Synthetic procedure for the Target compounds
2.1.1 Synthetic procedure for the compounds2a-d and 7a-c
Derivatives (1a-d) or derivatives of 6a-c (1.0 mmole) were dissolved in methanol. An equi molar amount of Thiobarbituric acid was added to it and the mixture was exposed to natural sunlight for 3-4 h.Product formation was confirmed by TLC, the mixture was cooled and the solid obtained was filtered and washed well with cold methanol.Recrystalization with methanol yielded pure compounds. The characterization data of compounds 2 a-d, 7a-c is given below.
2.1.1.1 5-[1-(2-Oxo-2-phenyl-ethyl)-2-phenyl-1H-indol-3-ylmethylene]-2-thioxo-dihydro-pyrimidine-4,6-dione (2a)
Yield 70%, m.p 279-280 oC.FTIR (KBr, υmax, cm-1) 3362,2876,1690, 1649, 1508, 1459, 1270, 1137, 937, 765; 1H-NMR (300 MHz, DMSO-d6) δ 5.96 (s, 2H), 7.19-8.20 (m,14H), 7.98 (s,1H), 12.3 (s, 2H, NH);13C-NMR (75 MHz, DMSO-d6) δ 51.6, 111.4, 113.7, 120.5, 127.3, 125.6, 125.6, 127.2, 128.5, 128.9, 129.9, 130.4, 130.7, 134.5, 134.7, 138.3, 147.5, 150.2, 151.8, 161.5, 162.5, 176.2, 193.4;MS ESI: 466 (m+1) (100%) For the M.F C27H19N3O3S, M.Wt 465;Anal.Calcd for C27H19N3O3S,(465): C, 69.66; H, 4.11; N, 9.03; O, 10.31; S 6.89. Found: C, 68.88; H, 4.23; N, 9.08; O,10.37; S 6.70.
2.1.1.2. 5-{1[2-(4-Chloro-phenyl)2-oxo-ethyl]-2-phenyl-1H-indol-3-ylmethylene}-2-thioxo-dihydro-pyrimidine-4,6-dione (2b)
Yield 75.4%, m.p 250-255 oC.FTIR (KBr, υmax, cm-1)3389,2870, 1679, 1647, 1500, 1460, 1270, 1137, 937, 765;1H-NMR (300 MHz, DMSO-d6)δ 5.99(s, 2H), 7.2-8.0 (m,13H), 7.98 (s, 1H), 12.17(s, 2H, NH); 13C-NMR (75 MHz, DMSO-d6)δ 51.5, 111.2, 112.7, 113.1, 121.6, 123.7, 124.5, 125.9, 128.9, 127.7, 129.4, 130.1, 133.2, 132.7, 138.3, 139.4, 148.1, 150.4, 152.7, 162.4, 164.5, 175.4 192.6;MS ESI: 500(m+1) (30%) For the M.F C27H18ClN3O3S, M.Wt 499;Anal.Calcd forC27H18ClN3O3S (499): C, 64.86; H, 3.63; Cl, 7.09; N, 8.40; O, 9.60; S, 6.41.Found: C, 64.79; H, 3.67; Cl, 7.12; N, 8.47; O, 9.71; S, 6.48.
2.1.1.3. 5-{1[2-(4-Bromo-phenyl)2-oxo-ethyl]-2-phenyl-1H-indol-3-ylmethylene}-2-thioxo-dihydro-pyrimidine-4,6-dione (2c)
Yield 77.2%, m.p250-255 oC.FTIR (KBr, υmax, cm-1) 3370,2920, 1689, 1560, 1440, 1250, 1079, 940,760;1H-NMR (300 MHz, DMSO-d6)δ 5.96 (s, 2H), 7.27-7.81 (m, 13H), 7.98 (s, 1H), 12.3 (s, 1H, NH),12.10 (s, 1H, NH);13C-NMR (75 MHz, DMSO-d6)δ 51.9, 111.7, 112.9, 113.6, 121.6, 123.4, 124.9, 125.1, 127.6, 128.6, 128.8, 129.1, 130.3, 130.9, 133.0, 137.3, 146.2, 150.5, 150.7, 161.5, 163.4,175.6, 192.9;MS ESI: 545 (m+2) (98%) For the M.F C27H18BrN3O3S, M.Wt 543;Anal.Calcd forC27H18BrN3O3S C, 59.57; H, 3.33; Br, 14.68; N, 7.72; O, 8.82; S, 5.89.Found:C, 59.60; H, 3.37; Br, 14.70; N, 7.75; O, 8.86; S, 5.91.
2.1.1.4. 5-{1[2-(4-Methoxy-phenyl)2-oxo-ethyl]-2-phenyl-1H-indol-3-ylmethylene}-2-thioxo-dihydro-pyrimidine-4,6-dione (2d)
Yield 65.7%, m.p267-269 oC.FTIR (KBr, υmax, cm-1) 3398,2878,1694, 1650, 1600, 1509, 1463, 1283, 1131, 933, 761; 1H-NMR (300 MHz, DMSO-d6) δ 3.86 (s, 3H), 5.91 (s, 2H), 7.10-8.03 (m, 13H), 7.99 (s, 1H), 12.15 (s, 1H, NH), 12.16 (s, 1H, NH);13C-NMR (75 MHz, DMSO-d6)δ 51.4, 55.6, 111.4, 114.11, 114.17, 122.0, 123.7, 125.0, 125.2, 126.8, 128.2, 128.7, 130.4, 130.6, 130.8, 138.5, 148.1, 153.6, 159.3, 162.3, 164.0, 177.9, 191.3; MS ESI: 496 (m+1) (75%) and 518 (m+23) (100%). For the M.F C28H21N3O4S, M.Wt 495;Anal.Calcd forC28H21N3O4S C, 67.86; H, 4.27; N, 8.48; O, 12.91; S, 6.47. Found C, 67.89; H, 4.30; N, 8.53; O, 12.97; S, 6.50.
