Molecules 2016, 21, 1598
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1444.68, 1355.96 (C-H bending), 1228.66, 1211.30, 1188.15, 1157.29, 1072.42, 1037.70 (C-N stretching,
C=S stretching and aromatic C-H in plane bending), 937.40, 856.39, 835.18, 810.10, 790.81, 738.74, 711.73,
1
651.94, 596.00 (aromatic C-H out of plane bending and C-S stretching). H-NMR (400 MHz, DMSO-d6):
6.05 (s, 2H, O-CH2-O), 6.90-6.95 (m, 2H, benzodioxole), 7.17 (s, 1H, benzodioxole), 7.26 (t, J = 8.8 Hz,
2H, phenyl), 7.99 (m, 2H, phenyl), 8.16 (s, 1H, N=CH), 10.04 (s, 1H, NH), 11.81 (s, 1H, NH). 13C-NMR
(100 MHz, DMSO-d6): 101.26 (O-C-O), 107.35 (benzodioxole C4), 108.03 (benzodioxole C7), 115.64
(d, J = 21.3 Hz, phenyl C3 and C5), 119.45 (benzodioxole C6), 129.81 (d, J = 8.4 Hz, phenyl C2 and C6),
130.68 (d, J = 3.0 Hz, benzodioxole C5), 133.09 (phenyl C1), 141.57 (benzodioxole C7a), 144.89 (N=C),
146.59 (benzodioxole C3a), 164.36 (phenyl C4), 176.41 (C=S). MS (ESI) (m/z): [M + H]+ 318. Anal. Calcd.
for C15H12FN3O2S: C, 56.77; H, 3.81; N, 13.24. Found: C, 56.76; H, 3.42; N, 5.98.
4-(1,3-Benzodioxole-5-yl)-1-(4-chlorobenzylidene)thiosemicarbazide (7 ν
). Yield: 80%. Mp 201.4 ◦C. IR
max
(cm−1): 3344.57 (N-H stretching), 3138.18 (aromatic C-H stretching), 2981.95 (aliphatic C-H stretching),
2895.15 (O-CH2 stretching), 1595.13, 1539.20, 1508.33, 1485.19 (C=N, C=C stretching and N-H bending),
1446.61, 1402.25, 1352.10 (C-H bending), 1278.81, 1253.73, 1228.66, 1186.22, 1083.99, 1035.77, 1010.70
(C-N stretching, C=S stretching and aromatic C-H in plane bending), 933.55, 893.04, 846.75, 812.03,
1
752.24, 659.66, 605.65 (aromatic C-H out of plane bending and C-S stretching). H-NMR (400 MHz,
DMSO-d6): 6.05 (s, 2H, O-CH2-O), 6.90–6.96 (m, 2H, benzodioxole), 7.16 (s, 1H, benzodioxole), 7.48
(d, J = 8.4 Hz, 2H, phenyl), 7.95 (d, J = 8.8 Hz, 2H, phenyl), 8.14 (s, 1H, N=CH), 10.07 (s, 1H, NH),
11.86 (s, 1H, NH). 13C-NMR (100 MHz, DMSO-d6): 101.26 (O-C-O), 107.35 (benzodioxole C4), 108.04
(benzodioxole C7), 119.48 (benzodioxole C6), 128.65 (phenyl C3 and C5), 129.21 (phenyl C2 and C6),
133.02 (benzodioxole C5), 133.05 (phenyl C1), 134.43 (phenyl C4), 141.34 (benzodioxole C7a), 144.91
(N=C), 146.59 (benzodioxole C3a), 176.48 (C=S). MS (ESI) (m/z): [M + H]+ 334. Anal. Calcd. for
C15H12ClN3O2S: C, 53.98; H, 3.62; N, 12.59: C, 53.82; H, 3.50; N, 10.75.
