The Journal of Organic Chemistry
ARTICLE
1-Phenoxy-3-(4-phenyl-1H-1,2,3-triazol-1-yl)propan-2-ol14b
138 (18), 137 (10), 117 (23), 116 (100), 102 (18), 91 (15), 89 (23);
HRMS (EI) m/z calcd for C16H14ClN3O 299.0825, found 299.0830.
(1S*,2S*)-1,2-Diphenyl-2-(4-phenyl-1H-1,2,3-triazol-1-yl)-
ethanol (3ia): White solid; Rf 0.63 (hexane/EtOAc, 1:1); mp
209.0ꢀ212.0 °C; 1H NMR (300 MHz, DMSO-d6) δ 8.96 (s, 1H;
NCHdC), 7.87 (d, 3J(H,H) = 7.2 Hz, 2H; ArꢀH), 7.49ꢀ7.39 (m, 4H;
ArꢀH), 7.37ꢀ7.30 (m, 3H; ArꢀH), 7.25ꢀ7.17 (m, 6H; ArꢀH), 6.04
(d, 3J(H,H) = 4.8 Hz, 1H; NCHCH), 5.97 (d, 3J(H,H) = 8.7 Hz, 1H;
1
(3ca): Pale yellow solid; mp 125.0ꢀ127.0 °C; H NMR (400 MHz,
CD3CN) δ 8.15 (s, 1H), 7.86 (d, 3J(H,H) = 7.5 Hz, 2H; ArꢀH), 7.44 (td,
4
3J(H,H) = 7.5 Hz, J(H,H) = 1.6 Hz, 2H; ArꢀH), 7.40ꢀ7.17 (m, 3H;
ArꢀH), 7.08ꢀ6.72 (m, 3H; ArꢀH), 4.66 (dd, 2J (H,H) = 14.1 Hz, 3J (H,
H) = 3.8 Hz, 1H; CHHN), 4.52 (dd, 2J(H,H) = 14.1, 3J (H,H) = 7.6 Hz,
1H; CHHN), 4.43ꢀ4.27 (m, 1H; CHO), 4.09ꢀ3.87 (m, 2H; CH2O), 3.75
(d, 3J(H,H) = 5.4 Hz, 1H; OH); 13C NMR (100 MHz, CD3CN) δ 159.6
(NCCH), 147.8, 132.1 (2 ꢁ ArC), 130.5, 129.9, 128.9, 126.3, 122.8, 122.0
(10 ꢁ ArCH), 115.5 (NCCH), 70.1 (CH2O), 69.5 (CHO), 53.9 (CH2N).
(E)-2-Methyl-4-(4-phenyl-1H-1,2,3-triazol-1-yl)but-2-en-1-ol26
[(E)-3da]: Yellow oil; 1H NMR (400 MHz, CDCl3) δ 7.74ꢀ7.66 (m, 3H;
2 ꢁ ArꢀH, CHN), 7.35 (t, 3J(H,H) = 7.2 Hz, 2H; ArꢀH), 7.31ꢀ7.23
(m, 1H; ArꢀH), 5.70 (t, 3J(H,H) = 7.6 Hz, 1H; CHdCCH3), 4.92 (d,
3J(H,H) = 7.2 Hz, 2H; CH2N), 4.06 (br s, 2H; CH2O), 1.67 (s, 3H; CH3);
13C NMR (100 MHz, CDCl3) δ 147.5 (NCCH), 142.3 (CH3CdCH),
130.2 (ArC), 128.6, 127.9, 125.4 (5 ꢁ ArCH), 119.4 (NCCH), 115.9
(CHdCCH3), 66.5 (CH2O), 47.4 (CH2N), 13.7 (CH3).
OH), 5.58 (dd, 3J(H,H) = 8.7 Hz, 3J(H,H) = 4.8 Hz, 1H; CHO); 13
C
NMR (75 MHz, DMSO-d6) δ 146.0 (NCCH), 141.6, 137.2, 130.9 (3 ꢁ
ArC), 128.9, 128.4, 128.2, 128.0, 127.9, 127.8, 127.5, 127.2, 125.1 (15 ꢁ
ArCH), 121.2 (NCCH), 74.3 (CHO), 70.5 (NCHCH); IR (neat) ν~ 697,
750, 771, 1048, 1207, 1231, 1435, 1455, 2854, 2923, 3029, 3082, 3429;
MS (70 eV) m/z (%) 341 (0.3) [M+], 236 (15), 235 (85), 207 (20), 206
(100), 180 (11), 179 (12), 178 (21), 130 (10), 116 (16), 107 (10), 105
(20), 102 (23), 91 (10), 79 (15), 77 (28); HRMS (EI) m/z calcd for
C22H19N3O 341.1528, C15H13N3 235.1109, found 235.1136.
(1S*,2R*)-1,2-Diphenyl-2-(4-phenyl-1H-1,2,3-triazol-1-yl)-
ethanol (3ja): White solid; Rf 0.68 (hexane/EtOAc, 1:1); mp 206.5ꢀ
211.0 °C; 1H NMR (300 MHz, DMSO-d6) δ 8.71 (s, 1H; NCHdC), 7.72
(d, 3J(H,H) = 8.5 Hz, 2H; ArꢀH), 7.66 (d, 3J(H,H) = 8.5 Hz, 2H; ArꢀH),
7.44ꢀ7.12 (m, 11H; ArꢀH), 5.98 (d, 3J(H,H) = 4.8 Hz, 1H; NCHCH),
5.89 (d, 3J(H,H) = 9.0 Hz, 1H; OH), 5.54 (dd, 3J(H,H) = 9.0 Hz, 3J(H,
H) = 4.8 Hz, 1H; CHO); 13C NMR (75 MHz, DMSO-d6) δ 146.3
(NCCH), 142.3, 137.9, 130.9 (3 ꢁ ArC), 129.2, 128.9, 128.6, 128.4, 128.2,
128.1, 127.9, 127.2, 125.3 (15 ꢁ ArCH), 121.1 (NCCH), 74.0 (CHO),
69.8 (NCHCH); IR (neat) ~ν 701, 746, 766, 1451, 2850, 2919, 3078, 3123,
3421; MS (70 eV) m/z (%) 341 (0.3) [M+], 236 (15), 235 (89), 207 (19),
206 (100), 179 (10), 178 (20), 130 (10), 116 (14), 107 (11), 105 (21), 102
(22), 79 (14), 77 (26); HRMS (EI) m/z calcd for C22H19N3O 341.1528,
C15H13N3 235.1109, found 235.1092.
(Z)-2-Methyl-4-(4-phenyl-1H-1,2,3-triazol-1-yl)but-2-en-1-ol26
1
[(Z)-3da]: Yellow oil; H NMR (400 MHz, CDCl3) δ 7.76 (s, 1H;
CHN), 7.74ꢀ7.66 (m, 2H; ArꢀH), 7.39ꢀ7.31 (m, 2H; ArꢀH),
7.31ꢀ7.23 (m, 1H; ArꢀH), 5.45 (t, 3J(H,H) = 7.5 Hz, 1H; CHdCCH3),
5.01 (d, 3J(H,H) = 7.5 Hz, 2H; CH2N), 4.26 (br s, 2H; CH2O), 1.77
(s, 3H; CH3); 13C NMR (100 MHz, CDCl3) δ 147.5 (NCCH), 142.5
(CH3CdCH), 130.2 (ArC), 128.6, 127.9, 125.4 (5 ꢁ ArCH), 119.7,
119.2 (NCCH, CHdCCH3), 60.9 (CH2O), 47.2 (CH2N), 21.5 (CH3).
2-(4-Phenyl-1H-1,2,3-triazol-1-yl)cyclohexanol13a,30e (3ea):
1
White solid; mp 167.8ꢀ171.8 °C; H NMR (300 MHz, DMSO-d6) δ
8.58 (s, 1H; NCHdC), 7.85 (d, 3J(H,H) = 7.5 Hz, 2H; ArꢀH), 7.45 (t,
3J(H,H) = 7.5 Hz, 2H; ArꢀH), 7.32 (dt, 3J(H,H) = 7.5 Hz, 4J(H,H) =
3
1.2 Hz, 1H; ArꢀH), 5.00 (d, J(H,H) = 5.8 Hz, 1H; OH), 4.24 (ddd,
3J(H,H) = 12.1 Hz, 3J(H,H) = 9.9 Hz, 3J(H,H) = 4.2 Hz, 1H; CH2CHN),
3.85ꢀ3.65 (m, 1H; CHO), 2.13ꢀ1.11 (m, 8H; 4 ꢁ CH2); 13C NMR
(75 MHz, DMSO-d6) δ 145.6 (NCCH), 131.2 (ArC), 128.9, 127.6, 122.9
(5 ꢁ ArCH), 120.5 (NCCH), 71.3 (CHO), 66.0 (CHN), 34.7, 31.9, 24.4,
23.9 (4 ꢁ CH2).
2-(4-Hexyl-1H-1,2,3-triazol-1-yl)-2-phenylethanol13a (3gb):
Pale yellow solid; mp 64.2ꢀ66.3 °C; 1H NMR (300 MHz, CD3CN) δ
7.60 (s, 1H; NCHdC), 7.42ꢀ7.26 (m, 5H; ArꢀH), 5.68 (dd, 3J(H,H) =
8.7 Hz, 3J(H,H) = 4.8 Hz, 1H; CHCH2), 4.40ꢀ4.28, 4.15ꢀ4.03 (2 m,
3
3
2H; CH2), 3.32 (t, J(H,H) = 5.9 Hz, 1H; OH), 2.53 (t, J(H,H) =
7.7 Hz, 2H; CH2CN), 1.69ꢀ1.55 (m, 2H; CH2), 1.37ꢀ1.23 (m, 6H; 3 ꢁ
CH2), 0.81 ppm (t, 3J(H,H) = 7.0 Hz, 3H; CH3); 13C NMR (75 MHz,
CD3CN) δ 152.1 (NCCH), 137.8 (ArC), 129.7, 129.5, 128.4 (5 ꢁ
ArCH), 121.3 (NCCH), 66.7 (CHCH2), 65.3 (CH2O), 35.1, 29.3, 28.9,
26.3, 22.4 (5 ꢁ CH2), 13.9 (CH3).
2-Phenyl-2-(4-phenyl-1H-1,2,3-triazol-1-yl)ethanol13a,c (3ga):
Pale yellow solid; Rf 0.63 (hexane/EtOAc, 3:7); mp 125.0ꢀ127.0 °C;
1H NMR (300 MHz, CD3CN) δ 8.26 (s, 1H; NCHdC), 7.86 (d, 3J(H,
3
H) = 7.3 Hz, 2H; ArꢀH), 7.44 (t, J(H,H) = 7.3 Hz, 2H; ArꢀH),
7.40ꢀ7.31 (m, 6H; ArꢀH), 5.80 (dd, 3J(H,H) = 8.7 Hz, 3J = 4.7 Hz,
1H; CHCH2), 4.46ꢀ4.36, 4.21ꢀ4.12 (2 m, 2H; CH2), 3.40 (t, 3J(H,
H) = 6.5 Hz; 1H, OH); 13C NMR (75 MHz, CD3CN) δ 147.8
(NCCH), 138.1, 131.9 (2 ꢁ ArC), 129.9, 129.8, 129.5, 128.9, 128.2,
126.4 (10 ꢁ ArCH), 121.6 (NCCH), 67.6 (CHCH2), 64.7 (CH2); IR
(neat) ν~ 685, 700, 713, 757, 1026, 1050, 1079, 1148, 1212, 1361, 1436,
1457, 1497, 2939, 3032, 3087, 3123, 3478; MS (70 eV) m/z (%) 265
(22) [M+], 207 (14), 206 (86), 178 (17), 146 (10), 117 (30), 116
(100), 104 (42), 103 (40), 102 (17), 91 (17), 90 (11), 89 (27), 77 (26).
(S)-2-Phenyl-2-(4-phenyl-1H-1,2,3-triazol-1-yl)ethanol
[(S)-3ga]: The same physical and spectroscopic data as described for
racemic 3ga; [α]20D +14.5 (c 1.0, CHCl3); HRMS (EI) m/z calcd for
C16H15N3O 265.1215, found 265.1213.
2-(4-Cyclohexyl-1H-1,2,3-triazol-1-yl)-2-phenylethanol
(3gc): White solid; Rf 0.48 (hexane/EtOAc, 3:7); mp 128.2ꢀ131.8 °C;
1H NMR (300 MHz, CD3CN) δ 7.60 (s, 1H; NCHdC), 7.42ꢀ7.26 (m,
5H; ArꢀH), 5.68 (dd, 3J(H,H) = 8.7 Hz, 3J(H,H) = 4.8 Hz, 1H;
NCHCH2), 4.40ꢀ4.28, 4.15ꢀ4.03 (2 m, 2H; CH2O), 3.32 (t, 3J(H,H) =
5.9 Hz, 1H; OH), 2.77ꢀ2.65 (m, 1H; CH2CHCH2), 1.83ꢀ1.65 (m, 4H;
2 ꢁ CH2CH2CH), 1.46ꢀ1.34 (m, 4H; 2 ꢁ CH2CH2CH), 1.29ꢀ1.18
ppm [m, 2H; (CH2)2CH2(CH2)2]. 13C NMR (75 MHz, CD3CN) δ
153.4 (NCCH), 138.5 (ArC), 129.8, 129.4, 128.2 (5 ꢁ ArCH), 120.9
(NCCH), 65.0 (CH2O), 64.7 (NCHCH2), 36.1 (CH2CHCH2), 33.8,
26.9, 26.8 [(CH2)5]; IR (neat) ~ν 697, 756, 889, 1067, 1448, 2849, 2923,
3061, 3117, 3233; MS (70 eV) m/z (%) 271 (23) [M+], 213 (18), 212
(100), 149 (21), 130 (12), 123 (10), 122 (14), 121 (64), 109 (12), 104
(37), 103 (72), 95 (14), 94 (12), 93 (12), 91 (58), 81 (17), 80 (39), 79
(27), 78 (10), 77 (36), 69 (10), 67 (27), 65 (11), 56 (13), 55 (18), 43
(13), 41 (21); HRMS (EI) m/z calcd for C16H21N3O 271.1685, found
271.1685.
2-(4-Chlorophenyl)-2-(4-phenyl-1H-1,2,3-triazol-1-yl)-
ethanol (3ha): White solid; Rf 0.65 (hexane/EtOAc, 3:7); mp
139.6ꢀ142.1 °C; 1H NMR (300 MHz, CD3CN) δ 8.21 (s, 1 H; NCHd
C), 7.8 (d, 3J(H,H) = 7.5 Hz, 2H; ArꢀH), 7.46ꢀ7.27 (m, 7H; ArꢀH),
5.76 (dd, 3J(H,H) = 9.0 Hz, 3J(H,H) = 3.0 Hz, 1H; CHCH2),
3
4.39ꢀ4.27, 4.17ꢀ4.07 (2 m, 2H; CH2), 3.38 (t, J(H,H) = 6.0 Hz,
2-Phenyl-2-[4-(pyridin-2-yl)-1H-1,2,3-triazol-1-yl]ethanol
(3gd): White solid; Rf 0.26 (hexane/EtOAc, 1:9); mp 112.7ꢀ115.3 °C;
1H NMR (300 MHz, CD3CN) δ 8.52ꢀ8.47 (m, 1H; ArꢀH), 8.35 (s,
1H; OH); 13C NMR (75 MHz, CD3CN) δ 148.0 (NCCH), 137.0,
134.8, 131.9 (3 ꢁ ArC), 130.1, 129.8, 129.7, 129.0, 126.4 (9 ꢁ ArCH),
121.7 (NCCH), 66.8 (CHCH2), 64.6 (CH2); IR (neat) ν~ 691, 730, 764,
819, 1015, 1050, 1092, 1223, 1432, 1460, 1492, 2938, 3085, 3331; MS
(70 eV) m/z (%): 301 (4) [M+ + 2], 299 (13) [M+], 242 (16), 240 (41),
3
1H; NCHdCN), 8.02 (dt, J(H,H) = 7.8 Hz, 4J(H,H) = 1.1 Hz, 1H;
3
4
ArꢀH), 7.76 (td, J(H,H) = 7.8 Hz, J(H,H) = 1.8 Hz, 1H; ArꢀH),
7.34ꢀ7.27 (m, 4H; ArꢀH), 7.21 (ddd, 3J(H,H) = 7.5 Hz, 3J(H,H) = 5.0 Hz,
8403
dx.doi.org/10.1021/jo2016339 |J. Org. Chem. 2011, 76, 8394–8405