2.1.1.5 5-(1-Ethyl-2-phenyl-1H-indol-3-ylmethylene)-2-thioxo-dihydro-pyrimidine-4,6-dione (7a)
Yield 72.3%, m.p216-218oC.FTIR (KBr, υmax, cm-1) 3387,2876,1690, 1650, 1506, 1460, 1284, 1133, 935;1H-NMR (300 MHz, DMSO-d6) δ 1.29 (t, J = 5.1 Hz, 3H ), 4.28 (q,J = 5.1 Hz,2H), 7.25-7.8 (m, J = 6.3 Hz,9H), 7.93 (s, 1H), 12.15 (s, 1H, NH), 12.07 (s, 1H, NH); 13C-NMR (75 MHz, DMSO-d6)δ 37.1, 48.6, 110.4, 111.5, 112.6, 121.3, 122.7, 124.6, 125.1, 127.9, 130.2, 131.3, 137.2, 147.5, 150.5, 151.7, 162.2, 163.3,176.3; MS ESI: 376 (m+1) (23%).For the M.F C21H17N3O2S M.Wt 375;Anal.Calcd for C21H17N3O2S C, 67.18; H, 4.56; N, 11.19; O, 8.52; S, 8.54. Found C, 67.20; H, 4.50; N, 11.21; O, 8.57; S, 8.61.
2.1.1.6 5-(1-Allyl-2-phenyl-1H-indol-3-ylmethylene)-2-thioxo-dihydro-pyrimidine-4,6-dione (7b)
Yield 71.7%, m.p218-220oC,FTIR (KBr, υmax, cm-1) 3375,2875,1694, 1655, 1508, 1457, 1279, 1129, 930;1H-NMR (300 MHz, DMSO-d6)δ 4.9 (d,J = 10.2 Hz, 2H), 4.90 (d,J = 7.8,1H), 5.21 (d,J = 7.8 Hz, 1H ), 6.02 (m, J = 4.0 Hz, 1H) 7.27-7.81 (m,9H), 7.98 (s, 1H), 12.50 (s, 2H, NH); 13C-NMR (75 MHz, DMSO-d6)δ 46.3, 48.9, 110.7, 111.3, 112.8, 115.2, 120.9, 122.7, 123.5, 125.1, 126.7, 129.2, 130.6, 133.1, 136.4, 147.5, 150.6, 151.5, 161.3, 164.4,175.9;MS ESI: 388 (m+1) (30%). For the M.F C22H17N3O2S M.Wt 387; Anal. Calcd for C22H17N3O2S C, 68.20; H, 4.42; N, 10.85; O, 8.26; S, 8.28. Found C, 68.18; H, 4.52; N, 10.92; O, 8.30; S, 8.37.
2.1.1.7 5-(1-Butyl-2-phenyl-1H-indol-3-ylmethylene)-2-thioxo-dihydro-pyrimidine-4,6-dione (7c)
Yield 69.5%, m.p219-220oC.FTIR (KBr, υmax, cm-1) 3350,2869,1690, 1645, 1510, 1445, 1270, 1120, 929; 1H-NMR (300 MHz, DMSO-d6)δ 0.69 (t,J = 5.7, 3H), 1.20 (m,J = 5.7, 2H), 1.59 (m,J = 5.7 2H), 4.30 (t,J = 5.4, 2H), 7.22-7.70 (m,9H), 7.99 (s, 1H)12.20 (s,2H,NH); 13C-NMR (75 MHz, DMSO-d6) δ 13.5, 19.4, 32.5, 45.6, 110.7, 111.9, 112.7, 121.5, 122.7, 123.9, 125.4, 127.9, 130.2, 131.3, 135.3, 145.6, 1514, 161.1, 164.3,175.9;MS ESI: 403 (m+) (100%) For the For the M.F C23H21N3O2S M Wt 403; Anal. Calcd for C23H21N3O2S C, 68.46; H, 5.25; N, 10.41; O, 7.93; S, 7.95.Found C, 68.50; H, 5.30; N, 10.39; O, 7.87; S, 7.82.
2.1.2 Synthesis of pyrimidine 2,4,6 dione derivatives 3a-d and 8a-c
Derivatives of (1a-d) or derivatives of (6a-c) (1.0 mmole) were dissolved in methanol. An equi molar amount of Barbituric acid was added to it and the mixture was exposed to natural sunlight for 3-4 h.Product formation was confirmed by TLC, the mixture was cooled and the solid obtained was filtered and washed well with cold methanol.Recrystalization with methanol yielded pure compounds. The characterization data of compounds 3a-d, 8a-c is given below.
2.1.2.1 5-[1-(2-Oxo-2-phenyl-ethyl)-2-phenyl-1H-indol-3-ylmethylene]-pyrimidine-2,4,6-trione(3a)Yield 74.6%, m.p265-270 oC.FTIR (KBr, υmax, cm-1)3380, 3184,3054, 2936, 1732, 1696, 1665, 1539, 1442,1299, 1202, 933, 749; 1H-NMR (300 MHz, DMSO-d6) δ 5.96 (s, 2H), 7.19-8.20 (m,9H),7.38 (d,J = 5.2 Hz, 1H), 7.54 (d,J = 8 Hz, 1H), 7.61 (d,J = 8 Hz, 1H), 7.63 (d,J = 5.2 Hz,1H), 7.98 (s, 1H), 8.05 (d,J = 7.2 Hz, 1H), 11.02(s, 1H, NH), 11.08(s, 1H, NH);13C-NMR (75 MHz, DMSO-d6) δ 51.5, 111.2, 111.9, 113.1, 121.5, 123.3, 124.6, 125.0, 128.2, 128.5, 128.7, 128.9, 130.2, 130.7, 134, 134.2, 138.3, 147.1, 150, 151.8, 161.4, 164, 193.4; MS HRMS: Calculated m/z 449.14 found 449.056.(50%) For the M.F C27H19N3O4, M.Wt 449.07;Anal. Calcd for C27H19N3O4 C, 72.15; H, 4.26; N, 9.35; O, 14.24.Found C, 72.30; H, 4.30; N, 9.40; O, 14.30.
