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B. Agai, A. Proszenyak, G. Tarkanyi, L. Vida, F. Faigl
FULL PAPER
(210 mmol) and magnesium turnings (205 mmol, 4.94 g) in tetra-
10.5 Hz), 149.5 (2 C),151.3 (d, J ϭ 242.4 Hz), 153.9 ppm. IR (KBr
hydrofuran (300 mL). After 10 h of stirring, 80 mL of saturated pellet): ν˜ ϭ 3136, 1608, 1520, 1276, 1224, 1120, 1032 cmϪ1
.
ammonium chloride solution was poured into the reaction mixture,
the phases were separated, and the tetrahydrofuran solution was
dried and concentrated in vacuo. The residue was treated with hex-
ane or ethyl acetate to give carbinols 4aϪs, 5aϪd,f.
C13H12FNO2 (233.24): calcd. C 66.95, H 5.19, N 6.01; found C
67.09, H 5.27, N 5.90.
(5-Fluoro-2-methylphenyl)(pyridin-4-yl)methanol (4n): Pale-yellow
solid; m.p. 148Ϫ149 °C. 1H NMR (300 MHz, DMSO): δ ϭ 2.20
(2,2-Dimethyl-2,3-dihydrobenzofuran-5-yl)(pyridin-4-yl)methanol (s, 3 H), 5.85 (d, J ϭ 3.9 Hz, 1 H), 6.22 (d, J ϭ 3.9 Hz, 1 H),
1
(4e): White solid; m.p. 181Ϫ182 °C. H NMR (300 MHz, CDCl3):
δ ϭ 1.36 (s, 6 H), 2.94 (s, 2 H), 5.72 (s, 1 H), 5.92 (s, 1 H), 6.64
(m, 1 H), 7.13 (m, 1 H), 7.20 (m, 1 H), 7.29 (m, 1 H), 8.03 (m, 1
6.97Ϫ7.05 (m, 1 H), 7.14Ϫ7.24 (m, 2 H), 7.28Ϫ7.32 (m, 2 H),
8.48Ϫ8.54 (m, 2 H) ppm. 13C NMR (75 MHz, DMSO): δ ϭ 13.5,
65.4, 108.9 (d, J ϭ 20.4 Hz), 109.1 (d, J ϭ 20.5 Hz), 116.5 (2 C),
H), 8.40 (m, 1 H), 8.83 (m, 1 H) ppm. 13C NMR (75 MHz, CDCl3): 126.3, 127.1 (d, J ϭ 7.6 Hz), 139.5 (d, J ϭ 6.9 Hz), 144.9 (2 C),
δ ϭ 27.9 (2 C), 42.3, 72.9, 87.1, 109.7, 122.1 (2 C), 125.6, 127.4,
128.7, 130.1, 149.3 (2 C), 152.5, 158.1 ppm. IR (KBr pellet): ν˜ ϭ
2913, 2430, 1616, 1488, 1445, 1251, 1085 cmϪ1. C16H17NO2
(255.32): calcd. C 75.27, H 6.71, N 5.49; found C 75.02, H 6.92,
N 5.32.
147.5, 155.9 (d, J ϭ 241.0 Hz) ppm. C13H12FNO (217.24): calcd.
C 71.88, H 5.57, N 6.45; found C 71.68, H 5.71, N 6.33.
(3-Ethoxyphenyl)(pyridin-4-yl)methanol (4o): Pale-yellow solid; m.p.
109Ϫ110 °C. 1H NMR (300 MHz, DMSO): δ ϭ 1.30 (t, J ϭ
7.1 Hz, 3 H), 3.99 (q, J ϭ 7.1 Hz, 2 H), 5.67 (d, J ϭ 4.2 Hz, 1 H),
6.11 (d, J ϭ 4.2 Hz, 1 H), 6.75Ϫ6.81 (m, 1 H), 6.91Ϫ6.98 (m, 2
H), 7.17Ϫ7.25 (m, 1 H), 7.36Ϫ7.41 (m, 2 H), 7.45Ϫ7.52 (m, 2 H)
(Pyridin-4-yl)[3-(trifluoromethyl)phenyl]methanol (4f): Pale-yellow
solid; m.p. 113Ϫ114 °C. 1H NMR (300 MHz, CDCl3): δ ϭ 5.04
(br. s, 1 H), 5.81 (s, 1 H), 7.27Ϫ7.32 (m, 2 H), 7.39Ϫ7.56 (m, 3 H), ppm. 13C NMR (75 MHz, DMSO): δ ϭ 14.6, 62.9, 73.0, 112.5,
7.64 (s, 1 H), 8.31Ϫ8.37 (m, 2 H) ppm. 13C NMR (125 MHz,
CDCl3): δ ϭ 74.1, 121.4 (2 C), 123.4 (q, J ϭ 3.8 Hz), 123.9 (q, J ϭ
285.2 Hz), 124.9 (q, J ϭ 3.6 Hz), 129.2, 130.1, 131.1 (q, J ϭ
28.3 Hz), 143.9, 149.4 (2 C), 152.7 ppm. IR (KBr pellet): ν˜ ϭ 3096,
1328, 1184, 1168, 1120, 1072 cmϪ1. C13H10F3NO (253.23): calcd.
