The Synthesis of Novel p-Quinone Methides
FULL PAPER
100%), 91.05485 (C7H7, 9.28%), 57.07199 (7.70%). C28H2335ClO2:
calcd. 426.13866; found 426.13830.
3ЈЈ,6ЈЈ-Epoxy-11-(4-methoxyphenyl)-3ЈЈ,6ЈЈ-dihydro-tribenzo[a,c,e]-
cycloheptatrien-11-ol (27): (3.0 g, 80 %) m.p. 165.4–167.5 °C. IR
(CHCl ): ν = 3603 cm–1 (s, OH), 3481 (br., OH), 2838 (s), 1605,
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3
5-(4-Methoxyphenyl)-5H-dibenzo[a,d]cyclohepten-5-ol (13): (4.4 g,
1
1508, 1440, 1300, 1251, 1179, 1034. H NMR (300 MHz, CDCl3):
93%), m.p. 136.8–137.9 °C; ref.[58] m.p. 137–139 °C. IR (CHCl ): ν
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3
δ = 2.31 (s, 1 H, OH), 3.71 (s, 3 H, OCH3), 5.64 (s, 2 H, 3ЈЈ-H, 6ЈЈ-
H), 6.57 (s, 2 H, 4ЈЈ-H, 5ЈЈ-H), 7.10–7.57 (m, 10 H, Ar-H), 8.30 (d,
J = 7.9 Hz, 2 H, Ar-H). 13C NMR (75 MHz, CDCl3): δ = 55.5
(OCH3), 79.2 (C-11), 85.5 (C-3ЈЈ, C-6ЈЈ), 113.4, 121.7, 126.0, 127.2,
127.9, 128.8 (Ar C-H, C-5, C-6), 131.5, 138.3, 139.7 (quat. Ar),
142.1 (Ar C-H), 148.9, 159.3 (Ar, CH, C-4ЈЈ, C-5ЈЈ). EI HRMS
(70 eV); m/z: 380.14005 (C26H20O3, M+, 100 %), 351.13889
(C25H19O2, 30.57 %), 244.08829 (C18H12O, 20.68 %), 237.09117
(C16H13O2, 25.25 %), 215.08542 (C17H11, 38.65 %), 135.04455
(C8H7O2, 42.67%), 121.06561 (C8H9O, 12.22%). C26H20O3: calcd.
380.14124; found 380.14005.
= 3604 cm–1 (vs), 3391 (br), 3054, 1591, 1460, 1440, 1316, 1165,
1
1112, 1005. H NMR (300 MHz, CDCl3); δ = 2.23 (s, 1 H, OH),
3.69 (s, 3 H, OCH3), 6.49 (s, 4 H, 2×Ar, CH, 10-H,11-H), 6.69 (s,
2 H, Ar-H), 7.25–7.39 (m, 4 H, Ar-H), 7.42–7.52 (m, 2 H, Ar-H),
8.20 (d, J = 8.1 Hz, 2 H, Ar-H). 13C NMR (75 MHz, CDCl3); δ =
55.1 (CH3O), 78.3 (C-OH), 112.8, 124.1, 124.6, 126.5, 126.8, 127.6,
127.9, 128.0, 128.3, 128.6, 129 3, 130.1, 130.8, 131.0, 131.2, 131.5,
(Ar, C-H), 133.2, 133.4, 138.1, 142.6, 158.7 (quat. C-atoms). EI
HRMS (70 eV); m/z: 314.13128 (C22H18O2, M+, 100%), 313.12182
(C22H17O2, 6.88 %),297.12625 (C22H17O, 3.24 %), 207.08123
(C15H11O, 23.64 %), 178.07799 (C14H10, 32.70 %), 165.07037
(C13H9, 3.50%), 152.06262 (C12H8, 5.34%), 135.04466 (C8H7O2,
36.57%), 92.02633 (C6H4O, 6.35%). C22H18O2: calcd. 314.13068;
found 314.13128.