2.1.2.2 5-{1-[2-(4-Chloro-phenyl)-2-oxo-ethyl]-2-phenyl-1H-indol-3-ylmethylene}-pyrimidine-2,4,6-trione (3b) Yield 77.2%, m.p250-255 oC. IR (KBr, υmax, cm-1) 3404, 3188,3050, 2916, 1735, 1713, 1694, 1656, 1532, 1442, 1227, 1198, 930,747; 1H-NMR (300 MHz, DMSO-d6)δ 5.97(s, 2H), 7.2-8.0 (m, 9H), 7.37 (d, J = 6 Hz, 1H),7.58 (d, J = 6 Hz, 1H), 7.68 (d, J = 8.4 Hz, 1H), 7.98 (s, 1H), 8.08 (d,J = 8.8 Hz, 1H), 11.05(s, 1H, NH),11.11(s, 1H, NH); 13C-NMR (75 MHz, DMSO-d6)δ 51.6, 111.2, 112.0, 113.1, 121.5, 123.3, 124.6, 125.0, 128.5, 128.7, 129.0, 130.1, 130.2, 132.6, 138.2, 139.2, 147.1, 150.4, 151.7, 161.4, 164.0, 192.6;MS ESI: 484 (m+1) (20%). For the M.F C27H18ClN3O4, M.Wt 483;Anal. Calcd forC27H18ClN3O4 C, 67.02; H, 3.75; Cl, 7.33; N, 8.68; O, 13.23. Found C, 67.20; H, 3.69; Cl, 7.37; N, 8.72; O, 13.27.
2.1.2.3 5-{1-[2-(4-Bromo-phenyl)-2-oxo-ethyl]-2-phenyl-1H-indol-3-ylmethylene}-pyrimidine-2,4,6-trione (3c)Yield 65.3%, m.p235-240 oC.FTIR (KBr, υmax, cm-1) 3436, 3220,2923, 1686, 1577, 1424, 1228, 1098, 931,750; 1H-NMR (300 MHz, DMSO-d6)δ 5.96 (s, 2H), 7.27-7.97. (m, 9H), 7.28 (d,J = 5.2 Hz, 1H),7.36 (d, J = 6.0 Hz, 1H ),7.56 (d, J = 5.2 Hz, 1H), 7.81 (d, J = 8.8 Hz, 1H),7.98 (s, 1H), 11.03 (s, 1H, NH),11.10 (s, 1H, NH);13C-NMR (75 MHz, DMSO-d6)δ 51.6, 111.3, 112.1, 113.2, 121.6, 123.4, 124.7, 125.1, 128.5, 128.6, 128.8, 129.1, 130.3, 130.8, 132.0, 138.3, 147.2, 150.5, 151.8, 161.5, 164.1, 192.8; MS ESI: 528 (m+1) (100%). For the M.F C27H18BrN3O4, M.Wt 527;Anal. Calcd for C27H18BrN3O4 C, 61.38; H 3.43; Br, 15.12; N, 7.95; O, 12.11. Found C, 61.45; H 3.50; Br, 15.20; N, 7.89; O, 12.19.
2.1.2.4 5-{1-[2-(4-Methoxy-phenyl)-2-oxo-ethyl]-2-phenyl-1H-indol-3-ylmethylene}-pyrimidine-2,4,6-trione (3d) Yield 60.5%, m.p265-270 oC.FTIR (KBr, υmax,cm-1) 3411, 3179, 3030, 2932, 1729, 1693, 1650,1513, 1440, 1220, 1081, 938, 760;1H-NMR (300 MHz, DMSO-d6)δ 3.8 (s, 3H) 5.8(s, 2H), 7.0-8.0 (m, 10H), 7.56 (d, J = 6.0 Hz, 1H), 7.10 (d,J = 8.8 Hz, 1H),7.97 (s, 1H), 8.04 (d, 8.8Hz, 1H), 11.02(s, 1H, NH), 11.08(s, 1H, NH); 13C-NMR (75 MHz, DMSO-d6)δ 51.2, 55.6, 111.2, 111.8, 113.1, 114.1, 121.5, 123.3, 124.6, 125.0, 126.8, 128.5, 128.7, 130.2, 130.6, 130.7, 138.3, 147.2, 150.4, 152.0, 161.4, 163.9, 164.0, 191.5; MS ESI: 480(m+1) (50%). For the M.F C28H21N3O5, M.Wt 479;Anal. Calcd forC28H21N3O5 C, 70.14; H, 4.14; N, 8.76; O,16.68. Found C, 70.24; H, 4.21; N, 8.81; O, 16.72.
2.1.2.5 5-(1-Ethyl-2-phenyl-1H-indol-3-ylmethylene)-pyrimidine-2,4,6-trione (8a)Yield 71.4%, m.p 245-250 oC.FTIR (KBr, υmax, cm-1)3488,3174, 3040, 172, 1655, 1536, 1484, 1231, 936, 758; 1H-NMR (300 MHz, DMSO-d6) δ 1.28 (t,J = 5.1,3H ), 4.28 (q,J = 5.1, 2H), 7.26-7.7 (m,9H), 7.93 (s, 1H), 10.95 (s, 1H, NH), 11.02(s, 1H, NH);13C-NMR (75 MHz, DMSO-d6)δ 36.5, 47.9, 110.9, 111.3, 112.7,121.5, 123.3, 124.8, 125.2, 128.7, 130.1, 131.0, 137.3, 147.3, 150.4, 151.9, 162.4, 163.1. MS ESI: 360 (m+1) (30%). For the M.F C21H17N3O3, M.Wt 359;Anal. Calcd for C21H17N3O3 C, 70.18; H, 4.77; N, 11.69, O, 13.36. Found C, 70.21; H, 4.80; N, 11.72, O, 13.40.
