烯虫酯的立体选择性全合成StereoselectiveTotalSynthesisof.PDF

2008 年第 28 卷 有 机 化 学 Vol. 28, 2008 第 3 期, 436～439 Chinese Journal of Organic Chemistry No. 3, 436～439 ·研究论文· 烯虫酯的立体选择性全合成 周 容* 刘建福 苏利霞 杨华武 银董红 (湖南中烟工业公司技术中心 长沙 410007) 摘要 以香茅醛为起始原料, 通过羟醛缩合反应和 Reformatskii 反应得到 3,7,11-三甲基-2,4,10-十二碳三烯酸异丙酯的 双键顺反异构体混合物, 经苯硫酚两次催化双键顺反异构化, (2E,4E)-异构体 3a 的含量由原来的 26%提高到 85%. 再通 过醚化反应, 立体选择性地全合成了具有保幼激素活性的昆虫生长调节剂烯虫酯及其异构体, 即 11-甲氧基-3,7,11-三 甲基-2,4-十二碳二烯酸异丙酯. 其中具有较高生物活性的(2E,4E)-异构体的含量达 85%. 各步所合成的化合物的结构经 IR, MS 和 NMR 证实. 关键词 保幼激素类似物; 烯虫酯; 香茅醛; 双键顺反异构化 Stereoselective Total Synthesis of Methoprene ZHOU, Rong* LIU, Jian-Fu SU, Li-Xia YANG, Hua-Wu YIN, Dong-Hong (Research Center of China Tobacco Hunan Industrial Corporation, Changsha 410007) Abstract The cis- and trans-isomers of isopropyl 3,7,11-trimethyl-2,4,10-dodecatrienoate were prepared from citronellal by aldol condensation and Reformatskii reaction. After the isomeric mixture was subjected twice to the Z-E isometrization of the double bond using benzenethiol as a catalyst, the content of 2E,4E-isomer 3a was increased from 26% to 85%. The mixture of 3a and 3b was etherified to give metho- prene and its isomers possess somewhat juvenile hormone activity. Among them the content of 2E,4E-stereoisomer with quite higher activity can reach 85%. The structures of all the compounds were con- firmed by IR, NMR and MS spectra. Keywords jvenile hormone analogue; methoprene; citronellal; Z-E isomerization of double bond 烯虫酯(Methoprene), 其化学名称 11-甲氧基-3,7,11- Methoprene 及其各种异构体的合成及生物活性, 提出该 三甲基-2E,4E