J. M. Shreeve et al.
solvent was evaporated in vacuo, the residue was washed twice with Et
5 mL), and then recrystallized from EtOH/Et O.
Hydrazinium 4-amino-3-(5-tetrazolate)furazan (2): Colorless solid, yield:
2
O
(s), 1586 (m), 1504 (m), 1447 (w), 1432 (w), 1354 (m), 1246 (w), 1207 (w),
1190 (vw), 1153 (s), 1113 (w), 1007 (s), 984 (s), 908 (w), 878 (w), 735
(
2
ꢀ
1
(
vw), 680 (vw), 580 (w), 542 (w), 501 cm (w); elemental analysis calcd
1
13
(%) for C H N O (243.19): C 19.76, H 3.73, N 63.36; found: C 19.78, H
0.15 g (81%). H NMR: d=6.52 ppm (s); C NMR: d=155.9, 151.0,
140.2 ppm; IR: n˜ =3429 (w), 3327 (vw), 3167 (vw), 2704 (vw), 2599 (vw),
2214 (vw), 2150 (w), 1954 (w), 1784 (vw), 1633 (s), 1605 (s), 1568 (s),
1508 (m), 1427 (m), 1364 (s), 1242 (w), 1213 (w), 1153 (s), 1109 (s), 1034
4
9
11
2
3
.66, N 62.55.
1-Methylimidazolium 4-amino-3-(5-tetrazolate)furazan (10): 1-Methylimi-
dazole (0.246 g, 3.0 mmol) was added to a stirring solution of 4-amino-3-
(5-tetrazole) furazan (0.306 g, 2.0 mmol) in MeOH (30 mL) and the re-
sulting solution was stirred at 608C for 24 h. After removal of the solvent
(
5
w), 983 (s), 943 (s), 870 (w), 856 (m), 768 (vw), 724 (w), 611 (vw),
ꢀ
1
63(w), 465 cm
3 7 9
(w); elemental analysis calcd (%) for C H N O
(
185.15): C 19.46, H 3.81, N 68.09; found: C 19.44, H 3.70, N 67.29.
in vacuo, the residue was washed four times with Et
2
O (20 mL) to give a
1
colorless solid. Yield: 0.18 g (31%). H NMR: d=8.93 (s, 1H), 7.62 (s,
Guanidinium 4-amino-3-(5-tetrazolate)furazan (3): Colorless solid, yield:
1
3
1
13
1H), 7.58 (s, 1H), 6.51 ppm (s, 2H); C NMR: d=170.0, 155.9, 140.2,
0
1
3
1
.20 g (94%). H NMR: d=6.94 (s, 6H), 6.50 (s, 2H); C NMR: d=
58.4, 155.9, 151.0, 140.3 ppm; IR: n˜ =3599 (vw), 3493 (w), 3397 (w),
331 (w), 3211 (w), 3083 (w), 2828 (vw), 2206 (vw), 2142 (vw), 1686 (s),
642 (s), 1597 (s), 1558 (w), 1430 (m), 1364 (m), 1211 (vw), 1155 (s), 1084
1
2
36.4, 123.5, 120.8 ppm; IR: n˜ =3463 (w), 3357 (m), 3134 (m), 3071 (w),
974 (vw), 2726 (vw), 2479 (vw), 1939 (vw), 1762 (vw), 1630 (vs), 1589
(
(
s), 1555 (m), 1477 (vw), 1452 (vw), 1420 (w), 1366 (m), 1335 (w), 1275
m), 1194 (w), 1149 (w), 1090 (m), 1013 (vw), 977 (s), 883 (m), 853 (m),
(
(
vw), 1035 (w), 980 (s), 895 (w), 870 (m), 766 (w), 741 (w), 662 (vw), 567
w), 516 cm (w); elemental analysis calcd (%) for C
ꢀ
1
ꢀ
1
761 (s), 730 (vw), 629 (m), 567 (w), 507 cm (w); elemental analysis
calcd (%) for C O (235.21): C 35.75, H 3.86, N 53.60; found: C
5.52, H 3.79, N 52.45.
4 8
H N10O (212.17): C
7
9 9
H N
2
2.64, H 3.80, N 66.02; found: C 22.52, H 3.81, N 64.75.
