T. M. Klapçtke et al.
N(2)=N(3)), ꢀ47.7 (s, 2N; N(1)-C(5)=N(4)), ꢀ119 ppm (s, 1N; C-CN);
IR (KBr): v˜ =3520 (s), 3414 (vs), 3298 (s), 2863 (w), 2836 (w), 2474
mental analysis calcd (%) for C H N O: C 21.24, H 2.67, N 61.93;
found: C 18.29, H 2.30, N 62.25.
2
3
5
(
1
(
(
4
(
7
w), 2460 (w), 2260 (m), 2180 (w), 2142 (w), 2102 (w), 2087 (w),
704 (m), 1670 (w), 1619 (s), 1471 (w), 1422 (w), 1380 (m), 1369
Hydroxylammonium 5-carboxamide tetrazolate (5): Compound 4
0.710 g, 6.28 mmol, 1.00 equiv) was dissolved in H O (10 mL) and
(
w), 1196 (w), 1150 (w), 1055 (w), 1047 (w), 877 (w), 753 (w), 738
w), 728 (w), 671 (w), 660 (w), 602 (w), 549 (m), 533 (m),
2
hydroxylamine (0.39 mL of a 50% w/v solution in H O, 0.420 g,
2
ꢀ1
6.36 mmol, 1.01 equiv) was added. After cooling down the solution
99 cm (w); Raman (1064 nm, 300 mW, 258C): v˜ =3359 (1), 2266
to 28C, 5 crystallized from the mother liquor in 88% yield (0.810 g,
100), 1420 (59), 1200 (8), 1161 (5), 1095 (10), 1084 (6), 1060 (18),
ꢀ
1
1
ꢀ1
+
5.54 mmol). DSC (58C min ): decomp=1738C; H NMR (400 MHz,
[D ]DMSO, 258C, TMS) d=10.06 (s, 4H; NH OH), 7.91 (s, 1H;
37 (2), 608 (8), 495 (9), 226 cm (5); MS (DCI ): m/z calcd for
+
+
C H N O : 113.0 [M ]; found: 113.1; elemental analysis calcd (%)
for NaC H N O1.5: C 16.67, H 2.10, N 48.61; found: C 16.13, H 2.02,
6
3
2
3
5
13
CONH ), 7.59 (s, 1H; CONH ); C NMR (101 MHz, [D ]DMSO, 258C,
2
2
6
2
3
5
TMS) d=163.1 (CONH ), 157.4 ppm (CN ); IR (KBr): v˜ =3310 (s),
N 46.71; BAM drophammer: 40 J; friction tester: 160 N; ESD:
80 mJ (at grain size 100–500 mm).
2
4
3
201 (m), 2985 (s), 2859 (m), 2741 (vs), 2509 (m), 2178 (w), 2106
3
(
(
1
w), 1702 (s), 1671 (s), 1631 (m), 1616 (m), 1587 (m), 1517 (s), 1385
m), 1334 (m), 1240 (w), 1204 (m), 1173 (m), 1114 (m), 1069 (w),
5
-Cyanotetrazole (2): Sodium-5-cyanotetrazolate sesquihydrate (1;
050 (w), 1009 (m), 795 (m), 718 (m), 681 (m), 656 (m),
3
2
.27 g, 22.7 mmol, 1.00 equiv) was dissolved in 2m HNO (11.4 mL,
2.7 mmol. 1.00 equiv) at RT and the solvent was carefully removed
ꢀ1
3
536 cm (m); Raman (1064 nm, 350 mW, 258C): v˜ =3139 (4), 2939
(
(
(
(
5), 2723 (5), 1637 (5), 1605 (12), 1527 (53), 1395 (2), 1337 (5), 1207
33), 1175 (26), 1115 (19), 1098 (100), 1071 (47), 1051 (19), 1011
25), 811 (3), 783 (3), 725 (13), 521 (3), 440 (12), 310 (3), 284 (6), 250
under reduced pressure at a maximum temperature of 408C. The
residue was dried under high vacuum and suspended in dry EtOH
(
30 mL). Filtration and slow evaporation of the mother liquor yield-
ed slightly greenish crystals of compound 2 (1.20 g, 12.6 mmol,
6%). After almost complete evaporation of the mother liquor fur-
ther green/brown crystals of 2 (0.960 g, 10.1 mmol, 44%) were ob-
ꢀ1
+
+
+
12), 217 cm (10) ; MS (FAB ): m/z calcd for NH O : 34.0 [M ];
4
ꢀ
ꢀ
ꢀ
found: 34.0; MS (FAB ): m/z calcd for C H N O : 112.0 [M ]; found:
1
N 57.52; found: C 16.66, H 3.93, N 57.08; BAM drophammer: 40 J;
friction tester: 288 N; ESD: 0.15 J (at grain size 100–500 mm).
