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Journal of Materials Chemistry A
Page 5 of 6
DOI: 10.1039/C7TA00846E
Journal of Materials Chemistry A
COMMUNICATION
(188.10): Calcd C 19.16, H 2.14, N 44.68 %. Found: C 19.36, H 85%. Tm: 151 oC. Td: 153 oC. 1H NMR: δ 13.78 (br), 8.42 (s, 1H),
2.42, N 42.60 %. IS: 3 J. FS: 60 N.
8.16 (s, 2H), 6.05 (s, 2H) ppm. 13C NMR: δ 156.9, 150.7, 141.8,
Hydroxylammonium 6-nitro-pyrazolo[3,4-c]furazanate 5- 139.8, 123.9 ppm. IR (KBr): νꢀ 3589, 3482, 3341, 3222, 1694,
oxide (10): Compound (0.42 g, 2.0 mmol) was dissolved in 2 1653, 1634, 1568, 1534, 1500, 1433, 1391, 1366, 1292, 1208,
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M HCl (20 mL) hydrochloric acid. The solution was stirred for 1183, 1157, 1105, 1074, 981, 949, 860, 841, 821, 799, 734,
30 minutes and extracted with diethyl ether (15 mL × 3).The 669, 595, 546 cm-1. Elemental analysis for C5H8N10O5 (288.18):
organic phase was dried over anhydrous sodium sulfate. After Calcd C 20.84, H 2.80, N 48.60 %. Found: C 20.99, H 2.69, N
removing sodium sulfate, the filtrate was removed by air. The 49.08 %. IS: 18 J. FS: 240 N.
residue was dissolved in acetonitrile (5 mL), and an equivalent 3,7-diamino-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazol-2-ium
6-
amount of 50% aqueous hydroxylamine was added with nitro-pyrazolo[3,4-c]furazanate 5-oxide monohydrate (15)
:
vigorous stirring. The solvent was then removed under brown crystal, yield: 89%. Tm: 105 oC. Td: 164 oC. H NMR: δ
reduced pressure. The crude product was recrystallized from 13.97 (br), 8.79 (s, 1H), 8.56 (s, 2H), 6.24 (s, 2H) ppm. 13C NMR:
acetonitrile and diethyl ether (2 mL: 2mL), 10 (0.22 g, yield: δ 156.9, 152.6, 147.7, 142.2, 139.8, 123.9 ppm. IR (KBr): νꢀ
1
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53%) was obtained as yellow crystals. Td: 152 oC. H NMR: δ 3555, 3402, 3263, 1697, 1655, 1619, 1545, 1529, 1499, 1423,
7.15 (s, 4H) ppm. 13C NMR: δ 157.0, 140.0, 124.0 ppm. IR (KBr): 1394, 1353, 1297, 1160, 1104, 1079, 1003, 980, 969, 821, 733,
νꢀ 3265, 1686, 1650, 1508, 1422, 1391, 1350, 1289, 1185, 669 cm-1. Elemental analysis for C6H8N12O5 (328.21): Calcd C
1160, 1105, 1077, 982, 968, 840, 968, 840, 823, 801, 750, 731, 21.96, H 2.46, N 51.21 %. Found: C 21.78, H 2.32, N 50.88 %. IS:
692, 669, 591 cm-1. Elemental analysis for C3H4N6O5 (204.10): 15 J. FS: 240 N.
Calcd C 17.65, H 1.98, N 41.18 %. Found: C 17.64, H 2.18, N 3,6,7-Triamino-7H-[1,2,4]triazolo[5,1-c][1,2,4]triazol-2-ium 6-
41.19 %. IS: 2 J. FS: 40 N.
nitro-pyrazolo[3,4-c]furazanate 5-oxide (16): light-yellow
o
crystal, yield: 86%. Td: 186 C. H NMR: δ 13.29 (br), 8.18 (s,
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General procedure for preparing 11-16. The potassium salt
(0.50 g, 2.39 mmol) was dissolved in water (30 mL); then silver 2H), 7.21 (s, 2H), 5.75 (s, 2H) ppm. 13C NMR: δ 160.1, 156.9,
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nitrate (0.41 g, 2.39 mmol) was added. The reaction mixture 147.4, 141.1, 139.8, 123.8 ppm. IR (KBr): νꢀ 3394, 3321, 3256,
was stirred for 2 h at room temperature. The silver salt
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was 3177, 1699, 1653, 1617, 1582, 1449, 1433, 1393, 1376, 1323,
1298, 1162, 1104, 1074, 981, 841, 826, 596 cm-1. Elemental
obtained by filtration and washed with water (20 mL); then
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was suspended in water (40 mL), and a equivalent of the analysis for C6H7N13O4 (325.20): Calcd C 22.16, H 2.17, N 55.99
corresponding hydrochloride salt was added. The temperature %. Found: C 22.17, H 2.23, N 55.72 %. IS: 20 J. FS: 360 N.
of the reaction mixture was increased to 60 oC and it was
stirred for 4 h. After removing the insoluble solids, the Acknowledgements
filtration was concentrated to give the final products (11-16).
