A new procedure for preparing 3,4-dinitrobenzoic acid

Article abstract of DOI:10.1134/S1070427208030348

A new efficient procedure of synthesis of 3,4-dinitrotoluene from 3-nitro-4-aminotoluene was developed. Oxidation of 3,4-dinitrotoluene with an ozone-oxygen mixture to 3,4-dinitrobenzoic acid in the presence of cobalt(II) acetate was studied.

Full text of DOI:10.1134/S1070427208030348

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2008, Vol. 81, No. 3, pp. 503 505. Pleiades Publishing, Ltd., 2008.
Original Russian Text P.Yu. Andreev, E.V. Potapenko, I.P. Pogorelova, S.N. Krasil’nikov, A.N. Band, 2008, published in Zhurnal Prikladnoi Khimii,
008, Vol. 81, No. 3, pp. 518 520.
2
BRIEF
COMMUNICATIONS
A New Procedure for Preparing 3,4-Dinitrobenzoic Acid
P. Yu. Andreev, E. V. Potapenko, I. P. Pogorelova, S. N. Krasil’nikov, and A. N. Band
Institute of Chemical Technologies, Dal’ East-Ukrainian National University, Rubezhnoe,
Lugansk oblast, Ukraine
Received September 26, 2007
Abstract A new efficient procedure of synthesis of 3,4-dinitrotoluene from 3-nitro-4-aminotoluene was
developed. Oxidation of 3,4-dinitrotoluene with an ozone oxygen mixture to 3,4-dinitrobenzoic acid in
the presence of cobalt(II) acetate was studied.
DOI: 10.1134/S1070427208030348
Along with other isomeric dinitrobenzoic acids,
,4-dinitrobenzoic acid (DNBA) is widely used as
intermediate in synthesis of photosensitive materials
for electrophotography [1, 2], X-ray contrast agents
3, 4], and modifying and vulcanizing agents for
polyurethane plastics [5].
the aromatic ring and at the methyl group:
.
3
.
ArCH + HO ,
(1)
(2)
(3)
2
ArCH3 + O3
ArCH OH + O ,
2
2
[
ozonides,
In common practice, DNBA is synthesized by oxi-
dation of 3,4-dinitrotoluene (DNT) with Cr(VI) com-
pounds or potassium permanganate. Oxidation with
mineral oxidants proceeds under mild conditions;
however, it is characterized by low selectivity and
formation of large amounts of toxic wastes. Addition-
al and important problem in synthesis of DNBA is the
fact that the dinitrotoluenes are obtained as an isomer-
ic mixture from which the desired 3,4 isomer (DNT)
should be isolated.
where Ar is C H (NO ) .
6
3
2 2
Among the aromatic products, we identified 3,4-di-
nitrobenzaldehyde (DNBAld) and traces of 3,4-dini-
trobenzyl alcohol (DNBAlc) in the initial period of
the reaction and DNBA in deeper stages (Fig. 1).
The yield of products formed by oxidation of the
methyl group in DNT is 38%.
The selectivity of oxidation at the methyl group in-
creases on adding variable-valence metal salts [7, 8].
2
c
10 , M
With the aim to develop a new procedure of syn-
thesis of DNBA, we studied the synthesis of DNT
from 3-nitro-4-aminotoluene (NAT) and the liquid-
phase oxidation of DNT with ozone oxygen mixture
in glacial acetic acid.
For the synthesis of DNT we developed a proce-
dure based on the known procedure of synthesis of
2-dinitrobenzene from 2-nitroaniline [6]. This proce-
dure involves diazotization of NAT with subsequent
substitution of nitro group for diazo group. The yield
of DNT is 92%.
, h
Fig. 1. Content of components of the reaction mixture as
a function of time in oxidation of DNT with ozone oxygen
Considering drawbacks of mineral oxidants, oxida-
tion of DNT with ozone is of practical interest. At
3
1
mixture. W = 8.3 10 l s ; [ArCH ] = 0.125, [O ] =
O
3 0
3 0
2
4
9
.5 10 M; T = 30 C. (c) Concentration and ( ) time;
the same for Fig. 2. (1) DNT, (2) DNBA, (3) DNBAld, and
(4) peroxides.
3
0 C and atmospheric pressure, ozone reacts with
DNT by two competing pathways, at double bonds of
503

