Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers. This journal is the Partner Organisations 2016 Supporting information Copper-Catalyzed Oxidative Dehydrogenative - Bond Formation for the Synthesis of, -Diarylindazol-3-ones Guo Dai, Luo Yang, and Wang Zhou*, College of Chemical Engineering, Xiangtan University, Xiangtan 411105, China; College of Chemistry, Xiangtan University, Xiangtan 411105, China *Corresponding author s email address: wzhou@xtu.edu.cn List of the contents General Remarks and Typical Procedure...S2 Analytical Data for Compounds 2 and 3...S3 References...S11 1 H MR and 13 C MR Spectra of Compounds 2 and 3...S12 S1
General Remarks. 1 H-MR spectra were recorded on a Bruker AVIII-400 spectrometer. Chemical shifts (in ppm) were referenced to tetramethylsilane (δ = 0 ppm) in CDCl 3 as an internal standard. 13 C-MR spectra were obtained by using the same MR spectrometers and calibrated with CDCl 3 (δ = 77.00 ppm). Mass spectra were recorded using an Agilent 5975 GC-MS and Bruker APEX IV Fourier Transform Ion Cyclotron Resonance Mass Spectrometer. Substrate 1 were synthesized by the reaction of isatoic anhydride with different amines in ethyl acetate giving the aminobenzamides 1, followed by Ullmann -arylation of amino group. 2 Typical Procedure. To a tube equipped with a condenser was added -phenyl-2-phenylaminobenzamide 1 (0.2 mmol), CuBr (0.04 mmol, 20 mol%), and DMSO (1.0 ml). The mixture was stirred at 120 C and monitored by TLC. After completion of reaction, the mixture was cooled down to room temperature, dried under vacuum and purified by column chromatography on silica gel to obtain the desired products 2 (petroleum ether:ethyl acetate = 5:1). S2
Analytical Data for Compounds 2 and 3 1,2-Diphenyl-1H-indazol-3(2H)-one (2a). The reaction of -phenyl-2- phenylamino-benzamide (1a, 0.2 mmol, 57.7 mg), CuBr (0.04 mmol, 5.7 mg), and DMSO (1.0 ml) under typical procedure for 4 h afforded 54 mg (94%) of 2a as solid; m.p.: 158-159 o C; 1 H MR (CDCl 3, 400 MHz): = 7.95 (d, J = 8.0 Hz, 1H), 7.61-7.53 (m, 2H), 7.50 (t, J = 7.6 Hz, 1H), 7.35-7.10 (m, 10H); 13 C MR (CDCl 3, 100 MHz): = 162.6, 150.1, 142.2, 135.7, 133.0, 129.6, 128.8, 127.4, 125.8, 124.4, 124.1, 123.4, 123.2, 118.1, 112.3 ppm; IR (KBr): max = 3433, 1681, 1589, 1490, 1462, 1452, 1356, 1321, 1308, 1278, 932, 787, 760, 699, 692, 682 cm -1 ; HRMS (ESI) m/z calcd for C 19 H 15 2 O (M+H) + 287.1179, found 287.1176. 