J. M. Shreeve et al.
1,3-Bis(5-amino-1H-tetrazol-1-yl)urea (1)[2a]: Yield 79%; Colorless crys-
tals; M.p.: 2238C (dec.); 1H NMR ([D6]DMSO): d=11.09 (br. s, 2H;
NH), 7.01 ppm (s, 4H; NH2); 13C NMR ([D6]DMSO): d=154.8,
152.5 ppm; 15N NMR ([D6]DMSO): d=4.2 (N2), ꢀ19.4 (N3), ꢀ94.6 (N4),
(N,H)=88 Hz; NH2); IR: (KBr): n˜ =664, 1116, 1305, 1323, 1497, 1582,
1649, 3096, 3281, 3389, 3462 cmꢀ1; elemental analysis calcd (%) for
C4H11N15O (285.23): C 16.84, H 3.89, N 73.66; found C 16.89, H 3.92, N
73.41.
1
ꢀ172.8 (N1), ꢀ269.3 (br. s; NH), ꢀ331.9 ppm (t, J (N,H)=89 Hz; NH2);
Aminoguanidinium (5-amino-1H-tetrazol-1-yl)(5-amino-1H-tetrazol-1-yl-
carbamo-yl)amide (6): Aminoguanidinium sulfate (246 mg, 1.00 mmol),
which was synthesized from aminoguanidine hydrochloride (221 mg,
2.00 mmol) and silver sulfate (312 mg, 1.00 mmol), was mixed in the solu-
tion of barium salt (642 mg, 1.00 mmol) in water (10 mL). The reaction
mixture was stirred 20 min at ambient temperature and barium sulfate
was filtered off. The filtrate was dried with air. The white solid (570 mg,
1.90 mmol, 95%) was formed and washed with a small amount of water.
M.p.: 2018C, 2088C (dec.); 1H NMR ([D6]DMSO): d=7.53 (br. s, 6H),
5.98 (br. s, 4H), 4.66 ppm (br. s, 2H); 13C NMR ([D6]DMSO): d=161.4,
158.7, 153.8 ppm; IR (KBr): n˜ =536, 606, 990, 1319, 1491, 1614, 1657,
IR (KBr): n˜ =1659, 1707, 3146, 3331 cmꢀ1; elemental analysis calcd (%)
for C3H6N12O (226.16): C 15.93, H 2.67, N 74.32; found C 16.27, H 2.77,
N 72.71.
N,N’-Bis(5-amino-1H-tetrazol-1-yl)oxalamide (2)·2H2O[2a]
: Yield 64%;
White solid; M.p. 1158C, 2338C (dec.); 1H NMR ([D6]DMSO): d=12.69
(s, 2H; NH), 7.13 (s, 4H; NH2), 3.37 ppm (s, 4H; H2O); 13C NMR
([D6]DMSO): d=156.9, 154.4 ppm; IR (KBr): n˜ =548, 673, 1084, 1124,
1332, 1510, 1608, 1648, 1734, 2788, 2984, 3139, 3179, 3277, 3309, 3420,
3574 cmꢀ1; elemental analysis calcd (%) for C4H10N12O4 (290.20): C
16.56, H 3.47, N 57.92; found C 17.13, H 3.29, N 58.09.
3152, 3323, 3458 cmꢀ1
; elemental analysis calcd (%) for C4H12N16O
(300.24): C 16.00, H 4.03, N 74.64; found C 16.12, H 3.99, N 74.45.
N,N’-Bis(5-amino-1H-tetrazol-1-yl)oxalamide (2)[2a]: Yield 64%; White
solid; M.p.: 2328C (dec.); 1H NMR ([D6]DMSO): d=12.71 (s, 2H; NH),
7.13 ppm (s, 4H; NH2); 13C NMR ([D6]DMSO): d=156.9, 154.3 ppm; IR
(KBr): n˜ =672, 1075, 1115, 1452, 1661, 1738, 3183, 3223, 3283, 3339,
3402 cmꢀ1; elemental analysis calcd (%) for C4H6N12O2 (254.17): C 18.90,
H 2.38, N 66.13; found C 19.21, H 2.36, N 65.65.
