Isomerization of Caryophyllene Oxide Catalyzed by Solid Acids and Bases.
作者:Kazushi Arata、Kiyoharu Hayano、Haruhisa Shirahama
DOI:10.1246/bcsj.66.218
日期:——
The reaction of caryophyllene oxide over eleven catalysts of solid acids and bases gave 4,5-dihydrocaryophyllen-5-one (III), (1R, 5S, 8R, 9R)-4,4,8-trimethyltricyclo[6.3.1.01,5]dodeca-2-en-9-o1 (IV), (2S, 5R, 9R)-caryophylla-1(12),8(15)-dien-9-ol (V), (2S, 5R, 9R)-caryophylla-1(12),7-dien-9-ol (VI), and (2S, 5R, 9S)-caryophylla-1(12)-7-dien-9-ol (VII). A large amount of III was formed together with IV over FeSO4 and Zr(SO4)2. Allylic alcohols (V, VI, and VII) were preferentially given by Al2O3–II and TiO2–ZrO2 in >74% selectivity: 96% on TiO2–ZrO2. Other catalysts formed three to five species of the products uniformly.
石竹烯氧化物在十一种固体酸和碱催化剂上反应得到4,5-二氢石竹烯-5-酮(III),(1R,5S,8R,9R)-4,4,8-三甲基三环[6.3.1.01,5 ]dodeca-2-en-9-o1 (IV), (2S, 5R, 9R)-石竹-1(12),8(15)-dien-9-ol (V), (2S, 5R, 9R) -石竹-1(12),7-二烯-9-醇(VI),和(2S,5R,9S)-石竹-1(12)-7-二烯-9-醇(VII)。 FeSO4 和 Zr(SO4)2 上形成了大量的 III 和 IV。烯丙醇(V、VI 和 VII)优先由 Al2O3-II 和 TiO2-ZrO2 生成,选择性 >74%:在 TiO2-ZrO2 上为 96%。其他催化剂均匀形成三至五种产物。