18 台湾産ベニヒ材成分,特に三重結合を有するノルセスキテルペノイドの構造と合成

概要

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Acetylenic nor-sesquiterpene alcohols, dehydrochamaecynenol (I), C_<14>H_<18>O, [α]_D-193.1° and chamaecynenol (II), C_<14>H_<20>O, [α]_D+9.3°, and an acetate of II (III), C_<16>H_<22>O_2, have been isolated from Benihi tree (Chamaecyparis formosesis Matsum.) grown in Taiwan. The IR and NMR spectra of I and II show the prensence of a primaly hydroxyl, a terminal acetylenic linkage and a tertiary methyl group. UV spectrum of I showes the presence of a conjugated double bond. From NMDR and ORD, the structure (E) having a cis-decalin system was proposed for I. The structure (L) was also proposed for II and III from some reactions and NMDR of the derivatives of II. 1-Santonin (XIV) was transformed to cis-decalone carboxylic acid (XVII). Chlorodecarboxylation of XVII, followed by reduction with NaBH_4 and treatment with tBuO^- afforded ethylenic alcohol (XX). Bromination of XX, successive dehydrobromination and oxidation of the alcohol gave acetylenic ketone (XXIII). Bromination of XXIII in AcOH-HBr afforded two kinds of monobromide (XXIV, XXV). Dehydrobromination of XXIV with LiCl-Li_2CO_3 in DMF afforded chamaecynone (XXVI) identical with natural one.
天然有機化合物討論会の論文
1967-09-25