0

I . SOCI, 11 Br NaOH r;unrtional l k r i v a ~ i v e s01'

5) CI-13CH2Cr12COOHIr;H; + CH3CH2CH2CNH2---7'---. CH3CH2CH2NH2 Monocarhr~xylic rids
H,O
butanoic acid butanarniclc propanalnine

Terminal Questions
I ) Benzenecarbonyl chloride o n reaction with water yields benzenecarboxylic acid
which Further reacts with second molar equivalent of benzenecarbonyl chloride
-to yield benzcnccarboxyllc anIi>dridc.

OH
(molecular formula C5HIZO,)

T h e other product obtained is ethanoic acid.

\I
4) a) (CH,),CHCCI and 2 NH,

11 li
b) CH3COCCH3 and 2 CFi,NH2

c) H ~ O C H ~ and HN(CH,),

C) HOOCCH2 -NH2 + HOOCCH -NH2

F 1
CH2
I
CHJ
 UNIT 18 N1TR.O COMPOUNDS
Structure
Introduction
Obiectives
Structure and Properties of Nitro Compounds
Preparation of Nitro Cornpounds
Reactions of Nitro Compounds
Important Uses of Nitro Compounds
Summary
Terminal Questions
Answers

!n Unit 17, you studied the chemistry ofcarboxylic acid derivatives. In this unit, you
will study a very important class of nitrogen containing organic compounds called
nitro compounds. You may recall that the nomenclature of nitro cornpounds was
discussed in Block 1, Unit 1, Sec. 1.6. The nitro group can be converted to many
other functional groups which makes nitro compounds good starting materials for the
synthesis of other organic compounds. Let us first study how nitro compounds can
be prepared. Then, we will discuss various reactions of nitro compounds. Finally, the
uses of nitro compounds will be explained.

Objectives
After studying this unit, you should be able to:
ou'tline the synthesis of a nitro compound,
explain the acidic nature of nitro alkanes,
write reduction products of nitro compounds in different reaction conditions. ' ~ n d
list the uses of nitro compounds.

18.2 STRUCTURE AND PROPERTIES OF NITRO

COMPOUNDS
T h e nitro group, -NOz, which is the functional group of nitro compound. :- a
resonance hybrid of two equivalent contributing \tructures as bhown hclo:\.

+ /O +/ 0-
R-N +-+ R-N
\ -
0 b
Thus, it can be represented by the following hydrid structure:

Remember that a similar resonance hydrid was written in the case of carboxylatc ion.
N h Compound b.p.lK
You can see in the hydrid structure that there is a positive charge on the nitrogen
374
387
atom and the negative charge is distributed equally o n the two oxygen atoms. This
393 separation of charge is reflected in the high dipole moment values for nitro
JOJ compounds which range between 11.67 x 1 0 ~ C' ~m and 13.35 x C p,
depending upon the nature of the h!drocarbon group. Their polar nature is also
indicated by their high boiling point<.
 -
Spectral properties of nitro compounds
Aliphatic nitro compounds show an absorption near 270 ?m in their ultraviolet
spectrum due to n --, .rr' transitions. Huwcver, nromatic nitro compounds uhwrb at
'
longer wavelengths, i.e., -300 nm, due to the extended conjugation.
The infrared spectra of nitro alkanes show strong bands at about 1550 cm-' and
1375 cm-' whereas aromatic nitro compounds show these absorptions at slightly
lower frequencies.

18.3 PREPARATION OF NITRO COMPOUNDS

The nitro compounds can be prepared by a number of methods. Lct us now study
these methods.

1. By direct nitration of hydrocarbons

Hydrocarbons can'be nitrated using nitric acid. The reaction with aliphatic
hydrocarbons requires high temperatures and is carried out in the vapour phase. For
cxample,
Nitration is accompanied by
oxidation.

