Synthesis of 1,3,5-trinitrosobenzene [2]

Full text of DOI:10.1023/B:RUCB.0000041314.42029.a7

Russian Chemical Bulletin, International Edition, Vol. 53, No. 5, pp. 1133—1134, May, 2004
1133
Synthesis of 1,3,5ꢀtrinitrosobenzene
O. R. Klyuchnikovꢀ and F. G. Khairutdinov
Kazan State Technological University,
68 ul. K. Marksa, 420015 Kazan, Russian Federation.
Eꢀmail: oleg2004@telebit.ru
Mononitrosoarenes are wellꢀknown compounds, diꢀ
nitrosoarenes are significantly less familiar, while triꢀ
nitrosoarenes have not been described at all. This comꢀ
munication reports the synthesis of the first representative
of trinitrosoarenes, namely, 1,3,5ꢀtrinitrosobenzene (1).
This compound was obtained in 30—35% yield by oxidaꢀ
tion of the known cyclohexaneꢀ1,3,5ꢀtrione trioxime (2)
(see Ref. 1) with 30—35% HNO3 in the presence of cataꢀ
lytic amounts (∼0.1%) of nitrogen oxides (Scheme 1).
not oxidized into nitroso compound 1. Oxidation can be
initiated by adding a small amount of NaNO2 as a source
of nitrogen oxides.
The IR spectrum of trinitrosobenzene 1 (Bruker
Vectorꢀ22, KBr pellets) (Fig. 1) shows an intense band at
1272 cm–1 characteristic of transꢀdimeric nitrosoarenes,2
which suggests its structure with transꢀdimerized nitroso
groups. Because of this, compound 1 is relatively stable
and comparable in properties with polymeric pꢀdinitrosoꢀ
benzene having a similar transꢀstructure.3,4
The mass spectrum of completely sublimed trinitrosoꢀ
benzene 1 (Finnigan MATꢀ212, EI, 70 eV) shows peaks
with m/z (Irel (%)): 165.1 [M]+ (59), 135 [M – NO]+
(42), 105.1 [M – NO – NO]+ (8), and 75.1 [M – NO –
NO – NO]+ (100).
Scheme 1
Fragmentation of the molecular ion of compound 1
occurs with the loss of three NO groups, which is characꢀ
teristic of nitrosoarenes2 (Scheme 2).
As expected, the oxidation of trinitrosobenzene 1 yields
1,3,5ꢀtrinitrobenzene.2 1,3,5ꢀTrinitrobenzene was also
synthesized by the oxidation of trioxime 2 with 90%
In dilute 30—35% nitric acid free of nitrogen oxides,
trioxime 2 easily dissolves to give a brown solution but is
Transmittance (%)
100
90
80
70
60
50
40
30
20
10
3500
3000
2500
2000
1500
1000
ν/cm–1
Fig. 1. IR spectrum of 1,3,5ꢀtrinitrosobenzene (1).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1087—1088, May, 2004.
1066ꢀ5285/04/5305ꢀ1133 © 2004 Plenum Publishing Corporation

1134
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 5, May, 2004
Klyuchnikov and Khairutdinov
Scheme 2
N, 25.20. C6H3N3O3. Calculated (%): C, 43.65; H, 1.83;
N, 25.45.
1,3,5ꢀTrinitrobenzene. 1,3,5ꢀTrinitrosobenzene (1) (1 g) was
added to 98% HNO3 (20 mL) and the reaction mixture was
heated at 80 °C for 2 to 3 min and then diluted with water
(100 mL). The yield of 1,3,5ꢀtrinitrobenzene was 0.9 g (70%),
m.p. 121—122 °C. The compound obtained is identical with an
authentic sample (IR and 1H NMR spectroscopic and TLC data).
The mechanism of formation of 1,3,5ꢀtrinitrosoꢀ
benzene upon oxidation of cyclohexaneꢀ1,3,5ꢀtrione
trioxime with dilute nitric acid in the presence of nitrogen
oxides calls for a further investigation involving other comꢀ
pounds of this class.
References
1. E. Baeyer, Ber., 1886, 19, 159.
HNO3,5 but no intermediate nitroso compound 1 was
detected or isolated.
Nitroso compound 1 is virtually insoluble in organic
solvents at room temperature. Yet it is soluble at 100 °C in
toluene or xylene, giving an unstable green solution.
1,3,5ꢀTrinitrosobenzene (1). Nitric acid (98%, 16 mL) conꢀ
taining 0.2—0.4% nitrogen oxides was added to ice (50 g) and
then trioxime 2 (1.0 g) was added at 12—15 °C to the vigorously
stirred 35% HNO3 obtained. The light foam of product 1 that
formed almost immediately after dissolution of oxime 2 was
filtered off, washed with water to a neutral reaction and acetone,
and dried. The yield of compound 1 (a light turquoise powder)
was 0.32 g (34%), m.p. 170 °C (decomp.). No resinification of
the reaction mixture was observed. Found (%): C, 43.90; H, 1.65;
2. Comprehensive Organic Chemistry. The Synthesis and Reactions
of Organic Compounds, Eds. D. Barton and W. D. Ollis,
Pergamon Press, Oxford, 1979, 2.
3. N. P. Hacker, Macromolecules, 1993, 26, 5937.
4. O. R. Klyuchnikov, T. V. Makarov, S. I. Vol´fson, Yu. N.
Khakimullin, and R. Ya. Deberdeev, Izv. Vyssh. Uchebn.
Zaved., Khim. Khim. Tekhnol., 2004, 47, No. 2, 22 [Bull. Inst.
Higher Education, Chem. Chem. Technol., 2004, 47 (Engl.
Transl.)].
5. I. C. Bottaro, R. Malhotra, and A. Dodge, Synthesis,
2004, 4, 499.
Received February 3, 2004;
in revised form May 14, 2004