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A. Speicher et al.
PAPER
6.99 (br d, 1 H), 6.94 (br dd, 2 H), 6.82 (d, J = 8.4 Hz, 1 H), 6.76 (br
d, 1 H), 6.75 (s, 1 H), 4.69 (s, 2 H, CH2OH), 3.87 (s, 3 H, OCH3),
3.75 (s, 3 H, OCH3), 3.73 (s, 3 H, OCH3), 3.53(s, 3 H, OCH3), 2.66
(br s, 4 H, CH2CH2), 1.85 (br s, 1 H, OH).
13C NMR (CDCl3): = 190.2, 159.1, 156.9, 154.9, 154.0, 142.2,
140.1, 134.3, 133.8, 132.4, 132.3, 131.9, 131.5, 131.0, 130.5, 129.5,
128.9, 128.3, 125.5, 119.6, 118.7, 112.9, 110.9, 109.3, 65.2, 60.8,
56.2, 55.7, 55.5, 36.0, 35.9.
(s, 1 H, Ar-H), 6.76 (d, Jcis = 12.0 Hz, 1 H, CH=CH), 6.74 (d, J = 8.4
Hz, 1 H, Ar-H), 6.55 (d, Jcis = 12.0 Hz, 1 H, CH=CH), 6.41 (d,
J = 2.2 Hz, 1 H, Ar-H), 3.95 (s, 3 H, OCH3), 3.75 (s, 3 H, OCH3),
3.66 and 3.53 (2 s, 3 H, OCH3), 3.63 (s, 3 H, OCH3), 2.85–2.29 (m,
4 H, CH2CH2).
13C NMR (CDCl3): = 155.1, 154.3, 153.1, 135.2, 133.5, 132.7,
131.6, 131.1, 130.27, 129.2, 128.2, 127.7, 127.1, 120.9, 119.5,
112.1, 111.6, 110.9, 110.4, 60.7, 56.2, 55.7, 55.5, 37.7, 36.8.
MS (EI): m/z (%) = 584/580 (28/78, M+).
MS (EI): m/z (%) = 550/546 (16/100, M+).
Anal. Calcd for C32H30Cl2O6 (581.49): C, 66.10; H, 5.20. Found C,
65.96; H, 5.26.
Anal. calcd for C32H28Cl2O4 (547.47): C, 70.20; H, 5.15. Found C,
70.31; H, 5.07.
Stilbene-like Bisbibenzyls 53–55
Tetramethoxy Bisbibenzyls 56–58 by Hydrogenation
The dehydrobisbibenzyl 53, 54 or 55 (1.5 mmol) in EtOAc (150
mL) was hydrogenated (3.5 bar, 24 h) in the presence of 5% Pd/C
(250 mg). The mixture was filtered and evaporated. The crude prod-
uct was purified by column chropmatography (silica gel; CHCl3) to
give colorless crystals.
The benzylalcohol 50, 51 or 52 (2.50 mmol) and triphenylphospho-
nium hydrobromide (2.50 mmol) in CH3CN(80 mL) were refluxed
for 24 h. The solvent was evaporated and the residue filtered
through a silica gel pad eluting first with CHCl3 for impurities and
second with EtOH to obtain the product which after concentration
was dissolved in CH2Cl2 (600 mL) and added dropwise over 24 h to
NaOMe (7.50 mmol) in CH2Cl2 (500 mL). After additional stirring
for 24 h the mixture was filtered and evaporated. The cyclic product
was purified by column chromatography (silica gel, CH2Cl2) to give
colorless crystals
Bisbibenzyl 56
Yield: (88%); mp 145 °C; mixture of conformers.
