KAZEMINEJAD et al.
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fluxed for 45 min. The progress of the reaction was
monitored by TLC (n-hexane–EtOAc, 4:1). After
completion of the reaction, the mixture was cooled,
and the white solid was filtered off and recrystallized
from 96% ethanol to isolate hydrazinecarbothiohydra-
zide in excellent yield with high purity. The product,
10.6 g (0.1 mol) was added to a mixture of 100 mL of
glacial acetic acid and 100 mL of water, and the
mixture was refluxed for 4 h. After completion of the
reaction, the mixture was cooled, and the resulting
dough-like material was filtered off and recrystallized
from H2O to obtain 4-amino-5-methyl-2,4-dihydro-
3H-1,2,4-triazole-3-thione (1) as transparent crystals
with mp 210–220°C; yield 75%.
139.8, 167.1, 170.2, 182.3. Found, %: C 39.01; H 2.95;
N 24.81. C11H10N6O3S2. Calculated, %: C 39.05;
H 2.98; N 24.84.
4-Methyl-N-[(3-methyl-5-sulfanylidene-1,5-dihy-
dro-4H-1,2,4-triazol-4-yl)carbamothioyl]benzamide
(4c). Yield 95%, mp 218–219°C. IR spectrum, ν, cm–1:
3341, 3254, 3168 (N–H), 3031 (C–Harom), 2923
(C–Haliph.), 1736 (C=O), 1694, 1590 (C=C), 1433,
1
1400 (C=S), 1122, 1050 (C–N). H NMR spectrum
(acetone-d6), δ, ppm): 2.10 s (3H), 2.38 s (3H), 7.38 d
(2H, J = 8.1 Hz), 7.54 d (2H, J = 8.1 Hz), 9.32 s (1H),
10.06 s (1H), 11.98 s (1H). 13C NMR spectrum
(acetone-d6), δC, ppm: 18.6, 20.5, 121.5, 128.1, 129.3,
137.3, 139.3, 168.6, 169.1, 181.9. Found, %: C 46.85;
H 4.23; N 22.81. C12H13N5OS2. Calculated, %:
C 46.89; H 4.26; N 22.78.
N-Benzoyl-N′-(3-methyl-5-sulfanylidene-1,5-di-
hydro-4H-1,2,4-triazol-4-yl)thioureas 4a–4g (gener-
al procedure). Benzoyl chloride (5 mmol) was added
dropwise with stirring to a solution of ammonium
thiocyanate (21 mmol) in anhydrous acetone (10 mL).
The mixture was heated for 1 h under reflux and was
then cooled in an ice bath. A solution of triazole 1
(5 mmol) in acetone (5 mL) was added, and the
mixture was stirred under reflux for 2 h (TLC; CHCl3–
MeOH, 3:1). After cooling, the white solid was
filtered off, washed with cold water, and recrystallized
from ethanol. The IR and NMR spectra of compounds
4a–4g are available from the authors.
2-Chloro-N-[(3-methyl-5-sulfanylidene-1,5-dihy-
dro-4H-1,2,4-triazol-4-yl)carbamothioyl]benzamide
(4d). Yield 89%, mp 212–214°C. IR spectrum, ν, cm–1:
3425, 3411, 3379 (N–H), 3086 (C–Harom), 2919
(C–Haliph), 1618, 1589 (C=C), 1368, 1295 (C=S), 1112
1
(C–N). H NMR spectrum (CDCl3), δ, ppm: 1.25 s
(3H), 7.48 t (1H, J = 6.0 Hz), 7.65 t (1H, J = 8.0 Hz),
7.77 d (1H, J = 6.7 Hz), 7.96 d (1H, J = 6.5 Hz), 9.44 s
(1H), 9.92 s (1H), 11.41 s (1H). 13C NMR spectrum
(CDCl3), δC, ppm: 26.9, 127.3, 130.4, 130.8, 131.2,
132.0, 133.1, 138.3, 165.9, 169.0, 181.8. Found, %:
C 40.34; H 3.02; Cl 10.85; N 21.39. C11H10ClN5OS2.
