6
.76 (2H, s, NH ); 7.9 (2H, d, J = 8.2, Н Ar); 8.42 (2H, d, J = 8.2, Н Ar). Found, %: C 49.74; H 4.02; N 20.92.
2
Calculated, %: C 49.54; H 4.16; N 21.01.
Preparation of 5-Amino-1,2,3-triazoles 6a-f (General Method). Equimolar amounts of the azide 2a-d
and triethylamine were added to the thioamide 5a-c (1.0 mmol) in ethanol. The reaction mixture was stirred at
room temperature for 1 h and cooled to 10°C, and the precipitate was filtered off and crystallized from ethanol.
[
5-Amino-1-(4-nitrophenyl)-1H-1,2,3-triazol-4-yl](morpholin-1-yl)methanethione (6a). Yield 80%.
-
1
Colorless crystals, mp 164-167°C. IR spectrum, ν, cm : 3432, 3292 (NH), 3041 (Ar); 2987, 2857 (CH ).
2
1
H NMR spectrum, δ, ppm (J, Hz): 3.75-3.85 (4Н, m, 2CH
2
); 4.20-4.6 (4H, m, 2CH
2
); 7.30 (2H, s, NH ); 7.92
2
1
3
(
(
2H, d, J = 6.2, Н Ar); 8.45 (2H, d, J = 6.2, Н Ar). C NMR spectrum, δ, ppm: 49.9 (CH ), 54.0 (CH ), 66.6
2
2
CH ); 66.7 (CH ); 125.6 (=CH); 125.7 (=CH); 126.6 (C-5); 140.3 (=C); 147.1 (C-4); 147.5 (=C); 184.6 (C=S).
2
2
+
Mass spectrum, m/z (I , %): 334 [M] (33), 103 (11), 86 (100), 76 (24). Found, %: C 46.98; H 4.12; N 25.47;
rel
S 11.61. С Н N O S. Calculated, %: C 46.70; H 4.22; N 25.13; S 11.89.
1
3
14
6
3
[
5-Amino-1-(4-chlorophenyl)-1H-1,2,3-triazol-4-yl](morpholin-1-yl)methanethione (6b). Yield
-1
7
1%. Colorless crystals, mp 168-171°C. IR spectrum, ν, cm : 3367, 3226 (NH), 3040 (Ar), 2928, 2862 (СН ).
2
1
H NMR spectrum, δ, ppm (J, Hz): 3.65-3.85 (4Н, m, 2CH
2
); 4.25-4.55 (4H, m, 2CH
2
); 7.07 (2H, s, NH ); 7.60
2
+
(
4H, s, Н Ar). Mass spectrum, m/z (I , %): 323 [M] (27), 210 (100), 153 (67), 111 (34), 76 (14). Found, %:
rel
C 48.38; H 4.15; N 21.54; S 9.87. С Н N OSCl. Calculated, %: %: C 48.22; H 4.36; N 21.63; S 9.90.
1
3
14
5
[
5-Amino-1-(4-fluorophenyl)]-1H-1,2,3-triazol-4-yl](morpholin-1-yl)methanethione (6c). Yield
-
1
5
3%. Colorless crystals, 136-138°C. IR spectrum, ν, cm : 3340, 3246 (NH), 3046 (Ar); 2916, 2849 (СН ).
2
1
H NMR spectrum, δ, ppm (J, Hz): 3.65-3.85 (4Н, m, 2CH
2
); 4.20-4.55 (4H, m, 2CH
2
); 7.04 (2H, s, NH );
2
+
7
(
.35-7.42 (2H, m, Н Ar); 7.60-7.83 (2H, m, Н Ar). Mass spectrum, m/z (I , %): 307 [M] (33), 194 (100), 137
rel
77), 95 (99), 86 (50), 75 (36). Found, %: C 50.64; H 4.38; N 22.59; S 10.26. С Н N FOS. Calculated, %:
13
14
5
C 50.80; H 4.54; N 22.79; S 10.43.
[
5-Amino-1-(4-methoxyphenyl)-1H-1,2,3-triazol-4-yl](morpholin-1-yl)methanethione (6d). Yield
-1
6
7%. Colorless crystals, mp 155-158°C. IR spectrum, ν, cm : 3347, 3235 (NH), 3010 (Ar); 2916, 2856 (СН ).
