A. B. Sheremetev et al.
FULL PAPER
241, 121, 96. C9H10N10O·H2O (292.26): calcd. C 36.99, H 4.14, N
47.93; found C 37.07, H 4.19, N 47.85.
N-([1,2,4]Triazolo[4,3-b][1,2,4,5]tetrazin-3-yl)-4-phenylfurazan-3-
amine (5d): Yellow solid, m.p. 240–242 °C. 1H NMR ([D6]DMSO):
δ = 7.54 (br. s, 3 H), 7.84 (d, J = 7.7 Hz, 2 H), 9.60 (s, 1 H), 12.02
(br. s, 1 H) ppm. 13C NMR ([D6]DMSO): δ = 124.3, 128.1, 129.3,
N-[6-(3,5-Dimethyl-1H-pyrazol-1-yl)-1,2,4,5-tetrazin-3-yl]-4-phen-
ylfurazan-3-amine (3d): Red solid, m.p. 197–198 °C. 1H NMR
([D6]DMSO): δ = 2.22 (s, 3 H), 2.41 (s, 3 H), 6.19 (s, 1 H), 7.50
(br. s, 3 H), 7.80 (br. s, 2 H), 11.74 (br. s, 1 H) ppm. 13C NMR
([D6]DMSO): δ = 12.8, 13.2, 109.7, 124.7, 127.6, 129.1, 130.8,
131.0, 136.9, 149.1, 150.0, 150.6, 153.4 ppm. IR (KBr): ν = 3476,
˜
3144, 1592, 1556, 1476, 1380, 1324, 1268, 1228, 1032, 980, 964,
876, 824, 772, 696, 656 cm–1. MS: m/z = 281 [M]+, 251, 136, 124.
C
11H7N9O (281.23): calcd. C 46.98, H 2.51, N 44.82; found C
142.1, 149.5, 150.7, 151.3, 157.9, 160.5 ppm. IR (KBr): ν = 2928,
˜
47.05, H 2.54, N 44.77.
1582, 1483, 1449, 1420, 1262, 1083, 1063, 1047, 1027, 976, 878, 810,
770, 727, 701 cm–1. MS: m/z = 335 [M]+, 305, 121, 96. C15H13N9O
(335.32): calcd. C 53.73, H 3.91, N 37.59; found C 53.81, H 3.95,
N 37.49.
N-([1,2,4]Triazolo[4,3-b][1,2,4,5]tetrazin-3-yl)-4-azidofurazan-3-
amine (5e): Yellow solid, m.p. 194–195 °C (dec.). 1H NMR ([D6]-
DMSO): δ = 9.71 (s, 1 H), 12.29 (br. s, 1 H) ppm. 13C NMR
([D6]DMSO): δ = 137.3, 144.6, 148.6, 150.0, 152.3 ppm. 14N NMR
([D6]DMSO): δ = –149.18 ppm. 15N NMR ([D6]DMSO): δ = 57.56,
30.48, 13.22, 5.84, –37.56, –57.49, –141.32, –142.69, –154.18,
N-[6-(3,5-Dimethyl-1H-pyrazol-1-yl)-1,2,4,5-tetrazin-3-yl]-4-azido-
1
furazan-3-amine (3e): Red solid, m.p. 150–156 °C (dec.). H NMR
([D6]DMSO): δ = 2.25 (s, 3 H), 2.50 (s, 3 H), 6.27 (s, 1 H), 12.00
(br. s, 1 H) ppm. 13C NMR ([D6]DMSO): δ = 13.5, 13.8, 110.4,
142.8, 145.5, 149.8, 152.0, 158.6, 160.3 ppm. 14N NMR ([D6]-
–176.93, –225.88, –300.53 ppm. IR (KBr): ν = 3412, 3216, 3168,
˜
2152, 1604, 1560, 1512, 1416, 1400, 1264, 1232, 1144, 1028, 956,
840, 748, 676 cm–1. MS: m/z = 246 [M]+, 217, 204, 136, 124.
C5H2N12O (246.15): calcd. C 24.40, H 0.82, N 68.28; found C
24.44, H 0.87, N 68.21.
