37 Camellia Sapogenolの構造について

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Camellia sapogenol I,II,III(C. Sg. I,II,III) were produced by hydrolysis of camellia saponin isolated from Camellia japonica L.C. Sg. I, C_<30>H_<50>O_4 was a tetrol. And formation of acetonide suggested that C.Sg.I has a 1,3 -glicol moiety, since the presence of a 1,2-glycol moiety was eliminated the observed stability of C.Sg.I toward perhydroiodic acid. Selenium dioxide oxidation of (V) led to a diene, which on the basis of its characteristic triple ultraviolet absorption maxima could be assigned the heteroannularΔ^<11,13(18)>-formulation, thus showing that C.Sg.I vas a member of the β-amyrin class of triterpenes. By chromium trioxide-acetic acid oxidation of C.Sg.I, camellia trione (VI) was produced, and (VI) was proved to be identical with 28-nor-Δ^<12>-oleanene-3,16,22-trione derived from chichipegenin. So structural formula (4) was presented for C.Sg.I. From the production of (IX) and (X), C-28 carbinol did not concern for acetonide formation. So acetonide must be formed between C-16 and C-22-hydroxyl groups. If C-22 hydroxyl group had β-orientation, it must form acetonide with C-28 carbinol. And C-16(β), C-22(α)-diol type was excluded, because it is same with chichipegenin. Then it was assumed that 16α, 22α-diol type was best. Orientation of hydroxyl group at C-3 was determined as β by lithium aluminum hydride reduction of (X). Hence C.Sg.I can now be given systematic name 3β,16α,22α,28-tetrahydroxyolean-12-ene (I). C.Sg.II, C_<30>H_<48>O_5, having aldehyde group was derived to (I) by Wolff-Kishner reduction and also derived to C.Sg.III, C_<30>H_<50>O_5, by lithium aluminum hydride reduction. C.Sg.III formed diacetonide, and from the observation of NMR spectrum of (XIX), C.Sg.II and III were thus shown to be 23-oxo-3β,16α,22α,28-tetrahydroxyolean-12-ene(III and 3β,16α,22α,23,28-pentahydroxyolean-12-ene(III) respectively.
天然有機化合物討論会の論文
1966-09-15

37 Camellia Sapogenolの構造について

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