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Sapozhnikov et al.
1H NMR (DMSOꢀd6), δ: 7.79—7.74 (m, 2 H, C6H2(NO2)2);
7.62—7.56 (m, 2 H, Ph); 7.47—7.32 (m, 3 H, Ph); 7.13, 6.82
(both d, 1 H each, =CH, 3Jtrans = 16.3 Hz); 6.44 (s, 2 H, NH2).
MS, m/z: 285 [M]+.
lated (%): C, 63.15; H, 4.18; N, 19.38. 1H NMR (DMSOꢀd6), δ:
12.83 (s, 1 H, NH); 8.52, 8.18 (both s, 1 H each, C6H2(NO2));
8.02—7.96 (m, 2 H, Ph); 7.60—7.42 (m, 3 H, Ph); 6.97 (s, 1 H,
CH); 2.72, 2.50 (both s, 3 H each, Me). MS, m/z: 361 [M]+.
4ꢀ(4ꢀAcetylꢀ5ꢀmethylꢀ1Hꢀ1,2,3ꢀtriazolꢀ1ꢀyl)ꢀ2ꢀ(4ꢀchloroꢀ
phenyl)ꢀ6ꢀnitroꢀ1Hꢀindole (6b). The yield was 68%, m.p.
217—219 °C. Found (%): C, 57.43; H, 3.64; Cl, 9.11; N, 17.52.
C19H14ClN5O3. Calculated (%): C, 57.66; H, 3.57; Cl, 8.96;
2ꢀAminoꢀ4´ꢀchloroꢀ4,6ꢀdinitrostilbene (7b). The yield
was 73%, m.p. 140—141 °C. Found (%): C, 52.69; H, 2.86;
Cl, 10.84; N, 12.93. C14H10ClN3O4. Calculated (%): C, 52.60;
H, 3.15; Cl, 11.09; N, 13.14. 1H NMR (DMSOꢀd6), δ:
3
1
7.79—7.76 (m, 2 H, C6H2(NO2)2); 7.64 (d, 2 H, C6H4Cl, J =
N, 17.69. H NMR (DMSOꢀd6), δ: 12.90 (s, 1 H, NH); 8.51,
6.9 Hz); 7.47 (d, 2 H, C6H4Cl, 3J = 6.7 Hz); 7.14 (d, 1 H, CH,
8.17 (both s, 1 H each, C6H2(NO2)); 8.03, 7.62 (both d, 2 H each,
3
3
3Jtrans = 16.2 Hz); 6.79 (d, 1 H, CH, Jtrans = 16.3 Hz); 6.46 (s,
C6H4Cl, J = 6.7 Hz); 7.01 (s, 1 H, CH); 2.72, 2.50 (both s,
2 H, NH2). MS, m/z: 319 [M]+.
3 H each, Me). MS, m/z: 395 [M]+.
2ꢀAminoꢀ4´ꢀmethoxyꢀ4,6ꢀdinitrostilbene (7c). The yield
was 83%, m.p. 129—131 °C. Found (%): C, 56.88; H, 4.36;
N, 13.07. C15H13N3O5. Calculated (%): C, 57.14; H, 4.16;
N, 13.33. 1H NMR (DMSOꢀd6), δ: 7.78—7.74 (m, 2 H,
C6H2(NO2)2); 7.55 (d, 2 H, C6H4OMe, 3J = 6.9 Hz); 7.02—6.90
(m, 3 H, C6H4OMe + CH); 6.7 (d, 1 H, CH, 3Jtrans = 16.7 Hz);
6.37 (s, 2 H, NH2); 3.79 (s, 3 H, OMe). MS, m/z: 315 [M]+.
