Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
1
1
373 (62), 1357 (83), 1346 (80), 1315 (100), 1282 (48), 1264 (40), 2,3-Bis(hydroxymethyl)-2-,3-dinitro-1,4-butanediol Tetracarb-
243 (42), 1185 (47), 1031 (50), 993 (66), 920 (57), 833 (37), 728 amate (3b): The alcohol precursor 2,3-bis(hydroxymethyl)-2-,3-
dinitro-1,4-butanediol (3a) (1.56 g, 6.5 mmol) was added slowly to a
56), 295 (49), 263 (78), 251 (68), 213 (54) cm . IR: ν˜ = 3214 (w), ice-cooled solution of chlorosulfonyl isocyanate (CSI) (4.21 g,
(
(
37), 571 (42), 546 (44), 520 (37), 478 (44), 459 (80), 405 (56), 345
–1
2
1
987 (w), 1788 (s), 1690 (w), 1638 (m), 1617 (m), 1569 (s), 1442 (s), 29.7 mmol) in dry acetonitrile (25 mL). The ice bath was removed
400 (w), 1354 (w), 1323 (m), 1354 (w), 1155 (vs), 1101 (vs), 1036 after the complete addition and stirring at room temperature was con-
(
7
m), 990 (s), 966 (m), 910 (m), 849 (m), 831 (w), 813 (w), 745 (m),
tinued for 1 h. The solution was cooled again with an ice bath and
cold water (15 mL) was added slowly. After 10 min, the acetonitrile
was removed under reduced pressure and the precipitated solid was
–1
10 10 20
31 (w), 712 (w), 620 (m), 565 (m), 519 (m) cm . C10H N O
–1
(590.24 g·mol ): calcd. C 20.35, H 1.71, N 23.73%; found C 20.26,
H 2.05, N 21.57%. Dec. point: 160 °C. Sensitivities (BAM): impact
collected by filtration and washed with cold water to obtain the pure
1
4
J; friction 360 N (grain size Ͻ100 μm).
carbamate 3b (2.37 g, 88%). H NMR ([D
6
]DMSO): δ = 6.8 (br., 8
]DMSO): δ = 154.7
). Raman (800 mW): ν˜ = 3056 (6),
031 (8), 3004 (6), 2991 (52), 1702 (37), 1622 (9), 1568 (32), 1461
1
3
1
H, NH
2
2 6
), 4.65 (s, 8 H, CH ). C{ H} NMR ([D
(
CO), 92.0 (CNO ), 60.9 (CH
2
2
6b-Nitrohexahydro-2H-1,3,5-trioxacyclopenta[cd]-pentalene-2,4–
6-triol Tricarbamate (2b): The alcohol precursor 6b-nitrohexahydro-
2H-1,3,5-trioxacyclopenta[cd]-pentalene-2,4–6-triol (2a) (1.40 g,
6.0 mmol) was added slowly to a ice-cooled solution of chlorosulfonyl
3
(
1
8
2
7), 1449 (19), 1367 (28), 1335 (9), 1293 (23), 1285 (6), 1215 (5),
133 (5), 1104 (27), 1042 (6), 964 (52), 923 (24), 890 (33), 861 (41),
05 (16), 764 (7), 687 (15), 633 (10), 512 (15), 384 (24), 312 (11),
isocyanate (CSI) (2.85 g, 20.0 mmol) in dry acetonitrile (25 mL). The
ice bath was removed after the complete addition and stirring at room
temperature was continued for 1 h. The solution was cooled again with
an ice bath and cold water (10 mL) was added slowly. After 10 min,
the acetonitrile was removed under reduced pressure and the precipi-
–
1
91 (41), 221 (13) cm . IR: ν˜ = 3477 (m), 3312 (m), 3197 (w), 1706
(
vs), 1606 (m), 1593 (m), 1559 (s), 1470 (m), 1414 (s), 1327 (vs),
1
8
C
279 (m), 1125 (m), 1102 (s), 1063 (vs), 961 (m), 931 (m), 888 (m),
–
1
60 (m), 804 (w), 771 (m), 762 (m), 631 (m), 529 (m) cm .
