The Journal of Organic Chemistry
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(m, 2H), 3.76 (m, 2H), 3.26 (m, 2H), 3.31 (m, 2H). 13C NMR
(75 MHz, CDCl3): δ 174.6, 155.52 (d, J = 244.1 Hz), 146.0, 138.59
(d, J = 7.8 Hz), 133.3, 128.9, 125.0, 124.51 (d, J = 3.7 Hz), 123.38
(d, J = 7.3 Hz), 119.7, 119.2 (d, J = 2.4 Hz), 116.19 (d, J = 20.4 Hz),
113.7, 52.1, 51.1, 50.5, 49.7. IR (KBr) νmax: 3059, 2923, 2846, 1612,
1585, 1505, 1447, 1269, 1158, 1041, 1010, 737, 424 cm−1. MS: m/z
342 [M + H]+. Anal. Calcd for C17H16FN5S: C, 59.65; H, 4.95; N,
20.51. Found: C, 59.81; H, 4.72; N, 20.12.
1H), 3.65 (s, 3H), 3.32 (s, 3H). 13C NMR (75 MHz, CDCl3): δ 175.5,
145.8, 133.1, 128.8, 125.0, 119.7, 113.8, 44.1, 43.7. IR (KBr) νmax
:
3082, 2927, 1605, 1590, 1532, 1449, 1390, 1258, 1148, 1025, 784,
749 cm−1. MS: m/z 207 [M + H]+. Anal. Calcd for C9H10N4S: C,
52.41; H, 4.89; N, 27.18. Found: C, 52.02; H, 4.56; N, 26.97.
N,N-Diethyl-1H-benzo[d][1,2,3]triazole-1-carbothioamide (3h).
Yellow oil, 0.408 g, yield 87%. Rf = 0.6 (20% ethyl acetate/n-hexane).
1H NMR (300 MHz, CDCl3): δ 8.03 (m, 2H), 7.56 (dd, J = 8.1,
(E)-(1H-Benzo[d][1,2,3]triazol-1-yl)(4-cinnamylpiperazin-1-yl)-
7.2 Hz, 1H), 7.41 (dd, J = 7.8, 7.5 Hz, 1H), 4.11 (d, J = 6.6 Hz, 2H),
3.49 (d, J = 6.9 Hz, 2H), 1.47 (t, J = 6.9 Hz, 3H), 1.31 (t, J = 6.6 Hz,
3H). 13C NMR (75 MHz, CDCl3): δ 174.5, 145.6, 133.1, 128.6, 124.8,
119.5, 113.3, 48.1, 48.0, 13.8, 10.7. IR (KBr) νmax: 3060, 2984, 2937,
2875, 1611, 1592, 1519, 1448, 1279, 1031, 746 cm−1. MS: m/z 335
[M + H]+. Anal. Calcd for C11H14N4S: C, 56.39; H, 6.03; N, 23.93.
Found: C, 56.72; H, 6.42; N, 23.70.
methanethione (3b). White crystals, 0.662 g, yield 91%, mp 92−
1
94 °C. Rf = 0.7 (50% ethyl acetate/n-hexane). H NMR (300 MHz,
CDCl3): δ 8.06 (t, J = 8.4 Hz, 2H), 7.56 (dd, J = 7.8, 7.2 Hz, 1H),
7.43−7.18 (m, 6H), 6.53 (d, J = 15.9 Hz, 1H), 6.22 (ddd, J = 15.9, 6.7,
6.6 Hz, IH), 4.38 (m, 2H), 3.707 (m, 2H), 3.20 (d, J = 6.6 Hz, 2H),
2.77 (m, 2H), 2.62 (m, 2H). 13C NMR (75 MHz, CDCl3): δ 174.2,
145.9, 136.3, 133.5, 133.2, 128.8, 128.4 (2C), 127.5, 126.1 (2C), 125.2,
124.9, 119.6, 113.6, 60.1, 53.3, 52.9, 51.9, 51.0. IR (KBr) νmax: 3029,
2925, 2810, 2766, 1608, 1509, 1441, 1022, 1047, 780, 748, 695 cm−1.
MS: m/z 364 [M + H]+. Anal. Calcd for C20H21N5S: C, 66.09; H, 5.82;
N, 19.27. Found: C, 66.48; H, 6.06; N, 19.08.
