614
A. Schwa¨rzler et al. · 4-Amino-1,2,4-triazolium Salts
(t, J = 7.5 Hz, 3H), 1.38 (t, J = 7.2 Hz, 3H), 2.85 (q, J = H2O (10 mL) and sucked dry. The crude product was re-
7.5 Hz, 2H), 3.08 (q, J = 7.6 Hz, 2H), 3.71 (q, J = 7.1 Hz, crystallized from a hot mixture of MeOH (30 mL) and H2O
2H), 4.30 (q, J = 7.2 Hz, 2H), 6.5 (br s, 2H). – 13C NMR (30 mL), filtered, washed with MeOH/H2O (10 mL) and
(150 MHz, [D6]DMSO): δ = 10.0, 11.0, 14.4, 15.5, 16.3, Et2O (2×10 mL), and dried to give 6b as colorless needles.
◦
17.4, 45.8, 61.7, 155.4, 157.5. – IR (neat): ν = 3298, 3179, Yield: 12.0 g (74 %). M. p. 141 C. – 1H NMR (300 MHz,
2984, 2946, 1638, 1571, 1460, 1386, 1192, 1045, 1005, 915, [D6]DMSO): δ = 2.94 (s, 6H), 4.01 (s, 3H), 9.61 (s, 1H),
846, 745, 577 cm−1
.
10.44 (s, 1H). – 13C NMR (150 MHz, [D6]acetone): δ =
39.1, 47.6 (2C), 142.2, 142.3. – IR (neat): ν = 3161, 3127,
1581, 1458, 1135, 1063, 1020, 983, 884, 820, 742, 706, 669,
4-Amino-1,3,5-triethyl-1,2,4-triazolium hexafluorophos-
phate (5b)
642, 591, 555, 489, 459 cm−1
.
Yield: 1.1 g (52 %). M. p. 81 – 82 ◦C. – 1H NMR
(300 MHz, [D6]DMSO): δ = 1.22 (t, J = 7.5 Hz, 3H), 1.26 (t,
J = 7.5 Hz, 3H), 1.39 (t, J = 7.2 Hz, 3H), 2.85 (q, J = 7.5 Hz,
2H), 3.08 (q, J = 7.5 Hz, 2H), 4.30 (q, J = 7.2 Hz, 2H), 6.5
(br s, 2H). – IR (neat): ν = 3392, 3323, 2997, 2951, 1634,
1576, 1458, 1391, 943, 822, 741, 555 cm−1. – C8H17F6N4P
(314.21): calcd. C 30.58, H 5.45, N 17.83; found C 30.50,
H 5.10, N 17.52.
4-(Dimethylamino)-1-methyl-1,2,4-triazolium triflimide
(6c)
A mixture of 4-amino-1,2,4-triazole (1.0 g, 12 mmol)
and dimethyl sulfate (2 mL, 21 mmol, 1.8 equivalents) was
heated at 100 ◦C for 24 h. After cooling the viscous oil
was stirred with Et2O (3 × 5 mL), and the solvent was dis-
carded. The oil was dissolved in H2O (10 mL), and a solu-
tion of LiTf2N (3.6 g, 12 mmol) in H2O (50 mL) was added
with stirring. The resulting second dense phase was sepa-
rated, washed with H2O, and dried in vacuum. The prod-
uct ◦crystallized overnight. Yield: 3.4 g (70 %). M. p. 78 –
80 C. – 1H NMR (300 MHz, [D6]DMSO): δ = 2.94 (s,
6H), 4.01 (s, 3H), 9.61 (s, 1H), 10.44 (s, 1H). – 13C NMR
(150 MHz, [D6]DMSO): δ = 39.4, 48.2 (2C), 120.0 (q,
JC−F = 317 Hz, 2C), 142.8 (2C). – IR (neat): ν = 3141, 1574,
1466, 1346, 1181, 1138, 1050, 914, 837, 790, 740, 671, 612,
569, 512 cm−1. – C7H11F6N5O4S2 (407.31): calcd. C 20.64,
H 2.72, N 17.19, S 15.74; found C 21.01, H 2.83, N 16.80,
S 15.37.
