Chapter 4I

Aryldiazonium Salts

Aromatic amines when treated with nitrous acid in cold mineral acid solution, yield a
very important class of compounds known as Aryldiazosium Silts, For example, aniline reacts
with nitrous acid in hydrochloric acid solution at O-5°C toforma solution of beazenediazonium
chloride.

o— /\^
&N H, + HNO, + HQ-+ Cl 2H,0
KQ[NI +

aniline benzcnediazonjum
chloride
Such aryldiazonium salts were discovered by Johan Peter Griess in 1858, and the reaction pro.
ducing them is referred to as Diazotisatioa.

Diazonium salts have the general formula Ar—N1X, where X is any of a large number
of anions, such as Cl-, Br, NO, HSO, BF, etc. They are named by adding diazontum to
the name of the hydrocarbon followed by the name of the anion. Thus,

j
4- +-
N,Br NIBF1

6
beozenediazonium
bromide
00
NO,
3C9)
..naphthalcnethazonium
chloride
p-toluenediazooium p-nstrobenzenewazopluln
hydrogen sulphate fluorobofite
The aryldiazonium salts have proved of enormous value in the synthesis of organic
compounds and are comparable with Grignard reagents in versatility.

PHYISCAL PROPERTIES
(I) Aryldiazonium salts are colourless, crystalline solids which turn brown on exposur
to air.
(2) Most of them are unstable and explode when warmed or subjected to shock, when
dry.
(3) They are extremely soluble in water, sparingly soluble in ethanol and glacial acetic
acid, and insoluble in ether.
(4) They form double salts with metallic salts like zinc chloride e.g., (ArN1),'4 ZnC14'
which are generally stable in solution.

1029
1030
Advanced Organic Chemistry

current through them,

(5) Their aqueous solutions are neutral and conduct electric
showing their salt-like character, furnishing aryldiazonium ions.
+- +
Ar—N1CI -. Ar—N, + Cl
aryldiazonium aryldi&zonium
chloride ion

STRUCTURE
We will elucidate the structure of aryldiazonium salts by taking the example of benzene
diazonium chloride (C 1 l-lN,Cl). Of the threc p-orbitals of the central N atom, one overlaps
with sp' orbital of the carbon framework of benzene. The remaining two p orbitals overlap
with their counterparts of the second N atom, to form two n bonds between the two lilrogen
atoms. The nonbonded electron pair resides in the free lobe of the [Link] of the second N
atom. Hence orbital model of bcnzenediazofliUm chloride can be visualised as in Fig. 411.

^
TT

a Ot

Fig. Ill. Struclure Of Bentenediazonium chloride,

In true perpec1ive, two N atoms of the diazoniurn group are bonded by p-p a bond an
a bond. The third p orbtal of each of the N atoms is aligned with the p orbitals of the six
carbons of benzene ring. These available p arbitals of the Iwo N atoms interact with those of
the benzene sextet, and bring about the dclocalisation of electrons. The delocalised electrons
now encompass the six carbons of the ring as also the two N atoms of the diaLonium group.

___

C
0A €:HNN ic

Fig. 412. Delocalisation of elec t rons in CHNiO structure.

The C—N bond in the above structure gets some double bond character, and makes
aryldiazonium salts more stable than the alkyldiazonium salts which lack benzenoid structure.

rhe electronic structure of benzenediazonium chloride is shown, where the C1FJ—N1

cation exhibits resonance.

NN: 4-*
]
Cl
Thus the positive charge of the cation is distributed o . c-, both the nitrogen atoms.
 ryldiazonMait Salts 1031

The relative stability of the diazonium cation is also ascribed to the fact that its structure
is a resonance hybrid of the following canonical forms involving the participation of the benzene
ring.

N.N NN

11 11

0
10-0'Y
4.
6
[Link]
ThDRj)
The hybrid structure shows that (a) benzene ring is deactivated to the attack of dcc-
trophiles; (b) the C—N bond acquires some double bond character and becomes stronger.
Alkyldiazonium salts cannot exhibit such resonance and hence C—N bond in them is weak.
That is why they are unstable relative to their aromatic counterparts.
PREPARATION
Alkyldiazont'im salts are prepared by cooling a solution of the aromatic 1° amine in
excess of mineral acid (HCI or H 2 SO 4 ) in an ice-bath. This is then added to an icc-cold solution
of sodium nitrite with constant stirring. When the resulting solution gives test for presence of
excess of nitrous acid (starch-iodide paper turned blue), the reaction is complete.

Ar—NH, -}- HCl -_ Ar—NH1CI

I' amuse arylamxssonium
chloride
NaNO, -- HCI -_, NaCl + HNO8
4. + -
At—NH 5C1 + l-1NO 2 -. Ar—N 5 CI 4 2H10
aq xoh,elon aryldiazortium
chloride
The dry diazonium salts are unstable and explosive, and are seldom separated. For
synthetic purposes, they are prepared in aqueous solution and used at once. However, in rare
instances when the diaaonium salt is required to be isolated in the pure state, an etharsolic solu-
tion of the amine is treated with the requisite mineral acid and amyl nitrite, and added to the
cooled mixture. The salt either separates out immediately or is thrown out by the addition of
ether.
Preparation of Benzenediazonium Chloride. Benzenediazonium chloride may be prepared
by the addition of concentrated solution of 1 mole of sodium nitrite to I mole of aniline dis-
solved in 3 moles of hydrochloric acid at 0 * — VC.

'9_NH, + NaNO 5 + UCI _. ^0_ N,CI + NaCl + 2 H20

aniline [Link]
chloride
PROCEDURE One mole of aniline is dissolved in 3 motes of hydrochloric acid It mole to form
salt with aniline, I mole to liberate nitrous acid, and I mole to keep the reaction mixture acidic) and cooled
to OC in icc-bath. An aqueous solution of sodium nitrite, also cooled in ice . bath, is added to it at such a rate
that the temperature does not rise above 5-10C. The addition of sodium nitrite is stopped as soon as the
reaction mixture just gises a blue colour with starch—potassium iodide paper. Excess of nitrous acid must be
avoided as it i nlefferes with subsequent reactions of the diazonium salt so produced in solution. If necessary,
excess of nitrous acid may be destroyed by adding urea.
Fl1N-CO--Ntl, - 2 HONO ­4 CO5 - 2 N, 3 11,0
Since benzesed ta,i)flium chloride - lowly decomposes even at ice-bath temperature, t hr rtsuliing pale
yellow :o­ ; ­ is used immediately f- various synthetic reactions.
1032 Advanced Organic Chemistry

CHEMICAL PROPERTIES
Aryldiazonium salts give two types of reactions:
(a) those In which the —N I X Is replaced by another univalent atom or group, with the
liberation of No gas.
(b) those in which the two N atoms are retained.
The first type of reactions again can be subdivided into two classes:
the presence
(I) When the diazonium group is replaced by a free radical mechanism in
of a catalyst (A'),

— NICI+A---.

biases, free radica l

00 + tiu -.&Nu

14- +
+

A + -4 A (Catalyst regenerated)

(II) When N o is abstracted to form benzene cation which is then attacked by the
nucleophile to give the corresponding substituted benzene,

+ N2

^Dt7— -, 5
BENZENE CATION

00+ + :Nu ,

3S.#S571TUTE0 8ENZ(NE

A large number of benzene derivatives cpn be thus synthesised via diazoniulfl salts. This
will be illustrated by taking example of benzenediazonium chloride.

REPLACEMENT REACTIONS IN WHICH No IS LIBERATED

hypophos•
by Hyksge.. When an aryldlazonium nit Is reduced by
-
(Cu4 Cl-), the product is the corres-
phorus the presence of cuprous chloride
ponding aromatic hudrocarbon.

+ HO
—H + No + H,PO,

©-r O + H^ + H2O -.

blesses

MECHANISM. The reaction proceeds by a chain mechanism.

Initiation Step:
1+
+ +
C.H,—N, yp C.H. + Na + Cv
 Ary Idiazonln,n Salts 1033

Propagation Step:
H H
C.H. + H—P.0
I
—+ CH, +
I
OH OH
+ . H2O
C,H,—N, -- O=.PH(OH) —, CH, + N, + H,P0 1
-f H
(2) Replacement by CkIorl.e or BrmWne. The diazonium group can be replaced readily
by any of the halogens, although different conditions may be required. For replacàment by
chlorine (—Cl) or bromine (—Br), the aqueous solution of the diazonium salt is heated with
cuprous chloride (Cu-CI-) or cuprous bromide (CU4Br-).

NICI —. C1 + N,
0
0—

benzenediazenium chtorobea,eoc
chloride

NBr-. K'j — Br N,

ber,zenediszonium bromobcnzene
bromide
Such ceprous ion-catalysed reactions are examples of the Saadeyet Reiction.
MECHANISM, Cuprous ion Cu provides an electron for generation of bczene free
radical, when the former is converted to cupric ion Cs.'. In the subsequent step the benzene
free radical combines with halide ion (Cl- or Br), regenerating Cu,
1+ -
+ Cu + N. ± Cl
+ Cu
K'
-f Cl -. (5 —CI +

II.
Cu + . -. Cu
A modification of the above reaction in which the cuprous salts are replaced by copper
powder is named as the Cittermaiia Renctioc.

NI X ^&X 4- N, (X = Cl or Br)

This reaction forms some diphenyl as a byproduct.

2C,H,—? I X + 2Cu -. CHs—C,H + N, + 2 Cud

diphenyl
Therefore, the Sandmcyer reaction is to be preferred to Gattermann reaction as it gives
better yield.
(b) Replacement by Iodlae. The diazonium group may be replaced by iodine (-1) by
simply heating an aqueous solution of the diazonium salt and potassium iodide.

4ISO1lltIOfl
KI __l + N, +tCi

benzeocdiazooiuu, iodobcnzcne
cMo,idc
iic Cliemis t i'y -66
 Advanced Organic Chemistry
1034

This is regarded as the best method for introducing iodine into the benzene ring.
MECHANISM. The reaction occurs by the S2 mechanism.

CH—N=N + I -. CH,-1 + N,t

(3) Replacement by Fluosiae. Aryl fluorides are conveniently prepared by
adding the diazoniurn sah solution to fluoroboric acid, HRF 4 . The fluoroborate precipitates,
md is washed and dried When heated it decomposes into nitrogen, boron trilluoride and
tryl fluoride (8aL .Sciiieinann Reaction).

I —+ N,BF4 —' + N + BF,

NtCl + HBF (—FICI) A
benzened*zonium fluotObcttZefle
ltuorobThate
MECHANISM. Here one of the fluoride ions of BF 4 acts as nucleophile,

C4 H, + : f)_-8r3 - c,—: + ar

(4) Replacement by [Link] group. The diazonium group may be replaced by a cyano
roup (—CN) by using cuprous cyanide (instead of cuprous halide) in the Sandnieyer Reaction,

N,Cl + CuCN --+ (' )>--CN + N1 + CuCI

O—
phenyl cyanide.
beozonitrik
net the nitnle can be hydrolysed to the acid, the reaction affords a method for replacing the
azonium group by —COOH [Link] well.
+ - CuCN H2O,144
C,H5—N 1CI —.-+ CH,—CN . CH,—COOH
diaonium salt nitrite A benzoic acid

(5) Replacement- by Hydroxyl group. When arm aqueous solution of aryldiazocium

Ioride is heated, the diazonium group is replaced by —OH group. Thus a phenol results.

&N,CI + HSO —' K. )-OH + N 5 + HC1

[Link] phenol
chloride
This reaction is usually conducted in an acid medium to prevent the coupling of phenol
ith the unreacted diazonium salt. It is useful for the preparation of pbenols which cannot
synthesised by electrophilic chlorination of phenol, such as m..chlorophenOl.
C1 Cl

+ H10 OH + N, + HCI
 kyldiazonium Salts 1035

MECHANISM. In this reaction water (H 2O:) is the nucleophile.

+ + 11,0 —H+
C,H,N, - N, + CH, CH,—OH, .-_.+ C,H5—OH
phenol
(6) Replacement by Alkoxy group. On heating an aqueous solution of aryldiazonium
chloride in presence of an excess of an alcohol (R—OH), the diazonium group is replaced by the
alkoxy group —OR. Thus alkyl aryl ether is formed.

N j Cl + R—O—H _,±+ ()>_ oR + N, ± HCI

alcohol
alkyl aryl ether

MECHANISM. Here ROH acts as the nucleophile.

R-6—H.
4 + +.. .. _H+
C,H,N -p N, + C,H, -_-, C,}I,—o —R -. C,H,—O—R

(7) Replacement by Nitro group. When diazonium fluoroborates are heated with aqueous
sodium nitrite, the diazonium group is replaced by —NO, group.

kci N,BF4 NO,

—HCI . NsN

) fluoroboric
+ HBF4

acid
I
O Cu,A fIjJ
+ N. ± N,BF4

beozenediozonium nitrobenzene
fluoroborate
This reaction makes possible the synthesis of nitro compounds which cannot be prepared
by direct nitration. For example,

NaNO,
NaHF1 -. O,N—(---NO, + N, + NaBF4
O,N—©_+ - Cu. A
p-nilrobeozeaediazonlum [Link]
øuocobora
(8) [Link] b [Link] group. The arsono group, —AsO 3 H,. may be introduced in-
to the aromatic ring by heating benzenediazonium chloride solution with sodium arsenite in the
presence of cupric salts. In this way the sodium salt of phenylarsonic acid, C,H,AsO,H1, is
obta i ned. (Bars Reaction)
Cum, 21W1
C,H,,Cl + Na,AsO-_, C,HAsONa1j. C,H,AsO,H, + 2NaCl
bsmaoediazoojum (-N,,-Naa) sodium sail
cblo,lde acid
(9) Repiaceme.t by Aryl group. When an aryldiazonium chloride is treated with an aro-
matic hydrocarbon in the presence of sodium hydroxide, diary! results.

N,CI + H+ NaOH + N + H2O. + NaCl

^D_ —0
0 .
bcnzene diphenyl
1036 Advanced Organic Chemistry

MECHANISM. The reaction is believed to occur ly a free radical mechanism

+- +-
(i) CH1N,CI ± NaOH —. CH,—NN—OH + NaCI
(ii) C,H1 —NN—OH —.-. CH - N5 + -OH
(iii) C,H, ± -C,H,CH,--
-. ,CH, + H-

(iv) H + -OH -. 11,0

REACTIONS NOT INVOLVING LOSS OF NITROGEN
(I) Reduction to Hydraziur. Diazonium salts when reduced with sodium sulphite are
reduced to give phenylhydrazine. The process is carried in three steps : (i) addition of diazo-
nium salt solution to a warm solution of sodium sulphite heated to 100°C (ii) this is followed
by acidification with HCI when phenylhydrazonium chloride is produced (iii) the resulting
solution when treated with alkali yields phenylhydrazine.
Na,SO, + 211,0 —.. Na 1SO, + 4K
Rcl
NjCI + 4H !2' NH—NH, - NH—N HC1
1W
^5-1 - co ^—
bonienediazonium [Link]*zifle phenylhydrizonum
chloride chloride

^D—NH—NH,Cl + NaOH -p ( —NH—NH, + NaCi + H2O

phonylbydrazine
MECHANISM.. The mechanism of the reduction with sodium sulphite may be
illustrated as follows.

Comb—N PI + ____ CH—NN =0

c) 0 -

CH,—-NS 0 -+
CIUS_T_N_L0
S05 (J S0a 0
11 - 2H
-. C,}15 — N — NH — S01 -. C,H5—NH—NH,
I - —2S01 pbenylhydrazlne
SO,
(2) Coupling Reactions. Aryldiazonium salts react with aromatic rings of phenols and
tertiary amines (Ar-.-NR1), to form highly coloured azo compounds, in which the two
toms are retained. Thus.
+ ...t- .
(Ar—Na N: i-^ Ar—N=N ] CI + H—Ar' - Ar—N =N—Ar' - A 6
dlixçolum tall phenol or azt compound
3° smine
These reactions which bring about a union or coupling' of the diazonium cation with
the phenol or 30 amine, are called Coupling Reactions. The diazonium cation usually attacks the
aromatic ring of phenol or amine in r n position becausc of stcric hindrance in the orth
 11.137
Aryldtazonwrn Sohs

position, But if the para position is alreny occupied, the coupling occurs in the ortho position.
Phenol coupling gecTerally takes place in eakly basic solutions (pH 7 to 8), while amines do so
in weakly acidic solutions (pH 6 to 7).
EXAMPLES OF PHENOLIC COUPLING:

ON
-4 OH
©_OH (—MCI)
Phenol
@— N=N
p4iydroyazobenzene

OH OH

I
ON
© (—MCI)

berizenediazoniurn
chloride CH
p-cresol [Link]-azobcnzene

OH

- HO
Oil
(—MCI)
H
re5orcia0l
benzeneazorcsOrCiflol
EXAMPLE Of AMINE COUPLING.
CHCO0
+ N(CH,), N(CH1h

benzcnedjazomjum dimethylanilitie [Link]

chloride
MECHANISM. The phenol coupling is an e]ectrophilic substitution reaction. The
diazonium cation having positive charge on the N atom is the electrophile. The coupling with
phenols occurs via the phenoide anion which is considerably more strongly activated to
electrophiles than phenol its e lf. It is, therefore, necessary to carry out the reaction in alkaline
solution,

f—N N^^&c
V---.=

—0-4 --*
\--f-
fr- [Link](NE
AMINE COUPLING The amine coupling is also A similar electrophilic
substitution reaction. Here the diazonium cation adds to the tertiary amine in the pare position
and a proton is eliminated,
 1038 Advanced Organic Chemistry

— -4. =

—
DIAZONIuM CATICW DIWrMYLAMLIAE

* _Nfl—CH,),

/O -DIML iN YLAZOS(NZtWE
(3) Reaction with 10 m od 20
Amines. With primary and secondary aromatic amines, the
coupling reaction first forms diamino compounds ([Link] compounds). Thus benzcnediazo.
nium chloride reacts with aniline to yield diazoaminobcnzcnt.

- CH3COONaK_NNNH_K) + 1-ICI
&* _-^D Rro
urilliric 4sn,j&'cnzcne
MECHANISM:

_ 00
O/AZO4M(NCtyZfN(
When diazoamioobcozene is warmed with aniline and aniline hydrochloride, it rear-
ranges to the iminoazb isomer, with substitution occur5ing in the para position.
rearrange
—N=N H,
K -:::::: C4H5NH,,
C4HNH4-Cl, -0—N
diuoaminobcazene )arnl

is made alkaline, the diazonium

(4) React1o' with Alkalis. When an aryldiazonium salt
diazo hydroxide. This reacts with alkali to form
hydroxide liberated rapidly rearranges to the
salts which are called IMaxotites.
- NaOH . - -
C,H—NN : Cl - ([Link]—NN : 01-11
hydroidc
(we)

OH -- NaOH
+ -. ,.
CH,—N=N—OH
C1H5—N .N: —.' C,H4..—NN: ±
disco hydroxide
[C,H..—N—N--OI Na.
sodium di,zotate
the syn. (cis.) and anti- (trans.).
The diuotates exist in two geometrical isomeric forms
NN .
C.H/ 'ONa "N-N O -
NIquotate Na
sodium
(qu rdn) sodium [Link]
(Mil races)
 103?
Aryldlazonium Salts

[Link]*zlae, CH,—NH—NH,
It is the most important substituted hydrazine.

Preparation. Phenylbydrazinc may be prepared by the reduction of henzenedia,oniu

chloride with stannous chloride and hydrochloric acid.
• +- SnC1,IHCI
CH—N5 Cl + 4H -+ CH—NH—NHI,HCI
pbcnylhydrazinc
hydrochloride
The phenylhydrazine is liberated frcm the resulting salt solution by adding an excess nI
NaOH solution.
CH1—[Link] + NaOH -p CH,—NH—NH, + NaCl ± H10
phenyihydrazine

The free base separates as a brown ol which is extracted with ether and dried over solid
NaOH. Ether is removed by distillation and finally phenylliydrazine is purified under reduced
pressure.
The uction of benzeaediazonium chIorid is carried out industrially with sodium
sulphite, when sLsequent treatment with HCI and then NaOH [Link] phenylhydra,.ii)e.

uci NaOI-(
- NaSO
CH1—N1Cl + 4H CH,—NH—NH,
-+ -.. Ci4—NFl—NH,HCl
beozenediezonlurn 100
chlotid. CH,—NH—>H,
phenythydCAZillC

Properties. Phenyihydrazine is a colourless oily liquid. bp 241C. When freshly distilled

it has an unpleasant odour, suggestive of aniline, and quickly darkens on standing in air due to
oxidation by air. It is very slightly soluble in water but dksolves readily in organic solvents.
It is very poisonous and attacks skin. Its important reactions are listed below.

(I) Basic Nature. It is strongly basic in nature and forms well-defined salts e.g.,

C1 H5 —NH—NH, + HCI -* C4H3_NH—NHCl

phenythydrazofliUm chloride
It is best kept as its salt, since these are relatively stable to atmospheric oxidation.

(2) Reducing Nature. It is a powerful reducing (agent and reduces Fehling solution
CH_NH—NHe + 2CuO -p CH 4 Cu 10 + Ne t ± H2O
red ppt

(3) Reduction to Aniline. When reduced with a vigorous reducing agent e.g., zinc and
hydrochloric acid, phenylhydrazine yields aniline and ammonia.
zHO
C4 %—NH—NH, + 211 -+ C 1H—NH, + NH3
aoilinc

Formation of Phenyihydrazones and Osa:ones. It reacts with aldehydes and ketones

to form phenyihydrazones. These derivatives are usually well-defined crystalline salts. With
monosaccharides (glucose, fructose, mannose), it forms osazones. The formation or phenyl-
hydrazone3 and ouzones is used for characterisation of carbonyl compounds and simple
sugars.
(5) With A'etoacetk Ester. When treated with acetoacetic ester followed by methyla
tion, it gives antipyrene which is used in medicine as a febrifuge.
 i 040 Advanced Organic Chemistry

CI-4 3 C0—CI12—COOC 2 H5 CH3—C —C_COOC2Hs

( — H20)-—C1HSOH)
+

C6H5—Nl-4--NN2 N—NH—C&-15

CH3—C---CH2 CH—C
(CH3)2SO4
II I
NN/CO Ch3_NNCO
,

CR5 C6H5
ANTIPYRINE

Uses. Phenyihydrazine is used: (I) as a mild oxidising agent (2) for making anhipyrine
and some important dyestuffs ; (3) as a reagent for the identification of aldehydes, ketones and
sugars.

p-Ni trophenylhydrazine, O,N—ç-----NH - NH,

It is prepared by reduction of the corresponding diazonium salt with sodium sulphite.

It is used as a reagent in place of phenyihydrazinc itself, since it ives derivatives with carbonyl
compounds which crystallise readily..
2,4•Dinitro. and p-bromophenylhydrazinès are still better reagents for the identificaon
of aldehydes and ketones. Of these 2,4-dinitrophenylhydraziae1 which is most commonly used,
may be prepared by the action of hydrazine and 2,4-dinitrochlorobenzene in boiling alcohol.
Nucleophilic replacement of the chlorine atom takes place in this reaction.
NO, NO,

O,NCI + H---H O,NNR—NH2 + HCI

I boil

2,4-dinitrochlorobenzen, hydrazine

QUESTIONS
I. What are diazonjum salts? Write their general formula and assign names to the following
structures,
4-4— 4—
N2Br
""6N2HN20N20SO4
H3C

0 0. .
NO2 CH3

2, Describe the genët-aI physical charactegistics of aromatic diazonjum salts. Why are they soluble
in water and insoluble in nonpolar organic solvents?
3. Discuss the orbital model of benzenediazonium chloride. How do you account for the stability
of aryldiazonium salts as compared to their aliphatic counterparts.
4. State briefly the general methods of preparation of aryldiazonjum salts, taking example of
benzcnedlazonium chloride, Discuss the Cameos Process for the Industrial production of this compound.
 1041
Aryldiazonium Salts

S. Discuss in detail the preparation of beneenediazonium chloride starting from aniline. Why is it
not separated in solid state, and used as soon as produced in solution
& Describe broadl y the type of synthetic reactions shown by aromatic diazonium salts. Give the
general mechanism of reactions in which —N IX is replaced by various nucleophiles.
7. Write a note on Sandmcyer Reaction. Give its mechanism.
8. How can you convert benzene into the following via the formation of diazoniurn salt (i
chlorobenzene (Ii) fluorobeozene; (iii) benzoic acid ; (iv) nitrobenzene ; (v) diphenyl ; and (vi) phenyl.
hydrazine.
. What do you understand by 'Coupling* of diazonium salts with phenols and amines. Mention
two examples of the coupling reaction and discuss their mechanism.
II. Give the laboratory method of preparation, properties and uses of phenylhydrazine.
11. Describe the structure, preparation, and synthetic applications of brnzenediazonium chloride.
(Bangalore BSc, 1993; Osmania BSc How, 1994; Bombay BSc. 1994)
12. Write a note on: Sandmeyer reaction. (Madras BSc, 1994; Delhi BSc How, 1994)
13. Write a note on Coupling reactions. (Parrdicherry BSc. 1993)
14. How will you synthesist : (a) [Link] (p-rsstlbyip&nol) from toluer'e ; and (b) lodobcnzerar from nitrobenzene.
(Panja1'BSc, 1994)

Hint. (a) (1) HNO3/H2SO 4, (ii) Srs/HCI, (iii) NaNO2/HCl/O-5C, and (iv) H201W; (b) (i) Sn/HCI. (ii) NaNO2/HCl/O-5°C.
and (iii) Ki.
15. How will you synthesse:
(a)p-Toluidine from toluene ; and (b) AZObenZCnC from benzene. (Gulbarga BSc, 1994)
Hint. (a) (0 HNO3/H2SO4 . and (ii) Sn/Ha; (b) (i) HNO/H 2SO4, (ii) Sn/Ha, (iii) NaNO21HCl/O-S'C, and (iv) C6l16
1& How will you synthesist:
(a) Biphenyl from aniline and (b) m-Dichlorobenzese from benzene. (North Eastern Hill BSc Hons, 1994)
HInt. (a) (0 NaNOs/HCl/05eC, (i/) K!, and (iii) Na (Wurli reaction); (b) (') HNO3/H2SO4/lOO'C, (ii) Sn/HCI. (iii)
NaNO21HC14)-5 and (iv) CuCl.
17. An amide (A), C 1 3H 1 NO, was heated with aqueous sodium hydroxide When cooled, the mixture consisted of two
separate layers. The top oily layer contained compound (B), which was soluble in acid. The bottom layer on acidification gave a
precipitate, (C). Treatment of (B) with cold nitrous acid produced a compound, (D), that forjistd a dye with phenol. Treatment of (C)
with SOCl2 followed by NH3 produced (E) C7H3 NO. When (E) was treated with alkaline NaOBr, compound (B) was formed. Write
structures for (A) through (E) and give equations for all reactions.
Answer. (A) is [Link]; (B) is aniline; (C) is benzoic' acid; (D) is benzerthazonium chloride; and (E) is
bencamide.
 Chapter 42

Phenols and Aromatic Alcohols

The hydroxy derivatives of aromatic hydrocarbons can be divided into two main
classes
(a) Phenols, Ar—OH, in which the hydroxy group is directly attached to a carbon atom
of the aromatic ring and
(b) Aromatic alcohol;, Ar—CH,—OH, in which the hydroxy group is attached to a
carbon of a side-chain.
For illustration,

—OH

phenol 11
(OH directly attached to benzene beniyt alcohol
ring) (OH attached to bencnc ring
A PHENOL through a carbon or the side-chain)
AN AROMATIC ALCOHOL
While aromatic alcohols resemble closely with aliphatic alcohols, phenols differ from
them considerably in the methods of preparation and in chemical behaviour. In fact, the two
classes of compounds will be better studied separately.

PHENOLS
The class mime phenol' is adopted from the name of the simplest member—the mono-
hydroxybenzene (Gr, pheiierrbcnzene olrOH). They are classified as inonohydric, dihydric,
and trihydric phenols according as they contain one, two or three hydroxy groups on the
benzene ring.
Phenols, in general, occur in coal tar, wood tar and petroleum distillates. As a class they
occupy an important position in the modern synthetic organic chemistry for the preparation of
dyes, antioxidants, phenolic resins and certain pharmaceutical products A number of commer-
cial synthetic processes have been recently developed for the production or phenol to
meet its increased requirements.

STRUCTURE
The orbital representation of phenols can be illustrated by taking example of-the first
member' of the class. CHOH. In lad, the orbital structure of phenol is similar to that of
chlorobenzenc which we have discussed earlier. It is made of an oxygen atom forming a bond
with a hydrogen atom on one side and a carbon atom of the benzene ring. At the same time it
has a p orbital with a nonbonded pair of electrons, which lies in a plane of the o skeleton
of the molecule.
 1043
Phenols and Aromatic Alcohols

ATOMIC ORBITAL MODEL ELECTRON CLOUD MODEL

Fig. 421 1. Structure or phenol. C,HOH.

The p orbitals of the six carbons of the ring and the unused p orbital of the oxygen
atom of OH group interact to form an extended delocalised orbital (Fig. 421). The extended
cloud now encompasses the oxygen atom in addition to the six carbons of the benzene ring.
This delocalisation of the nonbonded electrons kods some double bond character to the C—O
bond.
The electronic structure of phenol can be represented as a resonance hybrid of the
following canonical forms.

Pt
+0

I IV RESONANCE
HYBRID

This explains the activation of benzene ring as also the ortho-para directive influence of
—OH group on the entering clectrophiles.
Phenols could well be regarded as enols of special type. Thus it exists as a tautomeric
mixture.

0
U
YH
PHENOL XE TO FORM
(CANONICAL FORM zr)

As shown by the actual bond energies of the two forms, the tautomeric mixture strongly
favours the phenol, and only a very small amount of the keto form is present in the equilibrium
mixture.

NOMENCLATURE

(I) Many phenols are known by distinctive trivial names. The hydroxy derivatives of
toluene have been given the common name Cresols.
 1044 Advcnced Organic Chemistry

(2) Phenols are generally named as derivatives of the simplest member phenol, In doing
so, the number I is assigned to the carbon bearing the OH group.
(3) Wln a phenolic moiety is inluded in a compound that is named by IUPAC system,
the hydroxy gr ' up is specified as a substituent according to the order of precedence. In such a
case a substituent (COOH or CHO) is assigned number I.
The nomenclature of phenols including systematic and common names is illustrated by
the following examples. The systematic names are followed by the common names.
MONOHYDRIC PHENOLS:

6 0
OH OH

phenol 2-methyiphenol,
CH,
3-methyiphenol,
0
I -hydroy.2-mcthylbenzeae, I -hydro*[Link],
o-creioi CH,
4-methylphenot
[Link].
benzene,
p-Cresol
OH CHO CHO

0
2-chiorophenot,
Cl

2-chioro-I .hydro2y-
benzene
(6r
2-hydroxybeflzaldchyde
o-hydroxybcnzatdehyde
&4-)H
3-hydronybeozoic acid,
'n-hydroxybenzojc acid

DIHYDRIC PHENOLS:
OH OH OH

c5OH

I .2-dihydrozybcnzene, I ,[Link], OH
catechol esorcinoI I,[Link],ybenan
hydroqumcuie
TRIIIYORIC PHENOLS:
OH OH OH
OH

cx
H OH
I ,2,3-trihydroxybcnzcne, I,3,.lfibydroxybcozene
pyropliol I,2.44rihydroxybcizene, phIofogxi
hydroyquinonc
The prefixes ortho, meta and para are also often used in place of numben 2, 3 and 4
while naming monohydric substituted phenols or hydroxytoluenes.
2hnols and ArnatJc Alcohols 1045

METHODS OF PREPARATION
The following general methods of synthesis of phenols are used for their laboratory
preparation.