N,N-Diisopropyl-1H-benzo[d][1,2,3]triazole-1-carbothioamide
(3i). Yellow oil, 0.441 g, yield 84%. Rf = 0.7 (20% ethyl acetate/
1
n-hexane). H NMR (300 MHz, CDCl3): δ 8.11−8.08 (m, 2H), 7.61
(t, J = 7.5 Hz, 1H), 7.46 (dd, J = 7.5, 7.8 Hz, 1H), 3.89−3.80 (m, 2H),
1.34 (s, 3H), 1.32 (s, 3H), 1.24 (s, 3H), 1.22 (s, 3H). 13C NMR
(75 MHz, CDCl3): δ 174.5, 146.8, 130.4, 126.8, 120.8, 113.7, 47.4,
47.2, 22.4 (2C), 20.6 (2C). IR (KBr) νmax: 3038, 2944, 2927, 2845,
1610, 1589, 1532, 1444, 1282, 1021, 738, 585, 487 cm−1. MS: m/z 263
[M + H]+. Anal. Calcd for C13H18N4S: C, 59.51; H, 6.92; N, 21.37.
Found: C, 59.25; H, 7.09; N, 21.13.
(1H-Benzo[d][1,2,3]triazol-1-yl)(4-(2-chlorophenyl)piperazin-1-
yl)methanethione (3c). Yellow crystals, 0.644 g, yield 90%, mp 144−
1
145 °C. Rf = 0.7 (30% ethyl acetate/n-hexane). H NMR (300 MHz,
CDCl3): δ 8.11 (d, J = 9.3 Hz, 1H), 8.07 (d, J = 9.6 Hz, 1H), 7.60 (t,
J = 7.8 Hz, 1H), 7.44 (dd, J = 7.8, 7.5 Hz, 1H), 7.38 (d, J = 7.8 Hz,
1H), 7.24 (dd, J = 7.5, 7.2 Hz, 1H), 7.03 (dd, J = 11.7, 7.8 Hz, 2H),
4.54 (m, 2H), 3.88 (m, 2H), 3.34 (m, 2H), 3.21 (m, 2H). 13C NMR
(75 MHz, CDCl3): δ 174.7, 147.6, 146.0, 133.3, 130.6, 128.9, 128.7,
127.6, 125.0, 124.5, 120.5, 119.7, 113.7, 52.4, 51.2 (2C), 50.3. IR
(KBr) νmax: 1597, 1536, 1067, 1007, 959, 891, 728, 692, 650 cm−1.
MS: m/z 358 [M + H]+. Anal. Calcd for C17H16ClN5S: C, 57.13; H,
4.52; N, 19.61. Found: C, 57.32; H, 4.18; N, 19.77.
(1H-Benzo[d][1,2,3]triazol-1-yl)(4-phenylpiperazin-1-yl)-
methanethione (3d). Yellow crystals, 0.588 g, yield 91%, mp 107−108
°C. Rf = 0.5 (20% ethyl acetate/n-hexane). 1H NMR (300 MHz,
CDCl3): δ 8.10 (d, J = 8.4 Hz, 1H), 8.06 (d, J = 8.4 Hz, 1H), 7.57 (dd,
J = 7.8, 7.2 Hz, 1H), 7.42 (dd, J = 7.8, 7.2 Hz, 1H), 7.28 (d, J = 7.5 Hz,
1H), 7.26 (d, J = 8.1 Hz, 1H), 6.91 (d, J = 7.2 Hz, 3H), 4.47 (m, 2H),
3.86 (m, 2H), 3.46 (m, 2H), 3.31 (m, 2H). 13C NMR (75 MHz,
CDCl3): δ 174.5, 149.9, 146.0, 133.3, 129.1 (2C), 128.9, 125.1, 120.5,
119.7, 116.3 (2C), 113.8, 51.8, 50.8, 49.3, 48.4. IR (KBr) νmax: 3060,
2909, 2828, 1602, 1581, 1505, 1448, 1280, 1230, 1167, 1049, 1016,
741, 517, 429 cm−1. MS: m/z 324 [M + H]+. Anal. Calcd for
C17H17N5S: C, 63.13; H, 5.30; N, 21.65. Found: C, 63.0; H, 5.57; N,
21.29.
