Method for azidoaminotriazole, nitrosoguanazine, and related compounds

The Method of Making Azidoaminotriazole (5-azido-2H-[1,2,4]triazol-3-ylamine)(4) from Guanazine ([1,2,4]triazole-3,4,5-triamine) (1)

In an exemplary embodiment of the present invention, guanazine (1) (approximately 0.90 g, 7.9 mmol) may be dissolved in about 18 ml of distilled water at 23° C. and the resulting solution then stirred and cooled in an ice bath. Sodium nitrite (approximately 0.54 g, 7.9 mmole) may then be added. After the sodium nitrite dissolves, a solution of acetic acid (approximately 1.50 g, 25 mmole) in about 6 ml of distilled water may be slowly added, dropwise over about 30 minutes. The solution may be held at an ice bath temperature for about one hour before it is allowed to warm to about 22° C. over about one and a half hours. After about 30 minutes at about 22° C., a red-orange precipitate may be removed by filtration and washed twice with about 2 ml of water. The red-orange precipitate may weigh approximately 0.38 g after air-drying. The filtrate may then be extracted 3× with about 20 ml of ethyl acetate. The solvent may be removed from the combined ethyl acetate extracts to give approximately 0.36 g (approximately 37% yield) of azidoaminotriazole (4) (mp approximately 160-165° C., decomposition) that contained small amounts of impurities by TLC and 1 H NMR analyses. TLC: R F of (4)=0.63 (chloroform/methanol/acetic acid, 40/8/1, v/v/v as developer). See 1 HNMR and 13 C NMR in Example 3, below.

The red-orange precipitate may contain very little azidoaminotriazole (4) by TLC analysis. The main component may be a yellow by-product that may be extracted into hot methanol. This yellow by-product may precipitate as a methanol solvate upon cooling. The yellow by-product has a melting point of about 160° C., with very rapid decomposition. Other analytical values of the yellow by-product may be as follows: TLC: R F =0.30 (chloroform/methanol/acetic acid, 40/8/1, v/v/v as developer); IR (ATR): 3500-3800, 2141 (medium), 1360,1327 (medium strong), 1209 (strong) cm −1 ; 1 H NMR (DMSO-d 6 ): 5.80 (s, 2H), 6.37 (s, 2H), 12.38 (s, 1H), 12.81 (s, 1H) with peaks for methanol at 3.15 and 4.09; and 13 C NMR (DMSO-d 6 ): 152.5, 156.0, 162.1 (broadened) with a peak for methanol at 49.0.

The Method of Making a Dimer of Nitrosoguanazine (N 3 -[(1E)-3-(4,5-diamino-4H-1,2,4-triazol-3-yl)-1,2-dioxidotriaz-1-enyl]-4H-1,2,4-triazole-3,4,5-triamine) (2a)

In another exemplary embodiment of the present invention, guanazine ([1,2,4]triazole-3,4,5-triamine) (1) (5.4 g, 0.0473 mole) may be dissolved in about 90 ml of distilled water at about 23° C. and the solution may then be stirred and cooled in an ice bath. Sodium nitrite of approximately 97% purity (approximately 3.36 g, 0.0487 moles) may be added to the solution. After the sodium nitrite is dissolved, a solution of acetic acid of 99+ % purity (approximately 2.92 g, 0.0487 mole) in about 54 ml of distilled water may be added, dropwise over about ten minutes. The flask may then be stoppered and stirring in the ice bath may be continued for about one hour. The ice may then be removed and the bath may be allowed to warm to about 23° C. over about two hours. The mixture, which now contains some yellow precipitate, may be stirred for about an additional hour at about 23-24° C. before the stirring is stopped. The mixture may be allowed to stand overnight, e.g., about 17 hours, in a water bath at about 22-24° C. The yellow precipitate of guanazine (2a) may be removed by filtration and washed 4× with about 20 ml of cold water. The resulting product may then be air dried at room temperature overnight to yield approximately 4.87 g (72%), with a melting point of about 143° C., decomposition. Other analytical values of the resulting product may be as follows: 1 H NMR (DMSO-d 6 ): 5.68 (s, 2H), 6.28 (s, 2H) 13.8 (broad); and IR (ATR): 3301, 3171, 1680 (strong), 1636, 1564, 1504, 1256 (strong), 1146, 1067, 980, 901, 800, 752, 720 cm 1 . Analysis: Calculated for C 4 H 10 N 14 O 2 : C, 16.79; H, 3.52; N, 68.51. Found: C, 16.69; H, 3.63; N, 68.29; DSC (20° C./min): Onset: 152; Peak: 154.

The Method of Making Azidoaminotriazole (5-azido-2H-[1,2,4]triazol-3-ylamine)(4) from Nitrosoguanazine Dimer (N 3 -[(1E)-3-(4,5-diamino-4H-1,2,4-triazol-3-yl)-1,2-dioxidotriaz-1-enyl]-4H-1,2,4-triazole-3,4,5-triamine) (2a) in Water

In yet another exemplary embodiment of the present invention, nitrosoguanazine (2a) (approximately 1.0 g, 0.0035 mole) may be stirred in about 30 ml of distilled water and the mixture may then be heated to about 70° C. over about 15 minutes and then may be held at about 70-75° C. for about 45 minutes. The mixture may then be cooled slightly before it is filtered to remove a small amount of a dark precipitate. This filtrate may then be extracted 5× with about 30 ml of ethyl acetate and the solvent may be removed from the combined ethyl acetate extracts to yield approximately 0.63 g (approximately 72% yield) of yellow crystals with a melting point of about 175° C., (decomposition) that were essentially pure azidoaminotriazole (4) by 1 HNMR analysis. The azidoaminotriazole (4) may tend to retain some residual ethyl acetate but this may be removed by crystallization from water or methanol. Alternatively, removing volatiles from the filtrate under reduced pressure may yield crystals of azidoaminotriazole (4). Analytical results for this preparation of azidoaminotriazole (4) may be as follows: 1 H NMR (DMSO-d 6 ): 6.31 (s, 2H), 11.91 (s, 1H); 13 C NMR (DMSO-d 6 ): 154.39, 157.26; IR (ATR): 3420, 3398, 3161, 2147 (N 3 , very strong), 1670, 1601, 1544 (strong), 1461, 1410, 1361, 1225, 1107, 718 cm −1 . Analyis: Calculated for C 2 H 3 N 7 : C, 19.20; H, 2.42; N, 78.38. Found (crystals from water): C, 18.90; H, 2.42; N, 77.65. Found (crystals from methanol): C, 18.97; H, 2.41; N, 77.55; Differential Scanning Calorimetry (20° C./min): Onset: 174; Peak: 184.

The Method of Making Azidoaminotriazole (5-azido-2H-[1,2,4]triazol-3-ylamine)(4) from Nitrosoguanazine Dimer (N 3 -[(1E)-3-(4,5-diamino-4H-1,2,4-triazol-3-yl)-1,2-dioxidotriaz-1-enyl]-4H-1,2,4-triazole-3,4,5-triamine) (2a) in Water and Acetic Acid

In yet another exemplary embodiment of the present invention, nitrosoguanazine (2a) (approximately 0.86 g, 0.003 mole) may be stirred in about 7 ml of distilled water and a solution of acetic acid (approximately 0.09 g, 0.0015 mole) in about 2 ml of water may then be added. This mixture may be heated to about 78-80° C. over about 15 minutes and then held at about 75-77° C. for about 45 minutes. The mixture may be cooled slightly before it is filtered to remove a small amount of dark solid that may be washed twice with about 2.5 ml of warm water. The volatiles may be removed from the filtrate under reduced pressure to yield approximately 0.71 g of a gummy yellow brown solid that is washed 3× with about 1.5 ml water to further yield 0.56 g (approximately 75% yield) of brownish yellow crystals of azidoaminotriazole (4). The water wash solution may be concentrated to give a second crop of 0.03 g, bringing the yield to approximately 79%.

Example 5 generally relates to the method of making acid salts of azidoaminotriazole (5-azido-2H-[1,2,4]triazol-3-ylamine) (4).

The Method of Making Azidoaminotriazole (5-azido-2H-[1,2,4]triazol-3-ylamine), nitric acid salt (6)

In yet another exemplary embodiment of the present invention, azidoaminotriazole (4) (approximately 50 mg) may be stirred in about 5 ml of water, while the mixture is acidified by the slow addition of dilute (approximately 8%) nitric acid. All material dissolved and the water may be allowed to evaporate to yield a crystalline residue (approximately 60 mg). Analytical values for this crystalline residue may be as follows: 1 H NMR (DMSO-d 6 ): 9.21 (bs); 13 C NMR (DMSO-d 6 ): 149.55, 153.69; IR (ATR): 3430, 3338, 2738, (2202, 2165, N 3 , weak), 1714 (medium strong), 1590, 1530, 1434, 1301 (strong), 1183, 1048, 1034, 1002, 843, 815, 803, 727, 707 cm −1 . Differential Scanning Calorimetry (20° C./min): Onset: 172; Peak: 174. Crystal structure analysis shows the product to be azidoaminotriazole, nitric acid salt (6). Analysis: Calculated for C 2 H 4 N 8 O 3 : C, 12.77; H, 2.14; N, 59.57. Found: C, 12.92; H, 2.31; N, 59.15.

The azidoaminotriazole nitric acid salt (6) may be expected to be useful as an intermediate towards the making of azidonitraminotriazole because analogously, nitraminotetrazole was prepared by dehydration of the aminotetrazole nitric acid salt with sulfuric acid by R. M. Herbst and J. A. Garrison as reported in J. Org. Chem., 1953, 18, 941.

Examples 6-8 generally relate to the making of azidonitraminotriazole (3-azido-N-nitro-1H-1,2,4-triazol-5-amine) (7) from azidoaminotriazole (5-azido-2H-[1,2,4]triazol-3-ylamine), nitric acid salt (6) and the conversion of the azidonitraminotriazole to mono- and di-potassium salts.

The Making of Azidonitraminotriazole (3-azido-N-nitro-1H-1,2,4-triazol-5-amine) (7) from azidoaminotriazole (5-azido-2H-[1,2,4]triazol-3-ylamine), nitric acid salt (6)

In yet another exemplary embodiment of the present invention, the nitric acid salt of azidoaminotriazole (6) (approximately 0.17 g, 0.0096 mole) may be added in about 0.1 g portions over about 15 minutes to concentrated (about 95-98%) sulfuric acid (about 13 ml) and stirred well at about 3° C. in an ice bath. The resulting mixture may be stirred in the ice bath for about an additional 10 minutes before the mixture is allowed to warm to about 8-10° C. over about 20 minutes. The mixture may be held at about 8-10° C. for about 20 minutes and then poured onto ice (about 72 g). A yellow solution may be extracted twice with about 60 ml of ethyl acetate, followed by another course (3×) with about 50 ml of ethyl acetate. The combined extracts may be dried with sodium sulfate and the volatiles may then be removed under reduced pressure to give approximately 0.98 g of a yellow-orange solid. The yellow-orange solid may be stirred with about 10 ml of chloroform at about 25° C. to yield (0.88 g (approximately 54% yield) of azidonitraminotriazole (7). The azidonitraminotriazole (7) may be stirred in about 35 ml of water at about 25° C. to dissolve all but a very small amount of impurity that is removed by filtration. The water may be removed from the filtrate under reduced pressure to give 0.80 g of yellow-orange crystals. When heated, the crystals may deflagrate (with a burst of flame) in the vicinity of 150° C. Analytical values for these crystals may be as follows: 1 H NMR (acetone-d 6 ): 10.8 (very broad); 13 C NMR (acetone-d 6 ): 151.2, 152.3; IR (ATR): 3400-2900 (broad absorption), 2192 (weak, N 3 ), 2163 (medium, N 3 ), 1690, 1593 (strong), 1560, 1496, 1419, 1304 (strong), 1260 (strong), 1118, 1098, 994 cm −1 ; and TLC (chloroform/methanol/acetic acid, 40/8/1, v/v/v as developer): R F =0.27 (visualized with uv light).

The Making of Azidonitraminotriazole (3-azido-N-nitro-1H-1,2,4-triazol-5-amine), mono-potassium salt (8)

In yet another exemplary embodiment of the present invention, azidonitraminotriazole (7) (approximately 0.17 g, 0.001 mole) may be stirred in about 7 ml of distilled water, while about 2 ml of potassium hydroxide solution (containing about 0.001 mole of KOH) is slowly added, dropwise. The postassium hydroxide may, for example, may be prepared by dissolving approximately 0.67 g of about 85% KOH in about 20 ml of distilled water. The reaction solution may be filtered to remove a very small amount of insoluble material, before the water is removed from the filtrate under reduced pressure. The resulting crystalline residue is washed with about 10 ml of chloroform to give 0.21 g (100%) of light orange crystals. The light orange crystals may be stirred with about 1.5 ml of methanol at about 25° C. for about 5 minutes before the crystals (approximately 0.18 g, 86%) are removed by filtration and washed with chloroform. The resulting product, cream colored crystals with an orange tint, may be stirred with methanol (about 2 ml) at about 25° C. for about one hour to give approximately 0.16 g of cream-colored crystals of the azidonitraminotriazole (3-azido-N-nitro-1H-1,2,4-triazol-5-amine), mono-potassium salt (8). When heated, the crystals may explode in the vicinity of 195° C. Analytical values for these crystals may be as follows: 1 H NMR (DMSO-d 6 ): 12.72 (s); and 13 C NMR (DMSO-d 6 ): 154.2, 157.3; IR (ATR): 3613, 3400-3000 (broad), 2146 (medium, N 3 ), 1529, 1508, 1431, 1344 (strong), 1259, 1230, 1099, 1003, 858, 740 cm −1 . A sample of the crystals, dried in a vacuum desiccator over Drierite for 18 hours, exhibited no change in the IR spectrum.

The Making of Azidonitraminotriazole (3-azido-N-nitro-1H-1,2,4-triazol-5-amine), di-potassium salt

In yet another exemplary embodiment of the present invention, azidonitraminotriazole (7) (approximately 0.085 g, 0.0005 mole) may be stirred in about 2 ml of methanol. A solution of approximately 0.08 g of about 85% potassium hydroxide in about 1 ml of methanol (containing approximately 0.0012 mole KOH) may be added to the stirred solution of azidonitraminotriazole in methanol. The resulting mixture, containing a precipitated salt, may be stirred for about an additional 15 minutes before the salt is removed by filtration and washed twice with about 0.5 ml of methanol and 4× with about 1 ml of chloroform to give approximately 0.09 g (75%) of 3-azido-N-nitro-1H-1,2,4-triazol-5-amine, di-potassium salt, as cream-colored crystals. When heated, these crystals may explode in the vicinity of 190° C. Analytical values for these crystals may be as follows: 1 H NMR (DMSO-d 6 /D 2 O, 90/10): no peaks; and 13 C NMR (DMSO-d 6 /D 2 O, 90/10): 160.1, 167.6; IR (ATR): 3661, 3400-3000 (broad), 2144 (medium, N 3 ), 1427, 1402, 1337 (medium strong), 1294 (strong), 1102, 1025, 1003, 863 cm −1 . A sample of these crystals, dried in a vacuum desiccator over Drierite for 18 hours, may exhibit a changed IR spectrum (mainly in the OH and N 3 region), where absorption in the OH region is essentially gone and the N 3 absorption is now two peaks at 2168 and 2151 cm −1 , with approximately equal intensities.

The Method of Making Azidoaminotriazole (5-azido-2H-[1,2,4]triazol-3-ylamine), Hydrochloric Acid Salt Hydrate

In yet another exemplary embodiment of the present invention, azidoaminotriazole (5-azido-2H-[1,2,4]triazol-3-ylamine) (4) (approximately 50 mg) may be stirred in about 5 ml of water, while the mixture is acidified by the slow addition of 1N HCl. All material dissolved and the water may be allowed to evaporate to yield a crystalline residue (approximately 60 mg). Analytical values for this crystalline residue may be as follows: IR (ATR): 3383, 3256, 3096, 2951, 2719, 2151 (N 3 , medium strong), 1685 (strong), 1593, 1522, 1358, 1201, 1049, 1009, 873, 801, 757, 718 cm −1 . Single crystal X-ray diffraction analysis shows the product to be the azidoaminotriazole, hydrochloric acid salt hydrate. Analysis: Calculated for C 2 H 6 ClN 7 O: C, 13.38; H, 3.37; C119.74, N, 54.60. Found: C, 13.85; H, 3.33; Cl, 19.88, N, 55.43.

Examples 10 and 11 generally relate to the method of making alkali metal salts of nitrosoguanazine.

The Method of Making Nitrosoguanazine (N 3 -nitroso-4H-1,2,4-triazol-3,4,5-triamine), Sodium Salt Hydrate (5a)

In yet another exemplary embodiment of the present invention, nitrosoguanazine dimer (N 3 -[(1E)-3-(4,5-diamino-4H-1,2,4-triazol-3-yl)-1,2-dioxidotriaz-1-enyl]-4H-1,2,4-triazole-3,4,5-triamine) (2a) (approximately 0.92 g, 3.2 mmol) may be stirred in about 15 ml of distilled water at room temperature, while slowly adding, dropwise, a solution of sodium hydroxide (approximately 0.27 g, 6.7 mmole) in about 9 ml of water. At the end of the addition, essentially all material may be dissolved. A small amount of additional dilute sodium hydroxide may slowly be added as necessary to give complete solution. The water may be evaporated from the solution to yield approximately 1.20 g of a yellow-orange solid that was stirred for a short time with about 5 ml of methanol. An insoluble yellow orange salt may then be removed by filtration for a yield of approximately 0.77 g. Methylene chloride (about 10 ml) may then be added to the filtrate to yield an additional 0.30 g of the insoluble yellow orange salt, bringing the total yield to approximately 1.07 g (91%). Analytical values for this insoluble yellow orange salt may be as follows: 13 C NMR (D 2 O): 154.72, 154.99; and IR (ATR): 3310, 3109, 1660 (strong), 1620, 1580, 1560, 1499, 1330, 1282, 1239 (strong), 1143, 983, 944, 904, 890, 748, 720, 696 cm −1 . Differential Scanning Calorimetry (20° C./min): Endotherm: 131; Onset: 259; Peak: 265. Single crystal X-ray diffraction analysis shows the insoluble yellow orange salt to be the nitrosoguanazine (N 3 -nitroso-4H-1,2,4-triazol-3,4,5-triamine), sodium salt hydrate (5a). Analysis: Calculated for C 2 H 6 N 7 NaO 2 : C, 13.12; H, 3.30; N, 53.55; Na, 12.56. Found: C, 12.92; H, 3.66; N, 51.44, Na, 12.64.

The Method of Making Nitrosoguanazine (N 3 -nitroso-4H-1,2,4-triazol-3,4,5-triamine), Potassium Salt (5b)

In yet another exemplary embodiment of the present invention, nitrosoguanazine dimer (N 3 -[(1E)-3-(4,5-diamino-4H-1,2,4-triazol-3-yl)-1,2-dioxidotriaz-1-enyl]-4H-1,2,4-triazole-3,4,5-triamine) (2a) (approximately 0.90 g, 3.15 mmole) may be stirred in about 15 ml of distilled water at room temperature, while slowly adding, dropwise, a solution of approximately 85% potassium hydroxide pellets (approximately 0.43 g, 6.42 mmole) in about 7 ml of water. At the end of the addition, essentially all material may be dissolved. A small amount of additional dilute potassium hydroxide may be slowly added as necessary to give complete solution. The water may be evaporated from the solution to give about 1.27 g of a yellow-orange solid that may be washed 4× with about 3 ml of methanol to yield approximately 1.04 g (91%) of a yellow orange salt. Analytical values for this yellow orange salt may be as follows: 13 C NMR (D 2 O): 154.88, 155.00; and IR (ATR): 3319, 3131, 1657, 1631, 1574, 1518, 1491, 1276, 1244, 1143, 1038, 956, 889, 723, 701 cm −1 . Differential Scanning Calorimetry (20° C./min): Onset: 228; Peak: 247. Single crystal X-ray diffraction analysis shows the yellow orange salt to be the nitrosoguanazine (N 3 -nitroso-4H-1,2,4-triazol-3,4,5-triamine), potassium salt (5b). Analysis: Calculated for C 2 H 4 KN 7 O: C, 13.26; H, 2.23; K, 21.58; N, 54.11. Found: C, 13.51; H, 2.70; K, 20.99; N, 52.92.

Examples 12-14 generally relate to the method of making copper salt complexes of nitrosoguanazine (N 3 -nitroso-4H-1,2,4-triazol-3,4,5-triamine).