C 61.66, H 3.98, N 5.53; found C 61.57, H 3.81, N 5.37.
112.9, 118.4, 121.1 (2 C), 129.4, 146.0, 149.4 (2 C), 154.0,
158.5 ppm. IR (KBr pellet): ν˜ ϭ 3056, 1600, 1448, 1260, 1144, 1048
cmϪ1. C14H15NO2 (229.27): calcd. C 73.45, H 6.67, N 6.29; found
C 73.45, H 6.67, N 6.29.
(3,5-Difluorophenyl)(pyridin-4-yl)methanol (4p): Pale-yellow solid;
1
m.p. 165Ϫ168 °C. H NMR (300 MHz, DMSO): δ ϭ 5.77 (d, J ϭ
(3-Fluorophenyl)(pyridin-4-yl)methanol (4h): Pale-yellow solid; m.p. 4.2 Hz, 1 H), 6.39 (d, J ϭ 4.2 Hz, 1 H), 7.04Ϫ7.18 (m, 3 H),
120Ϫ121 °C. 1H NMR (300 MHz, DMSO): δ ϭ 5.77 (d, J ϭ
4.2 Hz, 1 H), 6.28 (d, J ϭ 4.2 Hz, 1 H), 7.05Ϫ7.10 (m, 1 H),
7.40Ϫ7.45 (m, 2 H), 8.48Ϫ8.54 (m, 2 H) ppm. 13C NMR (75 MHz,
DMSO): δ ϭ 72.0, 102.6 (t, J ϭ 25.7 Hz), 109.2 (dd, J ϭ 9.3, J ϭ
7.21Ϫ7.27 (m, 2 H), 7.32Ϫ7.43 (m, 3 H), 8.48Ϫ8.54 (m, 2 H) ppm. 24.9 Hz, 2 C), 121.2 (2 C), 149.1 (t, J ϭ 8.4 Hz), 149.6 (2 C), 152.9,
13C NMR (75 MHz, DMSO): δ ϭ 72.4 (d, J ϭ 1.6 Hz), 113.0 (d, 162.3 (dd, J ϭ 245.0, J ϭ 12.9 Hz, 2 C) ppm. IR (KBr pellet): ν˜ ϭ
J ϭ 21.7 Hz), 114.0 (d, J ϭ 20.9 Hz), 121.3 (2 C), 122.4 (d, J ϭ
3088, 1624, 1600, 1456, 1304, 1120 cmϪ1. C12H9F2NO (221.21):
2.6 Hz), 130.4 (d, J ϭ 8.1 Hz), 147.4 (d, J ϭ 6.7 Hz), 149.5 (2 C), calcd. C 65.16, H 4.10, N 6.33; found C 65.27, H 4.28, N 6.47.
153.8, 162.2 (d, J ϭ 242.3 Hz) ppm. IR (KBr pellet): ν˜ ϭ 2841,
[3-Methoxy-5-(trifluoromethyl)phenyl](pyridin-4-yl)methanol (4q):
1605, 1448, 1343, 1258, 1134, 1050, 1005 cmϪ1. C12H10FNO
(203.22): calcd. C 70.92, H 4.96, N 6.89; found C 71.07, H 4.83,
N 6.95.
Pale-yellow solid; m.p. 143Ϫ144 °C. 1H NMR (300 MHz, DMSO):
δ ϭ 3.82 (s, 3 H), 5.82 (d, J ϭ 4.2 Hz, 1 H), 6.34 (d, J ϭ 4.2 Hz, 1
H), 7.12 (s, 1 H), 7.29 (s, 1 H), 7.33 (s, 1 H), 7.40Ϫ7.45 (m, 2 H),
(4-Ethylphenyl)(pyridin-4-yl)methanol (4k): Pale-yellow solid; m.p. 8.49Ϫ8.53 (m, 2 H) ppm. 13C NMR (75 MHz, DMSO): δ ϭ 55.7,
104Ϫ105 °C. 1H NMR (300 MHz, DMSO): δ ϭ 1.13 (t, J ϭ 72.3, 109.1 (q, J ϭ 3.8 Hz), 114.8 (q, J ϭ 4.0 Hz), 116.3, 121.2 (2
7.1 Hz, 3 H), 2.54 (q, J ϭ 7.1 Hz, 2 H), 5.71 (s, 1 H), 6.12 (d, J ϭ C), 124.0 (q, J ϭ 270.8 Hz), 130.4 (q, J ϭ 31.4 Hz), 147.7, 149.7
2.4 Hz, 1 H), 7.13Ϫ7.18 (m, 2 H), 7.28Ϫ7.34 (m, 2 H), 7.36Ϫ7.40
(2 C), 153.3, 159.7 ppm. IR (KBr pellet): ν˜ ϭ 3128, 1600, 1360,
(m, 2 H), 8.46Ϫ8.50 (m, 2 H) ppm. 13C NMR (75 MHz, DMSO): 1168, 1128, 1048 cmϪ1. C14H12F3NO2 (283.25): calcd. C 59.37, H
δ ϭ 15.6, 27.8, 73.0, 121.2 (2 C), 126.4 (2 C), 127.7 (2 C), 141.7,
142.8, 149.4 (2 C), 154.3 ppm. IR (KBr pellet): ν˜ ϭ 3128, 1600,
1416, 1064, 1046, 1000 cmϪ1. C14H15NO (213.28): calcd. C 78.84,
H 7.09, N 6.57; found C 78.71, H 7.22, N 6.51.