2-enyl-1-o-tolyl-1H-indazol-3(2H)-one (2b). The reaction of -phenyl-2-otolylamino-benzamide (1b, 0.2 mmol, 60.5 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 60 mg (> 99%) of 2b as solid; m.p.: 159-160 o C; 1 H MR (CDCl 3, 400 MHz): = 8.00 (d, J = 8.0 Hz, 1H), 7.58-7.45 (m, 3H), 7.38-7.00 (m, 8H), 6.87 (d, J = 8.8 Hz, 1H), 2.48 (s, 3H) ; 13 C MR (CDCl 3, 100 MHz): = 162.3, 149.6, 139.9, 135.3, 135.1, 132.9, 131.6, 128.8, 128.3, 127.2, 126.2, 125.5, 124.4, 123.7, 122.8, 118.0, 112.1, 17.7 ppm; IR (KBr): max = 3433, 1686, 1594, 1495, 1479, 1382, 1308, 1273, 1154, 958, 727, 705, 689 cm -1 ; HRMS (ESI) m/z calcd for C 20 H 17 2 O (M+H) + 301.1335, found 301.1334. 2-enyl-1-m-tolyl-1H-indazol-3(2H)-one (2c). The reaction of -phenyl-2-mtolylamino-benzamide (1c, 0.2 mmol, 60.5 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 54 mg (90%) of 2c as solid; m.p.: 159-160 o C; 1 H MR (CDCl 3, 400 MHz): = 7.97 (d, J = 8.0 Hz, 1H), 7.62-7.58 (m, 2H), 7.56-7.48 (m, 1H), 7.40-7.00 (m, 9H), 2.31 (s, 3H); 13 C MR (CDCl 3, 100 MHz): = 162.7, 150.2, 142.2, 139.6, 135.8, 133.0, 129.3, 128.7, 128.3, 125.8, 124.6, 124.3, 123.3, 123.1, 121.2, 118.1, 112.4, 21.3 ppm; IR (KBr): max = 3436, 1689, 1605, 1589, 1487, 1477, 1456, 1381, 1310, 958, 759, 706, 691 cm -1 ; HRMS (ESI) m/z calcd for C 20 H 17 2 O (M+H) + 301.1335, found 301.1335. 2-enyl-1-p-tolyl-1H-indazol-3(2H)-one (2d). The reaction of -phenyl-2-p- S3
tolylamino-benzamide (1d, 0.2 mmol, 60.5 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 54 mg (90%) of 2d as solid; m.p.: 114-115 o C; 1 H MR (CDCl 3, 400 MHz): = 7.97 (d, J = 8.0 Hz, 1H), 7.62-7.58 (m, 2H), 7.51 (t, J = 7.6 Hz, 1H), 7.40-7.10 (m, 9H), 2.30 (s, 3H) ; 13 C MR (CDCl 3, 100 MHz): = 162.5, 150.3, 139.6, 137.4, 135.7, 132.9, 130.1, 128.7, 125.8, 124.3, 124.2, 123.3, 123.2, 118.1, 112.4, 20.9 ppm; IR (KBr): max = 3433, 1682, 1495, 1476, 1458, 1354, 1309, 926, 789, 756, 719, 681 cm -1 ; HRMS (ESI) m/z calcd for C 20 H 17 2 O (M+H) + 301.1335, found 301.1335. 1-(3-Methoxyphenyl)-2-phenyl-1H-indazol-3(2H)-one (2e). The reaction of 2-(3- methoxy-phenylamino)--phenyl-benzamide (1e, 0.2 mmol, 63.7 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 60 mg (95%) of 2e as solid; m.p.: 67-68 o C; 1 H MR (CDCl 3, 400 MHz): = 7.97 (d, J = 8.8 Hz, 1H), 7.62-7.58 (m, 2H), 7.53 (t, J = 7.6 Hz, 1H), 7.38-7.10 (m, 6H), 6.96-6.72 (m, 3H), 3.72 (s, 3H); 13 C MR (CDCl 3, 100 MHz): = 162.6, 160.4, 150.0, 143.4, 135.8, 133.0, 130.2, 128.8, 125.8, 124.4, 123.4, 123.0, 118.1, 116.3, 112.8, 112.3, 109.8, 55.3 ppm; IR (KBr): max = 3439, 2926, 1686, 1602, 1589, 1490, 1477, 1309, 1126, 1043, 752, 704, 690 cm -1 ; HRMS (ESI) m/z calcd for C 20 H 17 2 O 2 (M+H) + 317.1285, found 317.1282. 