2
2
5
5
12.0; elemental analysis calcd (%) for C H N O : C 16.44, H 4.14,
2 6 6 2
1
tained. H NMR (400 MHz, [D ]DMSO, 258C, TMS): d=14.80 ppm (s
1
6
1
3
H; NH); C NMR (101 MHz, [D ]DMSO, 258C, TMS): d=139.2
6
(
CN ), 113.3 (CN) ppm; IR (KBr): v˜ =3461 (w), 3158 (m), 2979 (w),
Tetrazole-5-carboxamide oxime monohydrate (6): To a solution
4
2
881 (w), 2781 (w), 2680 (w), 2548 (w), 2278 (w), 2266 (w), 2153
of 5-cyanotetrazole (2) (1.66 g, 17.5 mmol, 1.00 equiv) in H O
2
(
w), 1947 (w), 1788 (w), 1686 (m), 1560 (w), 1513 (w), 1466 (w),
(30 mL) was added hydroxylamine (1.07 mL of a 50% w/v solution
1
1
8
2
438 (w), 1414 (w), 1393 (w), 1372 (w), 1323 (m), 1294 (s), 1222 (w),
in H O, 1.15 g, 17.5 mmol, 1.00 equiv) at RT. Crystallization started
immediately after addition and yielded 6 (1.89 g, 12.9 mmol, 74%)
as colorless precipitate.
2
209 (w), 1184 (w), 1170 (m), 1112 (m), 1044 (s), 1022 (s), 976 (w),
ꢀ1
71 (w), 834 (s), 741 (m), 697 cm (w); Raman (1064 nm, 300 mW,
58C): v˜ =3165 (2), 2280 (100), 1468 (14), 1439 (14), 1413 (34), 1386
Alternatively, a solution of 1 (11.5 g; 80.0 mmol; 1.00 equiv) in
water (30 mL) was treated with an aqueous solution of hydroxy-
lammonium chloride (20 mL, 5.91 g; 85.0 mmol, 1.04 equiv). The
solution was heated at reflux for 10 min, until precipitation of 6
started. The crude product was filtered off and recrystallized from
hot water. The filtrate was left to stand for a few more days to im-
prove the yield. 6 (7.01 g; 48.0 mmol; 60%) was gained as colorless
(
(
3), 1297 (4), 1221 (7), 1173 (10), 1110 (26), 1068 (15), 1024 (10), 744
4), 725 (3), 608 (13), 542 (4), 494 (15), 214 cm (23); MS (DEI ):
ꢀ
1
+
+
+
m/z calcd for C HN : 95.0 [M ]; found: 95.0; elemental analysis
calcd (%) for C HN : C 25.27, H 1.06, N 73.67; found: C 25.41,
H 1.03, N 72.44.
2
5
2
5
Silver 5-cyanotetrazolate (3): Compound 1 (432 mg, 3.00 mmol,
.00 equiv) was dissolved in H O (10 mL) at RT. Afterwards an aque-
ꢀ1
1
solid. DSC (58C min ): 1208C (H O), decomp=2448C; H NMR
2
1
2
(270 MHz, [D ]DMSO, 258C, TMS): d=10.51 (br. s, 1H; NH),
6
ous solution of AgNO (10 mL, 510 mg, 3.00 mmol, 1.00 equiv) was
13
3
7.09 ppm (s, 2H; C-NH ) ; C NMR (68 MHz, [D ]DMSO, 258C, TMS):
2
6
added. A thick, white precipitate started to form immediately,
which was stirred for further 15 min under the exclusion of light.
