Syntheses of 5H-Benzocycloheptenes
J. Chin. Chem. Soc., Vol. 51, No. 4, 2004 811
15.6 Hz, 10.4 Hz, 5.6 Hz, 1H, CH2=CHCH2Ar), 6.85, 7.23
(each d, J = 8.4 Hz, 1H, ArH); 13C-NMR (CDCl3, 100 MHz) d
29.74, 43.03, 55.61, 60.78, 69.17, 110.62, 115.10, 117.88,
121.41, 130.68, 135.05, 135.29, 137.57, 146.92, 151.88; EI-
MS (70 eV) m/z (rel. intensity, %) 248 (M+, 43.67), 202
(9.90), 189 (12.12), 161 (10.81), 131 (9.61), 118 (10.99), 91
(100), 65 (10.31); HRMS calcd for C15H20O3: 248.1412.
Found: 248.1412.
151.80; EI-MS (70 eV) m/z (rel. intensity, %) 276 (M+,
21.68), 259 (19.27), 235 (100), 193 (83.69), 175 (15.57), 143
(42.86), 115 (13.62); HRMS calcd for C17H24O3: 276.1725.
Found: 276.1723.
1-(2-Allyl-3-butoxy-4-methoxyphenyl)-3-buten-1-ol (2d)
Pure 2d (1.09 g, 75%) was obtained as colorless liquid;
Rf 0.51 (EA/n-Hexane = 1/3); 1H-NMR (CDCl3, 400 MHz) d
0.96 (t, J = 7.4 Hz, 3H, OCH2CH2CH2CH3), 1.49 (sixt, J = 7.4
Hz, 2H, OCH2CH2CH2CH3), 1.74 (quint, J = 7.4 Hz, 2H,
OCH2CH2CH2CH3), 2.45 (t, J = 7.4 Hz, 2H, OCH2CH2-
CH2CH3), 2.06 (br. s, 1H, OH), 2.45 (t, J = 7.0 Hz, 2H,
CH2=CHCH2CH(OH)Ar), 3.44, 3.55 (each dd, J = 15.6 Hz,
5.6 Hz, 1H, CH2=CHCH2Ar), 3.82 (s, 3H, OCH3), 4.84 (t, J =
7.0 Hz, 1H, CH2=CHCH2CH(OH)Ar), 4.89 (dd, J = 15.6 Hz,
2.0 Hz, 1H, CH2=CHCH2Ar), 4.99 (dd, J = 10.4 Hz, 2.0 Hz,
1H, CH2=CHCH2Ar), 5.09 (dd, J = 10.4 Hz, 1.6 Hz, 1H,
CH2=CHCH2CH(OH)Ar), 5.13 (dd, J = 16.8 Hz, 1.6 Hz, 1H,
CH2=CHCH2CH(OH)Ar), 5.83 (ddt, J = 16.8 Hz, 10.4 Hz,
7.0 Hz, 1H, CH2=CHCH2CH(OH)Ar), 5.96 (ddt, J = 15.6 Hz,
10.4 Hz, 5.6 Hz, 1H, CH2=CHCH2Ar), 6.83, 7.20 (each d, J =
8.6 Hz, 1H, ArH); 13C-NMR (CDCl3, 100 MHz) d 13.85,
19.11, 29.78, 32.32, 43.00, 55.54, 69.13, 72.86, 110.52,
114.93, 117.64, 121.13, 130.65, 135.07, 135.31, 137.58,
146.11, 151.89; EI-MS (70 eV) m/z (rel. intensity, %) 290
(M+, 9.46), 250 (15.58), 249 (100), 193 (24.92), 175 (43.35);
HRMS calcd for C18H26O3: 290.1882. Found: 290.1880.
1-(2-Allyl-3-ethoxy-4-methoxyphenyl)-3-buten-1-ol (2b)
Pure 2b (0.97 g, 74%) was obtained as colorless liquid;
Rf 0.47 (EA/n-Hexane = 1/3); 1H-NMR (CDCl3, 400 MHz) d
1.36 (t, J = 7.0 Hz, 3H, OCH2CH3), 1.90 (br s, 1H, OH), 2.46
(t, J = 7.8 Hz, 2H, CH2=CHCH2CH(OH)Ar), 3.37, 3.57 (each
dd, J = 15.6 Hz, 6.0 Hz, 1H, CH2=CHCH2Ar), 3.84 (s, 3H,
OCH3), 3.98 (q, J = 7.0 Hz, 2H, OCH2CH3), 4.88 (t, J = 7.8
Hz, 1H, CH2=CHCH2CH(OH)Ar), 4.91 (dd, J = 15.6 Hz, 1.8
Hz, 1H, CH2=CHCH2Ar), 5.01 (dd, J = 10.4 Hz, 1.8 Hz, 1H,
CH2=CHCH2Ar), 5.12 (dd, J = 10.2 Hz, 1.2 Hz, 1H,
CH2=CHCH2CH(OH)Ar), 5.16 (dd, J = 17.4 Hz, 1.2 Hz, 1H,
CH2=CHCH2CH(OH)Ar), 5.84 (ddt, J = 17.4 Hz, 10.2 Hz,
7.8 Hz, 1H, CH2=CHCH2CH(OH)Ar), 5.97 (ddt, J = 15.6 Hz,
10.4 Hz, 6.0 Hz, 1H, CH2=CHCH2Ar), 6.85, 7.21 (each d, J =
8.4 Hz, 1H, ArH); 13C-NMR (CDCl3, 75 MHz) d 15.55,
29.79, 42.96, 55.47, 68.67, 69.09, 110.40, 114.87, 117.53,
121.15, 130.61, 135.04, 135.28, 137.50, 145.94, 151.79; EI-
MS (70 eV) m/z (rel. intensity, %) 262 (M+, 4.74), 244 (2.58),
222 (16.68), 221 (100), 193 (3.56), 190 (2.05), 177 (2.28),
161 (2.26); HRMS calcd for C16H22O3: 262.1569. Found:
262.1568.