–
1
10 16 6
H N O12 (412.27 g·mol ): calcd. C 29.13, H 3.91, N 20.38%;
tated solid was collected by filtration and washed with cold water to
found C 29.23, H 3.87, N 20.21%. Tmelt: 207. Dec. point: 214 °C.
Sensitivities (BAM): impact 40 J; friction 360 N (grain size Ͻ100 μm).
1
obtain the pure carbamate 2b (1.74 g, 80%). H NMR ([D
6
]DMSO):
δ = 6.9 (br., 6 H, NH
2
), 6.09 (s, 3 H, HC(O)O), 5.30 (s, 3 H, HC(O)
C). 13C{ H} NMR ([D
]DMSO): δ = 154.1 [C(O)N], 104.9 (CNO ),
01.0 [C(O)O], 91.2 [C(O)C]. Raman (800 mW): ν˜ = 3284 (11), 3029
1
6
2
2
,3-Bis(hydroxymethyl)-2,3-dinitro-1,4-butanediol Tetranitrocarb-
amate (3): Fuming nitric acid (5 mL) was cooled with an ice bath and
,3-bis(hydroxymethyl)-2,3-dinitro-1,4-butanediol tetracarbamate (3b)
0.83 g, 2 mmol) was added in small portions below 5 °C. The solution
was stirred at this temperature for 1 h and poured into ice water
100 mL). The precipitate was filtered and washed with cold water to
1
(
(
59), 3020 (75), 3009 (100), 2988 (62), 2980 (62), 2938 (17), 2255
10), 1741 (29), 1703 (33), 1599 (22), 1557 (34), 1389 (35), 1370 (32),
2
(
1352 (56), 1311 (40), 1285 (37), 1267 (22), 1131 (56), 1106 (52), 1106
(52), 1050 (42), 1019 (65), 1008 (87), 978 (45), 921 (35), 902 (30),
(
8
4
69 (65), 836 (14), 807 (89), 732 (18), 635 (20), 587 (39), 471 (80),
54 (32), 406 (91), 298 (51), 268 (62) cm . IR: ν˜ = 3502 (w), 3409
–1
obtain the nitrocarbamate 3 (1.12 g, 95%) as a colorless solid. The
compound was dried at 50 °C under reduced pressure to remove traces
(
(
(
(
w), 3336 (w), 3282 (w), 3198 (w), 1732 (s), 1705 (s), 1598 (m), 1557
s), 1393 (m), 1347 (s), 1333 (s), 1279 (m), 1163 (w), 1134 (m), 1102
m), 1053 (m), 1017 (vs), 964 (vs), 912 (m), 832 (m), 803 (m), 772
1
of water. H NMR ([D
[
6
]acetone): δ = 13.9 (br., 4 H, NH), 5.15/5.08
2
1
1
13
1
8 H, J( H, H) = 12.3 Hz, CH
= 147.6 (CO), 92.2 (CNO ), 62.7 (CH
–10 (CNO ), –47 (NHNO
). Raman (800 mW): ν˜ = 3059 (37), 2997
46), 2985 (45), 1776 (43), 1578 (43), 1474 (22), 1449 (44), 1406 (22),
A
H
B
]. C{ H} NMR ([D
6
]acetone): δ
1
4
–1
–1
2
). N NMR ([D ]acetone): δ
2 6
m), 633 (m), 583 (m) cm . C10
12 4
H N O11 (364.22 g·mol ): calcd. C
=
2
2
32.98, H 3.32, N 15.38%; found C 32.31, H 3.49, N 14.84%. Dec.
(
point: 212 °C. Sensitivities (BAM): impact 40 J; friction 360 N (grain
size Ͻ100 μm).