DMSO): δ = –142.7 ppm. IR (KBr): ν = 3516, 3398, 2144, 1600,
˜
1484, 1424, 1288, 1260, 1076, 1024, 988, 972, 952, 832, 812,
760 cm–1. MS: m/z = 300 [M]+, 276, 216, 122, 106, 101, 97, 95.
C9H8N12O·H2O (318.25): calcd. C 33.97, H 3.17, N 52.81; found
C 34.07, H 3.21, N 52.78.
N-([1,2,4]Triazolo[4,3-b][1,2,4,5]tetrazin-3-yl)-4-nitrofurazan-3-
amine (5f): Yellow solid, m.p. 235–236 °C (dec.). 1H NMR ([D6]-
DMSO): δ = 9.81 (s, 1 H) ppm. 13C NMR ([D6]DMSO): δ = 137.3,
145.2, 149.9, 151.5, 154.9 ppm. 14N NMR ([D6]DMSO): δ = –33.26
N-[6-(3,5-Dimethyl-1H-pyrazol-1-yl)-1,2,4,5-tetrazin-3-yl]-4-nitro-
furazan-3-amine (3f): Pink solid, m.p. 188–190 °C. 1H NMR
([D6]DMSO): δ = 2.25 (s, 3 H), 2.52 (s, 3 H), 6.28 (s, 1 H), 12.42
(br. s, 1 H) ppm. 13C NMR ([D6]DMSO): δ = 13.2, 13.5, 110.3,
142.6, 145.5, 151.9, 155.7, 158.4, 159.2 ppm. 14 N NMR
(Δν1/2 = 183 Hz, NO ) ppm. IR (KBr): ν = 3364, 3160, 3144, 1604,
˜
2
1572, 1536, 1452, 1392, 1348, 1324, 1220, 1188, 1148, 1140, 1052,
1028, 988, 960 cm–1. MS: m/z = 250 [M]+, 219, 204, 187, 146, 101.
C5H2N10O3 (250.14): calcd. C 24.01, H 0.81, N 56.00; found C
24.09, H 0.85, N 55.93.
([D ]DMSO): δ = –33.4 (Δν1/2 = 191 Hz, NO ) ppm. IR (KBr): ν
˜
6
2
= 3400–3300, 2928, 1604, 1576, 1540, 1480, 1424, 1372, 1348, 1076,
1052, 1028, 976 cm–1. MS: m/z = 304 [M]+, 257, 241, 163, 121, 106,
95. C9H8N10O3 (304.23): calcd. C 35.53, H 2.65, N 46.04; found C
35.59, H 2.68, N 45.95.
Supporting Information (see footnote on the first page of this arti-
cle): Description of crystal structure of compounds 3e and 5e.
4,4Ј-Azobis{3-[6-(3,5-dimethyl-1H-pyrazol-1-yl)[1,2,4,5]tetrazin-3-
yl]-furazan-3-amine} 3g: Orange solid, m.p. 260–261 °C (m.p. 260–
261 °C[9]).
Acknowledgments
This work was partially supported by the Presidium of the Russian
Academy of Sciences (the program OKhNM-04).
N-([1,2,4]Triazolo[4,3-b][1,2,4,5]tetrazin-3-yl)-4-methylfurazan-3-
amine (5a): Yellow solid, m.p. 237–238 °C. 1H NMR ([D6]DMSO):
δ = 2.46 (s, 3 H), 9.69 (s, 1 H), 12.07 (br. s, 1 H) ppm. 13C NMR
([D6]DMSO): δ = 8.2, 137.1, 147.5, 149.9, 150.1, 152.8 ppm. IR
[1] a) J. H. Boyer, Nitroazoles, VCH, Deerfield Beach, Florida,
1986; b) Organic Energetic Compounds (Ed.: P. L. Marinkas),
Nova Science Publishers, New York, 1996; c) V. A. Ostrovskii,
M. S. Pevzner, T. P. Kofman, M. B. Shcherbinin, I. V. Tselin-
skii, Targets Heterocycl. Syst. 1999, 3, 467–526; d) P. F. Pago-
ria, G. S. Lee, A. R. Mitchell, R. D. Schmidt, Thermochim.
