Copper-Catalyzed Oxidative Dehydrogenative N-N Bond. Formation for the Synthesis of N,N -Diarylindazol-3-ones

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1 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 , China; College of Chemistry, Xiangtan University, Xiangtan , China *Corresponding author s 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

2 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 = 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

3 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.: o C; 1 H MR (CDCl 3, 400 MHz): = 7.95 (d, J = 8.0 Hz, 1H), (m, 2H), 7.50 (t, J = 7.6 Hz, 1H), (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, 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) , found 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.: o C; 1 H MR (CDCl 3, 400 MHz): = 8.00 (d, J = 8.0 Hz, 1H), (m, 3H), (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) , found 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.: o C; 1 H MR (CDCl 3, 400 MHz): = 7.97 (d, J = 8.0 Hz, 1H), (m, 2H), (m, 1H), (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) , found enyl-1-p-tolyl-1H-indazol-3(2H)-one (2d). The reaction of -phenyl-2-p- S3

4 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.: o C; 1 H MR (CDCl 3, 400 MHz): = 7.97 (d, J = 8.0 Hz, 1H), (m, 2H), 7.51 (t, J = 7.6 Hz, 1H), (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) , found (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.: o C; 1 H MR (CDCl 3, 400 MHz): = 7.97 (d, J = 8.8 Hz, 1H), (m, 2H), 7.53 (t, J = 7.6 Hz, 1H), (m, 6H), (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) , found (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.: o C; 1 H MR (CDCl 3, 400 MHz): = 7.97 (d, J = 8.4 Hz, 1H), (m, 2H), 7.51 (t, J = 7.6 Hz, 1H), (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) , found (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

5 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.: o C; 1 H MR (CDCl 3, 400 MHz): = 7.99 (d, J = 8.0 Hz, 1H), (m, 3H), (m, 9H); 13 C MR (CDCl 3, 100 MHz): = 162.5, (d, J C-F = Hz), 149.9, 135.4, 133.2, (d, J C-F = 7.6 Hz), 128.9, (d, J C-F = 29.3 Hz), (d, J C-F = 3.7 Hz), 124.4, 123.5,123.1, 118.4, (d, J C-F = 19.1 Hz), (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) , found (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.: o C; 1 H MR (CDCl 3, 400 MHz): = 7.98 (d, J = 8.4 Hz, 1H), (m, 3H), (m, 9H); 13 C MR (CDCl 3, 100 MHz): = (d, J C-F = Hz), 162.8, 149.8, (d, J C-F = 8.8 Hz), 135.7, 133.3, (d, J C-F = 9.2 Hz), 128.9, 126.1, 124.6, 123.8, 123.0, (d, J C-F = 3.3 Hz), 118.3, (d, J C-F = 20.8 Hz), 112.2, (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) , found (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.: o C; 1 H MR (CDCl 3, 400 MHz): = 7.98 (d, J = 8.0 Hz, 1H), (m, 3H), (m, 9H); 13 C MR (CDCl 3, 100 MHz): = (d, J C-F = Hz), 162.5, 150.4, (d, J C-F = 2.7 Hz), 135.5, 133.1, 128.9, (d, J C-F = 8.6 Hz), 126.1, 124.5, 123.6, 123.4, 118.2, (d, J C-F = 22.8 Hz), 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) , found (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

6 5.7 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 63 mg (98%) of 2j as solid; m.p.: o C; 1 H MR (CDCl 3, 400 MHz): = 7.98 (d, J = 7.6 Hz, 1H), (m, 3H), (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, 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) , found 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.: o C; 1 H MR (CDCl 3, 400 MHz): = 7.97 (d, J = 8.0 Hz, 1H), (m, 1H ), 7.47 (s, 1H), (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) , found 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.: o C; 1 H MR (CDCl 3, 400 MHz): = 7.97 (d, J = 7.2 Hz, 1H), (m, 3H ), (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) , found (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.: o C; 1 H MR (CDCl 3, 400 MHz): = 7.97 (d, J = 7.2 Hz, 1H), (m, 9H), 7.17 (d, J = 8.0 Hz, 1H), 6.87 (d, J = 6.4 Hz, 2H), S6