1-(4-Methoxyphenyl)-2-phenyl-1H-indazol-3(2H)-one (2f). The reaction of 2-(3- methoxy-phenylamino)--phenyl-benzamide (1f, 0.2 mmol, 63.7 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 61 mg (96%) of 2f as solid; m.p.: 87-88 o C; 1 H MR (CDCl 3, 400 MHz): = 7.97 (d, J = 8.4 Hz, 1H), 7.59-7.56 (m, 2H), 7.51 (t, J = 7.6 Hz, 1H), 7.38-7.06 (m, 7H), 6.85 (d, J = 8.4 Hz, 2H), 3.76 (s, 3H); 13 C MR (CDCl 3, 100 MHz): = 162.4, 158.8, 150.8, 135.5, 134.7, 132.9, 128.7, 126.1, 126.0, 124.3, 123.6, 123.1, 118.0, 114.7, 112.5, 55.3 ppm; IR (KBr): max = 3546, 3472, 1656, 1589, 1507, 1479, 1421, 1315, 1251, 1033, 759, 692 cm -1 ; HRMS (ESI) m/z calcd for C 20 H 17 2 O 2 (M+H) + 317.1285, found 317.1283. 1-(2-Fluorophenyl)-2-phenyl-1H-indazol-3(2H)-one (2g). The reaction of 2-(2- fluoro-phenylamino)--phenyl-benzamide (1g, 0.2 mmol, 61.3 mg), CuBr (0.04 S4
mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 57 mg (94%) of 2g as solid; m.p.: 140-141 o C; 1 H MR (CDCl 3, 400 MHz): = 7.99 (d, J = 8.0 Hz, 1H), 7.63-7.53 (m, 3H), 7.40-7.00 (m, 9H); 13 C MR (CDCl 3, 100 MHz): = 162.5, 157.6 (d, J C-F = 249.3 Hz), 149.9, 135.4, 133.2, 129.5 (d, J C-F = 7.6 Hz), 128.9, 126.3 (d, J C-F = 29.3 Hz), 125.0 (d, J C-F = 3.7 Hz), 124.4, 123.5,123.1, 118.4, 117.0 (d, J C-F = 19.1 Hz), 112.6 (d, J C-F = 2.9 Hz) ppm; IR (KBr): max = 3432, 1675, 1588, 1492, 1475, 1311, 803, 761, 691 cm -1 ; HRMS (ESI) m/z calcd for C 19 H 14 F 2 O (M+H) + 305.1085, found 305.1082. 1-(3-Fluorophenyl)-2-phenyl-1H-indazol-3(2H)-one (2h). The reaction of 2-(3- fluoro-phenylamino)--phenyl-benzamide (1h, 0.2 mmol, 61.3 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 50 mg (82%) of 2h as solid; m.p.: 142-143 o C; 1 H MR (CDCl 3, 400 MHz): = 7.98 (d, J = 8.4 Hz, 1H), 7.61-7.53 (m, 3H), 7.42-6.90 (m, 9H); 13 C MR (CDCl 3, 100 MHz): = 163.1 (d, J C-F = 247.7 Hz), 162.8, 149.8, 144.0 (d, J C-F = 8.8 Hz), 135.7, 133.3, 130.8 (d, J C-F = 9.2 Hz), 128.9, 126.1, 124.6, 123.8, 123.0, 119.7 (d, J C-F = 3.3 Hz), 118.3, 114.5 (d, J C-F = 20.8 Hz), 112.2, 111.5 (d, J C-F = 23.3 Hz) ppm; IR (KBr): max = 3433, 3022, 1687, 1591, 1476, 1350, 1309, 1150, 1002, 887, 785, 758, 703 cm -1 ; HRMS (ESI) m/z calcd for C 19 H 14 F 2 O (M+H) + 305.1085, found 305.1083. 1-(4-Fluorophenyl)-2-phenyl-1H-indazol-3(2H)-one (2i). The reaction of 2-(4- fluoro-phenylamino)--phenyl-benzamide (1i, 0.2 mmol, 61.3 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 61 mg (> 99%) of 2i as solid; m.p.: 132-133 o C; 1 H MR (CDCl 3, 400 MHz): = 7.98 (d, J = 8.0 Hz, 1H), 7.59-7.51 (m, 3H), 7.38-7.00 (m, 9H); 13 C MR (CDCl 3, 100 MHz): = 161.4 (d, J C-F = 246.7 Hz), 162.5, 150.4, 138.2 (d, J C-F = 2.7 Hz), 135.5, 133.1, 128.9, 126.3 (d, J C-F = 8.6 Hz), 126.1, 124.5, 123.6, 123.4, 118.2, 116.6 (d, J C-F = 22.8 Hz), 112.4 ppm; IR (KBr): max = 3432, 3067, 1684, 1614, 1504, 1359, 1311, 1220, 1138, 908, 754 cm -1 ; HRMS (ESI) m/z calcd for C 19 H 14 F 2 O (M+H) + 305.1085, found 305.1083. 