(I) Hydrolysis of Dlazonlum Silts. Phenols can be obtained by heating aqueous solutions
of diaionium salts.
A
Ar—N 5 HS01 4- HO - Ar—OH + N 5 + H,SO4
aryldiaronlum phenol
hydroeo sulphate

..zonium chlorides are not used as they lend to the formation of byproducts (e.g.,
ArCl), For example, phenol is obtained from aniline as follows.

N.
HNO1
.4. -
N1HSO4 (.YH
©v
aniline dii zonium hydoicn pheani
sulphate
It is a valuable method for making phenols front aryl amities produced by nitration and
reduction of arenes.

(2) Alkali fusion of Sodium irenesulphonati Simple phenols are prepared conveniently
by fusing sodium arenesuiphonates with sodium hydroxide at about 300 C. A mixture of sodium
phenoxide and sodium sulphite is produced from which phenol may be liberated by acidification.

.4

Ar—SONa + 2NIaOH Ar—ONa + Na5S03 + HSO

sod arcoesulpisonale sod phenoxide

Ar—ONa + HCI -.4 Ar—OH + NaCl

Phenol

1-or ;pk thcnol is syntliesised from benzene as follows.

+Q/OH
NaOH
- M
EJ/ONa HCI
30

benzene berszenesuIphOiC sod PtD05de phenol

acid
(3) Hydrolysis of Aryl halides. Aryl halides yield phenol when hydrotysed with aqucoub
sodium hydroxide. For example, chlorobenzefle is hydrolysed to phenol at high temperature
and pressure by NaOI-t (Dan s Froces0.

C1 jOa _L. OH

z0
 1046 Advanced Organic ChemIstry

The above hydrolysis can also be effected by water in the presence of copper as catalyst.

Cu catalyst H

o
ff-C
400', l( -
psi Ui'° +HCI

(4) Decarboxylitiou of Phenolic acids. When phenolic acids are distilled with sodalime,
they decarboxylate to form sodium phenoxide. This on acid hydrolysis gives phenol, Thus,

(-N-OH

fl COONla

sod salicylale
+ NaOH(CaO)
sodali me
____
____
—Na,CO5
9 .
sod phemoxide
((DD
+
MCI

ptcnol
H
+ NaCl

(5) Oxidation of Grignard Reagent followed by hydrolyses. An aryl Grignard reagent on

treatment with oxygen in the presence of light, and subsequent hydrolysis of the product with
mineral acid yields phenol in fair yield.

Mgflr gO—O—MgBr

-.
light
©7
OMgBr -+ g,OH
2H2O
2 ©/
—MgOHBr

COMMERCIAL PREPARATION
A certain amount of phenoi are still obtained from coal-tar but most of ther. (over
90 %) are now produced industrially by synthetic methods. Besides the syntheses described
before, special synthetic prX,SCS for preparing certain of these members from petroleum
sources have been developed recently.

(I) From Coal Tar. Middle oil and Heavy oil fractions, which contain phenols and
naphthalene, are subjected to excessive cooling. Napthalene crystals thus separated are
removed by filter press. The remaining oil is treated with aqueous NaOH when phenols dissolve
as phenoxides. Carbon dioxide is then blown through the solution to liberate phenols.

Ar—OH + NaOH -. A,—ONa + H,0

phenols sod phenoxide

2 Ar—ÔNa + CO5 H10 -.p 2 Ar—OH -'- NaCO,

phenol

The aqueous layer containing Na 1 CO 3 is drawn off, leaving crude phenols behind. This
fractionated to recover the ind ; ­ ual plienul.
 Phenols ond Aromatic A&ohols 1047

1W oH

F" H,

OH
CRUDE
PHENOLS
CI)NOH
O'Craw ".Owl
i
P- Crosol

OH

CHS

0. 101
Licii3
& CU,
gyms

(2) From Came derived from Petrolcom. The most recent commercial synthesis of
phenol involves two step.:

(a) Preparation of isopropylbenzcne or cw,sene from propylene and benzene, both deriv-
ed from petroleum, by Friedel-Crafts Reaction.
CH,
+
propylece CD-11
cum=
(b) Curnene is then oxidised by oxygen at 130°C in the presence of a metal catalyst (or
initiator) which yields cunienc hydroperoxide. Treatment of the hydroperoxide with dilute
sulphuric acid induces a molecular rearrangement s leading to phenol and acetone.

CH, CH,
02
©OH + ZO
l3r. cat ©Th\OH
comma bpkogeroaidc pbeeol acoe
This method is assuming great importance as it provides two very useful commercial
chemicals, phenol and acetone.

PHYSICAL PROPERTIES
(I) The simplest phenols are liquids or low-melting solids. They are colourless when
pure but as usually seen they are red coloured owing to thC presence of oxidation products.
(2) Melting and Eoiling Poinls Phenols have the same capabilities for hydrogen bond
formation as aliphatic alcohols,
1048 Adyrnced Organic Chemistry

-H—&--•H--Q.H—_ -H--O H—O-

6
Fig. 422. Association among phenol molecules due to hydrogen bonding.

The capacity of intermolecular hydrogen bonding and high dipole moment are reflected
in marked differences in their melting and boiling points compared to aryl hydrocarbons of corn-
pa able molecular weights. Thus,
mol WI nip bAr,

Phenol, 94 41°C 182°C

Toluene, 92 —95°C
^D_CH,
(3) Solubility. Phenols are generally water-soluble as they farm hydrogen bonds with
ater much in the same fashion as do aliphatic alcohols.

A 111 H

60
Pig. 423. Solubillty ol phonoli In water ii due to hydrogen
bonding Wit water malceule,.
Uis interesting to note that phenol, similar
in molecular weight to hezanol, is much
more soluble in water (93 g/100 ml HSO).
(4) Effect of Ita'ata OS boiIlq pouts sad sobffity.
group is present in the ortho position to the phenolic OH group, When an aldehyde or a nitro
bonding occurs giving rise to a six - membered cyclic structure. intramolecular hydrogen

fl-80N0

M-8OND
ML/C YL4LDU?Y( O-t/ITROPA'ENOL
 Phenats and Aron,acic Alcohols 1049

Therefore, here the phenolic Oil group is no longer available for intermolecular hydro.
gen bonding. Hence salicylaldehyde and nitrophenol exhibit lower boiling point and solubility
compared to their meta and para isomers which are capable of forming intermolecular hydro-
gen bonding as also with water molecules.
H
H— O—N—O...

"H •• Ow" O— H -

II

Intermolecular hydrogen Hydrogen bonding between

bonding in pnitrophcnol [Link] and water molecules
(5) Toxic Character, Phenols are highly toxic and kill all types of cells. On account
of their toxic effect on [Link], phenols have antiseptic properties.

Table. Physical Properties of some Phenols

Name mp 'C bp 'C Solubility Acidity Constant

g1100 1tO at 25°C K. x 100

Phenol 41 182 9.3 I-I

o-Cresol 31 191 25 063
m-Cresol 201 2-6 098
p-Cresol 35 202 23 067
Catechol 104 246 45
Hydroquinone 173 286 8 2
Resorcinol 110 281 123 3
Salicylaldehyde —7 196-5
o-Chlorophenol 9 173 28 77
m-Chlorophenol 33 214 2-6 16
p-Chlorophenol 43 220 27 63
o-Nitrophenol 45 217 02 600
m-Nitrophcnol 96 14 50
p-Nitrophenol 114 l7 690
2,4,6-Trinitrophenol 122 14 very large

CHEMICAL PROPERTIES
Phenols and alcohols both are made of a carbon frame-work carrying a hydroxy group,
but they differ significantly in their chcmical reactions. This is attributed to the structural
difference between the two classes of compounds.

Oi-gitiic C hi iistt - 67
050 Advanced Organic Chemistry

As already discussed, a nonbonded electron pair of oxygen atom of the phenolic OH

ateracts with the i system of the benzene ring and is delocalised. The delocalised electrons
OW belong to all the six carbons of the ring as also to the oxygen atom. This delocalisation
if nonbonded electrons caused by resonance is represented by the hybrid structure of phenol
;iven below. As a result of delocalisation of electrons as shown in Fig. 421, the
C—O bond acquires some double bond character and becomes stronger than 0—H a bond.
lso, the increased electron density in the benzene ring activates it, and gives electrophilic
ubscitution reactions.

R651Sr3 CL(AVAGE RESISTS CLEAVAGE

EAS/L V Ct (4VE0'
ALCOHOL
PHENOL
(RESONANCE HYBRID)

In alcohols, no resonance is obviously possible and the nonbonded pairs of electrons

-emain localised on the oxygen atom. The C—O)inkage thus retains its a bond character and
weak as compared to that in phenols.

Thus, while alcohols give reactions in which Oil group is replaced by other substituents
C—O cleavage), phenols do not do so normally. On the other hand, phenols ar dissociated
.t the 0—H bond and behave as weak acids, forming salts with alkalis. Alcohols do not form
alts with alkalis.

Now we proceed to discuss the general reactions of phenols (Ar—OH) under two main
eads
(a) those involving the phenolic OH group ; and
(b) those involving the aromatic ring.

. REACTIONS INVOLVING —OH GROUP

(1) Acid Charac(er; Salt Formation. The acidity of a compound is defined as Its proton
-leasing ability in the presence of water tLewis base). Phenols behave as weak acids because
icy ionise when dissolved in water, to form phenoxide anions. Thus,

O—H 4- .. +

phenol phenoxide anionum

Phenols are markedly more acithc than alcohols, although less so than carboxylic acids.
'his i5 evident from the values of K. given in
ic table.
Table. K. values at i.s I,.
The ease with which a phenol releases a Ethanol -10-11
roton, is explained by the difference in the
Phenol X
sonauce sabilisation of the phenol and its
hecoxide anion. As we know, phenol is a Acetic acid I'S x lO-
sonance hybrid of five forms. i___________________________________
Phenol, and Aromatic Alcohols
1051

H OH +0+1 .cji

1 if 1ff y RESONANCE
Hrg.e/D
The pherioxide anion also occurs in five resonance forms

:0 :0

:0
RuJOP14Nc(Hyg,,,0
I if m EVv

It may be noted that both phenol and phenoxidc anion have two Kekule forms. In
addition, they have three other charged forms each with the negative charge on the onho and para
position. In phenol these charged forms (Ill to 'I) contribute much less to the hybrid than do
Kekul forms (I and U). This is so because charge separation costs energy and high-energy forms
cannot stabilise the hybrid much. The resonance forms of the phenoxide ion in which the charge
is in the ring, however, acquire no charge separation. The charge is only delocalised. Hence
these forms (III to V) stabilise the phenoxide anion very much. Thus relatively the resonance
hybrid of phenoxide anion is much more stable than the resonance hybrid of phenol itself.

1-
—a'-

PHENOL 8'8fD PHE1ox/OE ANION Ry9Ri

(MORE 5M8L)

Since phenoxide anion hybrid is more stable than the phenol hybrid, the equilibrium in
displaced to the right, releasing H I ions. This explains why phenols can behave as acids.
Alcohols, on the other hand, are neutral in the sense that their acidity (K 1 = ..40-I8) ,
no more than that of water (K.=lO). This is understandable because the formation of
alkoxide anion is not favoured as it IS not resonance stabilised.

R—O R—O + H
"H alkoxiije
anion
alcohol (not resonance
stabilised)
Considering from another view point, ionisation of both phenol and alcohol requires
energy. But the ionisation of phenol would require smaller energy ( L E 1 ) owing to iesOnance
st abilisation of phcnoxide anion, than the ionisation of alcohol ( E) as the alkoxy anion is not
resonance stabilised. This is why the ionisation of phenol is favoured greatly as compared to
that of phenols. Or That, phenol is much more acidic than alcohols.
 Adnced Organ Chemistry
i052

r +

it T0 + H IVPHINOYJO f/ON

I I .tSONAA(C1 5 'A&LLSATION
IN P1E/1OL

E '-O
\(4

REAcr,ON PR06ES5

Fig. 424. Ioalcailoo energy of phenol lieu (Mn that of alcohol (SE, > AEI) due to resonance
stabilization In phenol and pheo*ldi, favouring the former reaction,

flect of Substituents on the Acidity of Phenols. We have already discussed that the
staFlity of the phenoxide anion it produces. An
acidit y a phenol is determined by the
of
Ixcon relcasing substituent A' (say CH) pumps electrons into the benzene systes
and tntensiftes the negative charge of the phenoxide anion. Ths makes the anion less
stable, :hereby decreasing the acidity of phenol. On the other hand, at electron withdrawing
substituent 'B' (X, NO,, CHO, cOOH, withdraws electrons from the ring system which
results in the dispersal of the negative charge of the phenoxide anion This stabilises
the phenoxida anion and, therefore, the acidity of phenol s increased. The two situations are
illustrated below.

ÔH.

Pig. 421. 'A' pumps etecteoni lain th Fit. 426. 'B' withdraws electrons from the
ring, thereby decrcuing the negIise charge
ring, icrengiheal the nephive chirge
on [Link] anion and destabilises it, or phenonide anion and stabilising it, which
decreasing acidity of phsaol. eohancet the acidity of phenol.

This explains why mcthylnzenes are less acidic than phenol, while chiorophcnols ace
more acidit than phenol.
Phenols and Aromatic Alcohols 1053

The intensification of the negative charge on the isomeric c'hlorophenoxide anions will
depend on the distance of the electron pumping group from the —0 group.

0 0 0

t ci

Cs
0-C/1,WRJ?PHEN0XIDE TI). -CHWROP,1(NQF Ci
AN/ON AN/W
b-C/1L OOPHE A/OXIDE

That is why the values of K. for the isomeric chiorophenols follow the order
K onF.i > K. meta > K. para.
A substituent such as the —NO1 group, when present at ortho or para o the —OH
group, withdrawi electrons from the benzene ring system by Inductive and resonance effects.
This stabilises the phenoxide anion by dispersal of the negative charge as shown below ir case
of p-nitrophenol.

Therefore, nitrophenols are much more acidic than phenol.

JH .-NO, /N

9J\NO,E
[Link] [Link]
rocno
K- OOxlO- K4 - xtO NO,
[Link]
- 60 X 10-10
The marked lower acidity in case of mats isomer is explained by the fact that
m-nitropheooxjde anion is stabilised by inductivcffect only and no resonance effect operates
with —NO, group (absence of [Link] system).

NO FTk( ESON4NC(
-. p. • WaAe NC G1UP

s9."
1054 Advanced Organic Chemistry

The cumulative effect of three —NO 1 groups in 2,46-trinitrophenOl (picric acid) makes
it as strongly acidic as mineral acids.
Salt Formation. Phenols dissolve in aqueous NaOH or KOH (but not Na 1CO3) to form
soluble sodium salts known as phenoxides.

+ raOH ONa + H10

phenol sod phenozide

Phenol can be regenerated by acidification of the resulting solution either by a mineral
acid or by blowing carbon dioxide through it (phenol is a weaker acid than carbonic acid).
This sequence of reactions may be used for the separation of phenols from mixtures of organic
uhstances. The nonreactivily of phenols with sodium caronale may he made use for the
separation of mixtures of phenols and carboxylic acids. Like alcohols, phenols also react with
alkali metals, Grignard reagents and lithium aluminium hydride, to form the respective
alkox ides.
C,H6OH + Na -p CH 5ONa +
sod phenoxide
CH 5OH + CH 1 Mgl - C6 HOMgl +CH4
magnesium
phenosv iodide
4C5 HOH + LiAlh1 -p LiAl (OCeH1s ± 4111
lithium aluminium
phenoxide
(2) Coloured Complexes with FeCl. Phenols form coloured iron complexes when treated
with neutral ferric chloride solution. These complexes have characteristic colours and this reaction
is often u\cd as a test for phenols. Phenol gives violet colouration resorcinol, violet ; catechol,
green pyrogallol, red phloroglucinol, dark violet and so on.
The formation of the iron complexis is attributed to the existence of keto-enol tautome-
rism in phenols as already mentioned. Since a phenol is mostly in the enol form, it forms
coloured complexes with ferric chloride - a character associated with compounds containing
enolic structure,

H H
H Cr C

HC

EPIOLtCSTRtJCTU8E H H
PHENOL CONTAIN/NC,
ENOLIC STRUCTURE

(3) Replacement of OH by H. When a phenol is distilled with zinc dust, the —OH
function is replaced by a hydrogen atom. Zinc removes the oxygen of the phenolic group as
Linc oxide, to yield the parent hydrocarbon.

OH + Zn -
± ZnO
phenol
This reaction is useful in gelling the first clue to the structure of an unknown complex
phenolic compound.
Phenols and Aromatic Alcohols 105

(4) Replacement of OR by Halogens. Unlike alcohols, phenolic OR cannot be replace(

by halogen by reaction with hydrogen halides.

OR + HCI No Reaction

(Cf. C2 HS OH + HCI -.- C,H 5CI + HO)

However, PCI5 or P11r5 reacts with phenols to form aryl halides.

I) / OH + PCL : Cl + POCI5 + HCI

The yield is very poor owing to the main reaction of phenol with PCI to form esters o
phosphoric acid e.g., (c1 H 5 )PO Phosphorus trichloride reacts with phenol to form only the
ester of phosphorus acid, (C6H.)jP03, and no aryl chloride is obtained.
(5) Replacement of OR by Nifa function. The replacement of phenolic OR by amin1
function can be brought about by heating a phenol with ammonia in presence of zinc chlojidc
ZnCl1 //(
p—OH +Nh3 -p K i HNIj5
/ 300' ± HO
phenol aniline
Polyhydric phenols undergo the reaction even more readily.
(6) Ether Formation, Phenols form ethers easily by reaction of sodium phenoide with
alyl halides (Williamson Synthesis). The phenonide ion is nucleophilic and will displace the
halogen from an alkyl halide, giving a mixed alkyl aryl ether.

6Na+ —O—R + NaX

sod pbenoxide alkyl aryl ether

SQdium phenoxide is obtained easily by dissolving phenol in aqueous NaOH solution. e.g.,

OH CH3I /c:\
- ;7- OH -a \//O T• '—O—CH,
phenol phenoxide anisole,
anion methyl phnyt ether
(,iscleophi'Ie)
Unlike alcohols, phenols can also be alkylated by reagents such as diazomethane and
dimethyl sulphate in alkali solution.

OR + CH 1 N, -, O_CHt + N1
diazomethane
methyl phenyl ether
OR OCH5

+ 2::>< + 2NaOH +2

dimethyl
OR
sulphate 1OCH3
hydroqwnooc hydroquinotte
dimethyl ether
1056 Advanced Organic Chemistry

(7) [Link]. Phenols react with acyl halides or anhydrides to form esters, in
presence of a base (NaOH or pyridine)

©- 0—H + CI—C—CH,
0
A bale ©- 0.
II
CH, 4- HCI
0—C—

phenol phenyl acetate

0 0
II I;

Q^_ Cu3 —C-0—C—CH, -.

acetic anhydride
q^—O—C—CH,+ CH,COOH

phnyl acetate

Unlike alcohols, phenols are not directly esterificd by reaction with a carboxylic acid in
presence of mineral acid catalyst. This is attributed to a lesser nucleophilic oxygen of the
phenol compared to that of alcohol (See reactions of carboxylic acids).

B. REACTIONS INVOLVING THE BENZENE RING

(I) Direct Electrophilic Substitution. As previously discussed , the delocalisation of a
nonbonding electron pair of OH function into the bentene ring system activates it to electro-
philic E ) attack. Further the points of attack are the ortho and pars position to OH, since a
negative charge is placed here 'due to resonance. This is illustrated by the resonance hybrid
structure shown below.

H16+
0

Fig. 427. Benzene ting to Fig. 428, Elcctrophitc (E') attacks at

phenol activated by increase of ortho and pars positions which being
overall electron density by delo- electron rich bear a negative charge ()
callsation of nonbonding elect-
ron pair.

Thus phenols readily undergo electrophilic reactions and the OH function directs them
to ortho and para positions.

CARSON/UM
01.1 OH OH

0RriOATTAClc

6-
1N7EQ,4eDM1f ORT/1V PROCLJCT
PHEiVOL
frE.50A'A'K[ d YSR/D
Phenols and komauc Akohols 1057

C"

+st 4
6

NTCP51EO(ATE PARA PRo$CT

(1) HALOGENATION. The —OH group on the benzene ring is a very powerful activator
and special precautions are necessary to check polysubstitution in the ring.
Phenol when treated with excess of aqueous bromine solution yields 2,4,6tribromo-
phenol straightway.
Br, - Br 1Br + Br a -
OH OH
Br
Br
± 3Br
+ 3H4

2,4,64ribromophcnoi
However, bromination may be limited to monobromination stage by using catculatek'
amount (I mole) of bromine tissolved in less polar solvent such as CS, or CHCI 3 . Thus,
014 OH OH

(/I ( Br
BrO
+ HBr
S, +
obroipophcnoI
Tr
[Link]

(Ii) SULPHONATION, Phenols are readily suiphonated with conc. H ISO4, Here SO5H
is the electrophile.

H,SO4 '-i- H5SO4 O,H + HSO + HO

OH OH OH
SOIH
0+ 2O1H -. + 2}
+
A-phlTioISulphOflic
acid SO1H
[Link] acid

If sulphonation is carries st room temperature, ortho isomer is the chief product,

while at IOOC the para isomer. On prolonged heating with concentrated sulphuric acid,
another —SOH group is introduced in mete position to the previous one.
 1058 Advanced Organc Cernisty

OR OR
SO3H
+ cone HSO4 +

60 + 2S03 H
prolonged heat

SO3H
+ 2K

phenol-2,4-disulphonic acid
(ill) NITRATION. Benzene ring in phenols being highly activated, phenols undergo
+
nitration . ith dilute nitric acid, NO, (nitronium ion) is the electrophile.
+
HNO3 - HNOI NO, + NO 3 + H2O
OH OR OR

NO,

60 + 2NO1 -

[Link]
+[ I,?J 2H

NO,
; p-rntrophcnol

(iv) NITROSATION. Here the electrophile is nitrosonlum ion, NO.

-I,-
FiONO + H 1SO, NO ± HS01 + 1110
H H OH

NO +

2O +

c flhlrolopbcnol
NO
p-riilrosophezoI
(2) Alkylatloa. Phenols are alkylated in the aromatic ring when treated with alkyl
halides, alkali solution, and acidified.

0
OH H OR
CH,

benzem +
".
QVW
CH,
p-ctesol
MECHANISM. NaOH solution reacts with phenol to give sod phenoxidc which reacts
with methyl iodide.
Ol
- o
ON* fib
LII CH,

CH, l - H

ceo
Phenob and Aromatic Alcohols 1059
(3) Acylation. Phenols react with aryl chlorides in the presence of MCI 3 to form ortho
and para. acylphenols (Friedel-Craft Reaction).
0
II .4 -

CHI—C--CI .1- A1C1 ± CH—CO + AId1

OH acylium ion
(e(vctrophd()

1L7COCH,
[] + CH,—=O
-i + 0 +
o acctylphcool
COCH3
p-acctylphenot
(4) Mercuration. When a phenol is refluxed with aqueois mercuric acetate, o-acetoxy-
mercuriphenol is obtained.
OH 9H
ç—O—COCH
+ (CHCOO)5Hg CH1COOH
-+
[Link]
(5) Coupling Reaction. Phenol reacts with aryIdiazonirn salt. in the tese pce of alkali
to form azo compounds, Thus

^q^IC[ + (')_0H
I. NaOH
—N=N -.(C5_OH

phenyldiazonium phenol p-hydrozyizobcnzene

chloride (dye)
This reaction is referred top Coupling Reaction and is used extensively for the synthesis
of dyes.
MECHANISM. It is a typical example of electrophilic substitution on an aromatic ring
activated by —OH group in the para position.

H) Wa3

—H

(6) Kolbe's Reaction. On passing carbon dioxide over sodium phenoxide at 1251, COOH
is directly introduced into the aromatic ring in ortho position to OH. Thus:
Na OH OH
.10 + NCI

+ a coaN+a ( COO"
sod phccoz o-hoxybcneo4c acid
(salicylic acid)
1060 Advanced Organic Chemistry

If the carbonation of sodium pbenoxide is carried at 250-300C, p-carboxylation product

is obtained.

o
ONa OH OH

o + C
HO

wdphenoaide
J
COO Na COOH
p-hydrosybenzoic acid
This reaction involving the carbonation of phenols to give phenolic acids is named as
Kalbe's Reaction.

& I
MECHANISM. Carbon dioxide ( O=C=O ) acts as a weak electrophile and brings
about cicctrophilic substitution by usual mechanism.

+ &H
0

JCöN+
11
czi^o

s,4LjCYtc ACIO
(7) Gattermaau Reaction ; Formyla(ion. When a phenol is treated with a mixture of
hydrogen cyanide, hydrogen chloride and zinc chloride catalyst, an aldehyde (or formyl,
—CHO) group is introduced in the ortho position to OH. Thus, phenol yields o-hydroxy-
bcnzaldehyde.
OH OH

Zn0 5H9 CHO

+ HCN + HCI

[Link]
This reation known as Gattermann Reaction is a general one and is used for formylation
of aromatic rings to which an electron withdrawing group (—OH , —OCH, etc) is attached.
+
MECHANISM. The electrophile HC=NH is derived from formisninochioride, and the
electrophiiic substitution takes place by the usual mechanism.

H—CN -- HCl -+ Cl—CH=NH

rormimjnohloridc

ZnCI1 ± C!—CHNH -, ZnCI 3 + CHNH

OH 0H ON
C .cM=NH HO

SAL CYLALEHVDE
'Phenols and Aromatic Alcohols 1061

(K) [Link].o Reaction. The treatment of a phenol with chioform (CHCI 3) and
aqueous NaOH at 60°C, followed by acidification, introduces a —CHO group in the aromatic
ring mainly in the ortho position to OH group. For example
H OH OH

l 4qt°*OH,0' jj70
+ cI{C13

ohydroxybeczaIdehyde
(main product) CHO
p-hydroybcnzaIdehyt$
(small amount)
This reaction known as employed for preparing phenolic
[Link] Reaction is
aldehydes.
MECHANISM. The reaction is believed to proceed by the following steps
(I) Formation of dichloromethylene (dichiorocarbene) from chloroform
Cl Cl,
I -
H—C—Cl + OH —+ HO + t C—Cl — Cl + CCI,
I dichtorornelhy
d (riecirc$ile)

(ii) Electrophilic substitution in the phenol ring

—4 —
C .0. Na
cla
NeOR
cc,2 ------

(iii) Hydrolysis and acidification

0 0 OH
CHCl CHO +
+ 20H
tJ_CH0

[Link]
If Cd 4 is [Link] in place of CHCI, salicylic acid is obtained, ortho derivative being the
main product.
H OH H
I. NaOH COOH
(:Cl,
2.11+
• o4iydroxobczoIc acid
(iwui proticI)
COOK
[Link] acid
(small proâ.cf)
 062 Advanced Organic Chemistry

(9) Houben-Hoesch Reaction. Highly reactive polyhydric phdnols in which OH groups

are meta to one another, may be acylated when treated with alkyl cyanides in the presence of
zinc chloride and hydrogen chloride. The product is a phenolic ketone.

OH OH

HO i
resorcinol
+ R—CN + H30
aher
HO CO—R + NH,

phenolic ketone

For example,

OH OH OH

HO2 ¼) HO CO—CH3 + NH3

CH,
ketimine resacelophenone
(intermediate)

This reaction given by Houben and Hoesch in 1927, is named after them. Phenol
does not respond to Hauben-Hoesch Reaction.

(10) Condensation with Aldehydes. Phenols undergo condensation with aldehydes by

electrophilic substitution in ortho and para positions in presence of acids or alkalis as
catalyst.

OH OH 011

&CHR-014

phenol clecirophile j o•hydroxy-alk lb zy

CH—OH alcohol

R
p•hydroxy-alkylberszyl
alcohol
• (mainproduct)

Formaldehyde undergoes such condensation to give o and p-hydroxybenzyl alcohols.

OH OH OH

8^ a
+ CH5=O CHtOH +
J formaldehyde

o-hydroxybenzyl
alcohol CHIOH
p-hydroxylbenzyt
alcohol
(mein proja)
 Phenols and Aromatic A?cohoI 1063

This reaction is known as [Link] Reaction, lithe reaction mature contains

excess of formaldehyde disubstitution and trisubstitution occurs. Thus,

0 -
OH OH OH
CHOH CH1=0 HOH1C,J,,CH2OH
CHO
-p

CH 2OH CHSOH CH2OH

[Link] ybcnz'd 2,4-Ilutiydrosymethvl- 2,46•lrihvdcosymeihvl
alcohol phenol phenol
Intermolecular condensation of these hydroxymeihyiphenols leads to the formation o a
high molecular weight and highly cross-linked polymer, known as formildehyde resin or
Bakelite.

Fit. 421, Phenol-formaldehyde resin t8aAehiei.

(II) Condensation with PhIhalic .nkydride. Many phenols undergo condensation with
phlhilic anhydride to give useful products. Thus phenol when heated with H,SO 4 gives phenol-
phihalein, a colourless compound which produces beautiful pink colour with alkali solutions due
to formation of coloured sodium salt.

ROA OH +
HO,vN H 0

'.0/ CONC. HISO4 rum

ON.+

PHENOLPHTHALEIN SODIUM SALT O

([Link]) PHENOLPHTHALEIN
(PINK)

Phenolphthalei n is a popular indicator for acid-alkali titrations

(12) Oxidation. Phenol is easil y oxidised without disruption of 'is carbon skeleton to
form p-bcn2oqulnonc.
 1064 Advanced Organic Chemistry

©
- CrO,C11
OH + 2[Oj - o ' O + H2O

phenol [Link]
Similarly hydroqulnone on oxidation with silver salts yields [Link].

+ 2Ag + 2H10
HO-
0— OH + 2A0 o'o
_
* hydroquiflOfle p-benzoquinone
This reaction leads to the use of hydroquinonc as a photographic deveiuper.
The ready oxidation of phenols is explained by the fact that the presence of —OH group
on the ring, furnishes electrons to the ring which is thus rendered susceptible to oxidation,
especially in alkaline medium.
With a drastic .oxidising agent such as alkaline KMnO 1, the aromatic ring of phenol
cleaves to form tartaric acid, oxalic acid and carbon dioxide.
(13) seduction. The —01-I group is stable, and the catalytic rerton of phenol yields
cyclohexanol.
OH OH

Ni

150--175*
phenol cyclohexanol

Substituted phenols would similarly form substituted cyclohexanols.

OH

/NVCH Ni
LJ +
o-cresol o-mclhytc'ctohcxaflol
IDENTIFICATION OF PHENOLS
(I) Solubility Test, if the substance is more soluble in NuGH solution than in water,
but insoluble in sodium bicarbonate, ills probably a phenol.
(2) Ferric Cbloiide Test. To the aqueous or ethanolic solution of the substance, add a
few drops of neutral FeCl solution. The appearance of an intense colour—red, green or black
—confirms the presence of a phenol.
(3) Bromine [Link] Test. Bromine water is added to aqueous solution of the substance
until the yellow colour of bromine persists. The Formation of a precipitate (substitution
product) confirms the presence of a phenol.
(4) Llbcrmanas Test. The substance is warmed with a little concentrated sulpburic acid
and sodium nitrate. The'dark-coloured product so obtained is treated with dilute NaOH
solution. The production of intense blue or green colour confirms the presence of a phenol.
(5) SpectTsl Analysis. While alcohols are almost transparent in the ultraviolet spectrum,
phenols have moderately strong absorption, arising from the benzenr ring. Thus phenol has a
baDdat 2lOnm (e 6200)
 Phenols and [Link].,tic Alcohols 1065

The infrared absorption region of phenolic hydroxy group (0—H stretch) is the same
as that for alcohols (3600 cm- 1 ). In addition a C-0 stretching absorption is also characteristic
olbydroxy containing compounds. In phenols it occurs near 1200 cm- 1 and in alcohols at
1100 ± 50 cm- 1 . The benzene nucleus is identified by its own absorption spectrum. However
there are complications due to intermolecular hydrogen bonding, or intramolecular hydrogen
bonding in various ortho derivatives.

