K. Muralidharan et al.
General procedure for the catalytic N arylation of substituted azoles with
4,6-dinitro-5-chloro-1H-benzo[1,2,3]triazole (3): A round-bottomed flask
with a magnetic stirrer was charged with CuI (8.0 mg, 0.2 mmol), Cs2CO3
1-(4,6-Dinitro-1H-benzo[d]
2-Amino-1H-tetrazole (0.041 g, 0.00049 mol), 5-chloro-4,6-dinitro-1H-
benzo[1,2,3]triazole (0.100 g, 0.00041 mol), CuI (0.0156 g, 0.00082 mol),
ACHTUNGTREN[NGNU 1,2,3]triazol-5-yl)-1H-tetrazol-5-amine (14):
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
Cs2CO3 (0.267 g, 0.00082 mol), and DMF (3 mL) were subjected to the
general method to give a crude product. The crude product was purified
over a silica gel column with ethyl acetate/hexane to obtain pure com-
pound 14 (0.060 g, 50%). M.p. 1608C; IR (KBr): n˜ =3342 (m), 3080 (m),
2924 (vs), 2854 (vs), 2258 (vs), 1741 (s), 1633 (s), 1548 (vs), 1464 (s), 1342
(vs), 1263 (s), 1224 (s), 1024 (s), 821 (s), 702 cmꢀ1 (s); 1H NMR
(500 MHz, DMSO): d=9.36 (s, 2H), 9.15 ppm (s, 1H); 13C NMR
(101 MHz, DMSO): d=162.75, 146.30, 138.32, 134.85, 128.24, 119.77,
114.02 ppm; LCMS (EI): m/z: 293 [M]+; elemental analysis calcd (%) for
C7H4N10O4 (292.17): C 28.78, H 1.38, N 47.94; found: C 28.61, H 1.41, N
47.85.
(0.422 g, 2.0 mol), substituted azoles (1.4 mmol), 5-chloro-1H-benzo-
ACHTUNGTRENNUNG[1,2,3]triazole (1.0 mmol), and DMF (3 mL) under a nitrogen atmos-
phere. The reaction mixture was stirred at 110–1208C for 24 h, and then
diluted with ethyl acetate (3 mL), filtered through a plug of silica gel,
and washed with ethyl acetate (10–20 mL). The filtrate was concentrated
and the resulting residue was purified by column chromatography on
silica gel to provide the desired product.
4,6-Dinitro-5-(4-nitro-1H-imidazol-1-yl)-1H-benzo[d]
4-Nitroimidazole (0.325 g, 0.0028 mol), 5-chloro-4,6-dinitro-1H-benzo-
[1,2,3]triazole (0.500 g, 0.00205 mol), CuI (0.078 g, 0.00041 mol), Cs2CO3
ACHTUNGERTN[NUNG 1,2,3]triazole (10):
ACHTUNGTRENNUNG
(1.34 g, 0.0041 mol), and DMF (4 mL) were subjected to the general
method to give a crude product. The crude product was purified over a
silica gel column with ethyl acetate/hexane to obtain pure brown color
compound 10 (0.320 g, 48.6%). M.p. 1328C; IR (KBr): n˜ =3483 (m), 3142
(s), 3015 (s), 2881 (s), 2820 (m), 1730 (s), 1631 (s), 1556 (vs), 1493 (s),
1433 (s), 1381 (s), 1334 (s), 1253 (s), 1224 (s), 1086 (s), 989 (s), 945 (s),
866 (s), 817 (s), 787 (s), 758 (s), 698 cmꢀ1 (s); 1H NMR (500 MHz,
DMSO): d=9.14 (s, 1H), 8.21 (s, 1H), 7.77 ppm (s, 1H); 13C NMR
(101 MHz, DMSO): d=147.69, 146.16, 136.25, 134.29, 132.25, 131.99,
121.76, 119.66, 119.37 ppm; LCMS (EI): m/z: 321 [M]+; elemental analy-
sis calcd (%) for C9H4N8O6 (320.02): C 33.76, H 1.26, N 35.00; found: C
33.65, H 1.21, N 35.11.
4,6-Dinitro-5-[(trifluoromethyl)-1H-pyrazol-1-yl]-1H-benzo[d]-
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
(0.0235 g, 0.000123 mol), Cs2CO3 (0.401 g, 0.00123 mol), and DMF
(3 mL) were subjected to the general method to give a crude product.