2.1.2.6 5-(1-Allyl-2-phenyl-1H-indol-3-ylmethylene)-pyrimidine-2,4,6-trione(8b)Yield 75.7%, m.p220-225 oC.FTIR (KBr, υmax, cm-1) 3449, 3186,3050, 2831, 1729, 1686, 1655, 1530, 1440, 1225,943, 746; 1H-NMR (300 MHz, DMSO-d6)δ 4.86 (d,J = 12.1Hz 2H), 4.95-4.90(d,J = 7.7Hz 1H) 5.19 (d, J= 7.8Hz 1H ), 6.02 (m,J = 4.0 Hz, 1H) 7.25-7.65 (m, 9H), 7.96 (s, 1H), 10.98 (s, 1H, NH), 11.05 (s, 1H, NH);13C-NMR (75 MHz, DMSO-d6)δ 46.9, 48.5, 111.5, 111.6, 112.9, 117.2, 121.6, 123.3, 124.7, 125.2, 128.7, 130.2, 130.9, 133.0, 137.4, 147.3, 150.4, 151.4, 161.2, 164.6; MS HRMS Caliculated 371.39 found 371.23. For the M. F C22H17N3O3, M. Wt 371.39; Anal. Calcd forC22H17N3O3C, 71.15; H, 4.61; N, 11.31; O, 12.92. Found C, 71.25; H, 4.73; N, 11.45; O, 12.89.
2.1.2.7 5-(1-Butyl-2-phenyl-1H-indol-3-ylmethylene)-pyrimidine-2,4,6-trione(8c) Yield 73.7%, m.p220-230oC.FTIR (KBr, υmax, cm-1) 3203, 3080,2931,1727, 1688, 1550, 1443, 1295, 970, 749; 1H-NMR (300 MHz, DMSO-d6 )δ 0.69 (t,J= 5.4Hz, 3H ), 1.07(m,J= 5.4 Hz, 2H), 1.58 (m,J= 5.4 Hz, 2H), 4.27(t, J= 5.1 Hz,2H), 7.2-7.7(m, 9H),7.9(s, 1H),10.96(s, 1H, NH), 11.03(s, 1H, NH);13C-NMR (75 MHz, DMSO-d6) δ 13.1, 19.1, 31.0, 43.9, 110.9, 111.3, 112.9, 121.5, 123.3, 124.9, 125.2, 128.7, 130.1, 131.0, 137.3, 147.3, 150.4, 151.9, 161.4, 164.1;MS HRMS Caliculated 387.16 found 387.084. For the M.FC23H21N3O3, M. Wt 387.16;Anal. Calcd for C23H21N3O3 C, 71.30; H, 5.46; N, 10.85; O, 12.39. Found C, 71.25; H, 5.52; N, 10.79; O, 12.45.
2.1.3 Synthetic procedure for the compounds4a-d and 9a-c
Derivatives of (1a-d) or (6a-c) (1.0 mmole) were dissolved in methanol. An equi molar amount of Thiosemicarbazide was added to it and the mixture was exposed to natural sunlight for 3-4 h.Product formation was confirmed by TLC, the mixture was cooled and the solid obtained was filtered and washed well with cold methanol. Recrystalization with methanol yielded pure compounds. The characterization data of compounds 4 a-d,9a-c is given below.
2.1.3.1 2-((1-(2-oxo-2-phenylethyl)-2-phenyl-1H-indol-3-yl)methylene)
hydrazinecarbothioamide(4a)
Yield 59.6%, m.p186-188oC.FTIR (KBr, υmax, cm-1) 3370, 3264, 2929, 1688, 1568, 1461,1380, 1219, 1091, 810, 745;1H-NMR (300 MHz, DMSO-d6)5.72 (s, 2H), 7.23-8.85 (m, 16H), 7.98(s, 1H), 11.2(s, 1H);13C-NMR (75 MHz, DMSO-d6) δ50.24,109.7, 110.9, 120.7, 121.9, 122.7, 123.9, 127.6, 128.4, 129.2, 129.6, 130.9, 137.2,140.9, 144.2, 176.7;MS ESI: 413 (m+1) (30%) for the M.F C24H20N4OS, MWt 412; Anal. Calcd for C24H20N4OS C, 69.88; H, 4.89; N, 13.58; O, 3.88; S, 7.77.FoundC, 69.79; H, 4.76; N, 13.63; O, 3.96; S, 7.69.
2.1.3.2 2-((1-(2-oxo-2-phenylethyl)-2-phenyl-1H-indol-3-yl)methylene)hydrazinecarbothioamide(4b)
Yield 58.6%, m.p230-232oC.IR (KBr, υmax, cm-1) 3369, 3259, 2920, 1682, 1560, 1459, 1329, 1210, 1070, 820, 750; 1H-NMR (300MHz, DMSO-d6) 5.75(s, 2H), 7.23-8.0 (m, 15H), 7.98 (s, 1H), 11.20 (s, 1H);13C-NMR (75 MHz, DMSO-d6) δ50.30,109.1, 110.3, 111.5 121.7, 122.9, 123.8, 124.3, 127.9, 128.9, 129.2, 129.8, 130.4, 136.5,141.7, 144.6, 176.8.MS ESI: 448 (m+2)(30%) for the M.FC24H19ClN4OS, MWt 446;Anal. Calcd for C24H19ClN4OS C, 64.49; H, 4.28; Cl, 7.93; N,12.54; O,3.58; S,7.17. Found C, 64.54; H, 4.32; Cl, 7.87; N,12.60; O, 3.63; S,7.20.
