the positive charge is on the carbon atom adjacent to the
carbon carrying the -C00 ion
The inductive stabilisation of this ion is less.
Therefore, acidity ofp-nitrobenzoic acid is more than that of the m
isomer.

CO0 CO0

Cl

For p- chlorobenzoic acid isomers, similar arguments can be used.

Theresonance structures shown depict that the m-isomer is a
stronger acid than the p-isomer because the negative charge is
positioned ortho to the -Co0 ion in the former.
On the other hand, the effect of electron-donating groups is just the
opposite as they destabilise the ion and place a negative charge on
the -CO0* ion.
/ This increases the ion's ability to regain the proton.
Lower the pk, value, stronger is the acid.

COOH

X
Table : pK, Values of Substituted Benzoic Acids
Substitue pka
nt (X) Ortho Meta Para
-NO 2.21 3.49 3.42

-0CH, 4.09 4.09 |4.47

-OH 2.98 4.08 4.57

-CN 3.14 3.64 3.55

-Br 2.85 3.81 3.97

-CI 2.92 3.83 3.97

-CH, 3.91 4.27 4.38

-H 4.20 4.20 4.20

The values in the table state that an alkyl group produces a little effect
on the strength of benzoic acids. But the electron-withdrawing groups
increase the acidity.
These groups when present in 0- and p-positions produce a more
prominent effect. The electron withdrawing effect of o-NO, group is
significant due to the short distance over which the powerfulinductive
effect along with the resonance effect of this group is operating

Presence of groups like -0CH, -0H,or halogens(electron

withdrawing groups inductively but electron-donating
mesomerically)in 0- and p-positions weakens the p-substituted
acids than the m-substituted acids

Sometimes it is also observed that some 0-substituted benzoic acids

behave strangely and their acidity is higher than expected.
This is because the group interacts with the adjacent carboxyl group,
forming intermolecular hydrogen bond.
 J BENZOICACID (C,H,COOH)
Benzoic acid (the simplest aromaticacid) is naturally present in gum
benzoin (a resin obtained from plants) and in other resins, and in
balsams of Peru and Tolu either in the form of free acid or ester:
It got its name from gum-benzoin from which it was firstly obtained.
It isone of the earliest known organic compounds.
Liebig and Wohler established the structure of benzoic acid in 1832.

JPHYSICAL PROPERTIES OF BENZOIC ACID

1. Itis a white crystalline solid.
2. It has a melting point of 121°C.
3. Itissparingly soluble in cold water but fairly soluble in hot water,
alcohol, and ether:
4 It has a faint aromatic odour.
5 It readily sublimes and is volatile in steam.

OUSES OF BENZOIC ACID

1. Itssalts are used in medicines.
2. Its sodium salt is used as a food preservative.
3. It isused for synthesizing variousorganic compounds.
4. It is used for treating infection in bronchial tubes
 OIMPORTANT REACTIONS OF BENZOIC ACID
Chemically, benzoicacid is identicalto aliphatic acids; but is
stronger than acetic acid.
> Following are the reactions which benzoic acid undergoes:

Reactions due to Carboxyl Group

> Carboxyl group gives the following reactions:

NaOH
CH,cOONa + H,0
Sodium benzoate

CCH OH
Conc. H,SO,
heat
H,0
Ethylbenzoate
PCI,
CH,COOH c,H,coCI POCI, + H,0
Benzoic acid Benzoyl chloride

Ca0 Na0H
cH, 4 CaCO,
Benzene

NH, A
c,H,coONH, CzH,cONH, H,0
Ammonium benzoate Benzamide

Ac,0
2C,H-C00H CH CO.0.0C.C,Hs
-H,0 Benzoic anhydride
 Reactions due to Phenyl Group GDC

> Phenylgroup gives the following reactions:

COOH
Nitration

Conc. HNO3/H,SO4
NO,
m-nitrobenzoic acid

COOH COOH

Sulphonation
So,/H,S04
so,H
Benzoic acid m-sulphobenzoic acid
COOH

Halogenation
FeBrs/Brz Br
m-bromobenzoic acid
 UNIT I|
AROMATICAMINES
Points to be covered in this topic

E
1. INTRODUCTION

2.CLASSIFICATION
3. NOMENCLATURE

OINTRODUCTION
Aromatic amines are very important class of nitrogenous compounds
which can be regarded as derivatives of ammonia in which one or more
hydrogen atoms have been replaced by aryl groups or an aromatic
amine is an organic compound consisting of an aromatic ring attached to
an amine

