【作者】 张健；

【导师】 张志德；

【作者基本信息】 山东师范大学 ， 有机化学， 2010， 硕士

【摘要】 本论文主要分为两部分:第一部分:二(三氟甲磺酰)亚胺锂的合成工艺研究二(三氟甲磺酰)亚胺锂( (CF3SO2)2 NLi)是二(三氟甲磺酰)亚胺盐化合物系列的第1个成员,在强拉电子效应的三氟甲基协同参与下,二(三氟甲磺酰)亚胺锂阴离子中N原子上的负电荷可通过共振作用分散到整个O -S -N骨架上而高度离域化,从而大大增强了离子的稳定性;另一方面两个大体积三氟甲基的空间位阻,使该类离子的配位能力大大削弱,使它展现出潜在的强的化学亲电性、高Lewis酸酸性及优良的固体表面特征,从而使得该类物质在众多领域具有广泛的用途,如制锂离子二次电池电解质、离子液体、选择性氟化试剂和环境友好的高效Lewis酸催化剂。本部分论文用两种方法分别讨论并比较了合成二(三氟甲磺酰)亚胺锂的过程。第一种方法是以三氟甲磺酸为起始原料,它先与五氯化磷反应生成三氟甲磺酰氯,三氟甲磺酰氯经过氨解在三乙胺或吡啶催化作用下再次与三氟甲磺酰氯发生反应生成二(三氟甲磺酰)亚胺的三乙胺或吡啶盐,此盐在氢氧化钠作用下成为二(三氟甲磺酰)亚胺钠盐,钠盐又经过硫酸酸化生成二(三氟甲磺酰)亚胺,最后在碳酸锂或氢氧化锂作用下生成最终产物二(三氟甲磺酰)亚胺锂,总产率为25%左右。第二种方法以三氟甲磺酰氟代替三氟甲磺酰氯为起始原料,采取与第一种方法类似地过程合成二(三氟甲磺酰)亚胺锂,最终产率为78%左右。后者工艺流程简单、成本较低、污染小、收率高、产品质量好。同时得副产物氟化铵、氟化钠和硫酸钠。适合工业生产,具有重要的应用价值。第二部分苯氧菌酯的合成工艺研究苯氧菌酯又叫醚菌酯(Kresoxim-methy1)是由巴斯夫公司以自然界中的一种蘑菇的天然产物为基础仿生合成的一种具有全新作用方式的杀菌剂。其制剂的商品名称为翠贝(Stroby),是一种优秀的新型杀菌剂,它有四个特点:一是具有很高的活性,同时兼具良好的保护和治疗作用;二是持效期长,与其它常用杀菌剂无交互抗性;三是杀菌谱广,对半知菌、子囊菌、担子菌、卵菌纲等真菌引起的多种病害具有很好的活性;四是高效低毒、低残留,具有高度的选择性,对作物、人畜、非靶标生物和环境安全。本论文先后研究了多种合成方法,首先选取对叔丁基甲苯为原料,通过两次Friedel-crafts反应得到酮酯,因收率较低不得不放弃该方法。最终选择邻溴甲苯为起始原料制得格氏试剂,格氏试剂和草酰氯单甲酯进行偶联反应得到酮酯,进而与甲氧胺盐酸盐缩合得到重要的中间体肟酯,再经NBS溴化后与邻甲苯酚钠反应制得(Z),(E)-醚菌酯混合物,此混合物在干燥甲醇中经过氯化氢作用下得到(E)-醚菌酯,总产率大于30%。该工艺流程简单、原料易得、成本较低、污染小、收率高、质量好、值得工业化推广。两部分合成研究的中间体和最终产物通过核磁、红外、元素分析等对化合物进行了表征。更多还原

【Abstract】 The thesis is divided into two parts.Part I: The study on the preparation process for Lithium bis(trifluoromethane- sulfonyl)imide.Lithium bis(trifluoromethanesulfonyl)imide ((CF3SO2)2NLi) is the first member of bis(trifluoromethanesulfonyl)imide salt of the compound series. In the strong effect of the electron’s collaborative participation of trifluoromethyl. Lithium bis- (trifluoro- methanesulfonyl)imide ion in the negative charge on N atoms can be resonantly scattered throughout the O-S-N backbone and a high degree of delocalization, thereby greatly enhancing the stability of ion. On the other hand, two large volume trifluoromethyl steric make such coordination capacity of the ion are highly reduced. It demonstrates the potential power of a strong chemical affinity, high Lewis acidity and high-quality solid surface characteristics.Thus making such material in many fields have a wide range of uses. For example,preparation of lithium ion battery electrolyte, ionic liquid, selective fluorination reagents and environmentally friendly and efficient Lewis acid catalyst.This part of the thesis, two methods were discussed and compared the process for preparation of bis(trifluoromethanesulfonyl)imide lithium. The first method was to use trifluoromethanesulfonate acid as a starting material. First, it reacted with phosphorus pentachloride to obtain trifluoro methanesulfonyl chloride. Under the catalytic action of triethylamine or pyridine. After ammonolysised, trifluoro methanesulfonyl chloride, Again reacting trifluoroacetic methanesulfonyl chloride, obtained bis(trifluoromethanesulfonyl)imide triethylamine or pyridine salt. It was under the effect of sodium hydroxide obtained bis (trifluoromethanesulfonyl)imide sodium salt. After acidulating of sulfuric acid obtained the bis- (trifluoromethane- sulfonyl)imide. Finally, obtained the final product lithium bis (trifluoromethane- sulfonyl)imide under the action of lithium carbonate. The total yield was about 25%.The second method used trifluoro methanesulfonyl fluoride instead of trifluoro methanesulfonyl chloride as the starting material, taken withthe first method similar to the process. Final yield was about 78%.The latter process is simple, low cost, low pollution, high yield and good quality. At the same time, by-product ammonium fluoride, sodium fluoride and sodium. It is suitable for industrial production, which has important application value. This method is suitable for industrial production, which has important application value.PartⅡ: The study on the preparation process for kresoxim-methyl.Kresoxim-methyl was prepared by BASF which followed a nature-based mushroom biomimetic synthesis of natural products with new modes of action of a disinfectant.The preparation of the product name for“Stroby”, It is an excellent new fungicide. It has four characteristics. First, it has high activity, at the same time it has good protection and treatment. Second, there is a long period could be kept. And no cross-resistance to other commonly fungicides. Third it has a broad spectrum bactericidal, and it imperfect fungi, Ascomycetes,Basidiomycetes, Oomycetes and other fungi caused by a variety of diseases has good activity. Fourth, it has low toxicity and high efficiency, low-residue, highly selective, It makes crops, livestock, non-target organisms and environmental safety.This paper had discussed a variety of synthesis methods. First, we selected the tert-butyl toluene as the starting material. Through two Friedel-crafts reaction, and then get keto ester. However, duing to the lower yield of the method had to be abandoned. Finally,we selected o-bromo toluene as the starting material to obtain Grignard reagent, Grignard reagents and monomethyl oxalyl chloride was conjugated reaction and obtained keto esters. And then condensation with the methoxamine hydrochloride obtained important intermediate oxime. It is then brominated by NBS, then it reacted with o-cresol sodium and obtained (Z), (E) - kresoxim mixture. This mixture dissolved in dry methanol, under hydrogen chloride obtained by the (E) - kresoxim, the total yield more than 30%. The process is simple and readily available raw materials, low cost, low pollution, high yield, good quality, it is worth to promote industrialization.The two parts of the intermediate and final products were characterized by NMR, IR and elemental analysis.更多还原