1,4-Benzoquinones with Styryl Substituents
FULL PAPER
(50 mL) was kept at room temperature for 4 days. The solution was
concentrated under vacuum (102 Pa) followed by the addition of a
3J ϭ 10.6 Hz, 2 H) [4-H/5-H and 10-H/11-H], 6.45 (d, 1 H, arom.
H), 6.54 (dd, 1 H, arom. H), 6.61 (d, 1 H, arom. H), 6.65 (m, 2 H,
mixture of petroleum ether (b.p. 40Ϫ70 °C)/ethyl acetate (5:2) arom. H) ppm. 13C NMR (CDCl3): δ ϭ 10.4, 10.8 (CH3), 22.5,
which caused the precipitation of pure 10a as a yellow solid (yield
22.6, 22.9 (CH2), 37.5, 38.0, 41.9, 43.0 (C-1, C-14, C-15, C-16),
840 mg, 84%), m.p. 152 °C. 1H NMR (CDCl3):[24] δ ϭ 2.11 (s, 3 38.9, 45.6 (C-8, C-13), 70.3, 70.4 (OCH2), 112.3, 112.5, 113.7,
H, CH3), 2.16 (s, 3 H, CH3), 2.26 (s, 3 H, CH3), 2.31 (s, 3 H, CH3), 114.4, 114.7, 115.0 (arom. CH), 124.2, 125.6, 137.9, 139.5, 151.0,
3.47 (m, 1 H, 4a-H), 4.07 (d, 3J ϭ 4.3 Hz, 1 H, 4b-H), 4.48 (t, 3J ϭ
5J ϭ 3.5 Hz, 1 H, 9-H), 6.00/6.27 (AB, 3J ϭ 10.6 Hz, 2 H) and
151.1, 152.5, 152.7 (C-2, C-7 and arom. Cq), 135.0, 136.9, 138.7,
139.1 (C-4, C-5, C-10, C-11), 182.0, 182.9, 189.4, 190.6 (C-3, C-6,
6.96/7.02 (AB, 3J ϭ 10.6 Hz, 2 H) [2-H/3-H and 6-H/7-H], 6.37/ C-9, C-12) ppm. MS (EI, 70 eV): m/z (%) ϭ 652 (100) [Mϩ· ϩ 2H],
3
6.75 (AB, Jtrans ϭ 16.4 Hz, 2 H, olefin H), 6.40 (br. s, 1 H), 6.89 650 (83) [Mϩ·]. C40H42O8 (650.8): calcd. C 73.83, H 6.51; found C
(dd, 1 H), 6.96 (d, 1 H), 7.02 (m, 2 H), 7.29 (br. s, 1 H, arom. H), 73.64, H 6.48.
7.02 (m, 1 H, 10-H) ppm. 13C NMR (CDCl3):[24] δ ϭ 19.4, 19.7,
Simultaneous Transformation of rac-10a into rac-12a,b: Compounds
12a,b were primarily obtained by column chromatography of 10a
(70 mg) over silica gel (70Ϫ230 mesh, 3 ϫ 70 cm) using chloroform
(contaminated with small amounts of ethanol and water)/ethyl
acetate (5:1) as eluent. The ethanol adduct 12b was obtained as the
first fraction (yield 32 mg, 40%) and the water adduct 12a as the
second fraction (yield 26 mg, 35%).
20.8, 20.9 (CH3), 42.9, 43.0 (C-4a, C-9), 53.4 (C-4b), 59.1 (C-8a),
126.6, 129.0, 129.1, 130.4, 131.8, 132.0 (arom. CH), 129.9, 132.1
(olefin CH), 131.7 (C-10a), 132.5, 133.0, 134.7, 135.8, 135.9, 136.0
(arom. Cq), 137.8 (C-10), 138.8, 140.3, 140.6, 142.3 (C-2, C-3, C-6,
C-7), 184.1 (C-1), 194.3, 195.2, 198.1 (C-4, C-5, C-8) ppm. FD-
MS: m/z (%) ϭ 477 (100) [M ϩ H]ϩ. C32H28O4 (476.6): calcd. C
80.65, H 5.92; found C 80.68, H 5.56.