5-(4-Methoxynaphthalen-1-yl)-10,11-dihydro-5H-dibenzo[a,d]cyclo-
hepten-5-ol (7a): 1-Bromo-4-methoxynaphthalene (4.30 g,
19.1 mmol) in THF (100 mL), magnesium (0.72 g, 29.6 mmol) and
5H-dibenzo-10,11-dihydro[a,d]cyclohepten-5-one 3 (2.65 g,
12.74 mmol) gave a sparingly soluble white solid, which, after
washing with benzene and drying, afforded pure 7a (3.2 g, 60%),
1,1-Dichloro-6-(4-methoxyphenyl)-1,1a,6,10b-tetrahydrodibenzo-
[a,e]cyclopropa[c]cyclohepten-6-ol (21): (3.7 g, 92%), m.p. 247.1–
249.1 °C. IR (CHCl ): ν = 3603 cm–1, 3413 (OH), 1605, 1508, 1484,
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m.p. 209.7–210.8 °C. IR (nujol): ν = 3526 cm–1 (OH), 1619, 1588,
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1298, 1250, 1179, 1038, 837. 1H NMR (300 MHz, CDCl3): δ = 2.09
(s, 1 H, OH), 2.59 (s, 2 H, 1a-H, 10b-H), 3.82 (s, 3 H, OCH3), 6.83
(d, J = 6.8 Hz, 2 H, Ar-H), 7.0 (d, J = 6.7 Hz, 2 H, Ar-H), 7.26–
7.40 (m, 6 H, Ar-H), 7.99 (m, 2 H, Ar-H). 13C NMR (75 MHz,
CDCl3): δ = 38.5 (C-1a, C-10b), 55.7 (OCH3), 63.7 (quat., C-1),
114.5, 125.1, 127.9, 128.0, 128.6, 133.3 (CH, Ar), 129.8, 141.0,
146.3, 159.4 (quat. Ar). EI HRMS (70 eV); m/z: 398.06798
(13.14 %), 396.06846 (C23H1835Cl2O2, M+, 22.05 %), 361.10057
(C23H1835ClO2, 40.26%), 325.12290 (C23H17O2, 100%), 297.12693
(C15H1835ClO2, 16.45 %), 290.13172 (C20H18O2, 35.80 %),
265.10012 (C15H1835ClO2, 19.39 %), 253.04036 (C16H1035ClO,
29.79%), 218.07236 (C16H10O, 27.77%), 77.03913 (C6H5, 20.97%).
C23H1835Cl2O2: calcd. 396.06839; found 396.06846.
1514, 1479, 1460, 1389, 1365, 1323, 1274, 1250, 1215, 1157, 1091,
1007, 968. 1H NMR (300 MHz, CDCl3): δ = 2.76 (s, 1 H, OH),
2.62–2.86 (m, 4 H, 10-H, 11-H), 6.65 (d, J = 7.3 Hz, 1 H, Ar-H),
7.02–7.42 (m, 9 H, Ar-H), 8.03 (d, J = 8.7 Hz, 1 H, Ar-H), 8.10
(dd, J1 = 7.9, J2 = 1.3 Hz, 2 H, Ar-H), 8.30 (d, J = 10.6 Hz, 1 H,
Ar-H). 13C NMR (75 MHz, CDCl3): 32.2 (2×CH2), 55.9 (CH3),
80.1 (quat., C-5), 102.6,122.8, 124.9, 125.3, 126.3, 126.58, 126.64
(Ar, C-H), 127.2 (quat. Ar), 127.7, 127.8, 131.0 (Ar, C-H), 131.6,
134.0, 137.2, 146.1, 156.1 (quat. Ar). EI HRMS (70 eV); m/z:
366.16188 (C26H22O2, M+, 21.73%), 348.15093 (C26H20O, 3.94%),
209.09303 (26.64 %), 208.08888 (C15H12O, 100 %), 185.06017
(C12H9O2, 36.43%), 178.07835 (C14H10, 6.13%), 165.07015 (C13H9,
5.68%), 158.07227 (C11H10O, 6.59%), 115.05423 (4.55%), 91.05498
(C7H7, 3.58%). C26H22O2: calcd. 366.16198; found 366.16188.
10-Bromo-5-(4-methoxyphenyl)-5H-dibenzo[a,d]cyclohepten-5-ol
(18): (3.1 g, 76%), m.p. 145.5–146.6 °C. IR (CHCl ): ν = 3606 cm–1
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3
5-(3,4-Dimethoxyphenyl)-10,11-dihydro-5H-dibenzo[a,d]cyclohep-
ten-5-ol (7b): 1-Bromo-3,4-dimethoxybenzene (p-bromoveratrole)
(7.82 g, 37.2 mmol) in THF (100 mL), magnesium (0.91 g,
37.2 mmol), and ketone 3 (5.0 g, 24.0 mmol) yielded a crude solid
residue, which crystallized from benzene/petroleum ether affording
white crystals of 7b (5.0 g, 60%), m.p. 189.1–190.2 °C. IR (CHCl3):
(OH), 3387 (OH), 2838, 1608, 1508, 1479, 1439, 1327, 1300, 1249,
1180, 1164, 1118, 1035. H NMR (300 MHz, CDCl3): δ = 2.28 (s,
1
1 H, OH), 3.76 (s, 3 H, OCH3), 6.69 (s, 4 H, Ar-H), 7.20–7.59 (m,
6 H, Ar-H), 7.87 (d, J = 7.5 Hz, 2 H, 11-H), 8.16 (dd, J1 = 4.6 Hz
and J2 = 5.2 Hz, 2 H, Ar-H). 13C NMR (75 MHz, CDCl3): δ =
55.6 (OCH3), 113.7, 124.2, 124.8, 125.2, 127.1, 127.4, 127.9, 128.7,
130.0, 129.98, 134.3 (Ar. CH, C-11), 125.2, 132.5, 133.3, 137.9,
144.3, 144.4, 159.6 (quat. Ar, C-10). EI HRMS (70 eV); m/z:
394.03914 (C22H1781BrO2, M + 2, 0.25 %), 392.03842 (C22
H1779BrO2, M+, 0.25%), 313.12325 (C22H17O2, 100%), 295.11193
(C22H15O, 2.60 %), 269.09456 (C20H13O, 2.79 %), 252.09424
(C20H12, 4.86%), 189.07012 (C15H9, 2.58%), 135.04509 (C8H7O2,
13.83 %), 78.04645 (C6H6, 28.35 %). C22H1779BrO2: calcd.