You have studied, under the nitration of alkanes in subBec. 6.6.2. Unit 6, Block 2,
that nitration of higher alkanes yields a mixture of nitroalkanes which are separated
using fractional distillation.
In contrast to this, nitration of aromatic compounds takes place readily in the liquid
phase and can be carried-sutnear room temperature o r on a steam bath. You have
- already studied about the nitration of benzene in sub-Sec. 9.6.1, Unit 9, Block 2.
You may recall that nitration of aromatic compounds is an electrophilic substitution
reaction, the electrophile being the nitronium ion, NO;.
The products of nitration of-substituted benzenes depend upon the nature of the
substituent groups already present in the molecule. The nitro group'itself is meta-
directing and, therefore, nitration of nitrobenzene yields 1,3-dinitrobenzene as the
inajor product.
NO2 NO2
HNO,, HzSO4

NO2
nitrobenzene 1,3-dinitrobenzene

I 1,4-Dinitrobenzene can be prepared by starting with benzenamine. Since the amino

group is o-, p- directing, nitration of benzenamine followed by the conversion of the
amino group to nitro group, should give the desired compound. Benzenamine,
however, is susceptible to oxidation, so the amino group is first protected by
ethanoylation (acetylation). 'The sequence of reactions is outlined below:

I
benzenamine
NO2
(aniline) N-(4-nitropheny1)- N-(2-nitrophenyl)
ethanamide -ethanamide
(para-nitroacetanilide) (ortho-nitroacetanilide)

,$
(90%) (1-270)

&ZBF~

6
NaOH,

Q
NaNO; ,Cu(1) NaNOz
< .h,2..

NO:
7NO2 NO2
Diazonium salts will be discussed
in detail in Unit 19.
a diazonium
salt
Nitration reactions to yield trinitro derivat~vesrequire verk harsh reaction conditions.
e.g. prolonged heating of the starting nitro compound with nitric.actd in fuming
sulphuric acid. But, by using activating groups further nitration is fscilltated and
methylbenzene can be codverted morc readily to 2 n1cthjl-?,3.5-trini?robc'rizcne
(2,4,6-trinitrotoluene), TNT.
CkI

- HN03 (30 g)

HBO4 (200 g)
343 K , 3 0 minute
NO:
(90%)

TNT is an important explosive. It is relat~velyinsensitive to shock and hence i:, used

with a detonator. When mixed with ammonium nitrate it yields the explosive arrztrtol

2. Substitution by nitrite ion

Some nitro compounds can be prepared by the reaction of alkyl halides with sodium
nitrite using dimethylmethanamide as solvent.

Some alkyl nitrite is usually obtained as by-product in tliis reaction.

Better yields of nitroalkanes are obtained when silver nitrite ib used instead of sodium
nitrite. But as you know, silver nitrite is expensive and is not econornical'for large
scale production of nitro compounds.

-
CH3(CH2)6CH21+ A g N 0 2 ether CH3(CH2)6CH2N02+ CH3(CH2)6CH,0N0
(8396 ) ( 1 1"';I )

Aryl nitro compounds o r nitroarenes cannot be synthesised from aryl halide by a

similar route. Instead, nitroarenes are prepared by displacement of the diazonium
group. This will be dealt with in Unit 19. The reaction of arenamines to yield
diazonium salts which can be used t o prepare nitroarenes can be represented as

-
shown below:
HONO + CuNO,
ArNH2 ArN, - + ArN02
arenamine a diazonium nitroarene
cation

Let us now study the reactions of'nitro compounds.

1 8 . 4 REACTIONS OF NITRO C O M P O U N ~
1. As weak acids
The hydrogen atoms bonded to the carbon atom carrying the nitro group are acidic nirocrlkanr
in nature. Thus, nitro compounds dissolve in bases like sodium hydroxide. The anion nitromethane
so produced is resonance stabilised as shown below: nitroethane
nitropropane

nirrornetharle methylnitronate ion

On acidification, the anion yields the acidic isomer of nitromethane known as the aci

-
form which slowly changes to the more stahlc: nitro form.
The aci for111can behave both a
nuclephile as well as an
OH electrophile.
+/
C H ~ N ~ +
H+
CH: =N
slow
CH3N02 ,is t~ucleophile:

"0-
aci form

2. Henry reaction as electrophile:

The anions obtained from nitroalkanes as explained above can undergo nucleophilic OH
reactions with carbonyl compounds similar to the aldol type addition reaction. o/
Nu..nc=.
\

1I
CH2(CH2)7C-H + CH3N02 - NaOH
C2H50H
1
CH~(CH~)~CHCH~NO~

In case of aromatic aldehydes, the product obtained undergoes dehydration as shown

below:

3. Reduction (75%)
Nitro compounds can be reduced with a variety of reducing agents. Nitroalkanes can
be converted to alkanamines as shown below:

CH3(CH2)5CHCH3
NO2
I
- Fe, FeSO,
H2SOd, H20
NH2
1 .
CH3(CH2),CHCH3

The product of reduction of aromatic nitro compounds depends on the reaction

conditions employed. Catalytic reduction and reduction in acidic media yields
aromatic amines.
Catalytic hydrogenation is carried out by using platinum, palladium or nickel as the
catalyst.

298 K, pressure

nitrohenrene benzenamine
lkrivatives or Hydrocarbons -11 For reduction in acidic medium a metal and an acid is used. Usually iron or zinc and
hydrochloric acid are taken.
C1 C1

Reduction of a nitro compound to an amine requires six equivalents of the reducing

agent, i.e.,
+ 6 H t + 6 e'--, RNH2 + 2H20

-
R-NO2
The reduction actually proceeds in a seriei of two-electron steps via the nitroso
compounds (R-N = 0 ) and N-substituted azanols (RNHOH) as successive
intermediates.

a RNHOH 3RNH2
RNO~~[H]-
RN=O
-HzO
No2 NO NHOH NH2

0 T . 6 -6
nitrobenzene
2 r + ZH*

nitresobenzene N-phenylazanol
-H20
6
benzena-

Reduction can be stopped at the N-substituted azanol stage when reduction is carried
out in neutral conditions using zinc and ammonium chloride.

nitrobenzene

N-phenylazanol N-nitrosobenzene
(65-70%)
Reduction of nitro compounds ih basic, medium gives binuclear compounds. Given
below are the products of reduction of nitrobenzene in basic media.
0-

Sefecttue reduction ofthe nitro group is also possible as shown below:

Uabh-qe* 3-nitrobenzen&ine1(79-WYO)
18.5 IMPORTANT USES OF NITRO COMPOUNDS
-
In addition to the synthetic utility of nitro compounds, you have studied that they
are used in the preparation of explosives.
~everaipolynitro compounds possess an odour resembling musk and are used in
perfumery. Some such examples are listed below:

OCH3 (CH3)3C
NO2 NO2
musk xylol musk ambrette must ketone

Nitro compounds have important herbicidal uses. Some nitro compounds used as
weedicides for the cotton, soyabean and peanut crops are shown below:

a CF3
p,d-diethy14~uommethyl- N, N-dipropyMtrifioromethyl-
2,edinitro-1,s benzenediamine 2,6-dinitrobenzenamine
(dinitramine) (trifluralin)

18.6 SUMMARY
In this unit, you have studied that :
Drastic conditions are required for the preparation of nitroalkanes whereas
aromatic nitro compounds are easier gp synthesise.
Primary and secondary nitro compounds behave as weak acids and they show
nitro-acinitro tautomerism.
Nitro compounds react with carbonyl compounds in alkaline medium to yield aldol
type products.
Nitroalkanes can be reduced to alkanamiines.
' ,
Aromatic nitro compounds on catalytic reduction and reduction in acidic
conditions yield amines whereas in neutral media the product is N-substituted
azanol. The reduction in basic media leads to a series of bimolecular reduction
products, depending upon the nature of the reducing agent.

18.7 TERMINAL QUESTIONS

1) Write equations for the reactions of 3-nitropentane with
a) H2/Catalyst
b) dil. NaOH, HCI-IO
2) Write the major product of reduction of
a) Zntalc. NaOH
b) Pm2
c) m a q . w C f
d) SnCl2/HCl