1H NMR (CDCl3): = 7.20–7.13 (m, 2 H, Ar-H), 7.10–6.96 (m, 3
H, Ar-H), 6.90–6.83 (m, 2 H, Ar-H), 6.73 (dd, J1 = 8.1 Hz, J2 = 3.6
Hz, 1 H, Ar-H), 6.39–6.20 (m, 3 H, Ar-H), 3.95 (s, 3 H, OCH3),
3.80–3.45 (s, m, 9 H, 3 OCH3), 3.30–3.23 (m, 1 H), 3.10–2.40 (m,
7 H, 2 CH2CH2).
Bisbibenzyl 53
Yield: (68%); mp 120 °C; mixture of conformers.
1H NMR (CDCl3): = 7.22 (m, 2 H, Ar-H), 7.13 (d, J = 7.5 Hz, 1
H, Ar-H), 7.05 (m, 2 H, Ar-H), 6.90–6.82 (m, 4 H, Ar-H), 6.74 (d,
J = 8.4 Hz, 1 H, Ar-H), 6.64 (m, 2 H, CH = CH), 6.47 (s, 1 H, Ar-
H), 3.95 and 3.84 (2 s, 3 H, OCH3), 3.81 and 3.80 (2 s, 3 H, OCH3),
3.76 (s, 3 H, OCH3), 3.68 and 3.51 (s, 3 H, OCH3), 2.90–2.30 (m, 4
H, CH2CH2).
13C NMR (CDCl3): = 157.1, 156.5, 155.3, 154.1, 154.0, 142.6,
142.5, 142.2, 141.7, 135.3, 135.0, 134.3, 134.0, 133.9, 133.8, 132.9,
132.8, 132.2, 132.0, 131.5, 131.2, 130.7, 129.1, 128.2, 127.6, 127.3,
127.2, 127.0, 126.8, 123.3, 120.7, 119.3, 113.9, 112.3, 112.0, 111.2,
111.0, 110.7, 110.4, 110.2, 55.9, 55.8, 55.8, 55.7, 55.6, 55.3, 39.1,
38.8, 38.5, 38.3, 37.6, 36.9, 36.6, 36.0.
13C NMR (CDCl3): = 157.4, 156.8, 156.2, 155.4, 154.2, 142.2,
141.7, 140.5, 139.8, 135.2, 133.7, 135.2, 133.7, 131.9, 131.8, 131.6,
131.3, 131.2, 131.0, 130.4, 130.2, 129.8, 129.7, 128.9, 128.7, 128.3,
127.9, 127.6, 127.5, 127.2, 126.9, 120.9, 120.9, 119.4, 119.3, 112.3,
112.0, 111.6, 110.9, 110.6, 110.6, 110.4, 56.1, 55.9, 55.8, 55.7,
55.6, 55.5, 55.4, 38.1, 37.7, 37.5, 36.8.
MS (EI): m/z (%) = 517/514 (13/100, M+).
Anal. Calcd for C32H31ClO4 (515.04): C, 74.62; H, 6.07. Found C,
74.56; H, 5.96.
Bisbibenzyl 57
Yield: (72%); mp 140 °C; mixture of conformers.
MS (EI): m/z (%) = 515/512 (12/100, M+).
1H NMR (CDCl3): = 7.21–7.15 (m, 2 H, Ar-H), 7.12–6.95 (m, 3
H, Ar-H), 6.88–6.81 (m, 2 H, Ar-H), 6.75 (dd, J1 = 8.0 Hz, J2 = 3.2
Hz, 1 H, Ar-H), 6.41–6.23 (m, 3 H, Ar-H), 3.91 (s, 3 H, OCH3),
3.80–3.45 (s, m, 9 H, OCH3), 3.28–3.24 (m, 1 H), 3.15–2.30 (m, 7
H, 2 CH2CH2).
13C NMR (CDCl3): = 157.3, 156.7, 155.5, 154.5, 154.1, 142.7,
142.4, 142.2, 141.1, 135.6, 135.0, 134.5, 134.1, 133.7, 133.5, 132.8,
132.6, 132.4, 132.2, 131.4, 131.2, 130.2, 129.4, 128.5, 127.4, 127.3,
127.2, 127.0, 126.5, 123.1, 120.4, 119.5, 113.6, 112.5, 112.3, 111.8,
111.0, 110.5, 110.3, 110.0, 56.0, 55.8, 55.7, 55.6, 55.4, 55.3, 39.1,
38.8, 38.6, 38.3, 37.5, 36.7, 36.5, 36.2.
