1,2,3-Triazole N(2)-Coordinated C-O Coupling: Access Toortho Aryloxyl 1,4-Diaryl

1,2,3-Triazole N(2)-Coordinated C-O Coupling: Access Toortho Aryloxyl 1,4-Diaryl

SUPPORTING INFORMATION

1,2,3-Triazole N(2)-coordinated C-O coupling: Access toortho aryloxyl 1,4-diaryl 1,2,3-triazoles

YAOWEN LIU, FEN ZHAO, HAOHUA ZHOU, KAI XIE and YUBO JIANG*

Faculty of science, Kunming University of Science and Technology, Kunming, 650500, China

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*For correspondence

Table of Contents

  1. General information……………………………………….…….……………S2
  2. General Procedures for the N(2)-coordinated C-O coupling…………………S2
  3. Spectral data of the compounds………………………………………………S2
  4. 1H and 13C NMR spectra of the compounds……………………………….…S6
  1. General Information

All the reactions were conducted using CEM Discover-SP microwave instrument. 1H and 13C NMR spectra were recorded with a MercuryPlus 300 (300 MHz) or a Bruker ACF400 spectrometer (400 MHz) in d6-DMSO or CDCl3 with TMS as an internal standard. All reactions were monitored by TLC with HuanghaiGF 254 silica gel coated plates. Column chromatography was carried out using 300–400 mesh silica gel at medium pressure.Infrared spectra were taken on a Bruker Vertex Series FTIR (KBr) and are reported in reciprocal centimeters (cm–1). Melting points were obtained using a Büchi melting point apparatus and are uncorrected. HRMS spectra were recorded on Waters Micromass Premier Q-TOF spectrometer.

2. General procedure for N(2)-coordinated C-O coupling of 1,4-diaryl 1,2,3-triazole bromides 1 with phenols 2

1, 4-Diary 1,2,3-triazoles1(0.3mmol), phenols 2(0.33mmol),CuI(0.03mmol),X-Phos(0.06mmol), K3PO4(0.6mmol),and PhMe (2mL) were added to a 15 mL pressure tube. Then the tube was sealed with a teflon screwcap and stirred at 100oCfor 24hours. After consumption of 1, 4-diary 1,2,3-triazoles1 monitored by TLC analysis, the mixture was added with H2O(15mL) and extracted with EtOAc (3×15mL). The combined organic layer was washed with brine (3×5mL), dried over Na2SO4 and concentrated under reduced pressure to afford a crude product. Purification by column chromatography on silica gel afforded the desired product3.

  1. Spectral data of the compounds

1-(2-Phenoxyphenyl)-4-phenyl-1H-1,2,3-triazole(3a). White solid,yield 86%, mp 83.0-83.9oC. 1H NMR (400 MHz, CDCl3) δ 8.38 (s, 1H), 7.99 (dd, J = 7.9, 1.6 Hz, 1H), 7.89–7.82 (m, 2H), 7.42 (t, J = 7.7 Hz, 3H), 7.38 – 7.24 (m, 4H), 7.14 (t, J = 7.4 Hz, 1H), 7.09–6.99 (m, 3H). 13C NMR (100 MHz, CDCl3) δ 155.80, 148.54, 147.59, 130.41, 130.06, 129.98, 128.79, 128.49, 128.16, 125.82, 125.60, 124.33, 124.19, 121.30, 119.63, 118.85. IR (KBr): 3141, 2356, 1949, 1658, 1588, 1485, 1402, 1237, 1022, 751, 460cm-1.HRMS (ESI): m/z [M + H+] calcd for C20H16N3O: 314.3288, found 314.3291.

4-Phenyl-1-(2-(o-tolyloxy)phenyl)-1H-1,2,3-triazole(3b). Yellow oil, yield 75%. 1H NMR (400 MHz, CDCl3) δ 8.43 (s, 1H), 7.98 (dd, J = 8.0, 1.7 Hz, 1H), 7.90–7.86 (m, 2H), 7.45–7.41 (m, 2H), 7.36–7.31 (m, 2H), 7.28–7.18 (m, 3H), 7.12 (dt, J = 7.4, 3.7 Hz, 1H), 6.94 (dd, J = 8.0, 1.0 Hz, 1H), 6.85 (dd, J = 8.3, 1.3 Hz, 1H), 2.22 (s, 3H).13C NMR (100 MHz, CDCl3) δ 153.18, 149.09, 147.51, 131.79, 130.47, 129.96, 129.76, 128.81, 128.16, 127.50, 125.82, 125.61, 125.04, 123.26, 121.40, 119.67, 117.48, 114.93, 16.12. IR (KBr): 3743, 3141,2357, 1592, 1491, 1240, 1031, 873, 757, 448cm-1.HRMS (ESI): m/z [M + H+] calcd for C21H18N3O: 328.1444, found: 328.1441.

4-Phenyl-1-(2-(m-tolyloxy)phenyl)-1H-1,2,3-triazole(3c). Light yellow oil, yield 89%. 1H NMR (400 MHz, CDCl3) δ 8.39 (s, 1H), 7.99 (dd, J = 8.0, 1.7 Hz, 1H), 7.88–7.85 (m, 2H), 7.42 (dd, J = 8.0, 6.8 Hz, 2H), 7.39 – 7.30 (m, 2H), 7.29 – 7.20 (m, 2H), 7.05 (dd, J = 8.3, 1.3 Hz, 1H), 6.96 (d, J = 7.7 Hz, 1H), 6.83 (d, J = 7.6 Hz, 2H), 2.32 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 155.79, 148.67, 147.60, 140.42, 130.48, 129.93, 129.76, 128.80, 128.45, 128.16, 125.86, 125.52, 125.18, 124.81, 124.05, 121.34, 120.48, 119.63, 119.57, 115.91, 21.33. IR (KBr): 3741, 3163, 2357, 1585, 1471, 1253, 1022, 760, 688, 447cm-1. HRMS (ESI): m/z [M + H+] calcd for C21H18N3O: 328.1444, found: 328.1448.

4-Phenyl-1-(2-(p-tolyloxy)phenyl)-1H-1,2,3-triazole(3d). Yellow oil, yield 91%. 1H NMR (400 MHz, CDCl3) δ 8.49 (s, 1H), 8.05 (d, J = 7.9 Hz, 1H), 7.96 (d, J = 7.3 Hz, 2H), 7.50 (t, J = 7.4 Hz, 2H), 7.42 (dd, J = 6.1, 4.8 Hz, 2H), 7.32 (t, J = 7.7 Hz, 1H), 7.23 (d, J = 8.0 Hz, 2H), 7.09 (d, J = 8.2 Hz, 1H), 7.00 (d, J = 8.1 Hz, 2H), 2.40 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 153.29, 148.95, 147.46, 134.03, 130.48, 129.83, 128.72, 128.07, 125.75, 125.38, 123.69, 121.32, 118.96, 20.62. IR (KBr): 3433, 2928, 1598, 1502, 1471, 1416, 1385, 1244, 1029, 765, 695, 501 cm-1. HRMS (ESI): m/z [M + H+] calcd for C21H18N3O: 328.1444, found 328.1442.

1-(2-(4-Chlorophenoxy)phenyl)-4-phenyl-1H-1,2,3-triazole(3e).Yellow oil, yield 78%. 1H NMR (400 MHz, CDCl3) δ 8.24 (s, 1H), 7.87 (dd, J = 8.0, 1.5 Hz, 1H), 7.77 (d, J = 7.3 Hz, 2H), 7.33 (ddd, J = 7.5, 6.6, 2.6 Hz, 3H), 7.29 – 7.14 (m, 4H), 6.97 (dd, J = 8.2, 1.1 Hz, 1H), 6.91 – 6.81 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 154.44, 148.26, 147.63, 130.23, 130.19, 130.03, 129.42, 128.81, 128.57, 128.24, 125.85, 125.78, 124.64, 121.27, 119.96, 119.70. IR (KBr): 3429, 3069, 2926, 1591, 1500, 1250, 1089, 1026, 835, 759, 697, 496 cm-1.HRMS (ESI): m/z [M + H+] calcd for C20H15ClN3O: 348.0898, found 348.0899.

1-(2-(2-(Tert-butyl)phenoxy)phenyl)-4-phenyl-1H-1,2,3-triazole(3f). Yellow oil, yield 69%. 1H NMR (400 MHz, CDCl3) δ 8.38 (s, 1H), 7.98 (dd, J = 8.0, 1.6 Hz, 1H), 7.86 – 7.78 (m, 2H), 7.45 – 7.36 (m, 4H), 7.34 – 7.29 (m, 1H), 7.26 (dt, J = 7.8, 1.9 Hz, 1H), 7.19 – 7.15 (m, 1H), 7.12 (dd, J = 7.6, 1.4 Hz, 1H), 6.97 (dd, J = 8.3, 1.0 Hz, 1H), 6.84 (dd, J = 7.9, 1.3 Hz, 1H), 1.38 (s, 9H). 13C NMR (100 MHz, CDCl3) δ 154.70, 149.26, 147.56, 141.08, 130.40, 130.18, 128.82, 128.61, 128.16, 127.62, 127.53, 125.75, 125.73, 124.32, 123.64, 121.25, 120.02, 119.31, 34.68, 30.20. IR (KBr): 3427, 3175, 2969, 1598, 1494, 1250, 1187, 1135, 1027, 875, 765, 526, 501 cm-1. HRMS (ESI): m/z [M + H+] calcd for C24H24N3O: 370.1914, found 370.1916.

4-(p-Tolyl)-1-(2-(o-tolyloxy)phenyl)-1H-1,2,3-triazole(3g). White solid,yield 85%, mp 158.6-159.2 oC. 1H NMR (400 MHz, CDCl3) δ 8.39 (s, 1H), 7.98 (dd, J = 8.0, 1.6 Hz, 1H), 7.77 (d, J = 8.1 Hz, 2H), 7.33 (td, J = 8.3, 1.7 Hz, 1H), 7.30 – 7.16 (m, 5H), 7.11 (dd, J = 7.4, 6.5 Hz, 1H), 6.94 (d, J = 7.9 Hz, 1H), 6.85 (dd, J = 8.3, 1.1 Hz, 1H), 2.38 (s, 3H), 2.22 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 153.18, 149.04, 147.58, 138.01, 131.77, 129.89, 129.77, 129.50, 127.61, 127.50, 125.71, 125.61, 125.01, 123.26, 121.05, 119.67, 117.45, 114.90, 21.29, 16.15. IR (KBr): 3424, 3161, 2922, 2859, 1591, 1496, 1254, 1184, 1115, 1039, 875, 814, 755, 526, 456 cm-1. HRMS (ESI): m/z [M + H+] calcd for C22H20N3O: 342.1601, found 342.1605.

4-(p-Tolyl)-1-(2-(m-tolyloxy)phenyl)-1H-1,2,3-triazole(3h). Yellow oil, yield 93%. 1H NMR (400 MHz, CDCl3) δ 8.34 (s, 1H), 7.99 (dd, J = 8.0, 1.6 Hz, 1H), 7.75 (d, J = 8.1 Hz, 2H), 7.41 – 7.35 (m, 1H), 7.31 – 7.19 (m, 4H), 7.05 (dd, J = 8.3, 1.2 Hz, 1H), 6.95 (d, J = 7.5 Hz, 1H), 6.82 (d, J = 7.7 Hz, 2H), 2.38 (s, 3H), 2.32 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 155.81, 148.63, 147.67, 140.40, 138.01, 129.86, 129.74, 129.48, 127.63, 125.76, 125.53, 125.14, 124.04, 120.99, 119.63, 119.56, 115.90, 112.31, 21.33, 21.28. IR (KBr): 3392, 3043, 2928, 2861, 1594, 1493, 1378, 1254, 1153, 1049, 1000, 931, 768, 691, 528, 446 cm-1.HRMS (ESI): m/z [M + H+] calcd for C22H20N3O: 342.1601; found 342.1598.

1-(2-(4-Chlorophenoxy)phenyl)-4-(p-tolyl)-1H-1,2,3-triazole(3i). Yellow oil, yield 82%. 1H NMR (400 MHz, CDCl3) δ 7.80 (d, J = 7.7 Hz, 1H), 7.30 (t, J = 7.4 Hz, 1H), 7.17 (d, J = 8.9 Hz, 2H), 7.13 – 7.08 (m, 2H), 7.00 (d, J = 8.7 Hz, 2H), 6.93 (d, J = 8.2 Hz, 1H), 6.82 (d, J = 8.9 Hz, 2H), 6.74 (d, J = 8.7 Hz, 2H), 2.25 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 155.20, 154.28, 148.45, 138.42, 130.44, 130.00, 129.58, 129.46, 129.14, 125.83, 125.71, 124.55, 124.44, 119.99, 119.57, 116.89,21.20. IR (KBr): 3389, 2929, 2863, 1591, 1468, 1240, 1092, 826, 756, 642, 502 cm-1. HRMS (ESI): m/z [M + H+] calcd for C21H17ClN3O: 362.1055, found 362.1058.

4-(2-Fluorophenyl)-1-(2-(p-tolyloxy)phenyl)-1H-1,2,3-triazole(3j). Yellow oil, yield 76%. 1H NMR (400 MHz, CDCl3) δ 8.59 (d, J = 3.6 Hz, 1H), 8.38 (td, J = 7.5, 1.7 Hz, 1H), 7.98 (dd, J = 7.9, 1.2 Hz, 1H), 7.45 – 7.39 (m, 1H), 7.37 – 7.26 (m, 3H), 7.16 (t, J = 7.6 Hz, 3H), 7.07 (d, J = 8.2 Hz, 1H), 6.95 (d, J = 8.4 Hz, 2H), 2.35 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 160.44, 157.97, 153.42, 149.16, 141.01, 133.93, 130.46, 130.01, 129.24, 128.21, 127.90, 125.67, 124.52, 123.77, 119.21, 118.83, 115.74, 115.53, 20.65. IR (KBr): 3436, 1594, 1557, 1468, 1414, 1250, 1031, 871, 818, 693, 505 cm-1. HRMS (ESI): m/z [M + H+] calcd for C21H17FN3O: 346.1350, found 346.1348.

4-(2-Methoxyphenyl)-1-(2-(p-tolyloxy)phenyl)-1H-1,2,3-triazole(3k). Yellow oil, yield 92%. 1H NMR (400 MHz, CDCl3) δ 8.67 (s, 1H), 8.47 – 8.39 (m, 1H), 8.08 – 7.95 (m, 1H), 7.44 – 7.38 (m, 1H), 7.32 (dt, J = 14.0, 4.2 Hz, 2H), 7.20 – 7.08 (m, 4H), 6.96 (dd, J = 11.8, 8.6 Hz, 3H), 3.85 (s, 3H), 2.35 (s, 3H).13C NMR (100 MHz, CDCl3) δ 155.59, 153.80, 148.64, 142.87, 133.46, 130.32, 129.71, 128.80, 127.54, 125.56, 124.74, 123.93, 120.82, 119.69, 119.15, 118.27, 115.27, 110.72, 55.11, 20.53. IR (KBr): 3430, 2932, 2847, 1596, 1500, 1461, 1245, 1205, 1117, 1080, 1030, 870, 819, 753, 500 cm-1. HRMS (ESI): m/z [M + H+] calcd for C22H19N3O2: 3578.1550, found 358.1554.

4-(Thiophen-3-yl)-1-(2-(p-tolyloxy)phenyl)-1H-1,2,3-triazole(3l). White solid, yield 81%, mp 102.7-103.3 oC. 1H NMR (400 MHz, CDCl3) δ 8.34 (s, 1H), 7.99 (dd, J = 8.0, 1.5 Hz, 1H), 7.75 (d, J = 2.0 Hz, 1H), 7.51 (d, J = 4.4 Hz, 1H), 7.38 (ddd, J = 10.0, 6.7, 2.3 Hz, 2H), 7.31 – 7.25 (m, 1H), 7.18 (d, J = 8.3 Hz, 2H), 7.03 (dd, J = 8.3, 1.0 Hz, 1H), 6.95 (d, J = 8.5 Hz, 2H), 2.35 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 153.28, 148.99, 143.68, 134.08, 131.56, 130.50, 129.85, 128.02, 126.21, 125.84, 125.42, 123.69, 121.21, 119.02, 118.93, 115.23, 20.65. IR (KBr): 3432, 3139, 3065, 2925, 1591, 1501, 1469, 1250, 1108, 1033, 866, 825, 755, 620, 502 cm-1. HRMS (ESI): m/z [M + H+] calcd for C19H16N3OS: 334.1009, found 334.1006.

2-(1-(2-(p-Tolyloxy)phenyl)-1H-1,2,3-triazol-4-yl)pyridine(3m). White solid, yield 73%, mp 86.8-87.6 oC. 1H NMR (400 MHz, CDCl3) δ 8.70 (s, 1H), 8.47 (d, J = 4.2 Hz, 1H), 8.13 (d, J = 7.9 Hz, 1H), 7.85 (dd, J = 7.9, 1.4 Hz, 1H), 7.66 (td, J = 7.8, 1.5 Hz, 1H), 7.28 – 7.19 (m, 1H), 7.15 – 7.07 (m, 2H), 7.03 (d, J = 8.3 Hz, 2H), 6.84 (dd, J = 16.5, 8.4 Hz, 3H), 2.20 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 153.01, 150.11, 149.52, 149.27, 147.97, 136.74, 134.11, 130.39, 129.92, 127.69, 125.46, 123.73, 123.28, 122.71, 120.32, 119.48, 118.36, 20.60. IR (KBr): 3442, 3211, 2923, 1599, 1503, 1468, 1405, 1250, 1159, 1019, 871, 834, 753, 501 cm-1. HRMS (ESI): m/z [M + H+] calcd for C20H17N4O: 329.1397, found 32.1394.

4-(3-Bromophenyl)-1-(2-(p-tolyloxy)phenyl)-1H-1,2,3-triazole(3n). Yellow oil, yield 81%. 1H NMR (400 MHz, CDCl3) δ 8.34 (s, 1H), 7.94 (t, J = 1.6 Hz, 1H), 7.90 (dd, J = 8.0, 1.5 Hz, 1H), 7.73 (d, J = 7.8 Hz, 1H), 7.38 (d, J = 7.9 Hz, 1H), 7.29 (dd, J = 11.3, 4.5 Hz, 1H), 7.25 – 7.14 (m, 2H), 7.09 (d, J = 8.3 Hz, 2H), 6.93 (dd, J = 8.3, 0.9 Hz, 1H), 6.86 (d, J = 8.5 Hz, 2H), 2.26 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 153.21, 149.12, 146.13, 134.28, 132.57, 131.04, 130.58, 130.35, 130.04, 128.72, 127.87, 125.44, 124.37, 123.71, 122.88, 121.73, 119.19, 118.86, 20.71. IR (KBr): 3431, 2928, 1598, 1502, 1471, 1416, 1244, 1029, 871, 830, 696, 501 cm-1. HRMS (ESI): m/z [M + H+] calcd for C21H17BrN3O: 406.0550, found 406. 0551.

1-(4-Bromo-2-(p-tolyloxy)phenyl)-4-(p-tolyl)-1H-1,2,3-triazole(3o). White solid, yield 71%, mp 138.5-139.3oC. 1H NMR (400 MHz, CDCl3) δ 8.40 (s, 1H), 7.90 (d, J = 8.6 Hz, 1H), 7.79 (d, J = 8.0 Hz, 2H), 7.39 (dd, J = 8.6, 1.8 Hz, 1H), 7.30 – 7.20 (m, 4H), 7.13 (d, J = 1.7 Hz, 1H), 6.98 (d, J = 8.4 Hz, 2H), 2.41 (s, 3H), 2.39 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 152.43, 149.72, 147.77, 138.06, 134.94, 130.77, 129.45, 127.39, 126.93, 126.60, 126.37, 125.70, 122.75, 121.39, 120.78, 119.48, 21.25, 20.72. IR (KBr): 3431, 3100, 2922, 1583, 1501, 1438, 1387, 1235, 1091, 1030, 985, 891, 818, 509 cm-1. HRMS (ESI): m/z [M + H+] calcd for C22H19BrN3O:420.0706, found 420.0708.

1-(5-Bromo-2-(p-tolyloxy)phenyl)-4-(o-tolyl)-1H-1,2,3-triazole(3p).Yellow oil, yield 68%. 1H NMR (400 MHz, CDCl3) δ 8.34 (s, 1H), 8.25 (d, J = 2.3 Hz, 1H), 7.88 – 7.78 (m, 1H), 7.50 (dd, J = 8.8, 2.3 Hz, 1H), 7.35 – 7.27 (m, 3H), 7.19 (d, J = 8.4 Hz, 2H), 6.95 (dd, J = 11.4, 8.7 Hz, 3H), 2.47 (s, 3H), 2.36 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 153.06, 147.70, 147.05, 135.64, 134.34, 132.54, 130.83, 130.63, 129.45, 129.13, 128.96, 128.26, 128.03, 126.03, 123.30, 120.76, 118.54, 116.03, 21.22, 20.64. IR (KBr): 3421, 2925, 2863, 1593, 1500, 1380, 1248, 1085, 1027, 875, 812, 758, 504 cm-1. HRMS (ESI): m/z [M + H+] calcd for C22H18BrN3O:420.0706, found420.0705.

  1. 1H and 13C NMR spectra of the compounds

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