926 J. Chin. Chem. Soc., Vol. 55, No. 4, 2008
Li et al.
chloride (2.0 M in THF) (36 mmol) in drops. And then the
reaction mixture was continually stirred for 2 hr at room
temperature. The resulting solution was concentrated in
vacuo, and the residue which was obtained was purified by
column chromatography on silica gel (ethyl acetate: n-hex-
ane = 1: 15) to give pure 3a-g.
(dd, J = 17.2, 1.2 Hz, 1H, OCH2CH=CHHtrans-gem), 5.89
(ddt, J = 17.2, 10.2, 5.8 Hz, 1H, OCH2CH=CH2), 6.03 (d, J
= 4.6 Hz, 1H, ArCH(OH)Ph), 6.83 (dd, J = 7.8, 1.8 Hz,
1Hz, ArH), 6.99 (m, 2H, ArH), 7.28 (m, 5H, ArH); 13C-
NMR (CDCl3, 50 MHz) d 55.63, 71.99, 73.46, 111.75,
117.50, 119.67, 123.91, 126.31, 127.01, 128.02, 133.89,
137.62, 143.74, 144.99, 152.45; EI-MS (70 eV) m/z (rel.
intensity, %) 271 ([M+1]+, 3), 270 (M+, 14), 251 (18), 229
(52), 212 (39), 211 (100), 170 (23), 196 (83), 152 (18), 151
(21), 141 (49), 115 (17), 105 (30), 77 (25); HRMS calcd for
C17H18O3: 270.1250. Found: 270.1253.
(2-Allyloxyphenyl)phenylmethanol (3a)
(6.62 g, 92%) was obtained as colorless crystals, mp
50-51 °C, Rf = 0.10 (ethyl acetate: n-hexane = 1: 15), 1H-
NMR (CDCl3, 400 MHz) d 3.30 (br d, J = 5.6 Hz, 1H, OH),
4.49 (dt, J = 5.2 Hz, 1.2 Hz, 2H, OCH2CH=CH2), 5.12 (ddt,
J = 10.4 Hz, 1.2 Hz, 1.2 Hz, 1H, OCH2CH=CHaHb), 5.28
(ddt, J = 17.2 Hz, 1.2 Hz, 1.2 Hz, 1H, OCH2CH=CHaHb),
5.92 (ddt, J = 17.2 Hz, 10.4 Hz, 5.2 Hz, 1H, OCH2CH=CH2),
6.07 (d, J = 5.6 Hz, 1H, ArCH(OH)Ph), 6.84 (d, J = 8.4 Hz,
1H, ArH), 6.93 (d, J = 7.4 Hz, 1H, ArH), 7.18-7.48 (m, 7H,
ArH); 13C-NMR (CDCl3, 100 MHz) d 69.00, 72.28, 112.11,
117.54, 120.99, 126.50, 127.07, 127.86, 128.07, 128.55,
132.44, 132.91, 143.44, 155.68; EI-MS (70 eV) m/z (rel.
intensity, %) 240 (M+, 12), 200 (13), 199 (100), 197 (10),
194 (10), 182 (13), 181 (83), 153 (13), 152 (27), 121 (90),
107 (11), 105 (30), 77 (37); HRMS calcd for C16H16O2:
240.1145. Found: 240.1147.
(2¢-Allyloxyphenyl)-(4²-methoxyphenyl)methanol (3d)
(7.77 g, 96%) was obtained as colorless liquids, Rf =
0.30 (ethyl acetate: n-hexane = 1: 6), 1H-NMR (CDCl3, 400
MHz) d 3.19 (br d, J = 5.2 Hz, 1H, OH), 3.71 (s, 3H,
OCH3), 4.44 (dt, J = 5.2 Hz, 1.6 Hz, 2H, OCH2CH=CHaHb),
5.18 (ddt, J = 10.4 Hz, 1.6 Hz, 1.6 Hz, 1H, OCH2CH=CCHaHb),
5.28 (ddt, J = 17.2 Hz, 1.6 Hz, 1.6 Hz, 1H, OCH2CH=CHaHb),
5.91 (ddt, J = 17.2 Hz, 10.4 Hz, 5.2 Hz, 1H, OCH2CH=CH2),
6.00 (d, J = 5.2 Hz, 1H, ArCH(OH)Ph), 6.80 (d, J = 8.8 Hz,
2H, ArH), 6.80 (dd, J = 7.6, 1.2 Hz, 1H, ArH), 6.92 (td, J =
7.2, 1.2 Hz, 1H, ArH), 7.18 (ddd, J = 7.6, 7.2, 1.6 Hz, 1H,
ArH), 7.26 (d, J = 8.8 Hz, 2H, ArH), 7.30 (dd, J = 7.2, 1.6
Hz, 1H, ArH); 13C-NMR (CDCl3, 100 MHz) d 55.01,
68.66, 71.36, 111.74, 113.33, 117.31, 120.76, 127.32,
127.69, 128.24, 132.46, 132.84, 135.55, 155.31, 158.50;
EI-MS (70 eV) m/z (rel. intensity, %) 270 (M+, 1), 230 (16),
229 ([M-41]+, 100), 224 (18), 211 (19), 168 (13), 135 (26),
122 (24), 121 (79); ESI-HRMS calcd for C17H18O3Na
[M+Na]+: 293.1154. Found: 293.1155.