2.1.3.3 2-((1-(2-(4-bromophenyl)-2-oxoethyl)-2-phenyl-1H-indol-3- yl)methylene) hydrazinecarbothioamide (4c)
Yield 54.6%, m.p225-227 oC.FTIR (KBr, υmax, cm-1) 3350, 3236, 2915, 1679, 1545, 1445,1328, 1200, 1060, 830,740;1H-NMR (300 MHz, DMSO-d6) 5.77 (s, 2H), 7.22-8.81 (m, 15H), 7.99 (s, 1H), 11.08 (s, 1H); 13C-NMR (75 MHz, DMSO-d6) δ50.23,108.9, 109.7, 110.3, 121.3, 122.6, 123.0, 124.2, 127.8, 128.6, 129.1, 129.4, 130.6, 136.1,141.1, 144.1, 176.4; MS ESI:492 (m+2) (100%) for the M.FC24H19BrN4OS, MWt 490; Anal. Calcd for C24H19BrN4OS C, 58.66; H, 3.90; Br, 16.28; N,11.40; O,3.26; S,6.53. Found C, 58.62; H, 3.78; Br, 16.23; N,12.00; O, 3.30; S,6.46.
2.1.3.4 2-((1-(2-(4-methoxyphenyl)-2-oxoethyl)-2-phenyl-1H-indol-3-yl)methylene)
hydrazinecarbothioamide(4d)Yield 57.6%, m.p239-242 oC.FTIR (KBr, υmax, cm-1) 3390, 3269,2925, 1690, 1608, 1565, 1210, 1090, 820, 750; 1H-NMR (300 MHz, DMSO-d6) 3.85 (s, 3H), 5.69 (s, 2H), 7.04-8.39 (m, 15H), 7.96 (s, 1H), 11.08 (s, 1H, NH);13C-NMR (75 MHz, DMSO-d6):δ50.34, 55.7,108.5, 109.9, 120.7, 121.9, 122.2, 123.4, 126.8, 127.9, 128.1, 129.5, 131.8, 139.6,140.3, 146.3, 176.9;MS ESI: 443(m+1) (70%) for the M.F C25H22N4O2S, M. Wt 442; Anal. Calcd for C25H22N4O2S C 67.85; H, 5.01; N, 12.66;O,7.23; S 7.25. Found C, 67.75; H, 5.43; N, 12.70;O,7.32; S 7.40.
2.1.3.5 2-((1-ethyl-2-phenyl-1H-indol-3-yl)methylene)hydrazinecarbothioamide(9a)
Yield 52.8%, m.p230-232 oC.FTIR (KBr, υmax, cm-1) 3360, 3240,2929, 1688, 1612, 1568, 1217, 1091, 832, 745;1H-NMR (300 MHz, DMSO-d6) 1.17 (t,J= 5.2 Hz, 3H), 4.14 (q, J= 5.2 Hz, 2H), 7.22 (d, J = 5.2 Hz, 1H), 7.33 (d, J = 8 Hz,1H), 7.61(d,J = 8 Hz, 1H), 8.06 (s, 1H), 8.36 (d,J = 8.8 Hz, 1H). 7.20-8.32 (m, 7H), 11.04 (s, 1H);13C-NMR (75 MHz, DMSO-d6)δ 14.8, 38.4, 108.9, 110.3, 121.3, 122.6, 123.0, 124.2, 128.6, 129.1, 129.4, 130.6, 136.1,141.1, 144.1, 176.4. MS ESI: 324 (m+2) (50%). For the M.F C18H18N4S, M.Wt 322;Anal. Calcd for C18H18N4S C 67.05; H, 5.63; N, 17.38; S, 9.94. Found C 67.20; H, 5.72; N, 17.42; S, 9.80.
2.1.3.6 2-((1-allyl-2-phenyl-1H-indol-3-yl)methylene)hydrazinecarbothioamide(9b)
Yield 57.6%, m.p225-227oC.FTIR (KBr, υmax, cm-1) 3350, 3210,2929, 1688, 1610, 1569, 1219, 1090, 829, 740; 1H-NMR (300 MHz, DMSO-d6) δ 4.86 (d, J= 12.3 Hz,2H), 4.95-4.90 (d,,J= 7.7 Hz, 1H) 5.19 (d,J= 7.6 Hz, 1H ), 6.02 (m, J = 4.2 Hz,1H) 7.25-7.65 (m, 9H), 7.96 (s, 1H),11.1 (s, 1H);13C-NMR (75 MHz, DMSO-d6)δ 46.9, 48.5, 111.5, 111.6, 112.9, 117.2, 121.6, 123.3, 124.7, 125.2, 128.7, 130.2, 130.9, 133.0, 137.4, 147.3, 156.2,176.2;MS ESI: 335 (m+1) (60%) For the M.F C19H18N4S, M.Wt 334; Anal. Calcd for C19H18N4S C 68.23; H, 5.42; N, 16.75; S, 9.59. Found C 68.19; H, 5.40; N, 16.65; S, 9.64.
2.1.3.7 2-((1-butyl-2-phenyl-1H-indol-3-yl)methylene)hydrazinecarbothioamide(9c)
Yield 52.6%, m.p212-215oC.IR (KBr, υmax, cm-1) 3390, 3290,2925, 1679, 1600, 1559, 1210, 1089, 837, 750;1H-NMR (300 MHz, DMSO-d6) δ 0.69 (t,J= 5.1 Hz, 3H), 1.07 (m, J= 5.1 Hz, 2H), 1.58 (m,J= 5.1 Hz, 2H), 4.27 (t,J= 5.4 Hz, 2H, ), 7.20-7.62 (m, 9H), 7.99 (s, 1H), 11.10 (s,1H); 13C-NMR (75 MHz, DMSO-d6) δ 13.2, 19.1, 31.2, 42.8, 109.3, 110.3, 120.9, 122.2, 122.7, 124.2, 128.6, 128.9, 129.0, 129.9, 130.7, 136.4, 137.4, 142.5,175.5;MS ESI: 351 (m+1) (100%) For the M.F C20H22N4S, M.Wt 350; Anal. Calcd for C20H22N4S C 68.54;H, 6.33; N, 15.99; S, 9.15.Found C 68.32; H, 6.24; N, 15.98; S, 9.20.