1-(4-Chlorophenyl)-2-phenyl-1H-indazol-3(2H)-one (2j). The reaction of 2-(4- chloro-phenylamino)--phenyl-benzamide (1j, 0.2 mmol, 64.6 mg), CuBr (0.04 mmol, S5
5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 63 mg (98%) of 2j as solid; m.p.: 140-141 o C; 1 H MR (CDCl 3, 400 MHz): = 7.98 (d, J = 7.6 Hz, 1H), 7.61-7.50 (m, 3H), 7.42-7.11 (m, 9H); 13 C MR (CDCl 3, 100 MHz): = 162.6, 149.9, 140.8, 135.5, 133.2, 133.0, 129.8, 128.9, 126.1, 125.4, 124.5, 123.7, 123.2, 118.2, 112.2 ppm; IR (KBr): max = 3433, 3068, 1689, 1590, 1481, 1477, 1355, 1309, 1081, 947, 752, 718, 693 cm -1 ; HRMS (ESI) m/z calcd for C 19 H 14 Cl 2 O (M+H) + 321.0789, found 321.0787. 1-enyl-2-m-tolyl-1H-indazol-3(2H)-one (2k). The reaction of 2-phenylamino- -m-tolyl-benzamide (1k, 0.2 mmol, 60.5 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 56 mg (93%) of 2k as solid; m.p.: 130-131 o C; 1 H MR (CDCl 3, 400 MHz): = 7.97 (d, J = 8.0 Hz, 1H), 7.57-7.48 (m, 1H ), 7.47 (s, 1H), 7.40-7.16 (m, 9H), 6.96 (d, J = 7.2 Hz, 1H), 2.33 (s, 3H) ; 13 C MR (CDCl 3, 100 MHz): = 162.6, 150.0, 142.2, 138.6, 135.6, 132.9, 129.5, 128.5, 127.3, 126.8, 124.3, 124.1, 124.0, 123.2, 120.4, 118.1, 112.2, 21.4 ppm; IR (KBr): max = 3433, 3050, 1693, 1464, 1385, 1302, 935, 779, 765, 703, 679 cm -1 ; HRMS (ESI) m/z calcd for C 20 H 17 2 O (M+H) + 301.1335, found 301.1335. 1-enyl-2-p-tolyl-1H-indazol-3(2H)-one (2l). The reaction of 2-phenylamino-p-tolyl-benzamide (1l, 0.2 mmol, 60.5 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 52 mg (87%) of 2l as solid; m.p.: 130-131 o C; 1 H MR (CDCl 3, 400 MHz): = 7.97 (d, J = 7.2 Hz, 1H), 7.55-7.41 (m, 3H ), 7.39-7.10 (m, 9H), 2.28 (s, 3H) ; 13 C MR (CDCl 3, 100 MHz): = 162.5, 149.9, 142.1, 135.7, 133.1, 132.8, 129.5, 129.4, 127.4, 124.3, 124.2, 123.3, 123.2, 118.1, 112.2, 20.9 ppm; IR (KBr): max = 3432, 1686, 1609, 1509, 1474, 1356, 1311, 1261, 927, 808, 766, 706 cm -1 ; HRMS (ESI) m/z calcd for C 20 H 17 2 O (M+H) + 301.1335, found 301.1335. 2-(4-Methoxy-phenyl)-1-phenyl-1H-indazol-3(2H)-one (2m) 3. The reaction of - (4-methoxy-phenyl)-2-phenylamino-benzamide (1m, 0.2 mmol, 63.7 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 55 mg (87%) of 2m as solid; m.p.: 145-146 o C; 1 H MR (CDCl 3, 400 MHz): = 7.97 (d, J = 7.2 Hz, 1H), 7.55-7.20 (m, 9H), 7.17 (d, J = 8.0 Hz, 1H), 6.87 (d, J = 6.4 Hz, 2H), S6
