268
E. ?ukasik, Z. Wróbel
Paper
Synthesis
13C NMR (150 MHz, CF3CO2D): δ = 18.1, 58.8, 94.6, 122.8, 123.9, 127.9,
131.4, 132.1, 134.6, 138.8, 140.9, 146.3, 147.2, 158.5, two signals not
observed.
13C NMR (150 MHz, DMSO-d6): δ = 97.2 (d, JC–F = 29 Hz), 110.4 (d, JC–F
=
20 Hz), 110.6 (d, JC–F = 3 Hz), 127.6, 129.5, 129.9, 133.4, 133.8, 134.0
(d, JC–F = 13 Hz), 158.7 (d, JC–F = 237 Hz), 170.2.
MS (EI): m/z (%) = 335 (77), 303 (25), 302 (100), 287 (27), 272 (10).
HRMS (EI): m/z calcd for C19H17N3OS: 335.1092; found: 335.1101.
MS (EI): m/z (%) = 280 (34), 279 (50), 278 (92), 277 (100), 242 (15).
HRMS (EI): m/z calcd for C13H8N2FS35Cl: 278.0081; found: 278.0078.
6-Chloro-1-(4-methoxyphenyl)-2,3-dihydro-1H-1,3-benzodiazole-
1-(4-Methoxyphenyl)-6-phenyl-2,3-dihydro-1H-1,3-benzodiazole-
2-thione (5j)
2-thione (5f)26
Yield: 123 mg (85%); white solid; mp 253–255 °C.
Yield: 120 mg (72%); white crystals; mp 221–224 °C.
IR (KBr): 3127, 3069, 2946, 1610, 1517, 1487, 1335, 1256, 1211, 1170,
IR (KBr): 3159, 3056, 1611, 1585, 1519, 1478, 1447, 1351, 1302, 1255,
801, 609 cm–1
.
1026, 826, 757 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 3.90 (s, 3 H), 6.93 (s, 1 H), 7.01–7.21
(m, 4 H), 7.35–7.47 (m, 2 H), 12.02 (s, 1 H).
13C NMR (100 MHz, CDCl3): δ = 55.7, 110.4, 110.9, 115.2, 124.1, 127.3,
129.1, 129.3, 129.4, 135.3, 160.4, 170.2.
1H NMR (600 MHz, acetone-d6): δ = 3.90 (s, 3 H), 7.12–7.17 (m, 3 H),
7.31–7.34 (m, 1 H), 7.40–7.43 (m, 3 H), 7.51–7.55 (m, 3 H), 7.57–7.59
(m, 2 H), 11.98 (s, 1 H).
13C NMR (150 MHz, CDCl3): δ = 55.6, 108.5, 110.4, 115.0, 123.2, 127.2,
127.3, 127.7, 128.8, 129.1, 130.2, 135.1, 137.0, 140.7, 160.0, 169.4.
1H-15N NMR (600 MHz, acetone-d6): δ = –230.37 (d, J = 100 Hz, NH),
–216.31.
MS (EI): m/z (%) = 292 (38), 291 (42), 290 (100), 289 (65), 275 (23).
HRMS (EI): m/z calcd for C14H11N2OS35Cl: 290.0281; found: 290.0295.
MS (EI): m/z (%) = 332 (100), 331 (49), 317 (18).
6-Chloro-1-(4-ethoxyphenyl)-4-methoxy-2,3-dihydro-1H-1,3-
benzodiazole-2-thione (5g)
HRMS (EI): m/z calcd for C20H16N2OS: 332.0983; found: 332.0989.
Yield: 153 mg (92%); white solid; mp 257–260 °C.
4-(4,6-Dichloro-2-sulfanylidene-2,3-dihydro-1H-1,3-benzodiazol-
1-yl)benzonitrile (5k)
IR (KBr): 3029, 2888, 1636, 1610, 1585, 1519, 1497, 1478, 1345, 1250,
1229, 1119, 896, 660 cm–1
.
Yield: 138 mg (86%); white solid; mp >280 °C.
1H NMR (400 MHz, CDCl3): δ = 1.46 (t, J = 6.4 Hz, 3 H), 3.92 (s, 3 H),
4.11 (q, J = 6.4 Hz, 2 H), 6.55 (s, 1 H), 6.70 (s, 1 H), 7.03–7.10 (m, 2 H),
7.34–7.41 (m, 2 H), 11.04 (s, 1 H).
IR (KBr): 3106, 3047, 2898, 2233, 1603, 1508, 1488, 1329, 1257, 1177,
840 cm–1
.
13C NMR (100 MHz, CDCl3): δ = 14.9, 56.4, 64.0, 103.4, 106.5, 115.6,
1H NMR (600 MHz, DMSO-d6): δ = 6.99 (d, J = 1.7 Hz, 1 H), 7.46 (d, J =
119.3, 127.5, 129.0, 129.6, 135.9, 144.5, 159.6, 169.7.