MONOHYDRIC MEMBERS

PHENOL, CARBOLIC ACID, Hydroxybenzene

It was discovered by Runge in 1834 in coal-tar. He named it carbolic acid (carb—_coal;

olewn=oil). It is also present in wood-tar.

Phenol may be prepared by any of the general methods. As already described, it is still
obtained commercially from coal-tar Middle oil and Heavy all fractions. But over 90 per cent
of phenol is now prepared by synthetic methods of which the most important and recent one is
from cunene derived from petroleum.

Pre,erlles, (Physical). Phenol is a colourless crystalline solid, nip 41°C, bp 182T, having
characteristic odour, [Link] pink when exposed to air and light. It is sparingly soluble in
water but dissolves readily in ethanol and other organic solvents. It is a violent poison when
taken orally, and produces painful blisters in contact with skin. Phenol is rarely used as an anti-
cptic because of its extreme toxic character.

(Chemical). The reactions of phenol ha,e been discussed in detail under the general
properties of this class of compounds. However, a resume of these reactions, which are in fact
the reactions of the hydroxy group and the phenyl group will be given here by way of recapitu-
lation.

REACTIONS OF —OH GROUP:

- wiSer - +
+ NaOH - C,11,-0Ns + 11,0
sod phanoxid.
+ FeCI 3 -.- Coloured complex; violet colosiralion

A
+Zn —. C,H,

+ PCI. .-.-. CI EI—CI + POd, + HCI

chloobezae

INZ Phenol
Zach
+ NH [Link]—NH, + 11,0
A aaiIe

+ NaOH -, C.H2ON4i C,H,—O—CH1

sodium inMole
phnoside
+ CH,N, —. C,,H,—O—CH 1 + N.
anisols

+ CH,cOCl —p C i H,-0—00—C}13 + HCI

pbsnyl icasaic

Organic hemistry - 68
066 Ad,anced Orgonic Chemrsry

REACTIONS INVOLVING BENZENE RING:

+ aq 3Br, Br OH + 3HBr (BrOmifla(iOn)

at
2.46-inbtomopbciioI

SO,H

conc H ISO HO1SOH (Suiphonat ion)

plieool. [Link] acid

NO1

+ dii HNO3OH + O1 NOH (Ni(ration)

&OH o4uIrophelIol pnitropheno

phenol NO

HSO
+ HONO • OH + ON OH(Nitrosation)
—&
o-niuosophcnol pnitrosophenoI

CH

+ Na(. H
cull
.

,-ct,oI
OH + H3C
— ^D—
p•creiol
OH
(Me(hylaiion)

COCH3

+ CHCOCI- OH + CHCO—OH
Acetylaf ion)
o-a cetylphcnol [Link]
Hg—O—COCH3

+ (CH 3COO)1 Hg
6 OH

[Link],,ineccuriphcflol
- CRCOOH
(Mercuration)

CF11..O
+ CH 1 =O - HOCH2—.—OH -p BAKELITE
(exeesA)

pbyd1OybCUZi iiJiJ1
 Phesols and A,onijJc Alcohols 1067

• [Link]
+ C.H 1a -- --o (Coupling)
2. H+ &
p'.hyroxyuobcnzrn
COOH

125 HC1 ---

OH (Kolbe Reaction)

sahcyllc acid
CHO

ZnCI 1 H-f
+ HCN + HCI - _-+ 40H (Gallermana Reaction)

ulicylildehyde
CHO

&
—I
OH [Link]
+ CHCI1 ---1.
0 OH (Reimer-Tiemana Reaction

sahcylaldchyde

I. HSO4/
+ Phthabc anhydride -. phenolphthalein (Condensation)
2 NaOH
toj
CrO,CI-, + HO

p-benzoqulnooc

Ni
+3d. - -
150-1 75 a
cyclobsainci

Uses. Phenol has a number of commercial uses: (1) in the manufacture of phenol.
formaldehyde plastics e.g., Bakelite; (2) for the production of cyclohexanol, required for the
production of Nylon; (3) as a starting material for the manufacture of pharmaceutical prod u'-r
such as salicylic acid, salol, aspirin tIc; '(4) for making picric acid; for phenolphthalein and cer-
tain other dyes; (5) for preparing 2,4-dichlorophenoxyacetic acid (a weed killer), and
2,4-dichioro-354methylphenol (a powerful antiseptic, Dettol").
1068 Advanced Organic Chemistry

O-.-CH,—COOH
.,cl

cJ H1CCH,

CI
2.4.dichIor0PbenOaYaCctic acid 2,4-dicMoro .[Link]
(weed killer) (Dellot)

Nitromols, O,N—C,114-0H (a, in, p)

a- and [Link] are prepared by direct nitration of phenol with dilute nitric acid
at room temperature. The mixture is separated by steam distillation, the a-isomer passing over
leaving the p-isomer behind. m-Niirophenol is obtained by diazotisation of [Link] and
heating the resulting aqueous solution.
-
NH, NHSO4 OH

NANO
-J
N. H6504
NO, NO, NO,
s,.altrosniliie dMzosiwn all w-aJtrop&ienal
Properties. o-Nitrophenol is a yellow solid, rap 45°C, having a powerful odour, in- and
p-Nitroplienols [Link] solids, mp 96°C and 114°C respectively. They are all sparingly
soluble in water, and only the o-isomer is steam-volatile. Owing to the presence of an electron
withdrawing —NO, group on the ring, they are all more acidic than phenol, the ortho and pars
isomers more so than meta. They dissolve in alkalis, forming coloured salts. They are all
readily red uced to the respective amino phenols. When treated with bromine water, they
split out the nitro group forming 2,4,64ribroniophetiol.
Pkrlc AcM, 2,4,6-TrinisropSenol
It can be prepared readily by direct nitration of phenol with a mixture of concentrated
nitric acid and sulphuric acid.
OH OH

O,N
HN
R,SO'
phenol
NO,
2,4,[Link]
(picnc acid)
Since phenol is largely destroyed by oxidation with nitric acid, the yield of picric acid is
poor. For this reason this high explosive is now produced commercially through a synthesis
that bcgias with chlorobenzene.
a a OH OH
NO, O* NSJ.. / NO,
HNO.
-+1
H 0 1
NO, NaOH
- 0
NO, NO,
NO,
44-dinutrochlorobenune 2,4-dialtroplienol piceksc
(2,4,[Link])
?[Link] and Aromatic AkoioIs 1069

Two —NO, groups in 2,4-dinitrophenol are dcactvating and thus their presence suffi-
ciently counteracts activation due to —OH group. Hence the oxidation of the ring is avoided in
the last stages of nitration.

Properties. Picric acid is a yellow crystalline solid, mp 122°C, having a bitter taste (hence
its name, Or. pikros.. bitter). It is sparingly soluble in cold water gising intensely yellow solu-
tions. It dissolves readily in ethanol and benzene. Ii is poisonous.

- (I) The elcctron•withdrawing effect of the three —NO, groups greatly increases the acidity
of phenolic —OH group, making the compound nearly as acidic as mineral acids. For this reason
it goes under the name of picric acid. Thus it reacts with alkalis and decomposes carbonates
to form salts'.

(2) When treated with PCl, it readily gives piety! chloride. On boiling with water
picryl chloride forms picric acid, and when shaken with ammonia, picrarnide. Tliee reactions
are made possible because the Cl atom is activated by presence of three —NO 1 groups.

OH Cl NH,

O' N )No, O,NNO, NI!,

H2O

boil 1-1K!)

NO,
V.- NO, NO,
picric acid picryl chloride picramide

(3) It forms molecular complexes with aromatic hydrocarbons. These are well-defined
crystalline compounds (picrale) and are used for the isolation and identification of aromatic
hydrocarbons. For example, picric acid produces red, crystalline, high-melting compound with
anthracene. The bond between the reactants, is formed by interaction between the electron-
poor ring of picric acid (Lewis acid) and the electron-rich ring of anthracenc (Lewis base). The
compounds of this type are often referred to as 'Chargetransfcr Complexes'.

ON

.
D_N(:i,
OK I
03 0. ,NO3

MO2 AMrHRA CENt

0
PICRIC AC1t

C
CHARGE 7RANSAFR CCMPC Ix

Uses. Picric acid is used i (I) for making explosives (Lyddile and Melinite) as a
reagent for the identification of aromatic hydrocarbons, amines ctc; (3) as a direct yellow dye
for silk and wool; (4) Butesin picrate, picrate of [Link] is a useful surfacç
anaesthetic for the testment of burns .... .-
1070 Advanced Organic Chemistry

Amlopeok. They may be prepared by the reduction of the corresponding nitro

phenols with metal and acid (Sri Fc/HCI). [Link] is obtained commercially by
reaction of resorcinol with ammonia and aqueous ammonium chloride under pressure at 200°C.
OH OH

a# NH4C1
+ NH, '(& + H10
OH NH,
resorcinol [Link]
p-Arninophenol is prepared commercially by the electrolytic reduction of nitrobenzene
insulphuric acid solution. The nitrobenzene is reduced to N-hydroxyaniline,
CH—[Link], which rearranges to yield phenol. It is also obtained from phenol by nitrou•
(ion, followed by reduction.
OH OH OH

ucNaNjFHOj

N=O NH,
p-iniinøphcDOl
Properties. All the three aminopbcnols are colourless solids, melting points are b-137°,
,,-123°, p-186C. The o- and p-aminophenols are less acidic than phenol, and do not form phen-
G'ides with alkalis. On the other hand, they form salts with Strong acids e.g., hydrochlorides.
The o- and p• aminophenols are very readily oxidised to o and [Link]
respectively.

[0j
+ NMI

I-!
/.,AMlNOpAVJ1

Therefore, they act as reducing agents, and are used as photographic developers.
The amino group is more readily acetylated than the phenolic hydroxy group. Thus,
acetylation with acetic anhydride leads to N-acetylation.
OH OH

CH1COONa
+ (CH —CO W

[Link] ,''. NH—COCH2

[Link]
 1071
Phenols and Aromatic Alcohols

o..AminopheoOl reacts with acetic acid to form [Link]

H:\
+
__ [1'CCH3

o-amino p tscnol acetic acid [Link]

p-Aminophenol is an important photographic developer, This is also used as a dye
intermediate. [Link] is also an intermediate in dyestuff manufacture.

CRESOLS, Hydroxytoluenes, CH,—05H4—OH

The mixture of o, m- and p-cresols is called Creosote' as these form major constituent
of Creosote Oil—a coal, wood or petroleum tar fraction. The mixture is separated into individual
cresols by using a sophisticated fractionating column.
Preparation. (I) Each of the isomeric cresols may be synthesised by diazotisaiOn of the
corresponding toluidine and warming the resulting aqueous solution. For example,
CU, CU, CU,

NaNO2 N + H,SO4

NH,
H,S01
I& N,HSO
diuonium salt
&OH
,n-cresol
,.toIuidine
Cresols may also be obtained by fusion of the corresponding toluenesulphoflic acid
(2)
with NaOH.
CH, CH CU,
CH

fuse

SO,H S?j,r,ta OH

p.toIuenesuIPb00c
acid
or [Link] e is heated with aqueous NaOH at 300-320°C
(3) When either o.
under pressure, [Link] is produced.
CU,
CH,

NaOH OH ± NaCl

Cl
[Link] ,n-cresol

Properties. Cresols are colourless liquids having phenolic odour. Their boiling points
201°, p. 202°C. They are less toxic than phenol but have a greater germicidal value.
are o. 191°. m-
They produce violet colouration with ferric chloride and give most of the reactions of phenols.
In addition, cresols are readily oxidised with chromic acid to give corresponding carboxylic acids
if the _.-OH group is blocked by alkylation or acylation.
 1072
Advanced Organic Chemistry

CH, CH, COOH cOOH

o) (LN$,oI

o-cresol
(CH3)jSO4
- _ HO
LçI J
IaIiCyIjciId
Uses. Mixture of cresols (creosote) is used (I) as preservative for timber, railway
sleepers etc., (2) for making liquid disinfectant lysol,
a solution of cresol in soapy water; (3) for
manufacture of synthetic resins, plasticisers, dyes and explosives.
THYMOL AND CARYACROL
These are two isomeric higher homologues of phenol which are extensively used in

00
perfumery and as antiseptics.
CH3 CH]
,OH

1110H
CI1(CH,)2 CH(CH)2
Thymol Cervacro
$
(2-hydroxy-4-ioprop yltoiuBne) (3hydro$[Link] toluene)

Thymol occurs in the essential oil, oil of thyme, and is prepard by heating m-cresol and
isopropanol with sulphuric acid. Carvacrol is obtained by heating camphor with iodine.

DIHYDRIC MEMBERS
CATECHOL, o-Dilzydroxybenzene
Catechol occurs in Indian catechu (obtained from Acids Catechu tree) and hence its
name.
Preparation. (I) By alkaline fusion of ophenolsulphonic acid.
OH OH +OH
O+ N&011.

S
—4
f-'
lul
oN —• (aOH
techol

(2) By heating o-chlorophcnoj or o'dichlorobcnzenc with aqueous NaOH in presence of

tracea of CuSO at 190C.

/N'
O. OH

a
[Link]
+NaOH -,
or
C0906OH
rilacliol
(3) By the action of alkaline hydrogen peroxide on salicylildehyde.
mahodi (Labora*j.
 Plieacls end Aromatic Alcohols
1013

CHO
(aONa + aOH
NaOH H
+ H,05 -4
( – HCOONa)
OH ON + OH
salicylaldchydc cftechol
Properties. Catechol is a while crystalline solid, mp 104C. It is readily soluble in water,
ethanol and ether. It gives green colouration with ferric chloride. Its aqueous solutions darken
due to oxidation. It reduces cold AgNO 1 and warm Fehling's solution. On oxidation with silver
oxide in ether solution, it is oxidised to 12-benaoquinone, hence its use as a photographic
developer.

OH 0
OH
+ H 2 0 + 2 Ag

O-BENZOOVINONE
(1,2 bnlQqurnon,)

It condenses with phthalic anhydride in the presence of sulphonic acid to form alizarin.

Uses. Catechol is used : (I) as a photographic developer (2) for manufacture of

alizarin ; ( 3) as antioxidant in gasoline.

Guicol and Adrenalin. These are the two valuable derivatives of catechol.

OH H

Q . CH—CH,--N--CH3
(OH ©—ll
uaicot adrenalin
(mp 32") (hormone secreted by adrenal gland)

RESORCINOL, m-Dihydroxyben:ene
It gets its name from the fact that it was originally obtained by the fusion of certain resins
with alkalis.

Preparation. Resorcinol is prepared by fusion of sodium m . benzenedisulphonatc with

sodium hydroxide and subsequent acidification.
- + -
SO3 Na ONa OH

+ acidification
+
SO3Na ONa &OH
sod m-benzrnedisulphonste resorcnoi

Properties. Resorcinol forms white needle-like crystals mp I lO"C. It turns grey in air
due to oxidation. It is highly soluble in water, ethanol and ether. It gives a deep violet coloura.
lion with Fed 5 and forms a precipitate of 2, 4, 6-tribromoresorcinol with bromine water. On
nitration resorcinol forms 2,4,6-trinitroresorcinol known as sxyphnic arid whose salts are used
to identify certain compounds.

It couples with diazonium salts to form azo dyes and condenses with phthalic anbydride
to form fluorescein which shows intense green fluorescence when alkalised.
 Advanced Organic Chemistry
1074

ON

[Link]
0

FL UOfSC(iti

0
Resorcinol exhibits keto-enol tautomerism which is shows by the fact that it forms a
dioximc and bisuiphite compound.
ON 0

CN• MCl/ C
HC CH
I - -

I tI
H HC/C
ON
H
olK g tO FORM

When heated with n-caproic acid and zinc chloride it forms n4.hexanoyIrtSOrCifl0I which
on Cterñmeflsefl reduction yields n4heylresorcinol a powerful antiseptic.
OH 01-1
OH

Zn--Hg/Rd 60H
. HOOC—0 5 H1 -
0H_ [Link] acid OH
H
C005H11 C1H3
H
n4-hcxanoyt- n-4 . he*yt-
resorcinol resoreinol

Uses. Resorcinol is used : (I) as antiseptic in ointments for eczema; 2) for manu-
facturing a number of dyes such as azo dyes, fitiorescein, eosin, etc., (3) for preparing n.4-hesyl-
resorcinol, a powerful antiseptic for curing hookworm and urinary disorders; and (4) for pre-
paring certain sldehydc resins needed for bonding plywood.

QUINOL, IIYDROQUINONE, p-Dihydroxybenzene

It may be prepared by reducing p-benzoquinone with sulphurous acid.
OH

+ HS01 + H 10 : + H1SO4

0 OH
[Link] quinol
 Phenols and Arwwtk [Link] 1075

Commercially it is made from aniline by the following steps.

6
NH, 0 OR

101 IHI
S
Ms0H0 Fe/HSO
injUre
0
OR

PropertIes. Quinol is a white crystalline solid, mp 173 1 C. It is highly soluble in water,

ethanol and ether. Its aqueous solutions turn brown in air due to oxidation. Quinol is a power-
ful reducing agent and thus even a mild oxidising agent like ferric chloride converts it into
[Link] (a green solid).

OR
+ H2O
HO -K--
[Link]
Quinol exhibits tautomerism like resorcinol, and forms dioxime with NH 5OH and a
bisulphitc addition compound with NaHSO3.
Atnmonolysis of hydroquinone with a primary amine in presence of zinc chloride gives
N. N'-dialkyl-p-phenylenediamine. It is an important antioxidant for preserving gasoline and
rubber products.
zncll
RNH, + HO—._.OH + H1NR _. RHN—— NHR + 2HRO

N, N'-[Link]
Uses. Quinol is used (I) as a photographic developer; (2) as an antioxidant or inhibitor
in autoxidation and polymerisation reactions; (3) as antiseptic solution in the treatment of
conji4ctiYiIus.

TREHYDRIC MEMBERS
PYROGALLOL, I,2,3•Trihydroxybenzene
Preparation. It is obtained by heating aqueous solution of gallic acid at 210°C under
pressure.
OR

J
OR
,OH OR
+ H80 + H1co
HOOC OH OH
gallic acid pyropitol
Properties. Pyrogallol is a white crystalline solid, mp 133°C. It is soluble in water,
ethanol and ether. Its aqueous solutions produce red colouration with FeCl. Alkaline
solution of pyrogallol absorbs oxygen rapidly from air and turns brown. This property is used
in gas analysis for the absorption of oxygen. Of all the phenols, it is the most powerful
reducing agent. It rçduccs AgNO 3 and Febling's solution in cold. It can also reduce salts of
silver, gold, platinum and mercury to the respective metals.
Uses. Pyrogallol is used : (I) as an excellent photographic developer: (2) for preparing
antiseptic ointments for skin; (3) as a hair dye; and (4) for absorbing oxygen in gas analysis.
1076 Advanced Organic Chemistry

HYDROXYQUINOL. 1,2,4. T,ihydroxyben:ene

It is r rcpared by alkaline fusion of quinol in air.

OH OH

OH
NaOH

H OH
quinol hdroiyquinol
Hydroxyquinol is a white crystalline solid, mp 140C. Like other isomers it is very solu-
ble in water. Its aqueous solutions give a greenish-brown colouration with FeCI,.

PHIOROG LUCINOL, I,3,[Link]

It is prepared by fusing resorcinol with NaOH in air.

OH OH

NaOH
+ -+
fuse

&OH HO OH

csorcu no1 I ,3.5-snhydrosybcri2ne

In the laboratory it is obtained conveniently by the following sequence of reactions.

COOK COOK
HO ouCoo+
O,NNO1H,N NH,
Reduction HCl/A
3 NH4CI
ZnIHCI
OH
NO ' NH5

2,4,6-triah1robencoic 2,4,6-iria minobenzoic phioroglucinol

acid acid

In the last step, 2,4,6-triaminobenzoic acid decarboxylates and the —NH1 groups are
replaced by —OH groups.

Properties Phioroglucinol is a white crystalline solid, mp 218°C. It is fairly soluble in

water. Its aqueous solutions taste sweet and give bluish violet colouration with FeCI. Its alka-
line solutions rapidly darken on exposure to air due to oxidation.

Phioroglucinol behaves as a trihydric phenol, forming tripotassium derivative, triethcrs,

and triesters. Also, it gives atrioxinle as if it were a triketocyclohexanr. Thus phioroglucinol
exhibits tautotnerism.
Pbenth ad ktk Mcc,oIs 1017

041
0

/CN
CH M,C Oh
HC

-$ -
N0,4
PIO

Tflh(MOLIC •rRrnlro PM

Phioroglucinol is used for detecting carbohydrates, producing a red coloration with them
in presence of sulphuric acid.

AROMATIC ALCOHOLS

Aromatic alcohols contain the —OH group in [Link]. They may well be regarded
as aryl-substituted aliphatic alcohols. Aromatic alcohols may also be classified as i, r, or
3 alcohols. They resemble aliphatic alcohols both, in the methods of preparation and

BENZYL ALCOHOL, Pheiykarbinol. C,H,—CH2OH

It-is the simplest member of the class and is isomeric with cresols. It occurs is Peru
and Tolu balsams as free alcohol and as esters (acetate and benzoate) oil of Jamie and
other essential ode.
Prsralks. (I) By hydrolysis of benzyl chloride With aqueous sodium hydroxide.
(Commercial)

aCH,Cl - NaOH - &CH10" + NaCI

- bcazyl chloride bcnzyl alcohol

(2) By reducing beazaldehyde with zinc and HCI.

9-0 + 2(H1 _CH2OH

benzaldsydc benayl alcohol

(3) By treatment with concentrate(l NaOH solution. ([Link] Reertiot)

Beazyl alcohol may also be produced from benzaldehyde and formaldehyde by crossed
Cannro Reaction.
Prsss1k.. Beuzyl alcohol is a colourless liquid bp 206C, having a faint pleasant odour.
it is slightly soluble in water, but readily soluble in most organic solvents.
 1078 Advanced Organic Chemistry

Chemically it behaves like aliphatic primary alcohols and also gives substitution reactions
in the aromatic ring It is oxidised in two stages, it first forms benzaldchyde and finally ben.
wwacid.
0 0
I I
CH1H
OH 101 C—H 101 C—O

@1
brazyl alcohol
NHSO4©'

benzaldehydc brazoic tid

The oxidation can be stopped at the beozaldehyde stage by oxidation of benzaidehyde
with chromium trioxide in pyridine solution.
0

CH1OH 91U—n
+ 2[O]
Pyrhufte

bcnmldchyde
Benzyl alcohol may be reduced with hydrogen in the presence of palladium as catalyst,

(0/—CHOH + H. -! ( >— CH, +

beazyl alcohol toluene
Ua. Benzyl alcohol and its esters are largely used in the perfumery industry. Being
a local anaesthetic and antiseptic, it is used in making ointments for relieving itching. Benzyl
benzoate Is a remedy for asthma and whooping cough.
-Hj'*[Link] akebr,l, Saucy! alcohol, Saligenin. It occurs as glucoside, Soiicin. It is
prepared by the Lederer-Manasse Reaction.
OH OH
CHIOH

0 +CH1O -.
0
salicyl alcohol
It is a crystalline solid, mp 87°C, and is used in medicine as antipyretic.
. pHNYLE'rHYL ALCOHOL, Phenykihanol, CH—CH5--CH--0H
It occurs in the oil of roses. Ac synthetic product and its esters are now used in per-
fumery.
Prasratls.. (I) By reducing ethyl phenylacetate with sodium and absolute ethanol.

Na/CIH4ON&
CH,—C-0qI-I, + (HI ()_CHi—CHr—OH + CIHOH
0
a
ethyl pbenylacetate -pbenyIethyt alcohol
(2) By reaction between ethylene oxide and benzene in the presence of aluminium
chloride.

+ CH5—CH5---0H
Aid1 '(>..
Nreaois and Aromatic Alcohols 1019

Properties. Pbenylethyl alcohol is a colourless liquid, bp 221°C, having astrong rose-

like odour. It is only slightly soluble in water but freely miscible with ethanol and ether.
When heated with alkali, it forms styrene (vinyl benzene).

NaOH
CH,--CH,—OH —CH—CH I + H2O
& a a
styrene

QUESTIONS
I. What are phenols and how do they differ structurally from aromatic alcohols. Give an example of
each class of such compounds.
2. Discuss the structure of phenol, drawing the picture of its orbital model. Give the various
canonical forms of phenol and write down the approximate tiructure of the resonance hybrid.
3 How are pbcools named? Write the systematic and common names of any of the following
strtaures.
OH OH OH C1

OH [Link]
11N05

OH
CL CflO

NOs NOR
4. (live five Important methods of introducing OH group in an aromatic ring.
5. Describe the following methods of preparation of phenol: (a) Hydrolysis of Aryl halide ; (5) De-
boyIstioa of phenolic acids; (c) Alkali fusion of sodium arenesulphonaic; (d) Hydrolysis of diazonisan
sells.
t
6. How is phenol obtained from coal tar ? Give amodern synthetic method for the prepara ion of
phenol from a petroleum source.
7. (n) How do you explain high melting and boiling points of phenol 1(5) How Is It that phenol is
very muds more soluble than hexanol which hiss comparable molecular weight 1(c) Sallcylaidehydc and
citrophenol exhibit lower solubility relative to their mete and pairs Isomers. Why?
I. Phenols are acidic in character, while alcohols are almost neutral. ' Explain In detail.
Howls it that for isomeric chloropbcool., K is in the order Ortho>Meta> paea 1
acidity? 5. 'Nitrophenols arc more acidic than phenol': Comment Why the mats Isomer has significantly low

is. Discuss the reactions of phenols due to the OH group. Compare and contrast these reactions
with those of aliphatic alcohols.
It. Discuss five important reactions of phenols involving the aromatic ring. Give general mechanism
of in electrophilic substitution reaction of benzene ring of phenol.
ii. Slate the following reactions with reference to phenol and give mechanism In each case.
(I) Kolbes Reaction; (II) Gatterinann Reaction ; (1lt Reimer Tiessison Resction ; and (In) Lederer
Maniac Reaction.
13. Write the methods of preparation and properties of picric acid and benzyl alcohol.
14. E lain: (a) A nilro sulaliluent group increases the acidity or Phenol but a methyl group
it. . ( My sore BSc 11. 1980)
(5) Phenol is more acidic than eth y l alcohol.
15. (I) Write the various canonical Forms for the phenoxide ion.
(ir) With bcnzene as the stifling material, how would you prepare resorcinol
(Kerala B& M. 1980)
16. (a) How does sodium pheisoxide react with:
(i) CH5CH5CI (ii) CH3CQCI.
(h) Explain : Phenol is acidic in nature. (Panjab RSr Cirrsi Egg. I9,10)
1080 Advanced Organic Chemistry

17 Describe the preparation of Beonyl alcohol. Give the action of the following on benzyl akoliol.
(I) Nitric acid (ii) SOdIUfli
(iii) Acetyl chloride (iv) Phosphorus pentachloride
(Kashmir Sc, 1980)
11 How will you convert phenol into:
(I) Salicylic acid (ii) Phenoiphihalein
(iii) Eihoxybcnzene.
Give mechanism where neces. ry. - ([Link] 111. 198))
19 How is pehnol obtained from coal-far ? Compare the properties of phenol with the properties of
alcohol (Jabelpwr .BSc ii!. 1981)
20. (a) Why is phenol acidic while alcohols are not
(b) How are the following obtained from phenol?
(i) Salicylaldehyde (ii) p-hydroxyacetophenooe.
Discuss the mechanism involsed in each case. (Vexkaieiwrsra ASr 11, 1981)
21 Describe the preparation of phenol from
(I) lumene (Ii) aniline. ([Link] BSc Ill, 1981)
22. (a) Give four important properties of phenol to show how it differs frens.)cohol.
(b) Write the graphic formulae of any three:
(j) Catechol (ii) Rcsorcinoi
(iii) Picric acid (iv) Hydroqurnonc. (Sasar BSc ii, 1981)
23. Phenol can be nitrated with nitric acid alone, Explain this giving mechanism. (Pociva BSc, 1981.
24. How can Catechol and quinol be ptcnard? Whal are their uses' (8aa1ore 8Sc 11. 1981)
25. How is picric add prepared? (Jadaspvr8Sc. 1994)
Zt Write a nor on: Reinws-Tienwwi reaction. (KaspsrilSc 1994; SkvOi M 1990
27. Describe the mechanism ofRein-Ticmann reaction. (Delhi BSc Hoes 1994, Om,msAa8ScHoiss. 1994)
2$. Write a note on: Fries iearonsgenieal. (K*aii BSc Hmis. 1993)

29. Explain: Phenol is mom acidic than ethanol. (Mysore8Sc. 1994)

30, Exain: Phenol is aweaker acid dsanp-mtrophenoi (Noflh&agal8ScHow, 1994)
31. What is ([Link]. 1994)
32. How will you synthesiac in-nitrophenal from benzene? (Dibnga,* BSc, 1993)
Hint Use the following steps (i) HNO3/H2SOd60 (it) Cone. H 2SO4 . (ill) NaOH/ room temperature. (iv) NaOH/fusc,
and H5(M{.
33. How will you athesiselphenyiethanoL from benzene ?
Hint. Use the following oseps : (i) BrfleBr 3 . (i) Mg/ether. (iii) (31CHO, and (iv) H20IH
34 How will you distinguish between phenol and beazyl alcohol? (Pendicheriy8Sc 1994)
Hint. When a solution of phenol in water is treated with Sr2 in ljO, a pale yellow precipitate of 24.6-snbiomophenol is
formed. Bcnzyl alcohol does riot give this reaction. Also, phenol is soluble in aqueous NaOH solution. Beuzyl alcohol is insoluble.
35. Compound (A), C7H40. is a solidthatis thghtly soluble inqroussodiwn hydroxide. When (A) isireatedwithbumnine
water, the solid (B), C 7It6Br2 0. is formed. Write possiblestructuresfor (A) and (B).
Ai*w (A) Isp-redo1; and (B) is 2i.dibeomo4-mcthylpbenOL
 Chapter 43

Aromatic Aldehydes and Ketones

I. ALDEHYDES
Aromatic aldehydes are of two types: (a) those in which the aldehyde group (CR0)
is directly attached to a carbon of the aromatic ring ; and (b) those in which the aldehyde group
is attached to a carbon of the side-chain. Aldehydes of type (a) are called aromatic aldehydes,
while those of type (b) are best regarded as aryl-substituted aliphatic aldehydes. i
0 0

Ar—C—H Ar—CH1---C—H
aromatic aldehyde aryl-substituted aliphatic aldehyde
(CR0 attached to aromatic ring) (CHO attached to side-chain)
Benzaldehyde is a typical aromatic aldehyde, while phenylacetaldehyde and cinnamic
aldehyde are to be designated as aryl-substituted aliphatic aldehydes.

CR0 CH,—CHO CH=CH—CHO

'6.
benzaldehyde phenylacetaldehyde clnnamlc aldehyde

NOMENCLATURE

6r
(I) The IUPAC Name of an aromatic aldehyde is derived by dropping the ending
-ene of the name of the parent hydrocarbon and appending the suffix -al. Thus,

CE1O CEO CEO

6 6o"OH

CH1

benul 2-methylbenzal [Link]

(2) They are generally called by their Common Names which are derived from
the nam es of the corresponding carboxylic acid by replacing the -Ic or -ok acid by -aldehyde.
Thus the name benzaldehyde is derived from benzoic acid, o-tolualdehyde is derived from
o-toluic acid, and shjicylaldehydq from sJicylic acid.