NH2 NHCH; N(CH3)2

Aniline N-Methylaniline N,N-Dimethylaniline

Compounds of nitrogen connected to a carbonyl group are called as

amides

Basically, they are derived from ammonia (NH,) in which one or more
hydrogen atoms is replaced by an alkylor arylgroup, and so they are
known as alkylamines and arylamines respectively.
 CLASSIFICATION
Aromatic amines areclassified asPrimary (1), Secondary (2°) and
Tertiary (3°) amines according as one, two or three hydrogen atoms of
mmonia have been replaced by aryl groups.
1. Primary aromatic amines:
These are the aminesin which one hydrogen atom of ammonia has
been replaced by aryl group
NH,

Aniline

> If amino group is attached to an substituted alkyl group is known as

aryl alkyl amines
CH,NH,

Benzylamine

2. Secondary Aromatic amines:

In this type of amines two hydrogen atoms of ammonia have been
replaced by aryl groups
H

Diphenylamine
If two group attached to the imino group -NH- are diferent then it is
known as mixed aliphatic aromatic amine

-N-CH,
N-Methylaniline
3. Tertiary aromatic amnines:
Tertiary aromatic amines are those in which all three hydrogens of
mmonia have been replaced by arylgroups.

Triphenylamine

Again,tertiary aromatic amines may purely aromatic or mixed

aliphatic aromatic

-CH3
CH3
N,N-Dimethylaniline

NOMENCLATUR
Accordingto IUPACsystem, while naming arylamines suffix 'e' of arene
is replaced by amine.
Thuscommon name of parent member C,H,NH, is aniline but in IUPAC
system it is named as benzenamine
Other aromatic amines are named as derivatives of aniline.

NH,
N(C,Hs)2

NO, N,N-Diethylaniline
p-nitroaniline or
or
4-nitroaniline N,N-Diethylbenzenamine
NH,
NH,
CH3

o-toluidine dCH,
or
panisidine
2-Methylaniline or
or 4-Methoxyaniline
or
2-Methylbenzenamine
4Methoxybenzenamine
Secondary or tertiary aromaticamines are named as the aryl or
alkyl derivative of the parent amine, aniline.

Diphenylamine
or Triphenylamine
N-phenyl benzenamine or

N,N-Diphenyl benzenamine

Side chain aromaticamines or aralkyl amines are named by adding

'amine' to the end of the name of the aralkyl group or the name of the
longest chain. For e.g.

CH,NH, CH,CH,NHz

Benzylamine 2-phenyl ethanamine

or or

Phenyl methylamine P-phenyl ethylamine

Saltsof amines are generallynamed by replacing amine by

ammonium (or aniline by anilinium) and adding the name of anion
(chloride, sulphate, nitrate etc.)

-2
(C,H-NH,)So, C,H,NH,CI
Ethylammonium sulphate Anilinium chloride
 UNIT - II
AROMATIC AMINES

Pointstobe covered in this topic

1. METHODSOF PREPARATION
2. CHEMICAL REACTIONS

O METHODSOF PREPARATION
1. Reduction of Nitro Compounds:
Thisreaction is used for the preparation of amines as well as many
aromatic compounds.
This reaction is of the following types:

i.Chemical Reduction:
This reduction occurs in the presence of tin and hydrochloric acid.
However, combinations of titanous chloride-hydrochloric acid, iron
hydrochloricacid, zinc-acetic acid, and alcoholic ammonium
sulphide-alcoholicstannous chloride can also be used.

Sn/HCI
CGHsNO, + 6H
CçH_NH, + 2H,0
Nitrobenzene Aniline

CH,C,H,NO, + 6H
Sn/HCI
CH3CçHNH, + 2H,0
Nitrotoluene Toluidine
ii.Catalytic Reduction:
In this reaction, alcoholic solutions of nitro compounds are reduced
with finely divided nickel, palladium,or platinum, by passing hydrogen in
the suspension. The nitro compounds are also reduced by hydrogen in the
presence of Raney nickel.

Ni
ArNO, 6H ArNH, 2H,0
Ni
CGH;NO, 6H CçHsNH, + 2H,0
Nitrobenzene Aniline

iii. ElectrolyticReduction:
In this reaction, the aromatic compounds reduce to amino compounds
at a suitable pH

Weakly acid
CçH,NO, Solution CH;NH,
Nitrobenzene Aniline

2. Ammonolysis of Halogen Compounds:

The nuclear halogen is not easily replaced with ammonia,
therefore a reaction is carried under high temperature and pressure
conditions in which ammonia reacts in the presence of Cu,0
(catalyst).
250°C
2C6H_Cl + 2NH3 + Cuz0 2C,H5NH, + 2CuCl + H,0
Pressure

3. Ammonolysis of Phenols:
In this reaction, ammonia and phenols react at 300°C in the
presence of zinc chloride.

ZnCl,
GH;OH + NH, CçH,NH, + H,0
300°C
Phenol Aniline
4. Hofmann's Method:
. Inthis reaction, amides of aromatic acids are treated with bromine
and alkalito yield amines containing one carbon less than the amide.
Br,/KOH
ArcONH, ArNH,

5.Schmidt Reaction:
Inthis reaction, an aromaticcarboxylic acid solution in concentrated
sulphuric acid is shaken with chloroform solution of hydrazoic acid
(HN,)to yield an amine.