3.76 (s, 3H); 13 C MR (CDCl 3, 100 MHz): = 162.6, 157.7, 149.8, 141.9, 132.8, 129.5, 128.6, 127.5, 125.3, 124.5, 124.3, 123.2, 118.1, 114.1, 112.2, 55.3 ppm; IR (KBr): max = 3526, 3441, 3054, 1675, 1611, 1512, 1452, 1302, 1256, 931, 769, 699 cm -1 ; MS (70 ev): m/z (%) 316 (M +, 100). 2-(4-Fluoro-phenyl)-1-phenyl-1H-indazol-3(2H)-one (2n). The reaction of -(4- fluoro-phenyl)-2-phenylamino-benzamide (1n, 0.2 mmol, 61.3 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 61 mg (> 99%) of 2n as solid; m.p.: 107-108 o C; 1 H MR (CDCl 3, 400 MHz): = 7.97 (d, J = 8.4 Hz, 1H), 7.59-7.50 (m, 3H), 7.41-7.22 (m, 6H), 7.19 (d, J = 9.2 Hz, 1H), 7.08-7.00 (m, 2H) ; 13 C MR (CDCl 3, 100 MHz): = 161.6, 161.0 (d, J C-F = 253.1 Hz), 150.1, 141.9, 133.1, 131.7, 129.6, 127.6, 125.0 (d, J C-F = 7.9 Hz), 124.4, 124.2, 123.5, 117.9, 115.7 (d, J C-F = 22.4 Hz), 112.3 ppm; IR (KBr): max = 3401, 3067, 1692, 1602, 1492, 1475, 1351, 1300, 1259, 1151, 927, 827, 768, 684 cm -1 ; HRMS (ESI) m/z calcd for C 19 H 14 F 2 O (M+H) + 305.1085, found 305.1083. 2-(4-Chloro-phenyl)-1-phenyl-1H-indazol-3(2H)-one (2o). The reaction of -(4- chloro-phenyl)-2-phenylamino-benzamide (1o, 0.2 mmol, 64.6 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 64 mg (> 99%) of 2o as solid; m.p.: 149-150 o C; 1 H MR (CDCl 3, 400 MHz): = 7.96 (d, J = 6.4 Hz, 1H), 7.58-7.50 (m, 3H), 7.41-7.22 (m, 8H), 7.19 (d, J = 8.4 Hz, 1H) ; 13 C MR (CDCl 3, 100 MHz): = 162.7, 150.3, 142.1, 134.3, 133.3, 131.2, 129.7, 129.0, 127.6, 124.4, 124.1, 124.0, 123.6, 117.9, 112.4 ppm; IR (KBr): max = 3432, 1687, 1612, 1489, 1358, 1315, 1111, 935, 818, 759, 708 cm -1 ; HRMS (ESI) m/z calcd for C 19 H 14 Cl 2 O (M+H) + 321.0789, found 321.0787. 2-(4-Bromo-phenyl)-1-phenyl-1H-indazol-3(2H)-one (2p). The reaction of -(4- bromo-phenyl)-2-phenylamino-benzamide (1p, 0.2 mmol, 73.5 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 63 mg (86%) of 2p as solid; m.p.: 147-148 o C; 1 H MR (CDCl 3, 400 MHz): = 7.96 (d, J = 7.6 Hz, 1H), 7.57-7.22 (m, 11H), 7.19 (d, J = 8.0 Hz, 1H) ; 13 C MR (CDCl 3, 100 MHz): = 162.6, 150.3, 142.1, 134.9, 133.3, 131.9, 129.7, 127.7, 124.5, 124.4, 124.0, S7
123.6, 119.1, 118.0, 112.4 ppm; IR (KBr): max = 3431, 1688, 1611, 1488, 1385, 1314, 1284, 814, 758, 707 cm -1 ; HRMS (ESI) m/z calcd for C 19 H 14 2 OBr (M+H) +, 365.02840, found 365.02835. 