Chemistry of 2,4,6-trinitrobenzonitrile
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 12, December, 2001 2405
extracted with ethyl acetate. The organic layer was washed
with water and dried with MgSO4, the solvent was distilled off,
and the solid residue was dried to yield a mixture of sulfones
5a and 5b in a ratio of 1 : 1 (74%). Found (%): C, 48.48;
H, 3.26; N, 12.01; S, 9.45. C14H9N3O6S. Calculated (%):
at 05 °C. The reaction mixture was stirred at this tempera-
ture for 3 h and then poured into water. The precipitate that
formed was filtered off, washed with water, and dried to yield
a mixture of azides 11a and 11b. 1H NMR, δ, 11a: 8.60
(s, H(3)); 8.65 (s, H(5)); 11b: 8.00 (s, H(3), H(5)). IR,
ν/cm1: 1350 (NO2); 1540 (NO2); 2160 (N3); 2246 (CN).
2-Chloro-4,6-dinitrobenzonitrile (12). A solution of TNB
(4.2 mmol) in anhydrous DMF (6 mL) was saturated with
gaseous HCl at 5060 °C with stirring for 1.5 h. The reaction
mixture was kept at 100110 °C for 1 h, cooled, and poured
onto ice. The precipitate that formed was filtered off, washed
with water, and dried to yield chloride 12, m.p. 118120 °C
(propan-2-ol). Found (%): C, 36.74; H, 0.94; N, 18.14;
Cl, 15.38. C7H2N3O4Cl. Calculated (%): C, 36.93; H, 0.88;
N, 18.46; Cl, 15.59. 1H NMR, δ: 8.89 (s, 1 H, H(3)); 9.04 (s,
1 H, H(5)). 13C NMR, δ: 119.2; 129.7; 139.9; 149.5; 150.5.
2,6-Dichloro-4-nitrobenzonitrile (13). A solution of TNB
(4.2 mmol) in anhydrous DMF (6 mL) was saturated with
gaseous HCl at 5070 °C with stirring for 2 h. The reaction
mixture was refluxed for 30 min, cooled, and poured onto ice.
The precipitate that formed was filtered off, washed with water,
and dried to yield dichloride 13, m.p. 145147 °C (EtOH).
Found (%): C, 38.58; H, 1.01; Cl, 32.70. C7H2N2O2Cl2.
Calculated (%): C, 38.71; H, 0.92; Cl, 32.72. 1H NMR, δ:
8.55 (s, 2 H, H(3), H(5)). 13C NMR, δ: 117.7; 123.8; 128.8;
143.7; 155.3.
1
C, 48.41; H, 2.59; N, 12.10; S, 9.22. H NMR, δ, 5a: 5.00
(s, CH2); 7.307.50 (m, Ph); 8.70 (s, H(3)); 9.20 (s, H(5));
5b: 5.00 (s, CH2); 7.307.50 (m, Ph); 8.80 (s, H(3), H(5)).
4-Benzylsulfonyl-2,6-dimethoxybenzonitrile (6). A mixture
of sulfones 5a and 5b (1 : 1) (2.4 mmol) and a 1.5% solution of
MeONa in MeOH (2 mL) was refluxed for 3 h, cooled, poured
into water, and extracted with ethyl acetate. The organic layer
was washed with water and dried with MgSO4. The solvent was
distilled off and an oil was obtained in a yield of 0.7 g. The oil
was passed through a column with silica gel (3263 µm; a 5 : 2
CCl4ethyl acetate mixture was used as the eluent) to yield
compound 6, m.p. 177178 °C (EtOH). Found (%): C, 60.48;
H, 5.24; N, 4.39; S, 9.06. C16H15NO4S. Calculated (%):
C, 60.57; H, 4.73; N, 4.42; S, 10.09. 1H NMR, δ: 3.92 (s, 6 H,
OMe); 4.80 (s, 2 H, CH2); 7.08 (s, 2 H, H(3), H(5)); 7.21 (m,
2 H, Ph); 7.39 (m, 3 H, Ph).
4,6-Dinitro-2-phenylthiobenzonitrile (7a) and 2,6-dinitro-
4-phenylthiobenzonitrile (7b). A. A solution of K2CO3
(7.6 mmol) in water (2 mL) was added to a solution of TNB
(4.2 mmol) and PhSH (4.2 mmol) in DMF (8 mL) at 02 °C.
