【作者】 刘成荡；

【导师】 沈德隆； 孔小林； 彭伟立；

【作者基本信息】 浙江工业大学 ， 农药学， 2007， 硕士

【摘要】 嘧啶水杨酸类除草剂是由日本组合化学公司于20世纪90年代初首先开发成功的一类新的ALS抑制剂，可控制多种难治的杂草，适合芽后或土壤处理。这类除草剂以其超高效、广谱、低毒、低残留、高选择性和良好的环境相容性而倍受关注，它是在嘧啶磺酰脲类的基础上经结构优化而成，主要针对水稻、棉花等作物除草，杀草谱和活性均优于嘧啶磺酰脲类除草剂，又克服了嘧啶磺酰脲类化合物在土壤中降解慢，对后茬作物易产生药害等缺点。这类化合物开发较晚，但进展较快，结构改造与修饰的余地还很大，是除草剂创制的重要领域之一。二苯甲酮腙衍生物类杀虫剂有着广谱、高效、环境友好等特点，符合当代农药发展要求；N’-取代-4-卤代-N-甲基-4’-甲烷磺酰氨基二苯甲酮腙衍生物作为一种二苯甲酮腙衍生物类杀虫剂，在具备上述优点的同时，对鳞翅目害虫防治方面比其他同类杀虫剂有着优势。国内对N’-取代4-卤代-N-甲基-4’-甲烷磺酰氨基二苯甲酮腙衍生物的需求日益增加，而目前我国尚无该化合物的原药生产厂家，且无关于其合成的研究报道；因此，对N’-取代-4-卤代-N-甲基-4’-甲烷磺酰氨基二苯甲酮腙衍生物合成路线的探索有着重要的现实意义。它们的结构通式如下：1、6-甲氧基-2-嘧啶氧基苄胺类化合物2、N-取代-4-卤代-N-甲基-4’-甲烷磺酰氨基二苯甲酮腙衍生物本论文重在研究合成6-甲氧基-2-嘧啶氧基苄胺类衍生物和N’-取代-4-卤代-N-甲基-4-甲烷磺酰氨基二苯甲酮腙衍生物，6-甲氧基-2-嘧啶氧基苄胺类衍生物是以2，6-二羟基甲苯为原料，经甲基化、再与甲磺酰嘧啶缩合、NBS溴化，最后与胺缩合．N’取代-4-卤代-N-甲基-4’-甲烷磺酰氨基二苯甲酮腙衍生物以对硝基苯甲酰氯，卤代苯，甲烷磺酰氯，水合肼等为原料合成4-卤代-N′-甲基-4′-甲烷磺酰氨基二苯甲酮腙，后者与酰氯、醛和酮等反应得到21种新型化合物，总收率65％。所有化合物结构均经核磁共振氢谱，质谱表征；生物活性测试由浙江省化工研究院生物活性测试中心完成，生测结果表明，这两种化合物衍生物具有良好的生物活性。更多还原

【Abstract】 Pyrimidinylthiobenzoates, used as herbicides were at first developed by Kumiai Chemical Industry Company in 1990s。It is an ALS inhibitor and can control many stubborn kinds of weeds by after it is budded or in soil. This kind of herbicide is paid extremely close attention to for its wide spectrum, high-efficiency, low toxicity, low remains, high selection and good environmental compatibility o It is optimized by the structure on the basia of Pyrimidinessulfonylureas. It is mainly used as herbiacide derected to such crops as rice, cotton and so on. It is superior to Pyrimidines sulfonylureas in wider grass table and better activation. Also it overcome some shortcomings of Pyrimidines sulfonylureas, such as slowly degradation in soil and being not safe enough for later crops. This kind of chemical compound is developed relatively late; thereof there is much room in its reconstruction and modification. It is one of the most important fields of herbicide development.Benzophenonehydrazone derivatives(insecticides) are a group of insecticides characterized as broad-spectrum, efficient and pro-environmental, which is in accordance with the demand of our society to the development of modem pesticides. N’-substituted-4.-halogine-N-methyl-4-methanesulfanilamidebenzophenonehy drazone derivatives(insecticides), as a member of this group, shows priority to other congeneric compounds in the use against Lepidoptera pests. The need of N’-substituted-4-halogine-N-methyl-4-methanesulfanilamidebenzophenonehy drazone derivatives(insecticides) in our country is growing rapidly, while there is neither domestic manufacturer nor report about the synthesis of this compound. So researching work in the synthesis of the title compound is of great significance.The structures were described as follows:1.6-methoxyl-2-pyrimidinyloxy-benzylamine derivatives2. N’-substituted-4-halogine-N-methyl-4-methanesulfanilamidebenzophenonehy drazone derivativesThe paper focuses its main attention on synthesizing6-methoxyl-2-pyrimidinyloxy-benzylamine derivatives (herbicides) and N’-substituted-4- halogine-N-methyl-4-methanesulfanil amidebenzophenonehydrazone derivatives (inseeticides).6-methoxyl-2-pyrimidinyloxy-benzylamine derivatives (herbicides)is with 2-methylbenzene-1,3-diol as starting compounds by methylate, condensation with methylsulfonylpyrimidine, bromization, finally condensation with amine; A series ofN’-substituted-4-halogine-N-methyl-4’-methanesulfanilamidebenzophenonehy drazone (insecticides) were synthesized by 4-nitrobenzoyl chloride, halogenate benzene, methanesulfonyl chloride, hydrazine hydrate, etc., which was then treated with various aldehyde and ketone, etc, In basic condition to twenty-one novel derivatives, with a total yield of 65%.The structures of these compounds were all confirmed by ~1H NMR and MS. The activation test will be finished by The Active. Test Center Of Zhejiang .Chemical Industry Research Institute. Their activations test show they are better.更多还原