2.1.4 Synthetic procedure for the compounds5a-d and 10a-c
Derivatives of (1a-d) or derivatives of (6a-c) (1.0 mmole) were dissolved in methanol. An equi molar amount of Isoniazide was added to it and the mixture was exposed to natural sunlight for 3-4 h.Product formation was confirmed by TLC, the mixture was cooled and the solid obtained was filtered and washed well with cold methanol. Recrystalization with methanol yielded pure compounds. The characterization data of compounds 5a-d,10a-c is given below.
2.1.4.1Isonicotinic acid [1-(2-oxo-2phenyl-ethyl)-2-phenyl-1H-indol-3-ylmethylene]-hydrazide (5a)
Yield 62.6%, m.p279-280 oC.FTIR (KBr, υmax, cm-1) 3440,3340, 2932, 1685, 1603, 1573, 1463, 1235, 1173, 982, 755;1H-NMR (300 MHz, DMSO-d6) 5.78 (s, 2H), 7.27-8.74 (m, 14H), 7.43 (d,J = 6.6 Hz, 1H),7.51 (d,J = 6.6 Hz, 1H), 7.57 (d,J = 6.7 Hz, 1H), 7.98 (s, 1H), 8.00 (d, J = 8.3 Hz, 1H),11.73 (s, 1H, NH);13C-NMR (75 MHz, DMSO-d6) δ 50.6, 109.9, 110.5, 121.4, 122.4, 123.2, 124.4, 128.0, 128.7, 128.8, 129.2, 129.3, 130.4, 134.1, 137.6, 140.8, 144.6, 145.5, 150.1, 160.7, 194.0; MS ESI: 459 (m+1) (100%). For the M.F C29H22N4O2, M.Wt 458;Anal. Calcd for C29H22N4O2 C 75.97;H, 4.84; N, 12.22; O, 6.98.Found C 75.92; H, 4.80; N, 12.12; O, 6.78.
2.1.4.2 Isonicotinic acid {1[2-(4-Chloro-phenyl)-2oxo-ethyl]-2-phenyl-1H-indol-3-ylmethylene}- hydrazide (5b)
Yield 68.6%, m.p239-241 oC.FTIR (KBr, υmax, cm-1) 3439,3326, 2930, 1687, 1601, 1570, 1461, 1230, 1172, 980, 752; 1H-NMR (300 MHz, DMSO-d6) 5.69 (s, 2H), 7.03-8.82 (s,16H), 7.98 (s, 1H), 11.74 (s, 1H, NH); 13C-NMR (75 MHz, DMSO-d6)δ 50.3, 109.4, 110.9, 120.9, 121.5, 122.9, 124.3, 128.5, 128.6, 128.5, 129.1, 129.8,130.1, 134.6, 136.9, 140.2, 144.5,145.6, 150.2, 160.8, 194.3; MS ESI: 494 (m+2) (30%). For the M.F C29H21ClN4O2, M.Wt 492;Anal. Calcd for C29H21ClN4O2C 70.66;H, 4.29; Cl, 7.19; N, 11.37; O, 6.49.Found C 70.62; H, 4.34; Cl, 7.25; N, 11.20; O, 6.38.
2.1.4.3 Isonicotinic acid {1[2-(4-Bromo-phenyl)-2oxo-ethyl]-2-phenyl-1H-indol-3-ylmethylene}- hydrazide (5c)
Yield 66.5%, m.p236-238oC.FTIR (KBr, υmax, cm-1) 3429, 3330,2940, 1684, 1600, 1570, 1465, 1232, 1173, 983, 754; 1H-NMR (300 MHz, DMSO-d6) 5.70 (s, 2H), 7.03-8.82 (m,17H), 7.99 (s, 1H), 11.74 (s, 1H, NH); 13C-NMR (75 MHz, DMSO-d6)δ 50.5, 109.3, 110.7, 121.8, 121.8, 122.7, 123.9, 128.4, 128.9, 129.8, 129.8,130.3, 133.7, 135.9, 141.3, 144.7, 147.6, 150.4, 160.9,194.2. MS ESI: 538 (m+2) (98%)For the M.F C29H21BrN4O2, M.Wt536;Anal. Calcd for C29H21BrN4O2C 64.81;H, 3.94; Br, 14.87; N, 10.43; O, 5.95.Found C 64.75; H, 3.78; Br, 14.90; N, 10.32; O, 5.85.
2.1.4.4. Isonicotinic acid{1[2-(4-Methoxy-phenyl)-2oxo-ethyl]-2-phenyl-1H-indol-3ylmethylene}- hydrazide (5d)
Yield 60.7%, m.p242-244oC.FTIR (KBr, υmax, cm-1)3442, 3309, 2989, 1684, 1600, 1570, 1450, 1230, 950, 750;1H-NMR (300 MHz, DMSO-d6) 3.85 (s, 3H), 5.70 (s, 2H), 7.05-8.74 (m, 17H), 7.99 (s, 1H), 11.73 (s, 1H, NH);13C-NMR (75 MHz, DMSO-d6) δ 50.23, 55.61, 109.8, 110.4, 114.0, 121.3, 122.3, 123.1, 124.4, 127.0, 128.7, 129.2, 130.4, 137.6, 140.8, 144.7, 145.5, 150.1, 160.6, 163.7, 192.1; MS ESI: 489 (m+1) (50%) For the M.F C30H24N4O3, M.Wt 488; Anal.Calcd for C30H24N4O3 C 73.81;H, 4.95; N, 11.47; O, 9.82.Found C 73.70; H, 4.80; N, 11.20; O, 9.78.
