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Organic & Biomolecular Chemistry
1H, ArH), 8.23 (d, J = 7.5 Hz, 2H, ArH), 9.02 (s, 1H, NH), 11.56 110.18 (ArCH), 120.27 (ArCH), 121.26 (ArCH), 124.25 (ArCH),
(s, 1H, NH); 13C NMR (75.6 MHz, CDCl3) δ 55.45 (OCH3), 99.36 124.80 (ArCH), 126.06 (ArCH), 127.69 (ArC), 128.32 (2 × ArCH),
(ArCH), 103.73 (2 × ArCH), 125.20 (ArCH), 125.68 (ArCH), 128.97 (ArCH), 129.23 (2 × ArCH), 137.17 (ArCH), 137.46 (ArC),
126.49 (ArC), 128.59 (2 × ArCH), 130.98 (2 × ArCH), 131.89 142.30 (ArC), 148.65 (ArCH), 149.78 (C–OCH3), 151.93 (CvN),
(ArCH), 136.75 (ArC), 139.68 (ArC), 143.08 (ArCH), 145.45 174.57 (CvS). HRMS (+ESI): found m/z 363.1267, [M + H]+
(ArCH), 147.46 (CvN), 160.18 (2 × C–OCH3), 175.63 (CvS). C20H19N4OS required 363.1280.
HRMS (+ESI): Found m/z 393.1375, [M + H]+ C21H21N4O2S
required 393.1385.
2′-Benzoylpyridine 4-(p-methylphenyl)-3-thiosemicarbazone
(8i). Pink powder (243 mg, 55%); mp 124–127 °C; found: C,
2′-Benzoylpyridine
4-(p-methoxyphenyl)-3-thiosemicarba- 66.1; H, 5.1; N, 15.5. Calc. for C20H18N4S0.25CH2Cl2: C, 66.1;
zone (8f). Dark green needles (298 mg, 66%); mp 180–185 °C; H, 5.1; N, 15.2%; λmax(MeOH)/nm 250 (ε/M−1 cm−1 16 110) and
found: C, 61.5; H, 5.0; N, 14.3. Calc. for C20H18N4OS·1.5H2O: 333 (17 553). IR (KBr) νmax/cm−1: 3287, 3054, 1595, 1546, 1534,
C, 61.7; H, 5.4; N, 14.4%; λmax(MeOH)/nm 331 (ε/M−1 cm−1 1467, 1442, 1418, 1319, 1303, 1271, 1250, 1202, 1171, 1106,
20 787); IR (KBr) νmax/cm−1: 3317, 3038, 2831, 2524, 1612, 1075, 935, 922, 814, 796, 770, 702, 681, 666, 642, 612, 505, 471;
1599, 1561, 1533, 1509, 1453, 1414, 1354, 1319, 1297, 1252, 1H NMR (300 MHz, CDCl3) δ 2.35 (s, 3H, CH3), 7.18 (d, J =
1232, 1204, 1164, 1105, 1028, 979, 920, 836, 812, 772, 729, 711, 8.7 Hz, 2H, ArH), 7.33 (d, J = 8.0 Hz, 1H, ArH), 7.41 (d, J =
1
672, 622, 522, 509, 461; H NMR (300 MHz, CDCl3) δ 3.79 (s, 7.8 Hz, 1H, ArH), 7.45–7.48 (m, 3H, ArH), 7.51 (d, J = 8.1 Hz,
3H, OCH3), 6.91 (d, J = 8.9 Hz, 2H, ArH), 7.32–7.56 (m, 5H, 1H, ArH), 7.53–7.57 (m, 3H, ArH), 7.79 (d, J = 7.5 Hz, 1H, ArH),
ArH), 7.66 (m, 3H, ArH), 7.77 (d, J = 8.1 Hz, 1H, ArH), 8.18 (d, 8.86 (d, J = 5.4 Hz, 1H, ArH), 9.44 (s, 1H, NH), 14.01 (s, 1H,
J = 8.0, 2H, ArH), 8.98 (s, 1H, NH), 11.53 (s, 1H, NH); 13C NMR NH); 13C NMR (75.6 MHz, CDCl3) δ 21.00 (CH3), 124.26
(75.6 MHz, CDCl3) δ 55.33 (OCH3), 113.59 (ArCH), 124.28 (ArCH), 124.43 (2 × ArCH), 126.26 (ArCH), 128.50 (2 × ArCH),
(ArCH), 125.20 (ArCH), 126.38 (ArCH), 126.72 (ArC), 127.32 129.11 (2 × ArCH), 129.23 (2 × ArCH), 130.56 (ArCH), 135.36