108!

)rganic Clieniislrs' - 69
 Advanced Organic Chemistry
1082

6
CHO CHO CHO
CHO

C H1

[gJ & OH
OCHz
benIdehydc o-toluildebyde islicylaldebydo
/ (bcazil) ([Link]) (24ydzoxybenza1) OH
v*riillln
([Link].
benIdchydC)

STRUCTURE
The molecular structure of aromatic aldehydes will bc illustrated by taking the case of
benzaldehydc. It is similar to the structure of nitrobenzene which we have already discussed.
The p orbitals involved in the it bond of the carbon-oxygen double bond are aligned with the
corresponding p orbitals of the benzene ring and, Aherefore, interact with them. The extended
molecular orbital so formed encompasses the carbonyl carbon and oxygen atoms as also the
ring carbons of benzene.

ATOMIC ORBITAL MODEL ELCTRON CLOUD MODEL

Pig. 431. Molccular structure of Benzatdehyde.

Electronic structure of beozaldehyde is the resonance hybrid of the followiug four

%nonical forms.

C—H C—H

6ó
C—H C—N

A_r'c_
I (1
6+65+

RESONANCE
HYBRID

BENZALDEHYDE, Benzal, CeH 6—( = 0

Benzaldehydt is a typical and the simplest aromatic aldehyde and will be used for illus
trating the preparation and properties of this class of compounds,
 komacft Aldehydes and Know 1083

Benzaldehyde is found in nature as the glycoside amygdalln

in bitter almonds which on
hydrolysis with dilute acids or the enzyme emuLcin
produces free benzaldehyde, §-D-glucose and
hydrogen cyanide. This is why in pharmacy it is known as 'Oil
of bitter almonds'

CM,OH
UNIT 01,0k
OE__5

QH KYQRQL$ c +kojØ
^H
KW
ON
A-DGUco.s 8ZAL O?yac
cxlmwyM,M
OH 0
)L 0.
H

AMYGOAL IN

=t o=c-.-
' + HCN
K
benzaldehydr
twnzithicbyd. cy$nohy4frfn

AmygdaThs is poisonous because it

hyd rolyses to give HCN. Benzaldehyde cyanohydtiji
assuch is found in the reactor glands of raililpedu.
When attacked, the millipede ejects ,46
benzaldehyde cyanohydrin past an enzyme which breaks
it into benzaldehyde plus HCN on the
way ou:.

Metodi of Presuratlois
Benasidehyde may be prepared by the following methods
which are applicable to aro-
matic aldehydes in generaL

(1) OxJdaUae
OfTO1USO.. Benzaldchycle may be conveniently
prepared by oxidising
toluene with chrominum trioxide in acetic anhydride, and hydrolysis of the benzal acetate-86
produced with HCl or HISO4.

CM O—CO---CH, H10
C,H5—CH1
tol uene (CH1CO)10 C1H-0 + 2CHSC00H
o—co—CH, H+ benzaldehyde
bcnuj acetate
Another procedure (Etard Reaction) uses chromyl chloride as the
oxidising agent. The
intermediate complex thus formed is hydrolyed to give benzaldehyde in
good yield.
- H
CH—C}11 + 2Cr01CI, -.. C1
3Hç—CH'
O—[Link] H 10
-+
I
toluene chromyl "O—CrCI1---0H
' chloride Intermediate complex
Commercially the oxidation of toluene is done with air diluted
wtb aiuogen(to preven t
complete oxidation) at 500C in the presence of V104 as a caralyst.
1084 Advanced Organic Chemistry

fleazaldehyde is produced by the oxidation of benzyl

(2) Oxld*tloø of Benzyl chloride.
chloride by boiling with aqueous copper or lead nitrate.
H
Pb(NO2)a. boil 5 + HCI
CH1—CUCl + HNO 2C,Fk—C=O + HNO
bcozyl chloride (from hydrolysms
of Pb-nitrate)
This is a convenient method for preparing benzaldehyde in the laboratory and industry. Benzyl
chloride is made cheaply by chlorination of toluene.
BenzaldehYde is manufactured by the hydrolysis of
(3) Hydrolysis of Beam) chloride.
benzal chloride.
H
•1
C.H1—CH" Cl + H 50 -p cH=O —0 + 2HCI

bcazal chloride
Beozal chloride is obtained by chlorinating toluene until the gain in weight corresponds to the
substitution of two chlorine atoms per molecule.

C,H5—CH. + 2Cl, CH,—CHCI.

-.. + 2HCI
bcnzal chloride
When an equimolecular mixture of carbon monoxide
(4) GattermaniKotch Reaction.
and hydrogen chloride is bubbled through a solution of benzene in ether containing anhydrous
aluminium chloride, beezaldehyde is produced.
Carbon monoxide and hydrogen chloride bebavà as formyl chloride (H—CO—Cl), which
enters into Priedel-Crafts type reaction with benzene.

CO + HCI
formyl chloride

+ CI----H -. /_=o + HCI

beozene benzaldebydc
:
(5) Gatterinann Aldehyde Reaction, Benzene is treated with a mixture of hydrogen
cyanide and hydrogen chloride in the presence of anhydrous aluminium chloride. An addition
product (formimir'O chloride) first formed enters into FriedelCrafts type reaction with benzene
to give the iminc which is decomposed with water to produce benzaldehyde.
H
HCI + HCN -p HN—Cl
formimino
chloride

AICI1 HSO
C,H + CI—C=NH -sW C,H5—C " NH -+ CH—C=O + NH.
Imine benzaldohyde
iliis method is particularly used to introduce CHO group in phenols with convenience.
 1085
Aromatic Aldehydes and Ke*cnu

Benzaidehyde may be produced by the reduction of beuzoyl

(6) RoselihInd Reaction.
chloride with palladium-barium sulphate catalyst.
0 0
I II

+ H, Pdo c1c_H -- HCl

beüzoyl chloride . beozaldebyd

(7) Stephen's Reaction. Phenyl cyanide on reduction with stannous chloride and hy-
drochloric acid forms an aldimine complex. This on subsequent hydrolysis yields benzaldehydc.
I H
1150 I
-+ C,H5—C=.O
2C5H1—CN + 4HCI + SnCl, ---
phenyl cyanide aldiminc complex
+ 2NH4CI + SnCL

(8) Grlgnard Reaction. Benzaldehyde may be obtained by producing phenylmagnesiuin

bromide and then reacting with ethyl formate.

phenyl bromide
Br
+Mg —+
ether

(Y MgBr

pheaylInUnelIUm

Lo
bromide

MgBr

i 5(
j

phenylmagnelium bromide
0

+ H—COC,1, -
ethyl formate 9 +

Benzaldehyde can also be made by the oxidation of benzyl alcohol and by beating a
mixture of calcium benzoate and calcium formate. But these methods are not actually used for
aromatic aldehydes.
Physical Properties
Benzaldehyde is a colourless, highly refractive oily liquid, bp 179 0C. It has a pleasant
almond-like odour. It is only slightly soluble in water but dissolves readily in organic solvents
like ethanol, diethyl ether, etc. It is steam-volatile. Like all other aromatic aldehydes, it gives
a band near 2800 cur' in the infrared spectrum which is not shown by the ketones.

(etilc$1 Properties
BenzaldebYde having the aldehyde group (CHO) attached to the aryl ring undergoes
most of the general reactions of the aliphatic aldehydes in which .hydrogen atom is not involved.
However, conjugation of the carbonyl carbon with the aryl ring reduces the electrophilic reacti-
vity of the carbonyl-carbon atom due to delocalisation of it electrons. Hence in general aro-
matic aldehydes react less readily at the CHO group than their aliphatic counterparts.

LESS P05/FIVE
H H ,qAAcrEq
I.(I
H—c—c=o
I s 5-
N
£ENZALLéW;,,,
ACi TALOENVDE

(e-R present; carbonyl carbon has (no a-H; carbot i ' , rbcr, i1, uvn
positive character) less pronounced pciiv '''M
 Advancei Organic Chemistry

Also, the absence of a-hydrogen atom in benzaldehyde makes it possible to employ stronger
basic or acidic catalysts in condensation reactions. Thus it undergoes a number of condensations
which are not possible with aliphatic aldehydes.
A. REACTIONS OF CHO GROUP SIMILAR TO ALIPHATIC ALDEHYDES

(1) Oxidatlou. Benzaldehyde is not oxidised as readily as aliphatic aldehydes by solution

of oxidisino agents. While it reduces ammoniacal silver nitrate forming a mirror, it does not
reduce Fehling's solution. Nevertheless, benzaldchyde undergoes oxidation by atmospheric
oxygen at ordinary temperature. This process known as autoxidation is catalysed by light.

0 0

2C,H—C—H + 0
benzaldcbyde
-i 2C1H1—C-0H
beozoic acid

The autoxidation which possibly proceeds by free radical mechanism is very slow in the
case of simple aliphatic aldehydes.

(2) Reduction. When benzaldehyde is reduced with zinc and hydrochloric acid, or with
sodium amalgam and water or alcohol, benzyl alcohol is produced along with pinacol.

c.i J=o + ri ZUMCI

th CH,--OH

ii
bcnzyl alcohol

2C,H5—.=O + 2[Hj
ZcfHCIi.
- C,H1--C—C1H5

H àH
dtphcayl pinacOl

When sodium in ether is used as the reducing agent, higher yield of the pinacol is
obtained.

MECHANISM.

• H

CeH-C + Na C0H__c_$: + Na

WATER CH_C_C6h15
2CaH5.-.4 C.H5J.-_LC6H5

This condensation reaction which is given by aliphatic aldehydes as well, although not
to readily, is known as the pinacol condensation.
AomatJc sAJ4ehydes and ketonet 1087

(3) Addition of Hydrogen Cyanide. When hydrogen cyanide is added to benzaldehyde

in presence of alkali cyanide (NaCN) the cyanohydrin, (mandelonitrile) is produced. This on
hydrolysis with concentrated hydrochloric acid gives racemic mandelic acid,

&X O — + HCN
NsCN

© 1CN
1110
&H

VtI
bcnzaldehyde gnande Ion itrik mandeUc acid
(4) Addition of Sodium blaniphite. Beozaldehyde adds sodium bisuiphite to form the
bisuiphite compound.

II
& y -
+
+ 'taHSO, -.-..& I -

bcoz&debyde sodium bianiphite

(5) Conileumlioti with Hydroxylamine and Phenylbydrazone. Benzaldehyde condenses
with hydroxylamine(NH 1 OH) and phenyihydrazine (C.H 5NHNH1 ), to form benzaldoxime [Link]
the phenylhydrazone respectively.

&^=N-011 + H10

benzaldehyde benzaldoxime

-4 'ñ —(=N—NH—Ci H1 + H10

phenyhydrazonc
Similarly, benzaldehyde reacts with hydrazine and semicarbazide to give the hydrzaone and
semicarbazone respectively.

(6) Reaction WIth PCI1 . Bcnzaldehyde reacts with phosphorus pentachioride to form
the gem-dihalide.

-p + poct,

bent chloride
(7) Reaction with Scblft'a Reagent It restores the pink colour of Schiff I
s reagent.
B. REACTIONS OF CHO GROUP GIVEN PARTICULARLY BY AROMATIC ALDE}1YDES

(I) Reaction with Ammonia. With ammonia, beozaldehyde does not form a simple
aldehyde-ammonia, but a more complex condensation product called hydrobeniamide
 Advanced Organtc Chemistry
1088

I l-1
Ii'
3C,H,10 + 2NH1 -+ C,H5-4=N—C--N=C—C,H + 3H10
benzaldehyde

hydrobeGzam4de

(2) Reunion with Atnues Benzaldehyde jeacts with primary aliphatic or aromatic
amines to form derivatives known as Sch9s bases.

H
CH—C=0 + - CH=N—CH, + 1740
bcnzaldehyde H' [Link]
(benzalmethylamine)

+ -9. C.H5_(LN_-C 1 R + R10

bcnzytideneànilhie
antlla* (bonEahanhline)

The products from aromatic amines are also called wills. Scbiffs bases in general can be reduced
easily by hydrogen and Raney nickel to yield secondary amines. Thus,

H H
[Link]
CH5—LrN—C.H i + H1 .- -. 9. CH,—C—N--C1H5
benzylideneaniJhc
H
N.beczylail1nc
(benzyIphcnylmlae)

Aliphatic aldehydes do not react with amines to form compounds similar to Schiff's
bases.

(3) (utermqlecul*r Oxidation and Reduction Cannizzaro ReactIon. Benzaldehyde does

not contain an a, hydrogen atom and hence cannot undergo aldol condensation. When heated
with a concentrated sodium or potassium hydroxide solution, it undergoes an intermolecular
oxidation-reduction reaction. One molecule of it is reduced to benzyl alcohol at the expense
of another molecule which is oxidised to . benzoic acid. Thus benzaldehyde on treatment with
concentrated sodium hydroxide solution yields, in dYed, bcnzyl alcohol and sodium benzoate.

2 6
CHO

+ NaOH -.
CH1OH

+
COONa

The above reaction involving the mutual oxidation-reduction of two molecules of beuzsldhYdC

is called the Canniz'atO Reaction.

 089
Aromatic Aldehydes and K etones

MECHANISM, (i) Attack of the nucleophile OH at the carbonyl group to from the

adduct I.

H H
C6H5—C—O:
OH

The adduct then transfers a hydride ion (H) to the carbonyl carbon of another
(ii)
molecule of benzaldehYde, to form benzoic acid (II) and alkoxide ion (Ill).

:o. 0 H
J4,-- __
II I -:
C.H 5 —.Z.4H +,,cdo: _- ) C 6 H—C ± H—c—b
OH - oil- C6H5
I U ill
8tWZOIC ACID ALXOXItE ION

(iii) Proton transfer from II to HI yields benzoate anion and benzyl alcohol.

0 H

CH—C + H--C-0 c 6 i-i 5 --c--0: + H—C---CH2--OH

C6H /

- 8EA/ZOAT ANION 86NZYL ALC01,4

II

(4) Benzoin condensation. When benzaldehyde is heated with aqueous- ethanolic NaCN
or KCN it dimerizei to form an -hydroxy ketone called benzoin. This reaction involving
self-condensation of an aromatic aldehyde in the presense of CN anion as catalyst, is referred
to as benzoin condensation.

H - OOH
I &CN I I
2CH 6—C=0 . C5H5—C—C—CH6
benzaldehyde C5H0EI, H10 I
H
beozom
(i-bydroxy ketone)
I Oo A dv anced Otgah ic ChenHtry

MECHANISM. (i)Nucleophilic addition of a cyanide anion to the carbonyl carbon.

H H

—4- CHs4—.

CN

(ii) The CN group acidities the former aldehyde H atom which migrates to the former
carbonyl group.

'I. ________
csH—c_bf CH,-_C—OH

CN CN
RESONA NC! .5 rA 8/L isea
CAR8AA'ION

(iii) The resonance-stabilised carbanion adds to the carbonyl carbon of another mole-
cule of benzldehyde,

OHA,0: OH
cH—.c . C--CSHS
i\JI
.CN H
C0H5—C--C—CH5

INTERMEDIATE

(iv) The migration of the proton of OH to the oxygen accompanied by abstraction of

cyanide anion, forms bezoin.

:0: OH 0 OH
H -Q 0: II I
I N
__ CH_—C—C6Hs ----'- CH—C—C---05
C6H3—C-C—C6H
H
CNH CN
BENZO/N

Benzoin can be readily oxidised to a diketone, benzil, and reduced to a number of sbs-
tances such as dcsoxybcnzoin, hydrobcnZoifl, stilbene and dibenzyl.
Aromatic Aldehydes and Ketones 109!

CuSO1
+ (0) -._, CH—CO—CO—C1 H5 + H20
pyridine, H 2O bcazil
Sn/HCI
+ 2[H] -__, C,H—CO—CH,—C6 H5 + H10
dcaoxybenzoin
0 OH
NafH8/EtO}t
CH1—C—t—C.H + 2[H] -_ CI1—CHOH_-CHOHCSFI5
hydxoberizojn
H
bcnzoin Zn/HgRC!
± 6[H] -_ CH—CHCH—C,F{ + 2H20
Clemmensen stilbene
Hi/Raney Ni
+ 4H 2 -__, C4 H—CH1 —CH,—C4 H + 2HO
dibeiizyl

(5) Perkin Reactloa or Perkin CondensatIon, When an aromatic aldehyde is heated with
the anhydride of an aliphatic acid in the presence of the sodium salt of the same acid (catalyst).
; p-unsaturated acid results. Thus benzaldchyde on heating with acetic anhydride and sodium
acetate for several hours at l8OC, yields cinnamic acid.

&Y C=O+ CH3_&_O__CH,

11 CHICO0
-?4

180
CH=CH—COOH + CHICOZH
acetic anhydride cinnamic acid
benzaldehyde

This condensation reaction between an aromatic aldehyde and aliphatic anhydride is named as
Perkin Reaction (W.H. Perkin, 1868), or Perkin Condensation. It is a useful synthetic method
for the synthesis of x, p-unsaturated acids (P-aryl acrylic acids).

MECHANISM (I) In Perkins Reaction the CH ICOO anion furnished by sodium

acetate acts as a basic catalyst and helps in the abstraction of an a . hydrogcn from the aliphatic
anhydride to form carbanion (1).

00 0 0
II __ II
- Ol.-.oH Ii
CH3 — C-0 4 H_cH2 -c N -* +
0
ACTA7E ANOM CH3—C11;O ACTIC ACIO CH3.—C/
I
0 0
4CE71C ANdYOftJ cML4rnw(r)
(ii) Carbanion I adds to the carbonyl of aromatic aldehyde to form intermediate 11.

-0: 0
I II
C
a H Cti—C
Ii
II 0
0
(Ii)
 Advanced Organic Cherrnstr
1092

(iii) Protonation of the intermediate II at the anionic oxygen produces hydroxy acid
anhydride HI.

41
H
11
0 0

O^H/
4
CH_C_0_C3
II II
-f H -
0

HVDROAY ACID ANHYDRIDE (Irr)

(iv) Internal proton transfer leads to elimination of a water molecule to form

a, n-unsaturated mixed anhydride (IV).

-.
0 0
, II _____
__C_C_0—C--CH3
_C—C_-0--C--CH3 -
______
HH HH
CRI1SATLIRATED ,%fIXD A NfiYQIDE(II)

Hydrolysis of the unsaturated mixed anhydride (IV) finally yields cinnamic acid,
(v)

'?
CH=CH—C—O—C—CH
+io I? -+ çQ/—CH=CH—C—OH + CHCOOH

mixed anhydride cinnamic acid acetic acid

(6) Claisen-Schmidt Condensation. Benzaldehyde condenses

with aliphatic aldehyde or
methyl ketones in the presence of dilute alkali at room temperature to form unsaturated
aldehydes or ketones. This type j mixed aldo] condensation is known as the Claisen-
Schmidt Condensation.
OH
dii NaOH —HO
CH5—CH=O + CH 3 —CHO CeH5_CH_CH1_CHO
bcnzaidehydc acetaldehyde unscable 'mixed aldol'
C5H5CH=CHCHO
cinnamaldehyde

0 OH 0
II dii NaOH I I —H10
CH5 —CH=O + CF!—C—CH1,. CB,—CH—CH 1—C—CH1 -
acetone unstable 'mixed aldol'
CH1—CH= CH—CO—CH
benzylideneacerone

This reaction proceeds well because benzaldehyde, having no a hydrogen, cannot undergo self-
condensation. The mechanism of the Claisen-Schmidt Condensation is similar to that of aldol
condensation.

(7) Knoevenagel Condensation. Benzaldehyde undergoes condensation with substances

containing active methylene groups such as diethylmalonate, ethylacetoacetate, ethyl
 1093
Aromatic Aldehydes and Ketones

cyanoacetate etc., in the presence of an organic base (piperidine, pyridine) to form a, a-unsaturated
esters which upon hydrolysis and heating give the respective a -unsatuared acids. Thus,

&LO + H2 C
COOIC2U6 pperidlne,

cooc1H
&O / H

CI-- C
CO )C 1I1
COOC2H1 hydrolysis'
1-lEO

COOH A
—CH=CHCOOH + CO,
CooH
©—c=c/
cinnamic acid

MECHANISM. (i) Proton abstraction by base (8); (ii) nueleophilic addition at the

carbonyl carbon : (iii) elimination of water;

(iv) hydrolysis and decarboxylation.
OH
I
0

C 6 Hs_C__C8(COO C 2)
BH 1, I
" C 6H—C ^CH(tOOC^HS)
C6H5_1+CH(c00c2H5)2 ----

H H
H

OH
1. H2O
—+ [Link](COOC1H1)i
2. —COs

H C1H5_CHCH_C0011
clnrnaniic acid

Action with Grignird Reagents. BenzaldehYde reacts with Grignard reagents to form
(8)
a product which hydrolyses to give a secondary alcohol.

OMgX
H HjO
ether
+
H
r alcohol 1+ - -
+ MgOHX

. halogenated esters in the presence of zinc to

(9) RefornhatSkY Reaction. It reacts with s
give -hydroxY esters.

=0 + BrCH,—C—OC,Hs —-p
Zo OZnBr
C_CH5—C-0C1H1
II H10

©—I

OH 0
()__CH*.C_0_CIHI

.hydroxy ester

The .hydroxY ester may be hydrolysed to give the -hydroxy acid which is readily dehydrated
to form the unsaturated acid.
 1094 Advanced Organic ChernittY

(IO) Condensation with Tertiary Aromatic amines, Benzaldehyde condenses with tertiary
aromatic amines such as N, Ndirnethylaniline, in the presence of strong acids (HCI
or H,SO4)
to form derivatives of triphenylmeihane, Thus,

043
HCI
2 N'
CH3
ENZAI_DEJ VOC
N,N — o,MErfiyjAJAr
_& NICH,),

The above product is readily oxidised by means of lead dioxide and hydrochloric acid to give
the dyestuff Malachite Green.

(Ii) Action with Chlorine to form Beozoyl chloride. Becausce, benzaldehyde has no
-hydrogen atoms, it behaves differently with chlorine from the simple aliphatic aldchydes. The
aldehyde group attached directly to the benzene ring is deactivating and hence chlorine does not
substitute in the ring in the absence of a catalyst. Instead, the chlorine substitute, in the
aldehyde group and benzoyl chloride is formed.

0
catalyst
+ Cis C—Cl + HCI
absent
bcnzaldebydc benzoyl chloride
C. REACTIONS OF THE BENZENE RING
The CHO group withdraws electrons from the benzene ring of benaaldehyde by induc-
tive effect and resonance. This causes a drain of electrons from the benzene ring and renders
it positive and hence deactivated to electrophilic reagents. Although the benzene ring is deacti-
vated, attack by electrophiles will still take place under difficult conditions.

6•+
-'
H

Pig. Electrons are withdrawn from the benzene ring of benz&dtbydc, by inductive effect
of dO and resonance. The overall effect is that the benzene ring becomes positively
cbuged and hence resistant to attack by electrophiles.

An Clectrophile (E) seeking to attack the most negative positions will avoid the ortho and
Pam positions, and hence will attack the meta poii r ion which does not have a positive charge.

0•
C'H (HO
 Aromatic Aldehydes and Ketones 1095

Electrophilic Substitution Reactions. Benzaldehyde undergoes nitration, sulphonation

and halogenation in the aryl ring, the substitution taking place in the meta position to the CHO
group.
(1) Nitration with a mixture of nitric acid and sulphuric acid.

(HO dc

+
Il 2 SO4
'JO2

yde p72- 1pabenza1dele

(ii) Suiphonation with fuming sulphuric acid,

CHO CHO

6 so3d
HSO

o -*
SO3H
+ H 10

rn-benzaldchydesutpbonic acid
(iii) Halogenation with chlorine or bromine in the presence of halogen carrier.

('10 CHO

Caorler
6CI
'77 cfo'n'aIdehyae

Uses of Beazaidehyde

Benzaldehyde is used: (I) in formulating perfumes and as a flavouring agent; (2) in the
manufacture of dyes (malachite green) ; (3) as a starting material for the syntheis of several
other organic compounds e.g., cinnamaldehyde, cinnamic acid, benzoyl chloride etc

SOME IMPORTANT AROMATIC ALDEHYDES

CINNAMALDEHYDE, 3-Phenyipropenal, C,H5—CH=CH--CHO

It is the pleasant smelling constituent of cinnamon oil and can be isolated from it through
the formation of its bisuiphite compound. It is prepared synthetically by the action of dilute
sodium hydroxide upon a mixture of benzaldebyde and acetaldehyde (Claisen Condensation).
H H H
0 c=o + H—C—C=O -+
I NaOH I I I
C=C—C=O +
Q
benzatdehyde acetaldehyde cinnamaldehyde
Properties. Cinnamaldehyde is a colourless oil, bp 252°C. (1) On mild oxidation with air
or ammoniacal silver nitrate, it is converted into cinnamic acid.
1096 Advanced Organic Chemistry

Qmr,wnlacal

©__CH=CH.Cll0
+ H AgNO.
P__CH=CH_-0OH

cinnamic acid
crnnamaldebydc
With a vigorous oxidising agent like potassium permanganate, the molecule is split out
at the double bond, forming benzoic acid.
(21 Cinnamaldehyde is reduced with aluminium isopropoxide or aluminium hydride
to yield cinnamyl alcohol and adds bromine at the double bond to form the dibromide.

CH=CH—CH0 + 2H -+ /CHCH_CHI0H

cinnamaldehyde cinnamyl alcohol

(3) It forms the normal bisulphite compound with NaHSO 1 . However, on prolonged
treatment with this reagent, the sodium salt of a disuiphonic acid is produced.

—CH,=CH— CH0 + NaHSO5 t

[Link] bjiulpbite compound

Q
+NaHSO3
CH.=CH—CHO -+ CH—CHI—CHO
SO5Na
(1, 4-addition)
un
+NaHS01 - +
CH—CHI— H—SO5Na
o ^^

I-4
SO,Na
sodium salt of disulptOniC
acid

SALlCYLAL, oHydroxybenzaIdehYdebe made from phenol with the help of Rennet-

It occurs, in Oil of Spirea. (I) It may
Tiemann'ReaCtiOn &n alkaline solution of phenol is refluxed with chloroform tils
at 60°C, acidified
sulphuric acid, and then steam-distilled. o_HydroxYbeflZaldChVdeover dis, le aving
with
behind [Link]
.,OH . OH
OH NaOH 11'\Y 2NaOø
-.
( + CHC I1 -+ I I
A N2"-CHCl1 C
salicylaldehyde
,phenol (Steam. volatile)

12) It is manufactured by the oxidation of ohydroxybefllYl alcohol.

CHO
+ (0)
^al OH
-+ @^OH + HSO
uIicyladeivde
[Link] a lcebol

gives
Salicylaldthyde is a colourless oil, bp 196°, having a pleasant smell. It
reactions of both aldehydes and phenols. Its aqueous solution gives a violet colorati n
theProperties. o
with ferric chloride. It may be oxidised to salicylic acid or reduced to [Link] acohol,
 Aromatic Adehdes and Ketone s 097

Salicylaldehyde is high boiling compared to m- and p. isomers 'which is attributed to

hydrogen bonding.'
H-50NL

0 1H

Saicylaldebyde is used for the preparatiQn of coumarin by Pcrkin's reaction.

VANILLIN, [Link]
It is the sweet-smelling principle of vanilla bean and is extracted from it by means of
ethanol. It is obtained industrially
(I) By oxidation of isocuginol with nitrobenzene.
CH,—CH=CH 1CH=CH—CH, CHO

OCH 1OCHS
-
KOH
0
OH OH OH
engenot isoeugiflol ,vanillin
(2) By Reimer-Tiemann reaction from guaiaco!.

- CHO

CUC1ÜNBOH

0CM, OCIl,
OH OH
gualacol vanillin
(3) By Lederer-Manasse reaction from guaiacol.
CHIOH

HN}iOH
+ HCHO NaOH
'OCH3 OCHI
OH OH
guaiacol
CHO CHO

N0CHa OCHI

CH=N—C.H OH
vanillin

0 ra lie (licinistr - 70
1098 Adcned [Link] Ci.C'T5iTf

(4) Much of our present-day supply of vanillin is obtained by the hydrolvc, of lignin,
which is a by-product of paper industry.

Properties. Vanillin i5 a white crystalline solid, mp 81°C. It gives blue coloration with
ferric chloride solution. On hydrolysis by heating with hydrochloric acid, it forms protocate-
chualdehyde. Oxidation with silver oxide in aqueous sodium hydroxide converts vanillin into
vanillic acid.

2j per cent ethanolic solution of vanillin is much used for flavouring confectionery.

PROTOCATECHUALDEHYDE, 3, 4Dihydroxybenzaldehyde

(I) It may be prepared by heating vanillin with hydrochloric acid.

C FbI çuo

"Cl
ocn, ([Link])
OH

OH OH
vanillin protocatechualdehyde

(2) By adding phophorus pentachtnride Ii' piperonal, then treating the product with
cold water, and fiuially boiling the solution.

CHO - CHO CHO CHO

PUS H20

cold boil
0 OH

0—Cl-I 20—CC, 0—CO OH

PIP ERONAL PxQTo(AItCHU-

AL (It fl y DE

(3) By synthesis from catechol by Reimer-Tiemann reaction.

HO
HO
+ CHCI,
HO )C) HO CHO

catechol protocatechualdelcyde

Properties. Prolocatechualdehyde is a crystalline solid. mp I53'C. It produces green

coloration with ferric chloride and reduces ammoniacal silver nitrate solution. On oxidation
it gives prococatechuic acid. When treated with dimethyl sulphate it gives vanillin and veratral-
dehyde.
Aromatic Aldehydes and Ketones 1099

CHO CHO CHO

(CH1O4

(excess)
OH 60CH,
OCH,
OH OH CH,
vanillin veratraldchydc
PIifRONAL, 3, 4•Methylenedioxybenzaldehyde
It is the methylene ether of protocatechu&dchyde [[was so named as it is produced
by oxidation of piperic acid (from alkaloid piperine). Ii may be synthesised by treating proto-
catechtaldehyde with nethylene di-iodide (CHI,) and alkali.

0
Nook
H1C + 2H1
--
--. H2C1J
j HO CHO CHO
potocotechuoIdeliyde piperonol
It is made industrially from safrole by the same steps as for vanillin from eugenol

H
2CI\ D aOCH2—CH=CH2
Sofro'
0 )aCH=CH—CHj
Is osaf rOle

J21.
HZC(°):1N
0 CHO
piperonol

Properties. Piperonal is a white solid, nip l37C. It has the smell of helitrope, hence
its name heliofropin. It can be oxidised to piperonylic acid and reduced to piperonyl alcohol.

1H1
HZC"© CH4 0 CR0 0 cacti
ppnaiyl aicr" piperonylic acid
When heated with dilute hydrochloric acid, piperonal is decomposed to form proto-
catechuic aldehyde together with formaldehyde or methanol. Piperonal has a pleasant odour
and is used in perfumery,

It. KETONES
Ketones in which one or both the hydrocarbon groups attached to the carbonyl
(—CO--. ) are aryl,are referred to as Aromatic Ketones Thus these could be designated as
alkaryl or diary! kerones.
0
if
Ar—C—R Alkaryl ketone
0
Ar_-C—Ar Diaryl ketone
 1100 Advoned Organic Chemistry

Ketones containing the carbonyl group attached to a benzene ring are named Phenoues.
to the stem
The individual name of such a ketone is derived by adding -phenone or -ophenc'ne
formed by removing -ic from the name of the corresponding acid (RCOOH or ArCOOH).