2.1.4.5. Isonicotinic acid(1-ethyl-2-phenyl-1H-indol-3-ylmethylene)-hydrazide (10a)
Yield 61.7.6%, m.p180-185oC.FTIR (KBr, υmax, cm-1) 3424, 3315,2939, 1680, 1610, 1578, 1467, 1230, 1170, 984, 752; 1H-NMR (300 MHz, DMSO-d6)δ 1.29 (t,J= 5.1Hz,3H ), 4.30 (q,J= 5.1Hz,2H),7.10-8.80 (m, 13H), 7.98 (s,1H), 11.80 (s,1H, NH);13C-NMR (75 MHz, DMSO-d6)14.8, 38.4, 108.2, 110.9, 120.9, 121.5, 123.5, 123.9, 128.2, 128.9, 129.8, 130.5, 135.9, 141.2, 144.6, 147.3, 150.3, 160.9;MS ESI: 369 (m+1) (80%) For the M.F C23H20N4O, M.Wt 368;Anal.Calcd for C23H20N4OC 74.98;H, 5.47; N, 15.21; O, 4.34.Found C 74.80; H, 5.53; N, 15.30; O, 4.52.
2.1.4.6. Isonicotinic acid(1-allyl-2-phenyl-1H-indol-3-ylmethylene)-hydrazide(10b)
Yield 67.5%, m.p185-187oC.IR (KBr, υmax, cm-1) 3420, 3320,2937, 1682, 1607, 1575, 1460, 1231, 1173, 982, 770;1H-NMR (300 MHz, DMSO-d6) δ 4.87 (d,J= 10.4 Hz, 2H), 4.96(d,J= 7.6Hz, 1H) 5.20 (d, J= 7.6Hz, 1H), 6.10 (m,J = 4.0 Hz, 1H) 7.15-8.89 (m,13H), 7.99 (s, 1H), 11.83 (s, 1H, NH);13C-NMR (75 MHz, DMSO-d6)δ 45.9, 49.5, 110.5, 111.2,120.6, 121.7, 124.5, 124.9, 128.5, 128.5, 129.8, 130.7, 135.8, 141.3, 144.7, 147.6, 150.4, 160.4;MS ESI: 381(m+1) (70%) For the M.F C24H20N4O M.Wt 380;Anal.Calcd for C24H20N4OC, 75.77;H, 5.30; N, 14.73; O, 4.21.Found C 75.69; H, 5.32; N, 14.68; O, 4.30.
2.1.4.7. Isonicotinicacid(1-butyl-2-phenyl-1H-indol-3-ylmethylene)-hydrazide (10c)
Yield 68.9%, m.p190-192oC.FTIR (KBr, υmax, cm-1) 3430, 3300,2945, 1690, 1600, 1578, 1461, 1230, 1150, 960, 7740;1H-NMR (300 MHz, DMSO-d6) δ 0.71 (t,J= 4.9 Hz,3H), 1.12 (m, J= 4.9 Hz, 2H), 1.61 (m, J= 4.9 Hz, 2H), 4.31(t,J= 4.7 Hz,2H), 7.20-8.88 (m, 13H),7.89 (s, 1H), 11.88 (s,1H, NH);13C-NMR (75 MHz, DMSO-d6) δ 13.5, 19.8, 32.5, 43.6,110.2, 111.4,120.9, 121.2, 123.6, 124.8, 128.6, 129.2, 129.6, 130.6, 134.9, 141.2, 144.6, 147.3, 151.5, 160.7;MS ESI: 397 (m+1) (100%) For the M.F C25H24N4O, M.Wt 396;Anal.Calcd for C25H24N4O C, 75.73; H, 6.10; N, 14.13; O, 4.04. Found C 75.65; H, 6.14; N, 14.25;O,4.14.
2.1.5. Synthetic procedure for the compounds11a-d and 12a-c
Derivatives of (1a-d) or derivatives of (6a-c) (1.0 mmole) were dissolved in methanol. An equi molar amount of malanonitrile was added to it and the mixture was exposed to natural sunlight for 3-4 h.Product formation was confirmed by TLC, the mixture was cooled and the solid obtained was filtered and washed well with cold methanol.Recrystalization with methanol yielded pure compounds. The characterization data of compounds 11 a-d,12a-c is given below
2.1.5.1.2-((1-(2-oxo-2-phenylethyl)-2-phenyl-1H-indol-3-yl)methylene)malononitrile (11a)
Yield 78.6%, m.p160-163oC.FTIR (KBr, υmax, cm-1)3065, 3028,2934, 2221, 1707, 1579, 1408, 1230, 980, 758; 1H-NMR (300 MHz, DMSO-d6) 5.93 (s, 2H), 7.39-8.21 (m, 14H), 8.22 (s, 1H); 13C-NMR (75 MHz, DMSO-d6)δ 51.31, 71.02, 110.7, 111.7, 113.4, 116.7, 116.9, 121.5, 122.9, 123.6, 124.7, 126.5, 127.9, 128.5, 130.8, 130.9, 138.6, 152.7, 153.9, 164.7, 192.3.MS ESI: 388 (m+1) (50%) For the M.F C26H17N3O, M.Wt 387; Anal.Calcd for C26H17N3O C,80.60; H, 4.42;N, 10.85; O, 4.13.Found C 80.55; H, 4.54; N, 10.70; O, 4.30.
2.1.5.22-((1-(2-(4-chlorophenyl)-2-oxoethyl)-2-phenyl-1H-indol-3-yl)methylene)malononitrile(11b)
Yield 72.5%, m.p170-173oC.FTIR (KBr, υmax, cm-1)3069, 3023,2932, 2229, 1715, 1579, 1420, 1227, 989, 750; 1H-NMR (300 MHz, DMSO-d6)5.92 (s, 2H), 7.30-8.18 (m,13H), 8.27 (s, 1H); 13C-NMR (75 MHz, DMSO-d6)δ 51.19, 72.10, 109.8, 110.9, 115.9, 116.5, 120.1, 121.6, 123.2, 124.5, 126.9, 127.8, 129.2, 131.3, 131.5, 135.6, 153.5, 153.9, 164.4, 194.5; MSESI: 423 (m+2) (30%) For the M.F C26H16ClN3O, M.Wt 421;Anal.Calcd for C26H16ClN3O C,74.02; H, 3.82;Cl, 8.40; N, 9.96; O,3.79.Found C 74.11; H, 3.70; Cl, 8.30; N, 9.89; O, 3.75.
