【作者】 姜广华；

【导师】 吴文君；

【作者基本信息】 西北农林科技大学 ， 农药学， 2002， 硕士

【摘要】 在进行苦皮藤素衍生合成时，偶然得到的一个化合物对粘虫有强烈的击倒活性，后经证实为甲基苯氨基甲酸酯。但迄今为止，N-苯基氨基甲酸酯类化合物主要是作为除草剂和杀菌剂开发使用，并已证实无杀虫活性。对这类化合物的结构与活性的关系亦未有深入系统的研究。本项研究合成了一系列苯基氨基甲酸酯类化合物，分别测定了其杀虫、杀菌和除草活性，并对其中的正丁基N-苯基氨基甲酸酯进行了作用方式和杀虫谱测定，并对这类化合物进行了二维构效和三维构效关系的研究。得到如下结果： 1．苯基氨基甲酸酯类化合物对粘虫和朱砂叶螨表现出明显的杀虫杀螨活性，其中15号化合物即2，4-二硝基苯基N-苯基氨基甲酸酯的活性最高，其LD₅₀为0.47μg／头和683.9mg／L。 2．丁基N-苯基氨基甲酸酯对供试粘虫主要表现为触杀作用，无胃毒和熏蒸作用。对供试的小菜蛾有明显活性，浓度为25mg／ml（点滴法），死亡率分别86.6％。对朱砂叶螨的活性最高，当浓度为0.1mg／ml （药膜法）时，死亡率为100％；当浓度为1.0mg／ml（喷雾法），死亡率为97.3％。丁基N-苯基氨基甲酸酯对家蝇（点滴法）、玉米象、小地老虎、菜青虫（点滴法）、甘蓝夜蛾（胃毒与点滴法）没有活性，对家蝇（药膜法）、菜蚜、桃蚜活性较差。 3．20个化合物在200mg／L浓度下对反枝苋和狗尾草根和芽的生长都有明显的抑制活性，对种子萌发没有影响。特别是9号化合物，即2-戊基N-苯基氨基甲酸酯对反枝苋的杀草活性最强，其EC₅₀值为6.6mg／L。 4．20个化合物都有一定的杀菌活性。其中以2-戊基N-苯基氨基甲酸酯最高，其EC₅₀为17.12mg／L。 5．单因变量回归分析表明，苯基氨基甲酸酯类化合物杀虫、杀菌和除草活性与分子的疏水性参数、立体参数、电性参数存在一定的相关性，其中疏水性参数对其影响最大。疏水参数越小，活性越高。 6．汉施方程同样证明苯基氨基甲酸酯类的杀虫、杀菌和除草活性与化合物的保留时间、立体参数也存在一定的相关性，其中保留时间对活性的影响最大。保留时间越短，即化合物极性越大，活性越强。 7．3D-QSAR的研究发现除草活性和和杀菌活性与配体-受体相互作用能存在线形相关，并确定实际受体的活性位点应在1、3位存在氢键供体，2位存在氨基氮原子作为氢键受体。更多还原

【Abstract】 During Synthesizing Celangulins, a compound determined as Methyl N-phenylcarbamate was discovered accidentally which had strong knocking down activity against Mythimma separata. So far, N-phenylcarbamate compounds mostly were used as fungicide and herbicide, never a one used as insecticide. The systemic study on the quantiviative relationship of between activity and structure of N-phenylcarbamate compounds has not been carried out. This study was proceeded on synthesizing a series of N-phenylcarbamate compounds, bioassaying activities against several insect, fungius and weed targets and focused on 2D-QSAR and 3D-QSAR of compounds. The results are given as follows:1. Synthesized N-phenylcarbamate compounds exhibited obvious activities against Mythimma separata and Tetranychus viennensis.Of these compounds, 2,4-dinitryl N-phenylcarbamate was most effective, and had a LDso of 0.47 u g/larva2. The bioactivities of butyl N-phenylcarbamate against Mythimma separata had contact poison, no stomach and fumigant poison. The compound had a mortality of 86.6% against Plutella xylostella larval at the concentration of 25mg/ml by means of topical application. The compound also had a high activity against Mythimma separata with a mortality of 100% at the concentration of 0.1 mg/ml by means of residual film, or with a mortality of 97.3% at the concentration of 1.0 mg/ml by means of spray. Butyl N-phenylcarbamate was no obvious activity against Musca domestica Stitophilus zeamais Agrotis ypsilon Pieris brassicae Barathra brassicaeL Musca domestica Brevicoryne brassicae and Myzuspersicae.3. The elongation of root and sprout ofAmaranthus retroflexus and Polypogon fugax was inhibited significantly by the synthesized 20 compounds, but the germination of the tested seeds was not affected. 2-amyl N-phenylcarbamate had the strongest herbicidal activity against Amaranthus retroflexus with an ECso of 6.6 mg/L.4. Synthesized 20 compounds had obvious fungicidal activity against Glomerella Cingulata. Of these, 2-amyl N-phenylcarbamate was the strongest; its EC50was 17.12 mg/L.5. Single-variant regression analysis showed the bioactivities of N-phenylcarbamate compounds against insects fungi and weeds existed pertinence with aliment water parameter tridimensional parameter and electric parameter, ofwhich aliment water parameter was the most important factor; The smaller of aliment water parameter, the stronger of activity.6. Hansch equation also showed the bioactivities of N-phenylcarbamate compounds against insects fungi and weeds existed pertinence with reservation-time and tridimensional parameter, of which the reservation-time was the most important factor; the shorter of reservation-time, this is to say the bigger of polarity, the stronger of activity.7. The analysis of 3D-QSAR shows the bioactivities against weeds and fungi exist linearity correlation with ligand-receptor interaction-energy and furthermore approved that the sites of the real receptors should lies in hydrogen-bond offerorl, 3 active sites and hydrogen-bond receptor N atom of amine in 2 sites.更多还原