The crude product was purified over a silica gel column with ethyl ace-
tate/hexane to obtain pure compound 15 (0.110 g, 53%). M.p. 1828C; IR
(KBr): n˜ =3339 (m), 3121 (m), 2926 (vs), 2854 (vs), 2256 (m), 2129 (m),
1739 (s), 1633 (s), 1550 (vs), 1477 (s), 1390 (s), 1342 (s), 1304 (s), 1265
(s), 1143 (s), 1026 (s), 968 (s), 821 (s), 777 (s), 742 cmꢀ1 (s); 1H NMR
(500 MHz, DMSO): d=9.17 (s, 1H), 8.56 (d, J=2 Hz, 1H), 7.13 ppm (d,
J=3 Hz, 1H); 19F NMR (500 MHz, DMSO): d=ꢀ60.850 ppm; 13C NMR
(101 MHz, DMSO): d=162.86, 144.60, 144.30, 142.98, 137.35, 137.27,
131.90, 122.48, 120.35, 107.12 ppm; LCMS (EI): m/z: 344 [M]+; elemental
analysis calcd (%) for C10H4F3N7O4 (343.17): C 35, H 1.17, N 28.57;
found: C 35.11, H 1.23, N 28.5.
4,6-Dinitro-5-(4-nitro-1H-pyrazole-1-yl)-1H-benzo[d]
4-Nitropyrazole (0.142 g, 0.0012 mol), 5-chloro-4,6-dinitro-1H-benzo-
[1,2,3]triazole (0.235 g, 0.00096 mol), CuI (0.0368 g, 0.000193 mol),
ACHTUNGERTN[NUNG 1,2,3]triazole (11):
ACHTUNGTRENNUNG
Cs2CO3 (0.630 g, 0.00193 mol), and DMF (4 mL) were subjected to the
general method to give a crude product. The crude product was purified
over a silica gel column with ethyl acetate/hexane to obtain pure com-
pound 11 (0.180 g, 58%). M.p. 1688C; IR (KBr): 3130 (vs), 2934 (s), 2405
(m), 1984 (m), 1880 (m), 1643 (vs), 1548 (vs), 1518 (s), 1404 (s), 1385 (s),
1342 (s), 1282 (s), 1215 (s), 1109 (vs), 1060 (s), 1012 (s), 949 (vs), 873 (s),
815 (s), 787 (s), 748 (s), 704 (s), 669 (s), 590 cmꢀ1 (s); 1H NMR
(500 MHz, CD3OD): d=9.33 (s, 1H), 9.19 (s, 1H), 8.47 ppm (s, 1H);
13C NMR (101 MHz, DMSO): d=143.82, 142.78, 137.76, 137.54, 133.79,
131.36, 130.58, 125.19, 121.46 ppm; LCMS (EI): m/z: 321 [M]+; elemental
analysis calcd (%) for C9H4N8O6 (320.17): C 33.76, H 1.26, N 35.0; found:
C 37.61, H 1.32, N 35.12.
5-[2,4-Bis(trifluoromethyl)-1H-imidazol-1-yl]-4,6-dinitro-1H-benzo[d]-
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
0.00041 mol), CuI (0.0156 g, 0.000082 mol), Cs2CO3 (0.267 g,
0.00082 mol), and DMF (3 mL) were subjected to the general method to
give a crude product. The crude product was purified over a silica gel
column with ethyl acetate/hexane to obtain pure compound 16 (0.090 g,
54%). M.p. 1788C; IR (KBr): n˜ =3412 (m), 2926 (m), 2856 (m), 2590
(m), 2254 (vs), 2127 (s), 1711(m), 1658 (s), 1548 (s), 1348 (s), 1313 (s),
1275 (s), 1026 (m), 825 (s), 763 cmꢀ1 (s); 1H NMR (500 MHz, DMSO):
d=9.17 (s, 1H), 7.96 ppm (s, 1H); 19F NMR (500 MHz, DMSO): d=
ꢀ61.40, ꢀ59.60 ppm; 13C NMR (101 MHz, DMSO): d=170.07, 164.90,
162.77, 138.28, 134.88, 128.27, 124.77, 124.67, 118.90, 114.00 ppm; LCMS
(EI): m/z: 412 [M]+; elemental analysis calcd (%) for C11H3F6N7O4
(411.17): C 32.13, H 0.74, N 23.85; found: C 32.21, H 0.82, N 23.76.
