【作者】 刘璐；

【导师】 杜振亭；

【作者基本信息】 西北农林科技大学 ， 化学生物学， 2020， 硕士

【摘要】 七叶树是世界上著名的观赏树之一,七叶树潜叶蛾的存在严重影响了七叶树的美观与寿命,因杀虫剂等产品有抗药性、污染环境等局限性,故利用信息素来防治害虫是一种比较理想的方式。现今已报道的关于它的合成方法有成本高、路线长或纯度低等缺陷,因此,我们设计了一种简便高效、路线短又经济的方法来合成此信息素。本论文针对七叶树潜叶蛾性信息素的合成采用了C8+C2+C4的策略,该路线以廉价的1,8-辛二醇为原料,首先经TBSCl单保护以45.7%的产率得到8-叔丁基二甲基甲硅烷氧基-1-辛醇,然后经PCC或DMP氧化以83%的产率得到8-叔丁基二甲基甲硅烷氧基-1-辛醛,接着利用Wittig反应与稳定型二碳季膦盐对接,以91%的产率得到第一个关键中间体（E）-10-（叔丁基二甲基甲硅烷氧基）-十二碳-2-烯酸乙酯,然后利用DIBAL-H还原得到（E）-10-（叔丁基二甲基甲硅烷氧基）-十二碳-2-烯醇（75.6%）,再经Mn O₂氧化以76.3%的产率得到（E）-10-（叔丁基二甲基甲硅烷氧基）-十二碳-2-烯醛,然后再利用Wittig反应与活泼型的正丁基季膦盐对接,得到第二个关键中间体（8E,10Z）-十四烷基-8,10-二烯-1-叔丁基二甲基硅烷氧基（78%）,接着用TBAF脱TBS保护以93.6%的产率得到（8E,10Z）-十四碳-8,10-二烯醇,最后经DMP氧化以64.6%的产率得到（8E,10Z）-十四碳-8,10-二烯醛。总的来说,七叶树潜叶蛾性信息素的合成以8步反应,9.4%的总收率得到。同时,我们利用该策略合成了4种同样具有共轭顺反双键结构的信息素,一种为Acria ceramitis性信息素,它采用C8+C2+C2的策略,经8步,以10%的总收率得到,另外三种Idaea biselata,Matsumuraeses falcana,Lobesia botrana性信息素的合成则采用了C7+C2+C3的策略,分别以8步、8步、7步反应,8.7%,11.2%,12.9%的总收率分别得以合成。证明了此法对其他信息素的合成也适用。更多还原

【Abstract】 Horse chestnut is one of the famous ornamental trees in the world.The existence of notorious horse chestnut leafminer seriously affects the beauty and longevity of horse chestnut.Due to the limitations of pesticide resistance and environmental pollution,the use of pheromone controlling pests is an ideal way.The synthetic methods reported to have the disadvantages of high cost,long route or low purity.Therefore,we designed a simple,efficient,short and economical method to synthesize this pheromone.Horse chestnut is one of the famous ornamental trees in the world.The existence of horse chestnut leafminer seriously affects the beauty and lifespan of horse chestnut trees.Due to the limitations of pesticide resistance and environmental pollution,the use of pheromone Controlling pests is an ideal way.The synthetic methods reported to date have the disadvantages of high cost,long route or low purity.Therefore,we designed a simple,efficient,short and economical method to synthesize this pheromone.In this paper,the strategy of C8+C2+C4 is adopted for the synthesis of sex pheromone of horse chestnut leaf miner.The route uses cheap 1,8-octanediol as the starting material,and 8-（（tert-butyldimethylsilyl）oxy）octan-1-ol with TBSCl monoprotection was obtained（8.45%）.Thereafter,after a PCC or DMP oxidation,8-（（tert-butyldimethylsilyl）oxy）octanal in 83%yield was given.It was subjected a Wittig protocol using a stable two-carbon quaternary phosphonium,the first key intermediate ethyl（E）-10-（（tert-butyldimethylsilyl）-oxy）-dec-2-enoateis was obtained with a yield of 91%.After reduction with DIBAL-H,（E）-10-（（tert-butyldimethylsilyl）oxy）dec-2-en-1-ol was yileded（75.6%）.And then this compound was oxidized by Mn O₂,（E）-10-（（tert-butyldimethylsilyl）oxy）dec-2-enal was afforded.As previously,another Wittig reaction was involved with unstable（n-Butyl）-triphenylphosphonium bromide,the second key intermediate tert-butyldimethyl-（（（8E,10Z）-tetradeca-8,10-dien-1-yl）oxy）silane was obtained（78%）,followed（8E,10Z）-tetradecane-8,10-dienol was obtained by TBAF de-protection（93.6%）,（8E,10Z）-tetradeca-ne-8,10-dienal is finally obtained by DMP oxidation（64.6%）.In general,the synthesis of sex pheromones of horse chestnut leaf miner is obtained in 8 steps,with a total yield of9.4%.At the same time,we tested this strategy to synthesize four pheromones that have a conjugated cis-trans double bond structure as well.One is Acria ceramitis sex pheromone,which adopts the C8+C2+C2 strategy,which is obtained in 8 steps at a total yield of 10%.The other three Idaea biselata,Matsumuraeses falcana,and Lobesia botrana sex pheromone are synthesized with the C7+C2+C3 strategy,the reaction was performed in8 steps,8 steps,and 7 steps,respectively,and the total yields of 3.9%,5%,and 5.7%were synthesized.It proves that this method is also applicable to the synthesis of other pheromones.更多还原