1i C

acetophenone bcnzopheslOfle
(methyl phenyl ketone) (dipheflyl ketone)

The common names of aromatic ketones are obtained as usual by naming the alkyl or
aryl groups to the carbonyl group followed by the word ketone. These are given in
the brackets above.
Although aromatic ketones may be prepared by any of the methods used for aliphatic
ketones, they are generally orepared by means of Friedel-Crafts reaction between an aromatic
hydrocarbon and acyl chIn ide or acid anhydride.

The reactivity ni the arbonyl group in aromatic ketones is not greatly affected by the
aryl groups attached to it In consequence, they undergo the same general reactions as aliphatic
ketones However, they decine to form the bisuiphite compound, and in addition give the
usual substitution reactions in the aromatic ring.

ACETOPHENONE, Methyl phenyl ketone, lceylbenzene

It is the best known alkaryl ketone.

Preparation. (I) it may bc prepared by distilling a mixture of calcium benzoatc and
-alden' acetate.
- .- . 41 2+ S—
2CI46—CO—CH, + 2CaCO
(C.H—CO- . 0)1 Ca +(CH,—CO-_O)aCa
calcium acetate acciophenone
calcium benzoate
(2) It is obtained conveniently ill the laboratory by Friedel-Crafts reaction from benzene
and acetyl chloride.
0 0
Aid,
©-
+ CH3—C—CI C—CH,+HCI
acctyt chloride
©
acetophtnone

(3) IL is produced industrially by the catalytic oxidation of ethylbenrene with air at

1261 C under pressure in the presence of manganese acetate

l26,pressure
CH,—CH + 0, + H20
(__•)

ettiylhenrtI\c accLopenoflr
 hO!
Aromatic Aldehydes and Ketones

Properties (Physical). Acetophenone is a colourless, crystalline solid, nip 20C, bp

202°C, having a smell of hay.. It is sparingly soluble in water but dissolves readily in ethanol
and diethyl ether. It is steam - volatile. When administered orally, it produces a natural type
of sleep.
(Chemical). Acetophenone gives all the reactions of aliphatic ketones, except that it does
not form a bisuiphite compound, probably owing to steric hindrance offered by the phenyl
group.
l) On oxidation with NaOCI in water, or with potassium permanganate, or nitric acid.
it is converted to benzoic acid.
0 0
II
+ 2[H]
NaOC)
-+ Q - CO, + }i3O

acetophenonc benzoic acid

(2) On reduction with sodium and ethanol, it form methytphenylcarbinol.

0 H
Na/C1H1OH

&
11
+ 2[H1

acetophenoric OH

r
methylphenyt carbinol
( alcohol)

On reduction with amalgamated zinc and hydrochloric acid, it forms ethylbenzenc.

0
H
Zn/Hg
± 4[HJ __. ()_CHI_CH. H1U
HC1

ethylbeneene

(3) On chlorination it readily forms phenacyl chloride which is a relatively harmless but
powerful lachrymator and is used by police as 'mob gas'.

+ Cl, -+ ()–C--(—Cl or C1H,COCH,Cl

ki
acetopheiione phenacyl chloride
(4) in the presence of aluminium ier g. butoxide, acetophenone condenses with itself to
give dypnone.
CH,

()._=CH_C—.() + H2O
+CH1—c--K) -.
ao CH, ^

acetophcnone , (2 moles) dyprione

(5) When acetophenone is heated with euimolecular quantities of sulphur and an anhy-
drous amine a thioamidc is the product This on hydrolysis with acid or alkali yields aryl-
substituted aliphatic acid, The total reaction (Wlllgerodt Reaction) is used for the synthesis of
such acids.
 Advanced Organic Chemistry

16 1
1102

S
II H2O1H4-
C H —CO—CH - S + HNR -* CH1—CH,—C—NR.
Icetoph!nnne a thioimlde
C1 H 1 —CH,---COOH ± H1 S -.- HNR1
phenylacelic acid

(6; Aryl alkyl ketones containing a hydrogen atom in the i position to the carbonyl
group e.g., acelophenone reacts with formaldehyde and ammonia (or a primary or secondary
amine) to form •amino-ketome. The product is often referred to as Afannicir Bose and the

11
reaction is called Mannith Reaction.

0 0 0
V
C—CH, + H—C—H + NH -p Q7_C_CH –
II CH —Nr, H0

acetophenone -án,ino-ketone

The further reaction of the product with excess of ammonia takes place in a similar
fashion.
Uses. Acetopheflonc has been used in perfumery; and as hypnotic under the name
iiypnone' but it has now been replaced by more effective drugs.

BENZOPHENONE, Diphenyl ketone, C,H5—00—C,H2

4
It it a diaryl ketone with two benzene rings bonded to carbony. group.

Preparation. (I) By distilling calcium benzoate.

- 2+ . 14 1--

(CH_C0—Oi1Ca -+ C,H—00—C H - CaCO1

calcium benzoate berzophcnonC

(2) By FriedelCrafts reaction between benrene and benzoyl chloride.

+ c1J
-2. (_C_(() ± MCI

benrophenone

Carbonyl chloride may be used in place of benzoyt chloride.

(3) It is often prepared by Friedel•Crafts reaction b2tween benzene and carbon tetra-
chloride followed by hydrolysis of the gemnal dichloride.

Aid,

: > aoC1 G
© Cl—CC(2.–Cl
carbon I 21-10)

ao
tetrachloride

11 -
cCl2
hcnzophenone
Properties. Benzophenone exists in two crystalline forms a stable rhombic form,
nip 49C, and the other unstable monoclinic form, mp 26C. It has an agreeable odour and
is used in perfumery
Aromatic Aldehydes and Ketones 1103

(1) Reduction. (1) When reduced with zinc and ethanolic potassium hydroxide, it gives
diphenylcarbhol or henzhydrol (mp 68CC).

0 H
11 _^D Z.
-C-0
CHOH/KOH &8 0

diphenylcarbinol
(benzhydrol)

(ii) When reduced with zinc and acetic acid, it yields benzopinacol.

CH C1H5 C4H5

2C1 H 5 —C + 2[H] —a- C,H6—C---C—C1H5

ii
0 OHOB
bcnzopinacoi

Ben'..,nacol is also obtained by the reduction of benzophenone with a mixture of

magnetum and magnesium iodide. Benzopinacol undergoes the pinacolpinacolone rearrange-
ment when heated in aceli acid and in the presence of iodine as catalyst.

C$ H b C1H5 C'H'

CaH1—C_CI—CaH5 -p CH,_C-C'-CsHa + H10

11 1
OH OH 0 CH5
beozopinacol beozopinacolOfle

(uI) On reduction with hydrogen iodide, or with a mixture of lithium aluminium hydride
and aluurinium chloride, benophenone produces diphenylmethane.

+ 4[Hj - + H20
0—CH,_00
diphenyt methane

(2) Oxidation. On oxidation it yields benzoic acid, one benzene ring is completely
oxidised.

11 _^D + 15101 + 6CO3 + 2H20

benzoic acid

(3) On fusion with potassium hydroxide its molecule is split out to form benzene and
potassium benzoate.

KOH -p ©+j_o
11-0 pot. berixoalt
H 04 Adiincrd Organic Chem ,try

(4) Sodium dissolves in benzopbenone in ether without the evolution of hydrogen to

form a blue solution Containing sodium salt of a free radical, Metal ketyl.

C5H6 C,H5
I. ether I - +
C1 H—C=O + Na -. C1H—C--ONa
ketyl (blue solutio

Mlehkr's Ketone. It is an important derivative of benzophenone. It is prepared

by tieating dimethylanilinc with carbonyl chloride in the presence of zinc chloride.

–2HCI
,- Cl—CO—Cl -+ (CH),N-_ _'__ N(CH3)2
00—
dimethylaniltac carbonyl cloride Michler's ketone

Michlcr's ketone is used to prepare certain triphenylmethane dyes.

QUINONES

Quinones are cyclic a, 3-unsaturated diketones. In these compouitls the double bonds
and the keto groups arc conjugated. Truly speaking they are not aromatic derivatives, but
they are readily prepared from, and converted into aromatic derivatives. The quinones derived
from benzene are called Beozoquinones In benzoquinones, the two keto groups usually exhibit
the parc configuration, although ortho quinones are known.

p-BENZOQU'wO aJ(, 0-8ENZOQ&)40A'E,

2-8ENZOUfNON(

A similar formula for the m-quinOflCS cannot be constructed and it is not known to
exist
The name quinone is used both as a common name for p-benzoquinone and as a generic
term for all compounds having an ortha or parc s1uinonuid yp,: of structure.
In quinones the low energy molecular orbitals of the original benzene ring have
been replaced by other orbitals which extend over the carbon atoms of the ring and the two
carbon-oxygen atoms. The structures of quinones are, therefore, stabilised by this delocalisation
of the electrons.
Of the two benzoquinones, p-benzoquinone is by far the more impoiiatit,
 los
Aromatic Aldehydes and Ketones

[Link], [Link]
Being the most important member of the class, it is frequently referred to as simply
quinone. In the classical structure of [Link], each of the carbonyl double bonds is
seen to be conjugated with both carbon carbon double bonds. The structure is known as
crossed conjugated system.

0 0
H

II /C
H/ H

0 o

Fig. Crossed conjugation in p-benzoquinone.

Preparation. (I) Qqinone may be prepared by the oxidation of quinol with ferric chlo-
ride, manganese dioxide and sulphuric acid, or with acid dichromate.

OH 0

FeCI5
[O + HSO

OH 0
qutnol p quinone

2) It may be obtained by the oxidation olp-aminophenol with dichromate and sulphu-

ric acid.

OH
0

K3Cr,07H1S05
0+ (0 + NH.

0
NH,
[Link] [Link]

(3) It is prepared industrially by the oxidation of aniline with manganese dioxide and
sulphuric acid or other oxidants.

NH, 0

MnO,fH5SO4
+ NH,
+2

0
I Adnced Organic Chemistry

(4) it is also produced on a technical scale by the electrol ytic oxidation of benzene in
the presence of sulphuric acid.

+ 3(0] + H10

Properties. (Physia), [Link] forms deep-yellow needle-like crystals, mp

116°C. It has a sharp pungent odour and causes sneezing. It is only slightly soluble in water
but dissolves readily in ethanol ether and chloroform. It sublimes when heated and is steam-
volatile.
(Chemical). As expected from its structure, p-benzoquinone behaves as an a, .unsatu-
rated ketone. Thus it gives the reactions of alkenes as well as simple ketones. At any rate,
quinone is not aromatic since it lacks the conjugate structure characteristic of aromatic
compounds.

HCcAL(NE

HC\,
11 lk
oval E BONDS

TON/c

(I) Reaction with Hydroxylamine. Like simple ketones,p-quinone reacts with hydroxyl-
amine to form a inonoxirne and dioxime, according to the proportions taken.
o N-OH N-ON

NH 2 OH N H70H
I-

O 0, N—OH
,bQwNOPiE MOVOX/ME D/O/ME

The monoxir tautomeric with [Link].

N-0H N0

- Q WNO, N'rRoSoPHENOL
,u)
 ho?
Aromatic Aldehydes and Ketones

(2) Reaction with PCI5. p-Quinone reacts with phosphorus pentachloride to form
[Link] robe nzefle.
o Cl

o I
This reaction also illustrates the tendency of the quinonoid structure to pass to the more etable
benzenoid structure. The net result of the reaction is that the carbonyl oxygen atoms are
replaced by only one atom of chlorine, and not by two as is the case with normal ketones.
(3) Reduction. Quinone is reduced by sulphur dioxide, or NaHSO,, or by Zn and HCI
to form hydroquinone.
o OH
IL1 REDUCTION
+ 2H' 4 2;
oxIDATION

011
0

QUINONE HVDROQUIAPONF
(y&LOw) (COL OUR E55)

Since bydroquifloilt can easily be oxidised to quinone, these two compounds form an oxidation-
reduction pair that may be used as indicator in redox reactions. While the quinone is yellow,
hydroqUiflOfle is colourless.
When ethanolic solutions of quinone and hydroquinone are mixed, dark green crystals
of quinh)drofle are produced. Quinhydrone is a molecular complex composed of equimolecular
amounts of quinone and hydroqutoone.

H Y0ROuI/1OwE Q U/NONE Qu INHYORONE

(DARK G&W)

Quinhydrone is stable in the solid state but dissociates into its components in solution.
It has an important practical use is the measurement of hydrogen ion concentration by the poten.
tiometric method (quinhydrone electrode).
(4) Oxidation. When quinone is oxidised with air over vanadium pentoxide as catalyst,
it yields maleic acid and then maleic anhydride. The reaction proceeds by ring fission.
o 0 0
n.H
Hc—C—OH HC—C
+ 30 -- H -. 1 >0 + H10
(-2C01) HC—C---OH HC—C
c a 0
o maleic acid maleic inbydIiISc
1108 Advanced Organic Chemistry

(5) Addition of Bromine. The carbon-carbon double bonds in p-quinone are olefinic in
character. It undergoes addition reactions with reagents capable of adding to double bonds.
Thus bromine will add to quinone in a I, 2-addition to give the dibromide or the tetrabromide.
o 0 0

H H H H
Or { Or
+ Br, J
BrBr
H "H H Or
o 0 0
Q (i/NONE QU/NOJVE O/8R)f4IO( QW,/o,jr TfrRABRO400E

(6) Addition of HCI. When hydrogen chloride gas is passed into a chloroform solution
of p-quinone, I, 4-addition takes place to form chlorohydroquinone.
OH OH
0

cI
OH
CHLOROU/NOL,
0LOOHYDR0QU'NONE

(7) Addition of Dienes. Dienes add across the carbou-carbon double bond of the
quinone to yield cyclic compounds. (Diels. Alder Diene Synthesis)
0

CH: CN ,C
Ho HoN CH HO7 OH c
II • II I ii
HC HO OH CH
HON/H N0/ c /
H:
0

O-BENZOQUINONE, o-QUINONE
It is prepared by the oxidation of catechol with silver oxide in ether.
OH
OH
+ Ag10 -. + 2Ag +
["01
Anhydrous sodium sulphate is added to absorb the water produced in the reaction.
Properties. o-Quinone forms light-red crystals, mp 60_700 C with decomposition. It
has no. odour and is not volatile with steam. It is exceedingly unstable and decomposes spon-
taneously on standing. When reduced with sulphur dioxide in aqueous solution, it gives catechol.
OH
0
OH
+ H,SO4
+ SO, + H2O

catechol
0 UINONE
 1109
Aromatic Aldehydes and Ketones

QUESTIONS

1. flow do you differentiate between aromatic aldehydes rod aryl-substituted atiphutic aldehydes
Gise one example of each type.
2. Assign ILJPAC names to the following aromatic aldeydes.
CHO CHO CHO CHO

OR 7N01

0 60-- 60 OH
Br OCH3

3. Draw the molecular structure of benzahlehyde. In what way the presence 0' benzene ring
modifies its behaviour compared to aliphatic aldehydes.
4. Discuss the methods of preparation of .benzaldehydc as a representative of the aromatic
aldehydes.
5 Bring out the differences in the chemical behaviour of aliphatic and aromatic aldehydes, taking
raiiiples of acetaldehyde and beozaldClsyde.
6. Write notes on the following reactions, giving theji mechanisms, at applied to bensaldehyde,
(a) Cancizzaro reaction ; (6) Ilenzoin Coniterssation Ic) Perkin Condensation
(d) Knoevenagel Condensation ; (e) Reformaisky Reactki,.
7. Write the methods of preparation, reaction and uses of
• Chanamaldehyde (ii) Salicylaldehyde (iii) Vanillin ; ( ii) Protocatcclrualdehyde
(v) Piperonal.
8. How do you define the teems Aromatic Ketone: and Pitenones. Write their general structural
formulas.
9 110w is Acetophenone obtained by synthesis on a large scale? Give its reactions, making a
special reaction of 'Willgerodi Reaction and 'Mannich Reaction'.
10. Discuss the Frielel-Craft synthesis of benzophcnone. What happens when it in subjected to
oxidation and reduction.
II. What are Quinones ? Discuss in detail the preparation and reactions of [Link]
12. Hon is benzaldchyde converted into Cinnamic acid (Mysore RSc 11, 1980,
13. How, do you obtain bcnzoin from bcn?aldehyde V Indicate the mechanism irsolsed in We formatior
(Andhra BSc 11, 1980,
of benzoin from bcsizaldehydc.
14. Gibe an example of a Crossed Canniizaro reaction, with bencaldeh)de as ore of the reactants.
With benzophenooe as the starting material, how would You prepare (1) Benanilde and (1) Diphenyl-
tnelhare. (Kerala BSc ill, 1980)
IS. How do the following reagents react separately with acetaldehyde and benzildehyde(; cv live):—
(1) Hydrogen Cyanide (ii) NajI-lg and water (iii) Anirroniu
(iv) Caustic soda (a) Feblitsg solution
(iv) Phosphorus pentahloride. (Nugpur BSc ii, 198))
16. How is acetopbenone synthesised b y Friedel-Crafcs method? Discuss the mechanism involved in.
it How can you convert acetophenonc into benzoic acid; rtsethyl phenyl carbrnol; crhylbenzerie.
(Rajasthan BSc 111, 1981)
17. Give any two methods of preparing beiizaldehyde from toluene, (Gu!barga 8Sc 11, 1981)
18. What is Beozoin Condensation ? Explain it with mechanism. (Poona uSC 111. 1981)
19. A compound CHj.O reacts with NaHSO 3 to a white ppt. What structures it niig/ir base?
(Oarrrania BSc 111, 1981)
20. (a) How is pure bcnzaldehydc prepared in lab
(6) Explain the action of the following on bcnzaldehydc:
(1) Sodium bisuiphite
(ii) Phenylhvdrazine
1110 Advanced Organic Chemistry

(iii) Phosphorus pentachlocidc

(/v) Tollcn's reagent
Nagpur BSc 11, 1982)
(c) How will you distinguish between acetaldehyde and benzaldehyde.
21 Give three reactions to show that benzaldehydc and acetaldehyde rtact similarly and gist four reac•
(Saugior B& lii, 1982)
Iion to sb'ow that they react differently.
(Delhi BSc 11, 1982)
22. Write methods of preparation o( bencaldehyde.
istinguish between beuzal-
23 What reagent would best serve as the basis for a simple chemical test to d (Kerala BSc 111, 1982)
dehde and acetophenone ?
24. Give two methods of preparation and two reactions of benzaldettyde (Kerala uSc, 1992)
25. Describe a method of preparation of salicylaldehyde Give an example of Caniuzzaro inaction (Kerala BSc, 1994)
26. Write a note on Perkin reaction. (Madras BSc. 1994; Delhi 8Sc Hons, 1994)
27. Write a note on. Cannizzsro reaction. (Delhi BSc, 1993)
28. Write a note on: Beozoin condensation (Madarai BSc. 1994)
29. Discuss the ntechasusmof Perkin reaction. (Bont&p BSc. 1993: Anna BSc, 1994, Baroda BSc, 1994)
30. Discuss the mcchanisinof [Link] reaction. (Marathwada BSc. 1993)
31. Discuss the irtechanismof Bt:toin condensation, (Karnataka BSc, 1994)
32. How will you synthesise beitzeac from benaalilehyde . (Agra BSc, 1993)
Hint. Use the following steps (i) KhinO4ilseat. (ii) NaOH, and (iii) NaOH/CaO/treat.
33. Outline the methods of preparation, chemical piopeulies, and uses of acetophenone. (South Giijwur BSc, 1994)
34. Give preparation and properties of aromatic aldehydes. (Manipur BSc, 1994)
35. Describe the laboratory preparation of bencaldehyik from benzyl chloride. From benzalitehyde how will you prepare
the following
(o) Cinnainic acid, and (h) Benzaldositne. (Judavpur BSr. 1994)
36. How will you distinguish between benzaldthyde and ace1op4senose (Madami BSc, 1994)
37. What tiapçetss when bensaldebyde is treated with acetic anhydride and sodium acetate at I RCPC? (Delhi BSc. /994)
38. An unknown compound of molecular formula CaHtO given the following results
Tollens' test. Negator
2. 4-Dinitrophenylhydrazine Positive
todoform . Positive
Suggest a possible structure of the compound.
0
Answer. CH 3 -C-C,H 5 (Acetophenorre I
39. Compound (A). C8H9CI. is hydrolysed by dilute acid to form (B), CH 1 oCl Compound (B) can be oxidised under mild
reaction conditions to (C). CaHaO Compound (C) gives positive sodoform test Deduce and write structural formulas of compounds
(A), (B) and (C).
Answer, (A) isi -chloro- l'phenylethane. (B) is l .phesiylethanol; and (C) is acetophenone
 Chaper 4
Aromatic Carboxylic Acids and Their Derivatives

Aromatic acids contain one or more carboxyl groups (COOH) attached directly to the
aromatic nucleus. The acids in which the COOH group is attached to the side-chain may be
regarded as aryl-substituted aliphatic acids. However, there are no characteristic differences in
the behaviour of the nuclear and side-chain acids and the term 'aromatic acids' is rather loosely
extended to include both classes of compounds.
These are called by their common names or after the name of the parent hydrocarbon
(ILJPAC). Thus
COOH

[9J
COOH

JcH I I COOH

I cOOH

.6
benzoic acid,
enzenecarboyiC
o-toluic acid,
e-methylbenzoic acid,
[Link] acid,
[Link] acid, CH.
acid 2-methylben- 2-mcthylbenzene- p-tolulc acid
zenecarboxylic add carboxylic acid [Link] add,
2-znethylbcczzcc-
carboayllc acid
STRUCTURE
Let us take the example of benzoic acid to illustrate the structure of this doss of corn-
pounds. The structure of benzoic acid is very similar to the structure of nitrobenzene. Here
the carbon of the carbonyl group is close enough to the benzene carbon so that the it electrons
of the carbon-oxygen double bond interact with the r. electrons of the benzene ring.
The p orbitals of the C =O bond of the carboxyl group are aligned and they interact with the
orresponding p-orbitals of the ring carbons to give an extended delocalised orbital. -

Fig. 441. Orbital structure of benzoic acid Fig. 442. Electron Cloud representation of benzoic acid

III
1112 Advanced Oreantc Chemistry

MVTHOD6 OF PREPARATION
Aromatic acids can be prepared by the same general methods which are available for
aliphatic acids. In addition they may be obtained by oxidation of aromatic hydrocarbons having
a sidechairi. It will suffice to list below the reactions by means of which aromatic acids can be
prepared.

(1) Oxidation of primary alcohols and aldehydes:

CHIOH * CR0 COOR

beozyl alcohol beozaldehyde beazoic acid

(2) Hydrolysis of Nitriles

9 CN

phenyl nitrite
+ 2H 1 0

(3) Carbonation of Grignard Reagents

-- @r
COOH

benzoic acid

Mg—Br Co. gCO—OMgBr gCO—OH

L9J intermediate benzoic acid

phcnyhnagne$ium
bromide

(4) Oxidation of carbon side-chains

CH, COOH
KMnO4)OH
+1°]
A
(a cr
toluene benzoic acid

(5) Hydrolysis of frichiorotnethyl group on benzene nucleus

Cl OH OH

LCI + -4
boll HIO

Ca(OH), @_
1H
benzotrlchloride (wistabie) benzotc acid

(6) Friedel-Craft: Reaction

9
H10
+ Cl—CO—Cl -p -
carbony l chloride —HCl
© ©-—Cl
benzeae bnnzoyl chloride benzoic acid

Properties (Physical). Aromatic acids are white crystalline solids, having higher melting
points than aliphatic acids, They are slightly solublein cold water but fairly so in hot watel
and organic solvets.
 Aromatic Cocboathc Ac,ds and their Dera3tivei 1113

The infrared absorption region of the C=.O group in aromatic acids is 1700-1680cm-'(s).
This is a lower frequency than for saturated aliphatic acids, and so can be distinguished
from the latter.

(Chemical). For the most part the reactions of aromatic carboxylic acids are identical
with those of aliphatic acids, the more important differences being in degree rather than in kind.
(I) Acidity. Aromatic carboxylic acids with unsubstituted benzene ring are slightly
stronger acids than the aliphatic acids. Thus benzoic acid is somewhat stronger acid than acetic
acid.
0 0
11 0-

-f H Ka=6.3Xl0
@
benzoic acid benzoate ion

0 0
II 'II -
G1,—C—OH CH.—C-0 + H+ Ka=..l75x 10-'
acetic acid acetate ion

The effect of substituent groups in the ring on the acidity of benzoic acid (i.e., on ioni-
sation of —COOH) depends not only on the nature of the group but also its position with
respect to the position of the COOH group.
- The acidity of aromatic carboxylic acids, in fact, is determined by the inductive effect
as also the resonance effect. Electron-releasing substitucnts and ortho-para directors increase
the electron-density in the ortho and para positions. Thus with OH group in thç ortho or para
position; the benzene ring is unable to delocalize the negative charge of the carboxylate anion
(coo-).

0C\\;
0 "0: 0 0
1'-HvtaV8ENZO4TE

L$0
q0--H

YOROXYBLIOATE
AJ!O?

With long distances between the electron-releasing OH group, and carboiyl group,
the inductive effect is important. However, with the decreasing distance, the inductive
effect dominates over the resonance effect. That is why o-hydroxybcnzoic acid is stronger
(Ka100x 1O-) and p-hydroxybenzojc acid weaker (Ka=29 x 10-') than benzoic acid
(Ka=63x 10-').
Or2alIic ( heinistr y - 71
1114 Advanced Organic Chemistry

Electron-withdrawing substituents and meta directors like NO, group, on the other hand,
decrease electron density ortho and para to them. Thus the negative charge of the carboxylate
anion is delocalized and hence it is stabilised.

:0; :0: :O+f :0::O:

\ /

(Ar
/S\
0'—'0 0' — '0 0— '0

p-nitrobeazoate anion
That is why p-nitrobenzoic acid (Ka=40X lO) is stronger than benzoic acid
(Ka=6-3x l0). However, p-nitrobenzoic acid is weaker than o-nitrobenzoic acid
(Ka=620 x 10-6), where the strong inductive effect of the NO, group close to COO-anion
causes additional strong delocalization of the negative charge.

(2) Esterification. Aromatic acids having no substituent in the ortho position to COOH
group, are readily converted into esters by direct reaction with alcohols in the presence of mine-
tal acids (HCl or H2SO4 ) as catalyst. If, however, the ortho substituent is present, the rate of
esterification is considerably reduced. When both ortho positions are occupied, esterification
does not occur at all.

— COOH + C6H1011 -p
H+ _COOC1H5 + H10

ethyl benzoate
benzoic acid
Cl-Is . CH,

()_COOH + C 1H60H -L C COOCHs + H10

[Link] acid low yield of ester

CHs

+ C5H1OH ---+ No esterifi cat Ion

H $C_< ._COOH

CH,
2,4. 6.trImCthYlb0lG acid
the esters of ortho- substituted benzoic acids can be prepared by the action of silver
However,
salts with alkyl halides. But once they arc £ççed, they cannot be hydrolysed easily. These
'ortho effects' are observed regardless Of tli'näture of substituents and are apparently due to
steric hindrance. Groups larger than hydrogen so effectively occupy the space around the car-
n of the COOH group that the intermediate transition complex necessary for the reaction to
pzoceed cannot be formed.
'i.
(3) Anhydride Foraitke. The reaction of an aromatic acid chloride with sodium salt
of the acid yields the anhydride.
.è(omatic CarboxylIc Acids and their Derivatives Ills

Kl-Cl
+ NOL
_ LO-C-'Q^ +aa

benzoytdiloridc sod. beazosic beuzoic aah

An aromatic dicarboxylic acid in which the two COOl! groups are close together, give
anhydride simply on heating. Thus, o-phthalic acid when heated forms o-phthalic anhydride,
while p-phthalic acid is not decomposed.

0
I 0
C—OR

HO
C—OH @^Cxol +
o
I I
0
opbtba&icid pbthaljc anbydilde

(4) ACM Halide [Link]. Aromatic acids, like the aliphatic acids, are converted to
the corresponding acid halides by healing with phosphorus pentachioride or with thionyl'
chloride.

& paosoa,
0—OH + HCl

brczuk add — diloride

The aromatic acid chlorides (aroyl chlorides), are insoluble in water and react with it very
slowly. Hence alcohols, phenols and amines can be acylated in aqueous solution. When the
acylation reaction is carried in the presence of alkali (NaOH), it is catalysed and the HCI formed
in the reaction mixture is r . vwved. This is called Sdiottes .Bu..m Reaction. Thus,

o 0
sake
C—O+R—OH+NaOH -.
I'
C—OR +NaCI+H2O
©I ilcobci Rae U
bcnzoyi chloride astor o(baszoic acid

o 0•
I
Q
N
C—Cl + R—N}l, + NaOH
-p
Rosaueaç 0 C—NHR + NaCl + H10

This is a good method of preparing benzoyl derivatives of alcohols or phenols, and of

primary or secondary amines. It consists of shaking together at room temperature benzcrl
chloride, dilute NaOH solution, and alcohol, pflo9r,n1ine.
An improvement on the original Schottcn-Baumann method is the eac of pyridino in
plam of aqueous NaOH. The pyndine functions both as a solvent and a base for the
of HCl produced in the reaction. Pyridine itself being a tertiary base does not react With ben-
zoyl chloride. The use of NaOli on the other hand_ - convert the l(ter into sodium benzoate,
thus lowenag the yield of the product.
11 16 Advanced Organic Chemistry

(5) Add [Link] [Link]. Aromatic acids form ammonium

carboxylates which upon
heating yield acid amides.

C—OH- LNH, + HO
—f-,
amis bsnzoae bczamidc
beazoic acid
In the presence of phosphorus pentoxide, amides further dehydrate to form nitrites.

PA
—.,.CoN + H10
&' 0
bcnzonittile

(6) Decarboxylatlos. Aromatic acids are readily decarboxylated by heating their salts
with sodalime.
0
^^
J + NOH -±- + NCO,

sod benzoate benzmie

As compared to similar decarboxylation of aliphatic acids, the reaction here is much

cleaner as less byproducts are produced.
(7) Rectlon. Aromatic acids on reduction with lithium aluminium hydride give benzyl
alcohols in 80 to 99 per cent yield.

0 UAII
+ 41H1 -.-- ()—CH,—OH + Rio

bonsoic acid beozyl alcohol

Ordinary reducing agents, like hydrogen and metal catalyst or sodium and alcohol, fail
to reduce the carboxyl group and rather bring about the reduction of the aromatic ring. Thus
benzoic acid when reduced with sodium and boiling amyl alcohol is converted to cyclohexane
carboxylic acid.
0
+ 3% -4- /J_OH
hull

beozoic odd cyclobexanec*rboxyllc acid

(8) Electro,killc [Link] ring. Aromatic acids undergo electrophilic subs-

titution reactions in the benzene ring. The COOH group is meta director and the substitution
takes place less readily than in the parent hydrocarbon ring. For example, benzoic acid under-
goes halogenation, nitration and suiphonation giving ,-chlorobenzoic acid, [Link]
.and m-benzenesutpbonic acid.
 Aromatic Carboxylic Acids and their DIvatIves 017

COOH 000H COOH COOH

cis

[93
HONOt H5504

A &C1 NO, SOH

benzoic acid m-cblorobcnzoiC .n-nitrobenzoic m-benzenesulphonic
acid acid acid

The rn-directive influence of COOH group operates through inductive and resonance
effects,

OH O\
C*' 0\ OH

6óD O+
The overall result is a pi electron drain from the benzene ring which is rendered
electron-delicieiit. This means that the benzene ring has become deactivated towards attack by
electrophilic reagents. Although the benzene ring is deactivated, the electrophilic attack will
still take place, but less readily. Owing to resonance effect the carbon atoms 2, 4, and 6 become
positively charged with respect to carbon atoms 3 and 5. Thus the electrophilic reagents will
attack at carbon atoms 3 and 5.

