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(s, 2H), 6.61 (t, J ¼ 7.77 Hz, 2H), 6.82 (d, J ¼ 8.07 Hz, 1H), 7.00 (d, 6.58 (d, J ¼ 8.61 Hz, 2H), 6.77 (d, J ¼ 8.04 Hz, 1H), 7.00 (d, J ¼
J ¼ 8.97 Hz, 2H), 7.81 (d, J ¼ 8.76 Hz, 2H), 7.92 (s, 1H). ESI-MS: 8.76 Hz, 2H), 7.81 (d, J ¼ 8.79 Hz, 3H), 7.91 (s, 1H). ESI-MS:
356.41 (C18H18N3O3S, [M + H]+). Anal. calcd for C18H17N3O3S: C, 370.44 (C19H20N3O3S, [M + H]+). Anal. calcd for C19H19N3O3S: C,
60.83; H, 4.82; N, 11.82%. Found: C, 60.81; H, 4.81; N, 11.85%. 61.77; H, 5.18; N, 11.37%. Found: C, 61.76; H, 5.17; N, 11.36%.
4.1.16 5-(2,3-Dihydrobenzo[b][1,4]dioxin-6-yl)-3-phenyl-4,5-
4.1.22 5-(3,4-Dihydro-2H-benzo[b][1,4]dioxepin-7-yl)-3-phenyl-
dihydro-1H-pyrazole-1-carbothioamide (16a). White crystal, 4,5-dihydro-1H-pyrazole-1-carbothioamide (22a). White crystal,
yield: 57%. MP: 198–200 ꢂC. 1H NMR (DMSO-D6, 300 MHz): 3.12 yield: 67%. MP: 201–203 ꢂC. 1H NMR (DMSO-D6, 300 MHz): 2.10
(dd, J1 ¼ 3.09 Hz, J2 ¼ 17.91 Hz, 1H), 3.83 (dd, J1 ¼ 11.16 Hz, J2 ¼ (s, 2H), 3.12 (dd, J1 ¼ 3.02 Hz, J2 ¼ 17.98 Hz, 1H), 3.84 (dd, J1 ¼
17.94 Hz, 1H), 4.22 (d, J ¼ 20.49 Hz, 4H), 5.81 (dd, J1 ¼ 3.12 Hz, 11.34 Hz, J2 ¼ 18.02 Hz, 1H), 4.13 (s, 4H), 5.86 (dd, J1 ¼ 2.96 Hz,
J2 ¼ 11.16 Hz, 1H), 6.58–6.61 (m, 2H), 6.78 (d, J ¼ 8.04 Hz, 1H), J2 ¼ 11.24 Hz, 1H), 6.72 (d, J ¼ 8.01 Hz, 2H), 6.86–6.98 (m, 2H),
7.41–7.47 (m, 3H), 7.86–7.89 (m, 3H), 8.00 (s, 1H). ESI-MS: 7.34 (t, J ¼ 8.78 Hz, 2H), 7.80–8.05 (m, 4H), 8.03 (s,1H). ESI-MS:
340.41 (C18H18N3O2S, [M + H]+). Anal. calcd for C18H17N3O2S: C, 354.12 (C19H20N3O2S, [M + H]+). Anal. calcd for C19H19N3O2S: C,
63.70; H, 5.05; N, 12.38%. Found: C, 63.72; H, 5.04; N, 12.37%. 64.57; H, 5.42; N, 11.89%. Found: C, 61.47; H, 4.87; N, 11.32%.
4.1.17 5-(2,3-Dihydrobenzo[b][1,4]dioxin-6-yl)-3-(4-uoro-
4.1.23 5-(3,4-Dihydro-2H-benzo[b][1,4]dioxepin-7-yl)-3-(4-
phenyl)-4,5-dihydro-1H-pyrazole-1-carbothioamide (17a). uorophenyl)-4,5-dihydro-1H-pyrazole-1-carbothioamide (23a).
