Selective reduction of nitro groups in trinitrobenzene Russ.Chem.Bull., Int.Ed., Vol. 55, No. 5, May, 2006
939
3,5ꢀDinitroaniline (2). A solution of hydrazine hydrate (8 mL,
160 mmol) in methanol (50 mL) was added with cooling and
vigorous stirring to a mixture of TNB (20 g, 93.8 mmol), charꢀ
coal (16 g), and FeCl3•6H2O (0.7 g, 3.5 mmol) in methanol
(220 mL) under nitrogen for 2.5 h, the temperature being mainꢀ
tained at 20—25 °C. Then the temperature was raised to 35 °C,
and the reaction mixture was vigorously stirred at this temperaꢀ
ture for 3.5 h. The charcoal was pressed on a filter and washed
with hot methanol (2×300 mL). The mother liquors were comꢀ
bined and concentrated to ∼150 mL. Water (250 mL) was added
with stirring to the solution, and the mixture was cooled to 5 °C.
The precipitate that formed was pressed on a filter and dried
in vacuo. Yellowꢀgreen crystals were obtained in a yield of 11.75 g
(68.4%), m.p. 161 °C (158—159 °C (see Ref. 14) or 162 °C (see
Ref. 15)), decomposition started at 313 °C. Found (%): C, 39.38;
H, 2.83; N, 22.85. C6H5N3O4. Calculated (%): C, 39.35; H, 2.75;
combined extracts were concentrated to dryness, the residue was
dissolved in methanol (200 mL), and concentrated hydrochloric
acid (100 mL) was added dropwise with cooling (0—5 °C) and
constant stirring. The precipitate was filtered off, washed on a
filter with methanol (2×50 mL), and dried over P2O5. 1,3,5ꢀTriꢀ
aminobenzene trihydrochloride was obtained in a yield of 36.54 g
(60%) as paleꢀcream crystals, decomposition started at 163 °C.
1H NMR (DMSOꢀd6), δ: 6.53 (s, 3 H, H(2), H(4), H(6)); 7.02
(br.s, 9 H, 3NH2•HCl). Found (%): C, 30.5; H, 5.30; Cl, 45.84;
N, 18.36. C6H7N3O2. Calculated (%): C, 30.99; H, 5.20;
Cl, 45.74; N, 18.07.
This study was financially supported by the Internaꢀ
tional Science and Technology Center (Project No. 419).
References
N, 22.95. 1H NMR (CD3CN), δ: 8.05 (d, 1 H, H(4), J4,2
=
2.05 Hz); 7.70 (d, 2 H, H(2), H(6), J2,4 = 2.05 Hz); 5.18 (s, 2 H,
NH2). MS (70 eV), m/z (Irel): 183 [M]+ (100); 137 [M –NO2]+
(35); 107 [M – NO2 – NO ]+ (90).
1. S. A. Shevelev, M. D. Dutov, I. A. Vatsadze, O. V.
Serushkina, A. L. Rusanov, and A. M. Andrievskii, Mendeleev
Commun., 1995, 157.
1,3ꢀDiaminoꢀ5ꢀnitrobenzene (2). Reduction was performed
as described above for 3,5ꢀdinitroaniline. A solution of TNB
(30 g, 140 mmol), charcoal (16 g), and FeCl3•6H2O (0.96 g,
3.5 mmol) in methanol (300 mL) was used. A solution of hydrꢀ
azine hydrate (24 mL, 500 mmol) in methanol (30 mL) was added
for 10 min, the temperature being maintained at 20—25 °C.
Then the temperature was allowed to spontaneously raise
to 50 °C. The reaction mixture was stirred at this temperature
for 1.5 h and then at 60 °C for 1.5 h. The charcoal was filtered
off and washed with hot methanol (5×100 mL). The combined
mother liquors were concentrated to 100 mL, mixed with an
equal volume of hot water, and cooled to 0—–5 °C. The precipiꢀ
tate that formed was pressed on a filter and dried in vacuo.