The dimers rac-10b and rac-10c were prepared as described previ-
ously.[13] The compound rac-10d was not isolated and was directly
transformed into rac-11d.
rel-(8aS,9R,10R)-9-(2,5-Dimethylphenyl)-8a-[(E)-2-(2,5-dimethyl-
phenyl)ethenyl]-8aH-9,10-dihydro-1,4,5,10-tetrahydroxyphenan-
thren-8-one (rac-12a): An increased yield of the water adduct 12a
was accomplished by eliminating possible formation of the ethanol
adduct 12b. Column chromatography of 10a (90 mg) over silica gel
(70Ϫ230 mesh, 3 ϫ 50 cm) with dichloromethane/ethyl acetate (5:1)
as eluent delivered exclusively 12a as a yellow solid (yield 52 mg,
rel-(1S,8S,13R,14R,15R,16R)-14,15-Bis(2,5-dimethylphenyl)penta-
cyclo[6.6.2.02,7.08,13.013,16]hexadeca-2(7),4,10-triene-3,6,9,12-tetrone
(rac-11a): Column chromatography of the crude dimer 10a
(160 mg) over silica gel (70Ϫ230 mesh, 3 ϫ 70 cm) with petroleum
ether (b.p. 40Ϫ70 °C)/ethyl acetate (5:2) provided 11a, a viscous
oil, as the first fraction (yield 39 mg, 24%). 1H NMR (CDCl3): δ ϭ
1.98 (s, 3 H, CH3), 2.20 (s, 3 H, CH3) 2.40 (s, 3 H, CH3), 2.41 (s,
3 H, CH3), 2.92 (br. s, 1 H, 16-H), 3.93 (dd, 3J ϭ 4.7, 3J ϭ 2.3 Hz,
1
58%), m.p. 142 °C. H NMR (C2D2Cl4): δ ϭ 1.80 (s, 3 H, CH3),
2.02 (s, 3 H, CH3), 2.18 (s, 3 H, CH3), 2.36 (s, 3 H, CH3), 2.64 (d,
3J ϭ 9.2 Hz, 1 H, OH attached to C-10), 4.36 (br. s, 1 H, 9-H),
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4.81 (d, J ϭ 9.2 Hz, 1 H, 10-H), 5.62/6.70 (AB, J ϭ 10.2 Hz, 2
H, 6-H/7-H), 6.27/6.39 (AB, 3Jtrans ϭ 16.0 Hz, 2 H, olefin H), 6.57
(br. s, 1 H, arom. H), 6.76/6.86 (AB, J ϭ 8.6 Hz, 2 H, 2-H/3-H),
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3
1 H, 15-H), 4.34 (t, J ϭ 4.7 Hz, 1 H, 1-H), 4.42 (d, J ϭ 4.7 Hz,
3
3
1 H, 14-H), 6.14/6.52 (AB, J ϭ 10.2 Hz, 2 H) and 6.76/6.92 (AB,
6.81 (d, 1 H, arom. H), 6.84 (m, 2 H, arom. H), 6.91 (d, 1 H, arom.
H), 6.99 (s, 1 H, OH attached to C-1), 7.14 (br. s, 1 H, arom. H),
8.42 (br. s, 1 H) and 8.51 (br. s, 1 H) [OH attached to C-4, C-5]
ppm. 13C NMR (C2D2Cl4): δ ϭ 19.0, 20.5, 21.3, 21.5 (CH3), 53.6
(C-9), 57.4 (C-8a), 71.9 (C-10), 116.5, 122.0, 124.5 (C-4a, C-4b, C-
10a), 117.5, 118.0 (C-2, C-3), 125.7 (C-7), 126.1, 128.3, 128.3,
129.3, 130.5, 130.6 (arom. CH), 132.2, 133.4 (olefin CH), 132.9,
132.9, 135.1, 135.4, 136.1, 137.2 (arom. Cq), 144.6 (1 C, C-6), 144.8,
146.5, 150.9 (C-1, C-4, C-5), 201.4 (C-8).[24] FD-MS: m/z (%) ϭ
477 (100) [M Ϫ OH]ϩ. C32H30O5 (492.6): calcd. C 77.71, H 6.11;
found C 77.57, H 6.03.
3J ϭ 10.6 Hz, 2 H) [4-H/5-H and 10-H/11-H], 6.17 (br. s, 1 H), 6.68
(br. s, 1 H), 6.75 (m, 1 H), 6.88 (m, 2 H), 6.95 (d, 1 H) [arom. H]
ppm. 13C NMR (CDCl3): δ ϭ 18.9, 19.0, 20.7, 21.2 (CH3), 36.4,
40.6, 43.3, 44.3 (C-1, C-14, C-15, C-16), 38.9, 46.0 (C-8, C-13),
126.7, 127.9, 128.1, 128.2, 130.5, 130.7 (arom. CH), 132.1, 132.8,
132.9, 133.7, 135.0, 135.6, 138.1, 138.3 (C-2, C-7 and arom. Cq),
134.7, 137.0, 138.8, 139.0 (C-4, C-5, C-10, C-11), 181.8, 182.8,
189.1, 190.6 (C-3, C-6, C-9, C-12) ppm. FD-MS: m/z (%) ϭ 474
(100) [Mϩ·]. C32H26O4 (474.6): calcd. C 80.99, H 5.52; found C
80.73, H 5.49.