2.1.5.32-((1-(2-(4-bromophenyl)-2-oxoethyl)-2-phenyl-1H-indol-3-yl)methylene)malononitrile(11c)Yield 70.4.6%, m.p165-167oC.FTIR (KBr, υmax, cm-1)3073, 3020,2929, 2225, 1710, 1569, 1415, 1230, 986, 755;1H-NMR (300 MHz, DMSO-d6)5.91 (s, 2H), 7.32-8.20 (m,13H), 8.25 (s, 1H); 13C-NMR (75 MHz, DMSO-d6)δ 52.09, 71.19, 110.8, 114.9, 117.5, 120.1, 121.9, 123.5, 124.7, 126.8, 127.9, 129.5, 130.1, 131.8, 134.7, 152.4, 153.9, 163.5, 195.4;MSESI: 467 (m+2) (100%) and 466 (m+1) (40%) For the M.F C26H16BrN3O, M.Wt 465; Anal.Calcd for C26H16BrN3O C, 66.97; H, 3.46; Br,17.13; N,9.01;O 3.43. Found C, 66.89; H, 3.35; Br,17.23; N,9.14;O 3.24.
2.1.5.42-((1-(2-(4-methoxyphenyl)-2-oxoethyl)-2-phenyl-1H-indol-3-yl)methylene)malononitrile(11d)
Yield 72.7%, m.p231-233 oC.FTIR (KBr, υmax, cm-1)3063, 3020,2929, 2221, 1701, 1570, 1407, 1223, 983, 748;1H-NMR (300 MHz, DMSO-d6) 3.85(s, 3H), 5.85 (s, 2H), 7.06 (d, 1H),7.42 (d, 1H), 7.08-7.97 (m,10H), 7.99 (s, IH). 8.21(d,J = 8.5 Hz, 1H); 13C-NMR (75 MHz, DMSO-d6)δ 51.24, 55.65,72.06, 110.5, 111.9, 114.1, 115.5, 116.3, 122.1, 122.7, 123.4, 124.4, 126.7, 127.6, 128.9, 130.5, 130.6, 138.3, 152.6, 153.8, 164.0, 191.1; MS ESI: 418 (m+1) (30%) and 440 (m+23) (100%). For the M.F C27H19N3O2, M.Wt 417;Anal.Calcd for C27H19N3O2C, 77.68; H, 4.59; N,10.07;O 7.67. Found C, 77.72; H, 4.65; N,10.12;O 7.76.
2.1.5.5 2-((1-ethyl-2-phenyl-1H-indol-3-yl)methylene)malononitrile (12a)
Yield 73.6%, m.p160-163 oC.IR (KBr, υmax, cm-1)3059, 3018,2927, 2227, 1707, 1560, 1410, 1215, 979, 748;1H-NMR (300 MHz, DMSO-d6) 1.17 (t, J= 5.4Hz, 3H), 4.14 (q,J= 5.4Hz, 2H), 7.25-7.69 (m, 9H), 8.27 (s, 1H);13C-NMR (75 MHz, DMSO-d6) δ14.8, 43.9, 70.7, 110.9, 111.9, 113.9, 115.4, 120.3, 121.7, 124.6, 125.4, 127.6, 128.9, 130.5, 131.8, 135.3, 151.7, 152.6;MS ESI: 298(80%). For the M.F C20H15N3,M.Wt 297;Anal.Calcd for C20H15N3 C, 80.78; H, 5.08; N,14.13. Found C,80.68; H, 5.20; N, 14.20.
2.1.5.6 2-((1-allyl-2-phenyl-1H-indol-3-yl)methylene)malononitrile(12b)
Yield 70.4%, m.p180-183 oC.IR (KBr, υmax, cm-1) 3063, 3023, 2920, 2215, 1644, 1568, 1443, 1223, 921,744;1H-NMR (300 MHz, DMSO-d6) δ 4.80 (d,J= 12.3Hz, 2H ), 4.95 (d, J= 7.8Hz, 1H), 5.19 (d,J= 7.8Hz, 1H), 6.02 (m, 1H), 7.25-7.65 (m, 9H), 8.21 (s, 1H);13C-NMR (75 MHz, DMSO-d6) δ 46.90, 48.5, 71.59, 110.3, 112.3, 115.5, 116.3, 117.2, 122.2, 122.7, 123.5, 124.4, 127.7, 128.8, 130.5, 130.6, 132.5, 137.4, 151.2, 153.7;MS ESI: 310 (m+1) (80%). For the M.F C21H15N3,M.Wt 309;Anal.Calcd for C21H15N3 C, 81.53; H, 4.89; N,13.58. Found C,81.63; H, 4.90; N, 13.62.
2.1.5.7 2-((1-butyl-2-phenyl-1H-indol-3-yl)methylene)malononitrile(12c)
Yield 71.2%, m.p150-155 oC. IR (KBr, υmax, cm-1) 3060, 3020, 2918, 2222, 1650, 1569, 1440, 1218, 930,754;1H-NMR (300 MHz, DMSO-d6)δ 0.69 (t,J= 5.6Hz, 3H), 1.07 (m,J= 5.6Hz, 2H), 1.58 (m,J= 5.6Hz, 2H), 4.27 (t,J= 5.6Hz, 2H), 7.20-7.65 (m, 9H), 8.25 (s, 1H); 13C-NMR (75 MHz, DMSO-d6): δ 13.13, 19.12, 30.81, 44.12, 70.80, 110.4, 112.2, 115.7, 116.5, 122.3, 122.7, 123.6, 124.4, 127.9, 128.9,130.4,130.8,137.3,151.5,153.6;MS ESI: 326 (m+1) (40%). For the M.F C22H19N3,M.Wt 325;Anal.Calcd for C22H19N3 C, 81.20; H, 5.89; N,12.91. Found C,81.35; H, 5.95; N, 12.80.