392.04119; found 392.03842.
ν = 3603 cm–1 (s, OH), 3410 (br., OH), 3010, 2837, 1601, 1509,
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1482, 1464, 1410, 1326, 1256, 1138, 1026. 1H NMR (300 MHz,
CDCl3): δ = 2.39 (s, 1 H, OH), 2.74 (m, 2 H, CH2–CH2), 2.94 (m,
2 H, CH2–CH2), 3.63 (s, 3 H, OCH3), 3.85 (s, 3 H, OCH3), 6.55
(d, J = 7.0 Hz, 2 H, Ar-H), 6.72 (d, J = 7.0 Hz, 1 H, Ar-H), 7.03–
7.40 (m, 6 H, Ar-H), 8.10 (dd, J1 = 1.5 Hz and J2 = 7.6 Hz, 2 H,
Ar-H). 13C NMR (75 MHz, CDCl3): δ = 32.9 (C-10, C-11), 56.2
(OCH3), 56.3 (OCH3), 110.3, 111.1, 119.7, 125.9, 126.2, 128.0,
130.9 (Ar, CH), 138.3, 141.8, 144.1, 148.9, 149.3 (quat. Ar). EI
HRMS (70 eV); m/z: 346.15677 (C23H22O3, M+, 63.85 %),
328.14640 (C23H20O2, 8.88 %), 255.10110 (C16H15O3, 5.87 %),
209.09502 (C15H13O, 39.20 %), 208.08912 (C15H12O, 100 %),
191.08552 (C15H11, 9.75 %), 165.05694 (C9H9O3, 54.20 %),
91.05479 (C7H7, 8.36 %). C23H22O3: calcd. 346.15689; found
346.15677.
9-(4-Methoxyphenyl)-9H-tribenzo[a,c,e]cyclohepten-9-ol (24):
(2.65 g, 72%), m.p. 169.6–170.7 °C. IR (CHCl ): ν = 3604 cm–1
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3
(OH), 3391 (OH), 2838, 1606, 1582, 1508, 1438, 1298, 1248, 1178,
1124, 1035, 1020. 1H (300 MHz, CDCl3): δ = 2.21 (s, 1 H, OH),
3.62 (s, 3 H, OCH3), 6.40 (d, J = 8.8 Hz, 2 H, Ar-H), 6.71 (d, J =
8.8 Hz, 2 H, Ar-H), 7.00–7.62 (m, 10 H, Ar-H), 8.19 (d, J = 7.8 Hz,
2 H, Ar-H). 13C NMR (75 MHz, CDCl3): δ = 55.5 (OCH3), 113.2,
123.7, 127.4, 127.6, 127.7, 128.5, 129.2, 130.4 (Ar, CH, C-9), 136.7,
5-(4-Methoxy-3,5-dimethylphenyl)-10,11-dihydro-5H-dibenzo[a,d]-
137.6, 139.6, 146.9, 158.8 (quat. Ar). EI HRMS (70 eV); m/z: cyclohepten-5-ol (7c): 4-Bromo-1-methoxy-2,6-dimethylbenzene
364.14597 (C26H20O2, M+, 20.17%), 229.10214 (C18H13, 59.53%),
(4.65 g, 21.6 mmol) in THF (100 mL), magnesium (0.54 g,
228.09491 (C18H12, 52.69%), 135.04493 (C8H7O2, 100%), 77.03919 22.3 mmol) and ketone 3 (3.0 g, 14.4 mmol) yielded a solid, which
(C6H5, 3.61%). C26H20O2: calcd. 364.14633; found 364.14597. crystallized from benzene/petroleum ether as 7c (2.9 g, 59%), m.p.
Eur. J. Org. Chem. 2005, 2607–2619
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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