【作者】 付颖；

【导师】 叶非；

【作者基本信息】 东北农业大学 ， 农药学， 2002， 硕士

【摘要】 本文较详细地研究了潜在除草剂安全剂Ⅰ：N-二氯乙酰基-3-甲基-2-正丙基-1-氧杂-4-氮杂-螺[4.5]癸烷，Ⅱ：N-二氯乙酰基-3，3-二甲基-1-氧杂-4-氮杂-螺[4.5]癸烷，Ⅲ：4，4-二甲基-3-二氯乙酰基-1，3—噁唑烷的合成、表征及生物活性测定。选用正丁醛、硝基乙烷合成了2-硝基-3-己醇，以铁粉和浓盐酸为还原剂将其还原为2-氨基-3-己醇；选用易得的三氯化磷、二氯乙酸为原料，N，N—二甲基甲酰胺作催化剂合成了重要原料二氯乙酰氯。分别用氢氧化钠和三乙胺作缚酸剂，用2-氨基-3-己醇、2-甲基-2-氨基丙醇、环己酮、多聚甲醛和二氯乙酰氯为原料合成了三种潜在除草剂安全剂；并采用正交实验设计，确定了较佳反应条件；对所合成产物进行了结构表征；利用土培法测定玉米幼苗中GSH的含量，对三种潜在的除草剂安全剂进行了初步的生物活性测定。 本研究对以下内容进行了比较深入的研究： 1．采用正丁醛、硝基乙烷合成了2-硝基-3-己醇。 2．采用还原铁粉为还原剂将2-硝基-3-己醇还原为2-氨基-3-己醇。 3．采用三氯化磷、二氯乙酸为原料，N,N—二甲基甲酰胺作催化剂合成了重要反应原料二氯乙酰氯。 4．以氢氧化钠为缚酸剂，2-氨基-3-己醇、环己酮和二氯乙酰氯为原料，采用一步法合成化合物Ⅰ：N-二氯乙酰基-3-甲基-2-正丙基-1-氧杂-4-氮杂-螺[4.5]癸烷。采用三因素三水平正交实验设计，确定最佳反应条件。 5．以三乙胺为缚酸剂，2-氨基-3-己醇、2-甲基-2-氨基丙醇、环己酮、多聚甲醛和二氯乙酰氯为原料，采用两步法合成化合物Ⅰ：N-二氯乙酰基-3-甲基-2-正丙基-1-氧杂-4-氮杂-螺[4.5]癸烷，Ⅱ：N-二氯乙酰基-3，3-二甲基-1-氧杂-4-氮杂-螺[4.5]癸烷，Ⅲ：4，4-二甲基-3-二氯乙酰基-1，3-噁唑烷。采用二因素三水平正交实验设计，确定最佳反应条件。 6．产品经熔点测定、薄层色谱(TLC)、紫外光谱(UV)、红外光谱(IR)、核磁共振谱(’HNMR)和元素分析表征。 7．采用土培法，用不同浓度的以上合成的化合物浸种处理，在除草剂绿磺隆、普施特不同浓度时，测定玉米幼苗中GSH含量的变化。结果表明：本文所合成的三种化合物在不同程度上均能减轻除草剂绿磺隆、普施特对作物的伤害。更多还原

【Abstract】 The synthesis and activity test of potential herbicide safeners of dichloroacetyl oxazolidine were described in this paper. Three compounds were synthesized in this paper,I:N-dichloroacetyl-3-methyl-2-n-propyl-l -oxa-4-aza-spiro-4.5-decane, II :N-dichloroacetyl-3,3-dimethyl-l-oxa-4-aza-spiro-4.5-decane and HI:3-dichloroacetyl-4,4-dimethyl-l,3-oxazolidine.When hydroxide sodium acted as catalyst,the dichloroacetyl chloride was directly dropped into the system after the intermediate product was synthesized by the condensation of the 2-amino-3-hexanol and cyclohexanone. The optimum experimental conditions of the product I were as following:trichloromethane acted as solvent,temperature was-10-0C and stirring time was 3hr,the yield was 92.4%. The three compounds also can be synthesized by two steps with triethylamine as catalyst .The methode is that after the water produced in the course of synthesis of oxazolidine removed with benzene by water segregator the triethylamine was added and the dichloroacetyl chloride was dropped at proper temperature with stirring. The optimum experimental conditions of the product I were as followingrbenzene was solvent,temperature was 5-10C and stirring time was 3hr,the yield was 93.7%. The optimum experimental conditions of the product II were as following:benzene was solvent,temperature was -10---5C and stirring time was 1hr,the yield was 68.9%. The optimum experimental conditions of the product III were as following:benzene was solvent,temperature was -10--5C and stirring time was 2hr,the yield was 50.4%.The structures of product I,II and III were confirmed by TLC,UV,IR,1HNMR and elementary analysis.A bioassay was developed for determining the influence of compound I .. II and III on the content of GSH in maize. With the increasing of chlorsulfuron or imazethapyr concentration,the content of GSH decreasing. When the seeds of maize were immerged with different concentrateion compound I II or III,the content of GSH increased.When the concentration of chlorsulfuron was 1 ug kg-1 or the concentration of imazethapyr was lOug kg-1,the content of GSH in maize was the highest at the level of 5 mg kg-1 compound I orII or of 10 mg kg-1 compound III. In a word,compound I II and III can protect maize from being injuried by chlorsulfuron and imazethapyr.Postgraduate:Fuying Major:Pesticides Tutor:Prof. Ye Fei更多还原