Four phloroglucinol derivatives (kamalins) have been isolated from Mallotus philippinensis. These are rottlerin (la), isoallorottlerin (II), the ,,red compound" (III) and the ,,yellow compoundc' (IV). In addition. methylene-bis-rnethylphloroacetophenone (V) has been detected by TLC. The natural occurence of these substances is discussed. Rksumk Quatre de'rivks phloroglucinoliques (kamalines) ont e'tk isolks de Mallotus philippinensis. Ils sont la rottlkrine (la), Pisoallorottle'rine (II), la ,,substance rougeP (Ill), et la ,,substance jaune" (IV). De plus, le mkthylkne-bis-me'thylphloroacktophknone (V) a ktk dktectk par la CCM. L'existence naturelle des ces substances est discutke. Mallotus philippinensis (LAM.) M~~LL.-ARG. (Euphorbiaceae)' is a dioecious shrub or small tree indigenous to southeastern Asia and widely distributed throughout tropical Asia, Australia and the Philippines [I]. The drug, Kamala, a red powder consisting of glandular and stellate non-glandular hairs from the cHpsules of the plant, has long been used as an anthelminticum and as an orange dye for silk. Kamala has been included in several European pharmacopoeias. According to early chemical investigations [I], kamala contains phenolic compounds of which rottlerin (mallotoxin) is the main compound. It was first isolated in 1855 by ANDERSON [l]. AS a result of extensive studies by British [3-71, Indian [8-91, and German [10-111 investigators before World War I1 the structure (Ia) was accepted for rottlerin [ 6 ]. NARANG et al. [8-91 also isolated in 1937.a The genus Mallotus LOUR. consists of 140 species distributed in eastern and southeastern Asia, Indomalesia, New Caledonia, Fiji and northern and eastern Australia. Two taxa also occur in tropical Africa and Madagascar [2].
Phloroglucinol derivatives o f eleven Dryopteris species from Japan hai~e been investigated. Aspidin AB, trisdesaspidin BBB, trisflavaspidic acid, rnethylene-bisaspidinol, and trisaspidinol have been found for' the first time in Japanese Dryopteris. D. erythrosora is unique among the Dryopteris species examined so far in containirzg isobutyryl (iB) side chain homologues. The phlorogl~~cinol derivatives of the eleven Dryopteris taxa investigated have been compared with those of related taxa on a worldwide basis. Les de'rivks phloroglucinoliques de onze espkces de Dryopteris d'origine japonaise orzt e'tk examinb. L'aspidine AB, le trisdesaspidine BBB, l'acide trisflavaspidique, le mkthylkne-bis-aspidinol et le trisaspidinol ont e'te' trouve's pour la premikre fois duns les Dryopteris japonais. D. erythrosora est unique parmi les espkces de Dryopteris examinkes jusqu'ici contenant des homologues isobutyryles (iB) des chaines late'rales. Les dkrivks phloroglucinoliques des onze taxons exa m i n b de Dryopteris ont e'te' compares avec ceux des taxons apparentb stir la base globule. Dryopteris is largely a north-temperate genus with many abundant species in Eurasia, especially in China. However, there are scattered species in all parts of the world, including the southern hemisphere. In the tropics these ferns are confined to the mountains and higher altitudes. HOLTTUM [I] notes that some 90 species have been recorded from China, but only three from the Malay Peninsula. HIRABAYASHI [2] lists 59 species from Japan of which 56 have been cytologically investigated. The phloroglucinol derivatives of thirty five Japanese Dryopteris species have been studied by HISADA and coworkers [3-171 in a series. of works from 1961. However, in continuation of our investigations on anthelmintically active phloroglucinol derivatives in European [18-231, North American 10 rhizomes sent by K. IWATSUKI); According to ITO [31], the Dryopteris genus of Japan can be divided into four sections: Eudryopteris, Polysticho-drys, Lophodium, and Nephrocystis, which are still divided into several subsections [cf. also ref. 21. The divisions of ITO were later changed so that two Japanese ferns, which previously were considered to belong in the genus Ctenitis, at present are included in the Dryopteris genus as an separate group, Dryopteris snbg. Nothoperanema TACAWA. This group is sometimes also separated as an own genus Nothoperanema (TACAWA) CHING. Excellent photographs of most Japanese Dryopteris species are published by TACAWA [32].
Carbon-13 NMR spectra of eight 2-acyl- and -6-methyl-substituted filicinic acid (4,4-dimethyl-1,3,5-cyclohexantrione) derivatives were recorded in hexadeuterioacetone and in deuteriochloroform and the signals assigned on basis of chemical shifts and J (CH) coupling considerations. The data prove that the prevailing tautomeric structure of these derivatives is the monoketonic one with the carbonyl function in position 3 and hydroxyl groups in positions 1 and 5, the former being hydrogen bonded to the acyl side chain carbonyl. The 2-acyl-6,6-dimethyl compounds have the diketonic structure and a hydrogen-bonded hydroxyl group in position 3. The skeletal structure of 2-butyryl-4-hydroxy-4,6-dimethyl-1,3,5-cyclohexantrione is identical with that of humulone. This compound and its homologues also exist in the monoketonic tautomeric form, where C-3 carries the carbonyl function. In the solvents used the 6-methyl-2,3-dihydropyrane-2,4-dione exists predominantly as a single tautomer having two ring double bonds; the remaining carbonyl group is a part of an alpha, beta-unsaturated lactone grouping.
The structure of internal glands in the rhizomes of Dryopteris assirnilis S. WALKER is investigated by electron microscopy. The anthelmintically active phloroglucinol derivatives are biosynthesized in the glandular cytoplast and subsequently excreted through the plasmalemma and the cell wall to be accumulated under the cuticle as constituents of a subcuticular excretion layer. Some of the final reaction steps in the biosythesis of these compounds are possibly associated with the excretion process.
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