White crystal, yield: 74%. MP: 205–207 ꢂC. 1H NMR (DMSO-D6, White crystal, yield: 72%. MP: 207–210 ꢂC. 1H NMR (DMSO-D6,
300 MHz): 3.10 (dd, J1 ¼ 3.27 Hz, J2 ¼ 18.09 Hz, 1H), 3.80 (dd, 300 MHz): 2.11 (s, 2H), 3.13 (dd, J1 ¼ 2.94 Hz, J2 ¼ 17.94 Hz, 1H),
J1 ¼ 11.34 Hz, J2 ¼ 18.12Hz, 1H), 4.17 (s, 4H), 5.79 (dd, J1 ¼ 3.09 3.82 (dd, J1 ¼ 11.24 Hz, J2 ¼ 17.87 Hz, 1H), 4.14 (s, 4H), 5.84 (dd,
Hz, J2 ¼ 11.31 Hz, 1H), 6.55–6.59 (m, 2H), 6.76 (d, J ¼ 7.86 Hz, J1 ¼ 2.94 Hz, J2 ¼ 11.16 Hz, 1H), 6.70 (d, J ¼ 8.04 Hz, 2H), 6.87–
1H), 7.28 (t, J ¼ 8.96 Hz, 2H), 7.89–7.99 (m, 4H). ESI-MS: 358.40 6.97 (m, 1H), 7.30 (t, J ¼ 8.78 Hz, 2H), 7.78–8.01 (m, 4H). ESI-MS:
(C18H17FN3O2S, [M + H]+). Anal. calcd for C18H16FN3O2S: C, 372.43 (C19H19FN3O2S, [M + H]+). Anal. calcd for C19H18FN3O2S:
60.49; H, 4.51; N, 11.76%. Found: C, 60.51; H, 4.50; N, 11.78%. C, 61.44; H, 4.88; N, 11.31%. Found: C, 61.47; H, 4.87; N,
4.1.18 3-(4-Chlorophenyl)-5-(2,3-dihydrobenzo[b][1,4]dioxin- 11.32%.
6-yl)-4,5-dihydro-1H-pyrazole-1-carbothioamide (18a). White
4.1.24 3-(4-Chlorophenyl)-5-(3,4-dihydro-2H-benzo[b][1,4]-
crystal, yield: 76%. MP: 225–226 ꢂC. 1H NMR (DMSO-D6, 300 dioxepin-7-yl)-4,5-dihydro-1H-pyrazole-1-carbothioamide (24a).
MHz): 3.11 (dd, J1 ¼ 3.12 Hz, J2 ¼ 17.70 Hz, 1H), 3.82 (dd, J1 ¼ White crystal, yield: 78%. MP: 220–222 ꢂC. 1H NMR (DMSO-D6,
11.34 Hz, J2 ¼ 18.09 Hz, 1H), 4.19 (s, 4H), 5.81 (dd, J1 ¼ 3.12 Hz, 300 MHz): 2.06 (s, 2H), 3.11 (dd, J1 ¼ 3.09 Hz, J2 ¼ 17.91 Hz, 1H),
J2 ¼ 11.34 Hz, 1H), 6.57–6.60 (m, 2H), 6.77 (d, J ¼ 8.25 Hz, 1H), 3.81 (dd, J1 ¼ 11.16 Hz, J2 ¼ 17.94 Hz, 1H), 4.08 (s, 4H), 5.82 (d,
7.52 (dd, J1 ¼ 2.01 Hz, J2 ¼ 6.75 Hz, 2H), 7.88–7.90 (m, 2H), 7.92 J ¼ 8.25 Hz, 1H), 6.67–6.70 (m, 2H), 6.88 (d, J ¼ 8.40 Hz, 1H),
(d,
J
¼ 7.68 Hz, 1H), 8.03 (s, 1H). ESI-MS: 374.86 7.50 (d, J ¼ 8.43 Hz, 2H), 7.86–7.89 (m, 2H), 7.92 (s, 1H), 8.03 (s,
(C18H17ClN3O2S, [M + H]+). Anal. calcd for C18H16ClN3O2S: C, 1H). ESI-MS: 388.88 (C19H19ClN3O2S, [M + H]+). Anal. calcd for
57.83; H,4.31; N,11.24%. Found: C, 57.81; H, 4.30; N, 11.22%. 19H18ClN3O2S: C, 58.83; H, 4.68; N, 10.83%. Found: C, 58.81;
4.1.19 3-(4-Bromophenyl)-5-(2,3-dihydrobenzo[b][1,4]dioxin- H, 4.67; N, 10.81%.
C
6-yl)-4,5-dihydro-1H-pyrazole-1-carbothioamide (19a). White
4.1.25 3-(4-Bromophenyl)-5-(3,4-dihydro-2H-benzo[b][1,4]-
crystal, yield: 64%. MP: 236–238 ꢂC. 1H NMR (DMSO-D6, 300 dioxepin-7-yl)-4,5-dihydro-1H-pyrazole-1-carbothioamide (25a).