3
Aminoguanidinium 4-amino-3-(5-tetrazolate)furazan (4): Colorless solid,
yield: 0.18 g (79%). H NMR: d=8.52 (d, J=7.7 Hz, 1H), 6.92 (s, 2H),
6
1
(
(
(
6
1
General procedures for the preparation of the energetic compounds 11–
13: Barium hydroxide (0.1578 g, 0.5 mmol) was added to a stirring solu-
tion of 4-amino-3-(5-tetrazole)furazan (0.1531 g, 1.0 mmol) in
1
3
.73 (s, 2H), 6.51 (s, 2H), 4.65 ppm (s, 2H); C NMR: d=159.3, 155.9,
51.1, 140.4 ppm; IR: n˜ =3489 (w), 3429 (w), 3377 (w), 3269 (w), 3192
2
H O
(
30 mL) and the resulting mixture was stirred at 258C until all of solids
vw), 3039 (w), 2883 (vw), 2755 (w), 2195 (vw), 1842 (w), 1665 (s), 1630
s), 1599 (m), 1566 (m), 1443 (m), 1430 (m), 1362 (m), 1213 (vw), 1152
m), 1101 (w), 1042 (vw), 988 (s), 904 (w), 864 (m), 773 (vw), 741 (vw),
2 4
had dissolved. This solution was added to a stirring mixture of Ag SO
(
2
0.1559 g, 0.5 mmol) and iodide salts (0.5 mmol) in H O (30 mL). The re-
sulting mixture was stirred at 258C for 0.5 h. After the mixture had been
filtered, slow evaporation the of filtrate gave rise to desirable products,
ꢀ
1
76 (m), 565 (w), 513 cm (vw); elemental analysis calcd (%) for
11O (227.19): C 21.15, H 3.99, N 67.82; found: C 21.15, H 3.91, N
4 9
C H N
6
which were washed twice with Et
2
O.
7.38.
1
,4-Dimethyltriazolium 4-amino-3-(5-tetrazolate)furazan hemihydrate
Diaminoguanidinium 4-amino-3-(5-tetrazolate)furazan (5): Colorless
solid, yield: 0.21 g (87%). H NMR: d=8.56 (s, 2H), 7.14 (s, 2H), 6.51 (s,
2
3
1
1
1
(
11): Colorless solid, yield: 0.16 g (62%). H NMR: d=9.96 (s, 1H), 9.07
1
13
(
s, 1H), 6.52 (s, 2H), 4.04 (s, 3H), 3.87 ppm (s, 3H); C NMR: d=155.9,
1
3
H), 4.58 (s, 4H); C NMR: d=160.3, 155.9, 151.1, 140.4 ppm; IR: n˜ =
455 (w), 3349 (w), 3273 (w), 3204 (w), 3144 (vw), 2983 (vw), 2363 (vw),
954 (vw), 1682 (s), 1630 (s), 1593 (s), 1482 (vw), 1422 (w), 1356 (m),
213 (m), 1180 (m), 1155 (s), 1123 (w), 1013 (s), 976 (m), 864 (m), 756
1
51.1, 145.8, 143.9, 140.4, 39.0, 34.4 ppm; IR: n˜ =3513 (vw), 3383 (vw),
3
279 (vw), 3148 (vw), 2497 (vw), 2212 (vw), 2112 (vw), 1967 (vw), 1798
(
w), 1633 (s), 1589 (s), 1569 (s), 1437 (m), 1429 (s), 1360 (s), 1292 (vw),
1
234 (vw), 1205 (m), 1153 (s), 1098 (vw), 1071 (m), 1028 (m), 981 (s), 909
ꢀ
1
(
w), 679 (m), 565 cm (m); elemental analysis calcd (%) for C
4
H
10
N
12
O
ꢀ1
(
(
m), 869 (m), 771 (vw), 732 (m), 660 (vw), 621 (w), 569 (w), 525 cm
w); elemental analysis calcd (%) for C 10O·0.5H
(
242.20): C 19.84, H 4.16, N 69.40; found: C 19.86, H 4.14, N 68.92.
7
H
10
N
2
O (259.23): C
Triaminoguanidinium 4-amino-3-(5-tetrazolate)furazan (6): Colorless
solid, yield: 0.19 g (74%). H NMR: d=8.57 (s, 3H), 6.52 (s, 2H),
32.43, H 4.28, N 54.03; found: C 32.19, H 4.10, N 53.85.
1
1
,4,5-Trimethyltetrazolium 4-amino-3-(5-tetrazolate)furazan (12): Color-
1
3
4
3
1
1
.47 ppm (s, 6H); C NMR: d=159.5, 155.9, 151.1, 140.4 ppm; IR: n˜ =
424 (w), 3379 (w), 3331 (w), 3179 (vw), 2797 (vw), 2497 (vw), 2195 (vw),
937 (w), 1844 (vw), 1686 (s), 1634 (s), 1600 (m), 1572 (m), 1444 (w),
427 (m), 1358 (s), 1211 (vw), 1198 (m), 1138 (s), 1033 (vw), 978 (s), 900
1
less solid, yield: 0.20 g (75%). H NMR: d=6.51 (s, 2H), 4.21 (s, 6H),
2
13
.83 ppm (s, 3H); C NMR: d=155.9, 153.2, 151.0, 140.4, 36.7, 8.7 ppm;
IR: n˜ =3422 (w), 3393 (w), 3283 (vw), 3150 (w), 3040 (vw), 2293 (vw),
2
1
094 (vw), 1634 (s), 1586 (m), 1566 (m), 1534 (w), 1443 (m), 1427 (w),
358 (s), 1329 (w), 1242 (vw), 1201 (m), 1144 (s), 1036 (m), 981 (s), 879
ꢀ
1
(
w), 864 (m), 770 (vw), 730 (vw), 649 (w), 624 (vw), 505 cm (w); ele-
mental analysis calcd (%) for C 13O (257.22): C 18.68, H 4.31, N
0.79; found: C 18.52, H 4.26, N 70.03.