The precipitate was filtered off, washed with water to remove re-
d=150.7 (CN ), 144.9 ppm (C(NH )NOH); IR (KBr): v˜ =3315 (vs),
4
2
3
(
128 (vs), 3002 (vs), 2849 (vs), 2745 (vs), 2649 (s), 2250 (w), 2211
w), 2141 (w), 2117 (w), 1814 (w), 1801 (w), 1712 (vs), 1650 (s), 1559
(m), 1500 (w), 1462 (m), 1394 (s), 1386 (s), 1306 (m), 1199 (w), 1173
w), 1159 (w), 1133 (w), 1121 (w), 1092 (w), 1062 (w), 1047 (w), 1024
sidual NaNO and air-dried. Yield: 595 mg (2.95 mmol, 98%). DSC
3
ꢀ
1
(
58C min ): decomp=2848C; elemental analysis calcd (%) for
(
C AgN : C 11.90, N 34.68; found: C 11.99, N 34.37; BAM dropham-
2
5
(w), 977 (w), 774 (s), 736 (s), 723 (s), 668 (m), 660 (m), 638 (s), 599
mer: <1 J; friction tester: <5 N; ESD: 1 mJ (!; at grain size
100 mm).
ꢀ1
(
m), 525 (w), 501 cm (m); Raman (1064 nm, 300 mW, 258C): v˜ =
<
3
116 (9), 1648 (9), 1578 (58), 1452 (18), 1400 (6), 1315 (13), 1199
(
6
41), 1161 (30), 1125 (100), 1085 (84), 1062 (59), 1038 (41), 770 (17),
Tetrazole-5-carboxamide (4): Compound 1 (3.20 g, 22.2 mmol)
ꢀ1
31 (8), 422 (47), 353 (12), 326 (9), 192 (10), 157 cm (28); MS
was dissolved in 6m HNO (10 mL) and the solution was heated to
+
+
+
3
(FAB ): m/z calcd for C H N O : 128.0 [M ]; found: 128.0; elemen-
2 4 6
tal analysis calcd (%) for C H N O : C 16.44, H 4.14, N 57.52; found:
8
08C for 15 min. The solvent was removed under reduced pressure
2
6
6
2
and the residue was extracted with boiling ethanol (3ꢂ100 mL).
After the solvent was removed from the combined extracts, the
C 17.10, H 3.76, N 57.83; BAM drophammer: 40 J; friction tester:
52 N; ESD: 80 mJ (at grain size 100–500 mm).
2
residue was recrystallized from boiling water. Yield: 1.74 g
1
(
8
15.4 mmol, 69%). H NMR (400 MHz, [D ]DMSO, 258C, TMS): d=
Hydroxylammonium 5-carboxamide-oxime tetrazolate (7): To
6
13
.57 (s, 1H; CONH ), 8.19 ppm (s, 1H; CONH ); C NMR (101 MHz,
a suspension of 6 (0.713 g, 4.88 mmol, 1.00 equiv) in H O (40 mL)
2
2
2
[
(
(
D ]DMSO, 258C, TMS): d=157.2 (CONH ), 152.0 ppm (CN ); Raman
1064 nm, 300 mW, 258C): v˜ =3361 (3), 3250 (10), 3192 (5), 2808
2), 1688 (42), 1649 (6), 1604 (31), 1571 (64), 1442 (38), 1298 (20),
was added hydroxylamine (0.5 mL of a 50% (w/v) solution in H O,
6
2
4
2
0.539 g, 8.16 mmol, 1.67 equiv) and the resulting mixture was
stirred at RT until everything was dissolved. Rapidly beginning crys-
tallization yielded small colorless crystal needles of compound 7
(435 mg, 2.69 mmol, 55%). Crystals suitable for X-ray diffraction
1
229 (100), 1108 (82), 1090 (79), 1059 (35), 997 (7), 804 (13), 759
ꢀ1
(
2), 696 (30), 630 (2), 511 (6), 415 (58), 241 (46), 221 cm (24); ele-
&10
&
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ChemPlusChem 2012, 00, 1 – 13
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