6-Chloro-1,2-diphenyl-1H-indazol-3(2H)-one (2q). The reaction of 4-chloro-phenyl-2-phenylamino-benzamide (1q, 0.2 mmol, 64.6 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 62 mg (97%) of 2q as solid; m.p.: 125-126 o C; 1 H MR (CDCl 3, 400 MHz): = 7.89 (d, J = 8.4 Hz, 1H), 7.58-7.52 (m, 2H), 7.42-7.14 (m, 10H); 13 C MR (CDCl 3, 100 MHz): = 161.8, 150.4, 141.4, 139.4, 135.5, 129.8, 128.9, 127.8, 126.2, 125.6, 124.23, 124.18, 123.3, 116.6, 112.4 ppm; IR (KBr): max = 3432, 2924, 1693, 1614, 1560, 1494, 1458, 1302, 1068, 948, 824, 750, 718 cm -1 ; HRMS (ESI) m/z calcd for C 19 H 14 Cl 2 O (M+H) + 321.0789, found 321.0788. 5-Chloro-1,2-diphenyl-1H-indazol-3(2H)-one (2r). The reaction of 5-chloro-phenyl-2-phenylamino-benzamide (1r, 0.2 mmol, 64.6 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 61 mg (95%) of 2r as solid; m.p.: 153-154 o C; 1 H MR (CDCl 3, 400 MHz): = 7.94 (s, 1H), 7.60-7.10 (m, 12H); 13 C MR (CDCl 3, 100 MHz): = 161.6, 148.4, 141.7, 135.4, 133.3, 129.7, 129.0, 18.9, 127.8, 126.2, 124.2, 123.8, 123.3, 119.4, 113.7 ppm; IR (KBr): max = 3431, 3071, 1693, 1594, 1497, 1465, 1358, 1294, 825, 759, 719, 695 cm -1 ; HRMS (ESI) m/z calcd for C 19 H 14 Cl 2 O (M+H) + 321.0789, found 321.0788. 5-Bromo-1,2-diphenyl-1H-indazol-3(2H)-one (2s). The reaction of 5-bromo-phenyl-2-phenylamino-benzamide (1s, 0.2 mmol, 73.4 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 69 mg (94%) of 2s as solid; m.p.:179-180 o C; 1 H MR (CDCl 3, 400 MHz): = 8.10 (d, J = 1.2 Hz, 1H), 7.62-7.54 (m, 3H), 7.40-7.14 (m, 8H), 7.07 (d, J = 8.0 Hz, 1H); 13 C MR (CDCl 3, 100 MHz): = 161.1, 148.7, 141.6, 135.9, 135.3, 129.7, 128.9, 127.8, 127.0, 126.2, 124.2, 123.3, 119.9, 116.2, 114.1 ppm; IR (KBr): max = 3432, 3072, 1693, 1591, 1497, 1452, 1357, 1293, 1253, 822, 756, 711, 692 cm -1 ; HRMS (ESI) m/z calcd for C 19 H 14 Br 2 O (M+H) + 365.0284, found 365.0282. S8
5-itro-1,2-diphenyl-1H-indazol-3(2H)-one (2t). The reaction of 5-nitro-phenyl-2-phenylamino-benzamide (1t, 0.2 mmol, 66.7 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 61 mg (92%) of 2t as solid; m.p.:161-162 o C; 1 H MR (CDCl 3, 400 MHz): = 8.91 (s, 1H), 8.39 (d, J = 9.2 Hz, 1H), 7.54-7.18 (m, 11H); 13 C MR (CDCl 3, 100 MHz): = 160.9, 151.1, 143.6, 139.4, 134.6, 130.0, 129.1, 128.6, 128.1, 127.0, 124.7, 123.9, 121.7, 117.6, 112.2 ppm; IR (KBr): max = 3376, 3073, 1699, 1616, 1593, 1526, 1497, 1342, 1300, 916, 821, 777, 708, 692 cm -1 ; HRMS (ESI) m/z calcd for C 19 H 14 3 O 3 (M+H) + 332.1029, found 332.1027. 6-Methyl-1,2-diphenyl-1H-indazol-3(2H)-one (2u). The reaction of 4-methyl-phenyl-2-phenylamino-benzamide (1u, 0.2 mmol, 60.5 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 60 mg (> 99%) of 2u as solid; m.p.: 149-150 o C; 1 H MR (CDCl 3, 400 MHz): = 7.86 (d, J = 7.2 Hz, 1H), 7.58-7.53 (m, 2H), 7.39-7.13 (m, 10H), 1.91 (s, 3H); 13 C MR (CDCl 3, 100 MHz): = 162.5, 150.4, 142.9, 135.0, 134.5, 129.0, 128.9, 128.6, 127.9, 126.6, 125.0, 124.6, 124.1, 121.8, 120.2, 17.9 ppm; IR (KBr): max = 3432, 2970, 1681, 1592, 1496, 1483, 1457, 1364, 751, 704, 694 cm -1 ; HRMS (ESI) m/z calcd for C 20 H 17 2 O (M+H) + 301.1335, found 301.1335. 