The Method of Making Nitrosoguanazine (N 3 -nitroso-4H-1,2,4-triazol-3,4,5-triamine) Copper Salt Complex from Copper Nitrate

In yet another exemplary embodiment of the present invention, nitrosoguanazine (N 3 -nitroso-4H-1,2,4-triazol-3,4,5-triamine) potassium salt (5b) (approximately 0.08 g, 0.44 mmole) in about 1 ml of water may be stirred at room temperature, while a solution containing approximately 0.10 g (0.43 mmole) of copper (II) nitrate hemipentahydrate in about 1 ml of water is added, dropwise. A brownish black precipitate may immediately form and may eventually turn to a green precipitate as more copper nitrate solution is added. The mixture may be stirred at room temperature for about 15 minutes before being cooled to about 5° C. for about 15 minutes. The mixture may then be filtered and the product washed 3× with about 1 ml of ice water to yield approximately 0.10 g of a green solid. Analytical values for this green solid may be as follows: IR (ATR): 3312, 1661 (strong), 1623, 1544, 1503, 1390-1318 (very strong), 1166, 1138, 1080, 1070, 1046, 918, 820, 747, 726 cm −1 . Differential Scanning Calorimetry (20° C./min): Onset: 218; Peak: 231. Single crystal X-ray diffraction analysis shows the green solid to be a nitrosoguanazine (N 3 -nitroso-4H-1,2,4-triazol-3,4,5-triamine) copper salt complex, containing three Cu 2+ ions, three nitrosoguanazine anions, two nitrate anions, one hydroxide anion and two water molecules.

The Method of Making Nitrosoguanazine (N 3 -nitroso-4H-1,2,4-triazol-3,4,5-triamine) Copper Salt Complex from Copper Perchlorate

In yet another exemplary embodiment of the present invention, nitrosoguanazine (N 3 -nitroso-4H-1,2,4-triazol-3,4,5-triamine) potassium salt (5b) (approximately 0.09 g, 0.49 mmole) in about 1 ml of distilled water may be stirred at room temperature, while a solution containing approximately 0.18 g (0.44 mmole) of copper (II) perchlorate hexahydrate in 1 about ml of distilled water is added, dropwise. A brownish black precipitate may immediately form and may eventually turn to a green precipitate as copper perchlorate solution is added. This mixture may be stirred at room temperature for about 15 minutes before it is cooled to about 5° C. for about 15 minutes. The precipitate may be filtered and the product may then be washed with about 1 ml of ice water to yield approximately 0.10 g of a green solid. Analytical values for this green solid may be as follows: IR (ATR): 3335, 1665 (strong), 1557, 1505, 1388, 1357, 1080 (very strong), 921, 726 cm −1 . Differential Scanning Calorimetry (20° C./min): Onset: 206; Peak: 232.

The Method of Making Nitrosoguanazine (N 3 -nitroso-4H-1,2,4-triazol-3,4,5-triamine) Copper Salt Complex from Copper Sulfate

In yet another exemplary embodiment of the present invention, nitrosoguanazine (N 3 -nitroso-4H-1,2,4-triazol-3,4,5-triamine) potassium salt (5b) (approximately 0.16 g, 0.88 mmole) in about 1 ml of water was stirred at room temperature, while a solution containing approximately 0.23 g (0.92 mmole) of copper (II) sulfate pentahydrate in about 1 ml of water was added, dropwise. A brownish black precipitate may immediately form and may eventually turn to a green precipitate as more copper sulfate solution is added. The mixture may be stirred at room temperature for about 15 minutes before it is cooled to about 5° C. for about 15 minutes. The mixture may then be filtered and the product may be washed 3× with about 1 ml of ice water to yield 0.21 g of a green solid. Analytical values for this green solid may be as follows: IR (ATR): 3321, 1657, 1626, 1549, 1504, 1386, 1324, 1100-1040 (very strong), 972, 920, 746, 724 cm −1 .

Examples 15-17 generally relate to the method of making 4,6-diazido-N-nitro-1,3,5-triazin-2-amine (11a) and its cesium (11b) and rubidium (11c) salts, respectively.

A Method for Making 4,6-diazido-N-nitro-1,3,5-triazin-2-amine (11a)