Aminoguanidinium 6-nitro-pyrazolo[3,4-c]furazanate 5-oxide Financial support of the Office of Naval Research (N00014-16-
o
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(11): yellow crystal, yield: 86%. Td: 163 C. H NMR: δ 8.52 (s, 1-2089), the Defense Threat Reduction Energy (HDTRA 1-15-1-
1H), 7.22 (s, 2H), 6.69 (s, 2H), 4.66 (s, 2H) ppm. 13C NMR: δ 0028), and the M. J. Murdock Charitable Trust (No.
158.7, 156.9, 139.8, 123.8 ppm. IR (KBr): νꢀ 3455, 3407, 3373, 201420:MNL:11/20/2014) for funds supporting the purchase
3227, 1667, 1506, 1438, 1393, 1353, 1296, 1177, 1161, 1072, of a 500 MHz NMR spectrometer is gratefully acknowledged.
979, 942, 821, 799, 729, 671, 593 cm-1. Elemental analysis for
C4H7N9O4 (245.16): Calcd C 19.60, H 2.88, N 51.42 %. Found: C
Notes and references
19.60, H 2.71, N 51.47 %. IS: 12 J. FS: 120 N.
Diaminoguanidinium 6-nitro-pyrazolo[3,4-c]furazanate 5-
1
(a) D. E. Chavez, J. C. Bottaro, M. Petrie and D. A. Parrish,
Angew. Chem. Int. Ed., 2015, 54, 12973; Angew. Chem.,
2015, 127, 13165; (b) J. P. Agrawal and R. D. Hodgson,
Organic Chemistry of Explosives, Wiley, New York, 2007; (c)
T. M. Klapötke, Chemistry of High-Energy Materials, 2nd
English ed., de Gruyter, Berlin (Germany), New York (USA),
2011.
(a) P. Yin, J. Zhang, L. A. Mitchell, D. A. Parrish and J. M.
Shreeve, Angew. Chem. Int. Ed., 2016, 55, 12895; Angew.
Chem., 2016, 128, 13087; (b) P. Yin, J. Zhang, D. A. Parrish,
o
o
1
oxide (12): yellow solid, yield: 88%. Tm: 106 C. Td: 131 C. H
NMR: δ 8.52 (s, 2H), 7.12 (s, 2H), 4.57 (s, 4H) ppm. 13C NMR: δ
159.7, 156.9, 139.8, 123.8 ppm. IR (KBr): νꢀ 3449, 3383, 3307,
1678, 1642, 1590, 1501, 1424, 1389, 1348, 1283, 1178, 1151,
1102, 1078, 1043, 980, 968, 925, 846, 823, 800, 729, 669, 594
cm-1. Elemental analysis for C4H8N10O4 (260.17): Calcd C 18.47,
H 3.10, N 53.84 %. Found: C 18.45, H 2.95, N 53.94 %. IS: 10 J.
FS: 120 N.
2
and J. M. Shreeve, J. Mater. Chem. A, 2015,
(a) J. Zhang, D. A. Parrish and J. M. Shreeve, Chem. Asian J.,
2014, , 2953; (b) Y. Li, Y. Shu, B. Wang, S. Zhang and L. Zhai,
RSC Adv., 2016, , 84760.
3, 8606.
Triaminoguanidinium 6-nitro-pyrazolo[3,4-c]furazanate 5-
3
4
o
o
1
oxide (13): yellow solid, yield: 87%. Tm: 119 C. Td: 141 C. H
NMR: δ 8.58 (s, 3H), 4.48 (s, 6H) ppm. 13C NMR: δ 159.0, 156.9,
139.8, 123.8 ppm. IR (KBr): νꢀ 3360, 3319, 3212, 1684, 1530,
1500, 1432, 1396, 1364, 1293, 1180, 1160, 1132, 1103, 1065,
978, 965, 845, 823, 803, 731, 669, 638, 591 cm-1. Elemental
analysis for C4H9N11O4 (275.19): Calcd C 17.46, H 3.30, N 55.99
%. Found: C 17.46, H 3.11, N 56.05 %. IS: 15 J. FS: 240 N.
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(a) A. B. Sheremetev, V. L. Korolev, A. A. Potemkin, N. S.
Aleksandrova, N. V. Palysaeva, T. H. Hoang, V. P. Sinditskii
and K. Y. Suponitsky, Asian J. Org. Chem., 2016, 5, 1388; (b)
G. K. Khisamutdinov, V. L. Korolev, T. N. Parkhomenko, V. M.
Sharonova, E. S. Artem'eva, I. S. Abdrakhmanov, S. P.
Smirnov and B. I. Ugrak, Russ. Chem. Bull., 1993, 42, 1700.
(a) V. Thottempudi, P. Yin, J. Zhang, D. A. Parrish and J. M.
Shreeve, Chem. -Eur. J., 2014, 20, 542; (b) I. B. Starchenkov,
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3,4-Diamino-1,2,4-triazolinium
6-nitro-pyrazolo[3,4-
c]furazanate 5-oxide monohydrate (14): yellow crystal, yield:
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J. Name., 2013, 00, 1-3 | 5
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