BENZOIC ACID, Benzenecarboxylic acid, CH5COOH

It is the simplest and the most familiar aromatic acid. It was first obtained by Scheele
(1775) from gum benzoin (whence its name), a natural resin got from trees in Java and Sumatra.
It occurs as benayl ester in Peru and Tolu balsams and as benzoyl glycine in the urine of horses
and oxen.

Preparation. Benzoic acid may be obtained by any of the general methods. Commer-
cially it is prepared:

(1) By oxidation of toluene with air and Co-Mn acetates as catalyst.

170
2CH—CH + 30 -. 2C,H4 —COOH + 2I1O
toluene benzoic acid

(2) By chlorinating toluene to benzotrichloride and hydrolysing the latter by boiling

with aqueous calcium hydroxide in the presence of iron powder as catalyst.

C12
CH—CH3 -. CHI—CCI
boil bcnzochJoride

ci OH . o
I Ca(OH)1
C,H1—C—CI -. CSH.I
I I
——OH -+ C1H1—C—OH + H2O
Fe I ' benwicacid
OH
(uiutable)
P ;8 Advanced Organic ChemI!ry

(3) By passing phthalic anhydride and steam over a metal phthalate catalyst (zinc,
chromium or nickel phthalate) at 200-300'C. The resulting phthalic acid is converted to
benzoic acid by decarboxylation.

EI0\ o
+
Zn pbthzl*te
2OO-3OO
@^CIDOH

tiji'
COOH

+co,
Co COOH
phlhalic anbydride phthalic acid benzoic acid

Properties (Physical). Benzoic acid is a white solid, mp 1 22T, crystallising from water in
pearly flakes. It is sparingly soluble in cold water but dissolves readily in hot water, ether,
ethanol and benzene. It is steam-volatile and may be sublimed. Its vapours have a peculiarly
pungent odour which causes coughing and sneezing. Benzoic acid is a slightly stronger acid
than acetic acid (Ka63x10 1 ; 1-75x lO-).
(Chemical). The reactions of benzoic acid are those of the carboxyl group and the
benzene ring.
(a) Reactions of COOH:
+ NaOH -0 C,H5COONa + H10
sod beazoate
H5S01
+ C1H5OH -+ CHCOOCH1 + H2O
ethyl benzoate

+ p j1
__ C,H 5COCI + Pod. + HCI
C,}IcOOR beozoyl chloride
Beowio acid
A
+ NH5 -+ CH1cOONH4 —o C,H 1CONH, + HSO
amm benzoate. benzamidc

+ NaO}1/CaO - C1H. + Na5CO5

benzene

The benzene ring of benzoic acid gives the usual electrophilic

() Reacileas of C.115.
substitution reactions. The COOR group is meta director and substitution, therefore, takes
place less readily than with benzene. Thus:

COOH Htxh q_cooH

+ H10
g

w-nitrobcnzolc acid
Similarly with sulphuric acid it gives ,n-sulphonic acid and with chlorine m-chlorobenzoic acid.
Uses. Beozoic acid is used: (I) in medicine as urinary antiseptic and in vapour, form
for disinfecting bronchial tubes; (2) in the dye industry for making aniline blue; and (3) as a
preservathe. Sodium benzoate being less toxic, is used for preserving food products such as
tomato ketchup and fruit juices.
 I I 19
Aromatic Carboxylfc kIda and their Derivatives

BENZOYL CHLORIDE, Ben zenecarbonyl chloride, CH,—CO—Cf.

It is a typical aromatic acid chloride and occupies the same position in the aromatic
series that acetyl chloride occupies among aliphatc compounds.
Preparation. (1) it is prepared most conveniently in the laboratory by distilling benzoic
acid with phosphorus pentachloride or with thionyl chloride (SOd2).
dfMll
C,H5—CO—OH - PCI -+ C 5C5—CO—Cl + POCI 3 + HCI
benzoic acid bencoyl chloride
A
CHr_COOH + CISO—CI --+ CH 6 CO—Cl + SO, + HCI
thionyl chloride
1) on
(2) Benzoyl chloride is also obtained by the action of carbonyl chloride (COCI
benzene in the presence of anhydrous aluminium chloride. (Friedel-Crafts Reaction)
Ala1
C,H1 + Cl—CO—Cl --* CH,—CO—Cl + HCI
phosgene

(3) It is made commercially by chlorination of boiling benzaldehyde.

0 0
II boil II
CH1—C--H + Cl, -.----* C 5H,—C—Cl + HCl
benza!dehyde beazoyl chloride

Properties. Benzoyl chloride is a colourless liquid, bp 198°C, fuming in moist air. It

W a pungent odour and its vapours cause profuse watering of eyes and nose. It is practically
insoluble in water.
Benzoyl chloride gives all the reactions of acetyl chloride but at a slower rate.

(1) Hydrolysis. It is slowly hydrolysed by hot water to form benzoic acid.

A
CH5 —CO—Cl + H—O—H -+ C,H 1—CO—OH + HCl
beozoyl chloride benzoic acid

(2) Aicoholysis. It reacts with alcohols (and phenols) to form esters.

C,H5—CO--Cl + HO—CH,CH,—CO-0C1H5
-+ + HCI
ethyl alcohol ethyl benzoate

(3) Arnmonolysic. It reacts with aqueous ammonia and amines to form benzamide and
[Link]-henzamideS.
C,H5—CO—Cl + aqNH 1 -.. CH,—CO—NH, + HCI
benzamidc

C,H 1—CO—C1 + RNHI -.. C,H5—CO—NH—R + HCl

[Link]

(4) Reaction with Sodium benzoate, It reacts with sodium benzoate to yield anhydride.

CH,—CO—Cl -- O—CO—C 1H1 -+ C4 H5_CO,—O—CO—C,H, + NCI

sod beozoate benzoic anhydride

(5) Friedel-Crafis Reaction. It reacts with benzene in the presence of AId 3 catalyst to
give benzophenone.
AICI,
CHaCOCI + C1 H,CH,CO—C1H
-.-* + HCI
bcsszophenorsc
1120 Advanced Organic Chemistry

Uses. Benzoyl chloride is used (1) in tear gases to disperse mobs; and (2) for intro-
ducing benzoyl group (CH 5CO—) in hydroxy and amino compounds (Schouen-B umann
Reaction).
BENZAM[DE, CH,—CO—NH,
It is the amide of benzoic acid, C 1 115 —CO—OH. It may be prepared
(I) By the action of concentrated aqueous ammonia or ammonium carbonate.
CH—CO—C1 + 2NH 3 -b CH5—00—NH1 + NFI4CI
beozoyt chloride benzarnide
(2) By Friedel-Crafts reaction between benzene and carbamy! chloride.
C,H 1—H + Cl—CO—NH, -..
CH,—CO—NH, + HCI
benzene carbamyl chloride
Properties. Benzamide is a white crystalline solid, mp 130°C. It is insoluble in cold water
but dissolves in hot. It undergoes most of the general reactions of aliphatic acid amides. It is
readily bydrolysed to benzoic acid and ammonia, on boiling with dilute mineral acid or alkali.
It forms benzonitrile on heating with

OH
CH1—CO—NH, + HO—H -, C1 H5—CO—OH + NH
bcnzamide water benzoic acid
plo'
CH,—CO—NH, -p C,H,—CN + H2O
benzonitrila
The negative benzoyl group (CH,—CO—) confers acidic properties to the hydrogen
atom bonded to the nitrogen atom. Thus beazamide dissolves in alkali (NaOH) to form salts,
e.g., CH,—CO—NHNa. With mercury oxide, it gives mercurybenzaniide, (CH,..CO—NH),Hg.
BENZOIC ANHYDRIDE, CH,—CO--O—CO—CH,
It may be prepared by heating benzoyl chloride with sodium benzoate.
-+ 6-
C1H5 —CO—ONa + Cl—CO—CH 5 -.. C,H5—CO—O—CO—C,H, + 'taCl
sbd benzoate benzoyl chloride benzoic anhydride
A better method is to boil a mixture of benzoic acid and acetic anhydride.
boil
2C,H,—CO—OH + (CH,—CO)10 -+ (CH,—CO),O + 2CH,COOH
benzoic, acid acetic anhydride benzoic: anhydride
Propefties. Benzoic anhydride is a white crystalline solid, mp 421C. Its reactions are
similar to those of acetic anhydride, but it is much less reactive. It is only slowly, decomposed
by water to regenerate benzoic acid.

C,H,—CO--O--CO—C,H5 + H-0--H -+ 2C1H5—CO—OH

benzoic anhydride benzoic acid
It may be used for bcnzoylation, but bencoyl chloride is more convenient for the purpose.

BENZOYL PEROXIDE, H6—CO-0O—COC1H5

It is prepared by adding sodium peroxide to stirred mixture of benzoyl chloride, ice and
water,
2C4H5—CO—CI + Na2O, -. CH5-0O-0 —O—CO—C4H5 + 2NaCl
benzoyl peroxide
Beozoyl peroxide is a relatively stable colourless solid, mp 108°C. It acts as an oxidising
and disinfecting agent. Hence it is a harmless bleaching agent and is often used for bleaching
edible oils and fats, and for wheat flour.
Aromatic Carboxylic Acids and their Derivatives 1121

PHENYL CYANIDE, Benzonitrlle, CH,—CN

It can be prepared by heating benzamide with phosphorus pentoxide.

0
F PO1
C6 H —C —NH, -+ CH—CN + H10
beozamide phenyl nitrite
It may also be obtained by fusing sodium benzenesulphotiate with sodium cyanide, or
by Sandmeyer reaction by treating benzcnediazonium chloride with potassivm cyanide.
Benzonitriie is a colourless oil, bp 191°C, having smell of biter almonds. It forms
benzoic acid on hydrolysis, and beozylamine on reduction.
+HO H10
CHaCN -+ C,HCO—NH1HCOOH + NH3
benzonitrile bcnzamide benzoic acid
C6H5—CsN + 4[H] .-p CeHs-CH,NHa
benzylamine

SUBSTITUTED BENZOIC ACIDS

TOLUIC ACIDS, MethyThvezoi acids, CH(CI13)C00H
a-, in- and [Link] acids are given the common name Toluic acids.
CH, CH, CH

COOH

.0 0 0
OOH
o-toluic acid, m-toluic acid, p-Iduic acid
2-methylbeozoic acid [Link] acid [Link],ezoic acid
These are isomeric with phenylacetic acid.

Preparation. The toluic acids may be prepared:

(1) By oxidation of one of the methyl groups of the corresponding xylene by dilute
nitric acid or permanganate. Thus
CH CH,

dii. HNO
& CH, COOH
[Link] [Link] acid
nitrile
(2) From corresponding toluidines via the diazonium salt which is converted to
and then hydrolysed. Thus
CH, CH, CH, CH,
NaNOH CuCN o

@^NH, ON
otoluidine,
NCl
diazonium salt
@^njtrik
CN @^ Coo f
o-tolujc acid
j
.methvIaiiilIfle
 Advanced Organic Chemistry
1122

Properties. The toluic acids are white solids, mps ortho 104;
meta I 11 ; para 178°.
Since the methyl groups are almost unreactive, toluic acids behave very similar to benzoic acid.
give the respective beozene-
However, on oxidation with dii HNO 3 or alkaline KMnO1 they
dicarboxylic acids. Unlike in- and [Link] acids, o-phthalic acid on heating eliminates a
molecule of water to yield phthalic anhydride.
COOH CO
CH,
(01

@^ COOIH
o-toluic acid
di!.
HNO5 @COOH
o-phthalic acid
co /
phthalic anhydride
0 ± H0

kNTHRANILIC ACID, o-Aminobenzoic acid

Of the three aminobeazoic acids, ortho derivative is the most important- It occurs as
methyl ether in jasmine. Methyl anthranilate contributes to the odour and flavour of grapes.

Preparation. Antbranihc acid may be prepared by reducing o-nitrobeflzoic acid, or by

boiling alkaline soluton of o•nitrotoluene in methanol (internal oxidation).

CH3 NaOH in CH5OIl Cool'

OA
NO, NH1
[Link] anthraniic acid

Technically, it is made from phthalimide by action with aqueous alkali and sodium hy-
pochiorite. (Hofmann Reaction)
CO ,,.000Na COONa
NaO H NaOCI
NH

CO /"Q C0NH, aONH,

, -,,CO0H
HCl
phthaliinidc sod aathranilate -*
NH,
Anthrinilic add

Properties. Anthranilic acid is a white solid, mp 145°C. It is readily soluble in water

and ethanol; and has sweet taste. It gives all the reactions of aromatic amine and carboxylic
add. On heating it is decarboxylated to form aniline.
Uses. At one time large quantities of anthranilic acid were used for the synthesis of
indigo. It is still used for the synthesis of thioindigo and other dyes. Methyl anthranitate is
a constituent of natural aroma of jasmine and orange blossoms, and of grapes; hence its use in
perfumery.
[Link] ACID (PAB14)
It is prepared by the reduction of p-nitrobenzoic acid. It is a solid substance, rap 186°C,
It is one of the substances present in the Vitamin B complex. It is used for the preparation of
certain local anaesthetics as novocaine.

i\ C1H5.
HiN_()_C_OCNr'CHr-N ( a
1?

(-4icthylaminoethyI ester hydrochloride)

Novocaine is much used in dentistry.
#°daraaUc Carboxylic Acids 01541 their De,*otivas 1 1 23

GALLIC ACID, 3, 4, S-Trlhydroxybenzoic acid, CH5(OH),COOH

It occurs widely in galls, tea, oak bark, kikar bark etc., in the free state and as a unit
of tannin (gatlic acid esters of glucose) molecule. It is best prepared by the hydrolysis of tannin
with dilute acid and extracting the gallic acid with ether.
properties. Gallic acid forms white needles, mp 222°C. It is readily soluble in hot water,
ethanol and ether. On heating at its melting point, it undergoes decarbozylation to pyrogallol.
COOH

HO*OH HO"OH
OH OH
gsllic acid pyrogallol
Gallic acid, like pyrogallol, is a reducing agent and has been used as a photographic
developer. Its alkaline solutions readily absorb oxygen from the air and turn brown. Gallic
acid forms colourless, water-soluble ferrous salts, which oxidise in air to blue black insoluble
ferric salts. This property is utilised in making 'permanent' blue-black inks because the
ferric salt so formed is morepermanent to light and air than the dye used to make the ink
initially visible.
Blue-black Inks. The blue-black writing inks consist chiefly of an aqueous solution of
gallic acid, ferrous sulphate and a little blue dye. Some gum (protective agent), a little sulphuric
acid (to retard oxidation of ferrous sulphate), and a trace of phenol (preservative) is also added.
When the ink flows from the pen on the paper, the sulphuric acid is neutralised by alumina of
the paper. The ferrous sulphate is then rapidly oxidised to ferric sulphate and this forms a deep
black precipitate with gallic acid. Hence, the ink writes blue but becomes intensely black on
drying.
SALICYUC ACID, o-Hydryxybenzolc acid
Of the hydroxy acids, the ortho isomer salicylic acid, is by far the most important. It
takes its name from sdkin, the glucoside of the corresponding alcohol, from which it was
first obtained (Piria, 1838) by hydrolysis and oxidation. It occurs as the methyl ester in many
essential oils.
Preparation. (1) Salicylic acid is prepared commerciajly by heating sodium phessoxide
(CH1ONa) with carbon dioxide at 130'C and under pressure of 5-7 atmospheres in an autoclave
(Kolbe -Schmitt Reaction).
ONa ONa @C OH

sod phenoxide
+ CO
5-7 @^
atm
COOH
(,,hoedmzu)
i
tOOH
salicylicatid
+ NaQ

The fused mass from the autoclave is dissolved in water and the solution acidified to liberate free
salicylic acid.
(2) It may also be made by heating phenol with carbon tetrachloride in alkali solution.
(Reimer Tiemarsa Reaction)
ONa
N&OH ONa OH

sod phenoild.
@^ .
Ms H10 COOH
ailcylic atid
 1124 Advanced Organic Chemistry

(3) It may also be obtained by the action of sodium nitrite and dilute HCI on anthra-
nilic acid via the diazonium salt,

NH, IC' 0II

@t.
NaNO1,HCI HIO

ro-Y COON
o.c @^
COOH
i

COOH
anthrinilic acid diazosium salt salicylic acid

Salicylic acid may also be obtained by oxidation of a-cresol with potassium hydroxide and
lead peroxide, or by fusion of the sodium salt of o-sulphobenzoic acid with sodium hydroxide.
Properties (Physical). Salicylic acid is a colourless, crystalline solid; mp 159°C. It is
difficultly soluble in cold water but dissolves readily in hot water, ethanol and ether. It sublimes
below its melting point and is steam-volatile. It is a stronger acid than benzoic: acid. Sal ic ylic
acid is somewhat poisonous and has powerful antiseptic action.

(Chemical). It behaves both as a phenol as well as a carboxylic acid.

(1) It reacts with aqueous sodium carbonate or sodium bicarbonate to form sodium
sahcylate. With excess of sodium hydroxide it forms a di-sodium salt.

OOH COONa ,7- /COONa

aNaOHj I

@^ OH

salicylic acid
OH

and lalicytale
0

Like other aromatic acids it reacts with alcohols to form esters.

(2) When heated slowly, or with sodalime it undergoes decathoxylation.

COOH

±4
a0H OH
+

uJlcyIIc add phenol

(3) When heated at 208°C, in a closed vessel it gives phenyl salicylate. The phenol first
produced by decarboxylation reacts with the remaining salicylic acid.

(D
CO—OH HO -co—o

+ ;
@XIOH
lalicylic add phenol phenyl salicylate
(4) Like most phenols, it gives violet coloration with FeCl, couples with diazonium
salts, and forms acetyl derivatives at the OH group.

.'COOH 7N./ Co
nT + ci3—co--ci -+
acetyl chloride 101 + Nd
LJ1,L COON O.:CO_..013
alicylic add acetylsalicylic icid
(5) Because the OH group is strongly activating, salicylic acid readily undergoes substi-
tution in the benzene ring by electrophilic reagents. During these reactions, the COON group
is replaced by the entering group. For example,
Aromatic Carboxylic Acids and their Derivatives 125

OH on
Br Br

0
Rromlae wee'
cj..cOOH
Br,IH1O

Br
2,4, 6trthroin0phCD0l

OH H.

(bCOOH O,N - . NO,

0
salicylic acid r
NO,
2,4, 6-trinitropbeeol
(picric acid)
group is
MECHANISM. The mechanism of this reaction of elimination of the COOH
similar to that of replacent of hydrogen of the aromatic ring.
4.
:OH 0 OW 0,1

Ir

2,4,6-7R1

(6) When reduced with sodium and boiling isopentinol, salicylic acid ring is hydro-
genated and cleaved to from pimelic acid
cow COON COO"
-o ,042—COOH
+ 4H KETOMiAJ 14 2 0 CII, ¶OOH
6(AUAJ /0.12

5AL(CYIJC ACID TETAHE1WOSALICYLIC . PIMELIC A CI P

ACID
for mating dyes; (3)
Uses. Salicylic acid is used (1) as antiseptic and disinfectant; (2)
for preparing aspirin, salol, methyl salicylate and (4) as medicine, when it is administered as
sodium salicylate in rheumatic conditions.
acetic anhy-
Acetylsalicylic acid, Aspirin. It is prepared by heating salicylic acid with
dude at 90'C in the presence of a small quantity of sulphuric acid. The scetylation of OH

@^
group occurs to give acetylsalicylic acid.
COOH
+ CH._cO_O_CO:CH,
COOH

acetic anhydride 9O
OH
acctylsallcyllc acid + CH,—CO—OB
acetic acid
iallcylic acid
 1126 Advanced Organic Chemistry

Salicylic acid is a white solid, mp 134°C. It is still the world's largest selling analgesic.
The annual production in US in 1964 was 28 million pounds, which comes to 204 5-gram tablets
for every member of the entire population. 'Aspirin' is a mild analgesic; relieving certain types
of pains such as headaches, toothache, and colds. It has also an antipyretic action.
Methyl Sallcylate. It is the methyl ester of salicylic acid and occurs naturally in oil of
wintergreen, oil of sweet birch and in other essential oils. It is prepared by esterifying salicylic
acid with methyl alcohol in the presence of sulphuric acid.
COON COOCH5

+ CH3OH —+ 1EOH + HO
salicylic acid .. methyl laiicylatc
Methyl salicylate is a colourless, pleasant smelling liquid, bp 224°C. It is used as a
ftavoing agent. It has a stimulating action on the skin and is, therefore, used in hair tonics,
and in liniments for treating aches, sprains and bruises.
Pheayl Salicylate, Salol. It is prepared by heatng salicylic acid in closed vessel at
200°C. This is possibly produced by the interaction of the phenol, formed by decarboxylation,
with the undecomposed salicylic acid.
COOHH C0
(X OH + ° TJ (XOH ° TJ + H20
Salicylic acid Phenol [Link] salicylate

It is a white solid, mp 43°C. It passes through the acidic medium of the stomach un-
changed and is hydrolysed to salicylic acid in the alkaline medium of the intestines. ft is used
in medicine as internal antiseptic under the name .salol. It is much used as coterie coating for
medicinals that otherwise would be destroyed by the acidic secretions of the stomach. When
the pill reaches the alkaline intestines, the salol coating gets hydrolysed, and the medicinal is
liberated. Salol absorbs ultraviolet light, and its main use now is a sun-screening agent and
stabiliser of plastics

BENZENEDICARBOXYLIC ACIDS
The or: ho, meta and para-benzenedicarboxylic acids have the trivial names phthalic,
isophiholic, and terephihalic acids respectively.
514
COOH cOOH

OOH
phihalic acid, isophthalic acid tercphthalic acid
benzene-
1,
2-dicarboxylic acid I, benzene-
3-dicarbozylic acid I, benzene.
4-dicarboxylic icid
Aramatic Carboxylic Acids and their Derivatives 1127

Senzenedicarboxylic acids can be prepared by the oxidation of the corresponding dialkyl-

benzenes (xylenes). They are white crystalline solids having relatively high melting points
phthalic acid 231° C; isophthalic acid 348° C; terephthalic acid 300° C. They give all the usual
reactions of aromatic dicarboxylic acid, forming acid and normal derivatives. Phthalic acid is
distinguished from the meta and pan isomers as it forms an inner anhydride due to the close
proximity of the two COOH groups on the benzene ring.

Of the t ree isomeric beozenedicarboxylic acids, phthalic acid (ortho) is the most
important.

PIITRALIC ACID, Benzene .1,2-dicarboxyllc acid, C1H4(COOH)1

It was discovered by Laurent (1836) as an oxidation product of naphthalene. It is pro-
duced by the oxidation of any benzene derivative having only two carbox-chains bonded directly
to benzene ring in ortho poitions.
Preparation. (I) Pbthalic acid is manufactured by passing a mixture of naphthalene
vapour and air, over vanadium pentoxide as catalyst at 400.500°C.

coo

i:ji?.jJ (AIR)400—
+ 402500
aCOOH

NAPHTHALENE PHrHALIC ACID

In fact, the product obtained by the high-temperature oxidation of naphthalene is

phthalic anhydride which is subsequently hydrolysed to yield the acid.
(2) In a newer method, introduced in USA, phthalic acid is produced on large scale
by the catalytic oxidation of o-xylcne derived from petroleum, As in the method (I) it is the
phthalic anhydride which results from the dehydration at high temperature. This is converted
to phtbalic acid by hydrolysis with HCI.
CH. COOH

+ 3% (air) -+ 1 + HSO
@"COOH + 2C0

Properties. Phthalic acid is a white crystalline solid which melts at about 231° C on
rapid heating. It is slightly soluble in cold water but dissolves fairly rapidly in hot.
Phthalic acid gives most of the typical reactions of a dicarboxylic acid.
(I) It decomposes to yield its anhydride when heated at the melting point.
COOH co"
+H2O
1(COOH
phihilic acid phthalic anhydride
(2) When heated with potassium hydroxide (or sodalime), it decarboxytates to benzene.

J
,COOH

[ COOH + KOH -*

phthatic aid
00. + K2COI

benzene
+
1128 Advanced Organic Chemis t r y

(3) Phthalic acid may be mercurated by fusing it with mercuric acetate, or by heating its
mercury salt.

©:Ico\
A
llg—+ +co1
CO / @^Hg Z
(4) When it is treated with sodium amalgam and sodium carbonate solution, the benzene
ring can readily be reduced to give cyclohexane -1,2 .dicarboxylic acid.

COOH COCH
+ .
Q00H - COOH
ry(LQHtXAN(_1,2 . DICARBOXYLIC ACIC

The chicl use of phthalic acid is the formation ot its anhydride which is of great techni-
cal value. Benzoic acid is now manufactured by debarboxylation of phthalic acid.
Pbtllk Anhydride, C1 H4(CO)2 0. It is made commercially by the catal y tic high tem-
perature oxidation of either naphthalene or o-xylene as described before. It is a whitc crystal-
line solid, nip 131 C, It gives all the normal reactions of acetic anhydride, though less readily.
(I) Phthalic anhydride reacts slowly with water to give phthalic acid On treatineili with
aqueous alkali or acid, the hydrolysis takes place quickly.

>
COCOOH

pisthalic anhydride
+ H10 —s

phiho tic acid

(2) When heated with alcohols, it$ives acid esters.
o_COOC2H
)o + CHaOH
wCo COOH

Ethyl hydrogen phtheiete

The1acid esters may be converted to the notmal dieslers by the usual method of heating
with excess of alcohol and sulphuric acid.
(3) When heated with aqueous ammonia, it gives phthalimide.
Cox 0 CO

co/
+ NH L. + HO
@^CO/
phthaIiniid
(4) On heating with benzene in prescnce of annydrous aluminium chloride, it yields
anthraquinone. (Friedel Crafts Reaction)
CO: N
IQI+Ho
@ A anihraquinane
(5) It is decarboxylated to benzoic acid in the presence of steam and a catalyst which
consists of sodium dichromate containing small amounts of nickel and calcium oxides. (Com-
mercial)
catalystVOOH
+ H10 CO,
O/CO\ C01
[Link] acid
 AromatIc Carboxylic Acids and their Derivatives II

(6) it reacts with PCI, to form phthayl chloride.

I I1
CO.
± c, [1 ±
pIthaoyI chloride

(7) When treated with zinc d'at and aqueous NaOH, phthalic anhydride is reduced to
give phthalide.

CHI
NeOH
+
+ )l2O
;
o

PrOhade

Phthande is a -actonc. [Link] treatment with KCN and hydrolysing the product
with dii H 2 SO 4 . hvrnophriw!ic acid is formed.
CH—CN ,- -CH2—COOH

P—. r,i oe
cc U co5
?O

cocvs
Homop'[Link] acd
(8) it condenses to form phenolphthalein and fluorescein, when heated respectively
with phenol and resorcinol, after adding a little sulphuric acid.
(9) Phthalic anhydride reacts with glycerol on heating to give polyesters which gise
resins known as g/vpta/s. These are used as paints and varnishes. On application the glyptals
form cross-linked giant molecules which offer a tough protective coaling.
0 0
11
11
—c C—o----c542--cal--042 —C

0
I)
CHa_CI4CH2
I I
00 O=C\
0

OH OH OH O=c
c
(2 MOe E5)
0 9
O
(3 MOLES) C\ C-0Ha—k4—O4---

&1YPTAL sW/I

Uses Phthalic anhdride is used br the industrial production of 1) a number of dye-

stuffs (fluorescein) ; (2) esters needed as plasticisers for snLiictic resins diutvl phthalate
dimethl phthalatc (DNIP) as a mosquito and other nsei rcpe!cn: ilieiliI phthalate
e
perfume; (3) ch micals such as phthIirnide. anthraquinone. phcnoiphthalcin cic: and (4)c y 'ihe-
tic resins (gfij fa/a).

( )taiiic htriti.i - 72
it 30 Advc'ced Ogr;c e'rsty

Pbthilimlde, '1 H4(C0 1 NH. it is prepared by heating phthaiic anhydride with a:nr
gas under pressure aL about 200°C.
0 0

± Nil1
[Link] ©C'NH ± 1110

phihatic anh>dride phihalimide

Phthalimide isa white, crystalline solid, nip 238° C. its insoluble in water.
(I) Hrdrol'sis. it is readily hydrolysed by hot aqueous sodium hydroxide (or KOHl
to go. e phthalrc acrd and ammonia.

C C—OH
'r' \ NH + H10
(NaOH)
-4 ± NH3
C
C' " Ii 1hh1'COH
0 0
phthaLimidc phthaiic acid
When allowed to stand in cold aqueous, or when warmed with barium hydroxide sold-
lion, only one C—N bond is broken and phihalamic acid is obtained.
o 0
C
co/Jag KOH

Ii
Nil
or 140110 a(OH)1 [9JN I!
O 0
phihalimide phtbaLamic acid
(half am/dc p'n(balic acid)
(2) Conversion to ,lnthran i/ic acid. When phthalirnide is treated with cold aqueous
sodium hypochiorite (NaCCI), it is converted to anthramlic acid.
0 0 0
/i l
C , C—H
og NaOCi —7C—OH HofnwM

>N H rsarraflgflL
C C—NH2 CIIi)LNH,
O C)
Intermediate
This is bow anthranilic acid is produced as an intermediate in the maruta.
indigotin dye.
(3) Weakly Acidic Character. Formation of Artzines and Amino Acid. Srre the
irnino g roup is att,iched to two electron-withdrawing carbonyl groups, it is weakl y acidic.
Thus phthaliniide reacts with ethanolic potassium hydroxide to form a salt, called porasourr
phthalirnide.
 Aromatic Carboxylic Ac i d, and their Der![Link] 1131
U 0
C
JC(CH5OH) -
NH + KOH ± H0

U o
phthalirnide pot phtha1ijiide
(a! Potassium phhalimide when heated with an alkvl halide forms Naikylphri:m'dc
which on livdrolvis s ith 3quenns alkali or cone, hdrochloric acid, yields phthaii a:d and a
primary amine, (Ja/'rj/.c .° tuhisc
o 0

—a- --- + B;
C, /

C)
II
0
ANiO4 OF P)T•
PHTHALIMjDE frl-ALKYLPHTtiALIMWE

C,
9
OH
aqaoit
1 ±R — NH,
1° amine
C

0
0
nhalhatic acid
(h) When potassium phthalimide is heated with -ch!oro or a-bromo acid in place ol
alkyl halide, the hydrolysis of the product yields an z-amino acid.
o o
R R
(—KCt)
Cl-CI-l--COOH N— HC00H
ffC NK

0
o
pot phthalimide
COOH R
hydro1y;i
0+ H1N—CH—COOH
"COOH -amioo acid
Uses. Phthalimide is used in the synthesis of primary amines, o:-amino acids and
indigotin.
Phthiloyl Chloride, Phihalyl chloride, C 6 H4(COCI)1 . It is prepared by heating phthalic
anhydride or phthalic acid with phosphorus pentachloridc at 15°C.
0

COOH (ac—Cl
Pc1

150 CCl
©i
COOH
0
phthalic acid phthIoyl chloride
 g:'.:
12

It may also be obtained by heating phihalic acid with thionyl chloride (SOCl) at 220°C
Phthaloyl chloride is a colourless mIN liquid, nip 15-16° C. On heating with aluminium
chloride for some time at 95° C, it is conserted into [Link][hnoyl chioride, mp 69' C.

c
1/ ---- - o -- HO
'-
g
PkTHALOYL 15-21-'THALQYI. i- -' I
CHLORiDE .E

When reduced with zinc and hydroch l or i c acid, as-phthaloyt cblor:de is reduced to
•bthalide.