6ꢀ(4ꢀAcetylꢀ5ꢀmethylꢀ1Hꢀ1,2,3ꢀtriazolꢀ1ꢀyl)ꢀ2ꢀazidoꢀ4ꢀ
nitrostilbenes 5 (general procedure). Sodium azide (0.31 g,
4.8 mmol) was added to a stirred solution of compound 4
(4 mmol) in DMF (20 mL). The reaction mixture was stirred at
room temperature for 4 h (TLC) and then poured into cold
water. The precipitate that formed was filtered off and recrystalꢀ
lized from MeCN.
6ꢀ(4ꢀAcetylꢀ5ꢀmethylꢀ1Hꢀ1,2,3ꢀtriazolꢀ1ꢀyl)ꢀ2ꢀazidoꢀ4ꢀ
nitrostilbene (5a). The yield was 60%, m.p. 165—167 °C
(decomp.). Found (%): C, 58.42; H, 3.60; N, 24.61.
C19H15N7O3. Calculated (%): C, 58.61; H, 3.88; N, 25.18.
1H NMR (DMSOꢀd6), δ: 8.39, 8.32 (both s, 1 H each,
C6H2(NO2)2); 7.41—7.30 (m, 5 H, Ph); 6.79—7.76 (m, 2 H,
CH=CH); 2.63, 2.37 (both s, 3 H each, Me). MS, m/z:
361 [M]+ – N2.
4ꢀ(4ꢀAcetylꢀ5ꢀmethylꢀ1Hꢀ1,2,3ꢀtriazolꢀ1ꢀyl)ꢀ2ꢀ(4ꢀmethoxyꢀ
phenyl)ꢀ6ꢀnitroꢀ1Hꢀindole (6c). The yield was 83%, m.p.
137—139 °C. Found (%): C, 61.12; H, 4.50; N, 17.81.
C20H17N5O4. Calculated (%): C, 61.38; H, 4.38; N, 17.89.
1H NMR (DMSOꢀd6), δ: 12.73 (s, 1 H, NH); 8.48, 8.11 (both s,
1 H each, C6H2(NO2)); 7.93, 7.11 (both d, 2 H each, C6H4OMe,
3J = 6.7 Hz); 6.82 (s, 1 H, CH); 3.83 (s, 3 H, OMe); 2.70, 2.50
(both s, 3 H each, Me). MS, m/z: 391 [M]+.
References
1. V. A. Tartakovsky, S. A. Shevelev, M. D. Dutov, A. Kh.
Shakhnes, A. L. Rusanov, L. G. Komarova, and A. M.
Andrievsky, in Conversion Concepts for Commercial Appliꢀ
cations and Disposal Technologies of Energetic Systems,
Ed. H. Krause, Kluwer Academic Publishers, Dordrecht,
1997, p. 137.
2. S. A. Shevelev, V. A. Tartakovsky, and A. L. Rusanov, in
Combustion of Energetic Materials, Eds K. K. Kuo and L. T.
deLuca, Begell House, Inc., New York, 2002, p. 62.
3. V. V. Rozhkov, A. M. Kuvshinov, V. I. Gulevskaya, I. I.
Chervin, and S. A. Shevelev, Synthesis, 1999, 2065.
4. O. Yu. Sapozhnikov, V. V. Mezhnev, M. D. Dutov, V. V.
Kachala, and S. A. Shevelev, Mendeleev Commun., 2004, 27.
5. O. Yu. Sapozhnikov, V. V. Mezhnev, M. D. Dutov, V. V.
Kachala, N. A. Popov, and S. A. Shevelev, Izv. Akad. Nauk,
Ser. Khim., 2005, 698 [Russ. Chem. Bull., Int. Ed., 2005,
54, 711].
6. O. Yu. Sapozhnikov, M. D. Dutov, M. A. Korolev, V. V.
Kachala, and S. A. Shevelev, Mendeleev Commun., 2001, 232.
7. O. Yu. Sapozhnikov, M. D. Dutov, V. V. Kachala, and S. A.
Shevelev, Mendeleev Commun., 2002, 231.
