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有机化学
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有机化学 ›› 2004, Vol. 24 ›› Issue (6): 654-657. 上一篇    下一篇

研究论文

保幼激素类似物11-甲氧基-3,7,11-三甲基-2,4-十二碳二烯酸异丙酯的简便全合成

朱新海a, 江焕峰*,a, 田兴山b, 冉学光a   

  1. a中国科学院广州化学研究所 广州 510650
    b广东省农科院农业生物技术研究所 广州 510640
  • 收稿日期:2003-07-18 修回日期:2003-12-10 接受日期:2003-12-30 发布日期:2022-09-21
  • 通讯作者: *E-mail: jhf@mail.gic.ac.cn

Simple Total Synthesis of Juvenile Hormone Analogue——Isopropyl 11-Methoxy-3,7,11-trimethyl-2,4-dodecadienoate

ZHU, Xin-Haia, JIANG, Huan-Feng*,a, TIAN, Xing-Shanb, RAN, Xue-Guanga   

  1. a Guangzhou Institue of Chemistry, Chinese Academy of Sciences, Guangzhou510650
    b Agricultural Biotechnology Research Institute, Guangdong Academy of Agricultural Science, Guangzhou 510640
  • Received:2003-07-18 Revised:2003-12-10 Accepted:2003-12-30 Published:2022-09-21

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从价廉的丙酮出发,首先经羟醛缩合、脱水、氧化、酯化、溴代反应合成了4-溴-3-甲基-2-丁烯酸异丙酯,继而与亚磷酸三乙酯反应得到了Wittig-Horner试剂,随后与香茅醛发生Wittig-Horner反应,最后在阳离子树脂催化作用下与甲醇醚化,成功地全合成了具有保幼激素活性的昆虫生长调节剂11-甲氧基-3,7,11-三甲基-2,4-十二碳二烯酸异丙酯.所得标题化合物的四种异构体中,具有较高生物活性的(2E,4E)-异构体的含量达66％.各步所合成化合物的结构经1H NMR, IR, MS分析确证.

关键词: 保幼激素类似物, 11-甲氧基-3,7,11-三甲基-2,4-十二碳二烯酸异丙酯, 香茅醛, Wittig-Horner 反应, 全合成

Isopropyl-4-bromo-3-methyl-2-butenoate was prepared from initial acetone via condensation, dehydrolysis, oxidation, esterification and bromination. Then, reaction of the synthesized isopropyl-4-bromo-3-methyl-2-butenoate with triethyl phosphite provided Wittig-Horner reagent. Subsequently, Wittig-Horner reaction of the Wittig-Horner reagent with citronellal was carried out, and followed by the etherification with methanol catalyzedby cation exchange resin, to finally give isopropyl-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoate with juvenile hormone activity. The 2E,4E stereoisomer (over 66% yield) showed considerably higher activity than other isomers. The structures of all the compounds were confirmed by 1H NMR, IR and MSspectra.

Key words: juvenile hormone analogue, isopropyl 11-methoxy-3,7,11-trimethyl-2,4-dodecadienoate, citronellal, Wittig-Horner reaction, total synthesis