5-Methyl-1,2-diphenyl-1H-indazol-3(2H)-one (2v). The reaction of 5-methyl-phenyl-2-phenylamino-benzamide (1v, 0.2 mmol, 60.5 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 51 mg (85%) of 2v as solid; m.p.: 152-153 o C; 1 H MR (CDCl 3, 400 MHz): = 7.68 (s, 1H), 7.56-7.52 (m, 2H), 7.35-7.00 (m, 10H), 2.36 (s, 3H) ; 13 C MR (CDCl 3, 100 MHz): = 162.7, 148.7, 142.7, 135.9, 134.5, 133.3, 129.5, 128.8, 127.3, 125.7, 124.0, 123.8, 123.1, 118.4, 112.2, 20.9 ppm; IR (KBr): max = 3435, 3056, 1690, 1595, 1488, 1455, 1357, 1293, 1267, 805, 759, 716, 697 cm -1 ; HRMS (ESI) m/z calcd for C 20 H 17 2 O (M+H) + 301.1335, found 301.1336. 6-Fluoro-1,2-diphenyl-1H-indazol-3(2H)-one (2w). The reaction of 4-fluoro-phenyl-2-phenylamino-benzamide (1w, 0.2 mmol, 61.3 mg), CuBr (0.04 mmol, 5.7 S9
mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 49 mg (81%) of 2w as solid; m.p.: 115-116 o C; 1 H MR (CDCl 3, 400 MHz): = 7.99-7.92 (m, 1H), 7.58-7.52 (m, 2H), 7.42-7.64 (m, 10H); 13 C MR (CDCl 3, 100 MHz): = 166.3 (d, J C-F = 250.1 Hz), 162.0, 151.2 (d, J C-F = 12.8 Hz), 141.6, 135.7, 129.8, 128.9, 127.8, 126.6 (d, J C-F = 11 Hz), 126.1, 124.1, 123.2, 114.3, 112.2 (d, J C-F = 24.4 Hz), 99.3 (d, J C-F =27.4 Hz) ppm; IR (KBr): max = 3373, 3059, 1693, 1626, 1605, 1441, 1323, 1229, 1163, 1098, 971, 843, 741, 697,674 cm -1 ; HRMS (ESI) m/z calcd for C 19 H 14 F 2 O (M+H) + 305.1085, found 305.1083. 4-Chloro-1,2-diphenyl-1H-indazol-3(2H)-one (2x). The reaction of 2-chloro-phenyl-6-phenylamino-benzamide (1x, 0.2 mmol, 64.6 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 36 mg (56%) of 2x as solid; m.p.: 160-161 o C; 1 H MR (CDCl 3, 400 MHz): = 7.62-7.54 (m, 2H), 7.44-7.04 (m, 11H); 13 C MR (CDCl 3, 100 MHz): = 160.6, 151.5, 141.7, 135.5, 133.4, 132.0, 129.8, 128.8, 127.9, 126.2, 124.6, 124.3, 123.4, 114.9, 110.8 ppm; IR (KBr): max = 3433, 2921, 1693, 1592, 1488, 1471, 1299, 1160, 962, 791, 755, 703 cm -1 ; HRMS (ESI) m/z calcd for C 19 H 14 Cl 2 O (M+H) + 321.0789, found 321.0788. 