4-(1,3-Benzodioxole-5-yl)-1-(4-bromobenzylidene)thiosemicarbazide (8 ν
). Yield: 82%. Mp 196.3 ◦C. IR
max
(cm−1): 3340.71 (N-H stretching), 3138.18 (aromatic C-H stretching), 2981.95 (aliphatic C-H stretching),
2895.15 (O-CH2 stretching), 1589.34, 1537.27, 1485.19 (C=N, C=C stretching and N-H bending), 1446.61,
1398.39, 1354.03 (C-H bending), 1280.73, 1253.73, 1236.37, 1186.22, 1126.43, 1066.64, 1035.77, 1004.91
(C-N stretching, C=S stretching and aromatic C-H in plane bending), 933.55, 893.04, 864.11, 844.82,
812.03, 752.24, 659.66, 601.79 (aromatic C-H out of plane bending and C-S stretching). 1H-NMR
(400 MHz, DMSO-d6): 6.05 (s, 2H, O-CH2-O), 6.91 (s, 2H, benzodioxole), 7.13 (s, 1H, benzodioxole),
7.61 (d, J = 8.8 Hz, 2H, phenyl), 7.87 (d, J = 8.8 Hz, 2H, phenyl), 8.11 (s, 1H, N=CH), 10.06 (s, 1H,
NH), 11.84 (s, 1H, NH). 13C-NMR (100 MHz, DMSO-d6): 101.24 (O-C-O), 107.34 (benzodioxole C4),
108.04 (benzodioxole C7), 119.50 (benzodioxole C6), 123.22 (phenyl C4), 129.46 (phenyl C3 and C5),
131.55 (phenyl C2 and C6), 133.03 (benzodioxole C5), 133.37 (phenyl C1), 141.40 (benzodioxole C7a),
144.89 (N=C), 146.56 (benzodioxole C3a), 176.47 (C=S). MS (ESI) (m/z): [M + H]+ 379. Anal. Calcd. for
C15H12BrN3O2S: C, 47.63; H, 3.20; N, 11.11. Found: C, 47.06; H, 3.37; N, 11.29.
◦
4-(1,3-Benzodioxole-5-yl)-1-(3,4-dichlorobenzylidene)thiosemicarbazide (
9
). Yield: 83%. Mp 213.2 C. IR
ν
max
(cm−1): 3228.84 (N-H stretching), 3128.54 (aromatic C-H stretching), 2981.95 (aliphatic C-H stretching),
2889.37 (O-CH2 stretching), 1510.26, 1489.05, 1463.97 (C=N, C=C stretching and N-H bending), 1438.90,
1398.39 (C-H bending), 1249.87, 1222.87, 1186.22, 1128.36, 1076.28, 1037.70 (C-N stretching, C=S
stretching and aromatic C-H in plane bending), 937.40, 866.04, 815.89, 721.38, 661.58, 601.79 (aromatic
1
C-H out of plane bending and C-S stretching). H-NMR (400 MHz, DMSO-d6): 6.06 (s, 2H, O-CH2-O),
6.90–6.95 (m, 2H, benzodioxole), 7.13 (d, J = 1.6 Hz, 1H, benzodioxole), 7.66 (d, J = 8.8 Hz, 1H, phenyl),
7.80 (dd, J = 8.4 Hz and J = 2 Hz, 1H, phenyl), 8.11 (s, 1H, N=CH), 8.34 (d, J = 2 Hz, 1H, phenyl), 10.16
(s, 1H, NH), 11.93 (s, 1H, NH). 13C-NMR (100 MHz, DMSO-d6): 101.28 (O-C-O), 107.37 (benzodioxole
C4), 108.34 (benzodioxole C7), 119.85 (benzodioxole C6), 128.03 (phenyl C5), 128.32 (phenyl C3), 130.69
(phenyl C6), 131.80 (phenyl C2), 132.03 (benzodioxole C5), 132.99 (phenyl C1), 134.91 (phenyl C4),
139.95 (benzodioxole C7a), 145.05 (N=C), 146.62 (benzodioxole C3a), 176.73 (C=S). MS (ESI) (m/z):