Anal. Calcd for C32H29ClO4 (513.03): C, 74.92; H, 5.70. Found C,
75.01; H, 5.64.
Bisbibenzyl 54
Yield: (72%); mp 86 °C; mixture of conformers.
1H NMR (CDCl3): = 7.26–7.24 (m, 2 H, Ar-H), 7.20–7.00 (m, 2
H, Ar-H), 6.88–6.86 (m, 2 H, Ar-H), 6.82–6.78 (m, 2 H, Ar-H),
6.75–6.73 (m, 2 H, Ar-H), 6.72 (d, Jcis = 12.0 Hz, 1 H, CH=CH),
6.62 (d, Jcis = 12.0 Hz, 1 H, CH=CH), 6.49 (br d, 1 H, Ar-H), 3.85
(s, 3 H, OCH3), 3.80 (s, 3 H, OCH3), 3.76 and 3.68 (2 s, 3 H, OCH3),
3.64 and 3.58 (s, 3 H, OCH3), 2.79–2.63 (br s, 4 H, CH2CH2).
13C NMR (CDCl3): = 159.1, 157.6, 152.9, 149.8, 142.8, 142.0,
137.5, 134.5, 132.1, 131.7, 131.0, 130.2, 129.7, 129.1, 127.5, 127.2,
120.7, 114.6, 114.4, 113.8, 111.5, 111.2, 110.0, 56.7, 56,4, 55.9,
55.6, 55.5, 55.2, 53.4, 53.0, 37.8, 37.4, 36.8, 36.2.
MS (CI): m/z (%) = 517/514 (21/100, M+).
Anal. Calcd for C32H31ClO4 (515.04): C, 74.62; H, 6.07. Found C,
74.52; H, 6.12.
Bisbibenzyl 58
Yield: (88%); mp 131 °C; mixture of conformers.
MS (CI): m/z (%) = 513/511 (45/100, M – 1+).
Anal. Calcd for C32H29ClO4 (513.03): C, 74.92; H, 5.70. Found C,
75.06; H, 5.64.
1H NMR (DMSO-d6): = 7.52–7.48 (m, 1 H, Ar-H), 7.27–7.12 (m,
5 H, Ar-H), 6.96 (dd, J1 = 10.1 Hz, J2 = 3.1 Hz, 1 H), 6.50–6.45 (m,
1 H, Ar-H), 6.25–6.23 (m, 1 H, Ar-H), 6.15–6.14 (m, 1 H, Ar-H),
3.90 (s, 3 H, OCH3), 3.67–3.33 (5 s, 9 H, OCH3), 3.16–2.87 (m, 4
H, CH2CH2), 2.49–2.11 (m, 4 H, CH2CH2).
13C NMR (DMSO-d6): = 155.0, 154.2, 142.1, 141.6, 136.8, 135.2,
135.0, 133.9, 133.7, 133.2, 132.9, 132.2, 132.0, 131.7, 131.2, 130.8,
Bisbibenzyl 55
Yield: (78%); mp 140 °C
1H NMR (CDCl3): = 7.26 (m, 1 H, Ar-H), 7.22 (m, 1 H, Ar-H),
7.14 (m, 1 H, Ar-H), 7.06 (dd, J1 = 8.4 Hz, J2 = 2.2 Hz, 1 H, Ar-H),
6.90 (m, 1 H, Ar-H), 6.88 (s, 1 H, Ar-H), 6.86 (s, 1 H, Ar-H), 6.81
Synthesis 2002, No. 17, 2503–2512 ISSN 0039-7881 © Thieme Stuttgart · New York