Conc. H, SO4
CGH_COOH + N,H CGH;NH, + N2 + Co,
Benzoic acid Hydrazonic
acid

6. Action of Hydroxylaminewith Hydrocarbons:

In this reaction, hydroxylamine reacts with aromatic hydrocarbons in
the presence of FeCl, or AlCI, (catalyst) to yield monoamines.

FeCl,
CGHH + HONH2 CGHsNH, + H,0

7. Isomerisation of Alkylanilines (A.W. Hofmann):

In this reaction, a hydrochloride of a mixed secondary or tertiary
aliphatic-aromatic amine is heated at 300°C. As a result, the position of
alkyl group changes from the side chain to the nucleus.

NH(CH,).HCI NH,.HCI

300°C

N-Methylaniline hydrochloride CH3

p-Toluidine hydrochloride
 OCHEMICAL REACTIONS
1.Reaction with Alkyl and Aryl Halides:
this reaction, secondary andtertiary amines, and quaternary
ammonium compounds are obtained by the alkylation or arylation of
aromatic aminocompounds.

ArNH2 + RX ArNHR + HX

Secondary amine

ArNHR + RX ArNR, HX

Tertiary amine

ArNR2 + RX [ArNR3]X
Quaternary
ammonium salt

2.Acylation:
Inthis reaction,the amino groups of the aromaticamines undergo
acylation on treatment with acid chlorides or acid anhydrides. These
reactions occur in the presence of pyridine (a base).

ArNH, + CH,COCI ArNHCOCH3 + HCI

Pyridine
ArNH, + CçH;COCI ArNHCOC,Hs + HCI

These aryl substituted acid amides are called anilides.

Pyridine
C,H,NH, CH,COCI CGH,NHCOCH, + HCI

Aniline Acetyl chloride Acetanilide

CçH,NH, + CçH;COCI CH,NHCOc,Hs + HCI

Aniline Benzoyl chloride Benzanilide
3. CarbylamineReaction:
In this reaction,the aromaticprimary amines are treated with
chloroform and alcoholic causticpotash to yield an unpleasant
smelling isocyanide (carbylamine)

CH,NH, CHCI, + 3KOH CH,NC 3KCI 3H,0

Aniline Phenyl isocyanide

4. Action with Grignard Reagent:

In this reaction, the aromatic primary amines react withGrignard
reagent to yield hydrocarbons corresponding to alkyl radical of
Grignard reagent.

CçHsNH, CzH,MgBr CzH, CzH_NHMgBr

Aniline

5. Condensation with Aldehydes:

In this reaction,the aromaticamines undergo condensation in the
presence of aldehydesto yield Schiff's bases or anils.

CGH_NH,
Aniline
+
0=-C,H; CGH_N=CHCGHs + H,0
Benzaldehyde N-Benzalaniline

These Schiff's bases undergo hydrolysis to yield free amines. Thus,

this reaction protects the -NH, group during nitration. The Schiff's
bases undergo reduction to yield secondary amines.

2H
CzH;N=CHAr C,H;NHC2Ar
Ni
6. Reaction with Carbon Disulphide:
Inthis reaction,the aromaticamines are refluxedwith ethanolic
carbon disulphide and solid potassium hydroxide to yield a diaryl
substituted thiourea.

CoH,NHH CçH,NH,
S=C=eS + 2KOH CS + K,S + 2H,0

C,H,NHH CçH,NH

7.Diazotisation (Reaction with Nitrousacid):

In this reaction, the aromatic primary amines react with nitrousacid
in the presence of a strong mineral acid at 0°C to yield diazonium
compounds.

ArNH, HCI ArNH,CI

ArNH Cl + OHNO ArN=N 2H,0

Diazonium chloride

This reaction is termed diazotisation, and it distinguishes between

aromatic primary aminesand aliphaticamines (which do not undergo
this reaction).
8.Substitution Reactions of the Nucleus:
The aromatic amines undergo electrophilic substitution reaction at
ortho- and para- positions. The presence of an amino group has an
activating effect on the nucleus, thus increasing the electron density at
ortho and para- positions:
i. Halogenation:
NH2
NH2
Br. Br

Brz

Br
Aniline 2,4,6-Tribromoaniline
ii. Sulphonation:

NH, NH,HSO, NHSO,H

- H,0
H,so,

Aniline Aniline acid Phenylsulphamic

sulphate acid

NH, NH2
60°c ,sO,H 180°C

Orthanilic acid
sOzH
(o-Aminobenzene
sulphonic acid) Sulphanilic acid
(p-Aminobenzene
sulphonic acid)

ii. Nitration:

NH, NHCOCH3 NHCOCH, NH,

NO, NO,
(CHCO),0 HNO,/H.S0, HOH

Acetanilide o-Nitroacetanilide o-Nitroaniline

Aniline
 9.Oxidation:
In this reaction, the aromaticamines undergo oxidation in the presenc
of different oxidising agents to yield avariety of oxidation products.
The actual product depends on the amine and the oxidising agent.
Thus, anilineoxidises to yield the following products:

i. Alkaline KMn0,:

+ CH,NH,
CH_NH, CH,NHOH c,H,NO CH,N=NC,H,
Aniline Phenylhydroxylamine Nitrosobenzene Azobenzene

ii.Caro's acid (H2SO,):

CçH_NH, CçH;NHOH CGH_NO CGH-NO,

iii. Chromic acid:

CGHsNH, - CçHsNHOH º HOC,HNH, 0= =0

p-Aminophenol
p-Benzoquinone
 UNIT - II
AROMATIC AMINES

Points to be covered in this topic

1. BASICITY OF AMINES

2. EFFECT OF SUBSTITUENTS ON BASICITY

3.ARYL DIAZONIUM SALTS

4.SYNTHETIC USES OF ARYL DIAZONIUM

SALTS

OBASICITY OF AMINES
Aromatic amines are basic innature due tothe lone pair of electrons
on the nitrogen atom.
However, the basicity of aromatic amines is lesser than that of
aliphatic amines.
The -NH, group in aromaticamines is directly attached to sp
hybridised carbon of benzene ring, while in aliphatic amines it is
attached to sp³ hybrid carbon.
The electronegativity of sp² hybridised carbon is more than that of sp'
hybridisedcarbon; thus, availability of lone pair on nitrogen is reduced
inaromatic amines.

sp² hybridised sp° hybridised

NH,
H,C-NH,
R
 Aromaticamine like aniline also shows a resonance effect (+R effect)
due to which the lone pair on its nitrogen involves in delocalisation
with -electrons of benzene ring system and is less shared with other
species.

8-3--&
NH, NH,

[Resonance effect (+R) in aniline]

The resonance effect in aniline makes it ortho- and para- directing

towards electrophilic substitution reactions.
> The basicity of amines in increasing order is shown below:

NH,

Amines: CH,NH, NH,

pK, 3.36 4.7 9.38 13.2 20.0

Increasing order of basic strength

The delocalisation of lone pair increases with increased number of

phenyl groups.
Presence of phenyl groups also increases steric hindrance
The combined effect of these two factors is that the availability of lone
pair of electrons on nitrogen is reduced, thus decreasing the basicity.
The basicity of diphenylamine is lesser than that of aniline, while
triphenylamine lacks basicity.
DEFFECT OF SUBSTITUENTS ON BASICITY
Presence of electron-releasing groups on the benzene ring of aro
amines enhances the electron density on nitrogen, thus increases the
basicity.
On the contrary, presence of electron-withdrawing groups reduces
the basicity of amines.
The basicity order of different substitutedamines is shown below:
NH2 NH,
NH,

NO2
ÖCH3
pK, 13.0 9.38 8.7

Presence of -NO, group indicates -Iand -R effect, thus enhancing the

delocalisation of lone pair on nitrogen with -electrons of the
benzene ring system and reducing the basicity of p-nitroaniline
compared to aniline.
Theelectron densityon nitrogen is increased due to +R effect of
methoxy group, further enhancing its basicity compared to aniline
>The basicity of aromatic amines depends on the following two
factors:
1. Inductive effect dependent on the substituent's position and occurring
in the order ortho- > meta- > para
2. Resonance effect observed in maximum intensity at ortho- and para
positions.

The presence of electron-withdrawing groups on aromatic ring

decreases the basicity of substituted anilines.
The -R effect of nitro group is maximum at ortho- and para
positions; thus, the basicity of m-nitroaniline is more than that of
ortho- and para- isomers as it withdraws electrons via - effect
(inductive effect) only.
Sincethe -Ieffect is stronger in o-nitroaniline than in p-nitroaniline,
the o-nitroaniline experiences a strong -R and -Ieffect and is least
basic.
 OARYL DIAZONIUM SALTS
The diazonium salts (di means two, azomeans nitrogen, and ium
indicates its cationic nature) or compoundsare organiccompounds
having general formula R-N,"X (X is an organic or inorganic anion,
e.g.,CI, Br,BE4, etc. and Ris an alkyl or aryl group).
Hence, diazonium salts carry two nitrogen atoms, one of which carries
acharge.
Benzenediazonium Chloride (C,H,N,CI), benzenediazonium hydrogen
sulphate (CçH,N,*HS04), etc., are some examples of diazonium salt.
Diazonium salts are ionic in nature, are water-soluble, and are
colourless crystalline solids.
Aryl diazonium salts are essential intermediates,prepared in cold
aqueous solution (0-10°C), and reacted with nucleophiles with loss of
nitrogen.
Benzenediazonium chloride iswater-soluble only when warmed.
Benzenediazonium fluoroborate is water insoluble; and is somewhat
stable at room temperature.

