|Place of Conferral||北京|
|Keyword||昆虫性信息素 合成 梨小食心虫 Wittig反应|
昆虫性信息素是指成熟的雌虫个体分泌到体外，以引诱雄虫前来进行交配的微量化学物质。利用人工合成的昆虫信息素，可以人工摸拟昆虫之间的信息通讯，来对昆虫进行虫情监测，大量诱捕，干扰交配以及综合防治。梨小食心虫(Grapholitha molesta)，简称梨小，俗名东方果蛀蛾(Oriental fruitmoth)，属鳞翅目，卷叶蛾科。Roelofs 等鉴定出其结构为 (Z)-8-十二碳烯醇乙酸酯(1)。很多的研究表明，用化合物1 和它的反式异构体(2)，以90/10~95/5 的比例混合制成的性诱芯对梨小的诱引能力有较好的诱蛾活性。本文对梨小食心虫的性信息素的合成进行了研究，主要通过两条路线合成了这两个目标化合物。路线一以10-羟基癸酸为起始原料，经酯化，Hunsdiecker反应，脱溴化氢，臭氧化和Wittig反应，以20%的总收率合成了(Z/E)-8-十二碳烯醇乙酸酯。路线二通过2-(6-溴己氧基)-四氢吡喃与烯丙基溴化镁的交叉偶联，再经官能团转换，合成了中间体8-壬烯醇乙酸酯。
Insect sex pheromones are referred as the trace amount of chemicals emitted by the mature female insects to send messages and attract the male ones to copulate with. Synthesized insect pheromones can be utilized to the monitoring, mass-trapping, mating disruption and the integrated control of the target pests. Grapholitha molesta (Lepidoptera: Tortricidae) is also named as the oriental fruit moth, is one kind of pests to peaches, apples, pears, apricots, etc. About 40 years ago its sex pheromone component was isolated and identified as (Z)-8-dodecenyl acetate (1). Many researchers found that the sex traps that contain 1 and 5%~10% its E-isomer (2) are more biologically active when used in the field evaluations. This paper is aimed to synthesize the sex pheromone of Grapholitha molesta by the following 2 main routies. The fist one is started from 10-hydroxydecanoic acid (17), which is esterification with acetic anhydride in pyridine to convert into 10-acetoxydecanoic acid (18). Then a classical Hunsdiecker reaction of the acid 18 gave an alkylbromide (19). Elimination of HBr upon reaction of 19 with LiBr and Li2CO3 produced a terminal olefin (8-nonenyl acetate, 20). Ozonolysis of the terminal olefin gave key intermediate 10 (8-acetoxyoctanal). Finally 1 and 2 was obtained by the Wittig reaction of 10 with n-butyltriphenylphosphonium bromide (9) under the condition of n-butyllithium as the base. Another route is designed to synthesize the intermediate 8-nonenyl acetate by the cross coupling reaction of the 6-bromohexanol (22) and the allylmagnesium bromide. The yield is relatively low if the alcohol was not protected; while the targeted compound can be obtained by the yield over 90% when 22 was protected by THP. The coupling between the allyl bromide and the Grignard reagent of 2-(6-bromohexyloxy)-tetrahydro-pyran was also tried and found that the outcome is not satisfactory. Thus, we demonstrated 2 novel and convenient pathways to the target sex pheromones.
|黄国正. 梨小食心虫性信息素的合成研究[D]. 北京. 中国科学院研究生院,2007.|
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