1.7 Hz, 1 H), 7.80–7.82 (m, 2 H), 8.10–8.12 (m, 2 H), 13.84 (s, 1 H).
MS (EI): m/z (%) = 336 (38), 335 (38), 334 (100), 333 (50), 307 (10),
13C NMR (150 MHz, DMSO-d6): δ = 108.4, 111.9, 114.5, 118.2, 122.9,
305 (28).
127.6, 128.4, 129.4, 133.7, 135.0, 138.7, 170.9.
HRMS (EI): m/z calcd for C16H15N2O2S35Cl: 334.0543; found: 334.0552.
MS (EI): m/z (%) = 321 (60), 320 (84), 319 (89), 318 (100), 75 (11).
HRMS (EI): m/z calcd for C14H7N3S35Cl2: 318.9738; found: 318.9736.
6-Chloro-1-(pyridin-4-yl)-2,3-dihydro-1H-1,3-benzodiazole-2-thi-
one (5h)
1-(4-Methoxyphenyl)-2,3-dihydro-1H-1,3-benzodiazole-2-thione
(5l)26
Yield: 52 mg (40%); white solid; mp 274–277 °C.
IR (KBr): 3029, 2888, 1636, 1610, 1585, 1519, 1497, 1478, 1345, 1250,
Yield: 114 mg (89%); white crystals; mp 217–220 °C.
1229, 1119, 896, 660 cm–1
.
IR (KBr): 3134, 3090, 3054, 2985, 1615, 1586, 1515, 1451, 1383, 1360,
1H NMR (600 MHz, DMSO-d6): δ = 7.12 (d, J = 1.9 Hz, 1 H), 1.27 (d, J =
8.5 Hz, 1 H), 7.29–7.31 (dd, J = 8.9, 1.9 Hz, 1 H), 7.70–7.72 (m, 2 H),
8.83–8.85 (m, 2 H), 13.35 (s, 1 H).
1313, 1249, 1217, 1161, 1034, 823, 732, 623, 565 cm–1
.
1H NMR (600 MHz, CDCl3): δ = 3.89 (s, 3 H), 6.96 (d, J = 8.0 Hz, 1 H),
7.08–7.10 (m, 2 H), 7.16 (t, J = 7.7 Hz, 1 H), 7.23 (t, J = 7.7 Hz, 1 H),
7.34 (d, J = 8.0 Hz, 1 H), 7.45–7.47 (m, 2 H), one signal not observed.
13C NMR (150 MHz, DMSO-d6): δ = 109.5, 111.1, 122.5, 123.8, 127.3,
130.2, 133.5, 142.3, 151.2, 169.6.
13C NMR (150 MHz, CDCl3): δ = 55.6, 110.1, 110.4, 114.9, 123.3, 123.9,
MS (EI): m/z (%) = 263 (37), 262 (51), 261 (100), 260 (95), 225 (12).
HRMS (EI): m/z calcd for C12H8N3S35Cl: 261.0127; found: 261.0135.
127.6, 129.0, 130.7, 134.5, 160.0, one signal not observed.
MS (EI): m/z (%) = 256 (100), 255 (70), 241 (35).
HRMS (EI): m/z calcd for C14H12N2OS: 256.0670; found: 256.0666.
1-(4-Chlorophenyl)-6-fluoro-2,3-dihydro-1H-1,3-benzodiazole-2-
thione (5i)
6-Chloro-1-(2-iodo-4-methylphenyl)-2,3-dihydro-1H-1,3-benzo-
Yield: 136 mg (98%); white crystals; mp 258–261 °C.
diazole-2-thione (5n)
IR (KBr): 3141, 3093, 1618, 1502, 1489, 1448, 1349, 1217, 1092, 799,
Yield: 162 mg (81%); white solid; mp 235–238 °C.
600 cm–1
.
IR (KBr): 3129, 3024, 2944, 2910, 1608, 1592, 1497, 1471, 1434, 1369,
1H NMR (600 MHz, DMSO-d6): δ = 6.82–6.84 (dd, J = 8.6, 2.2 Hz, 1 H),
7.06–7.10 (m, 1 H), 7.23–7.25 (d, J = 4.8 Hz, 1 H), 7.57–7.60 (m, 2 H),
7.66–7.68 (m, 2 H), 13.16 (s, 1 H).
1335, 1243, 1213, 1195, 1048, 945, 839, 796, 609, 588 cm–1
.
1H NMR (600 MHz, DMSO-d6): δ = 2.39 (s, 3 H), 6.64 (s, 1 H), 7.24–
7.26 (m, 2 H), 7.35 (d, J = 8.0 Hz, 1 H), 7.40–7.45 (m, 1 H), 7.90–7.91
(m, 1 H), 13.14 (s, 1 H).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, 263–270