+
-NEN CI

Benzenediazonium Chloride

O SYNTHETICUSES OF ARYL DIAZONIUM SALTS

1. They are used for manufacturing azo dyes.
2 They are used in various industries for preparing significant organic
compounds such as m- bromotoluene, m-bromophenol, etc.
3. They are also used for preparing some important halogen
substituted arenes.
4. They are used as intermediates for preparing numerous valuable
aromaticcompounds.
5. They are used for preparing some pure forms of organic compounds
(especially aryl halides), for example, pure form of 1,2,3-tribromo
benzene is not obtained by direct bromination of benzene; but by the
reaction shown below:
 N, cI Br Br
Br. Br
Br. Br Br. Br
CuBr Sn, HCI

NO, NH,

Diazotisation

Br Br

Br. Br Br. Br
HgPOz

1,2,3-Tribromo benzene N,°cI

 UNIT - II
PHENOL
Points to be covered in thistopic
1.INTRODUCTION

2. NOMENCLATURE & CLASSIFICATION

3. METHODS OF PREPARATION

4. PHYSICAL PROPERTIES

5. CHEMICAL PROPERTIES

OINTRODUCTION

Phenols are compounds containing an -OH group attached

directly toan aromatic ring.
Itconsists of a hydroxyl group and phenyl group attached to
each other.
Phenolis a crystalline solidwhite in color
Phenol isalso known as Carbolicacid.
Phenol is aconstituent of coaltar and is formed during the
decomposition of organic materials
OH

Phenol
 ONOMENCLATURE & CILASSIFICATION
Depending upon the number of hydroxyl groups
attached to the benzene ring, phenols can be classified
as monohydric, dihydric and trihydric phenols.
Monohydric phenol
OH
OH
CH, CH3 CH3
OH 0,N. NO,

OH
ÖH
Phenol 0-cresol m-cresol p-cresol 2,4,6-trinitro
phenol

* Dihydric phenol
OH OH OH

OH

OH

ÖH
1,2-dihydroxybenzene 1,3-dihy droxybenzene 1,4-dihydroxybenzene
(Catecol) (Resorcinol) (Quinol)

* Trihydric phenol
OH OH OH
OH
OH

HO OH
OH ÒH
Pyrogallol Hydroxy quinol Phloroglucinol
(1,2,3-Trihydroxy benzene) (12,4-Trihydroxy benzene) (1,3,5-Trihydroxy benzene)
V Some of the aromatic hydroxy compounds contain -OH
groupin a side chain which is attached to the aromatic
ring (-0H group is not directly linked to aryl ring). They
are regarded as arylderivatives of aliphatic alcohols.
Examples:
CH,OH CH,CH,0H

Benzylalcohol 2-Phenyl ethanol

When a functional group such as aldehyde, ketone,

carboxylic acid, acid chloride or ester is present in
phenol molecule then the phenols are named as hydroxy
derivatives of these compounds.
For example
COOH CHO cOoCH5

ÓH OH ÔH

4-Hydroxy 4-Hydroxy 4-Hydroxyaceto

benzoic acid benzaldehyde phenone
 OMETHODS OF PREPARATION
1.From sodium benzene sulphonate: By fusing sodium benzene
sulphonate with sodium hydroxide followed by treatment with
dilute hydrochloric acid,phenol is obtained.

OH
So,Na
NaOH HCI/H,0
300°C NaCl
|Sodium benzene NaHSO, Phenol
sulphonate
2. From chlorobenzene (Dow process): Hydrolysis of chlorobenzene with
NaOH at high temperature and pressure gives sodium phenoxide which
further reacts with HCl toyield phenol.

CI ONa OH

NaOH HCI /H,0

-NaCl
300 °C/ 150 atm
Chloro -HCI Sodium Phenol
benzene phenoxide
Mechanism of Dowprocess

Cl oH
NaOH -CI
-H,0

OH ONa OH
NaOH
H*/H,0
3. From cumene: 0xidation of cumene followed by treatment with HCI
yields phenol

CH, CH3 OH
H,C--H 100 °c
H,C--0OH
O2 HCl/H0 + CH,COCH,
Phenol
Cumene Cumenhydroperoxide

4. From benzene diazonium salts: By warming benzene diazonium

chloride at 50 °C, phenol is obtained.

