【作者】 吴敖荣；

【导师】 杜晓华；

【作者基本信息】 浙江工业大学 ， 有机化学， 2013， 硕士

【摘要】 甲氧基丙烯酸酯类杀菌剂来源于天然产物-Strobilurins,作为一类新型的线粒体呼吸抑制剂,它们具有高效、广谱、低毒、低残留、对环境友好等优点。另外由于其作用机制独特,目前已经成为杀菌剂领域研究开发的热点,自1996年第一个甲氧丙烯酸酯类杀菌剂上市,该类杀菌剂已经在世界杀菌剂市场占据重要地位。本文中介绍了甲氧丙烯酸酯类杀菌剂的发现研究过程以及目前商业化的主要产品,对肟菌酯的及其关键中间体的合成进行了系统的改进,对降低产品生产过程对环境的污染,改善我国农药产品结构有重要的意义。肟菌酯的合成选择以苯酞为初始原料,与双(三氯甲基)碳酸酯反应后得到邻氯甲基苯甲酰氯,再与氰化钠进行氰代反应得到邻氯甲基苯甲酰腈,用甲醇酯化后与甲氧胺盐酸盐肟化得到产物,最后与间三氟甲基苯乙酮肟缩合得到肟菌酯,五步总收率为38.8%。其中,间三氟甲基苯乙酮肟由间三氟甲基苯乙酮与盐酸羟胺经肟化反应制得,重结晶提纯后收率为86.3%。该线路中苯酞开环过程用固体光气替代亚硫酰氯或光气,提高了反应的安全性,使工艺更清洁、绿色。制备邻氯甲基苯甲酰腈时,选择Sm(OTf)3作为反应催化剂,不仅缩短了反应时间,而且反应也不需要使用相转移催化剂；另外,该催化剂能实现回收利用,节约了生产成本,反应也更易控制。在中间体2-氯甲基-α-甲氧亚胺基苯乙酸甲酯制备过程中,分别试验了两种不同的方法。其中,在加压条件下,通氯化氢气体连续进行邻氯甲基苯甲酰腈的酯化、肟化反应,副产物少,是适合工业化生产的工艺。总之,本论文中肟菌酯及其关键中间体的合成工艺操作简单、易于控制,符合绿色化工的要求,适合工业化生产。更多还原

【Abstract】 The β-methoxyacrylate fungicides are a new class of respiration inhibitors based on a group of natural products--Strobilurins. They have the characteristics of high efficiency, broad spectrum, low toxicity, short residual and environmentally friendly. Due to their special action mechanism, the research on them has been a hot topic in fungicidal fields, what’s more, this kind of fungicide has occupy the important status in the fungicide world since the first strobilurin-type fungicide launched in1996. This paper described the discovery and the recent development of strobilurins fungicides, some popular products are also introduced. The snythesis process of trifloxystrobin and its key intermediates were studied, It is very important to decrease the effect on the environment and improve the produce-consist of the pesticide in our country.The synthesis of trifloxystrobin was starting from phthalide, which react with bis(trichloromethyl)carbonate to give o-chloromethylbenzoyl chloride, followed by cyanidation with NaCN to give o-chloromethylbenzoyl cyanide, The cyanide was then esterified with methanol oximated with methoxyamine, and finally condensed with 3-(trifluoromethyl) acetopheneone oxime. The total yield of the five-step reactions was38.8%.3-(Trifluoromethyl)acetopheneone oxime was synthesized from3-(Trifluoromethyl)acetophenone and hydroxylammonium chloride in the yield of86.3%. In the ring-opening reaction, thionly chloride and phosgene were replaced by bis (trichloromethyl)carbonate, which improved the safety of the reaction and make the process more cleaner. In the preparation of2-(chloromethyl)benzoyl cyanide, a new catalytic cyanide reaction was investigated, using Sm(OTf)3as the optimized and reuseable catalyst and without use of phase transfer catalyst. Two methods were studied in the synthesis of methyl(E)-2-(chloromethyl)-a-oxyiminobenzeneacetate, and the better result was obtained under higher pressure of HCl gas.In conclusion, an optimized process of trifloxystrobin and its key intermeates was studied, which has such advantages as simple operations, readily available materials, safe conditions and less pollution. This work makes progress in green chemical process and the process is suitable for industrial application.更多还原