(2 × ArCH), 128.57 (2 × ArCH), 129.10 (ArCH), 130.86 (ArCH), (ArC), 135.75 (ArC), 137.17 (ArCH), 137.44 (C–CH3), 142.58
131.07 (ArC), 131.75 (ArCH), 137.19 (ArCH), 137.40 (ArC), (ArC), 148.57 (ArCH), 152.29 (CvN), 176.71 (CvS). HRMS
148.55 (ArCH), 152.27 (CvN), 157.81 (C–OCH3), 176.29 (CvS). (+ESI): found m/z 347.1319, [M + H]+ C20H19N4S required
HRMS (+ESI): found m/z 363.1264, [M + H]+ C20H19N4OS 347.1330.
required 363.1280.
2′-Benzoylpyridine 4-(m-methylphenyl)-3-thiosemicarbazone
2′-Benzoylpyridine
4-(m-methoxyphenyl)-3-thiosemicarba- (8j). White powder (163 mg, 36%); mp 190–193 °C; found: C,
zone (8g). Green powder (89 mg, 19%); mp 187–190 °C; found: 61.5; H, 4.9; N, 14.3. Calc. for C20H18N4S·0.65CH2Cl2: C, 61.8;
C, 55.3; H, 4.5; N, 12.5. Calc. for C20H18N4OS·1.1CH2Cl2: C, H, 4.8; N, 14.0%; λmax(MeOH)/nm 331 (ε/M−1 cm−1 19 295). IR
55.6; H, 4.5; N, 12.3%; λmax(MeOH)/nm 257 (ε/M−1 cm−1 (KBr) νmax/cm−1: 3482, 3443, 3321, 3184, 1612, 1549, 1522,
1
21 307) and 334 (21 999); IR (KBr) νmax/cm−1: 3319, 3177, 3035, 1495, 1481, 1448, 1340, 1316, 1225, 1211, 1164, 773; H NMR
2999, 2499, 1610, 1543, 1497, 1475, 1449, 1418, 1353, 1316, (300 MHz, CDCl3) δ 2.35 (s, 3H, CH3), 7.03 (d, J = 7.5 Hz, 1H,
1303, 1259, 1211, 1153, 1092, 1082, 1039, 989, 952, 867, 845, ArH), 7.23 (s, 1H, ArH), 7.34–7.40 (m, 3H, ArH), 7.57 (dd, J =
1
775, 734, 703, 687, 578, 509; H NMR (300 MHz, CDCl3) δ 3.83 7.2 Hz, 1H, ArH), 7.69–7.74 (m, 3H, ArH), 7.78 (d, J = 4.5 Hz,
(s, 3H, OCH3), 6.79 (s, 1H, ArH), 7.25 (d, J = 3.9 Hz, 2H, ArH), 2H, ArH), 8.19 (d, J = 7.5 Hz, 1H, ArH), 9.00 (d, J = 6 Hz, 1H,
7.37–7.40 (m, 3H, ArH), 7.47–7.53 (m, 2H, ArH), 7.69–7.70 (m, ArH), 9.48 (s, 1H, NH), 11.66 (s, 1H, NH); 13C NMR (75.6 MHz,
3H, ArH), 7.81 (d, J = 6.5 Hz, 1H, ArH), 8.23 (d, J = 8.1 Hz, 1H, CDCl3) δ 21.39 (CH3), 123.27 (ArCH), 125.30 (ArCH), 125.60
ArH), 8.99 (s, 1H, NH), 11.67 (s, 1H, NH); 13C NMR (75.6 MHz, (ArCH), 126.46 (ArC), 126.67 (ArCH), 127.29 (ArCH), 128.07 (2
CDCl3) δ 55.34 (OCH3), 111.11 (ArCH), 112.80 (ArCH), 118.06 × ArCH), 128.58 (ArCH), 130.95 (ArCH), 131.85 (2 × ArCH),
(ArCH), 125.18 (ArCH), 125.63 (ArCH), 126.47 (ArC), 128.58 (2 136.71 (ArC), 138.00 (ArC), 138.06 (C–CH3), 143.06 (ArCH),
× ArCH), 128.87 (ArCH), 130.98 (ArCH), 131.89 (2 × ArCH), 145.55 (ArCH), 147.35 (CvN), 176.26 (CvS). HRMS (+ESI):
136.65 (ArC), 139.16 (ArC), 143.09 (ArCH), 145.47 (ArCH), found m/z 347.1316, [M + H]+ C20H19N4S required 347.1330.
