J. W. Fronabarger et al. / Tetrahedron Letters 47 (2006) 7707–7709
7709
retrieving the crystallographic data9 (Figs. 1 and 2) for
publication.
C5H9N12Br (%): C, 18.95; H, 2.86; N, 53.00; Br, 25.20.
Found: C, 18.96; H, 3.09; N, 52.45; Br (by difference),
25.50.
9. Single-crystal X-ray diffraction analysis of 3 hydrate:
C5H11BrN12O, FW = 335.17, Orthorhombic, Ccc2, a =
References and notes
˚
˚
˚
15.7916(11) A, b = 25.510(2) A, c = 6.2985(9) A, a = 90°,
3
˚
1. Chapman, R. D.; Fronabarger, J. W.; Gilardi, R. D.
High-temperature explosives for insensitive-munitions
applications. ILIR Annual Report 2000; Naval Air War-
fare Center Weapons Division TP 8494: China Lake, CA,
2001; pp 195–200. Article available from the National
b = 90°, c = 90°, V = 2537.3(5) A , Z = 8, qcalcd
=
1.755 Mg/m3, l = 4.615 mmꢀ1
,
F(000) = 1344, R1 =
0.0608 for 1618 observed (I > 2rI) reflections and 0.0621
for all 1675 reflections, Goodness-of-fit = 1.114, 188
parameters. The data were collected on a Bruker P4
four-circle diffractometer. The crystals were irradiated
using
graphite
monochromated
CuKa
source
2. Wermann, K.; Walther, M.; Gunther, W.; Go¨ls, H.;
¨
Anders, E. Eur. J. Org. Chem. 2003, 1389–1403.
3. Wermann, K.; Walther, M.; Gunther, W.; Go¨ls, H.;
¨
Anders, E. Tetrahedron 2005, 61, 673–685.
4. Anders, E.; Wermann, K.; Wiedel, B.; Gunther, W.; Go¨ls,
¨
H. Eur. J. Org. Chem. 1998, 2923–2930.
5. Leonard, N. J.; Curtin, D. Y.; Beck, K. M. J. Am. Chem.
Soc. 1947, 69, 2459–2461.
(k = 1.54178). The corrections were applied for Lorentz,
polarization and absorption effects using SADABS [Bruker
(2000). SADABS v 2.03, Bruker AXS Inc., Madison,
Wisconsin, USA]. The structure was solved and refined
with the aid of the programs in the SHELXTL-plus system
of programs [Bruker (2000). SHELXTL v 6.10. Bruker AXS
Inc., Madison, Wisconsin USA]. The full-matrix least-
squares refinement on F2 included atomic coordinates and
anisotropic thermal parameters for all non-H atoms. The
H atoms were included using a riding model, except for the
water hydrogens, which were refined with fixed associative
distances. This structure was determined to be a two-
component merohedral twin with a relative population
ratio of 65:35.
6. Nam, G.; Lee, J. C.; Chi, D. Y.; Kim, J.-H. Bull. Korean
Chem. Soc. 1990, 11, 383–386.
7. Potts, K. T.; Hirsch, C. J. Org. Chem. 1968, 33, 143–150.
8. Preparation of 3: A mixture of 14.02 g (0.123 mol) of 3,4,5-
triamino-1,2,4-triazole (1) and 7.60 g (0.072 mol) of cyano-
gen bromide in 200 mL DMF was heated in a water
bath at 80–81 °C for 2.5 h. The mixture, which contained
a considerable amount of solid, was then cooled to
ambient temperature, and the solid was collected on a
medium-porosity fritted-glass filter funnel, washed twice
with 25-mL portions of DMF and finally thrice with 2-
propanol. After drying at 70 °C, the yield of a light olive
solid (3) was 13.36 g (0.042 mol, 68% based on 1). Multiple
crystallizations from water gave small colourless needles,
the form analyzed by X-ray crystallography. A sample for
elemental analysis was vacuum dried over P4O10. DSC:
exotherm 290 °C (onset), 293 °C (peak). 1H NMR
(DMSO-d6, 300 K) d 6.06 (s, 4H), 7.32 (s, 2H), 7.41 (s,
10. Claramunt, R. M.; Sanz, D.; Catala´n, J.; Fabero, F.;
Garc´ıa, N. A.; Foces-Foces, C.; Llamas-Saiz, A. L.;
Elguero, J. J. Chem. Soc., Perkin Trans. 2 1993, 1687–
1699.
11. Bowie, R. A.; Thomason, D. A.; Jarvis, J. A. J. Tetra-
hedron Lett. 1973, 1643–1644.
12. Child, R. G. J. Heterocycl. Chem. 1965, 2, 98–99.
13. Preparation of 1: A solution of 140.27 g (2.00 mol) of
dimethylcyanamide and 68.49 g (2.14 mol) of 98% hydra-
zine in 250 mL of 2-methoxyethanol was refluxed for 7 h
and then allowed to stand at an ambient temperature
overnight. The solid that formed was collected on a
medium-porosity fritted-glass filter funnel, washed once
with 2-propanol–2-methoxyethanol (4:1) and four times
with 2-propanol, and then allowed to air-dry overnight.
The yield of gray solid was 48.50 g (0.425 mol, 42.5%). Mp
255–258 °C dec; lit.12 262–263 °C dec.
1
2H), 7.63 (s, 1H). H NMR (DMSO-d6, 333 K) d 5.95 (s,
4H), 7.21 (bs, 4H), 7.58 (s, 1H). 13C NMR (DMSO-d6,
2
300 K): d 136.5 (non-1H-decoupled d, JCH = 6.0 Hz),
147.7, 149.0, 154.05 (1H-decoupled), 154.11 (1H-decou-
pled). IR (KBr): 3396, 3316, 1721, 1661, 1602, 1268, 1120,
1061, 993, 815, 766, 722, 638 cmꢀ1. Anal. Calcd for
14. Emilsson, H. J. Heterocycl. Chem. 1989, 26, 1077–1081.