Calculated, %: C 40.30; H 3.07; Cl 10.81; N 21.36.
N-[(3-Methyl-5-sulfanylidene-1,5-dihydro-4H-
1,2,4-triazol-4-yl)carbamothioyl]benzamide (4a).
Yield 93%, mp 280–281°C. IR spectrum, ν, cm–1:
3282, 3243, 3207 (N–H), 3155 (C–Harom), 2918, 2849
(C–Haliph), 1678 (C=O), 1576, 1528 (C=C), 1316
(C=S), 1294 (C–N). 1H NMR spectrum (DMSO-d6), δ,
ppm: 2.57 s (3H), 7.56 t (2H, J = 7.2 Hz), 7.66 d (1H,
J = 7.0 Hz), 8.08 d (1H, J = 7.2 Hz), 9.74 s (1H),
11.15 s (1H), 12.20 s (1H). 13C NMR spectrum
(DMSO-d6), δC, ppm: 19.7, 128.8, 129.2, 133.9, 136.3,
137.8, 166.8, 173.1, 181.2. Found, %: C 45.07; H 3.75;
N 23.84. C11H11N5OS2. Calculated, %: C 45.04;
H 3.78; N 23.87.
2-Methyl-N-[(3-methyl-5-sulfanylidene-1,5-dihy-
dro-4H-1,2,4-triazol-4-yl)carbamothioyl]benzamide
(4e). Yield 85%, mp 199–200°C. IR spectrum, ν, cm–1:
3385, 3325, 3236 (N–H), 3162 (C–Harom), 2962, 2925
(C–Haliph), 1675 (C=O), 1609, 1576, 1534 (C=C),
1
1458, 1382 (C=S), 1241, 1082 (C–N). H NMR spec-
trum (DMSO-d6), δ, ppm: 2.38 s (3H), 2.58 s (3H),
7.20–7.56 m (4H), 9.50 s (1H), 11.32 s (1H), 12.22 s
(1H). 13C NMR spectrum (DMSO-d6), δC, ppm: 20.0,
29.4, 128.7, 129.6, 130.9, 131.2, 131.6, 133.8, 136.2,
170.5, 171.7, 182.3. Found, %: C 46.86; H 4.23;
N 22.74. C12H13N5OS2. Calculated, %: C 46.89;
H 4.26; N 22.78.
N-[(3-Methyl-5-sulfanylidene-1,5-dihydro-4H-
1,2,4-triazol-4-yl)carbamothioyl]-4-nitrobenzamide
(4b). Yield: 92%, mp 184–185°C. IR spectrum, ν,
cm–1: 3388, 3295, 3154 (N–H), 3101 (C–Harom), 2922
(C–Haliph), 1724 (C=O), 1690, 1600 (C=C), 1522, 1350
(NO2), 1322, 1235 (C=S), 1105, 1006 (C–N). 1H NMR
spectrum (DMSO-d6), δ, ppm: 2.26 s (3H), 8.26 d (2H,
J = 8.1 Hz), 8.48 d (2H, J = 8.1 Hz), 8.98 s (1H),
11.03 s (1H), 12.05 s (1H). 13C NMR spectrum
(DMSO-d6), δC, ppm: 20.8, 121.8, 123.8, 130.5, 132.0,
4-Chloro-N-[(3-methyl-5-sulfanylidene-1,5-dihy-
dro-4H-1,2,4-triazol-4-yl)carbamothioyl]benzamide
(4f). Yield 94%, mp 210–212°C. IR spectrum, ν, cm–1:
3218, 3298, 3218 (N–H), 3165 (C–Harom), 2924
(C–Haliph), 1685 (C=O), 1662, 1598 (C=C), 1486, 1406
1
(C=S), 1233, 1103 (C–N). H NMR spectrum
(DMSO-d6), δ, ppm: 1.19 s (3H), 7.49 d (2H, J =
6.5 Hz), 7.86 d (2H, J = 6.5 Hz), 9.56 s (1H), 9.77 s
(1H), 11.33 s (1H). 13C NMR spectrum (DMSO-d6),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 10 2019