1
9
3
327 (100), 1274 (37), 1191 (23), 1143 (24), 1129 (23), 1061 (41),
86 (24), 867 (35), 551 (19), 465 (71), 452 (31), 369 (48), 345 (28),
34 (24), 302 (22), 292 (24), 284 (25), 272 (29), 238 (48) cm . IR:
–
1
6
6
b-Nitrohexahydro-2H-1,3,5-trioxacyclopenta[cd]-pentalene-2,4– ν˜ = 3634 (w), 3566 (w), 3489 (w), 2981 (w), 2771 (w), 1778 (m),
-triol Trinitrocarbamate (2): Fuming nitric acid (5 mL) was cooled 1595 (m), 1565 (s), 1470 (m), 1446 (m), 1331 (m), 1176 (vs), 1124
with an ice bath and 6b-nitrohexahydro-2H-1,3,5-trioxacyclopen- (m), 1104 (m), 988 (m), 966 (m), 928 (w), 861 (m), 807 (m), 786 (m),
–
1
ta[cd]-pentalene-2,4–6-triol tricarbamate (2b) (1.85 g, 5.1 mmol) was
added in small portions below 5 °C. The solution was stirred at this
temperature for 1 h and poured into ice water (100 mL). The precipi-
tate was filtered and washed with cold water to obtain the pure nitro-
740 (s), 730 (s), 699 (m), 636 (w), 575 (m), 547 (m), 519 (m) cm .
–
1
C H N O (592.26 g·mol ): calcd. C 20.28, H 2.04, N 23.65%;
found C 21.78, H 2.62, N 19.17%. Dec. point: 172 °C. Sensitivities
1
0 12 10 20
(BAM): impact 25 J; friction 360 N; (grain size Ͻ100 μm).
carbamate 2 (2.10 g, 83%) as a colorless solid. 1H NMR ([D
tone): δ = 13.7 (br., 3 H, NH), 6.47 (s, 3 H, HC(O)O), 5.62 (s, 3 H,
]ace-
6
HC(O)C). 13C{ H} NMR ([D
CNO
), 103.1 [C(O)O], 92.8 [C(O)C]. 14N NMR ([D
10 (CNO ), –46 (NHNO ). Raman (800 mW): ν˜ = 3015 (43), 1780 Financial support of this work by the Ludwig-Maximilian University
19), 1618 (13), 1561 (14), 1448 (13), 1371 (18), 1355 (26), 1328 (55), of Munich (LMU), the Office of Naval Research (ONR) under grant
328 (55), 1294 (17), 1111 (11), 1049 (41), 1031 (100), 995 (20), 975 no. ONR.N00014–16–1-2062, and the Bundeswehr - Wehrtechnische
1
]acetone): δ = 147.2 [C(O)N], 105.1 Acknowledgements
6
[
2
6
]acetone): δ =
–
2
2
(
1
(
(
15), 873 (24), 805 (31), 589 (11), 472 (40), 424 (11), 391 (27), 294
15), 260 (26), 216 (27) cm . IR: ν˜ = 3787 (w), 3199 (w), 3028 (w),
Dienststelle für Waffen und Munition (WTD 91) under grant no.
E/E91S/FC015/CF049 is gratefully acknowledged. The authors
–1
1775 (m), 1608 (m), 1560 (m), 1445 (m), 1374 (w), 1325 (m), 1293 acknowledge collaborations with Dr. Mila Krupka (OZM Research,
(
(
C
w), 1160 (s), 1135 (s), 1108 (m), 1972 (s), 969 (m), 921 (vs), 853 Czech Republic) in the development of new testing and evaluation
–
1
m), 804 (m), 787 (m), 744 (m), 636 (m), 599 (m), 587 (m) cm . methods for energetic materials and with Dr. Muhamed Suceska (Brod-
H
9
N
7
O
17 (499.22 g·mol–1): calcd. C 24.06, H 1.82, N 19.64 %;
arski Institute, Croatia) in the development of new computational
codes to predict the detonation and propulsion parameters of novel
explosives. We are indebted to and thank Drs. Betsy M. Rice, Jesse
10
found C 23.13, H 2.13, N 16.95%. Dec. point: 172 °C. Sensitivities
BAM): impact 10 J; friction 360 N; (grain size Ͻ100 μm).
(
Z. Anorg. Allg. Chem. 0000, 0–0
www.zaac.wiley-vch.de
7
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim