Jean’ne M. Shreeve et al.
3,6-Dinitropyrazolo
G
was added. The reaction mixtures were stirred with heating (508C) for
6 h and then cooled to room temperature. The resulting precipitate was
collected by filtration and washed with methanol to give solid products in
good yield.
With 7 in hand, intermediates 8, 9, and 10 were prepared according to lit-
erature procedures.[27] The synthesis of 4 was accomplished using a slightly
modified method. To cooled 100% nitric acid (9 mL, 0~58C), 10 (1.47 g,
7.5 mmol) was added in portions with stirring over a period of 10 min.
The mixture was stirred at 0–58C for 30 min and then at 658C for 12 h.
Subsequently, the reaction mixture was poured onto ice, the precipitate
was filtered, washed with cold water, and air dried to yield 4 (1.21 g,
82%) as an ivory solid; Tdec (onset): 3368C; IR (KBr): n˜ =3267, 1548,
Diguanidinium 3,6-dinitropyrazoloACTHNUTRGNEUNG[4,3-c]pyrazolate (16)
Orange red solid; Tm: 3188C; Tdec (onset): 3248C; IR (KBr): n˜ =3456,
1658,1459, 1412, 1365, 1219, 1089 cmꢀ1; 1H NMR: d=7.47 (s, 8H, NH2),
5.44 ppm (s, 12H, NH2); 13C NMR: d=158.37, 143.60, 141.36 ppm; ele-
mental anal. calcd (%) for C6H12N12O4 (316.24): C 22.79, H 3.82, N 53.15;
found: C 23.34, H 3.79, N 52.60.
1522, 1430, 1369, 1349, 1244, 1146, 1036, 835, 656, 480 cmꢀ1 1H NMR:
;
d=15.06 ppm (s, 2H, N H); 13C NMR ([D6]acetone): d=139.28,
132.70 ppm; elemental anal. calcd (%) for C4H2N6O4 (198.10): C 24.25, H
1.02, N 42.42; found: C 24.17, H 1.07, N 41.96.
Di(aminoguanidinium) 3,6-dinitropyrazoloACHTUNGRTEN[NUNG 4,3-c]pyrazolate (17)
Orange-yellow solid; Tm: 2138C; Tdec (onset): 2228C; IR (KBr): n˜ =3343,
3263, 1690, 1656, 1454, 1419, 1353, 1208, 1071, 820 cmꢀ1 1H NMR: d=
;
General Procedure for the Synthesis of Salts 11–15
8.60 (s, 2H, NH), 7.75 ppm (s, 12H, NH2); 13C NMR: d=159.01, 143.23,
141.24 ppm; elemental anal. calcd (%) for C6H14N14O4 (346.27): C 20.81,
H 4.08, N 56.63; found: C 20.97, H 3.98, N 55.97.
3,6-DinitropyrazoloACHTUNGTRENNUNG[4,3-c]pyrazole (0.20 g, 1 mmol) was suspended in
methanol (3 mL) and water (0.5 mL). Next, aqueous ammonia (0.14 g,
2.1 mmol), hydrazine monohydrate (0.105 g, 2.1 mmol), hydroxylamine
(0.139 g, 50 wt% in water, 2.1 mmol), 3,5-diaminotriazole (0.208 g,
2.1 mmol) or 3,4,5-triaminotriazole (0.239 g, 2.1 mmol) was added. The
reaction mixtures were stirred with heating (508C) for 6 h and then
cooled to room temperature. The resulting precipitate was collected by
filtration and washed with methanol to give solid products in good yield.
Di(diaminoguanidinium) 3,6-dinitropyrazoloACHTUGNTREN[NNUG 4,3-c]pyrazolate (18)
Yellow solid; Tdec (onset): 2098C; IR (KBr): n˜ =3337, 3274, 1675, 1456,
1429, 1346, 1215, 1069, 1018, 818 cmꢀ1 1H NMR: d=8.63 (br, s, 4H,
;
NH2+), 7.14 (s, 4H, NH), 4.54 ppm (brs, 8H, NH2); 13C NMR: d=159.92,
143.40, 141.34 ppm; elemental anal. calcd (%) for C6H16N16O4 (376.30): C
19.15, H 4.29, N 59.56; found: C 19.28, H 4.16, N 60.06.