The reaction mixture was stirred at this temperature for 3 h
and then poured into water. The precipitate that formed was
filtered off, washed with water, and dried to yield a mixture of
sulfides 7a and 7b. 1H NMR, δ, 7a: 7.60 (m, Ph); 8.20
(s, H(3)); 8.70 (s, H(5)); 7b: 7.60 (m, Ph); 7.70 (s, H(3), H(5)).
B. A mixture of TNB (1.26 mmol), PhSH (1.26 mmol),
and K2CO3 (2.4 mmol) in toluene (5 mL) was refluxed for 4 h.
The solvent was distilled off and the solid residue was dried to
yield sulfide 7a, m.p. 152154 °C (propan-2-ol). Found (%):
C, 51.62; H, 2.03; N, 13.85; S, 10.73; C13H7N3O4S. Calcu-
lated (%): C, 51.87; H, 2.32; N, 13.96; S, 10.65. 1H NMR, δ:
7.60 (m, 5 H, Ph); 8.20 (s, 1 H, H(3)); 8.70 (s, 1 H, H(5)).
Methyl 3-amino-4,6-dinitrobenzo[b]thiophene-2-carboxy-
late (9). A solution of KOH (7.5 mmol) in water (2 mL) was
carefully added dropwise with stirring to a solution of TNB
(4.2 mmol) and methyl thioglycolate (4.2 mmol) in MeCN
(10 mL) at 02 °C. The reaction mixture was stirred at 20 °C
for 3 h and then kept without stirring for 20 h. The precipitate
that formed was filtered off, washed several times with MeCN,
and dried to yield compound 9, m.p. 196198 °C (propan-
2-ol). Found (%): C, 40.88; H, 2.62; N, 13.98; S, 11.01;
C10H7N3O6S. Calculated (%): C, 40.40; H, 2.35; N, 14.14;
S, 10.77. 1H NMR, δ: 3.85 (s, 3 H, Me); 6.60 (br.s, 2 H,
NH2); 8.70 (s, 1 H, H(7)); 9.40 (s, 1 H, H(5)).
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 01-03-
32261) and by the International Science and Technol-
ogy Center (ISTC, Grant 419).
References
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Ethyl 3-amino-4,6-dinitrobenzo[b]thiophene-2-carboxylate
(10) was prepared analogously, m.p. 200 °C (propan-2-ol).
Found (%): C, 42.87; H, 3.35; N, 13.23; S, 9.89. C11H9N3O6S.
Calculated (%): C, 42.44; H, 2.89; N, 13.50; S, 10.29.
1H NMR, δ: 1.36 (t, 3 H, Me, J = 4.4 Hz); 4.37 (q, 2 H, CH2,
J = 4.4 Hz); 6.56 (br.s, 2 H, NH2); 8.67 (s, 1 H, H(7)); 9.26
(s, 1 H, H(5)). 13C NMR, δ: 14.2; 61.3; 105.8; 116.9; 124.1;
1
124.9; 125.5; 141.6; 144.9; 145.9; 163.7. IR (KBr), ν/cm
1350 (NO2); 1550 (NO2); 1730 (C=O).
:
2-Azido-4,6-dinitrobenzonitrile (11a) and 4-azido-2,6-
dinitrobenzonitrile (11b). Sodium azide (1.1 mmol) was added
to a solution of TNB (0.84 mmol) in anhydrous DMF (3 mL)
Received March 1, 2001;
in revised form June 14, 2001