147.48 (CvN), 159.39 (C–OCH3), 175.93 (CvS). HRMS (+ESI):
found m/z 363.1266, [M + H]+ C20H19N4OS required 363.1280.
2′-Benzoylpyridine 4-phenyl-3-thiosemicarbazone (Bp4pT).
Orange solid (292 mg, 59%); mp 130–132 °C; found: C, 68.0;
2′-Benzoylpyridine
4-(o-methoxyphenyl)-3-thiosemicarba- H, 4.8; N, 17.1. Calc for C19H16N4S·0.15H2O: C, 68.1; H, 4.9; N,
zone (8h). Green powder (113 mg, 23%); mp 121–125 °C; 16.7%; λmax(MeOH)/nm 248 (ε/M−1 cm−1 13 647) and 333
found: C, 65.7; H, 5.0; N, 15.5. Calc. for C20H18N4OS·0.1H2O: (17 093); IR (KBr) νmax/cm−1: 3299, 3050, 1594, 1533, 1498,
C, 65.9; H, 5.0; N, 15.4%; λmax(MeOH)/nm 251 (ε/M−1 cm−1 1469, 1439, 1417, 1367, 1318, 1303, 1271, 1253, 1204, 1173,
26 078) and 340 (29 385); IR (KBr) νmax/cm−1: 32417, 3048, 1107, 1074, 1047, 1029, 922, 798, 787, 756, 729, 704, 693, 673,
1
3007, 2968, 1600, 1583, 1545, 1466, 1443, 1419, 1333, 1299, 656, 644, 614, 606, 511, 498, 475; H NMR (300 MHz, CDCl3) δ
1249, 1227, 1179, 1150, 1113, 1074, 1044, 1029, 998, 936, 921, 7.33–7.43 (m, 5H, ArH), 7.46–7.58 (m, 5H, ArH), 7.69 (m, 2H,
1
798, 743, 699, 644, 507; H NMR (300 MHz, CDCl3) δ 3.83 (s, ArH), 7.78 (m, 2H, ArH), 9.54 (s, 1H, NH), 14.06 (s, 1H, NH);
3H, OCH3), 6.84–6.95 (m, 3H, ArH), 7.02–7.26 (m, 2H, ArH), 13C NMR (75.6 MHz, CDCl3) δ 124.11 (ArCH), 124.31 (ArCH),
7.34–7.41 (m, 2H, ArH), 7.54–7.57 (m, 3H, ArH), 7.76 (d, J = 124.59 (ArCH), 125.81 (ArCH), 126.32 (ArCH), 128.52 (ArCH),
7.7 Hz, 1H, ArH), 8.79–8.83 (m, 2H, ArH), 10.29 (s, 1H, NH), 128.63 (ArCH), 128.67 (ArCH), 129.12 (ArCH), 129.29 (ArCH),
13.58 (s, 1H, NH); 13C NMR (75.6 MHz, CDCl3) δ 55.77 (OCH3), 129.82 (ArCH), 130.42 (ArCH), 137.21 (ArCH), 137.40 (ArC),
6422 | Org. Biomol. Chem., 2013, 11, 6414–6425
This journal is © The Royal Society of Chemistry 2013