摘要
信息素自从蚕蛾醇的发现到现在,已经有五十余年的发展了,并且有些已经成功地应用到综合治理中,还有些正在直接或间接地在昆虫管理中发挥作用。信息素的应用具有化学杀虫农药不可比拟的优势,对于环境没有污染,对于人类没有害处,对于害虫不会产生抗药性,具有专一的针对性,所以是一种可以持续发展的一种防治害虫的手段。
本论文主要研究的是纵坑切梢小蠹的聚集信息素,主要以α-蒎烯为起始原料,合成了其聚集信息素的主要成分(-)-马鞭草烯酮、(+)-马鞭草烯酮、(-)-顺式马鞭草烯醇、(+)-顺式马鞭草烯醇、(-)-反式马鞭草烯醇、(+)-反式马鞭草烯醇。
本文实验从(-)α-蒎烯和(+)α-蒎烯出发,以三氧化铬为氧化剂,N-羟基邻苯二甲酰亚胺为催化剂,催化氧化α-蒎烯,分别合成了两种构型的马鞭草烯酮,收率在57%左右。
以上述合成出的马鞭草烯酮为原料,硼氢化钠为还原剂,在硝酸铈的催化下对马鞭草烯酮还原,进一步提纯后,得到相应的顺式马鞭草烯醇,产率在85%左右。
从两种构型的α-蒎烯为原料,四醋酸铅作为氧化剂,与α-蒎烯的烯丙基位发生反应,合成相对应的反式马鞭草烯醇乙酸酯,产率在26%-35%,然后进一步对反式马鞭草烯醇乙酸酯进行低温碱性条件水解,可以得到顺式马鞭草烯醇,最终马鞭草烯醇的收率在19%-25%。
通过本论文的实验工作达到了之前设计的预想,为以后的信息素研究提供了一些参考。自然界的多样性导致了信息素是一个庞大的系统,因此还有更多未知的东西有待于去发现,还有更多的信息素的合成方法和路径等待着人们去探索。
The pheromone has a history of more than 50 years since the identification of bombykol in 1959 made by Butenandt. Many of them have been practically and successfully used in the IPM (integrated pest management) systems as direct and indirect means for pest control. and yet the application is expected to spread wider worldwide in recent years. Pheromones come in a quite vast variety of chemical forms; therefore, their application has a rather large coverage. Compared with the traditional pesticide, pheromones act as an overwhelmingly superior role. Control of insects using pheromones can guarantee the public environmentally sound and chemical residue-free agricultural products, for pheromones are target-specific and not harmful to the livings.
This dissertation mainly focuses on the synthesis of the major components of the aggregation pheromones of bark beetles Tomicus piniperda L. It contains two chapters.
The first one describes the general historical development and the future of pheromones. The far-reaching significance is conveyed in this chapter as well.
The second one, also the last chapter, is primarily about the design and operation of the synthetic work, which is summarized as below:
1. (-)-verbenone and (+)-verbenone were synthesized with yield of from 40% to 57% by oxidation of (-)-a-pinene and (+)-a-pinene respectively. Chromium trioxide acts as the oxidant and N-Hydroxyphthalimied as the catalyst.
2. (-)-verbenol and (+)-verbenol were synthesized with yield of from 80% to 90% by respective reduction of (-)-verbenone and (+)-verbenone using sodium borohydride as the reductant and cerium(III) trinitrate as the catalyst.
3. (-)-cis-verbenyl and (+)-cis-verbenyl acetate were prepared with yield of from 26% to 35% using lead(IV) tetraacetate.
4. (-)-trans-verbenol and(+)-trans-verbenol were prepared with yield of from 19% to 25% by saponification of (-)-cis-verbenyl and (+)-cis-verbenylacetate in the solution of potassium hydroxide and methanol at 0℃.
The idea of using target-specific and environment-friendly chemicals for the management of insects has been a great driving motivation. And pheromones are just found and considered as this kind of chemicals. The challenge we are facing today is the production in large scale of the pheromone components and the development of appropriate dispenser system. which would cut the cost of the blends and facilitate their use for the sustainable insect management worldwide.
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