1,3ꢀDiaminoꢀ5ꢀnitrobenzene (2) was obtained in a yield of
16.13 g (74%) as darkꢀred crystals, m.p. 140 °C (140—141 °C
(see Ref. 16) or 139—140 °C (see Ref. 10)). Found (%): C, 46.92;
H, 4.51; N, 27.54. C6H7N3O2. Calculated (%): C, 47.06; H, 4.61;
N, 27.44. 1H NMR (DMSOꢀd6), δ: 6.63 (d, 2 H, H(2), H(4),
J6,2 = 1.91 Hz); 6.15 (t, 1 H, H(6), J2,6 = 1.91 Hz); 5.35 (br.s,
4 H, 2 NH2). MS (70 eV), m/z (Irel): 153 [M]+ (100); 108
[M – NO2 + H]+ (12); 107 [M – NO2]+ (86).
1,3,5ꢀTriaminobenzene trihydrochloride (4•3HCl). Reducꢀ
tion was performed as described above for 3,5ꢀdinitroaniline (2).
A solution of trinitrobenzene (56.3 g, 0.264 mol), charcoal (32 g),
and FeCl3•6H2O (1.9 g, 0.7 mmol) in methanol (700 mL) was
used (dissolution was carried out at 50 °C with constant stirꢀ
ring). A solution of hydrazine hydrate (130 mL, 2.64 mol) in
methanol (100 mL) was added at 10—15 °C for 45 min. After the
addition of hydrazine hydrate, the temperature was gradually
raised to 68 °C for 1 h. The reaction mixture was refluxed with
stirring for 12 h and then filtered off from charcoal. The latter
was washed on a filter with hot methanol (2×150 mL). The
2. S. A. Shevelev, M. D. Dutov, I. A. Vatsadze, M. A. Korolev,
and A. L. Rusanov, Mendeleev Commun., 1996, 155.
3. S. A. Shevelev, M. D. Dutov, and O. V. Serushkina, Izv.
Akad. Nauk, Ser. Khim., 1995, 2528 [Russ. Chem. Bull., 1995,
44, 2424 (Engl. Transl.)].
4. S. A. Shevelev, M. D. Dutov, M. A. Korolev, O. Yu.
Sapozhnikov, and A. L. Rusanov, Mendeleev Commun.,
1998, 69.
5. M. A. Korolev, M. D. Dutov, and S. A. Shevelev, Izv. Akad.
Nauk, Ser. Khim., 1999, 1822 [Russ. Chem. Bull., 1999, 48,
1798 (Engl. Transl.)].
6. O. Yu. Sapozhnikov, M. D. Dutov, M. A. Korolev, V. V.
Kachala, and S. A. Shevelev, Mendeleev Commun., 2001, 232.
7. V. V. Rozhkov and S. A. Shevelev, Izv. Akad. Nauk, Ser.
Khim., 2000, 1650 [Russ. Chem. Bull., Int. Ed., 2000,
49, 1640].
8. M. D. Dutov, I. A. Vatsadze, S. S. Vorob´ev, and S. A.
Shevelev, Mendeleev Commun., 2005, 202.
9. O. Temme, T. Dickner, S. Laschat, S. Kolita, and
K. Bergander, Eur. J. Org. Chem., 1998, 4, 651.
10. US Pat. 2768209; Chem. Abstr., 1957, 51, 5832a.
11. B. Flurscheim, J. Prakt. Chem., 1905, 71, 505.
12. US Pat. 2461498, Chem. Abstr., 1949, 43, 3456b.
13. T. Hirashima and O. Manable, Chem. Lett., 1975, 259;
J. Chem. Soc. Jpn, Chem. Indust. Chem., 1975, 1223.
14. J. J. Blanksma, Recl. Trav. Chim. PaysꢀBas, 1909, 28, 111.
15. G. Van Duin, Recl. Trav. Chim. PaysꢀBas, 1901, 39, 581.
16. B. Flurscheim, J. Prakt. Chem., 1903, 71, 538.
Received April 18, 2006