【作者】 耿会玲；

【导师】 周乐；

【作者基本信息】 西北农林科技大学 ， 植物学， 2003， 硕士

【摘要】 苯基脲类衍生物(Phenyl urea derivative,PUD)是20世纪70年代合成的一类新型农用生物活性物质，目前主要采用光气法和草酰氯法来合成。该类物质具有广泛的生物活性，生产上主要用作农作物的杀虫剂、杀菌剂、除草剂及植物生长调节剂，其中调节植物细胞生长是其最典型的活性特征。本文对苯基脲类衍生物的合成及其细胞分裂活性进行了研究，并对该类化合物的研究概况作了简要综述。 以苯胺或取代苯胺为基本原料，采用氯甲酸甲酯法合成了八种二苯基脲类衍生物，即N，N′-二苯基脲、N-苯基-N′-(3-硝基苯基)脲、N-苯基-N′-(4-甲基苯基)脲、N-苯基-N′-(2-甲基苯基)脲、N-苯基-N′-(3-甲基苯基)脲、N-苯基-N′-(2-氯代苯基)脲、N-苯基-N′-(3-氯代苯基)脲和N-苯基-N′-(4-氯代苯基)脲。采用红外光谱和质谱对合成的八种化合物进行了结构表征，证明所得化合物与目标化合物的结构一致。该合成由两步反应组成，首先让苯胺或取代苯胺与氯甲酸甲酯在三乙胺或三正丁胺中生成取代苯胺基甲酸甲酯，后者无需分离再与过量的苯胺或取代苯胺反应，生成目标化合物。实验中发现，对于含吸电子基团的产物和斥电子基团的产物，其合成中的加料顺序应该是不同的。对于含吸电子取代基的苯胺，应该在第一步反应中加入，对于含斥电子基团的苯胺则应该在第二步反应中加入，这样有利于提高总反应的速率和产率。对于决定总反应速度和产率的第二步反应设计了以反应温度和反应时间为主要因素的二因素三水平的正交试验。结果表明，该反应的最佳物料比(mol／mol)为，取代苯胺／氯甲酸甲酯／三乙胺／苯胺1.0:1.5:1.5:1.5，产物Ⅰ～Ⅷ的最佳反应温度分别为120℃、152℃、165℃、162℃、155℃、170℃、158℃和165℃，最佳反应时间为3.0h、4.0h、5.0h、5.5h、4.0h、4.5h、4.0h和5.0h。与经典的光气法和草酰氯法相比，氯甲酸甲酯法具有设备简单、反应步骤少、后处理简便、产物收率高、对环境污染较小等优点，适合实验室和工业生产。 以丰光萝卜种子为材料，采用萝卜子叶扩张生长法测定了化合物促进细胞分裂的活性。结果表明，合成的八种化合物在1.00～0.01mg／L范围内都能促进萝卜子叶生长，其中N-苯基-N′-(3-硝基苯基)脲的活性最高，约为对照的10倍。相对于含斥电子基团的产物来说，所有含吸电子基团的产物的均表现出较高的活性。对于同一类基团而言，其活性则按间位、邻位、对位取代依次递减。更多还原

【Abstract】 Phenyl urea derivatives are a kind of novel farming materials which were synthesized in the 1970s. At present, these compounds are mainly synthesized by two routes, the phosgene method and the oxalyl chloride method. Phenyl urea derivatives have wide-ranging biological activities. In agriculture production, they are chiefly served as the crops’ insecticides, bactericides, weeds’ killers and plant growth regulators. Among these regulating the flora cell growth is the most fascinating activated feature. In this dissertation, the synthesis and cell division activation of phenyl urea derivatives have been wholly researched. Their recent advances hi the relevant research were reviewed as well.Either aniline or substituted aniline acted as the fundamental material, the methyl chloroformate synthesis method was used to synthesize eight kinds of diphenyl urea compounds. They were N,N’-diphenyl urea, N-phenyl-N’-(3-nitrophenyl)urea, N-phenyl-N’-(4-methylpheny-l)urea, N-phenyl-N’-(2-methylphenyl)urea, N-phenyl-N’-(3-methylph enyl)urea, N-phenyl-N’-(2-chlorophenyl)urea, N-phenyl-N’-(3-chlorophenyl)urea and N-phenyl-N’-(4-chlorophenyl)urea respectively. The structures of synthetic compounds and target compounds have been elucidated with infrared spectrum and mass spectra. Two step of reactions were included in the general synthesis. Firstly, aniline or substituted aniline reacted with methyl chloroformate in tri-n-butylamine solvent or triethylamine solvent to generate substituted aniline-methanoate, then without any further separation the latter continued to react directly with excessive aniline or substituted aniline, and target compounds were obtained. In the research, it was found that , if the products with electron-withdrawing groups and the products of electron-repelling groups were concerned, the order to add raw materials should be different. To get target compounds in high production, the aniline substituted with electron-withdrawing group should be added in first step of reaction, but the aniline substituted with electron-repelling group should be added in second step of reaction. The orthogonal experiments with two factors and three levels in each during the second step of reaction were investigated. The result showed that,for the substituted aniline, methyl chloroformate, triethylamine and aniline, the optimal constituents ratio among them(mol/mol) is 1.0 : 1.5 : 1.5 : 1.5. The optimal reaction temperatures for the target compounds I-VIII are 120℃, 152℃, 165℃, 162℃, 155℃, 170℃, 158℃ and 165℃ respectively, and their optimal reaction duration are 3.0 h, 4.0 h, 5.0 h, 5.5 h, 4.0 h, 4.5 h, 4.0 h and 5.0 h respectively. Compared with the conventional methods-the phosgene method and the oxalyl chloride method, the present method-methyl chloroformate method, took the advantages of simple devices, less procedures, convenient post-treatment, higher yield, less environmental pollution etc. It is available for laboratory and industrial production.Using the seeds of Radish Fengguang as material, the biological activities of the above synthesized compounds in promoting cell division were investigated by the method of radish cotyledon stretching growth. The result showed that all the above compounds could promote radish cotyledon growth in the range of 0.01mg/L and 1.0mg/L. Furthermore, for the N-phenyl-N’-m-nitro phenyl urea, the highest biological activity appeared in the concentration of 1.0 mg/L. Compared with the products of electron-repelling group, the products of electron-withdrawing group displayed higher biological activity. For the same kind of groups, the biological activities decreased in the order of meta-, ortho-, para-substituted analine.更多还原