4-Amino-1,3,5-triethyl-1,2,4-triazolium triflimide (5c)
Yield: 2.4 g (79 %). M. p. 106 – 107 ◦C. – 1H NMR
(300 MHz, [D6]DMSO): δ = 1.22 (t, J = 7.5 Hz, 3H), 1.26 (t,
J = 7.5 Hz, 3H), 1.39 (t, J = 7.3 Hz, 3H), 2.85 (q, J = 7.5 Hz,
2H), 3.08 (q, J = 7.5 Hz, 2H), 4.30 (q, J = 7.3 Hz, 2H), 6.5
(br s, 2H). – 13C NMR (150 MHz, [D6]DMSO): δ = 10.1,
11.0, 14.4, 16.3, 17.4, 45.8, 120.0 (q, JC−F = 321 Hz, 2C),
155.4, 157.5. – IR (neat): ν = 3361, 3000, 2952, 1639, 1573,
1463, 1346, 1193, 1132, 1035, 965, 825, 795, 742, 611, 568,
514 cm−1
.
4-(Dimethylamino)-1-methyl-1,2,4-triazolium methylsulfate
(6a)
4-(Dimethylamino)-1-methyl-1,2,4-triazolium hydrogensulf-
ate (6d)
A mixture of 4-amino-1,2,4-triazole (5 g, 59 mmol) and
dimethyl sulfate (17 mL, 178 mmol, 3 equivalents) was
A mixture of 4-amino-1,2,4-triazole (5 g, 59 mmol) and
◦
◦
dimethyl sulfate (8.5 mL, 89 mmol) was heated at 100 C
heated at 100 C for 5 h. After cooling the viscous oil was
for 24 h. After cooling the viscous oil was stirred with Et2O
(3 × 20 mL), and the solvent was discarded. Volatiles were
removed in vacuum, and part of the resulting oil crystallized
overnight. The hygroscopic solid was collected by filtration
and dried. Yield: 1.1 g (8 %). M. p. 105 – 110 ◦C. – 1H NMR
(300 MHz, [D6]DMSO): δ = 2.94 (s, 6H), 4.02 (s, 3H), 6.0
(br s, 1H), 9.61 (s, 1H), 10.47 (s, 1H). – IR (neat): ν =
3099, 3063, 1567, 1460, 1331, 1233, 1160, 1143, 1049, 832,
stirred with Et2O (3 × 20 mL), the solvent was discarded,
and the residue was dried in vacuum. Yield: 2.7 g (95 %). –
1H NMR (300 MHz, [D6]DMSO): δ = 2.91 (s, 6H), 3.36 (s,
3H), 3.99 (s, 3H), 9.55 (s, 1H), 10.37 (s, 1H). – 13C NMR
(75 MHz, [D6]DMSO): δ = 40.1, 47.9 (2C), 53.3, 142.5
(2C).
4-(Dimethylamino)-1-methyl-1,2,4-triazolium hexafluoro-
phosphate (6b)
577 cm−1
.
A mixture of 4-amino-1,2,4-triazole (5 g, 59 mmol) and
dimethyl sulfate (10 mL, 105 mmol, 1.8 equivalents) was
heated at 100 ◦C for 24 h. After cooling the viscous oil
was stirred with Et2O (3×20 mL), and the solvent was dis-
Bis[4-(dimethylamino)-1-methyl-1,2,4-triazolin-5-
ylidene]silver(I) hexafluorophosphate (7)
A
suspension of 4-(dimethylamino)-1-methyl-1,2,4-
carded. The oil was dissolved in H2O (30 mL), and a so- triazolium hexafluorophosphate (6b) (1.0 g, 3.7 mmol) and
lution of NH4PF6 (10.7 g, 65 mmol) in H2O (30 mL) was Ag2O (0.42 g, 1.8 mmol) in MeOH (20 mL) was stirred
added with stirring. The precipitate was filtered, washed with in the dark for 18 h at r. t. The colorless precipitate was
Unauthenticated
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