Diammonium 3,6-dinitropyrazolo
Orange solid; Tm: 1608C; Tdec (onset): 3288C; IR (KBr): n˜ =3273, 3235,
Mono-triaminoguanidinium 3,6-dinitropyrazoloACTHNUGRTNEUNG[4,3-c]pyrazolate (19)
1686, 1474, 1401, 1350, 1217, 1074, 822 cmꢀ1 1H NMR: d=6.11 ppm (s,
;
8H, NH4+); 13C NMR: d=141.43, 140.52 ppm; elemental anal. calcd (%)
for C4H8N8O4 (232.16): C 20.69, H 3.47, N 48.27; found: C 20.76, H 3.44,
N 47.70.
Yellow solid; Tm: 2088C; Tdec (onset): 2158C; IR (KBr): n˜ =3345, 1686,
1
1497, 1375, 1343, 1231, 1108, 1036, 823 cmꢀ1; H NMR: d=13.70 (br, 1H,
ring N-H) 8.60 (s, 3H, NH), 4.49 ppm (s, 6H, NH2); 13C NMR: d=
159.08, 139.71, 137.85 ppm; elemental anal. calcd (%) for C5H10N12O4
(302.21): C 19.87, H 3.34, N 55.62; found: C 19.85, H 3.31, N 54.93.
Dihydroxylammonium 3,6-dinitropyrazoloACHTUNGERTN[NUNG 4,3-c]pyrazolate (12)
Orange-yellow solid; Tm: 1748C; Tdec (onset): 3278C; IR (KBr): n˜ =3156,
Mono-2-iminium-5-nitriminooctahydroimidazo [4,5-d]imidazole3,6-
1480, 1439, 1371, 1302, 1242, 1126, 1008, 826 cmꢀ1
;
1H NMR: d=
dinitropyrazoloACHTUNGTREN[NUGN 4,3-c]pyrazolate monohydrate (20)
8.16 ppm (s, 6H, NH3+); 13C NMR: d=139.68, 137.50 ppm; elemental
anal. calcd (%) for C4H8N8O6 (264.16): C 18.19, H 3.05, N 42.42; found:
C 18.56, H 3.03, N 41.62.
Yellowish gray solid; Tdec (onset): 2388C; IR (KBr): n˜ =3343, 1701, 1581,
1466, 1352, 1285, 1257, 1220, 1075, 892, 822 cmꢀ1 1H NMR: d=5.71 ppm
;
(s, 2H); 13C NMR: d=161.11, 160.04, 139.69, 137.93, 72.23 ppm; elemen-
tal anal. calcd (%) for C8H11N13O7 (401.26): C 23.95, H 2.76, N 45.38;
found: C 23.96, H 3.06, N 46.41.
Dihydrazinium 3,6-dinitropyrazolo
ACHTUNGERTN[NUNG 4,3-c]pyrazolate (13)
Yellow solid; Tdec (onset): 2478C; IR (KBr): n˜ =3351, 1470, 1439, 1362,
1297, 1233, 1104, 964, 822 cmꢀ1
;
1H NMR: d=6.10 ppm (s, 10H,
General Procedure for the Synthesis of Metal Salts 21--23
NH2NH3+); 13C NMR: d=141.11, 139.48 ppm; elemental anal. calcd (%)
for C4H10N10O4 (262.19): C 18.32, H 3.84, N 53.42; found: C 18.41, H
3.79, N 52.81.
A solution of 3,6-dinitropyrazoloACTHNUTRGNE[NUG 4,3-c]pyrazole (0.20 g, 1 mmol) in meth-
anol (6 mL) was stirred at room temperature while adding sodium hy-
droxide (0.084 g, 2.1 mmol in 2 mL H2O), potassium hydroxide(0.118 g,
2.1 mmol in 2 mL H2O), or silver nitrate (0.357 g, 2.1 mmol in 5 mL
H2O). The reaction mixtures were stirred for 1 h, and the resulting pre-
cipitate was collected by filtration and washed with methanol to give
solid products in good yield.