7 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.: o C; 1 H MR (CDCl 3, 400 MHz): = 7.97 (d, J = 8.4 Hz, 1H), (m, 3H), (m, 6H), 7.19 (d, J = 9.2 Hz, 1H), (m, 2H) ; 13 C MR (CDCl 3, 100 MHz): = 161.6, (d, J C-F = Hz), 150.1, 141.9, 133.1, 131.7, 129.6, 127.6, (d, J C-F = 7.9 Hz), 124.4, 124.2, 123.5, 117.9, (d, J C-F = 22.4 Hz), 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) , found (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.: o C; 1 H MR (CDCl 3, 400 MHz): = 7.96 (d, J = 6.4 Hz, 1H), (m, 3H), (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, 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) , found (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.: o C; 1 H MR (CDCl 3, 400 MHz): = 7.96 (d, J = 7.6 Hz, 1H), (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

8 123.6, 119.1, 118.0, 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) +, , found 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.: o C; 1 H MR (CDCl 3, 400 MHz): = 7.89 (d, J = 8.4 Hz, 1H), (m, 2H), (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, , , 123.3, 116.6, 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) , found 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.: o C; 1 H MR (CDCl 3, 400 MHz): = 7.94 (s, 1H), (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, 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) , found 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.: o C; 1 H MR (CDCl 3, 400 MHz): = 8.10 (d, J = 1.2 Hz, 1H), (m, 3H), (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, 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) , found S8

9 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.: o C; 1 H MR (CDCl 3, 400 MHz): = 8.91 (s, 1H), 8.39 (d, J = 9.2 Hz, 1H), (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, 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) , found 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.: o C; 1 H MR (CDCl 3, 400 MHz): = 7.86 (d, J = 7.2 Hz, 1H), (m, 2H), (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) , found 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.: o C; 1 H MR (CDCl 3, 400 MHz): = 7.68 (s, 1H), (m, 2H), (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) , found 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

10 mg), in DMSO (1.0 ml) under typical procedure for 4 h afforded 49 mg (81%) of 2w as solid; m.p.: o C; 1 H MR (CDCl 3, 400 MHz): = (m, 1H), (m, 2H), (m, 10H); 13 C MR (CDCl 3, 100 MHz): = (d, J C-F = Hz), 162.0, (d, J C-F = 12.8 Hz), 141.6, 135.7, 129.8, 128.9, 127.8, (d, J C-F = 11 Hz), 126.1, 124.1, 123.2, 114.3, (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) , found 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.: o C; 1 H MR (CDCl 3, 400 MHz): = (m, 2H), (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, 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) , found 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), (m, 7H), 7.02 (d, J = 8.4 Hz, 1H), 3.79 (t, J = 7.2 Hz, 2H), (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) , found 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), (m, 7H), 7.02 (d, S10

11 J = 8.0 Hz, 1H), 3.77 (t, J = 6.6 Hz, 2H), (m, 2H), (m, 6H), (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) , found 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), (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) , found 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, ) A. Correa, I. Tellitu, E. Domínguez and R. SanMartin, J. Org. Chem. 2006, 71, S11

12 1 H MR and 13 C MR Spectra of Compounds 2 and 3 O 2a S12

13 2a S13

14 Me 2b S14

15 Me 2b S15

16 2c Me S16

17 2c Me S17

18 2d Me S18

19 2d Me S19

20 2e OMe S20

21 2e OMe S21

22 2f OMe S22

23 2f OMe S23

24 F 2g S24

25 F 2g S25

26 2h F S26

27 2h F S27

28 2i F S28

29 2i F S29

30 2j Cl S30

31 2j Cl S31

32 Me 2k S32

33 Me 2k S33

34 Me 2l S34

35 Me 2l S35

36 2m OMe S36

37 2m OMe S37

38 2n F S38

39 2n F S39

40 2o Cl S40

41 2o Cl S41

42 Br 2p S42

43 Br 2p S43

44 Cl 2q S44

45 Cl 2q S45

46 Cl 2r O S46

47 Cl 2r O S47

48 Br 2s O S48

49 Br 2s O S49

50 2 2t O S50

51 2 2t O S51

52 Me 2u S52

53 Me 2u S53

54 Me 2v O S54

55 Me 2v O S55

56 F 2w O S56

57 F 2w O S57

58 Cl O 2x S58

59 Cl O 2x S59

60 Me 2y S60

61 Me 2y S61

62 Me 2z S62

63 Me 2z S63

64 3 S64

65 3 S65