Full Paper
[6]
Compound 1c
Compound 6
Compound 1a (70 g, 0.5 mol, 1.00 equiv) was dissolved in 2M hy-
HNO3 (2M, 1 mL) was added to a suspension of 2 (2.0 mmol,
drochloric acid (750 mL). Cyanogen bromide (105.9 g, 1.0 mol,
308 mg) in water (20 mL). The mixture was heated at reflux and
2
.00 equiv) was added and the solution was heated to 608C with
the solution was left to stand. Compound 6 (400 mg, 1.84 mmol,
À1
stirring, then kept at 608C for 2 h. After heating the reaction mix-
ture at reflux for 1 h the solution was cooled to 08C in an ice bath.
92%) crystallized as colorless plates. DTA (58Cmin ) onset T
=
dec.
1
2808C; H NMR ([D ]DMSO): d=13.31 (brs, 1H; H-2), 8.20 (s, 2H; H-
6
13
At 08C, 1c (50.3 g, 0.26 mol, 53%) was deposited as white plates.
9), 7.24 (s, 2H; H-11), 5.78 ppm (s, 2H; H-10); C NMR ([D ]DMSO):
6
1
À
H NMR ([D ]DMSO): d=13.41 (brs, 1H; H-2), 8.22 (s, 2H; H-9), 7.30
d=160.2 (s; C-6), 147.5 (s; C-8), 141.2 ppm (s; C-3); m/z (FAB ):
6
13
À
+
+
(
s, 2H; H-11), 5.84 ppm (s, 2H; H-10); C NMR ([D ]DMSO): d=
62.0 (NO ); m/z (FAB ): 155.0 (C H N ); IR (ATR): n˜ =3348 (m),
3 3 7 8
6
À
1
60.2 (s; C-6), 147.4 (s; C-8), 141.1 ppm (s; C-3); m/z (FAB ): 35.0
3290 (m), 3223 (m), 3166 (m), 3134 (m), 3053 (m), 2998 (m), 2873
(m), 2745 (m), 2362 (m), 2342 (m), 1773 (vw), 1767 (vw), 1698 (m),
À
+
+
(
Cl ); m/z (FAB ): 155.2 (C H N ).
3 6 8
1
1
8
670 (s), 1634 (vs), 1583 (m), 1552 (m), 1512 (m), 1427 (w), 1398 (s),
344 (vs), 1300 (s), 1163 (m), 1073 (m), 1050 (m), 978 (m), 912 (s),
43 (m), 819 (m), 767 (m), 724 (w), 715 (m), 700 (m), 676 (w),
[6]
À1
Compound 2
668 cm
(w); Raman (1064 nm, 300 mW, 258C): n˜ =3352(3),
3
1
1
9
3
294(3), 3246(4), 3233(5), 3205(3), 1707(6), 1671(13), 1639(10),
Neutral compound 2 was obtained by neutralizing a solution of 1c
50.3 g, 0.264 mol, 2.00 equiv) in water (500 mL) with sodium car-
586(7), 1559(9), 1513(3), 1458(8), 1427(5), 1396(4), 1383(5),
377(5), 1305(9), 1255(25), 1166(4), 1082(7), 1072(8), 1055(68),
14(3), 846(44), 718(11), 700(3), 680(9), 616(40), 603(19), 395(14),
(
bonate (14.0 g, 0.132 mol, 1.00 equiv). The solution was heated at
reflux, then left to crystallize to give compound 2 (32.3 g,
À1
36(5), 309(16), 255(9), 200(15), 164(47), 98(100) cm ; elemental
À1
1
0
.210 mol, 80%). DTA (58Cmin ) onset T =2458C; H NMR
dec.
analysis calcd (%) for C H N O (217.15): C 16.59, H 3.25, N 58.05;
3
7
9
3
(
[D ]DMSO): d=6.38 (s, 2H; H-11), 5.59 (s, 2H; H-10), 5.46 ppm (s,
6
H; H-9); C NMR ([D ]DMSO): d=158.5 (s; C-6), 149.1 (s; C-8),
6
43.5 ppm (s; C-3); m/z (DEI ): 154.1 (C H N ); IR (ATR): n˜ =3411(w),
298 (m), 3181 (m), 3141 (m), 2735 (w), 2361 (w), 2339 (w), 1616
found: C 16.87, H 3.22, N 57.81; BAM impact: 40 J, BAM friction:
60 N, ESD: 0.75 J (at grain sizes 100–500 mm).
1
3
2
1
3
3
+
3
6
8
(
1
vs), 1569 (vs), 1502 (s), 1403 (m), 1346 (m), 1293 (m), 1241 (w),
Acknowledgements
158 (w), 1106 (m), 1078 (w), 968 (m), 946 (m), 847 (w), 729 (w),
À1
7
2
1
1
4
04 (m), 667 (w), 667 (w), 659 cm (w); Raman (1064 nm, 300 mW,
Financial support of this work by the Ludwig-Maximilian Uni-
versity of Munich (LMU), the U.S. Army Research Laboratory
(ARL) [grant number W911NF-09-2-0018], the Armament Re-
search, Development and Engineering Center (ARDEC) [grant
number W911NF-12-1-0467], and the Office of Naval Research
58C): n˜ =3300(7), 3191(14), 3148(6), 1660(11), 1646(14), 1611(27),
584(21), 1498(5), 1413(10), 1402(14), 1296(18), 1247(12), 1121(12),
081(4), 984(7), 949(7), 852(44), 711(5), 677(21), 624(22), 604(26),
À1
01(19), 306(22), 306(22), 177(10), 109(100) cm ; elemental analysis
calcd (%) for C H N (154.13): C 23.38, H 3.92, N 72.20; found: C
2
-
3
6
8
3.67, H 3.85, N 72.20; Bundesanstalt für Materialforschung und
prüfung (BAM) impact: 40 J; BAM friction: 360 N, electrostatic dis-
(
ONR)
[grant
numbers
ONR.N00014-10-1-0535
and
ONR.N00014-12-1-0538] is gratefully acknowledged. We ac-
knowledge collaborations with Dr. Mila Krupka (OZM Research,
Czech Republic) for the development of new testing and eval-
uation methods for energetic materials and Dr. Muhamed Su-
ceska (Brodarski Institute, Croatia) for the development of new
computational codes to predict the detonation and propulsion
parameters of novel explosives. We are indebted to and thank
Dr. Betsy M. Rice and Dr. Brad Forch (ARL, Aberdeen, Proving
Ground, MD) for many inspired discussions. Last but not least
we thank Mr. St. Huber and Mrs. Regina Scharf for carrying out
the sensitivity and toxicity measurements, respectively.
charge (ESD): 1.5 J (at grain sizes <100 mm).
Compound 4
Ammonium
nitrotetrazolate-2-oxide
(296 mg,
2.00 mmol,
[9]
1
.00 equiv) and 1c (381 mg, 2.00 mmol, 1.00 equiv) were dis-
solved in water and heated to 908C. The resulting clear solution
was left to crystallize overnight to yield 4 (404 mg, 1.42 mmol,
À1
7
1%) as yellow needles. DTA (58Cmin ) onset T =2228C;
dec.
1
H NMR ([D ]DMSO): d=13.37 (brs, 1H; H-2), 8.21 (s, 2H; H-9), 7.24
6
1
3
(
s, 2H; H-11), 5.77 ppm (s, 2H; H-10); C NMR ([D ]DMSO): d=
6
1
60.2 (s; C-6), 157.2 (s; C ), 147.4 (s; C-8), 141.1 ppm (s; C-3); m/z
anion
À
À
+
+
Keywords: cations · crystal structures · energetic materials ·
nitrogen · triazoles
(
FAB ): 130.0 (CN O ); m/z (FAB ): 155.2 (C H N ); IR (ATR): n˜ =
5 3 3 7 8
3
430 (m), 3362 (m), 3295 (m), 3244 (m), 3161 (m), 3066 (m), 2968
(
(
(
(
6
3
1
1
6
2
m), 2734 (m), 2363 (w), 2342 (w), 1702 (s), 1693 (s), 1664 (s), 1643
vs), 1604 (m), 1552 (s), 1529 (s), 1471 (s), 1457 (m), 1422 (vs), 1395
m), 1368 (m), 1319 (s), 1319 (s), 1232 (s), 1148 (m), 1080 (m), 1048
[
1] a) J. P. Agrawal, High Energy Materials: Propellants, Explosives and Pyro-
m), 1025 (m), 1008 (m), 976 (m), 845 (s), 799 (w), 773 (s), 723 (m),
À1
97 (s), 658 cm
(w); Raman (1064 nm, 300 mW, 258C): n˜ =
246(2), 1706(4), 1668(3), 1645(4), 1561(4), 1534(4), 1482(5),
475(5), 1459(5), 1423(100), 1403(21), 1386(5), 1321(10), 1264(9),
151(2), 1101(41), 1052(12), 1009(68), 978(3), 849(14), 764(4), 726(1),
82(2), 624(10), 604(7), 492(5), 431(2), 396(7), 350(1), 309(5), 261(4),
[
À1
42(5), 200(6), 171(14), 96(34), 74(14), 65(12) cm ; elemental analy-
sis calcd (%) for C H N O (285.18): C 16.85, H 2.47, N 63.85;
4
7
13
3
found: C 17.29, H 2.50, N 63.76; BAM impact: 25 J, BAM friction:
60 N, ESD: 1.0 J (at grain sizes 100–500 mm).
3
Chem. Eur. J. 2015, 21, 9219 – 9228
9227
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim