Synthesis, Characterization, and Energetic Properties of Nitroso Compounds
+
4
[
6
4
5.2 °C (m.p.), 121 °C (dec.); m/z ( c ESI): 266.2(18), 338.3(51,
J. Molinet, V. Pasquet, A. J. Bougrine, H. Delalu, Kinet. Catal.
2009, 50, 715–724.
[2] a) F. W. Schueler, C. Hanna, J. Am. Chem. Soc. 1951, 73, 4996;
b) R. H. Poirier, F. Benington, J. Am. Chem. Soc. 1952, 74, 3192;
c) T. M. Klapötke, P. Mayer, A. Schulz, J. J. Weigand, Propellants
Explos. Pyrotech. 2004, 29, 325–332.
+
+
MЈ+H] ), 360.3(100, [MЈ+Na] ), 413.3(17), 531.3(7), 601.1(5),
+
+
1
75.7(23, [2MЈ+H] ), 697.7(4, [2MЈ+Na] ). H NMR (CDCl
00.18 MHz, TMS) δ = /ppm: 3.81 (s , 3 H, N-CH ), 6.02 (2 H, s(br.),
, 100.52 MHz, TMS) δ = /ppm: 39.3 (N-
, 40.51 MHz, NH ) δ = /ppm: +472.8 (1 n, s,
NO), +249.9 (1 n, s, -NCH ). +93.2 (1 n, t, JN–H = 57.3 Hz, -NH
Raman ν˜ /cm–1 (rel. int.): 3282(20), 3206(11), 3189(27), 3039(28), [4] S. Park, C. O. Kang, Choson Minjujuui Inmin Konghwaguk Kwa-
3
,
3
13
1
2 3
NH ); C [ H] NMR (CDCl
CH
15
3
). N NMR (CDCl
3
3
[
3] K. Klager, E. M. Wilson, G. K. Helmkamp, J. Ind. Eng. Chem.
960, 52, 119–120.
1
3
2
);
1
3
1
5
3
2
1
003(24), 2949(83), 2811(4), 1489(3), 1434(24), 1415(34), 1367(3),
hagwon Tongbo 2007, 96, 47–48.
[5] a) M. De Rosa, P. Haberfield, J. Org. Chem. 1981, 46, 2639–
2643; b) K. Banert, M. Hagedorn, J. Schlott, Chem. Lett. 2003,
338(48), 1263(15), 1168(51), 1075(35), 854(12), 802(3), 689(65),
–1
17(2), 440(100), 372(22), 263(5). IR ν˜ /cm (golden gate, rel. int.):
275(m) 3186(w) 3072(m) 2952(w) 2748(w) 2529(w) 2333(w)
161(w) 2015(w) 1576(w) 1491(m) 1435(m) 1377(w) 1340(w)
260(s) 1126(w) 1078(m) 1021(w) 963(m) 807(m) 686(s). UV/Vis
3
2, 360–361.
6] J. Heppekausen, T. M. Klapötke, S. M. Sproll, J. Org. Chem.
009, 74, 2460–2466.
[
2
[
[
7] W. E. Thun, W. R. McBride, J. Org. Chem. 1969, 34, 2997–3002.
8] a) R. A. Rowe, L. F. Audrieth, J. Am. Chem. Soc. 1956, 78, 563–
3.82 10–4 m, EtOH): 247 nm (ε = 6850 L·mol ·cm ).
–1
–1
(
5
64; b) H. H. Sisler, M. A. Mathur, S. R. Jain, R. Greengard, Ind.
Supporting Information (see footnote on the first page of this article):
Tables with the calculated IR and Raman frequencies and the corre-
sponding assignment can be found in the Supporting Information.
Eng. Chem. Prod. Res. Dev. 1981, 20, 181–185; c) W. E. Bull,
H. A. Seaton, L. F. Audrieth, J. Am. Chem. Soc. 1958, 80, 2516–
2518; d) L. J. Madgzinski, K. S. Pillay, H. Richard, Y. L. Chow,
Can. J. Chem. 1978, 56, 1657–1667.
9] E. Muller, W. Rundel, Chem. Ber. 1957, 90, 2673–2678.
[
Conclusions
[
10] a) Phrix-Werke A.-G. (E. Mueller, H. Haiss, W. Rundel), DE-BP.
1
,104,518, 1961; b) E. Mueller, W. Hoppe, H. Hagenmaier, H.
Haiss, R. Huber, W. Rundel, H. Suhr, Chem. Ber. 1963, 96, 1712–
719.
