N. Fischer, K. Karaghiosoff, T. M. Klapötke, J. Stierstorfer
ARTICLE
13C NMR ([D
]DMSO, 25 °C): δ = 150.6 (CN
), 67.6 (CH
), 39.9 tion (40 mL, 570 mg, 10 mmol). To this, dimethyl sulfate was added
]DMSO, 25 °C): δ = 9.9 drop wise at 60 °C and the mixture was heated under reflux for three
6
4
2
1
5
(H
3
CN(NO
2
)), 34.7 (CH
3
). N NMR ([D
6
3
(
N3), –5.5 (N2, q, JN–H = 1.9 Hz), –30.4 (N8, NO
2
2
), –40.8 (N6, hours. Afterwards, the solvent was reduced by half and the product was
Cl (2 × 30 mL). After evaporating the solvent, the
2
NO
), –57.8 (N4), –152.7 (N1, q, JN–H = 2.3 Hz), –295.0 (N7), –207.5 extracted using CH
2
2
+
+
(
N5); MS: m/z (DEI ): 233.3 [M + H] ; impact sensitivity: > 5 J; crude product was recrystallized from hot water yielding 1.34 g color-
friction sensitivity: > 240 N; ESD: > 0.20 J. less crystals (85 % yield). (C , 158.12) calcd.: C 22.79, H 3.82,
N 53.15 %; found: C 23.10, H 3.84, N 52.99 %; DSC (Tonset
3
6 6 2
H N O
,
1
-Methyl-4-(2-nitro-2-azapropyl)-aminotetrazole (14): The coup-
–
1
5
(
(
1
°C·min ): 85 °C (mp.), 200 °C (dec.). IR (KBr): ν˜ = 3029 (w), 2442
w), 2265 (w), 2115 (w), 1685 (w), 1664 (s), 1495 (m), 1436 (s), 1412
ling reaction of potassium 1-methyl-5-nitriminotetrazolate and 2 in ac-
etone (described above) delivered 1-methyl-5-NAP-nitriminotetrazole
m), 1376 (s), 1352 (m), 1258 (vs, br), 1229 (vs), 1115 (m), 1049 (m),
(
12), but also 1-methyl-5-NAP-aminotetrazole. It could be separated
from 12 due to its different solubility in ethanol. 14 was obtained from
the mother liquor in 12 % yield (0.68 g). (C , 187.16) calcd.:
C 25.67, H 4.85, N 52.39 %; found: C 25.71, H 4.84, N 52.51 %;
–1
007 (s), 918 (w), 874 (w), 791 (s), 774 (s), 750 (m), 676 (s) cm ;
Raman: (1064 nm, 200 mW, 25 °C): ν˜ = 3032 (31), 2964 (93), 1568
81), 1467 (26), 1439 (27), 1415 (46), 1378 (38), 1353 (41), 1278 (17),
1232 (15), 1050 (18), 1010 (62), 876 (11), 796 (31), 775 (11), 752
4
9 7 2
H N O
(
–
1
DSC (Tonset, 5 °C·min ): 142–147 °C (mp.), 184 °C (dec.). IR (KBr):
ν˜ = 3262 (m), 3122 (m), 3040 (m), 1617 (vs), 1500 (vs), 1450 (s),
(
(
38), 621 (100), 522 (7), 482 (29), 349 (10), 283 (33), 209 (13), 161
–
1
1
13
15) cm . H NMR ([D
6
]DMSO, 25 °C): δ = 3.78 (s, 3 H, CH
3
).
). N NMR
]DMSO, 25 °C):
C
1
343 (m), 1300 (vs), 1288 (s), 1248 (vs), 1226 (m), 1082 (m), 1041
14
NMR ([D
6
3 4
]DMSO, 25 °C): δ = 39.7 (CH ), 168.0 (CN
(
(
3
(
7
m), 1021 (m), 1002 (m), 843 (w), 768 (m), 742 (w), 668 (m), 653
15
–
1
([D
6
]DMSO, 25 °C): δ = –19.6 (NO
2
). N NMR ([D
6
m), 619 (w), 562 (m) cm ; Raman (1064 nm, 350 mW, 25 °C): ν˜ =
055 (30), 3027 (30), 2952 (65), 1605 (39), 1467 (31), 1450 (39), 1342
21), 1306 (54), 1244 (35), 1116 (33), 1081 (18), 1000 (61), 843 (90),
80 (100), 664 (23), 620 (16), 563 (13), 423 (21), 253 (36), 181 (21)
+
2
δ = –359.4 (N7, NH
4
), –149.3 (N5), –111.8 (C2, J(N–H) = 2.1 Hz), –
3
9
3.8 (N1, J(N–H) = 1.8 Hz), –63.9 (N4), –15.4 (N6, NO
2
), –6.4 (N3,
3
+
J(N–H) = 1.8 Hz); MS: m/z (DEI): 158(34) [M] , 112(58) [M –
] , 89(10), 83 (6) [M – NO
56(20), 55(12), 53(7), 46 (6) [NO
] , 41(11), 28(35) [N
> 30 J; friction sensitivity: > 360 N.
+
+
–
1
1
NO
2
2
– 2CH
3
] , 70(5), 69(10), 57(8),
cm . H NMR ([D
5
6
]DMSO, 25 °C): δ = 8.09 (t, J = 6.3 Hz, NH),
+
+
13
2
] , 45(24), 43 (100) [HN
] , 18(23), 15(34) [CH
3
] , 42 (12)
] ; impact sensitivity:
.21 (d, J = 6.3 Hz, CH
2
), 3.71 (s, CH
3
), 3.53 (s, H )).
