1124
M. E. Sitzmann, M. Bichay, J. W. Fronabarger, M. D. Williams, W. B. Sanborn and R. Gilardi
Vol. 42
resulting solution was allowed to cool to 25°. After 30 minutes,
the dark crystals were removed and washed with 4 x 1 mL of cold
water to give 75 mg (63%) of 5c; dsc (20°/minute): onset-194°,
peak-195°; ir (atr): 1698, 1595, 1575, 1542, 1462, 1364, 1336,
ate) was added slowly dropwise to 10 mL of the aqueous solution
of purified 1 [13]. A very light reddish precipitate formed and the
pH was 7-8 (by pH paper). The mixture was cooled to 5° for 1
hour before the crystals were removed by filtration and washed
with 3 x 2 mL of cold water. The light reddish crystals were air-
dried overnight to give 0.12 g of light yellow crystals of 5f. A sec-
ond crop of 5f (0.02 g obtained by removal of water from the fil-
trate and re-adding a small amount of water) brought the total yield
-1
1297, 1214, 1083, 971, 929, 884, 794, 773, 757 cm .
Anal. Calcd. for C N O Cs: Cs, 34.34. Found: Cs, 33.83.
6
5 7
Sodium 5-Nitro[1,2,5]oxadiazolo[3,4-e][2,1,3]benzoxadiazol-4-
olate-3,8-dioxide, Form A and/or B Not Established (5d).
1
to 0.14 g (74%); dsc (20°/minute): onset-187°, peak-190°; H nmr
13
A dilute solution of sodium hydroxide was prepared by adding
water (40 mL) to 0.48 g of sodium hydroxide pellets. Part (2.1
mL) of this solution (contains 0.025 g, 0.62 mmol of sodium
hydroxide) was added slowly dropwise to 10 mL of the aqueous
solution of purified 1 [13] stirred in an ice bath. The water was
removed under reduced pressure to give a red solid (0.18 g) that
was dissolved in 10 mL of acetone at 25°. The solution was fil-
tered to remove a small amount of insoluble solid and the filtrate
was concentrated under reduced pressure to a volume of 1-2 mL
before dichloromethane (7 mL) was slowly added to give 0.10 g
(56%) of 5d as the monohydrate; dsc (20°/minute): onset-149°,
peak-160°; ir (atr): 3516, 1698, 1652(this peak is somewhat larger
than usual for crystals that also exhibit the 1299 peak), 1602, 1578,
(300 MHz, dimethyl sulfoxide-d ): δ 6.88 (s); C nmr (75 MHz,
6
dimethyl sulfoxide-d ): δ 160.9, 158.5, 156.6 (guanidinium C),
150.3, 149.4, 139.6, 114.4, 109.5, 105.4, 101.4, 96.8 (the nmr solu-
6
tion is red-brown in color; removing the dimethylsulfoxide-d
6
under reduced pressure gave 5f as a yellow solid); ir (atr): 3490,
3374, 1646 (strong), 1571, 1558, 1418, 1289, 1247, 1083, 973,
-1
939, 802, 787, 777, 761 cm .
Anal. Calcd. for C H N O : C, 26.76; H, 1.92; N, 35.67.
7
6 8 7
Found: C, 26.91; H, 1.85; N, 35.52.
3,6-Dihydrazino-1,2,4,5-tetrazine, bis(5-nitro[1,2,5]oxadia-
zolo[3,4e][2,1,3]benzoxadiazol-4-ol-3,8-dioxide) Salt (6).
Purified 1 was prepared from 0.25 g (0.85 mmol) of 5a in sim-
ilar fashion to the procedure given in the general experimental
section above. To the solution of purified 1 in water (50 mL) was
added 0.12 g (0.85 mmol) of 3,6-hydrazino-1,2,4,5-tetrazine
[10]. The mixture was stirred for 30 minutes until all material
was dissolved. The water was removed under reduced pressure
to give 0.32 g of red-brown solid that was stirred with 25 mL of
isopropanol at 25° for 1 hour. The insoluble material (0.28 g)
was removed by filtration and stirred with 30 mL of isopropanol
at 25° for 1 hour to give 0.24 g (86%) of 6 as a red-brown solid;
-1
1548, 1468, 1384, 1338, 1299, 976, 931, 804, 763, 773 cm .