N,CI OH

H,0
A s0°c
Phenol

5. From alkali fusion of sulphonates: When sodium salt of aromatic

sulphonaticacid is mixed with an excessof NaOH,and heated to 573 -
623 K we get sodium phenoxide which on acidification yield phenol

so,ONa ONa OH

NaOH H,SO,
525-575 K
H, H3 H,
Sodium p-toluene p-Cresol
sulphonate

6. By oxidation of benzene: By passing a mixture of benzene and air

overvanadium pentoxide at high temperature, phenol is formed.
OH

+ Oz
Phenol
7. From Grignard reagent: Phenol may be prepared by treating aryl
magnesium bromide with oxygen followed by hydrolysis of the produ
MgBr ONa OH
Br
O2 H,0
Mg
H* OH
Phenyl Phenoxy Phenol
magnesium magnesium
bromide bromide

8. From pheolic acids: Distillation of sodium salt of phenolic acid with

soda lime (NaOH + CaO) followed by acidification with dilute HCl

OH OH
COONa Ca0
2NaOH
Na,CO, + H,0

Sodium salicylate Phenol

9. Rasching's process: A mixture of benzene vapour's, air and hydrogen

chloride is passedover heated CuCI, at 500 K, chloro benzene is formed
which on heating at 700Kgives phenol and HCI
CI OH

CuCl, H,0
+ 2HCI + O + HCI
500K 700K
Phenol

10. From coaltar

The middle oil fraction of coal tar contains phenols, cresols and
naphthalene.
Upon cooling naphthalene is deposited as solid and removed by
centrifuging the mixture.
The fraction of oil left, upon agitation with sodium hydroxide
solution dissolves phenols and cresols as sodium salts.
Phenols are liberated by passing co, into the solution and isolated
by fractional distillation.
 OPHYSICAL PROPERTIES OF PHENOL
1. Phenolis colorless, needle shaped crystalline substance (mp 42°C;
bp 182°C).
2. Phenolis partially miscible at temperature below 65.8 °C with
water but above this temperature it is miscible in all proportions,
moresoluble in ethanol, ether and other organic solvents.
3. Liquefied phenol contains 5% water at room temperature, known
as carbolic acid.
4. The needle shaped crystals are corrosive, hygroscopic and
poisonous, turn pink on exposure to air.
5. Phenols are more polar than cycloalkanols which have similar
skeleton hence they have higher melting point and boiling point.
6. Further, the ortho haloisomers have lower melting point and
solubilities are more than their paraand meta analogues due tothe
intramolecular hydrogen bonding in ortho isomers.
F F

H
OH...ÓH

o-Fluoro phenol p-Fluoro phenol

(Intramolecular (Intermolecular
hydrogen bonding) hydrogen bonding)
Low melting point High melting point
 OCHEMICAL REACTIONS OF BENZENE
() Reaction of -OHgroup
(I)Reaction of benzene ring
(II)Special reaction
Reactions of -OH group
1. Formation of salts: Phenols are acidic in nature and
hence react with NaOH or Na metal to form sodium salts.
OH ONa

+ NaOH + H,0

Phenol Sodium
phenoxide
OH ONa

+ 2Na 2 + H2

Phenol Sodium
phenoxide
2. Formation of benzene: Upon distillation of phenolwith
zinc dust, benzene is obtained
OH

+ Zn + Zn0

Phenol Benzene
3. Formation of ether:Phenols upon reaction with alkali
formssodium phenoxide, which upon further reaction
with alkyl halide yields ethers, this is called williomson's
ether synthesis

OH ONa

+ NaOH + H,0

Phenol Sodium
phenoxide
ONa

+ CH,CH,Br
OCH,CH,
+ NaBr
Sodium
phenoxide Ethyl phenyl
ether
4. Formation of esters:
Phenol in alkalisolution reacts with acid chlorides or
acid anhydride and forms ester.
" Thisreaction is called esterification.
OH ONa

NaOH + Hz0

Phenol Sodium
phenoxide
ONa
OcoCH3
(CH3C0)20
CH3C0ONa
Sodium Sodium acetate
phenoxide Phenyl
acetate
 The reaction of phenolwith benzoyl chloride is known
as Schotten - Baumann reaction.
ONa COCI

Sodium Benzoyl
phenoxide chloride Phenyl benzoate

5.Formation of amine: Phenol upon reaction with ammonia

inpresence of anhydrous zinc chloride or calcium chloride
yields aniline.
OH NH,
ZnCl,
+ H,0
NH3
Phenol Aniline

Reaction of benzene ring

1.Nitration: Phenol reacts with dilute nitric acid and gives
O
o- and p-nitro phenol is obtained
OH OH
OH
NO2
HNO,

Phenol
o-Nitrophenol
NO,
p-Nitrophenol
Phenol reactswith conc. HNO3, picricacid is obtained
OH OH
0,N. NO;
+ Conc.HNO,

Phenol NO,
2,4,6-Trinitrophenol
(Picric acid)
2. Sulphonation: Phenol upon reaction with sulphuric acid at 20 °C gives
o-phenolsulphonic acid whereas at 100 °C it yields p-phenol sulphonic
acid.
OH OH OH