MHz): 3.10 (dd, J1 ¼ 3.48 Hz, J2 ¼ 18.09 Hz, 1H), 3.81 (dd, J1 ¼ White crystal, yield: 71%. MP: 226–228 ꢂC. 1H NMR (DMSO-D6,
11.16 Hz, J2 ¼ 17.73 Hz, 1H), 4.19 (s, 4H), 5.81 (d, J ¼ 8.22 Hz, 300 MHz): 2.08 (s, 2H), 3.12 (dd, J1 ¼ 3.30 Hz, J2 ¼ 18.12 Hz, 1H),
1H), 6.57–6.60 (m, 2H), 6.77 (d, J ¼ 8.04 Hz, 1H), 7.65 (d, J ¼ 8.61 3.83 (dd, J1 ¼ 11.34 Hz, J2 ¼ 18.09 Hz, 1H), 4.08 (s, 4H), 5.85 (dd,
Hz, 2H), 7.80–7.93 (m, 2H), 8.04 (s, 1H), 8.31 (s,1H). ESI-MS: J1 ¼ 3.09 Hz, J2 ¼ 11.34 Hz, 1H), 6.68–6.72 (m, 2H), 6.89 (d, J ¼
419.31 (C18H17BrN3O2S, [M
+
H]+). Anal. calcd for 7.86 Hz, 1H), 7.65 (d, J ¼ 8.58 Hz, 2H), 7.82 (d, J ¼ 8.40 Hz, 2H),
C
18H16BrN3O2S: C, 51.68; H, 3.86; N, 10.05%. Found: C, 51.70; 7.95 (s, 1H), 8.06 (s, 1H). ESI-MS: 433.33 (C19H19BrN3O2S, [M +
H, 3.85; N, 10.06%.
H]+). Anal. calcd for C19H18BrN3O2S: C, 52.78; H, 4.20; N, 9.72%.
4.1.20 5-(2,3-Dihydrobenzo[b][1,4]dioxin-6-yl)-3-p-tolyl-4,5- Found: C, 52.80; H, 4.21; N, 9.74%.
dihydro-1H-pyrazole-1-carbothioamide (20a). White crystal,
4.1.26 5-(3,4-Dihydro-2H-benzo[b][1,4]dioxepin-7-yl)-3-p-tolyl-
yield: 75%. MP: 203–205 ꢂC. 1H NMR (DMSO-D6, 300 MHz): 2.34 4,5-dihydro-1H-pyrazole-1-carbothioamide (26a). White crystal,
(s, 3H), 3.08 (dd, J1 ¼ 2.94 Hz, J2 ¼ 17.91 Hz, 1H), 3.80 (dd, J1 ¼ yield: 69%. MP: 202–205 ꢂC. 1H NMR (DMSO-D6, 300 MHz): 2.07
11.16 Hz, J2 ¼ 17.76 Hz, 1H), 4.19 (s, 4H), 5.80 (dd, J1 ¼ 3.09 Hz, (s, 2H), 2.34 (s, 3H), 3.10 (dd, J1 ¼ 3.09 Hz, J2 ¼ 17.91Hz, 1H),
J2 ¼ 11.13 Hz, 1H), 6.56–6.60 (m, 2H), 6.77 (d, J ¼ 8.04 Hz, 1H), 3.81 (dd, J1 ¼ 11.16 Hz, J2 ¼ 17.91 Hz, 1H), 4.09 (s, 4H), 5.83 (d,
7.26 (d, J ¼ 8.04 Hz, 2H), 7.76 (d, J ¼ 8.22 Hz,2H), 7.81 (s, 1H), J ¼ 8.22 Hz, 1H), 6.68–6.72 (m, 2H), 6.89 (d, J ¼ 8.04 Hz, 1H),
7.96 (s, 1H). ESI-MS: 354.44 (C19H20N3O2S, [M + H]+). Anal. calcd 7.26 (d, J ¼ 7.86 Hz, 2H), 7.76 (d, J ¼ 8.07 Hz, 2H), 7.83 (s, 1H),
for C19H19N3O2S: C, 64.57; H, 5.42; N, 11.89%. Found: C, 64.55; 7.97 (s, 1H). ESI-MS: 368.46 (C20H22N3O2S, [M + H]+). Anal. calcd
H, 5.41; N, 11.87%.
for C20H21N3O2S: C, 65.37; H, 5.76; N, 11.44%. Found: C, 65.35;
4.1.21 5-(2,3-Dihydrobenzo[b][1,4]dioxin-6-yl)-3-p-tolyl-4,5- H, 5.75; N, 11.46%.
dihydro-1H-pyrazole-1-carbothioamide (21a). White crystal,
4.1.27 5-(3,4-Dihydro-2H-benzo[b][1,4]dioxepin-7-yl)-3-(4-
yield: 78%. MP: 212–214 ꢂC. 1H NMR (DMSO-D6, 300 MHz): 3.08 methoxyphenyl)-4,5-dihydro-1H-pyrazole-1-carbothioamide (27a).
(dd, J1 ¼ 2.94 Hz, J2 ¼ 17.96 Hz, 1H), 3.79 (dd, J1 ¼ 11.52 Hz, J2 ¼ White crystal, yield: 64%. MP: 214–217 ꢂC. 1H NMR (DMSO-D6,
19.20 Hz, 1H), 3.83 (s, 3H), 4.19 (s, 4H), 5.79 (d, J ¼ 8.22 Hz, 1H), 300 MHz): 2.08 (s, 2H), 3.10 (dd, J1 ¼ 3.16 Hz, J2 ¼ 18.04 Hz, 1H),
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RSC Adv., 2014, 4, 23904–23913 | 23911