N,N-Dibutyl-1H-benzo[d][1,2,3]triazole-1-carbothioamide (3j).
Yellow oil, 0.511 g, yield 88%. Rf = 0.7 (20% ethyl acetate/n-hexane).
1H NMR (300 MHz, CDCl3): δ 8.04 (d, J = 8.4 Hz, 1H), 7.97 (d, J =
8.4 Hz, 1H), 7.55 (dd, J = 7.8, 7.2 Hz, 1H), 7.40 (t, J = 7.5 Hz, 1H),
4.05 (d, J = 7.8, 7.5 Hz, 2H), 3.46 (dd, J = 7.8, 7.2 Hz, 2H), 1.91 (m,
2H), 1.61 (m, 2H), 1.47 (m, 2H), 1.11 (m, 2H), 1.01 (t, J = 7.2 Hz,
3H), 0.72 (t, J = 6.9 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ 174.6,
145.4, 132.9, 128.4, 124.5, 119.3, 113.0, 53.4, 53.3, 30.1, 27.4, 19.8,
19.4, 13.5, 13.1. IR (KBr) νmax: 3077, 2929, 2861, 1611, 1590, 1530,
1438, 1226, 1042, 1021, 757, 595 cm−1. MS: m/z 291 [M + H]+. Anal.
Calcd for C15H22N4S: C, 62.04; H, 7.64; N, 19.30. Found: C, 62.21; H,
7.88; N, 19.63.
(1H-Benzo[d][1,2,3]triazol-1-yl)(morpholino)methanethione (3k).
Yellow crystals, 0.528 g, yield 93%, mp 112−113 °C. Rf = 0.7 (30%
1
ethyl acetate/n-hexane). H NMR (300 MHz, CDCl3): δ 8.08 (t, J =
7.8 Hz, 2H), 7.59 (dd, J = 7.8, 7.5 Hz, 1H), 7.43 (dd, J = 7.8, 7.5 Hz,
1H), 4.36 (m, 2H), 3.95−3.75 (m, 6H). 13C NMR (75 MHz, CDCl3):
δ 174.5, 145.9, 133.2, 128.9, 125.0, 119.7, 113.7, 66.5, 66.0, 52.6, 51.3.
IR (KBr) νmax: 2927, 1860, 1610, 1589, 1497, 1447, 1237, 1115, 1051,
1024, 738, 524 cm−1. MS: m/z 249 [M + H]+. Anal. Calcd for
C11H12N4OS: C, 53.21; H, 4.88; N, 22.58. Found: C, 52.90; H, 5.07;
N, 22.21.
(1H-Benzo[d][1,2,3]triazol-1-yl)(4-(pyridin-2-yl)piperazin-1-yl)-
methanethione (3e). Yellow crystals, 0.596 g, yield 92%, mp 112−113
°C. Rf = 0.7 (30% ethyl acetate/n-hexane). 1H NMR (300 MHz,
CDCl3): δ 8.21 (d, J = 3.9 Hz, 1H), 8.16 (d, J = 8.4 Hz, 1H), 8.08 (d,
J = 8.4 Hz, 1H), 7.60 (dd, J = 8.1, 7.2 Hz, 1H), 7.52 (ddd, J = 7.2, 6.9,
1.5 Hz, 1H), 7.45 (dd, J = 7.8, 7.5 Hz, 1H), 6.69 (dd, J = 6.6, 6.9 Hz,
1H), 6.65 (d, J = 8.7 Hz, 1H), 4.46 (m, 2H), 3.89 (m, 4H), 3.74 (m,
2H). 13C NMR (75 MHz, CDCl3): δ 174.7, 158.3, 147.9, 146.1, 137.7,
133.7, 129.0, 125.1, 119.8, 114.1, 113.9, 106.9, 51.6, 50.8, 45.2, 44.0. IR
(KBr) νmax: 3026, 2924, 2810, 1612, 1579, 1443, 1044, 1020, 746, 685,
497 cm−1. MS: m/z 325 [M + H]+. Anal. Calcd for C16H16N6S: C,
59.24; H, 4.98; N, 25.92. Found: C, 58.91; H, 5.20; N, 26.19.
