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quenched by adding KOH (3.36 g, 60 mmol) dissolved in water
(30 mL). The aqueous phase was separated and the water was
evaporated under high vacuum. The residue was stirred in methanol
(50 mL) for a few hours. The white precipitate consisting of pure
KNO3 and K2DNAT was filtered, washed with a little methanol, and
dried. The solid was dissolved in HCl (30 mL, 2m) and extracted with
four portions of ethylacetate (4 20 mL). The solvent was removed
from the organic phase in vacuo at RT and the colorless crystalline
product was dried in high vacuum to give 950 mg (50%) of colorless 1.
DSC (58C minÀ1,8C): 1108C (dec.); IR (ATR): n˜ = 2967 (w), 2757 (w),
1636 (w), 1591 (vs), 1502 (s), 1304 (s), 1222 (s), 1136 (m), 1022 (m),
1006 (m), 964 (m), 886 (w), 836 (m), 773 (m), 695 cmÀ1 (m); Raman
(1064 nm, 300 mW, 258C): n˜ = 3101 (7), 1614 (17), 1596 (43), 1425
(45), 1320 (36), 1260 (100), 1139 (8), 1025 (11), 1011 (26), 979 (68), 891
(16), 841 (26), 781 (16), 762 (26), 632 (9), 492 (45), 418 (43), 315 (29),
284 (49), 217 cmÀ1 (10); 1H NMR (400 MHz, [D6]DMSO, 258C): d =
11.91 ppm; 13C NMR{1H} (400 MHz, [D6]DMSO, 258C) d =
147.6 ppm; EA calcd for CH2N8O4 (190.02 gmolÀ1): C 6.32, H 1.06,
N 58.95%; found: C 7.29, H 1.39, N 57.14%; BAM drophammer: 1 J
(< 100–500 mm); friction tester: < 5 N (< 100–500 mm); ESD: 0.3 J.
The synthesis of salts 5–8 as well as the general methods are
described in the Supporting Information.
Keywords: energetic materials · nitramines · sensitivity ·
structure elucidation · tetrazoles
How to cite: Angew. Chem. Int. Ed. 2015, 54, 10299–10302
Angew. Chem. 2015, 127, 10438–10441
[1] J. A. Agrawal, High Energy Materials, Wiley-VCH, Weinheim,
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Figure 5. Detonation test using 50 mg 5 and 500 mg RDX and
a conventional pyrotechnical igniter. A) Picture of the test setup;
B) representation of the test setup; C) perforated copper plate as the
result of RDX detonation.
3310 (w), 3258 (w), 3197 (w), 3095 (w), 2863 (w), 1740 (s), 1650 (vs),
1579 (w), 1483 (w), 1448 (m), 1322 (s), 1197 (w), 1117 (m), 1065 (s),
986 (m), 924 (w), 828 (m), 756 (m), 742 (m), 720 (w), 686 (w), 667 cmÀ1
(w); Raman (1064 nm, 300 mW, 258C): n˜ = 3257 (9), 3195 (18), 2964
(48), 2864 (15), 1747 (17), 1654 (30), 1580 (21), 1510 (8), 1485 (35),
1460 (9), 1338 (85), 1199 (9), 1119 (51), 1071 (16), 988 (43), 926 (41),
832 (100), 773 (43), 757 (53), 668 (9), 521 (26), 450 (33), 372 (29),
318 cmÀ1 (11); 1H NMR (400 MHz, [D6]DMSO, 258C): d = 11.21,
7.06, 3.72 ppm; 13C NMR{1H} (400 MHz, [D6]DMSO, 258C) d =
155.2, 155.1, 53.7 ppm; EA calcd for C3H6N6O2 (158.06 gmolÀ1):
C 22.79, H 3.82, N 53.15%; found: C 23.26, H 3.91, N 51.38%.
1,5-Di(nitramino)tetrazole (1): 3 (1.58 g, 10 mmol) was sus-
pended in dry acetonitrile (30 mL) at 08C. N2O5 (3.24 g, 30 mmol)
in acetonitrile (30 mL) was added in one portion and the mixture was
stirred at 08C for one hour. The reaction was vigorously stirred and
´
[9] M. Suceska, EXPLO5V6.02 program, Brodarski Institute,
Zagreb, Croatia, 2014.
[10] R. Mayer, J. Kçhler, A. Homburg, Explosives 5th edn., Wiley
VCH, Weinheim, 2002. p. 164.
[11] a) J. W. Fronabarger, M. D. Williams, PCT Int. Appl. WO
2012003031, 2012; b) Q.-L. Yan, S. Zeman, J.-G. Zhang, P. He,
ˇ
[12] N. B. Bolotina, M. J. Hardie, R. L. Speer, Jr., A. A. Pinkerton, J.
Received: March 30, 2015
Published online: June 19, 2015
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2015, 54, 10299 –10302