4.27, N 4.95; found C 59.15, H 4.21, N 4.78.
[3,5-Bis(trifluoromethyl)phenyl](pyridin-4-yl)methanol (4r): Pale-yel-
low solid; m.p. 139Ϫ141 °C. 1H NMR (300 MHz, DMSO): δ ϭ
6.00 (d, J ϭ 3.9 Hz, 1 H), 6.58 (d, J ϭ 3.9 Hz, 1 H), 7.40Ϫ7.48 (m,
2 H), 8.01 (s, 1 H), 8.10 (s, 2 H), 8.50Ϫ8.55 (m, 2 H) ppm. 13C
(3,4-Dimethylphenyl)(pyridin-4-yl)methanol (4l): Pale-yellow solid;
m.p. 183Ϫ184 °C. 1H NMR (300 MHz, DMSO): δ ϭ 2.17 (s, 3 H), NMR (75 MHz, DMSO): δ ϭ 71.6, 121.1 (2 C), 123.7 (q, J ϭ
2.18 (s, 3 H), 5.61 (d, J ϭ 3.9 Hz, 1 H), 5.96 (d, J ϭ 3.9 Hz, 1 H), 271.1 Hz, 2 C), 126.9 (2 C), 130.4 (q, J ϭ 32.6 Hz, 2 C), 147.8 (2
7.05 (s, 2 H), 7.12 (s, 1 H), 7.31Ϫ7.36 (m, 2 H), 8.43Ϫ8.48 (m, 2 C), 149.8 (2 C), 152.5 ppm. IR (KBr pellet): ν˜ ϭ 3136, 1608, 1376,
H) ppm. 13C NMR (75 MHz, DMSO): δ ϭ 19.0, 19.5, 73.0, 121.2
1280, 1172, 1128 cmϪ1. C14H9F6NO (321.22): calcd. C 52.30, H
(2 C), 123.9, 127.5, 129.4, 135.1, 136.0, 141.8, 149.4 (2 C), 2.82, N 4.36; found C 52.16, H 2.78, N 4.48.
154.4 ppm. IR (KBr pellet): ν˜ ϭ 3136, 1604, 1496, 1416, 1344, 1056
[3-(Benzyloxy)phenyl](pyridin-4-yl)methanol (4s): White solid; m.p.
cmϪ1. C14H15NO (213.28): calcd. C 78.84, H 7.09, N 6.57; found
C 78.69, H 6.98, N 6.72.
157Ϫ158 °C. 1H NMR (500 MHz, DMSO): δ ϭ 5.07 (s, 2 H), 5.68
(d, J ϭ 4.3 Hz, 1 H), 6.10 (d, J ϭ 4.3 Hz, 1 H), 6.86Ϫ6.90 (m, 1
H), 6.95Ϫ6.98 (m, 1 H), 7.05Ϫ7.08 (m, 1 H), 7.20Ϫ7.25 (m, 1 H),
(3-Fluoro-4-methoxyphenyl)(pyridin-4-yl)methanol (4m): Pale-yellow
solid; m.p. 140Ϫ142 °C. 1H NMR (300 MHz, DMSO): δ ϭ 3.81 7.29Ϫ7.34 (m, 1 H), 7.35Ϫ7.40 (m, 4 H), 7.41Ϫ7.45 (m, 2 H),
(s, 3 H), 5.70 (d, J ϭ 3.6 Hz, 1 H), 6.19 (d, J ϭ 3.6 Hz, 1 H),
7.07Ϫ7.25 (m, 3 H), 7.37Ϫ7.41 (m, 2 H), 8.48Ϫ8.52 (m, 2 H) ppm. 73.0, 112.9, 113.4, 118.8, 121.2 (2 C), 127.7 (2 C), 127.8, 128.4 (2
13C NMR (75 MHz, DMSO): δ ϭ 56.0, 72.1, 113.7, 113.9, 121.1
C), 129.4, 137.0, 146.05, 149.4 (2 C), 153.9, 158.3 ppm. IR (KBr
(2 C), 122.5 (d, J ϭ 3.3 Hz), 137.5 (d, J ϭ 5.4 Hz), 146.2 (d, J ϭ pellet): ν˜ ϭ 3128, 1600, 1452, 1264, 1048, 732 cmϪ1. C19H17NO2
8.44Ϫ8.49 (m, 2 H) ppm. 13C NMR (75 MHz, DMSO): δ ϭ 69.1,
3628
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2004, 3623Ϫ3632