Anal. Calcd. for C N O Na(H O): C, 24.42; H, 0.68; N,
6
5
7
2
23.73. Found: C, 24.13; H, 0.96; N, 23.19.
In another experiment performed in the same manner as above,
the crude 5d (obtained by removal of water from the reaction
solution) was dissolved in methanol and then filtered to remove a
small amount of insoluble material. Removal of the methanol
gave 5d with a significantly different ir spectrum than the spec-
trum given above (e.g., there are major peaks at 1645 and 1296
-1
1
cm ). However, the ir of this same sample, taken months later,
dsc (20°/minute): onset-148°, peak-169°; H nmr (300MHz,
was identical to the one above.
dimethyl sulfoxide-d ): δ 10.54 (s); ir (atr): 3150 and 2900 region
6
(broad peaks), 1702, 1592, 1547, 1477, 1385, 1361, 1339, 1303,
Ammonium 5-Nitro[1,2,5]oxadiazolo[3,4-e][2,1,3]benzoxadia-
zol-4-olate-3,8-dioxide, Form A and/or B Not Established (5e).
-1
1205, 1083, 1000, 929, 893, 800, 772, 761 cm [14].
Anal. Calcd. for C H N O : C, 25.78; H, 1.24; N, 38.65.
14
8 18 14
A dilute solution of ammonium hydroxide was prepared by
adding water (5 mL) to 0.75 g of 29% ammonium hydroxide. Part
(approximately 0.5 mL) of this solution was added slowly dropwise
to 10 mL of the aqueous solution of purified 1 [13] until the pH
reached 7-8 (by pH paper). The water was removed under reduced
pressure to give a residue (0.14 g) that was a mixture of darker and
lighter colored crystals. The residue was stirred with 2 mL of
methanol at 25° and the mixture was filtered to give 0.04 g (24%) of
insoluble red-brown crystals of 5e; dsc (20°/minute): onset-185°,
Found: C, 25.85; H, 1.65; N, 37.15.
Acknowledgement.
Support for this work was received from the Indian Head
Division, Naval Surface Warfare Center: (1) Research and
Technology Department (Core Program) and (2) CAD/PAD
Department. RG thanks the Office of Naval Research, Mechanics
Division, for support.
1
peak-192°; H nmr (300MHz, dimethyl sulfoxide-d ): δ 7.1 (broad
6
s); ir (atr): 3188, 1693, 1595, 1548, 1474, 1423, 1372, 1332, 1299,
REFERENCES AND NOTES
-1
1201, 1083, 1003, 976, 931, 892, 801, 781, 772, 760 cm .
Anal. Calcd. for C H N O : C, 26.48; H, 1.48; N, 30.88.
6
4
6
7
*
Authors to whom correspondence should be addressed.
Found: C, 26.58; H, 1.67; N, 30.23.
Regarding synthesis/ properties: MES/JWF; Regarding crystal structures:
RDG.
[1] R. J. Spear and W. P. Norris, Propellants, Explosives,
Pyrotechnics, 8, 85 (1983).
[2] W. P. Norris, A. Chafin, R. J. Spear and R. W. Read,
Heterocycles, 22, 8 (1984).
[3] By J. W. Fronabarger. In U. S. Patent application: John W.
Fronabarger and Michael E. Sitzmann, "Nitrobenzodifuroxan
Compounds, Including Their Salts, and Methods Thereof", 13 Aug 2003.
[4] P. N. Preston and G. Tennant, Chem. Rev., 72, 650 (1972).
[5] Our initial attempt to prepare such a hydrolyzable intermedi-
ate (namely, 3,5-diazido-2,4,6-trinitrochlorobenzene), by treating 1,3,5-
trichloro-2,4,6-trinitrobenzene with two equivalents of sodium azide was
When the methanol solvent was removed from the filtrate
above, the crystals obtained are a mixture of both forms as indi-
cated by the ir spectrum which shows a reasonably strong peak
-1
-1
at 1649 cm and peaks at 1299 and 1281 cm of about equal
intensities.
Guanidinium 5-Nitro[1,2,5]oxadiazolo[3,4-e][2,1,3]benzoxadia-
zol-4-olate-3,8-dioxide, Mostly Form A (5f).
A dilute solution of guanidine carbonate was prepared by adding
water (5 mL) to 0.28 g of guanidine carbonate. Part (1 mL) of this
solution (contains 0.056 g, 0.62 equivalents of guanidine carbon-