H
11
N
ꢀ1
4
(
(
m), 847 (m), 757 (m), 729 (w), 691 (vw), 663 (vw), 563 (m), 507 cm
vw); elemental analysis calcd (%) for C
7
7
H
11
N
11O (265.24): C 31.70, H
N-carbamoylguanidinium 4-amino-3-(5-tetrazolate)furazan hydrate (7):
4.18, N 58.09; found: C 31.62, H 4.14, N 57.46.
1
Colorless solid, yield: 0.17 g (62%). H NMR: d=8.04 (s, 4H), 7.11 (s,
1
,4-Dimethyl-5-aminotetrazolium 4-amino-3-(5-tetrazolate)furazan (13):
1
3
2
H), 6.51 ppm (s, 2H); C NMR: d=155.9, 154.8, 151.0, 140.4 ppm; IR:
1
Pale yellow solid, yield: 0.24 g (90%). H NMR: d=6.51 (s, 2H),
3
n˜ =3376 (w), 3198 (w), 2806 (w), 2211 (vw), 2144 (vw), 1731 (s), 1699 (s),
13
.84 ppm (s, 6H); C NMR: d=158.6, 155.9, 149.0, 140.3, 43.0, 34.4 ppm;
1
1
624 (s), 1593 (m), 1572 (w), 1466 (m), 1432 (vw), 1383 (m), 1364 (s),
215 (w), 1157 (m), 1127 (m), 1092 (w), 1035 (vw), 920 (w), 882 (m), 760
IR: n˜ =3441 (w), 3339 (w), 3256 (w), 3136 (w), 2943 (w), 2887 (vw), 2698
(
(
(
vw), 2486 (vw), 2219 (vw), 2145 (vw), 1699 (s), 1654 (m), 1626 (s), 1599
m), 1563 (w), 1541 (w), 1451 (m), 1413 (m), 1392 (vw), 1352 (m), 1201
m), 1146 (s), 1106 (vw), 1067 (w), 1028 (m), 985 (s), 895 (w), 858 (w),
ꢀ
1
(
m), 708 (w), 604 (w), 443 cm (w); elemental analysis calcd (%) for
·H O (273.21): C 21.98, H 4.06, N 56.39; found: C 21.62, H
.89, N 55.05.
C
3
5
H
9
N
11
O
2
2
ꢀ
1
782 (m), 731 (w), 675 (w), 575 (vw), 496 cm (vw); elemental analysis
Guanidylguanidinium 4-amino-3-(5-tetrazolate)furazan (8): Colorless
calcd (%) for C
26.75, H 3.79, N 62.20.
6
H
10
N
12O (266.22): C 27.07, H 3.79, N 63.14; found: C
1
solid, yield: 0.13 g (51%). H NMR: d=6.77 (s, 3H), 6.50 ppm (s, 2H);
1
3
C NMR: d=160.2, 155.9, 152.0, 151.1, 140.4 ppm; IR: n˜ =3464 (w),
426 (w), 3352 (w), 3238 (vw), 3171 (vw), 2778 (vw), 2127 (w), 1663 (s),
629 (s), 1602 (w), 1591(s), 1586 (s), 1427 (w), 1363 (m), 1214 (w), 1155
3
1
(
(
m), 1034 (vw), 990 (m), 904 (w), 868 (vw), 771 (w), 732 (w), 590 (w), 510
w), 455 cm (w); elemental analysis calcd (%) for C H N12O (254.21):
5 10
Acknowledgements
ꢀ
1
C 23.62, H 3.96, N 66.12; found: C 23.65, H 3.90, N 65.51.
The financial support of the DTRA (HDTRA1–07–1–0024), NSF (Grant
CHE0315275), and ONR (Grant N00014–06–1–1032) is gratefully ac-
knowledged. The Bruker (Siemens) SMART APEX diffraction facility
was established at the University of Idaho with the assistance of the
NSF-EPSCoR program and the M. J. Murdock Charitable Trust, Vancou-
ver, WA, USA.
Carbonic hydrazylhydrazidinium 4-amino-3-(5-tetrazolate)furazan (9):
1
Pale yellow solid, yield: 0.11 g (45%). H NMR: d=6.52 (s, 2H), 3.41
1
3
(
1
(
quart, J=7.0, 14.0 Hz, 2H) 1.03 ppm (t, J=7.0 Hz, 3H); C NMR: d=
59.4, 155.9, 151.1, 140.4 ppm; IR: n˜ =3442 (w), 3343 (m), 3240 (w), 3172
vw), 2854 (w), 2625 (w), 1982 (w), 1868 (vw), 1701 (m), 1630 (s), 1595
2632
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 2625 – 2634