In yet another exemplary embodiment of the present invention, nitric acid (100%, about 56 ml) may be placed in a 250 ml beaker and chilled in an ice bath to about 1° C. A starting material, 6-amino-2,4-diazido-[1,3,5]-triazine (10) (approximately, 4.27 g, 23.98 mmol), may be added as a solid in portions over about 15 minutes to the nitric acid, while the temperature is maintained at or below about 3° C. After the starting material is added, the resulting yellow mixture may be stirred for about 30 minutes at an ice bath temperature. The yellow mixture may then be removed from the ice bath and allowed to stand overnight at ambient temperature. The yellow mixture may be quenched by pouring it onto 520 ml of ice, giving about 400 ml of a liquid volume. A precipitate may form on stirring for about 45 minutes. The precipitate may be filtered over a medium frit and washed with ice water, giving a white material. The white material may then be dried in a drying oven at about 65° C. to yield approximately 3.26 g (14.61 mmol, 61% yield) of the desired 4,6-diazido-N-nitro-1,3,5-triazin-2-amine (11a). Analytical values for this white material may be as follows: 1 H NMR (DMSO-d 6 ): 12.10 (bs); 13 C NMR (DMSO-d 6 ): 150.39, 158.49, 163.44, 163.52, 170.41; and IR: 2183, 2153, 1623, 1553 (strong), 1393, 1333 (strong), 1279 (strong), 1192, 1159, 1073, 1016, 968, 808, 701 cm −1 . Differential Scanning Calorimetry (20° C./min): Onset: 175; Peak: 179.

The Method of Making 4,6-diazido-N-nitro-1,3,5-triazin-2-amine, Cesium Salt (11b)

In yet another exemplary embodiment of the present invention, 4,6-diazido-N-nitro-1,3,5-triazin-2-amine (11a) (approximately 5.0 g, 22.42 mmol) may be dissolved in about 130 ml of methyl alcohol by heating slightly in a hot water bath. Cesium hydroxide (approximately 1.05 eq., 3.95 g) may be dissolved in about 10 ml of methyl alcohol and added quickly to the solution of 4,6-diazido-N-nitro-1,3,5-triazin-2-amine (11a). A white precipitate may quickly form and the mixture may be stirred for about an additional 15 minutes. The white precipitate may be filtered over #1 Whatman paper and washed twice with methyl alcohol. The resulting material may then be dried at room temperature overnight to yield approximately 4.57 g (12.87 mmol) of the 4,6-diazido-N-nitro-1,3,5-triazin-2-amine, cesium salt (11b) (approximately 60% yield), as a white crystalline solid. Analytical values for this white crystalline solid may be as follows: IR: 2191, 2134, 1573, 1499, 1399, 1372, 1346, 1259 (strong), 1231, 1195, 1170, 1013, 974, 805, 779, 721 cm −1 . Differential Scanning Calorimetry (20° C./min): Endotherm: 178: Onset: 182; Peak: 223.

The Method of Making 4,6-diazido-N-nitro-1,3,5-triazin-2-amine, Rubidium Salt (11c)

In yet another exemplary embodiment of the present invention, 4,6-diazido-N-nitro-1,3,5-triazin-2-amine (11a) (approximately 6.0 g, 26.91 mmol) may be dissolved in about 160 ml of methyl alcohol by heating slightly in a hot water bath. Rubidium hydroxide (1.1 eq., 3.50 ml) may be dissolved in about 20 ml of methyl alcohol and added quickly to the solution of 4,6-diazido-N-nitro-1,3,5-triazin-2-amine (11a). A white precipitate may quickly form and the mixture may be stirred for about an additional 40 minutes. The white precipitate may be filtered over #1 Whatman paper and washed three times with methyl alcohol. The resulting material may then be dried at 65° C. for about 15 minutes and then at room temperature overnight to yield approximately 4.1 g (13.31 mmol) of the 4,6-diazido-N-nitro-1,3,5-triazin-2-amine, rubidium salt (11c) (approximately 50% yield), as a white crystalline solid. Analytical values for this white crystalline solid may be as follows: 13 C NMR (DMSO-d 6 ): 150.46, 158.51, 163.51; and IR: 2195, 2137, 1573, 1501, 1398, 1374, 1347, 1262 (strong), 1233, 1190, 1170, 1018, 975, 804, 780, 722 cm −1 . Differential Scanning Calorimetry (20° C./min): Endotherm: 187: Onset: 190; Peak: 214.

Because many varying and different exemplary embodiments may be made with the scope of the inventive concepts taught herein, and because many modifications may be made in the exemplary embodiments detailed herein in accordance with the descriptive requirements of the law, it is to be understood that the detailed descriptions herein are to be interpreted as illustrative and not in a limiting sense.

Finally, the numerical parameters set forth in the specification and attached claims are approximations (for example, by using the term “about”) that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of significant digits and by applying ordinary rounding