Functionalized Trimethylamine Derivatives
FULL PAPER
1
3
6
8.8 ppm (tquint JCH =155 Hz, JCH =4.6 Hz); IR (azide vibrations only):
À1
n˜ =2105 (nas
N
3
), 1237 (n
s
N
3
) cm
.
Tris(5-nitrotetrazol-2-ylmethyl)amine
(3):
Tris(chloromethyl)amine
[
[
[
[
Patent 2111721A1, 1972.
6] a) B. Krumm, Diploma thesis, Bergische Universitꢀt Wuppertal
8] M. Gçbel, T. M. Klapçtke, Adv. Funct. Mater. 2009, 19, 1–19.
[9] F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, A. G. Orpen,
R. Taylor, J. Chem. Soc. Perkin Trans. 1 1987, 12, S1–S19.
10] P. Politzer, J. S. Murray, Theoretical and Computational Chemistry,
12] SHELXS, SHELXL, G. M. Sheldrick, Universitꢀt Gçttingen (Ger-
many), 1997.
13] Gaussian 03, Revision A.1, M. J. Frisch, G. W. Trucks, H. B. Schlegel,
G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr.,
T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J.
Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega,
G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R.
Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao,
H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross,
C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev,
A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K.
Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakr-
zewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K.
Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz,
Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G.
Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox,
T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challa-
combe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonza-
lez, J. A. Pople, Gaussian, Inc., Pittsburgh PA, 2003.
(
0.64 g, 4 mmol) was dissolved under nitrogen in freshly distilled di-
chloromethane (10 mL). Ammonium 5-nitrotetrazolate (2.63 g, 20 mmol)
was added at ambient temperature, and the resulting suspension was
stirred for 18 h. The suspension was filtered, and the filter cake was
washed with acetone (20 mL). Eluate and filtrate were combined and
evaporated to yield 0.55 g (31%) 3 as a colorless crystalline solid suitable
for X-ray structure determination. DSC (25–3508C): decomposition
[
1
above 1258C (discoloration), no prior melting was observed. H NMR
1
3
1
(
(
(
[D
CNO
CN
6
]acetone): d=6.65 ppm;
C{ H} NMR ([D
6
]acetone): d=166.5
1
4
2
), 73.0 ppm (CH
2
); N NMR ([D
6
]acetone): d=0, À35, À68, À81
4
), À26 (CNO
2
), À363 ppm (amine-N); IR: n˜ =3024 w, 2982 w, 1562
[
vs, 1483 m, 1454 m, 1429 m, 1415 s, 1377 m, 1313 s, 1273 m, 1209 m, 1125
À1
m, 1068 w, 1028 w, 993 m, 959 w, 896 w, 839 m, 752 m, 690 m, 659 w cm
Raman (300 mW): n˜ =2983 (13), 1563 (9), 1484 (13), 1416 (100), 1309 (7),
;
[
1
227 (5), 1151 (9), 1064 (18), 1049 (24), 1029 (32), 958 (4), 893 (5), 836
À1
(
6), 774 (7), 690 (4), 539 (4), 398 (17), 352 (7), 232 (11) cm ; elemental
[
[
analysis calcd (%) for C
H 1.5, N 54.8.
6 6 16 6
H N O : C 18.1, H 1.5, N 56.3; found: C 17.9,
Reaction of
1
with KC
A
H
U
G
R
N
N
(NO
2
)
3
:
Tris(chloromethyl)amine (0.21 g,
[
1
.3 mmol) was dissolved under nitrogen in freshly distilled dichlorome-
thane (10 mL). Potassium nitroformate (0.7 g, 4 mmol) was added at am-
bient temperature, and the resulting suspension was stirred for 30 h. Fur-
ther potassium nitroformate (0.24 g, 1.3 mmol) was added, and stirring
was continued for five days. The suspension was filtered, and the filter
cake was washed with dichloromethane (2 mL). Eluate and filtrate were
combined and evaporated to yield mainly HN
2 2 3 2
ACHTUNGTNRENUNG[ CH C CAHUTNGTRENNUN(G NO ) ] as a color-
1
less crystalline solid suitable for X-ray structure determination. H NMR
3
(
CD
3
CN): d=4.45 (d,
J
HH =7.7 Hz, 4H; CH
CN): d=128.1 (C(NO
CN): d=À31 ppm (NO ).
2
), 3.27 ppm (quint, 1H;
1
3
1
NH); C{ H} NMR (CD
3
A
H
U
G
R
N
N
2
)
3
), 52.9 ppm (CH );
2
1
4
N NMR (CD
3
2
Acknowledgements
Financial support of this work by the Ludwig-Maximilian University of
Munich (LMU), the Fonds der Chemischen Industrie (FCI), the Europe-
an Research Office (ERO) of the U.S. Army Research Laboratory
Mourik, T. H. Dunning, Jr., J. Mol. Struct. 1996, 388, 339–349.
(
ARL) and ARDEC (Armament Research, Development and Engineer-
ing Center) under contract nos. N 62558-05-C-0027, R&D 1284-CH-01,
R&D 1285-CH-01, 9939-AN-01, W911NF-07-1-0569, W911NF-08-1-0372,
W911NF-08-1-0380 and R&D 1324-CH-01 and the Bundeswehr Research
Institute for Materials, Explosives, Fuels and Lubricants (WIWEB)
under contract nos. E/E210/4D004/X5143
& E/E210/7D002/4F088 is
gratefully acknowledged. F.X.S. thanks the Deutsche Forschungsgemein-
schaft for his doctoral position (project KL 636/11-1).
Received: April 27, 2009
Published online: September 18, 2009
Chem. Eur. J. 2009, 15, 11341 – 11345
ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
11345