2
1
H NMR spectrum, δ, ppm (J, Hz): 3.65-3.82 (4Н, m, 2CH
2
); 3.89 (3H, s, ОCH
3
); 4.20-4.65 (4H, m, 2CH );
2
6
[
.92 (2H, s, NH ); 7.15 (2H, d, J = 6.7, Н Ar); 7.45 (2H, d, J = 6.7, Н Ar). Mass spectrum, m/z (I , %): 319
2
rel
+
M] (16), 206 (100), 191 (48), 149 (68), 108 (20), 77 (52). Found, %: C 52.39; H 5.22; N 21.72; S 10.26.
С Н N O S. Calculated, %: C 52.65; H 5.36; N 21.93; S 10.04.
1
4
17
5
2
[
5-Amino-1-(4-nitrophenyl)-1H-1,2,3-triazol-4-yl](piperidin-1-yl)methanethione (6e). Yield 44%.
-
1
Colorless crystals, mp 167-170°C. IR spectrum, ν, cm : 3434, 3293 (NH), 3085 (Ar); 2903, 2857 (СН ).
2
1
H NMR spectrum, δ, ppm (J, Hz): 1.70-1.90 (6Н, m, CH
2
); 4.13 (4H, s, CH
2
); 7.18 (2H, s, NH ); 7.95 (2H, d,
2
1
3
J = 8.9, Н Ar); 8.45 (2H, d, J = 8.9, Н Ar). C NMR spectrum, δ, ppm: 27.4; 50.7; 54.1 (CH ); 125.6 (=СH);
2
+
1
(
27.0 (C-5); 140.4 (=C); 147.0 (C-4); 147.5 (=C); 183.6 (C=S). Mass spectrum, m/z (I , %): 332 [M] (19), 111
rel
15), 84 (100). Found, %: C50.95; H 4.32; N 25.59; S 10.01. С Н N O S. Calculated, %: C 50.54; H 4.85;
1
4
16
6
2
N 25.28; S 9.65.
[
5-Amino-1-(4-nitrophenyl)-1H-1,2,3-triazol-4-yl][4-(4-methoxyphenyl)piperazin-1-yl]methane-
-
1
thione (6f). Yield 58%. Colorless crystals, mp 201-203°C. IR spectrum, ν, cm : 3396, 3249 (NH), 3081 (Ar),
1
2
905, 2829 (СН ). H NMR spectrum, δ, ppm (J, Hz): 3.02-3.38 (4Н, m, 2CH ); 3.74 (3H, s, ОCH ); 4.25-4.65
2
2
3
(
4H, m, 2CH ); 7.25 (2H, s, NH ); 6.75-6.90 (4H, m, Н Ar); 7.95 (2H, d, J = 7.9, Н Ar); 8.49 (2H, d, J = 7.9, Н Ar).
2
2
+
Mass spectrum, m/z (I , %): 439 [M] (16), 190 (19), 175 (21), 162 (100), 134 (73), 108 (17), 77 (20). Found,
rel
%
: C 54.49; H 4.57; N 22.09; S 7.23. С Н N O S. Calculated, %: C 54.66; H 4.82; N 22.34; S 7.50.
20
21
7
3
5
-(Morpholin-4-yl)-N-tosyl-1,2,3-thiadiazole-4-carboxamidine (9a). The thioamide 5a (0.31 g,
2
.0 mmol) was suspended in a solution of sodium ethoxide prepared from sodium (0.046 g, 2.0 mmol) and
absolute ethanol (10 ml), and toluenesulfanyl azide 8 (0.39 g, 2.0 mmol) was added at 10°C with stirring. The
precipitate that separated after 30 min was filtered off and recrystallized from ethanol. Yield 80%. Colorless
-
1
1
crystals, mp 123-125°C. IR spectrum, ν, cm : 3400, 3291 (NH), 2960 (СН); 2859 (СН ); 1143 (S=O). H NMR
2
spectrum, δ, ppm (J, Hz): 2.38 (3H, s, CH ); 3.20-3.25 (4Н, m, CH ); 3.50-3.53 (4Н, m, CH ); 7.39 (2H, d,
3
2
2
9
76