2-Butyl-1,2-diphenyl-1H-indazol-3(2H)-one (2y). The reaction of -butyl-2- phenylamino-benzamide (1y, 0.2 mmol, 53.6 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 23 mg (41%) of 2y as solid; m.p.:58-59 o C; 1 H MR (CDCl 3, 400 MHz): = 7.90 (d, J = 8.4 Hz, 1H), 7.52-7.16 (m, 7H), 7.02 (d, J = 8.4 Hz, 1H), 3.79 (t, J = 7.2 Hz, 2H), 1.60-1.51 (m, 2H), 1.22 (q, J = 7.2 Hz, 2H), 0.83 (t, J = 7.2 Hz, 3H); 13 C MR (CDCl 3, 100 MHz): = 163.7, 149.6, 140.6, 132.1, 129.8, 128.1, 125.3, 123.9, 122.6, 118.1, 111.8, 42.2, 30.3, 19.7, 13.6 ppm; IR (KBr): max = 3393, 2925, 2860, 1655, 1480, 1455, 1312, 754, 711, 682 cm -1 ; HRMS (ESI) m/z calcd for C 17 H 19 2 O (M+H) + 267.1492, found 267.1492. 2-Hexyl-1,2-diphenyl-1H-indazol-3(2H)-one (2z). The reaction of -hexyl-2- phenylamino-benzamide (1z, 0.2 mmol, 59.2 mg), CuBr (0.04 mmol, 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 30 mg (51%) of 2z as liquid; 1 H MR (CDCl 3, 400 MHz): = 7.90 (d, J = 7.2 Hz, 1H), 7.52-7.16 (m, 7H), 7.02 (d, S10
J = 8.0 Hz, 1H), 3.77 (t, J = 6.6 Hz, 2H), 1.62-1.51 (m, 2H), 1.28-1.12 (m, 6H), 0.84-0.76 (m, 3H); 13 C MR (CDCl 3, 100 MHz): = 163.6, 149.6, 140.7, 132.1, 129.8, 128.1, 125.3, 123.9, 122.5, 118.2, 111.7, 42.5, 31.2, 28.1, 26.1, 22.3, 13.9 ppm; IR (KBr): max = 3476, 3060, 2929, 2859, 1684, 1616, 1593, 1455, 1306, 1284, 1151, 929, 766, 682 cm -1 ; HRMS (ESI) m/z calcd for C 19 H 23 2 O (M+H) + 295.1805, found 295.1804. 1-enyl-2-(4-(phenylethynyl)-phenyl)-1H-indazol-3(2H)-one (3). The reaction of 2-(4-bromo-phenyl)-1-phenyl-1H-indazol-3(2H)-one (2p, 0.2 mmol, 73.0 mg), phenylacetylene (0.4 mmol, 41 mg), CuI (0.01 mmol, 1.9 mg), Pd(P 3 ) 4 (0.01 mmol, 11.6 mg), in Et 3 (2.0 ml) at 90 o C under 2 for 12 hours afforded 3 in 98% (76 mg) yield as solid; 1 H MR (CDCl 3, 400 MHz): = 7.98 (d, J = 7.6 Hz, 1H), 7.65-7.19 (m, 17H); 13 C MR (CDCl 3, 100 MHz): = 162.6, 150.3, 142.3, 135.6, 133.3, 132.1, 131.5, 129.7, 128.3, 128.2, 127.6, 124.5, 124.0, 123.6, 123.0, 122.6, 120.4, 118.1, 112.4, 89.7, 88.8 ppm; HRMS (ESI) m/z calcd for C 27 H 19 2 O (M+H) + 387.1492, found 387.1492. References 1) F. Cabrera-Rivera, J. Escalantea, H. Morales-Rojasa and D. Ziglerb, otochem. otobio, A: Chem. 2014, 294, 31. 2) D. Hellwinkel and P. Ittemann, Chem. Ber. 1986, 119, 3165. 3) A. Correa, I. Tellitu, E. Domínguez and R. SanMartin, J. Org. Chem. 2006, 71, 3501. S11
1 H MR and 13 C MR Spectra of Compounds 2 and 3 O 2a S12
2a S13
Me 2b S14
Me 2b S15
2c Me S16
2c Me S17
2d Me S18
2d Me S19
2e OMe S20
2e OMe S21
2f OMe S22
2f OMe S23
F 2g S24
F 2g S25
2h F S26
2h F S27
2i F S28
2i F S29
2j Cl S30
2j Cl S31
Me 2k S32
Me 2k S33
Me 2l S34
Me 2l S35
2m OMe S36
2m OMe S37
2n F S38
2n F S39
2o Cl S40
2o Cl S41
Br 2p S42
Br 2p S43
Cl 2q S44
Cl 2q S45
Cl 2r O S46
Cl 2r O S47
Br 2s O S48
Br 2s O S49
2 2t O S50
2 2t O S51
Me 2u S52
Me 2u S53
Me 2v O S54
Me 2v O S55
F 2w O S56
F 2w O S57
Cl O 2x S58
Cl O 2x S59
Me 2y S60
Me 2y S61
Me 2z S62
Me 2z S63
3 S64
3 S65