(2-Allyloxy-4-methoxyphenyl)phenylmethanol (3b)
(7.73 g, 95%) was obtained as colorless liquids, Rf =
0.08 (ethyl acetate: n-hexane = 1: 19), 1H-NMR (CDCl3,
200 MHz) d 3.10 (br d, J = 3.6 Hz, 1H, OH), 3.73 (s, 3H,
OCH3), 4.44 (dt, J = 5.2, 1.4 Hz, 2H, OCH2CH=CH2), 5.21
(ddt, J = 10.2, 1.4, 1.4 Hz, 1H, OCH2CH=CHaHb), 5.29
(ddt, J = 17.2, 1.4, 1.4 Hz, 1H, OCH2CH=CHaHb), 5.91
(ddt, J = 17.2, 10.2, 5.2 Hz, 1H, OCH2CH=CCHaHb), 5.99
(d, J = 5.6 Hz, 1H, ArCH(OH)Ph), 6.41 (s, 1H, ArH), 6.42
(m, 1H, ArH), 7.22 (m, 6H, ArH); 13C-NMR (CDCl3, 50
MHz) d 55.21, 68.79, 71.54, 99.80, 104.38, 117.47,
125.03, 126.32, 126.83, 127.93, 128.38, 132.66, 143.59,
156.47, 160.01; EI-MS (70 eV) m/z (rel. intensity, %) 271
([M+1]+, 3), 270 (M+, 12), 229 (35), 227 (12), 211 (43),
168 (15), 165 (53), 164 (100), 152 (25), 151 (56), 137 (22),
106 (37), 77 (15); HRMS calcd for C17H18O3: 270.1250.
Found: 270.1253.
(2¢-Allyloxy-4¢-methoxyphenyl)-(4²-methoxyphenyl)-
methanol (3e)
(8.54 g, 95%) was obtained as colorless crystal, mp
1
46-47 °C, Rf = 0.14 (ethyl acetate: n-hexane = 1: 6), H-
NMR (CDCl3, 400 MHz) d 2.95 (br d, J = 4.0 Hz, 1H, OH),
3.76 (s, 3H, OCH3), 3.77 (s, 3H, OCH3), 4.48 (dt, J = 5.2,
1.6 Hz, 2H, OCH2CH=CH2), 5.24 (ddt, J = 10.4, 1.6, 1.6
Hz, 1H, OCH2CH=CCHaHb), 5.31 (ddt, J = 17.2, 1.6, 1.6
Hz, 1H, OCH2CH=CHaHb), 5.94 (ddt, J = 17.2, 10.4, 5.2
Hz, 1H, OCH2-CH=CH2), 5.86 (br d, J = 4.0 Hz, 1H,
ArCH(OH)Ph), 6.43 (d, J = 2.4 Hz, 1H, ArH), 6.45 (dd, J =
8.0, 2.4 Hz, 1H, ArH), 6.84 (d, J = 8.8 Hz, 2H, ArH), 7.13
(d, J = 8.0 Hz, 1H, ArH), 7.28 (d, J = 8.8 Hz, 2H, ArH);
13C-NMR (CDCl3, 100 MHz) d 55.16, 55.28, 68.83, 71.32,
99.82, 104.32, 113.41, 117.58, 125.23, 127.66, 128.27,
132.73, 135.77, 156.53, 158.56, 160.03; EI-MS (70 eV)
m/z (rel. intensity, %) 300 (M+, 25), 259 (94), 241 (23), 198
2-Allyloxy-3-methoxy-phenyl)phenylmethanol (3c)
(7.81 g, 96%) was obtained as colorless liquids, Rf =
0.27 (ethy lacetate: n-hexane = 1: 9), 1H-NMR (CDCl3, 200
MHz) d 3.16 (br d, J = 4.6 Hz, 1H, OH), 3.80 (s, 3H, OCH3),
4.21 (ddt, J = 11.8, 5.8, 1.2 Hz, 1H, OCHaHbCH=CH2),
4.35 (ddt, J = 11.8, 5.8, 1.2 Hz, 1H, OCHaHbCH=CH2),
5.15 (dd, J = 10.2, 1.2 Hz, 1H, OCH2CH=CHcis-gemH), 5.22