Synthese von polyhydroxy-flavonolmethyläthern mit potentieller cytotoxischer wirksamkeit—I: Synthese von quercetagetin- und gossypetin-dimethyläthern zum strukturbeweis neuer flavonole aus parthenium-, chrysosplenium-, larrea- und spinacia-arten

doi:10.1016/0040-4020(77)84092-1

Tetrahedron

Volume 33, Issue 11, 1977, Pages 1405-1409

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Zusammenfassung

Durch eine modifizierte Allan-Robinson-Methode und Verwendung der präparativen DC wurden die 3,3'-, 3,7- und 3,4'-Dimethyläther von Quercetagetin und der hierzu isomere Gossypetin-3,7-dimethyläther synthetisch dargestellt. Der Quercetagetin 3',7-dimethyläther wurde nach einer modifizierten Algar-Flynn-Oyamada-Reaktion synthetisiert. Durch Vergleich mit kürzlich isolierten Flavonolen aus Parthenium-, Chrysosplenium-, Larrea- und Spinacia-Arten wurden einige Verbindungen in ihrer Struktur bestätigt, andere als unrichtig festgestellt. Das Spinatin aus Spinacia oleracea L. hat nicht die Struktur eines 3,4'-Dimethyl-Quercetagetins, sondern ist das bisher nicht bekannte 3,6-Dimethyl-Quercetagetin-4'-O-glucuronid. Die synthetisierten Flavonole gehören in die Reihe von Substitutionstypen, für die eine cytotoxische Wirksamkeit nachgewiesen wurde.

Abstract

By a modified Allan-Robinson reaction and using the preparative TLC, the 3,3'-, 3,7- and 3,4'-dimethylethers of quercetagetin and the isomeric gossypetin-3,7-dimethylether have been synthesized. The quercetagetin-3',7-dimethylether was prepared via a modified Algar-Flynn-Oyamada-reaction. By comparison with some new flavonols, recently isolated from Parthenium-, Chrysosplenium-, Larrea- and Spinacia species, some of their structures could be confirmed, others as incorrect distincted. Spinatin of Spinacia oleracea L. has not the structure 3,4'-dimethyl-quercetagetin, but is the hitherto not described 3,6-dimethyl-quercetagetin-4'-O-glucuronide. The synthesized flavonols belong to the group of substitution types which have been described as cytotoxic active compounds.

Literatur (14)

E. Rodriguez et al.
Phytochem.
(1972)
M.C. Shen et al.
Phytochem.
(1976)
M. Jay et al.
Phytochem.
(1976)
M. Sakakibara et al.
Phytochem.
(1976)
M.G. Stout et al.
J. Pharm. Sci.
(1964)
H. Wagner et al.
Tetrahedron
(1973)
B.F. Anderson et al.
J. Chem. Soc. (London)
(1964)

There are more references available in the full text version of this article.

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Synthese von polyhydroxy-flavonolmethyläthern mit potentieller cytotoxischer wirksamkeit—I: Synthese von quercetagetin- und gossypetin-dimethyläthern zum strukturbeweis neuer flavonole aus parthenium-, chrysosplenium-, larrea- und spinacia-arten

Zusammenfassung

Abstract

Phytochem.

Phytochem.

Phytochem.

Phytochem.

J. Pharm. Sci.

Tetrahedron

J. Chem. Soc. (London)