November 2001
1281
7.64 (1H, d, Jϭ5.0 Hz, H-5), 7.66 (1H, d, Jϭ5.0 Hz, H-6),
3,4,3Ј,4Ј-Dimethylenedioxystilbene (13): Yield 358 mg
1
4.00 (3H, s, 7-OMe), 4.04 (3H, s, 8-OMe); 13C-NMR (63%); EI-MS m/z: 284 [Mϩ]; H-NMR (CDCl3) d: 5.97
(CD3OD) d: 57.5 (q, 7-OMe), 62.0 (q, 8-OMe), 121.8 (d, C- (4H, s, –OCH2O–), 6.79 (2H, d, Jϭ8.0 Hz, H-5), 6.86 (2H, s,
3), 122.2 (d, C-6), 123.9 (d, C-5), 125.4 (s, C-4a), 133.1 (s, –CHϭCH–), 6.90 (2H, dd, Jϭ8.0, 1.7 Hz, H-6), 7.03 (2H, d,
C-8a), 140.9 (d, C-1), 144.8 (s, C-8), 147.6 (d, C-4), 150.5 (s, Jϭ1.7 Hz, H-2); 13C-NMR (CDCl3) d: 111.5 (t, –OCH2O–
C-7).
ϫ2), 116.4 (d, C-2, 2Ј), 119.8 (d, C-5, 5Ј), 134.1 (d, C-6, 6Ј),
Stilbenes 3,4-Methylendioxybenzyl Bromide (23a): 140.4 (d, –CHϭCH–), 146.3 (s, C-1, 1Ј), 163.4 (s, C-3, 3Ј),
1
Yield 1.8 g (83%); EI-MS m/z: 215 [Mϩ]; H-NMR (CDCl3) 164.5 (s, C-4, 4Ј).
d: 4.55 (2H, s, –CH2Br), 5.95 (2H, s, –OCH2O–), 6.74 (1H,
3,3Ј,4,4Ј-Tetramethoxystilbene (14): Yield 396 mg (66%);
1
d, Jϭ7.8 Hz, H-5), 6.85 (1H, dd, Jϭ7.8, 1.7 Hz, H-6), 6.87 EI-MS m/z: 300 [Mϩ]; H-NMR (CDCl3) d: 3.90 (6H, s,
(1H, d, Jϭ1.7 Hz, H-2); 13C-NMR (CDCl3) d: 34.2 (t, –OMe), 3.95 (6H, s, –OMe), 1.86 (2H, d, Jϭ8.2 Hz, H-5),
–CH2Br), 101.3 (t, –OCH2O–), 108.3 (d, C-5), 109.5 (d, C- 6.93 (2H, s, –CHϭCH–), 7.04 (2H, dd, Jϭ8.2, 2.0 Hz, H-6),
2), 122.7 (d, C-6), 131.5 (s, C-1), 147.8 (s, C-3), 147.9 (s, C- 7.06 (2H, d, Jϭ2.0 Hz, H-2); 13C-NMR (CDCl3) d: 55.9 (q,
4).
4-, 4Ј-OMe), 56.0 (q, 3-, 3Ј-OMe), 108.6 (d, C-2, 2Ј), 111.3
3,4-Dimethoxybenzyl Bromide (23b): Yield 2.0 g (85%); (d, C-5, 5Ј), 119.6 (d, C-6, 6Ј), 126.6 (d, –CHϭCH–), 130.7
1
EI-MS m/z: 231 [Mϩ]; H-NMR (CDCl3) d: 3.88 (3H, s, (s, C-1, 1Ј), 148.7 (s, C-3, 3Ј), 149.1 (s, C-4, 4Ј).
–OMe), 3.90 (1H, s, –OMe), 4.50 (2H, s, –CH2Br), 6.81 (1H,
3,4-Dimethoxy-3Ј,4Ј-methylenedioxystilbene (15): Yield
1
d, Jϭ8.2 Hz, H-5), 6.92 (1H, d, Jϭ2.1 Hz, H-2), 6.98 (1H, 338 mg (63%); EI-MS m/z: 268 [Mϩ]; H-NMR (CDCl3) d:
dd, Jϭ8.2, 2.1 Hz, H-6); 13C-NMR (CDCl3) d: 34.4 (t, 3.88 (3H, s, 4-OMe), 3.93 (3H, s, 3-OMe), 5.95 (2H, s,
–CH2Br), 55.91 (q, 3-OMe), 55.93 (q, 4-OMe), 111.0 (d, C- –OCH2O–), 6.78 (1H, d, Jϭ8.0 Hz, H-5Ј), 1.84 (1H, d, Jϭ
2), 112.1 (d, C-5), 121.6 (d, C-6), 130.2 (s, C-1), 149.1 (s, C- 8.2 Hz, H-5), 6.88 (2H, s, –CHϭCH–), 6.91 (1H, dd, Jϭ8.0,
4), 149.3 (s, C-3).