8. O. Yu. Sapozhnikov, M. D. Dutov, M. A. Korolev, V. V.
Kachala, V. I. Kadentsev, and S. A. Shevelev, Izv. Akad.
Nauk, Ser. Khim., 2004, 561 [Russ. Chem. Bull., Int. Ed.,
2004, 53, 588].
6ꢀ(4ꢀAcetylꢀ5ꢀmethylꢀ1Hꢀ1,2,3ꢀtriazolꢀ1ꢀyl)ꢀ2ꢀazidoꢀ
4´ꢀchloroꢀ4ꢀnitrostilbene (5b). The yield was 66%, m.p.
101—103 °C. Found (%): C, 53.81; H, 3.03; Cl, 7.96; N, 22.84.
C19H14ClN7O3. Calculated (%): C, 53.85; H, 3.33; Cl, 8.37;
N, 23.13. 1H NMR (DMSOꢀd6), δ: 8.40, 8.31 (both s, 1 H each,
C6H2(NO2)2); 7.40—7.34 (m, 2 H, C6H4Cl); 6.73—7.69 (m,
2 H, CH=CH); 2.67, 2.38 (both s, 3 H each, Me). MS, m/z:
395 [M]+ – N2.
6ꢀ(4ꢀAcetylꢀ5ꢀmethylꢀ1Hꢀ1,2,3ꢀtriazolꢀ1ꢀyl)ꢀ2ꢀazidoꢀ
4´ꢀmethoxyꢀ4ꢀnitrostilbene (5c). The yield was 81%, m.p.
190—193 °C (decomp.). Found (%): C, 57.20; H, 3.89; N, 23.50.
C20H17N7O4. Calculated (%): C, 57.28; H, 4.09; N, 23.38.
1H NMR (DMSOꢀd6), δ: 8.35, 8.29 (both s, 1 H each,
3
C6H2(NO2)2); 7.29, 6.93 (both d, 2 H each, C6H4OMe, J =
3
7.0 Hz); 6.65, 6.52 (both d, 1 H each, =CH, Jtrans = 16.4 Hz);
9. A. Padwa, 1,3ꢀDipolar Cycloaddition Chemistry, J. Wiley and
Sons, New York, Vol. 1, 1984.
10. M. Regitz and G. Maas, Diazo Compounds. Properties and
Synthesis, Academic Press, Orlando, 1986.
11. E. Yu. Gudriniutse and V. V. Sokolova, Izv. Akad. Nauk
Latv. SSR, Ser. Khim., 1972, 81.
12. V. V. Sokolova and E. Yu. Gudriniutse, Khim. Geterotsikl.
Soedin., 1973, 256 [Chem. Heterocycl. Compd., 1973 (Engl.
Transl.)].
3.77 (s, 3 H, OMe); 2.68, 2.32 (both s, 3 H each, Me). MS, m/z:
391 [M]+ – N2.
4ꢀ(4ꢀAcetylꢀ5ꢀmethylꢀ1Hꢀ1,2,3ꢀtriazolꢀ1ꢀyl)ꢀ2ꢀarylꢀ6ꢀnitroꢀ
1Hꢀindoles 6 (general procedure). A stirred suspension of azide 5
(0.5 g) in ethylene glycol (30 mL) was heated to 160—180 °C
and kept at this temperature until nitrogen ceased to evolve
(~30 min). The mixture was poured into ice and the precipitate
that formed was filtered off and recrystallized from MeCN.
4ꢀ(4ꢀAcetylꢀ5ꢀmethylꢀ1Hꢀ1,2,3ꢀtriazolꢀ1ꢀyl)ꢀ6ꢀnitroꢀ2ꢀpheꢀ
nylꢀ1Hꢀindole (6a). The yield was 73%, m.p. 295—297 °C.
Found (%): C, 62.87; H, 3.92; N, 19.02. C19H15N5O3. Calcuꢀ
Received April 18, 2005