ACIDS WITH COOH GROUP IN THE SIDE-CHAIN

A number of acids in which the COOH grou p is in the side-chain are of theoretical
or practical importance

PH ENYLNCETIC ACID. [Link] acid, C5 H, — CH 1 --COOH

It is a ty pic;tI acid with the COOH group attached to the side-chain. It is someric
with toluic acids.
Preparation. k l Phenylacetic acid is prepared casily by boiling beazyl chloride with
ethanolic potassium cyanide, and hydro!ysing the resulting nitrile by boiling with dilute
sulphuric acid.
KCN HaO
C6 lfa—CUa--CL -* C6 H—CH,-(,N —k 1H5CH2cOOF(
beneyl chloride benz)l uiiriI (H2S01) pheiiyIaceic acid

2; It may also be prepared by reducing mandeloninie with hydriodic ac i d and red

phosphorus.
OH
HI1P H10
CH 5 —CH—CN -+ CH- CH—CN -. C51I6—CH—COOH
mandelonit rile
Properties. Phcnylacetio acid is a white -crystalline solid, nip 77 C, having unpleasant
odour. It is a stronger acid than acetic acid.

(I) Chlorination. It is reactive in the side-chain as well as in the benzene ring. Thus
on treatmentwith chlorine at room temperature in the presence of a catalyst, substitution
takes place in the ring to form o• and p-chlorophenytacetic acids.

CH,—COOH CH,--COOH CH,—COOH

Cl
C12
and

Cl
yhenylacci: acid o-chkrophenLiceiic acid [Link] acid

On he ohr hand, hen chlorine is passcd ni; plcnylacctc ic:.i at its boiling poin
in the ascncc calalsst, it g o e --chlor;ph;m la;cti: acid
 1133
Aromatic Carboxy lic Adds and their Drivaties
- Cl
CH—COOH - Cl -p
bp
f-.-

I + HCI

phenylacetic acid -chIorophenylacetiC acid

(2) Upon oxidation with chronic acid, it is converted into benzoic acid.

/
IN
y—CH,----COOH --.--+
CIi.O,,IiC a.'id \
(J ,_COO H
/

henzoic acid

MANDELIC ACID, •
Phnvig. rcollic 1(11,

- -

/- C--COO U
-
OH
nrIdedc occurs naturaI1 as tlo g nco'idc . :,vgu/uI.'r!. in. hitter alinonds from
which soucc it n.0 he obtaneJ h- hydrk . o i I . Un-eoUciii [Link], gives [Link] acid.
Preparation Mandeli cud may be prepared b the hvdo-lsis of henaldehydt Lsano-
hvdrin (mandeloflitrllef shIch in turn obtained ov treatrin the biuiphit compound of ben-
raIdehilc with concentrated solution of udiuiu cinidc.
H H H
H N HaO
NaHSOa +
CH—C -. ClJ 5 C—SO,N a -.* CFirCC -_.+ C 1 H C—COOH
tIcJj

OH OH OH
o
bJct.i ccl;-'iun.J ;icnatdehdc cyaiihdrin uandet,c acid
henzatdehyOe
Properlies. Maiidciic acid is a vliiie crysticilne solid, moderately soluble in water. Its
moloculu has an aSylTifliCtO. aLt'(ia iattachcd to El, OH. COOtI, C 6 F1 1.i. and hence the acid
exhibits optical isomerism. Mandclic acid obtatnec by hydrolysis ot araygdlain is the L-form, mp
133' C. DL-Mandehc .ictd m&is at 1 1 3; C.
Mandetic acid behaves as a hydroxy acid. When reduced with hot hydriodic acid, it gives
[Link] acid. Upon sigorous oxidation it is converted to benzoic acid. Mandelic acid is
used as internal antiseptic.
CINNAMIC ACID, :rans--phenyiacrYiiC acd
Owing to the presence of a double bond in the molecule, .phenytacrylic acid,
Ca11 5_ CH=CH_C OOH exists in two geometrical forms.
CH--H C1H6--tj—H

H—C—COOK HOOC—C--H
Irani phenylacrYlic acid cis..phenytacrytiC acid
(cinuamic acid) (altocinnamiC acid)
The trans-form is named ".5 cinnamic acid, while he cis-form is called allocinnamic
acid. Cinnamic acid is the stable form and occurs naturally, both free and as esters, in the oil
of cinnamon, in baiicems and resins.
Preparation. (t) It may be prepared b y heating henzaldchyde "nh acetic anhydride
and sodium acetate (Perkins Reaction.
CHC00Na
C6H5_CH= 1C00H CH,(--OOH
CH-CH=O + CH 5 C00C0CH 5 -
too*
benzatdehyde acetic anhydride ctonamic acid
1134 iricec Oanc Citemory

(2) It is also produced by the condensation LI t.en731dehvdc with ethy a:ctate in the
presence of sodium ethoxide, (CLiisen ('cwdenroli11
C1H()Na
C,H 5—CH=O + CH,—COOC,H --. ('Il --CH--CH--COOC2HS
[Link] ih acetate etS:: [Link].a1
HSO
--CH=C-{—CO.
nnamc ansi
(3) It is m ide tnmerctali l's the o-s'Ja' alal.i. sod:uro
ypotl o ri 1Cf, halciforrn of acetone i
NAG
C6 H----CH CFI —CO—CH J -•- . ( . l-1 ('H— CH —COGH
1eneaL4cec'ne c!rr:aCj
Proprtie Cinnamc acid is a wiite solid. rnp 33' C, h .ug a perSistent sharp odour.
ii cryrih '.lublc in wa:er. It goes the teaJiuns of ar, a, Liissaturated acid and the
Phenyl group.
i When rsidu',ci with sodurn amalgam and water, it gves . phenvl propionic acid.
N4 /HO
- CH =-Ct —COO{ -.- 2(H) - CH5-_CH,_CH_COOH
crsrianiic acid -phcnyiprapicr)c
With lithium alum i nium r:dr:d - boti ih' dobc bond and the arbun y ! group are
reduced, yielding 3-phen Iropanol
LiA H4
C1 H5—CH=CH--COOH (i{H] - C, H,-CH,--CHs—CH1OH
cisrunoc [Link] [Link]
(2) On oxidation with Cid potassium lierflangaic, tl!t dcche bond cleaves to form
benzaldehyde, while vigorous oxidation vdd hencoic acd.
10) to;
C 4 H—CH=CH--00OH -+ CU—C}I=O C4HS.--COOH
KMnO4
ciiinanhic astd brrzebJc cnzoic a;ij
(3) At the COOH group, cinnamic acid reaA 41 with alkali to form salts, and with
alcohols to form esters. On heat i ng w.:h sodalime, it uecarhoxlace to styrene (phenykelhyierie)
[Link]'e
C4 H5—CH=CFI--C1)OH -------- (i-{—CH =C}l - CO
so cc
(4) Nitration with concentratcd nitric acid Yield :i mixture of o- and [Link]
acids.
CE{CH-- COOH CH=Cli -- . COOH CHCH.—COOH
coxcHN0

LJ fl:

MO,
L,r1iirocinnans acid p-nLirocnnamic acid

(5) Whets exposed to aunlilst. cnnamc acid dimerses to two isomeric scobu-
tane derivatives—truxinic acid and i rv.011 C acid

C5 H CH "sCHCOOH __+ C t;H 5 CH - --- COOH

diradicsii
Aromifllc CcrbaxyUc Acids and their DeaivatIVe$ (133

HH H

C 1 H 5 —C —C—COOH
LcH 5 _CH_CH—CUOH , --- ±
C5H_C—t—COOH COOH—C--C—0 5 H

H
trux inic a,id trutillic acid
(3, 4-dipheti Icy CihUtafle 2, 4-diphenyIcyclobctar.c
I 2-d . ca , b.,Xyliz actd' [Link] acid)

(ounisrin. ishc Ii acr I:; ic . exits in two geometrically isomeric

OH
H :)oH HOOC
(C's.
c;oMk 1 (ii COJMARIN/C ACID
(isisrA8cE)
Coum;tnr Lid. a orn as it Is (srodUced, forms in i nternal cyclic ester or .lact,ne,
knosn as Cc'siitarn.
Cc itmarn i, the odoriicru p'tnciple of woodruff, newl> mown hay, and tonka bean,
s: ihcsed readily Perko's r:sciion from sai icy la(dehyde, acet:c anhydride, and
sodatu acclae.
r /CHO

£
- -.H CH

0
SAt! LAL0EH V f AcFrI A 11v'LF COcYAP'MC 4 f O)tIAP/ro

Coumarirt is a mhile cr y stalline solid, mp 67C, having flavour somewhat resembling that
he sodium
of vanriho. When warmed with sodium hydroxide. the ester ring opens up to form t
;att of coumarinic acid.
The use coumarin as flavouring agent has been discontinued because of its toxtcity.
it a used for inbibtttng the germination o f sceda.

QUESTIONS
!. Ibis do cu define the erm aromatic acid* ? Name the three aromatic cdt drivet from tolucor
according to the [Link], as also the IUPAC System.
2. Give the orbital structure of beozome acid. In what way it is similar to the stracrure of
nit robemi cene.
3. Discuss the general methods of preparation of aromatic inonocarboxytic acids, taking example
of benzoic aslit.
4. 'Aromatic carboxylic acids are slightly stronger acids than the aliphatic acids.' I:oerr and
elaborate
5. Describe the general reactions of arcuratic carb iic asids w,th special re:[Link] ro the
following
I at eSteetication () Schotca . Bau,i,ann reaction let acid halide formation : d) act
amide formation , and (e) reduction
 3c Adva n ced [Link] Cr p [Link], y

6. Lot the prcparatiaa, properties and uses of benzoic acid.

7. Write notes on : Reazoyl chloride, Benzamide, Benzoic anhydride. Reneonitrile and [Link]!
peroxide.
S. How are rirtho, meta and para tolitic acids obtained' What 'tippens when they are onidlited with
dilute nitric acid and the product is heated
9. G;vc the preparation, properties and uses
(n') anthrinittc acid (i') p-aminobenzoic acid and ( pp (ijtlic acid.

10. Ho's can IC hc acid be prepared from phenol id ft-,it' it itinhli icid Wh.,t h ppcas WitCh
(i) saucy ic acid is heatud with sod,i!t,nc
(ut it is heated at 20rc:
(iii) it is treated with bri'tcsinc \vCtCi
(is) it is heated with acetic anhydride.
14. Name two import ant dericaiiscs t,1 sit ,;iCid ,:;id hit.,.,
12. Which of [he three bcnr,'ce dtcarb,un!ic acid ' 's mpor;ari md wht
13. How is phthauic anhydride obtained lii a 'gc SC,IiC . 'ri; lws for ns reaCtirr with
e
hcit; p tic ir, th pretensc of A10 3 . anitricotia, PCI 5 . an! t , n uarboxylatiui's.
44. Gise a brief accusin of trc Iorciat'jn, reaciioos ant uses of rhuhahitiide, phthalosi clkormdc
phetvlacetic acid.
15 Write the structural formula of Mandelic acid and discuss ii chericI hh,aaiour.
46. How is Cinnamic acid prept d by Perkins reaction 1 Stitcu'ur of its rcc:ion t lo i p c,mn s of
'COOnS.
17. What is ('oumanin how can it be produced Wool hoppers 'whet' ti 's warmed with .sesiimn'
it dronide soiuticn 'and slate its aces.
is!, s lic 1100 Ii to pis, ii! ii ii hib. . mc .ini] I cam
19. 1-low icitull a no prcpa re betizoic am af roil Janet's /?5m ii!. !VPOI
o'!uha ire'
19 Show chicntkai react i ons ricw 0m,ir,d , ' is ii
tThr'art.' ,05r 1), 1i]50)
20 Show the s tep' 111101SCL, in itic C, ' essr' r. if i.S,S 51,5 ti's' Pitlais. ,.p!'.m:.!s
how would you pr'rsm'r Ohcr.f :1010 auf r,mm op tits! chIc'rimC' I &10ik 'thi III. 19.0)
21 How ti -phitsoiiit acia piepared How wm'i,: fm'u 511 iCti it Ill"
(o) Ant ttrao;iic acid (/) thu tie .n iii
(c) ilureucein ..' 85 !m .hOj
22. Artatigc the f']kw:i ui' the crdcr itt I :i..rca'i(mg a
COO H 'O(st i.O('tU

© © ©
H5
its, W. MCI
23' A "Dc',rtheIsounhiTCrmetdslo;PctI! I' it'
(.51 Iii sitn)itC cne rite: hoiS each for the r'cpa a' sr '' Hiit 'it (tici 'itt, l'.:'.'mum,C. Ii, i .'.ttii,Ji' .,rimi
,,,,,,,,,,,1: def,im (Ice/mis .cmd,
(it) V hi fW4m.!' a ' ft bc if ' rincd ii, '''FiSISOP in,! ,:htm',[Link],eir, ,'I tici
.11.-i ['it h/fail,')

24 IIi's' s rheni(aete ,ts! I s reismas! 1l5 ' ! ' iti'S'i/, .:ii] ii iris IfS i/f I' ' ' ft
it ii c,.-,
'is .1,1)1)11 es ,.cIi ini,s..jiicecl lt he het,eerit ':r,
i-i Ii' ,s p. '.iuii.s it 'id prs'tasct Ito,'- phi'ui't
( p rts'ss diw'sswIi ' ii id 'Ciii ss'ib
(i) Ads! ,hs.:.dc lisp t'rota,ric .i/ ii Mule 51.15

26 ( cO is ('tii'Pdii I' it ,m ntiCii,rs ol Iipas'attjc'hs'Js', a5cii,, i i -',.' ........- ' di

/, i '1'
 1137
Aromatic Carboxylic Acids and their Derivorires

27 Describe a method for the preparation, of SIic l ad

(a)
(lay are the following prepared from it.
(h)
(i) 2,4.t-Fnhrcf!lOphCflOI
(u 2.4.64rinhlrophcno'
(is) Salo[
(iv) Chlorobenzc'if chloride (Snogn, [Link] /11. [Link]
18. Got: rcacior' in he term of equation, of vi, mehids of preparing fien?ei. a.d Hcv
.iod ':oprcro3 'nb
tb' I bcn,oz'r!C (t) Berr . ,! Jirde () Renrn s!
(MObaiCChi ljuiica y d ftS', 1Q92)
29 li tY't,oh i' rrsare acidis krioo .)Lid oF c-cI')oiohint( acid ' V.
ft.) Hi'ri v.i)d IOU ObTain 1 Irtliif t,,d Oil) )'.tnr I i'eheil ii one 'ep 'rn' t'e;infeh'dv
Name 'ic 'etter, I )ir.o1a [Link] 1/!. 1921

30 Hen is phthalc aol rn:,' Iu!eU ' (to y ioIl '.t prrparv 0, C Iollovir,g (torn it
(i) Iihhafic ahrdrtdc !i') Pil'ba!miis ro) Bvl'ifnc
(oi) PhcneIphthktn (,i) Dcfh! pbbhufalc H;thre l&A Il.!9,2)
and propente' of ArThritui aod and Phthals nod J,tmnti' lhSi lii, 1982)
31 Drscr the nCnara'iOn
R. (at' Ii, [Link]. ro)s'nin.. ,iait us;. ,; ntithoiis!nI,drli le I1,' ni! sr :ovverl ahiha:; acid tilh orthrar.,f';
ii! '.hnau/Ti,i fir, Ii '91,
13 If's I, siam;; io.! I '.u.s is properties :it;pu It,; a_if ,,ni9 'f [Link] :,,,t;I',.!

34. (!o tin prepooCiwn and 'r ,ciirr.'' saH,,Iic ,, -f )7;r1 us, ! 1 0 lvi, r. if.' I
3. H1'.. PU .yitiiy si st ts!r,!r ., s aol)
heaven; I!.:u,t;r 99, 00.) .'iii;r.i.' Its; 1,941
3. He.1 .oiII ou ,oiiheris ...pI tin fr o m plorni) ', nc'vnria lI;i, /94 tIns, )t1 /99.0
37. Hon roll ''u c riib,_'sl ' c j' Claus .t. i d 1-urn lueiieh,r

Hint- thC T.'isiO)i)UsbCi',5 '01 H,i'I!AG,,,n,iir..htHr.,.,,,,hll.c!rnr ,,i,t_f,.,aaj,;,iI.!i.'H

HI. I );,nv ii!) 09. di,ijni,uish HeCiC ar,, )OC/l S F 1 .Oid and ,,a!,; Ii; inC , hi' err flit bs. A "l
Him. Suh;r ii Old react, aOl bromine rooter I' as to"
10 Ii,, 'arsi Air,. sail, iin 3'i CISC, sunlit cliv, rotC f'f I, ..).o.,i;; tier..'.,; ,:,,t .l, ...... . r,rr Fr.', iOn
39 ;i . rc 'nyc,, ornsund Ai. f-N a on f.'Os i C, i F,,)u!,ru,,i,,, lii,.,,! as S,n4nv' -Cr renoir ciur , . ' i s urrel
• l' -I) 40 If riot. OI!)I' uC;uent'ourrt, to bra ft )',[Link] 2 ffi 1 . itO .. Cr uu'!f C [Link] I;' iii',;' ii;. ( Il,)) I ,rnii,n.u.:,,l
0' l5 id,u letlirSSuI a. 10 iEl I,H,(;. fuel, in., I, ',s-',r..,to,uhs 0,14; I riu' UFO sirar:urai !,iri,ii:,a,r of f -S
1) 0 '9.0 • 5¼ 0; ;[Link] l a. 1,1,1k reaenn.'nr mIs/tub

lin,swer. A .,,. I ,-!un,tiq; . It','- t!n •iutr)li .turi,,' ',.,'. \),'O 5 tOftlf' !u;,40iu;snunl I':;';iudrt. .o' , . '• ulths hero
.uk,'In,, jun 'I. i' !.if,,!n.
 Chapter 45

Colour, Dyes, and Pigments

The dyeing of cloth and the fermentation of sugar to produce alcohol are the ta'.
specialized areas of organic chemistry that date back to antiquity. Fabrics dyed with indigo and
maddar have been found inthe tombs of predynastic Egypt. These, and a few matters extracted
from insects and tropical woodi formed the only sources of dyes until the middle of the last
cenluary.
The first synthetic dye was made in 1856 by William E. Perkin, which he named
mauvetne. He obtained this dye by oxidation of impure aniline. A few years later, the strir.
tares of natural d y es, indigo and alizarin, were determined, and these compounds were prepared
by synthesis. However, the major development in chemistry of synthetic dyes was the d:sco
very of diazotization and azo coupling. Since 1856, tens of thousands of dyes have ben syn.
thesizcd. Well over a thousand are commercially available now.

A. COLOUR AND CONSTITUTION

Witi's Theory of Colour
It was noticed by Otto N. Wilt in 1876 that colour in organic compounds is associated
with the presence of certain grups in the molecule. He designated a group that produces
colour as a Chromophore (Gr. chrorna, colour+phoros, to bear), and a molecule containing such
a group as Chrori ugen. The most effective chromophores are

/
—N=O N=N-
Ia,
c 0
AZO
Nitroso o
Nitro 0
p-Quisoid
The pre..encc of any one of these groups in a molecule is usiiaily sufficient do produce
colour. Thus nitrobenzene is pale-green, azoberizene is orange-red, p-quinoneS are yellow, arid
o-quinones are orange Or, red.
Certain other unsaturated groups produce colour onl y when several of them are present
in a molecule and when these are conjugatvd. They are

>c=O /C=N
ethylene carbonyl

0 0
Ii II U
[hus, a!thcugh acetone (CH—C—CH 5) is colourless. hiacct y l tCH1—C--CH 1 l is yellow, ad
1138
Colour, Dyes, and Pigments
1)

acetvlacetone tCH, - C- CIti,' - ' CHt i [Link] he I e .trhn ')u ,tuc5 not .:intiigt

is colourless.
Wtti aio noticed I ha! :Crteifl g ups. while not pr oucing colour . tre :h
nteissil the O,,ur hcts treseli t iii a :ri'Iect&ie together w'tb a ,'irrm.r,hnre 1 ree s
a'u\0 5 romcs ,t:c
A9sochromes i Si r au cii, to 'xrease - li-inc. cc our 1l i rn-ru :!Tc-:s'e
OH. N}{, -- NHR, an I h- tlse nstirphenok asid nit,ari!'n ar'- mic
coioued than nitriheneene and ae iee p -.cllow to orange.
Modern Iheory of Colour
Witts ssi!1. :01011 of gouc is L hom'roiiorcs 1!7id auxonr ;i ' u H'.'a ei er
for a better un-Jerstan ling of ri:Ietiuro ' hiti ii 'A-,'
ici•it ad ciititI 0 ti 'it. m .it nider the nature
of ight and itS tntesaJtiori ssill ma t ! ,- r . Etc ienct:n ii ccd- ar ' itodi eu when liiIrt [Link]
a avelengt 1c within thc hi' revi 1 e romaguetic [Link] toke t ' . :it!.t..' 't ee As
shoe-n t H 451 the oHe region of pcctruns etcttis s-rn - . 'hi ' o " , t ti

length I IA 1O- cm The cisrresn .rnsiingire those ." he .pecsr:'ni exsv'.disg Iron
coter-
violet Nosier wavetcngths. 4300 400 Ai to rid .icr A.'osg:h. i, tOil ,- '511(1 l
Bey ond the red end of the vt';ttcle sçc'.t ':r; . the ritrare.J . 51i 1. '.1ii ..i° i i',i b,ofl,1
the sioktend 'c, the ultrao-Iei ii l 4cIid :1 :ccn-crSt •' cc eL: .scases
we go irons red to the 1 Net end I tot'- 'ct .tit hi': title tet- bar sb!e light. rIrar 'd
hs l:s.
Cc-tour and Absorption of [Link] Whets girl iS Iit'tilt' 1
i1Li or is reflected from
it, sc'nse of the light ma be ahsorhct Ihe eneig:. -Ltgbt ta itd
' into energ y of motion

a -.
.4 1 6 k -'---.-.-- ---_--.----'- - -

- I
'-1 -T -

" ; 5; 8L '5"A4'

..............................
WA c,' -4

Fig, 451 Spectrum iIlusir:ing hew li-Slur cleprnili on ssorri .in of tight
ot noIectde, or cii',!ron in the rioletuIe ci,. 'c pr . iintcd to htghcr enere, levels The
enr:gs is e-,, enivalk transformed 010 heat This mpitci. when nut Icr cbsorh Ight energy, its
temperature v, raised. In rare cases, a pair nf lqhL rna be emitted as light of a longer wave-
ength, and this gives rise tO phenomenon ofJ?oiJrceceuce. The nc,t importifli sOUfCe of colour
in organic cornpourds is by absorption of light without subsequent emission
lithe light is absorbed from the infrared or ultraviolet regions, no colour will be seen:
but if light is absorbed from the visible region, that substance c-ill appear to he coloured. If
substance absorbs all visible light exceot that correporiding to scilow. for nitance, it will trans-
mit or reflect only yellow and will he iCeri as chow. More comrnonl, hoe eser, light of only
one colou r is absorbed, in which case the suhst:rnce a p pears to hse the complementary COlOUI,
as determined by the use of the colour wheel of Munceil (1915) (Fig. 45'2t. Thus, if the light is
absorbed from the iolct region of the spectrum, the substance ,ll be seen as 'selliw If light is
absorbed from the red region, the substance will appear green
Colour and Conjugated S y stems. When ultraviolet or visible light is absorbed by a mole-
cule, an electron is excited, that is, it is promoted to an orbital of higher energy. The mole.
cule is card to be in the excited state. The energ y req aired to proniote an elcctrun varies wit'
 Co $ced Orgonic C h emi st ry

the iv;rormelit of the etc roir The no re niv the bond, the more ditcult it is to promote
as ctrsn 'i that bond to the eicd state A higher energy is required. Sigma (a)-bond
cctr to .re tight I, C!J. 1: rrets high eiiergs iol short s%ave t enghs s neccassary to promote

00

No
/SO(ç

:/ •t 2 . Cotiur Wiic .o:

trori Fite eti-cr g rcl .; c i•. ro:itC i-chrtroa, e•.uugis to break the
'-boisd and irm Free cJtoa!s.
Pi 1-h nd Je5 troni :e in I ro- ess ri'erg to he piomoted.
Fictron :11 COirCgir/.l 55 .C)s [Link] VCi - sic; ('in ia,iuri end aruroiticity help
,iatiitie the excied s or 0 r'.g i iirh;:ih.':nr h:her energy of the excited electron
Org;tno imp rids _:or1,nn -r-hnd, absorb ligiv to the ultraviolet regtou of the
spe;i:unr. vi; tic I ito-n nta - in .g ;n! - b ,indN do not absorb l i ght in this region Conjugated
ri-hoods [Link] c-s energi jr Centrjr; rrnrnotm Unto sated-ri- hondi and absorb ultraviolet
;:ghr at a longer aevèlrngth. Ax von ni cr;ein rFe;uei, the wivelrngtn of tight absorbed increa-
sés. When w rveleirgih .rr 5ng , : i ipi to be in the vtst5i region, we observe colour. Thb
s illustrated b y itie !iowing [Link]'les.
Ethylena absorbs ugh' nI va. elengsn I,tr into the uvroiet part of the spectrum, at.
RhO £. Butadire, with to ociget rd domle hands, uh,orbs at 2 170 A. a wavelength closer
to the visible region thur thr absorbed by ihylenc. Ekeetriene, with three coniugated double
bonds, absorbs still clos er i-i ihr stone re g ion, at 25 C) t All three compounds are colourless.
However, as ttt g numbar ufonoigitcs: iioable hor.d increases, the position of absorption fai!s
clearer the vts!hle rego. and sitn enough .noCIuitJOn the mo!ecuic are coloured. For example,
carotene contains etevnn Cntu gatd double bonds and is recposihte for t ile colour of carrots.
It aosnrbs a: 451i.i S Ashritgn lire iigrlttn,sr ned htue, carrots are, (:f cOurse, crarigc.
CH= CH (:R CR -CU -CH, CU1=CH--C14=CH--CH=CH,
I 3-hutusiier.e 3,5-hc*airiene
('OLOURLESS (OL(tL!RLES COLOURLESS
CHI C H'3 C41 CH.
H c, ,CH1 HC (H
= oc= CHC4C(k=CHCH=CCH=c9

CH H
Colour, Dyes, and Pigments I' 4

Benzene absorbs light at 2550 A and c, tlerefw t , cfflo'Jrles, as are naphthalene and
anthracene. As the number of fused rngs Increases. the position of absorption approaches
the visible region. Thus naphtliacene. v,ith four linearly fused rings, is yellow (absorbs blue
light). Pentacene. with fise fused rings, is blue (absorbs orange light). Graphite is a sheet of
benzene rings fused in all directions it is black, absorbing all colours almost completely.

0 co = BENZENE
(COL oWL5S5)
NAPHTHALENE
((01. OUL (55)
ANTNRCfN(
((01. OIJR1. (.55)

C= NAPHrHACEN'
(YELL0V)
O I

PEN TA(frv(
(BLUE)

o'fl Y
tTo1oflb
1)1 I

GRA P/lire
(81. ACI()
Carbon-carbon double bonds and benzene rings are not the onl y groups Which produce
colour in organic compounds. Other groups which contain easily excitable --electrons also
form important light absorbing (colour producing) units. Thus it is significant to note that all
chromophores (Wilt's Theory) have multiple bonds, that is, they are ct-bonded systems. Intensi-
fication of colour by auxochromes is due to the formation of an extended, conjugated system
(through delocalization) with the chromophore.

B. DYES
All coloured compounds are not des. Dyes are those coloured compounds that can be
firmly fixed to the fabrics by chemical or ph ysical bonding. To be of commercial significance, a
dye must show fastness tQ light, washing, heat (sublimation) and bleaching.
Nomenclature of Dyes. No systematic nomenclature of dyes is available. Manufacturers
often assign trade names to dyes which the y snake, and hence the same dye may be sold under a
variety of names. For example, the names rosaniliuc. magenta. and fuchsine all apply to the
came rose-red dye. To avoid confusion, the Society of Dyers and Colourists (England), and the
American Association of Textile Chemists and Colorists have collectively compiled a CO/OUT
Index in which each dye is assigned its mdi'. dual colour number iC.I Vol
 dwrc O r gcn t (.scrratry

CI.SSlF1CATION OF DYES

Dyes ny be classified in two ways The organic chemist classifies them according to a
[Link] structure (Clic'ni a! Classification). The dyer who is only interested in fixing
the dc to the libre, [Link] them according to the method of application.

\ CLASSIHCATIUN ACCORDINu TO CHEMICAL STRUCTURE

Nitro D yes Nitrodses we polynitro derisatires of phenols containing at least ('Be

nilru g tour, or.-ho or para to the h y drox y l group. They are at relatively little importance
ir,d1SII`I.L;!v, hec:iuse the r,nouri are not ver last. Examples of this clas arc picric acid
2.4.6 . riniirophenol). Maritu5 yellow (2, 4-dnitr.- I -naphih(1l), and Naphthol yelkw S
i2,-t-diiniro- I -naphthol.7-sulphnic ucidj.

c+i OH
OaN NO MC

) 1)

PICRIC ACID lS 2Ai/7(j,5 Y1LUiW NAPHTHO L YEUOW S

Naphthi yellow S cd'S be used to dye wool, and is OOC of the colours permitted in
foods

1. 2) Azu Dyes. The ao iivcs represent the largest and the most important group of
dyes. The y are characterised by the prcicnce of one or more azo groups(— N— . , which harm
bridges between two or more dromatic r:ngs. Preparation of aco dyes makes the following
two steps

Step 1. Conversiin of primary aromatic amines into diaconium compounds by treat-

ment with socium nitrite in cxcess hydrochloric acid ([Link]).

-NH + HNO, + HCI -N2Cl + 21-120

A PRIMARY A OiAjONIiJpl
AROMATIC AMINE (OMPOUNO

Step 2. Coupling of diazonium compounds with phenols, naphthols, or other aromatic

amines. Coupling with phenols and naphthols i s carried out in basic solution: coupling with
amities is carried in acidic solution.
OH(-NH21
/ -NR2) OH(-NH2)
• -NR?)

'2 C + H -ww--

A Dwzosij A PHENOL
NAP p1I,O or
AN AillAf
 Colour, Dyes, and Pigments 1143

The above reactions are carried out at low temperatures (0- 5) because diazonium
compounds are usually unstable. In the resulting dyes an aromatic system joined to the azo
group is the chromophore, and the hydroxyl group or amino group is an auxochrome.
To simplif y the description of azo dyes, only the coupling step will be shown. It will
be assumed that the diazonum compound was obtained by diazotisation of the corresponding
amine.
(a) Aniline Yellow, Solvent Yelloic 1. It is p-aminoazobenzene. Aniline yellow is the
smp!est azo de and is obtained by oouping henzenediazoniuin chloride with aniline in acidic
medium,

+ -NN--fl>--NH + HCl
R-<ONH, -
TtILOW
(p - nnoazob.r, to,)

Aniline yellow is used as a dye for oils and lacquers, and is also an intermediate for
other dyes,
(li) Butter Yellow. It is p-N,W-dimethyiaminoazobenzene. Butter yellow is obtained
by coupling henzered:azonium chloride with N,[Link].

t - •
2 Ci + H— /
-Kö-
\-..'
CH,

'CHg
-+ K
N= O
^ N /CHI
CH,
ber,zer,cdiaznaiem MN-dimerhytariilinc B uller Yellow
;toride(p-N,W-di met hytaminoazobenzeoe)
Butter yellow has been used for colouring butter, margarine and oils.
(C) Chrysoldine, Basic Orange 2. It is 2,4-diaminoa7obenzene. Chrysoidine is pre-
pared by coupling benzenediazonium chloride with m-phenylenediamine.
NH, NH,

+
(O
____

_j N,C. H

[Link]
,' '.—NHI

m-phenyledjamine
=N'

CbTYsojthne
NH, + HCI

cbtorid (2,4-diaminoazobenzenc)
Chrysoidine is an orange-red dye. it is used for dyeing paper, leather, and jute.
(d) Meth y l Orange. It is prepared bytreatment of helianthine
with sodium hydroxide,
whereas helianthine Is obtained by coupling diazotised sulphanihc acid with NN-dimethyl.
Aniline.