H,SO, H,S0, s0,H

100 C 20°C
-H,0 Phenol -H,0
`0,H 0-Pheol
p-Phenol sulphonic acid
sulphonic acid

3. Halogenation: Bromination of phenol using bromine in CS, or CCI,

forms a mixture of o-and p-bromophenol
OH OH OH
Br
+ 2Br2 + 2HBr

Phenol o-Bromophenol Br
p-Bromophenol

4.Reimer -Tiemann reaction:

Reaction of phenol with chloroform in aqueous NaOH solution,
followed by acid hydrolysis yields salicylaldehyde
If CCI, is used in place of chloroform, salicylic acid is obtained.
Reimer -Tiemann reaction is used to introduce -CHO or -coOH
ortho to -OH group of phenol
OH OH CI ONa OH OH
CHO
CHCl, H
3NaOH HCI
H
-HCI Hz0 -H,0
-2NaCl -2NaCl
Phenol Salicylaldehyde

OH OH CI ONa OH OH

CCl, 4NaOH HCI COOH

CI oH
-HCI -H,0 -H,0
-3NaCl -NaCl
Phenol Salicylic acid
5. Kolbe's reaction: Phenol upon reaction with CO, in presence of NaOH
at high atmosphericpressure followed by hydrolysis yields salicylic
acid. This reaction is used to introduce -COOH group in ortho position. It
is known as Kolbe's-Schmidt reaction.

OH ONa OH OH

NaOH Co, coONa H//H,0

CoOH

125 °C / 6 atm -NaOH

Phenol Sodium Salicylic acid
phenoxide Sodium salicylate

6.Gattermann reaction: Phenolupon reaction with HCN and HCl in

presence of AICl, catalyst, salicylaldehyde is formed.
OH OH
HCN /HCI CHO
NH3
AlCl,
Phenol Salicylaldehyde

$ Special reaction
1. Phthalein reaction:When phenol reacts with phthalic
anhydride inpresence of Conc. H,S0, phenolphthalein is
obtained HO

OH
OH
H,S04
2 +

Phenol phthalie an1ydride

phenolphthalein
 UNIT - II
PHENOL
Points to be covered in this topic
1. ACIDITY OF PHENOL

- 2. EFFECT OF SUBSTITUENTS

3. QUALITATIVE TEST

DACIDITY OF PHENOL
> Phenols are much more acidic than alcohols but less so than
carboxylicacids or even carbonic acid.
This is indicated in order of acidity constants:
Formula K,lapprox)
Phenols Ar-OH 1019
10l8
Alcohols R-OH

R-COOH
105
Carboxylic acids
107
Carbonic acid H,C03
Phenols are acidic due to the formation of stable phenoxide ions in
aqueous solutions.
For example, phenol itself gives phenoxide ion on dissociation.
OH ONa
NaOH

-H,0
Phenol Sodium
phenoxide
 The phenoxide ion isstable due toresonance:
(OH OH oH OH ; OH

----
a) The oxygen atom gets positive charge due to resonance and attracts
the electron pair of the 0-H bond and hence facilitates the release of
proton.
b) Carbon atom of the -C-OH group in phenol being sp² hybridised is more
electron attracting than sp carbon atom in alcohols. Thus the -I effect
in phenol is greater and facilitates proton release. However the
inductive effect isless significant as compared to resonance effect.
c) The phenoxide ion formed after proton release is stabilized by
resonance, whereas in alcohols the resonance is not possible and
hence proton is not released and held tightly with oxygen.

OEFFECT OF SUBSTITUENTS

NATURE OF SUBSTITUENTS
(1) Effect of Electron-Withdrawing Substituents: An electron
withdrawing group (-NO2,-Cl,-CN, -CHO, -C00H)on the aromatic
ring is acid-strengthening. It enables the ring to withdraw more
electrons from the phenoxy oxygen. This stabilizes the phenoxide
ion still further and results in a stronger acid.
For example,p -nitro phenol is more acidic than phenol.
OH 0

+ H,0 + Hg0+

NO, NO2
p-Nitrophenol p-Nitropheoxide

NO, NO2 NO,

(2) Effect of Electron-Releasing Substituents: An electron-releasing
group (-CH, -0CH, -NH,) on the aromatic ring is acid-weakening. It
strengthensthe negative charge on phenoxy oxygen and inhibits the
charge delocalization due to resonance. This destabilizes the phenoxide
ion and results ina weaker acid.
For example, p-cresol is less acidic than phenol
OH OH OH OH OH

NO2 dCH, CH3

p-Nitro p-Nitro Phenol p-Methoxy p-Cresol
phenol phenol phenol

& POSITION OF SUBSTITUENT

>The presence of electron withdrawing and electron releasing group is
more pronounced at ortho and para positions than at meta position
Thisis due to the resonance effect
> A
nitro group, for example, is able to delocalize negative charge on
phenoxide ion more effectively.