(1H-Benzo[d][1,2,3]triazol-1-yl)(4-methylpiperazin-1-yl)-
methanethione (3f). Yellow crystals, 0.496 g, yield 95%, mp 103−
(1H-Benzo[d][1,2,3]triazol-1-yl)(piperidin-1-yl)methanethione
(3l). Yellow crystals, 0.453 g, yield 92%, mp 105−106 °C. Rf = 0.6
1
(20% ethyl acetate/n-hexane). H NMR (300 MHz, CDCl3): δ 8.04
(d, J = 8.7 Hz, 2H), 7.57 (dd, J = 7.8, 7.2 Hz, 1H), 7.41 (dd, J = 7.8,
7.2 Hz, 1H), 4.30 (m, 2H), 3.56 (m, 2H), 1.90 (m, 2H), 1.75 (m, 4H).
13C NMR (75 MHz, CDCl3): δ 173.9, 145.8, 133.1, 128.6, 124.8,
119.6, 113.4, 53.2, 52.5, 26.6, 25.2, 23.8. IR (KBr) νmax: 3086, 2942,
1859, 1612, 1589, 1513, 1446, 1257, 1049, 1021, 727, 534 cm−1. MS:
m/z 247 [M + H]+. Anal. Calcd for C12H14N4S: C, 58.51; H, 5.73; N,
22.76. Found: C, 58.24; H, 5.54; N, 22.55.
(S)-1-(1H-Benzo[d][1,2,3]triazole-1-carbonothioyl)pyrrolidine-2-
carboxylic Acid (3m). White crystals, 0.508 g, yield 92%, mp 152−
1
1
104 °C. Rf = 0.6 (80% ethyl acetate/n-hexane). H NMR (300 MHz,
154 °C. Rf = 0.5 (10% methanol/chloroform). H NMR (300 MHz,
CDCl3): δ 8.08 (d, J = 6.0 Hz, 2H), 7.59 (t, J = 7.5 Hz, 1H), 7.44 (dd,
J = 7.8, 7.5 Hz, 1H), 4.39 (m, 2H), 3.72 (m, 2H), 2.71 (m, 2H), 2.56
(m, 2H), 2.37 (s, 3H). 13C NMR (75 MHz, CDCl3): δ 174.5, 146.1,
133.4, 128.9, 125.1, 119.7, 113.7, 54.9, 53.0, 52.0, 51.0, 45.4. MS: m/z
262 [M + H]+. Anal. Calcd for C12H15N5S: C, 55.15; H, 5.79; N,
26.80. Found: C, 54.78; H, 5.94; N, 26.50.
CDCl3): δ 9.08 (bs, 1H), 8.22 (d, J = 8.4 Hz, 1H), 8.08 (d, J = 8.1 Hz,
1H), 7.60 (dd, J = 7.2, 7.5 Hz, 1H), 7.45 (dd, J = 7.8, 6.9 Hz, 1H),
5.13−5.10 (m, 1H), 4.21−4.18 (m, 1H), 4.02−4.00 (m, 1H), 2.52−
2.42 (m, 1H), 2.31−2.06 (m, 3H). 13C NMR (75 MHz, CDCl3): δ
174.9, 173.7, 145.7, 133.1, 129.1, 125.3, 119.8, 114.5, 65.9, 54.6, 29.3,
25.0. MS: m/z 277 [M + H]+. Anal. Calcd for C12H12N4O2S: C, 52.16;
H, 4.38; N, 20.28. Found: C, 51.89; H, 4.20; N, 20.05.
N,N-Dimethyl-1H-benzo[d][1,2,3]triazole-1-carbothioamide (3g).
Yellow crystals, 0.326 g, yield 79%, mp 111−112 °C. Rf = 0.7 (30%
(1H-Benzo[d][1,2,3]triazol-1-yl)(4-hydroxypiperidin-1-yl)-
1
ethyl acetate/n-hexane). H NMR (300 MHz, CDCl3): δ 8.06 (d, J =
methanethione (3n). White crystals, 0.372 g, yield 71%, mp 110−
1
8.1 Hz, 2H), 7.58 (dd, J = 7.5, 7.2 Hz, IH), 7.43 (dd, J = 7.5, 7.2 Hz,
111 °C. Rf = 0.7 (40% ethyl acetate/n-hexane). H NMR (300 MHz,
J
dx.doi.org/10.1021/jo4024107 | J. Org. Chem. XXXX, XXX, XXX−XXX