The preparation of the polycyclic compounds rac-11b and rac-11c
rel-(8aS,9R,10R)-9-(2,5-Dimethylphenyl)-8a-[(E)-2-(2,5-dimethyl-
phenyl)-ethenyl]-10-ethoxy-8aH-9,10-dihydro-1,4,5-trihydroxy-
phenanthren-8-one (rac-12b): A solution of 10a (50 mg, 0.1 mmol)
in chloroform (5 mL) together with ethanol (5 mL, 3.93 g,
has been described previously.[13]
rel-(1S,8S,13R,14R,15R,16R)-14,15-Bis(2,5-dipropoxyphenyl)-
pentacyclo[6.6.2.02,7.08,13.013,16]-hexadeca-2(7),4,10-triene-3,6,9,12-
tetrone (rac-11d): Na2SO4 (50 mg, 3.5 mmol) and freshly-prepared 85 mmol) and a small amount of silica gel (70Ϫ230 mesh) was
Ag2O (92.7 mg, 0.4 mmol) were added to a solution of 5d (100 mg,
0.3 mmol) in dry THF (20 mL). After stirring for 1 h at room tem-
stirred at room temperature for 2 h. After filtration, the solvents
were evaporated under vacuum (102 Pa) and the product purified
perature, the solid particles were removed and washed with THF from traces of the water adduct 12a by column chromatography
(80 mL) several times. The solvent of the combined organic phases
was then removed under vacuum (102 Pa). Column chromato-
graphy of the residue over silica gel (70Ϫ230 mesh, 3 ϫ 70 cm)
using petroleum ether (b.p. 40Ϫ70 °C)/ethyl acetate (5:2) as eluent
furnished 11d as a viscous oil (yield 31 mg, 16%). 1H NMR
over silica gel (70Ϫ230 mesh, 3 ϫ 20 cm) with chloroform/ethyl
acetate (5:1). Compound 12b was obtained as a yellow solid (yield
41 mg, 82%), m.p. 147 °C. 1H NMR (CDCl3): δ ϭ 1.32 (t, 3 H,
CH3 of OC2H5), 1.87 (s, 3 H, CH3), 2.10 (s, 3 H, CH3), 2.22 (s, 3
H, CH3), 2.41 (s, 3 H, CH3), 3.56 (m, 1 H, OCH2), 4.05 (m, 1 H,
(CDCl3): δ ϭ 0.89 (t, 3 H, CH3), 0.96 (t, 3 H, CH3), 1.12 (m, 6 H, OCH2), 4.42 (br. s, 1 H, 9-H), 4.64 (br. s, 1 H, 10-H), 5.57/6.67
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CH3), 1.59 (m, 4 H, CH2), 1.68 (q, 2 H, CH2), 1.90 (m, 2 H, CH2),
(AB, J ϭ 9.8 Hz, 2 H, 6-H/7-H), 6.16/6.30 (AB, 3Jtrans ϭ 16.0 Hz,
2.86 (br. s, 1 H, 16-H), 3.52 (m, 2 H, OCH2), 3.77Ϫ3.98 (m, 6 H, 2 H, olefin H), 6.59 (br. s, 1 H, arom. H), 6.76/6.83 (AB, 3J ϭ
OCH2), 4.10 (dd, J ϭ 4.7, J ϭ 2.3 Hz, 1 H, 15-H), 4.55 (d, J ϭ 8.6 Hz, 2 H, 2-H/3-H), 6.85 (m, 3 H, arom. H), 6.95 (d, 1 H, arom.
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4.5 Hz, 1 H, 14-H), 4.59 (t, J ϭ 4.5 Hz, 1 H, 1-H), 5.95 (d, 1 H, H), 7.10 (br. s, 1 H, arom. H), 7.47 (s, 1 H, OH attached to C-1),
arom. H), 6.17/6.51 (AB, 3J ϭ 10.3 Hz, 2 H) and 6.74/6.89 (AB, 8.12 (br. s, 2 H, OH attached to C-4, C-5) ppm. 13C NMR (CDCl3):
Eur. J. Org. Chem. 2002, 3162Ϫ3170
3169