4,6-Dinitro-5-(3-nitro-1H-1,2,4-triazol-1-yl)-1H-benzo[d]
(12): 3-Nitro-1,2,4-triazole (0.112 g, 0.00098 mol), 5-chloro-4,6-dinitro-
1H-benzo[1,2,3]triazole (0.200 g, 0.00082 mol), CuI (0.031 g,
ACHTUNGTREN[NGNU 1,2,3]triazole
ACHTUNGTRENNUNG
0.00016 mol), Cs2CO3 (0.536 g, 0.0016 mol), and DMF (3 mL) were sub-
jected to the general method to give a crude product. The crude product
was purified over a silica gel column with ethyl acetate/hexane to obtain
pure compound 12 (0.180 g, 68%). M.p. 1608C; IR (KBr): n˜ =3402 (s),
2958 (s), 2909 (vs), 2849 (vs), 1742 (m), 1709 (m), 1610 (m), 1545 (vs),
1463 (m), 1342 (s), 1260 (s), 1090 (m), 1019 (s), 882 (s), 794 cmꢀ1 (s);
1H NMR (500 MHz, DMSO): d=9.33 (s, 1H), 8.89 ppm (s, 1H);
13C NMR (101 MHz, DMSO): d=156.03, 150.87, 146.68, 144.58, 133.15,
131.69, 122.11, 121.12 ppm; LCMS (EI): m/z: 322 [M]+; elemental analy-
sis calcd (%) for C8H3N9O6 (321.16): C 29.92, H 0.94, N 39.25, O 29.89;
found: C 29.85, H 1.06, N 39.15.
Acknowledgements
Authors are thankful to Defence Research and Development Organiza-
tion (DRDO) India in the form of a grant to ACRHEM. Authors also
thank the School of Chemistry, University of Hyderabad for providing
experimental and computational facilities.
4,6-Dinitro-5-(1H-tetrazol-1-yl)-1H-benzo[d]
razole (0.0376 g, 0.00053 mol), 5-chloro-4,6-dinitro-1H-benzo-
[1,2,3]triazole (0.100 g, 0.00041 mol), CuI (0.0156 g, 0.000081 mol),
ACHTUNGTNER[NUNG 1,2,3]triazole (13): 1H-Tet-
ACHTUNGTRENNUNG
[1] a) M. von Denffer, T. M. Klapotke, G. Kramer, G. Spiess, J. M.
Welch, G. Heeb, Propellants Explos. Pyrotech. 2005, 30, 191–195;
b) J. Evers, T. M. Klapotke, P. Mayer, G. Oehlinger, J. M. Welch,
Holl, T. M. Klapotke, K. Polborn, J. Stierstorfer, J. J. Weigand,
Wang, Y. F. Wang, W. Zeng, N. Xiao, Y. Wu, Z. Zhou, J. Chen, F. X.
2634; g) H. Gao, Y. Huang, C. Ye, B. Twamley, J. M. Shreeve, Chem.
Cs2CO3 (0.267 g, 0.00082 mol), and DMF (4 mL) were subjected to the
general method to give a crude product. The crude product was purified
over a silica gel column with ethyl acetate/hexane to obtain pure com-
pound 13 (0.060 g, 53%). M.p. 1408C; IR (KBr): n˜ =3402 (m), 2958 (vs),
2920 (vs), 2849 (vs), 1742 (s), 1704 (s), 1550 (vs), 1457 (s), 1347 (s), 1260
(vs), 1095 (m), 1030 (s), 876 (m), 805 (s), 734 (s), 701 cmꢀ1 (s); 1H NMR
(500 MHz, DMSO): d=9.30 (s, 1H), 8.53 ppm (s, 1H); 13C NMR
(101 MHz, DMSO): d=146.36, 138.31, 134.87, 132.28, 121.58, 120.77,
114.03 ppm; LCMS (EI): m/z: 278 [M]+; elemental analysis calcd (%) for
C7H3N9O4 (277.15): C 30.33, H 1.09, N 45.48; found: C 30.18, H 1.16, N
45.56.
15036
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2012, 18, 15031 – 15037