504
ANDREEV et al.
Effect of catalyst on the selectivity of oxidation of methylbenzenes at 100 C. [ArCH ] = 0.50, [M(OAc) ] = 0.14,
3
0
2 0
4
[
O ] = 4.0 10
M
3
0
Maximum yield of acid, %
4-nitrobenzoic [13]
2
98
n
n+1
Catalyst
E
M /M , V
11]
p
[
benzoic [12]
3,4-dinitrobenzoic
Co(OAc)2
Mn(OAc)2
Pd(OAc)2
Cr(OAc)3
1.810
1.510
0.987
0.740
72.2
31.8
22.4
18.6
95.6
36.4
31.2
27.9
97.6
62.8
52.4
48.2
According to published data, the selective oxidation of
methylbenzenes depends on the redox potential of the
catalyst [9, 10]. As seem from the table, cobalt and
manganese compounds have the highest potential and
these compounds are the most efficient catalysts of
ozonation of methylbenzenes in acetic acid solutions.
which further participates in initiation of selective
oxidation of the substrate at the methyl group:
.
ArCH3 + Co3+
ArCH + Co2+ + H+.
(5)
2
Thus, we developed a new efficient procedure for
preparing DNT from 3-nitro-4-aminotoluene. Oxida-
tion of DNT with ozone in the presence of cobalt(II)
acetate gives DNBA with an overall yield of 89%.
The kinetic data for oxidation of DNT with ozone
oxygen mixture in the presence of cobalt(II) acetate at
1
00 C are presented in Fig. 2. The main product of
oxidation at the methyl group is DNBA with a yield
of 97%. DNBAld and traces of DNBAlc were also
found as intermediates. In the system, the equilibrium
between the oxidized and reduced cobalt species, in
which cobalt occurs predominantly in the form of
EXPERIMENTAL
3,4-Dinitrotoluene. 3-Nitro-4-aminotoluene of
chemically pure grade (5 g) was dissolved in 30 ml
of 60% sulfuric acid with heating. A 100-ml three-
necked round-bottomed flask was charged with 20 ml
of water and 10 g of ice, and a sulfuric acid solution
of NAT was added with vigorous stirring. To the
3+
Co throughout the process, is reached in the first
1
0 20 min.
It follows from the above facts that, in the presence
of cobalt(II) acetate, DNT is oxidized in two stages:
ozone predominantly reacts with Co2+ to form Co3+:
resulting mixture, 4 g of NaNO in 15 ml of water
2
was quickly added with vigorous stirring, and the
mixture was stirred for 20 min.
Co2+ + O3 + H+
Co3+ + HO + O ,
.
(4)
2
The resulting solution of diazonium salt was placed
into an ice bath. Then, a solution of 50 g of NaNO2,
2
c
10 , M
2
0 g of NaHCO , and 3 g of CuNO in 500 ml of
3 2
water was prepared in a 1-l three-necked round-bot-
tomed flask. To the resulting solution, a solution of
diazonium salt was added with vigorous stirring in
portions through a glass tube touching the flask
bottom. The solution temperature was maintained
within 10 20 C. Addition of the diazonium salt was
accompanied by active foaming. Ten minutes after
adding the whole amount of the mixture, the precipi-
tate was filtered off, washed with water, and dried
in air.
Oxidation of DNT was performed in a reactor
presenting a glass column with a finely porous mem-
brane for dispersion of the gas mixture. The reactor
was charged with 15 ml of glacial acetic acid and cal-
culated amount of DNT; then, the reactor was thermo-
stated and ozone oxygen mixture was fed at a flow
,
h
Fig. 2. Oxidation of DNT with ozone in the presence of
cobalt(II) acetate in acetic acid solution. W = 8.3
O
2
3
1
4
1
[
(
0
l s
;
[ArCH ]
=
0.25, [O ]
= 6.70 10 ,
Co(AcO) ] = 0.14 M; T = 100 C. (1) DNT, (2) DNBA,
3
0
3 0
2
0
3
+
3) DNBAld, and (4) Co
.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 81 No. 3 2008

A NEW PROCEDURE FOR PREPARING 3,4-DINITROBENZOIC ACID
1
505
rate of 8.3 10 1 l s . The amount of the initial DNT
2. US Patent 4302521.
and oxidation intermediates in the mixture was deter-
mined by gas liquid chromatography on an LKhM-80
chromatograph equipped with a flame-ionization
detector on a 2 m 3 mm column packed with Chro-
maton N-AW support with the applied PNFS-6 sta-
tionary phase. The concentration of DNBA formed
was determined by titration with 0.01 N NaOH solu-
tion on an EV-74 pH meter.
3. Kunisaburo, T. and Kimie, Y., J. Chem. Soc. Jpn.,
1964, vol. 85, no. 1, pp. 5 6.
4. Polish Patent 233328.
5. US Patent 4346014.
6
. Weygand-Hilgetag, Organisch-Chemische Experi-
mentierkunst, Leipzig: Johann Ambrosius Barth, 1964.
7
. Yakobi, V.A., Reaktsionnaya sposobnost’ organi-
cheskikh soedinenii (Reactivity of Organic Com-
pounds), Moscow: Mosk. Khim.-Tekhnol. Inst., 1978,
issue 103, pp. 66 92.
CONCLUSIONS
8
9
. Yakobi, V.A., Plakidin, V.L., Pokhila, S.E., et al.,
Zh. Obshch. Khim., 1963, vol. 33, pp. 3369 3373.
. Galstyan, T.M., Galstyan, G.A., and Yakobi, V.A., in
Trudy II Vsesoyuznoi konferentsii Ozon, poluchenie i
primenenie (Proc. 2nd All-Union. Conf. Ozone,
Synthesis and Applications ), Moscow: Mosk. Gos.
Univ., 1991. p. 73.
(1) 3,4-Dinitrotoluene was synthesized in 92%
yield by diazotization of 3-amino-4-nitrotoluene with
subsequent substitution of the nitro group for diazo
group.
(2) In ozonation of 3,4-dinitrotoluene in acetic
1
1
0. Nakamura, A. and Tsutsui, M., Principles and Ap-
plications of Homogeneous Catalysis, New York:
Wiley, 1980.
acid at 30 C, the yield of 3,4-dinitrobenzoic acid does
not exceed 38%; the use of cobalt(II) acetate as a
catalyst increases the yield of 3,4-dinitrobenzoic acid
to 97%.
1. Lur’e, Yu.Yu., Spravochnik po analiticheskoi khimii
(
Handbook of Analytical Chemistry), Moscow: Khi-
miya, 1967.
12. Pluzhnik, I.M. and Galstyan, G.A., Neftekhimiya,
999, vol. 39, no. 2, pp. 120 123.
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. Lebedev, B.A., Dolmatov, V.Yu., Zubarev, P.S.,
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RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 81 No. 3 2008