3
CN(NO
2
C
+
+
+
[N
3
2
3
NMR ([D
6
]DMSO, 25 °C): δ = 155.7 (CN
)), 32.4 (CH
4
), 60.8 (CH ), 39.0
2
1
5
(H
3
CN(NO
2
3
). N NMR ([D
6
]DMSO, 25 °C): δ = 1.3 (s,
3
3
N3), –20.3 (s, N2), –29.0 (m, JNH = 2.5 Hz, NO
2
), –93.8 (d, JNH
=
2
.2 Hz, N4), –184.5 (t, JNH = 2.2 Hz, N1), –199.9 (s, NNO
2
), –324.4
1
+
+
Acknowledgement
Financial support of this work by the Ludwig-Maximilian University
-Methyl-5-(2-nitro-2-azapropyl)-nitriminotetrazole (15): 2- of Munich (LMU), the European Research Office (ERO) of the U.S.
2
Methyl-5-nitraminotetrazolate (4.32 g, 30 mmol) was suspended in Army Research Laboratory (ARL), the Armament Research, Develop-
THF (25 mL) and triethylamine (3.04 g, 30 mmol) was added. A col- ment and Engineering Center (ARDEC) and the Strategic Environmen-
orless precipitate, which first was formed, disappeared within half a tal Research and Development Program (SERDP) under contract nos.
minute. 2-nitro-2-azapropyl chloride (3.74 g, 30 mmol), dissolved in W911NF-09-2-0018
(ARL),
W911NF-09-1-0120
(ARDEC),
THF (10 mL), was added drop wise. The mixture was stirred at room W011NF-09-1-0056 (ARDEC) and 10 WPSEED01-002 / WP-1765
temperature overnight, filtered off and the solvent was removed from (SERDP) is gratefully acknowledged. The authors acknowledge col-
the filtrate. The remaining yellow oil was suspended in pentane laborations with Dr. Mila Krupka (OZM Research, Czech Republic)
(
30 mL) and stirred vigorously. After a few minutes all the oil was in the development of new testing and evaluation methods for energetic
converted into fine, crystalline material, which was filtered off (6.55 g, materials and with Dr. Muhamed Sucesca (Brodarski Institute, Croatia)
9
1
4 % yield) and recrystallized from ethanol/methanol. (C
2
H
3
KN
6
O
2
,
in the development of new computational codes to predict the detona-
82.18) calcd.: C 20.69, H 3.47, N 48.27 %; found: C 21.71, H 3.81, tion and propulsion parameters of novel explosives. We are indebted
–
1
N 47.08 %; DSC (Tonset, 5 °C·min ): 68–78 °C (mp.), 116 °C (dec.). to and thank Drs. Betsy M. Rice and Brad Forch (ARL, Aberdeen,
IR (KBr): ν˜ = 3435 (m), 3043 (m), 1585 (vs), 1531 (vs), 1467 (s), Proving Ground, MD) and Mr. Gary Chen (ARDEC, Picatinny Arse-
1
1
458 (s), 1441 (m), 1412 (m), 1397 (s), 1365 (w), 1304 (s), 1282 (s), nal, NJ) for many helpful and inspired discussions and support of our
261 (s), 1214 (m), 1195 (m), 1147 (m), 1066 (m), 1048 (m), 1025 work. The authors also acknowledge financial support by CECD.
(m), 911 (m), 855 (w), 800 (m), 769 (m), 749 (m), 704 (w), 663 (m),
–
1
6
49 (m), 602 (m), 494 (w), 453 (w) cm ; Raman (1064 nm, 350 mW,
5 °C): ν˜ = 3043 (30), 2994 (43), 2969 (91), 2875 (15), 2837 (9), 1592
References
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1
214 (10), 1197 (15), 1146 (6), 1067 (8), 1046 (26), 1018 (73), 915
(
(
(
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23), 495 (11), 464 (32), 394 (30), 374 (11), 327 (13), 308 (22), 243
13), 221 (14) cm . H NMR ([D
.49 (s, CH ), 3.47 (s, CH NNO
δ = 159.1 (CN ), 67.1 (CH ), 41.2 (CH
–
1 1
6
]DMSO, 25 °C): δ = 6.09 (s, CH
2
),
1
3
4
3
3
2
). C NMR ([D
2
), 39.7 (CH NNO ). N NMR
6
]DMSO, 25 °C):
15
4
2
3
3
3
(
3
[D
6
]DMSO, 25 °C): δ = 1.4 (N3, q, JN–H = 1.5 Hz), –30.4 (N8), –
3
7.9 (N6), –53.4 (N4), –77.9 (N1, q, JN–H = 1.8 Hz), –101.6 (N2, q,
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Centr. Eur. J. Energ. Mater. 2008, 5, 13–30; J. Akhavan, The
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2
2
J
N–H = 2.4 Hz), –202.1 (N5, t, JN–H = 1.9 Hz), –204.9 (N7); MS: m/
+
+
z (DEI ): 233.3 [M + H] ; impact sensitivity: > 8 J; friction sensitiv-
ity: > 96 N; ESD: > 0.07 J.
1
,4-Dimethyl-5-nitriminotetrazole (16): 1-Methyl-5-nitriminotetra-
zole (1.44 g, 10 mmol) was deprotonated using an aqueous KOH solu-
7
48
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Z. Anorg. Allg. Chem. 2010, 735–749