Diaminoguanidinium (5-amino-1H-tetrazol-1-yl)(5-amino-1H-tetrazol-1-
ylcarbamoyl)amide
(7):
Diaminoguanidinium
sulfate
(276 mg,
1.00 mmol), which was synthesized from diaminoguanidine hydrochloride
(251 mg, 2.00 mmol) and silver sulfate (312 mg, 1 mmol), was added to
the solution of barium salt (642 mg, 1.00 mmol) in water (10 mL). The re-
action mixture was stirred 20 min at ambient temperature and barium
sulfate was filtered off. The filtrate was dried with air. The white solid
(590 mg, 1.87 mmol, 94%) was formed and washed with small amount
water. M.p.: 1788C, 2038C (dec.); 1H NMR ([D6]DMSO): d=8.05 (br. s,
5H), 6.00 (s, 4H), 4.58 ppm (br. s, 4H); 13C NMR ([D6]DMSO): d=
161.3, 159.7, 153.7 ppm; 15N NMR ([D6]DMSO): d=ꢀ3.8 (N2), ꢀ17.7
(N3), ꢀ92.5 (N4), ꢀ152.8 (N1), ꢀ241.2 (br. s, N-anion), ꢀ284.3, ꢀ308.7,
ꢀ324.3 (br. s, NH2), ꢀ335.4 ppm (t, 1J (N,H)=85 Hz; NH2); IR (KBr):
n˜ =1312, 1478, 1620, 1656, 1692, 3141, 3325 cmꢀ1; elemental analysis calcd
(%) for C4H13N17O (315.26): C 15.24, H 4.16, N 75.53; found C 15.28, H
4.13, N 74.31.
Barium
bis{(5-amino-1H-tetrazol-1-yl)(5-amino-1H-tetrazol-1-ylcarba-
moyl)amide} trihydrate: The reaction of 1,3-bis(5-amino-1H-tetrazol-1-
yl)urea (1) (452 mg, 2.00 mmol) with barium hydroxide octahydrate
(315 mg, 1.00 mmol) in water (5 mL) at ambient temperature gave a
brown solid (622 mg, 0.969 mmol, 97%) after air drying. M.p.: 2158C
(dec.); 1H NMR ([D6]DMSO): d=6.05 (s, 8H; NH2), 3.45 ppm (br. s;
8H; NH and H2O); 13C NMR ([D6]DMSO): d=161.6, 153.9 ppm;
13C NMR (D2O): d=164.4, 153.0 ppm; IR (KBr): n˜ =598, 1119, 1307,
1370, 1468, 1618, 1645, 3196, 3407 cmꢀ1; elemental analysis calcd (%) for
C6H10BaN24O2·3H2O (641.68): C 11.23, H 2.51, N 52.39; found C 11.24, H
2.67, N 55.60.
Ammonium (5-amino-1H-tetrazol-1-yl)(5-amino-1H-tetrazol-1-ylcarba-
moyl)amide hydrate (3): The reaction of 1,3-bis(5-amino-1H-tetrazol-1-
yl)urea (1) (290 mg, 1.28 mmol) with excess aqueous ammonia in water
(2 mL) at ambient temperature gave a white solid (310 mg, 1.28 mmol,
Triaminoguanidinium (5-amino-1H-tetrazol-1-yl)(5-amino-1H-tetrazol-1-
ylcarbamoyl)amide
(8):
Triaminoguanidinium
sulfate
(306 mg,
1.00 mmol), which was synthesized from triaminoguanidine hydrochloride
(281 mg, 2.00 mmol) and silver sulfate (312 mg, 1.00 mmol), was mixed
with the solution of barium salt (642 mg, 1.00 mmol) in water (10 mL).
The reaction mixture was stirred 20 min at ambient temperature and
barium sulfate was filtered off. The filtrate was dried with air. The white
solid (620 mg, 1.88 mmol, 94%) was formed and washed with small
amount water. M.p.: 2028C, 2098C (dec.); 1H NMR ([D6]DMSO): d=
8.77 (br. s, 4H), 6.06 (s, 4H), 4.47 ppm (br. s, 6H); 13C NMR
([D6]DMSO): d=160.8, 159.5, 153.7 ppm; 13C NMR (D2O): d=163.7,
159.6, 154.1 ppm; IR (KBr): n˜ =554, 980, 1289, 1312, 1340, 1479, 1575,
1628, 1661, 2805, 3127, 3272, 3350 cmꢀ1; elemental analysis calcd (%) for
C4H14N18O (330.27): C 14.55, H 4.27, N 76.34; found C 14.69, H 4.27, N
76.37.
1
99%) after air drying. M.p.: 1518C, 2188C (dec.); H NMR ([D6]DMSO):
d=6.73 (br. s, 1H), 6.28 (s, 4H), 6.00 ppm (br. s, 6H); 13C NMR
([D6]DMSO): d=154.1, 159.2 ppm; 14N NMR ([D6]DMSO): d=
ꢀ356.1 ppm (+NH4); 15N NMR ([D6]DMSO): d=ꢀ2.9 (N2), ꢀ18.0 (N3),
ꢀ93.2 (N4), ꢀ155.7 (N1), ꢀ244.7 (br. s; [N-CO-NH]ꢀ), ꢀ335.0 (t, 1J
(N,H)=85 Hz; NH2), ꢀ356.1 ppm (+NH4); IR (KBr): n˜ =523, 1305, 1458,
1648, 2144, 3161, 3326 cmꢀ1
; elemental analysis calcd (%) for
C3H9N13O·H2O (261.21): C 13.79, H 4.24, N 69.71; found C 13.95, H 4.27,
N 68.54.