- CH
+ -_. H "i - N"
CH1
diazotised suipbanitic acid N,N-mcthylanilioe

r —\ I-- CH
NaOH
HO 8 S , '—N =N ( N /
\ CH, -'
Helianib Inc

CH5
N01S - >N=N-\---- C(CH

Methyl Orange
 A.i sr'd Ogcnc Cheri''stry
44

Methyl orange is not a satisfactory dye for texlilcs because it is sensitive to acids. It is
used as an indicator in acid-base rIlraions. It is y ellow in basic soution; (above p1-1 4 4). while
red in acidic solutions (below pH 3 . This change in the colour is attributed to change in the
structure of its ions. Under alkaline condition; the ion contains the s:o chromphore, whie
under acidic conditions it contains [Link] chromophore.

5 [Link]

CH

-L
Y(. ( OW io
(A(ac 5JrON)

(e) Orange II. It is obtained by coupling diazotised sulphanilic acid with -naphthol
in basic medium.

n 0
HOIS N 26 + H — + HCt

HO HO

fl-NAPHTHOL ORAWOE 11
DIAZOT(SEO
SULPHANILIC ACID

Orange II is used to dye wool, silk, nylon, paper and leather.

(f) Pars Red. It is prepared by coupling [Link] chloride with

.naphthol.

_ ©

02N N,6 04_ +

DC- H_

HO

,.NITR05NZ(NEDfA .'-NAP/iflOL PARi' RED

ZON/UM CHLORIDE

Resorcia Yellow. It is made by coupling diazotised sulphanilic acid with resorcinol.

 1145
Colour, byes, and Pigments

OH

BOSNCi + H OH

diazolised resorcinol
suiphanilic acid

HOaSN = NH -- HO

Resorcin Yellow

Resorcin yellow is used for dyeing silk.

(h) Disperse Red 1. It is obtained by coupling p-nitrobenzenediazonium chloride with

[Link].N.(hYdrOXYethYI)afl11i0e in acidic medium.

Disperse red I is used for dyeing nylon, polyesters, cellulose acetates, and plastics.

O,N—& N,C71
CHICHI
+ H—K'_N(CHCHOH -*

piIZOflh&lfl [Link]) aniline

chloride

CHICH,
N=N—&NI + HCI
O,N
—^D—
\CH1CH2OH
Dlipczsc Red 1

(I) Congo Red. It is a diazo dye, that is, it contains two azo groups. Congo red is
made by coupling tetrazotised benzidine with two molecules of naphtbionic acid.

M NH3

Hk9
,+

SO3 H 503H
TETRA ZOTISED B ENZIDINE
NA PH THIONIC NA PH TI-i/ON/C
ACID
'I, ACID

riir
N

CONGO RED
Sot 503H

Orginic ( hniistry - 73
 146 Ad,anced Organic Chemistry

Congo red is not a good dye for textiles because the colour changes when-acid is added.
It was once an important stuff for dyeing paper. Congo red is used as an indicator. It is blue
in acidic solutions (below pH 3) and red in solutions above pH 3.

(j) Bismark Brown. It is also a diazo dye. Bismark brown is obtained by coupling
tetrazotised m•phenylenediamine with two molecules of m-phenylenediamine.

I.f N

-" "b-
60N
NHZ

0
& N ^NH2

r rRAZO TISFO
fP1YLENCO1Aft/NE HN
81SMAX BROWN
PH(NYLENED#AMINE
(2 MOLES)

Bismark brown is used for dyeing leather, wool, and cotton.

(3) Dlphenlymethane Dyes

Auramine 0. It is one of the most valuable of the diphenylmethane dyes. It is obtain.

ed by heating Michler's ketone with ammonium chloride and zinc chloride at 160°C.

ZoCI1
(CH,),N C__^^N(CH,). + NH4C1

Mcbler's Ketone
+

NH,

(CE11)1N——- -Kb--- N(CH 3)1 ci

Auramlne 0

Auramirle 0 is used to dye wool, silk, nylon, rayon and paper.

(4) Triphen0n3ethafle Dyes

be identified by common structural feature shown below.
[Liphenylmethane dyes can
to two benzene rings and to pquinoid group.
Notice that the central carbon atom is .]Oifled
 //4?
Colour, Dyes, and Pigments

Triphenylmethane dyes are not fast to light or washing, however, except when applied
to acrylic fibres. They are used in large quantities for colouring paper, and typewriter ribbons
where fastness to light is not so important.

(a) Malachite Green. It is obtained by condensing benzaldehyde (I molecule) with

N, [Link] (2 molecules) in the presence of concentrated sulphuric acid to give a leuco
base (Gr. leuco, colourless). Oxidation of the leuco base with lead peroxide followed by
treatment with hydrochloric acid yields the dye.

/I
)4 /

101
c=10+
co
"

8ENZALLtEHYDC N- DIA4T1YLA?.[Link] LEtJCO 8A5E OF MALACkIrECIEEW

(2 /'1OLtS)
+

0'/
H1 00- N(CH3)5 HCI

C CI
€-
N(CH3)2 N(CH3)

MALACHITE GR6N

Malachite green takes its name from the fact that it has a deep blue-green colour resem-
bling that of malachite (Copper ore). It is used as a dye for acrylic fibres, Leather, paper, and
lacquers.
I
(b) Pararosaniline. It is the simplest triphenylmetharie dye Pararosaniline is obtained
by condensing p-toluidine (I molecule) with aniline (2 molecules) in the presence of nitroben-
zene to give a colourless carbinol. Nitrobenzene serves both as a solvent and an oxidising agent.
Treatment of the carbinol with hydrochloric acid yields the dye.
148 Advanced Organic Chemistry

H-0—NH2 AH^_NHII
3ll
+
—2H70

H —NH2 NH?
5bTOLWDIW5

ANILINE COLOU R LESS CMBINOL

(a MOLtS) +
NH2

HCI
(-1120) ci
NH z

PARAROSAMIL INIE

Pararosaniline has been used to dye cotton, wool and silk.

It is closely related to pararosaniline. Rosanilirie
(c) Rosaniline, Puebsine, Magerila.
is prepared by condensing one molecule each of aniline, p-toluidine, and o-toluidine in nitro-
benzene to give a carbinol. Treatment of the carbinol with hydrochloric acid yields the dye.

-.--.
14C1
+ ANIUW 4(°l
11,11
*1C
-

\Q<NMI I j
ft-tC 0- T0LUIP INE COLOQLES5 CA RB/NOt ROSEAN,LINB

Rosaniline has a greenish metallic lustre. It dissolves in water to give a deep-red colour.
Rosaniline is used for dyeing cotton, silk and wool. Addition of sulphur dioxide to the dye
which is used to test the presence of aldehydes.
solution produces the colourless Sch ff's reagent,
(sf) Crytil Violet, It is obtained by condensing Michier's ketone with NN-dimethYl-
aniline in the presence of phosphorous oxychioride (POd 8 ) or phosgene (COd 5).
If phosgene
is used, then crystal violet can be prepared directly by heating phosgene and N,N-dimethyl-
aniline, since these two react to give Michier's ketone.

+
Poc13
+ H_ñ—N(CH orCoCl I ci
Mt/-DIME THYLAN/LIWE

N(CH3)5
M/CbfL(Rl KETONE CRYSTAL VIOLET
 1149
Colour, Dyes, and Pigments

Crystal violet has a greenish-brown metallic lustre. It dissolves in water to give a deep-
blue colour. Crystal violet is used in the manufacture of inks, stamping pads, and typewriter
ribbons It is also used as an indicator for the determination of hydrogen-ion concentration of
solutions.
(5) Xauthene Dyes.
Xanthene dyes can be identified by a common structural feature shown below.
They are obtained by condensing phenols with phthalic anhydride in the presence of zinc
chloride, sulphuric acid, or anhydrous oxalic acid. Examples of this class are fluorescein,
cosin, and rhodamine B.

©90(
(a) Fluorescein. It is prepared by heating resorcinol (2 molecules) and phthalic anhydride
(1 molecule) with zinc chloride at 190°C.
GH HWD 014 "D

r
'0190 ): 0

2W,0

rc00
CO .

e
FLIIOWC(,N £IRM'E
PNTHAL1C AN)JYDRIDIF

Fluorescein is of no value as a dye. It is a red powder, which is insoluble in water. A

dilute solution of fluorescein in sodium hydroxide gives a strong yellow-green fluorescence when
exposed to light. It is used to trace pollution of water supplies by sewrage, since if a small
quantity of it is put in at the suspected source of pollution, the colour will be detectable at some
distance from the source, even after extensive dilution. During World War II, fluorescein was
used as a sea marker for airmen who had to bail out from aeroplanes over water. It also aided
searchers in locating them. Fluorescein is also used as,a mild purgative.
The sodium salt of fluorescein is called Uranine. It is used to dye wool and silk.
(b) Eosin. It is the disodium salt of tetrabromofluorescein. Eosin is obtained by
brominating fluorescein in glacial acetic acid to give tetrabromofluorescein. Treatment of
this with sodium hydroxide yields the dye.
Si
ko'ao^v -0 0 0 OH "VO 0

6"
N-ON
CM COc
C60 M11

09
FL LfORSCflN 7EtO.(5cefN (OS/N

Eosin is a red solid, which is soluble in water. Alkaline solutions of eosin show a
yellow-green fluorescence. Eosin is used for dyeing wool, silk, and paper; for making red ink
and as the colouring matter in lipsticks and nail polishes.
(c) Rhodamine B. It is prepared by condensing phthalic anhydride with NN-diethyl.
[Link] in the presence of zinc chloride, and treating the product with hydrochloric
acid.
 dvnced Orgcnc C1 em(SUt
(150

-- N(C4H'J,
H —0 N(C2H4 CH.)N IC2HI^, ^'C,H,), N

MCI 0
tc'H

C \
(Y-0 órCoot
RHODANN A

qriuc

Rhodamine B is used for dyeing silk, wool and cottoi

(6) PhthIeins
Phthaleins are related to xanthene dyes and are made in the same way.

Phenolphthalein. it is prepared by condensing phenol 12 molecules) with phthalic anhy.

dride (1 molecule) in the presence of zinc chloride at 120C

HO\

to JJ=o

t..EDj (cOLOURLE.53)
PHTHA(.IC ANHVAVO

Phenolphthalein is not a dye. It is a colourless solid, mp 26[C. Phenolphthalein is

insoluble in water, but dissolves in alkalis to form deep red solutions. This is due to the for-
mation of a djsodiurn salt, the ion of which is coloured because of resonance. When excess of
strong alkali is added, the solution of phenolphthalein becomes colourless. This is attributed to
the formation of a trisodium salt, the jots of which is colourless because of loss of resonance
and quinoid structure.

ON. Wó_N
01 Pl'eO

0 "o -
I I
00N co I
O-j 0 SODIUM SALT tRf5O5w+ iAL7
PWENOL PHTNALF(N JaD) (CoLQ,R FS

Because of the colour changes shown above, phenolphthalein is used as an indicator in

acid-base titrations.
Phenolphthalein is an extremely powerful laxative, and this accounts for its widespread
use as a denaturani for laboratory alcohol.
(7) Imligoid and Tliioindigold Dyes
lndigo(d. It is the parent compound of indigoid dyes and has been used in
this country from times immemorial. Egyptian mummy clothes, which are 5000 years old, were
Colour, Dyes, and Pigments 11Sf

dyed with it. Indigo was originally obtained from plants of indigofera group. The leaves from
these plants were covered with water and allowed to stand for several hours. Enzymes present
in the plants brought about fermentation, as a result of which the -glucoside of indoxyl (known
as indican) in the leaves was converted into indoxyl and glucose. Upon exposure to air the
indoxyl was oxidised to indigo.

FER/4Ety rA riorv N
—I-
H +
OH
HO H
>OH
,8 -L/4'K H ON K
i D GLUCOSE /NDOXYL

H
II
CX/0hb0
2
V
CH2
a-
:> =
I II
H H
INDOXYL IN11
('No/CAN)

Natural indigo contains an isomer of indigo known as indirubin (Indigo Red), and other
impurities in varying proportions. Most of the indigo used at the present time is a synthetic
product. It has replaced the natural stuff because of cheapness, purity, and uniformity
of the manufactured dye.
Preparation of Indigo. It may be obtained
(1) By Heumann's First Indigo S y nthesis (1890). This involves the condensation of
aniline with chioroacetic acid to give N-phenylglycine. The phenyiglycine is then fused with
sodium hydroxide and sodatoide at 250°C to form indoxyl, which on oxidation by air yields the
dye.

0 4
I I
- 14 O4+ &ø',
14-

.14 14 0
14
AMIJNC J4L0 N pHeNvLoLyc,Nc INOOXYL (NJOO
4c(r,c ) (,NO,G0t/N'

N-Phenylglycine is now obtained in much higher yield by interaction of aniline and the
bisulphite compound of formaldehyde at 50-60°C, followed by treatment with aqueous sodium
cyanide, and hydrolysis of the resulting nitrile.
 Advanced Organic Chemistry
''Si

0 OH

H—C—H + NaHSO3I H—C—H

FOPPIALDEHYDE SODIUM 503 No
BISULPHITE
AN ADDITION
PROOUCI uo a
\,
SO3Na
so SeEN

P4—H HO—C—H
... a23 ©L NV 2HO1LP4
I I I
H H H H H
N-PHEN?I..SLYCINE
This involves the condensation of
(2) By [Link]'$ Second Indigo Synthesis (1896).
anthranilic acid with chioroacetic acid to form N-phenyl-o-carbox y lic acid. This is then fused
with sodium hydroxide and sodamide to produce unstable indoxylic acid, which decarboxylates
to give indoxyl. Oxidation of indoxyl by air yields the dye.
OH
I.
oC\O
ON—H + CH,—COOH —H2O

NaO}NaNH,,
aa N"

anthranilic acid chioroacetic acid N-phenylglycine. o-carboxylic acid

- Co.
'INDIGO
LI:1:-:°
cII111,N: :H
Indoxylic acid iodoxyl
(unitable) (2 molecules)
(3) From Aniline and Ethylene Oxide (1943). This involves treatment of aniline with
ethylene oxide to form N-phenyl-2-hydroxyethylamine. Fusion of N-phenyl-2-hydroxyethylamine
with sodium hydroxide and sodamide at 200°C produces its disodium derivative. The sodium
derivative is heated rapidly to 300°C and then cooled to 240°C to yield the sodium
salt of indoxyl. This on treatment with water and oxidation by air gives indio.

/O\ CHr0H NaOH+NaNH,

©\ + CH,—CH, ZOO'
øthylen5 oxide
N
NH,
aniline
[Link].2.bydroxyethyI8minc

CH1ON
L(1)300°
CFI1 (2)240°

Na
 1153
Colour, byes, and Pigments

OIIIIH - - C— ON a
ii
I1
N'
/N/GO

H H
sodium uh indoxyl indoxyl
of indoxyl (eno!fonn) (keto form)

Indigo is a dark-blue crystalline compound, mp 390-2°. It is insoluble in water and

most organic solvents, but soluble in aniline, nitrobenzene, and chloroform. It can be sub-
limed under reduced pressure to deep red vapours, which on cooling yield prismatic crystals
Indigo is used very extensively for dyeing cotton by the Vat Process, and in printing inks.

Structure of Indigo. The structure of indigo has been deduced from consideration ot
facts and conclusions such as the following. I

1. Elemental analysis and molecular weight determinations show that the molecular
formula of indigo is CH1001N1.

2. Fusion of indigo with sodium hydroxide at low temperatures produces anthranilic

acid. This indicates the presence of a benzene ring attached to one carbon atom and one nitro-
gen atom in the ortho position.

NaOH
I
C—OH

INDIGO

NH
anthranitic acid

3. Oxidation of indigo with nitric acid yields only two molecules of isatin. This indi-
cates that the indigo molecule contains two identical units joined together, and that each unit
on oxidation produces a molecule of isatin.

2[0]
INDIGO -p
(Cb

H
ISA TIN

The following two possible structures of indigo meet this requirement.

t
C

'^o 01,11
I '=^ C-1

H
cçr'6
yJNN> H H
(A) (8)
4. Oxidation of indoxyl by air yields indigo.
(54 4dysnced Organic Chemistry

0
-

H
H
indigo
[Link]
From above, it follows that (A) represents the structure of indigo. This has been con-
firmed by the following synthesis by Baeyer (1872).

nl-- el00 IL pc

- --
N%0 0]:JC1/'0
0H
•1
iSITiN 15A TiN ISA TIN CHLORIDE
(ETO fOii%f) (ENOL FQ,','4)
Zr, CH5COQH

-r° -4

:lH ^0
I I
H H
iNDIGO
TWO MOLfC tILES)

Two geometrical isomers are possible for (A).

0 0 0
II H
II I

W. /C C11"N
Q:C\C^!
H H II
H 0
cis-form Trans-form
X-ay analysis shows that mostly indigo exists in the more stable trans-form. However,
derivatives of both are known.
(a) Tyrian Purple. It is 66-dibromoindigo. Its discovery was later than that of indigo,
but it is believed to have been known in 1600 BC.

0 H
N'

Sr
H 0

TY1IAN PURPLE
(6,6LI8ROMQIN0160)
 1155
Colour, Dyes, and Pigments

Tyrian purple occurs naturally in the purple snail, Murex Brandaris. It takes about
12000 snails to produce 14 g of the dye. This explains its rarity and why the colour of
purple came to be the symbol of royalty in the former times. The dye is no longer of com-
mercial value.
(b) Thioindigo. It is analogous to indigo in which the two —NH— groups are
replaced by sulphur atoms. Thioindigo may be obtained by the reaction of thiosalicyhc acid,
with chloroacetic acid, followed by fusion with sodium hydroxide and oxidation by air.
Thiosalicylic acid itself is made by diazotisation and reaction with hydrogen sulphide.

ccoH COD OOH

,mAtorizc OOH Na OH

@ sH
S2
2. 1i5

9 ^
W2
ANTMRP1(L,C mIOSALICYLIC O-(CAR8OXYMETHYLMERCAPflJ).
sc/v ACID SENZD( AriD

9
H QH2
@( 2L.

C sj^
T/WO'[Link] Th(OINDQXfl
(E4V1 - FORM) (/CE TO FIJpi'l)

Thioindigo is used to dye cotton, wool and polyesters.

(8) Anthraquinoid Dyes
Anthraquinoid dyes can be identified by a common structural feature shown below.
Notice that a p-quinoid group is fused to two other benzene rings.

W.

[Link] dyes are used for dyeing wool, silk, nylon cotton, leather and paper.
The most important dye in this group is alizarin.
Alizirin. It is 1, 2-dihydroxyan thraqu i none. Alizarin derives its name from the fact
madder). It is now
that it was first obtained from the roots of the madder plant (Fr. Alizari,
prepared from phthalic anhydride by the following six steps.
5 to give
Step I. Phthalic anhydride is treated with benzene in the presence of MCI
[Link] acid. (Friedel-Crafts
o
I
Reaction)
0
II

CTo+©
O :©
1
o
O8ENl0YOC
0
11

ACID
 156 Advanced Organic Chemistry

Step 2. [Link] acid is cyclized by treatment with concentrated sulphuric acid

to form anthraquinone.

0 H'so'
c0 r_^
OH'-.
1 0 0011

anthraquinone
Step 3. Anthraquinone is heated with fuming sulphuric acid at 180°C to give anthraqui-
[Link] acid.

a
0
0
+
fuming
(D 9
anthraquinone anthraquinone-2-sulphonic acid
Step 4. Anthraquinoue.2-sulphonic acid is converted into its sodium salt by treat-
ment with sodium hydroxide.

SO,H SO3Na
NaOH

0 9 * 1
sodium s alt of
anthraquiaonc-2. onic acid
Step 5. Sodium salt of anthraquinone-2sUlphonic acid is fus with sodium hydro-
xide in the presence of potassium chlorate at 200°C under pressure to give sodium salt of
1, 2dthydroxyanthraquinone. The purpose of potassuim chlorate is to provide oxygen for
the oxidation of the carbon atom at C-I.

SO3Na
- ONa
Na
-*
pressure + Na1SO1

0 .1-2ff10

sodium salt of
1 [Link]
Step 6, Sodium salt of 1.2-dihydroxyanthraquinone is treated with sulphuric acid to
yield 1, [Link] (Alizarin).

ONa 014

/ONa

Alizarin
(I, [Link];n.
Colour, Dyes, ond Plgmenu 1 157

Alizarin can also be made by condensing phathalic anhydride with catechol in the
presence of sulphuric acid at 180°C (Sec Below).

Alzarin forms ruby red crystals, mp 290°C. It is insoluble in water and ethanol. It dis-
solves in alkalis to give purple solutions. Alizarin is used to dye cotton and wool. It is
also used for making printing inks.

Sfruchire of Allmrin. The structure of Alizarin has been deduced as follows.

1. Elemental analysis and molecular weight determinations show that the molecular
formula of alizarin is CriHeOi

2. Reduction of alizarin with zinc dust at 400°C produces anthracene. This indicates
that it has the same carbon skeleton as that of anthracene.

3. Alizarin reacts with acetic anhydride to form a diacetate. This indicates the presence
of two hydroxyl groups in the molecule.
4. Alizarin can be prepared by condensing phthalic anhydride and catechol in the
presence of sulphuric acid at 180°C. This shows that alizarin is a dihydroxy derivative of anthra-
quinone and both —OH groups are substituted in the same benzene ring.

o OH
OH
OH
+ ff,305
-+

0
cechoI
phihailcanhydride Alizarin
. (1, 24hydroxysnthraquinose)
The above facts limit our choice to two structural formulae for alizarin,

.' OH
H

(A) (B)

5. Alizarin on nitration yields two isomeric mononitro derivatives, both of which on

oxidation give phthalic acid. This shows that in each of these derivatives, the —NO, group is
substituted on the hydroxylated benzene ring.
Let us now write down the possible mononitro derivatives from (A) and (B).
Mononitro derivatives from (A)
OH

o OH
(Nr,Lr_yOH

o
OXON NO, 0 NO

0
DIFFERENT
 Advanced Organic Chemistry
1158

Mononirro deriativesfroin (B)

0
0 NO2
OH

06
GH

CH

IDENTICAL
0
o
q H02
OH

Since only formula (4) permits the formation of two isomeric mononitro derivatives,
represents the structure of alizarin.
(B) CLASSIFICATION ACCORDING TO METHOD OF APPLICATION
Methods for dyeing vary with the chemical structure of the fibre to be dyed.
A dye suitable for wool or silk may be entirely unsatisfactory for dyeing cotton or rayon.
Wool and silk are protein substances. They contain many acidic and basic (polar) groups.
These groups serve as points of attachment for a dye because it also has acidic or basic groups.
On the other hand, cotton and rayon fibres are composed of cellulose in quite pure form and
provide only neutral ether linkages and hydroxyl groups as points of attachment for hydrogen
bonds. Polyolefin fibres are formed from products of polymerisation of unsaturated hydro-
carbons, for example, propylene. They do not contain any polar groups and require still other
techniques for dyeing.
As already mentioned, a dye must do more than simply colour the surface of the fibre. It
should become part of the fibre, and wear and wash with the fibre. A dye should be fast to
light and should show resistance to the action of various organic solvents used in dry-cleaning,
dilute alkalis and acids, etc. A number of dyes satisfy these conditions very well when used
on some material but not when used on others. In all cases chemical structure of the material
determines the process and the dye to be used for dyeing it. A number of dyeing methods
and dyes adaptable to each method are described below.
(I) Direct Dyes. These contain acidic or basic groups and combine with polar groups
in the fibre. Such dyes colour a fabric directly when the fibre is immersed in a hot aqueous
solution of the dye. Direct dyes are used to dye wool and silk. Two examples of this class are
Naphthol Yellow S and Martius Yellow. Both compounds are acids and combine with the
free amino groups present in wool and silk fibres. Synthetic polyanside fibres (Nylon) can also
be dyed by this method.
(2) Mordant Dyes. This class of dyes require a pretreatment of the fibre with a
mordant material designed to bind the dye. The mordant becomes attached to the
fibre and then combines with the dye to form an insoluble coloured complex. This complex
is called a lake. Commonly used mordants are the oxides of aluminium, iron and chromium.
Mordant dyes may be used to dye wool, silk and cotton. Alizarin is an example of a mordant
dye. It gives different colours when used. with diffehit mordants. It gives ared colour with
aluminium and tin salts, browni . red tones with a chromium mordant, and black-violets
with an iron mordant.
Fibre

0 0

0 OH
OH

'- + Fibre .
 Colour, Dyes, and Pgrnents 1159

Mordant dyes have been used for many centuries. They have lost their origirsa,
importance because their use is no longer necessary. Equal or superior results can be obtained
with other classes of dyes at less expense in time and labour.

(3) Vat Dyes. These dyes are insoluble in water, but on reduction with sodium
hydrosulphite yield alkali soluble forms (Leuco-compounds) which may be colourless. It is
in this form they are introduced into the fabric. The reducing operation was formerly carried
out in wooden vats, giving rise to the name 'Vat Dyes'. After the reduced dye has been
absorbed in the fibre, the original insoluble coloured dye is reformed by oxidation with air
or chemicals. Vat dyes are used to dye cotton, and are very fast because of their insolubility in
water. Indigo is an example of a vat dye.

0 OH H
II I I
Reduction C

Oxidation

I-i 0 H OH

indigo indigo while

(blue; water-insoluble) (colourless water-soluble)
a leuco-compound

(4) Ingrain Dyes. These dyes are synthesised within the fabric, and may be applied to
any type of fibre. The azo dyes are good examples of ingrain dyes. The cloth to be dyed is
first soaked in an alkaline solution of a phenol (usually naphthol) .nd dried. It is then
immersed in a cold alkaline solution of a diazonium salt. Coupling reaction takes place within
the fabric. Since these dyes are insoluble in water, they are very fast.

(5) Disperse Dyes. These dyes are insoluble in water, but are capable of dissolving
certain synthetic fibres. Disperse dyes are usually applied in the form of a dispersion of
finely divided dye in a soap solution in the presence of some solubilising agent such as phenol,
cresol, or bcnzoic acid. The absorption into the fibre is carried out at high temperatures and
pressures. Disperse dyes are used to dye acetate rayons, Dacron, Nylon and other synthetic
fibres. Celliton Fast Pink B (l-amino-4-hydroxyanthraquinone) and Celliton Fast Blue B
(I ,4.N,N' . diinethylaminoa nI hraquinone) are examples of disperse d5's.

0 N—CH3
0 NH2

0 0 @*0
0 . N—C113
OH

H
Ocilitors Fast Pink B Celtiton Fast Blue B
(1-amino'4'hydrox)anthraqujnonej (1,4'N,N'-dimethylaminoatsthraquinone)

RAW MATERIALS FOR THE MANUFACTURE OF DYES

The raw materials for the manufacture of dyes are mainly aromatic compounds such as
benzene, toluene, naphthalene, anthracene, and phenol. In the past, these compounds came
exclusively from the distillation of coal-tar, but in recent years increasing quantities especially
of benzene and toluene, have become avajlblc from petroleum and natura l gas. A variety of
 Adiwiced Organic Chem,str
1160

inorganic materials are also required by the dye industry. These include sulphuric acid, oleum,
nitric acid, chlorine, bromine, caustic soda, sodium nitrite, hydrochloric acid, sOdium carbo-
nate,. sodium hydrosuiphite, sodium sulphide, aluminium chloride, sodium bicarbonate an
manganese dioxide.

DYE INTERMEDIATES
The raw materials for dyes are almost never directly used in dye synthesis. It is neces-
sary to convert them to a variety of derivatives which are in turn made into dyes. These deri-
vatives are called intermediates. They are produced by reactions such as nitration, reduction,
sulphonation, halogenation, oxidation, and condensation. Most of these reactions lead to the
formation of substituted hydrocarbons which are functional in nature, that is, they bear
groups capable of undergoing further chemical reaction. ihe number of dye intermediates
available is very large, and the technology of their manufacture is an important part of industrial
organic chemistry. Intermediates are used not only for dye manufacture but also for the
manufacture of other important products such as pharmaceuticals.

NON-TEXTILE USES OF DYES

Dyes are used in many ways other than for dyeing fabrics. Large quantities of dyes
are consumed by the paper industry. The most paper dyes contain acidic and basic groups,
and belong to group of direct textile dyes. Natural leather is a protein substance and can also
be dyed with direct dyes.
Dyes for many materials such as gasoline, lacquers, and varnishes are selected on the
basis of solubility and fastness.
Important and growing markets for dyes are the plastic and metal industries. Dyed
anodized aluminium, in particular, is finding increasing use in automotive and architectural
applications.
Dyes are also used as indicators for the control of chemical processes. They are also
used for staining biological substances, printing inks, and colour photography.

Dyes for food, drugs and c ..metics must he chosen with great care to avoid toxic
effects. In India, dyes are certified by the government when judged safe for such uses. Only the
certified dyes may legally be used. This restriction do.s not apply to natural dyes.

ORGANIC PIGMENTS
The difference between a dye and a pigment is that a dye is actually absorbed b y the

(%yCN
Cu
2000 a
ACN

Pt rHALQN(TR!LE
 Colour, Dyes, and Pigments 1161

material to he coloured, whereas a pigment is applied tothe surface. Pigments are highly insoluble
powders of very Fine particle size. They are applied in the form of dispersion in water or
some other liquid. Pigments are used in paints, plastics, rubber, printing inks, and other mate-
rials for imparting colour, opaqueness, and other desirable properties. In paints, for example,
pigments may also impart anticorrosive properties. Copper phthalocyanine is an example of
an organic pigment. It may be obtained by heeling phtbalonitrile with copper at 200°C.

QUESTIONS
I. 9', bait a d y e ' How are de. lassiuid on the [Link] of their consiliutloit Soth 8S1 1993
2. Discuss the Theories vi colour and conshitutiow (;ulbiirgst BSi. 199j. Uilirtpur RSc / Q94j
3. iai Give the saliert feature, of modem theory of cotour,and constitution
hi Hon is natural indi g o obtained from plants. Desenbe a synthesis of indigo (P inca BSc, 1993)
4. (a) Explain the relationship between colour and chemical constitution.
(/i) (line a short account of the application of mordant and vat dyes oifabrics (Magadh BS;Hsrn.c, /993)
5. Define (i) ('hromnphore and in) Auxochrome f/an/oh RS, 199./i
Is. Name one important ann dye and one important [Link] d y e. Wnie heir structures and uses
7. Name and give structure of (a) an azo dye. (5) a tnptienylmethajie dye (c) a vat dyc and Id/a pheniilpltthalein dye
X. How will you synthesise a)tcann from anthraccne ? (Andhra BSc in, 1994)
9. How will you consent resorcinol into a compound which dissolves in NaOH to give a reddish brown solution which
i,n dilution with watercohibits yellowish green fluorescence (Dihrmsgarh BSr Hoes, 1011)
10. Give the synthesis and uses of
(a)Alizartn
(b)Indigo (Mangalore i/Sc. 1994)
C() Malachite green
(d) Phenolphthalein (Bombay BSc, 1993)
(v) Fluorescein (Kerala USc, 1991)
If) Meilt y l orange (Madura: BSc, 1993)
ci) Congo red
(h( Bismauk brown
11. Given the classification of dyes nvcnrdbig to their structure. Give cauinçles for any three types. Indicate the synthesis
forts onc in : he examples you have given (llerhwepurftSc, 1994)
12. Write anote on. Azodyea (Shcva)i BSc. 19941
13. What is diflenertee between mordant and vat dYes. (Man/runt BSc. 1994)
14. Write a note on: Vat dyes and ibe process of vat dyeing
- (tIdsiipr BSc, 1994)

Otga nic ( lIL'IlIihI IV - 74