J. Coetzee et al. / Phytochemistry 52 (1999) 737±743
743
requires M+, 716.2833); dH (Table 1); CD [y]284.4
10530, [y ]244.6 47980 and [y ]230.8 5902.
(d, J 8.5, H-5'), 7.01 (dd, J 8.5 and 2.5, H-6'), 7.00 (d,
J 2.5, H-2'), 5.12 (dd, J 2.0 and 12.0, H-2), 5.07 (br m,
J 6.0 and 12.0, H-4), 2.50 (ddd, J 2.0, 6.0 and 13.0, H-
3ax), 2.16 (ddd, J 12.0, 12.0 and 13.0, H-3eq), 3.93, 3.91
and 3.78 (3 Â s, OMe).
The diastereomeric mixture obtained from the TiCl4
catalyzed coupling of 9 and 11 (Scheme 1) was separ-
ated by prep. TLC in benzene±Me2CO (9:1, Â2) to
give three bands at Rf 0.61 (129 mg), 0.54 (22 mg) and
0.41 (12.3 mg). The Rf 0.61 band yielded starting ma-
terial 11. Acetylation of the Rf 0.54 band followed by
prep. TLC in benzene±Me2CO (9:1, Â2) gave two
bands at Rf 0.52 (6.6 mg) and 0.43 (4.5 mg). The Rf
0.52 band yielded 7,3',4'-tri-O-methyl-ent-butini¯avan-
(4b 4 8)-5,7,3',4',5'-penta-O-methyl-3-O-acetylepi-
gallo-catechin 14 as a light-brown amorphous solid.
(Found: M+, 716.2835. C40H44O12 requires M+,
716.2833); dH (Table 1); CD [y]238.8 1595, [y]240.7 7,
[y]246.5 9881, [y]258.4 22, [y]273.1 3481, [y ]279.5 98,
[y]285.9 5553 and [y]298.9 201.
Acknowledgements
Financial support by the Foundation for Research
Development, Pretoria and by the `Sentrale
Navorsingsfonds' of the UOFS is gratefully acknowl-
edged. We thank Mrs L. Davies from Skukuza who
identi®ed Cassia petersiana after it was collected in the
vicinity of Hazyview, Mpumalanga.
The Rf 0.43 band was identi®ed as a diastereomer
of 14 viz. 7,3',4'-tri-O-methylbutini¯avan-(4a 4 8)-
5,7,3',4',5'-penta-O-methyl-3-O-acetylepigallocatechin
13. (Found: M+, 716.2830. C40H44O12 requires M+,
716.2833); dH (Table 1); CD [y]232.0 698, [y]235.6 1671,
[y]237.3 103, [y]243.7 21880, [y]255.1 27, [y ]274.3 5356
and [y ]282.9 22.
Acetylation of the Rf 0.41 band followed by prep.
TLC in benzene±Me2CO (9:1, Â2) gave a band at Rf
0.40 with 1H NMR, CD and MS data identical to
those of the natural product derivative 6.
References
De Angelis, G. G., & Wildman, W. C. (1969). Tetrahedron, 25, 5099.
Elliot, R. J., Sackwild, V., & Richards, W. G. (1982). Journal of
Molecular Structure, 86, 301.
Ferreira, D., Van der Merwe, J. P., & Roux, D. G. (1974). Journal
of the Chemical Society, Perkin Transactions 1, 1492.
Hatano, T., Yamashita, A., Hashimoto, T., Ito, H., Kubo, N.,
Yoshiyama, M., Shimura, S., Itoh, Y., Okuda, T., & Yoshida, T.
(1997). Phytochemistry, 46, 893.
Kawamoto, H., Nakatsubo, F., & Murakami, K. (1991). Kokuzai
Gakkaishi, 37, 488.
Kubo, I., & Kim, M. (1987). Tetrahedron Letters, 9, 921.
Malan, E., Sireeparsad, A., Swinny, E., & Ferreira, D. (1997).
Phytochemistry, 44, 529.
3.6. 7,3',4'-Tri-O-methylbutein 7
Nonaka, G., Miwa, N., & Nishioka, I. (1982). Phytochemistry, 21,
429.
Physical data corresponded to those in the literature
(Van der Westhuizen, et al., 1980).
Palgrave, K. C. (1983). In E. J. Moll, Trees of Southern Africa (p.
288). Cape Town: C. Struik Publishers.
Porter, L. J. (1988). In J. B. Harborne, The Flavonoids. Advances in
Research since 1980 (p. 21). London: Chapman and Hall.
Porter, L. J. (1994). In J. B. Harborne, The Flavonoids. Advances in
Research since 1986 (p. 23). London: Chapman and Hall.
Steynberg, J. P., Brandt, E. V., Ferreira, D., Helfer, C. A., Mattice,
W. L., Gornik, D., & Hemingway, R. W. (1995). Magnetic
Resonance in Chemistry, 33, 611.
3.7. 7,3',4'-Trimethoxy¯avanone 8
Physical data identical to those in the literature
(Van der Westhuizen, et al., 1980).
3.8. 7,3',4'-Trimethoxy¯avan-4-ol 9
Young, E., Brandt, E. V., Young, D. A., Ferreira, D., & Roux, D.
G. (1986). Journal of the Chemical Society, Perkin Transactions 1,
1737.
Compound 8 was treated with NaBH4 in EtOH to
give the diastereomeric mixture 9 (Hatano, et al., 1997;
Malan, et al., 1997). dH (CDCl3) d 7.42 (d, J 8.5, H-5),
6.60 (dd, J 8.5 and 2.5, H-6), 6.46 (d, J 2.5, H-8), 6.90
Van der Westhuizen, J. H., Ferreira, D., & Roux, D. G. (1980).
Journal of the Chemical Society, Perkin Transactions 1, 1003.
Van der Westhuizen, J. H., Ferreira, D. & Roux, D. G. (1981).
Journal of the Chemical Society, Perkin Transactions 1, 1220.