Ortho nitrophenoxide ion

Para nitrophenoxide lon

From the above resonating structure each o- and p- nitro phenoxide ions
conjugation is extended uptooxygen atom of nitro group.
That's why o- andp- resonating structure more stable
 OQUALITATIVE TEST
Any of the following test can be carried out to detect the phenolic
functional group.
1. Litmus test
2. Ferric chloride test
3. Libermann's test
4. Bromine water test
5. Phthalein dye test
1. Litmus Test: Phenol turns blue litmus paper red, this shows that
phenol is acidic in nature.
2. Ferric Chloride Test:Aqueous solution of phenol reactswith freshly
prepared ferric chloride solution gives coloured complex. Most phenols
give dark coloured solution
6C,H,OH + FeCl3 (Fe(C,H,)6i + 3HCI + 3H
Violet colour
complex
The coloursproduced by simple phenolic compoundswith ferric
chloride solution is listed below.
Phenol, resorcinol, ortho cresol, Violet or blue colouration
para cresol
Catechol Green colouration

Hydroquinone Violet or transient blue color

Pyrogallol Blue rapidly changing to red

3. Libermann's Test: Phenol reacts with concentrated sulfuric acid and
sodium nitrite forms ayellow colour quinone monoxime complex, with
excess of phenoland sulfuric acid a deep blue indophenolcomplex is
formed,on dilutiona red colour indophenol is formed which turns to deep
blue colour sodium salt solution of indophenol on treatment with sodium
hydroxide.
NaNO,
-OH HO -NOH
H,So,

CaH_OH|H,so,
NaOH
 4.Bromine Water Test: Phenol undergoes electrophilic substitution
reaction with bromine. When bromine water is added to aqueous solutio
of phenol the brown colour of bromine disappears and a white
precipitate of tribromophenol is formed
OH OH
Br. Br
+ 3Br2

Phenol Br
Tribromophenol
White ppt
5.Phthalein Dye Test: Phenol on heating with phthalic anhydride in the
presenceof concentrated sulfuric acid forms a colourless condensation
compound called phenolphthalein.
On further reaction with dilute sodium hydroxide solution gives a pink
colour fluorescent compound called fluorescein.
Characteristiccolours are produced by different phenolic compounds which
can be viewed under white background.
HO
OH
OH
2 +
H,SO4

Phenol
Pthalic
anhydride
Phenolphthalein

NaOH
HO
coo coo

Colourless Pink colour

 The colours produced by different phenolic compounds in phthalein dye
test is listed below.

Phenol Reddish pink

0-cresol Red
m-cresol Blue or violet blue
1-naphthol Green
2-naphthol Faint green
Resorcinol Yellow-green fluorescence
Hydroquinone Deep purple
 UNIT - II
PHENOL
Points tobe covered in this topic
T PHENOL

o-CRESOL, p-CRESOL, m-CRESOL

> RESORCINOL

NAPTHOLS

O
PHENOL
STRUCTURE

OH

USES:
1. Used in thepreparation of drugs.
2. Used in the preparation of several dyes.
3. Used as an antiseptic and disinfectant.
 Oo-CRESOL
STRUCTURE

OH

CH,

o-CRESOL

USES:
1. Used is for the synthesis of Mephenesin which used as muscle relaxant.
2. o-Cresol and its derivatives used as herbicides.

Om-CRESOL
STRUCTURE

OH

CH3
m-CRESOL

USES:
1. It is used as a precursor for tolamolol and Vitamin E.
2. It is also used for the synthesis of pesticides (Penthione).
3. Itis used as preservative in some insulin.
 Dp-CRESOL
STRUCTURE
OH

CH
p-CRESOL

USES:
1. Used for the Production of Butylated hydroxy toluidine (BHT) this is
used as an antioxidant.
2. It is also used for the synthesis of Buproponolol (Beta Blocker).

ORESORCINOL
STRUCTURE
OH

OH
RESORCINOL
USES:
1. It is used in the preparation of dyes like fluorescein and as an antiseptic
2. It isused as an antiseptic and disinfectant.
3. It'sointment (5to 10%) used in the treatment of psoriasis,eczema and
hidradenitis (skin disease characterized by occurence of inflamed and
swollen lumps).
4. It has been also employed in treatment of gastric ulcer.
5. It's29% solution is used in hay fever and in whooping cough.
D1-NAPTHOL
STRUCTURE
OH

a-napthol

USES:

1. It is used as a precursor for drug synthesis.

2. It is the main ingredient of Molisch reagent.

3. It is also used for the synthesis of dyes.

02-NAPTHOL
STRUCTURE

OH

B-napthol

USES:

1. It isused as an antiseptic for skin diseases.

2. Methyl & ethylethers of 2-naphthol such as nerolins are used in
perfume industries.
3. It is also used for synthesizing dyes.