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新烟碱类杀虫剂及其1-芳基乙基衍生物的合成和生物活性研究
于观平
Subtype博士
Thesis Advisor许良忠 ; 阿吉艾克拜尔·艾萨
2009-06-04
Degree Grantor中国科学院研究生院
Place of Conferral北京
Degree Discipline有机化学
Keyword新烟碱杀虫剂 噻虫胺 中试 生物活性
Abstract

噻虫胺和3-((1-4-氯苯基)乙基)噻唑烷-2-基-亚胺甲腈(NND-A)属于新烟碱类农药,对不同合成路线及影响合成收率与产物质量的因素,如适宜催化剂、反应时间、温度及溶剂等进行比较全面的研究,是这类化合物的开发应用的出发点。以对氯苯乙酮、氰亚胺荒酸二甲酯和2-氨基乙硫醇盐酸盐为主要原料经还原、氯代、环合、缩合四步合成NND-A,总收率大于80%(以对氯苯乙酮计)。探索工艺过程中意外发现金属离子(铁离子)在一定温度下对中间体α-氯对氯乙基苯的脱氯化氢具有催化作用。以甲基硝基胍、苄胺和2-氯-5-氯甲基噻唑为主要原料经Mannich反应、缩合、分解三步合成噻虫胺,总收率大于80% (以甲基硝基胍计)。重要中间体与目标化合物噻虫胺和NND-A采用气相色谱-质谱联用及核磁共振氢谱和X-射线衍射进行了分析。根据对噻虫胺和NND-A合成路线及反应条件的研究结果,设计了其工艺流程及设备安装图,建立了产品液相分析方法。进行了中试生产,运行结果表明工艺路线可行,收率稳定。依据新农药创制原则,利用生物等排原理对NND-A、噻虫嗪、AKD-1022、噻虫胺和Nithiazine进行了结构改造, 将1-芳基乙基引入新烟碱化合物结构中,设计合成了6个系列36个新化合物。研究了其合成方法、结构特点及生物活性,测定了部分化合物的晶体结构,对化合物的波谱性质及生物活性进行了分析。初步生物活性测试表明引入1-芳基乙基降低了杀蚜虫活性,部分新化合物有一定的植物生长调节活性,其中一个化合物在100 μg/mL浓度下对油菜的生产抑制率达到65.3%。

Other Abstract
Clothianidin and (3-(1-(4-chlorophenyl)ethyl)thiazolidin-2-ylideneamino)formonitrile (NND-A) are two important Neonicotinoid insecticides. There are several methods to synthesize them, but no reference data has exposed which is necessary in industry production. So study and contrast of different routes and reaction factors should be our researsh purpose. NND-A was prepared using 1-(4-chlorophenyl)ethanone, dimethyl cyanocarbonimidodithioate and Cysteamine hydrochloride et al as raw material by four steps of reduction, halogenation, cyclization and condensation reaction, yield 80%. Metal ions unexpected catalyzed the removal of hydrogen chloride from 1-chloro-4-(1-chloroethyl)benzene. Clothianidin was prepared using (Z)-methyl-2-nitroguanidine, phenylmethanamine, and 2-chloro-5-(chloromethyl)thiazole et al as raw material by three steps of Mannich reaction, condensation and decomposition, total yield 80%. Main intermediate and productions NND-A and Clothianidin were confirmed by GC-MS, 1H NMR and X-ray diffractions. The technological process of industry production of NND-A and Clothianidin was designed on the base of research on lab scale, and the analytical method of NND-A and Clothianidin was established. The result of pilot-scale experiments indicated that the production process was reasonable, the rules of operation and safety were feasible. Thirty six novel 1-aryethyl neonicotinoid derivatives in six types of structure were designed and synthesized through bioisosterism on NND-A, Thiamethoxam, Clothianidin, Nithiazine and AKD-1022. Their structures were confirmed by means of elemental analysis, 1HNMR and crystal structure determination. Spectral properties and biological activities were also researched and some of them were found to show plant growth regulation activities. The result of bioactivity test shows that the introduction of the 1-aryethyl group destroys the conjugation system of the molecular, leading to the lower insecticidal activities on aphid.
Document Type学位论文
Identifierhttp://ir.xjipc.cas.cn/handle/365002/3556
Collection资源化学研究室
Affiliation中国科学院新疆理化技术研究所
Recommended Citation
GB/T 7714
于观平. 新烟碱类杀虫剂及其1-芳基乙基衍生物的合成和生物活性研究[D]. 北京. 中国科学院研究生院,2009.
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