Sodium and potassium methyl(nitroso)amide (1 and 2) and
N-nitroso-N-methylhydrazine (3) were obtained in moderate to
1
high yields from monomethylhydrazine. Alternatively, reaction [11] R. Huber, R. Langer, W. Hoppe, Acta Crystallogr. 1965, 18, 467–
4
73.
of compounds 1 and 2 with the sodium salt of HOSA afforded
in good yield. All three compounds were characterized by
analytical (elemental analysis and mass spectrometry) and
[
[
12] L. K. Keefer, S. M. Wang, T. Anjo, J. C. Fanning, C. S. Day, J.
Am. Chem. Soc. 1988, 110, 2800–2806.
13] R. A. O’Hair, S. Gronert, C. H. DePuy, Eur. Mass Spectrom.
1995, 1, 429–436.
3
spectroscopic (infrared, Raman, UV and multinuclear NMR)
methods. Additionally, the crystal structure of 3 was deter- [14] N. Wiberg, H. Bayer, G. Ziegleder, Z. Anorg. Allg. Chem. 1979,
4
59, 201–207.
15] J. R. Perrott, G. Stedman, N. Uysal, J. Chem. Soc. Dalton Trans.
976, 20, 2058–2064.
[16] W. C. E. Higginson, Spec. Publ. Chem. Soc. 1975, 10, 95.
mined by low temperature X-ray measurements and is dis-
[
cussed thoroughly using graph-set analysis. The (gas phase)
1
–
structures of the cis- and trans-[CH N O] anions and that of
3
2
3
3
were optimized using the B3LYP method with a 6- [17] P. M. Gannet, C. Garrett, T. Lawson, B. Toth, Fd. Chem. Toxic.
1991, 29, 49–56.
11+G(d,p) basis set and used to compute the NBO charges of
[
18] a) C. T. Pedersen, Acta Chem. Scand. 1964, 18, 2199–2000; b) J.
Thiele, Justus Liebigs Ann. Chem. 1911, 376, 239–268.
19] W. E. Bull, H. A. Seaton, L. F. Audrieth, J. Am. Chem. Soc. 1958,
80, 2516–2518.
all three species. Due to the expected energetic character of
compounds 1–3, the thermal stabilities and sensitivities against
impact, friction and electrostatics of all three compounds were
[
assessed using DSC analysis and standard BAM tests, respec- [20] a) NATO standardization agreement (STANAG) on explosives, im-
pact sensitivity tests, no. 4489, Ed. 1, 17 September, 1999; b)
tively. Finally, the combustion energy of compound 3 was de-
WIWEB-Standardarbeitsanweisung 4–5.1.02, Ermittlung der Ex-
termined experimentally and used to calculate the heat of for-
plosionsgefährlichkeit, hier der Schlagempfindlichkeit mit dem
mation and performance parameters of pure 3 and mixtures of
Fallhammer, 8 November, 2002; c) http://www.reichel-partner.de/.
[21] a) NATO standardization agreement (STANAG) on explosive,
friction sensitivity tests, no. 4487, Ed. 1, 22 August, 2002; b)
WIWEB-Standardarbeitsanweisung 4–5.1.03, Ermittlung der Ex-
plosionsgefährlichkeit oder der Reibeempfindlichkeit mit dem
Reibeapparat, 8 November, 2002.
3
with an oxidizer.
Acknowledgement
[
[
22] http://www.bam.de.
23] a) T. M. Klapötke, C. Miró Sabaté, J. M. Welch, Dalton Trans.
Financial support by the Centre Nationale de la Recherche Scientifique
(
CNRS), the Centre Nationale d’Études Spatiales (CNES), the Societé
Nationale des Poudres et des Explosifs (SNPE) and the University
Claude Bernard of Lyon are gratefully acknowledged. The authors are [24] Impact: Insensitive Ͼ40 J, less sensitive Ն 35 J, sensitive Ն 4 J,
2
008, 6372–6380; b) T. M. Klapötke, C. Miró Sabaté, J. Stier-
storfer, New J. Chem. 2009, 33, 136–147.
indebted and would like to thank Dr. Erwann Jeanneau for his valuable
help with the crystallographic studies.
very sensitive Յ 3 J; friction: Insensitive Ͼ360 N, less sensitive
= 360 N, sensitive Ͻ360 N a. Ͼ80 N, very sensitive Յ 80 n,
extreme sensitive Յ 10 N; According to the UN Recommenda-
tions on the Transport of Dangerous Goods (+) indicates: not safe
for transport.
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Consolidated, Volume I, National Bureau of Standards 1, 1972.
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© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
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