J. M. Shreeve et al.
ꢀ
3
1
(
decomp);
1
=
1.60 gcm
,
H NMR (300 MHz, [D
.89 ppm (brs, 6H); C NMR (75 MHz, [D ]DMSO): d = 164.8, 159.8,
59.2, 151.7 ppm; IR (KBr): n˜ = 3434, 3344, 3262, 3206, 2791, 2344, 2201,
6
]DMSO):
d
=
1,2,4,5-Tetrazino-3,6-diguanidinium
2-nitroamino-4,6-diazido ACHTUNGTRENNUNG[ 1,3,5]-
1
3
6
1
2
6
ACHTUNGTRtEUNNNG riazinate (9): The same method was used as described for compound 5
by starting from 3,6-diguanidinium-1,2,4,5-tetrazine dichloride (134.5 mg,
0.5 mol) in water (80 mL) to form the product as a red solid (242 mg,
ꢀ
1
156, 1670, 1599, 1497, 1431, 1323, 1258, 1221, 1097, 779 cm ; elemental
(282.18): C 17.03, H 2.14, N 69.49;
ꢀ
3
1
analysis calcd (%) for C
found: C 17.14, H 2.04, N 68.34.
Aminoguanidinium 2-nitroamino-4,6-diazido ACHUTGTNRNENUGN[ 1,3,5]triazinate (4): The
4
H
6
N
14
O
2
75% yield). DSC 1938C (onset, decomp); 1 = 1.63 gcm
;
H NMR
]DMSO): d = 8.06 ppm (brs, 10H); C NMR (75 MHz,
]DMSO): d = 164.8, 159.9, 159.8, 155.9, 151.7 ppm; IR (KBr): n˜ =
389, 3195, 3073, 2197, 2142, 1698, 1609, 1568, 1512, 1433, 1342, 1268,
1
3
(300 MHz, [D
6
[
D
6
3
1
same method was used as described for compound 3 from aminoguanidi-
nium bicarbonate (136 mg, 1.0 mmol) to form the product as a white
solid (279 mg, 94% yield). DSC: m.p. 1688C (decomp); 1 = 1.68 gcm
]DMSO): d = 9.03 (brs, 1H), 7.21 (brs, 2H),
.60 (brs, 2H), 4.69 ppm (brs, 2H); C NMR
64.8, 160.7, 160.1, 151.7 ppm; IR (KBr): n˜ = 3430, 3340, 3156, 2398,
274, 2195, 2142, 1668, 1625, 1553, 1507, 1418, 1370, 1338, 1263, 1220,
ꢀ
1
233, 1033, 808 cm ; elemental analysis calcd (%) for C10
10 32 4
H N O
ꢀ
3
(642.40): C 18.70, H 1.57, N 69.77; found: C 18.88, H 1.52, N 69.59.
;
1
H NMR (300 MHz, [D
6
Guanizinium 2-nitroamino-4,6-diazido[1,3,5]triazinate (10): A solution of
ACHTUNGTRENNUNG
1
3
6
1
2
1
1
A
H
U
G
R
N
U
G
6
]DMSO): d =
guanazine (69 mg, 0.6 mmol) in water (5 mL) was added to a suspension
of NADAT (2) (134 mg, 0.6 mmol) in water (10 mL) at room tempera-
ture with stirring. A white solid precipitated slowly. After stirring for 3 h,
the reaction mixture was heated to ensure that the entire solid was dis-
solved. After standing at room temperature overnight, the resulting col-
orless crystalline solid was collected by filtration, washed with cold water
ꢀ
1
092, 807 cm ; elemental analysis calcd (%) for C
6.17, H 2.37, N 70.69; found: C 16.39, H 2.71, N 68.56.
[1,3,5]triazinate monohydrate
5): A solution of potassium carbonate (69 mg, 0.5 mmol) in water
3 mL) was added to a suspension of NADAT (2) (223 mg, 1.0 mmol) in
4 7 15 2
H N O (297.20): C
Biguanidinium 2-nitroamino-4,6-diazidoCAHTUNGTRENNNUG
(
(
(
(
5 mL), and dried in air to give the desired product as colorless needles
(
(
ꢀ
3
1
181 mg, 90%). DSC: m.p. 1918C (decomp); 1 = 1.68 gcm
300 MHz, [D ]DMSO): d = 7.06 (brs, 4H), 5.57 ppm (s, 2H); C NMR
75 MHz, [D ]DMSO): d = 164.8, 159.8, 151.7, 151.3 ppm; IR (KBr): n˜
3357, 3277, 3257, 2951, 2734, 2410, 2268, 2195, 2144, 1699, 1669, 1553,
; H NMR
1
3
6
water (15 mL) at room temperature with stirring. The reaction mixture
became a clear yellow solution, and then biguanidinium sulfate (100 mg,
.5 mmol) in water (5 mL) was added. A white solid precipitated slowly.
6
=
0
ꢀ
1
1
511, 1415, 1358, 1175, 1014, 903, 804, 708 cm ; elemental analysis calcd
After stirring for 1 h, the reaction mixture was heated to ensure complete
dissolution of the solid. After standing at room temperature overnight,
the resulting colorless crystalline solid was collected by filtration, washed
with cold water (3 mL), and dried in air to give the desired product as a
colorless flat crystal (262 mg, 93%), DSC: m.p. 1368C, 1518C (onset,
(
%) for C (337.22): C 17.81, H 2.09, N 70.61; found: C 17.77, H
5 7 17 2
H N O
1
.91, N 70.03.
General method for the preparation of guanizinium salts
Guanizinium 4-nitroamino-1,2,4-triazolate (11): A solution of 4-nitroami-
no-1,2,4-triazole (129 mg, 1.0 mmol) in water (2 mL) was added to a solu-
tion of guanazine (114 mg, 1.0 mmol) in water (10 mL) at room tempera-
ture with stirring. A white solid precipitated slowly. After stirring for 4 h,
the reaction mixture was heated to ensure that all solid was dissolved.
After standing at room temperature overnight, the resulting solid was
collected by filtration, washed with cold methanol (3 mL), and dried in
air to give the desired product as a colorless crystalline solid (231 mg,
ꢀ
3
1
decomp); 1 = 1.63 gcm ; H NMR (300 MHz, [D
6
]DMSO): d = 8.10 (s,
1
3
8
1
2
8
1
H), 4.98 ppm (brs, 1H); C NMR (75 MHz, [D ]DMSO): d = 164.8,
6
59.8, 156.7, 151.7 ppm; IR (KBr): n˜ = 3626, 3346, 3182, 3077, 2828,
395, 2256, 2195, 2139, 1711, 1568, 1514, 1420, 1371, 1343, 1261, 1086,
ꢀ
1
06 cm ; elemental analysis calcd (%) for C
7.00, H 1.96, N 66.89; found: C 16.79, H 1.81, N 66.52.
2-nitroamino-4,6-diazido
monohydrate (6): The same method was used as described for compound
but by using aminocarbonylguanidinium chloride to give the product as
colorless crystalline solid (246 mg, 72% yield). DSC: m.p. 1528C, 1968C
8 9 27 4 2
H N O ·H O (565.35): C
Aminocarbonylguanidinium
ACHTUNGTRENNUN[G 1,3,5]triazinate
ꢀ
3
1
9
(
2
5%). DSC: 2198C (onset, decomp);
300 MHz, [D ]DMSO): d = 8.32 (s, 2H), 7.08 (brs, 4H), 5.59 ppm (s,
H); C NMR (75 MHz, [D ]DMSO): d = 151.3, 143.1 ppm; IR (KBr):
1
=
1.71 gcm
;
H NMR
5
6
1
3
6
ꢀ
3
1
n˜ = 3411, 3370, 3294, 3194, 3113, 1702, 1668, 1622, 1516, 1389, 1294,
(
8
=
onset, decomp); 1 = 1.64 gcm ; H NMR (300 MHz, [D
6
]DMSO): d =
.64 (brs, 4H), 7.12 ppm (brs, 2H); C NMR (75 MHz, [D ]DMSO): d
164.8, 159.8, 156.8, 155.7, 151.7 ppm; IR (KBr): n˜ = 3628, 3342, 3188,
047, 2789, 2398, 2195, 2137, 1732, 1699, 1561, 1516, 1416, 1342, 1261,
ꢀ
1
1
3
4 9 11 2
1074, 964 cm ; elemental analysis calcd (%) for C H N O (243.19): C
6
1
9.76, H 3.73, N 63.36; found: C 19.66, H 3.67, N 63.05.
3
1
(
Guanizinium 5-(5ꢀ-tetrazolylamino)tetrazolate monohydrate (12): Color-
less crystalline solid (235 mg, 82%); DSC: m.p. 1708C, 2578C (onset,
ꢀ
1
5 7 15 3 2
221, 1080, 706 cm ; elemental analysis calcd (%) for C H N O ·H O
ꢀ
3
1
343.22): C 17.50, H 2.64, N 61.21; found: C 17.75, H 2.41, N 61.98.
-Amino-1,2,4-triazolium 2-nitroamino-4,6-diazido[1,3,5]triazinate (7): A
mixture of 4-amino-1,2,4-triazole (67 mg, 0.8 mmol) and NADAT (2)
178 mg, 0.8 mmol) in acetonitrile (15 mL) was heated at reflux and
stirred overnight. After removing the solvent, the residue was recrystal-
lized from methanol (10 mL)/diethyl ether (5 mL) to afford the desired
product as colorless crystalline solid (224 mg, 91%). DSC: m.p. 1308C
decomp); 1
(
1
1
=
1.63 gcm
;
H NMR (300 MHz, [D
6
]DMSO): d=7.03
]DMSO): d = 157.5,
51.4 ppm; IR (KBr): n˜ = 3340, 3285, 3159, 2982, 1669, 1645, 1564, 1512,
1
3
brs, 9H), 5.65 ppm (s, 2H); C NMR (75 MHz, [D
6
4
ACHTUNGTRENNUNG
ꢀ
1
315, 1240, 1038, 887 cm
;
elemental analysis calcd (%) for
(
4 9 2
C H N15·H O (285.23): C 16.84, H 3.89, N 73.66; found: C 17.20, H 3.61,
N 74.47.
Guanizinium 5-nitroiminotetrazolate (13): Colorless crystalline solid
ꢀ
3
1
ꢀ3
(
(
1
decomp); 1 = 1.68 gcm
;
H NMR (300 MHz, [D
6
]DMSO): d = 9.41
(212 mg, 87% yield); DSC: 2318C (onset, decomp); 1 = 1.78 gcm
;
1
3
1
s, 2H), 8.20 ppm (brs, 3H); C NMR (75 MHz, [D
59.8, 151.7, 145.3 ppm; IR (KBr): n˜ = 3441, 3330, 3231, 3111, 2371,
6
]DMSO): d = 164.8,
6
H NMR (300 MHz, [D ]DMSO): d = 7.08 (brs, 4H), 5.60 ppm (s, 2H);
1
3
C NMR (75 MHz, [D
6
]DMSO): d = 159.2, 151.3 ppm; IR (KBr): n˜ =
ꢀ
1
ꢀ1
2
191, 2141, 1644, 1565, 1519, 1451, 1339, 1249, 1206, 800 cm ; elemental
(307.19): C 19.55, H 1.64, N 68.39;
3468, 3387, 3323, 3208, 3136, 1665, 1552, 1447, 1333, 1244, 1094, 882 cm
elemental analysis calcd (%) for C
68.84; found: C 14.79, H 3.27, N 68.67.
;
analysis calcd (%) for C
found: C 19.82, H 1.55, N 68.08.
,5-Diamino-1,2,4-triazolium
8): A solution of 3,5-diamino-1.2,4-triazole (80 mg, 0.8 mmol) in water
or acetonitrile (5 mL) was added to a suspension of NADAT (2) (178 mg,
.8 mmol) in water or acetonitrile (10 mL) at room temperature with stir-
5
H
5
N
15
O
2
3 8 12 2
H N O (244.17): C 14.76, H 3.30, N
3
(
2-nitroamino-4,6-diazido
A
H
U
G
R
N
U
G
Guanizinium trinitroimdazolate (14): Colorless crystalline solid (295 mg,
93%); DSC: m.p. 1968C; thermogravimetric analysis: 2428C (onset,
ꢀ
3
1
decomp); 1 = 1.71 gcm
brs, 1H), 7.07 (brs, 4H), 5.57 ppm (s, 2H); C NMR (75 MHz,
]DMSO): d = 151.3 ppm; IR (KBr): n˜ = 3472, 3312, 3248, 3156,
6
; H NMR (300 MHz, [D ]DMSO): d = 12.45
1
3
(
0
[
D
6
ring. After stirring for 4 h, the resulting precipitate was collected by fil-
tration, washed with cold methanol (5 mL), dried in air to afford the de-
sired product as a white solid (242 mg, 94%). DSC: 1588C (onset,
ꢀ
1
1
705, 1663, 1625, 1542, 1329, 1111, 870 cm ; elemental analysis calcd
(317.18): C 18.93, H 2.22, N 48.58; found: C 18.89, H
(
%) for C
5 7 11 6
H N O
ꢀ
3
1
2.00, N 48.20.
decomp);
1
=
1.67 gcm
;
H NMR (300 MHz, [D
.51 ppm (brs, 4H); C NMR (75 MHz, [D ]DMSO): d = 164.8, 159.8,
52.7, 151.7 ppm; IR (KBr): n˜ = 3404, 3369, 3246, 3133, 2677, 2362, 2192,
6
]DMSO): d =
1
3
7
1
2
6
Guanizinium 6-amino-3-nitroamino-1,2,4,5-tetrazinate monohydrate (15):
Red crystalline solid (245 mg, 85% yield); DSC: m.p. 1038C, 2098C
ꢀ
1
ꢀ3
1
139, 1666, 1568, 1512, 1370, 1345, 1261, 1227, 1009, 802 cm ; elemental
(322.1) C 18.64; H 1.88, N 69.55;
6
(onset, decomp); 1 = 1.64 gcm ; H NMR (300 MHz, [D ]DMSO): d =
1
3
analysis calcd (%) for C
5
H
6
N
16
O
2
7.38 (s, 2H), 7.06 (s, 4H), 5.62 ppm (s, 2H); C NMR (75 MHz,
[D ]DMSO): d = 164.9, 163.0, 151.3 ppm; IR (KBr): n˜ = 3518, 3416,
found: C 18.66, H 1.73, N 69.02.
6
1544
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 1538 – 1546