Julia-Kocienski烯烃化在棉红铃虫性信息素全合成中的应用

Application of Julia-Kocienski Olefinization in the Synthesis of Sex Pheromone of Cotton Pink Bollworm

[目的]优化现有棉红铃虫性信息素合成方法。[方法]以1,4-丁二醇、正戊醇、庚二醇等廉价试剂为起始原料,采用"C4+C5+C7"骨架构建策略,通过硅醚化羟基保护、Julia-Kocienski烯烃化、溴代、氧化、Wittig反应等步骤,同步合成了棉红铃虫性信息素的2种异构体(Z,Z)-7,11-十六碳二烯-1-醇乙酸酯和(Z,E)-7,11-十六碳二烯-1-醇乙酸酯。[结果]通过对Julia-Kocienski烯烃化反应条件的优化,使2种异构体比值接近天然棉红铃虫性信息素的顺反比值1∶1,总收率为2.65%。[结论]实验不仅为棉红铃虫性信息素的全合成提供了新的简易方便、价格低廉的合成方案,也为其他含2个及以上非共轭双烯的直链性信息素合成提供了参考。

[Aims]This study aims to optimize the synthetic route of sex pheromone of pink bollworm.[Methods]The skeleton construction strategy of‘C4+C5+C7’was adopted,two isomers of pink bollworm sex pheromone(Z,Z)-7,11-hexadecadienol acetate and(Z,E)-7,11-hexadecadienol acetate were synthesized from 1,4-butanediol,n-pentanol and heptanediol by etherification,Julia-Kocienski olefination,bromination,oxidation and Wittig reactions.[Results]By optimizing the reaction conditions of Julia-Kocienski olefinization,the ratio of the two isomers was close to the natural pink bollworm sex pheromone 1:1,and the total yield was 2.65%.[Conclusions]This study not only provides a novel,convenient and low-cost scheme for the synthesis of sex pheromone of cotton pink bollworm,but also provides a reference for the synthesis of straight chain pheromones containing two or more non-conjugated double bonds.