9 うんなんそけいの苦味成分jasmininの構造

概要

論文の詳細を見る
A bitter principle, jasminin, C_<26>H_<38>O_<12>, mp.159-161°[α]_D-244.9°, isolated from the leaves of Jasminum primulinum HEMSL. ("unnan sokei." in Japanese) was proved to be represented by the structure (XIII) or (XIV) on the following evidences. The IR, UV and NMR spectral data, and titration suggested that jasminin was a iridoid glucoside having one lactone, one ethylidene, one hydroxyl and two secondary methyl groups. The relation between iridoid and ethylidene double bond was established as in IV by treatment of (5) with Ac_2O-KHSO_4. Further, alkaline fission of jasminin suggested the environment (VI) for jasminin. The system (VI) can be explained by the fact that acidic treatment of jasminin gave aldehydes (7), (8) and diacetate (9), and that nitric acid oxidation of jasminin gave methyl ester E (11). Derivatives from (5) suggested that the hydroxyl A was primary. The NMR spectral data of aldehyde (12) and diacetate (16) showed that the hydroxyl A was included in CH_3CHCH_2OH system. Hydrolysis of jasminin with NaOMe, followed by acetylation gave triacetate (18). The spectral data of anhydride (19) derived from (18) clarified the 1,5-relationship between the hydroxyl A and the hydroxyl B, and the presence of five-membered ring. From the spectra analysis and biogenetic reason, the oxidation products of (16) and (18) can be expressed in (23, R=H) and (17) respectively.
天然有機化合物討論会の論文
1967-09-25