1-(2-Allyl-3-benzyloxy-4-methoxyphenyl)-3-buten-1-ol
(2e)
Pure 2e (1.27 g, 78%) was obtained as colorless liquid;
Rf 0.42 (EA/n-Hexane = 1/3); 1H-NMR (CDCl3, 400 MHz) d
2.00 (br s, 1H, OH), 2.43 (t, J = 6.8 Hz, 2H, CH2=CH
CH2CH(OH)Ar), 3.41, 3.51 (each dd, J = 15.6 Hz, 5.6 Hz,
1H, CH2=CHCH2Ar), 3.84 (s, 3H, OCH3), 4.86 (t, J = 6.8 Hz,
1H, CH2=CHCH2CH(OH)Ar), 4.89 (dd, J = 15.6 Hz, 2.0 Hz,
1H, CH2=CHCH2Ar), 4.96 (s, 2H, OCH2Ph), 4.98 (dd, J =
10.4 Hz, 2.0 Hz, 1H, CH2=CHCH2Ar), 5.08 (dd, J = 10.4 Hz,
1.8 Hz, 1H, CH2=CHCH2CH(OH)Ar), 5.13 (dd, J = 16.8 Hz,
1.8 Hz, 1H, CH2=CHCH2CH(OH)Ar), 5.80 (ddt, J = 16.8 Hz,
10.4 Hz, 6.8 Hz, 1H, CH2=CHCH2CH(OH)Ar), 5.94 (ddt, J =
15.6 Hz, 10.4 Hz, 5.6 Hz, 1H, CH2=CHCH2Ar), 6.85, 7.23
(each d, J = 8.6 Hz, 1H, ArH), 7.29 (t, J = 7.2 Hz, 1H,
OCH2C6H5), 7.35 (t, J = 7.2 Hz, 2H, OCH2C6H5), 7.45 (t, J =
7.2 Hz, 2H, OCH2C6H5); 13C-NMR (CDCl3, 75 MHz) d
29.87, 43.05, 55.59, 69.11, 74.57, 110.61, 115.08, 117.66,
121.56, 127.70, 127.89, 128.24, 130.81, 135.02, 135.41,
137.46, 137.88, 145.62, 151.86; EI-MS (70 eV) m/z (rel. in-
1-(2-Allyl-3-isoproxy-4-methoxyphenyl)-3-buten-1-ol (2c)
Pure 2c (1.1 g, 80%) was obtained as colorless liquid;
Rf 0.35 (EA/n-Hexane = 1/3); 1H-NMR (CDCl3, 400 MHz) d
1.25 (t, J = 6.2 Hz, 6H, OCHMe2), 2.03 (br s, 1H, OH), 2.44
(t, J = 7.2 Hz, 2H, CH2=CHCH2CH(OH)Ar), 3.46, 3.60 (each
dd, J = 15.6 Hz, 5.6 Hz, 1H, CH2=CHCH2Ar), 3.81 (s, 3H,
OCH3), 4.50 (hept., J = 6.2 Hz, 1H, OCH(CH3)2), 4.88 (t, J =
7.2 Hz, 1H, CH2=CHCH2CH(OH)Ar), 4.91 (dd, J = 15.6 Hz,
2.0 Hz, 1H, CH2=CHCH2Ar), 4.99 (dd, J = 10.4 Hz, 2.0 Hz,
1H, CH2=CH-CH2Ar), 5.08 (dd, J = 10.4 Hz, 2.0 Hz, 1H,
CH2=CHCH2CH(OH)Ar), 5.13 (dd, J = 17.2 Hz, 2.0 Hz, 1H,
CH2=CHCH2CH(OH)Ar), 5.82 (ddt, J = 17.2 Hz, 10.4 Hz,
7.2 Hz, 1H, CH2=CHCH2CH(OH)Ar), 5.99 (ddt, J = 15.6 Hz,
10.4 Hz, 5.6 Hz, 1H, CH2=CHCH2Ar), 6.81, 7.19 (each d, J =
8.4 Hz, 1H, ArH); 13C-NMR (CDCl3, 100 MHz) d 22.47,
22.53, 30.10, 43.06, 55.43, 69.08, 74.39, 110.39, 114.92,
117.55, 120.75, 130.92, 135.08, 135.44, 137.43, 144.43,