Hydrazinium (5-amino-1H-tetrazol-1-yl)(5-amino-1H-tetrazol-1-ylcarba-
moyl)-amide dihydrate (4): The reaction of 1,3-bis(5-amino-1H-tetrazol-
1-yl)urea (1) (452 mg, 2.00 mmol) with excess hydrazine hydrate in water
(5 mL) at ambient temperature to form a white solid (565 mg, 1.92 mmol,
96%) after air drying for 2 months. M.p. 92 and 1208C, 2088C (dec.);
1H NMR ([D6]DMSO): d=6.18 (s, 4H, NH2), 5.87 ppm (br. s, 10H);
13C NMR ([D6]DMSO): d=159.9, 154.0 ppm; 15N NMR ([D6]DMSO):
d=ꢀ2.8, ꢀ18.1, ꢀ93.4, ꢀ156.6, ꢀ246.1, ꢀ328.7, ꢀ334.9 ppm (t, 1J
(N,H)=88 Hz; NH2); IR (KBr): n˜ =1109, 1317, 1509, 1570, 1603, 1628,
1669, 2619, 2743, 2965, 3129, 3321, 3574 cmꢀ1; elemental analysis calcd
(%) for C3H10N14O·2H2O (294.24): C 12.25, H 4.80, N 66.65; found C
12.64, H 5.17, N 63.45.
Barium oxalbis{(5-amino-1H-tetrazol-1-yl)amide} (Figure 3): The reac-
tion of N,N’-bis(5-amino-1H-tetrazol-1-yl)oxalamide (2)·2H2O (544 mg,
1.87 mmol) with barium hydroxide octahydrate (590 mg, 1.87 mmol) in
water (100 mL) at ambient temperature gave a white solid (750 mg,
1.76 mmol, 94%) after air drying. M.p.: 2738C (dec.); IR (KBr): n˜ =1311,
1447, 1532, 1583, 1626, 3350, 3389, 3530, 3598 cmꢀ1
.
Diammonium oxalbis{(5-amino-1H-tetrazol-1-yl)amide} dihydrate (9):
The reaction of N,N’-bis(5-amino-1H-tetrazol-1-yl)oxalamide (2)·2H2O
(580 mg, 2.00 mmol) with excess aqueous ammonia in water (10 mL) at
ambient temperature gave a white solid (620 mg, 1.91 mmol, 96%) after
air drying. M.p.: 1218C (H2O), 2268C, 2318C (dec.); 1H NMR
([D6]DMSO): d=6.27 (s, 4H), 4.98 ppm (br. s, 12H; +NH4 and H2O);
13C NMR ([D6]DMSO): d=162.4, 153.1 ppm; IR (KBr): n˜ =651, 712,
1093, 1307, 1463, 1559, 1587, 1657, 2853, 2970, 3122, 3185, 3327 cmꢀ1; ele-
mental analysis calcd (%) for C4H12N14O2·2H2O (324.26): C 14.82, H
4.97, N 60.47; found C 14.87, H 5.03, N 59.36.
Guanidinium (5-amino-1H-tetrazol-1-yl)(5-amino-1H-tetrazol-1-ylcarba-
moyl)-amide (5): Guanidinium sulfate (216 mg, 1 mmol), which was syn-
thesized from guanidine hydrochloride (191 mg, 2 mmol) and silver sul-
fate (312 mg, 1.00 mmol), was mixed in the solution of barium salt
(642 mg, 1 mmol) in water (10 mL). The reaction mixture was stirred
20 min at ambient temperature and barium sulfate was filtered off. The
filtrate dried in air. The white solid (550 mg, 1.93 mmol, 96%) was
formed and washed with small amount water. M.p.: 1978C, 2088C (dec.);
1H NMR ([D6]DMSO): d=6.96 (br. s, 7H), 6.09 ppm (s, 4H); 13C NMR
([D6]DMSO): d=161.9, 158.0, 153.8 ppm; 15N NMR ([D6]DMSO): d=
ꢀ3.6, ꢀ17.9, ꢀ92.5, ꢀ153.0, ꢀ240.3 (br. s), ꢀ302.4, ꢀ335.4 ppm (t, 1J
Dihydrazinium oxalbis{(5-amino-1H-tetrazol-1-yl)amide} (10): The reac-
tion of N,N’-bis(5-amino-1H-tetrazol-1-yl)oxalamide (2)·2H2O (580 mg,
2.00 mmol) with excess hydrazinium hydrate in water (10 mL) at ambient
temperature gave a white solid (624 mg, 1.96 mmol, 98%) after air
9102
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 9097 – 9104