Mono-3,5-Diamino-triazolium 3,6-dinitropyrazoloACHTNUGTREN[NUGN 4,3-c]pyrazolate (14)
Light yellow solid; Tdec (onset): 2878C; IR (KBr): n˜ =3447, 3372, 2445,
1832, 1615, 1543, 1414, 1386, 1240, 1145, 1009, 820, 749 cmꢀ1 1H NMR:
;
d=8.20 ppm (br, 6H, NH and NH2); 13C NMR: d=155.27, 138.68,
134.40 ppm; elemental anal. calcd (%) for C6H7N11O4 (297.19): C 24.25,
H 2.37, N 51.84; found: C 24.13, H 2.36, N 51.54.
Disodium 3,6-dinitropyrazoloACHTNUTRGNE[UNG 4,3-c]pyrazolate dihydrate (21)
Orange solid; Tdec (onset): 3958C; IR (KBr): n˜ =3607, 3544, 1650, 1477,
1440, 1355, 1225, 1086, 816, 752 cmꢀ1; elemental anal. calcd (%) for
C4H4N6O6Na2 (278.09): C 17.28, H 1.45, N 30.22; found: C 16.84, H 1.39,
N 29.87.
Di(3,4,5-triamino-triazolium) 3,6-dinitropyrazoloACTHUNGTRENN[GNU 4,3-c]pyrazolate (15)
Orange solid; Tdec (onset): 2898C; IR (KBr): n˜ =3345, 3167,1663, 1449,
1360, 1300, 1234, 1088, 1046, 820 cmꢀ1 1H NMR: d=6.86 (br, 8H, NH2),
;
5.44 ppm (s, 4H, NH2); 13C NMR: d=150.48, 139.67, 137.83 ppm; ele-
mental anal. calcd (%) for C8H14N18O4 (426.31): C 22.54, H 3.31, N 59.14;
found: C 22.70, H 3.30, N 59.68.
Dipotassium 3,6-dinitropyrazoloACHTUNTRGNEUNG[4,3-c]pyrazolate (22)
Orange solid; Tdec (onset): 3658C; IR (KBr): n˜ =1452, 1428, 1369, 1272,
1211, 1080, 824, 752 cmꢀ1; elemental anal. calcd (%) for C4N6O4K2
(274.28): C 17.52, H 0.00, N 30.64; found: C 17.23, H 0.14, N 30.98.
General Procedure for the Synthesis of Salts 16–20
Disilver 3,6-dinitropyrazoloACHTNUTRGNE[NUG 4,3-c]pyrazolate monohydrate (23)
A solution of 3,6-dinitropyrazoloACTHNUTRGNE[NUG 4,3-c]pyrazole (0.20 g, 1 mmol) in meth-
anol (4 mL) was stirred at room temperature while adding dilute sodium
hydroxide solution (5 mL, 0.4n). To this solution, guanidine nitrate
(0.256 g, 2.1 mmol), aminoguanidine monohydrochloride (0.232 g,
2.1 mmol), diaminoguanidine monohydrochloride (0.264 g, 2.1 mmol), tri-
aminoguanidine monohydrochloride (0.155 g, 1.1 mmol) or 2-iminium-5-
nitriminooctahydroimidazo [4,5- d]imidazole chloride (0.245 g, 1.1 mmol)
Orange solid; Tdec (onset): 3278C; IR (KBr): n˜ =3524, 1501, 1466, 1366,
1245, 1111, 827, 745 cmꢀ1; elemental anal. calcd (%) for C4H2N6O5Ag2
(429.83): C 11.18, H 0.47, N 19.55; found: C 10.99, H 0.47, N 19.74.
7
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Chem. Asian J. 2014, 00, 0 – 0
ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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