Acta 2002, 384, 187–204; e) B. P. Zhukov (Ed.), Energetic Con-
densed Systems , 2nd ed., Yanus-K, Moscow, 2000 (in Russian);
f) P. Politzer, J. Murray (Eds.), Energetic Materials, Elsevier,
USA, 2003; g) M. B. Talawar, R. Sivabalan, S. N. Asthana, H.
Singh, Fisika Goreniya I Vzryva 2005, 41, 29–45; Combustion,
Explosion, and Shock Waves 2005, 41, 264–277 (in Russian/
Engl. Transl.); h) T. M. Klapotke (Ed.), Structure and Bonding
Vol. 125: High Energy Density Materials, Springer, Berlin,
2007; i) J. P. Agrawal, R. D. Hodgson, Organic Chemistry of
Explosives, John Wiley & Sons, 2007; j) V. F. Zhilin, V. L. Zbar-
sky, N. V. Yudin, Malochuvstvitelnye vzryvchatye veshestva.
RCTU, Moskva, 2008 (in Russian) [Insensitive Explosives,
RCTU, Moscow, 2008]; k) L. Larina, V. Lopyrev, Nitroazoles:
Synthesis Structure and Applications, Springer, Berlin, LLC,
2009; l) L. Turker, S. Varis, Polycyclic Aromat. Compd. 2009,
29, 228–266; m) D. B. Lempert, G. N. Nechiporenko, S. I. Sog-
lasnova, Fizika Goreniya I Vzryva 2009, 45, 58–67; Combustion,
Explosion, and Shock Waves 2009, 45, 160–168 (in Russian/
Engl. Transl.); n) V. I. Pepekin, Khim. Fiz. 2010, 29, 8–17; Russ.
J. Phys. Chem. B 2010, 4, 954–962 (in Russian/Engl. Transl.);
o) V. E. Zarko, Fisika Goreniya I Vzryva 2010, 46, 3–16; Com-
(KBr): ν = 3504, 3384, 3120, 2800, 1616, 1596, 1560, 1500, 1472,
˜
1440, 1388, 1272, 1240, 1156, 1048, 1008, 968, 884, 816, 744,
660 cm–1. MS: m/z = 219 [M]+, 189, 163, 137, 124. C6H5N9O
(219.16): calcd. C 32.88, H 2.30, N 57.52; found C 32.97, H 2.33,
N 57.45.
N-([1,2,4]Triazolo[4,3-b][1,2,4,5]tetrazin-3-yl)-4-methoxyfurazan-3-
amine (5b): Yellow solid, m.p. 231 °C (dec.). 1 H NMR
([D6]DMSO): δ = 4.14 (s, 3 H), 9.71 (s, 1 H), 12.20 (br. s, 1 H) ppm.
13C NMR ([D6]DMSO): δ = 159.9, 152.3, 149.9, 142.4, 137.2,
59.9 ppm. 15N NMR ([D6]DMSO): δ = 57.34, 31.62, 10.38, –16.11,
–38.08, –57.87, –154.75, –176.84, –295.57 ppm. IR (KBr): ν = 3156,
˜
2790, 1610, 1550, 1460, 1405, 1376, 1260, 1212, 1150, 1027, 966,
831, 747, 657 cm–1. C6H5N9O2 (235.16): calcd. C 30.64, H 2.14, N
53.61; found C 30.70, H 2.16, N 53.54.
N-([1,2,4]Triazolo[4,3-b][1,2,4,5]tetrazin-3-yl)-4-aminofurazan-3-
amine (5c): Yellow solid, m.p. 275–278 °C. 1H NMR ([D6]DMSO):
δ = 6.30 (s, 2 H), 9.66 (s, 2 H) ppm. 13C NMR ([D6]DMSO): δ =
137.1, 142.8, 149.9, 151.5, 152.6 ppm. IR (KBr): ν = 3344, 3220,
˜
3124, 2816, 1636, 1608, 1560, 1472, 1440, 1408, 1388, 1344, 1292,
1264, 1232, 1160, 1048, 1020, 968, 836, 744, 660 cm–1. MS: m/z =
220 [M]+, 190, 163, 137, 124. C5H4N10O (220.15): calcd. C 27.28,
H 1.83, N 63.62; found C 27.35, H 1.90, N 63.58.
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