1.7 Hz, H-6Ј), 7.02 (1H, dd, Jϭ8.2, 2.0 Hz, H-6), 7.03 (1H, d,
3,4-Methylenedioxybenzylphosphonate (25a): Yield 2.3 g Jϭ2.0 Hz, H-2), 7.04 (1H, d, Jϭ1.7 Hz, H-2Ј); 13C-NMR
(85%); EI-MS m/z: 272 [Mϩ]; H-NMR (CDCl3) d: 1.26 (CDCl3) d: 55.88 (q, 3-OMe), 55.96 (q, 4-OMe), 101.1 (t,
1
(6H, t, Jϭ7.0 Hz, CH3CH2–), 3.03 (1H, s, H-1Јa), 3.09 (1H, –OCH2O–), 105.4 (d, C-2Ј), 108.4 (d, C-5Ј), 108.7 (d, C-2),
s, H-1Јb), 4.03 (4H, m, CH3CH2–), 5.94 (2H, s, –OCH2O–), 111.3 (d, C-5), 119.6 (d, C-6), 121.1 (d, C-6Ј), 126.6 (d,
6.72 (1H, dd, Jϭ8.0, 1.5 Hz, H-6), 6.75 (1H, d, Jϭ8.0 Hz, H- –CHϭCH–), 126.9 (d, –CHϭCH–), 130.6 (s, C-1), 132.1 (s,
5), 6.81 (1H, d, Jϭ1.5 Hz, H-2); 13C-NMR (CDCl3) d: 16.4 C-1Ј), 147.1 (s, C-4Ј), 148.2 (s, C-3Ј), 148.8 (s, C-4), 149.2
(q, CH3CH2–), 34.1 (d, C-1Ј, t), 62.2 (t, CH3CH2–), 101.0 (t, (s, C-3).
–OCH2O–), 108.3 (d, C-2), 111.0 (d, C-5), 122.9 (d, C-6),
125.1 (s, C-1), 146.6 (s, C-3), 147.8 (s, C-4).
Calculation All data were calculated by using CAChe
Ver. 4.02 of the SONY Techtronics Company. The structures
3,4-Dimethylenedioxybenzylphosphonate (25b): Yield 2.6 g were searched by the calculation that used the AM1 method.
1
(90%); EI-MS m/z: 288 [Mϩ]; H-NMR (CDCl3) d: 1.25 It was confirmed that they show no significant difference
(6H, t, Jϭ7.1 Hz, CH3CH2–), 3.07 (1H, s, –CH2–), 3.12 (1H, from the structures that was obtained by the PM3 method.
s, –CH2–), 3.86 (3H, s, -OMe), 3.88 (3H, s, –OMe), 4.02 By using the stable structure that was obtained by optimiza-
(4H, m, CH3CH2–), 6.82 (1H, d, Jϭ2.1 Hz, H-2), 6.84 (1H, tion calculation, the physicochemical characteristic value of
dd, Jϭ8.1, 2.1 Hz, H-6), 6.87 (1H, d, Jϭ2.1 Hz, H-5); 13C- the atom that is common to each compound was calculated to
NMR (CDCl3) d: 16.5 (q, CH3CH2–), 33.9 (d, –CH2–), 55.83 Project Leader. The characteristic values were calculated by
(q, 3-OMe), 55.88 (q, 4-OMe), 62.2 (t, CH3CH2–), 111.2 (d, using the standard method.
C-2), 113.0 (d, C-5), 122.0 (d, C-6), 123.9 (s, C-1), 148.1 (s,
C-3), 148.9 (s, C-4).
REFERENCES
3,4-Methylendioxybenzaldehyde (24a): Yield 56 mg (75%);
1
EI-MS m/z: 150 [Mϩ]; H-NMR (CDCl3) d: 6.08 (2H, s,
1) Yoneda K., J. Trad. Sino-Japanene Med., 13, 65—70 (1992).
2) Watanabe K., J. Trad. Sino-Japanese Med., 2, 37—43 (1981); Yamada
H., ibid., 13, 79—86 (1992).
3) Hirano H., Tokuhira T., Yokoi T., Shingu T., Natural Medicines, 51,
516—518 (1997).
4) Hirano H., Tokuhira T., Yokoi T., Shingu T., J. Trad. Med., 13, 338—
339 (1996).
5) Weinstein B., Hylton T. A., Tetrahedron, 20, 1725—1728 (1964).
6) Bevis M. J., Fordes E. J., Naik N. N., Uff B. C., Tetrahedron, 27,
1253—1259 (1971).
–OCH2O–), 6.93 (1H, d, Jϭ1.9 Hz, H-6), 7.33 (1H, d,
Jϭ1.6 Hz, H-2), 7.42 (1H, dd, Jϭ7.9, 1.6 Hz, H-5), 9.82 (1H,
s, –CHO); 13C-NMR (CDCl3) d: 102.1 (t, –OCH2–), 107.0
(d, C-2), 108.4 (d, C-5), 128.6 (d, C-6), 131.9 (s, C-1), 148.8
(s, C-3), 153.1 (s, C-4), 190.3 (d, –CHO).
3,4-Dimethoxybenzaldehyde (24b): Yield 65 mg (78%);
1
EI-MS m/z: 166 [Mϩ]; H-NMR (CDCl3) d: 3.95 (3H, s,
–OMe), 3.97 (3H, s, -OMe), 6.99 (1H, d, Jϭ8.2 Hz, H-5),
7.42 (1H, d, Jϭ1.9 Hz, H-2), 7.47 (1H, Jϭ8.2, 1.9 Hz, H-6),
9.86 (1H, s, –CHO); 13C-NMR (CDCl3) d: 56.0 (q, 3-OMe),
56.2 (q, 4-OMe), 109.0 (d, C-2), 110.5 (d, C-5), 126.8 (d, C-
6), 130.2 (s, C-1), 149.7 (s, C-3), 154.5 (s, C-4), 190.9 (d,
–CHO).
7) Sainsbury M., Brown D. W., Dyke S. F., Hardy G., Tetrahedron, 25,
1881—1895 (1969).
8) Takkar K., Geahlen R. L., Cushman M., J. Med. Chem., 36, 2950—
2955 (1993).
9) Robert A., Nezamasa J. E., Lancaster C., Hanchar A. J., Gastroenterol-
ogy, 77, 433—443 (1979).