唑草酮合成工艺改进及路易斯酸催化合成噻吩类衍生物反应研究

发布时间：2018-05-14 02:33

本文选题：除草剂 + 唑草酮　；参考：《青岛科技大学》2016年硕士论文

【摘要】：唑草酮,三唑啉酮类除草剂,1990年由FMC公司研发并报道。由于其毒性低,药力强,适合作物较广,因而引起农药合成工作者及各大厂家的巨大兴趣。但是目前唑草酮的合成技术不成熟,很多合成难点还没有解决,我们通过路线探索以及条件优化,找到一条适合工业化生产的合成唑草酮的工艺路线。第一章以4-氯-2-氟苯胺为原料,经九步单元反应合成产物唑草酮。此法采用“一锅法”合成关键中间体苯基三唑啉酮,Meerwein芳基化合成酰胺物,最后由酰胺物合成唑草酮,为首次报道。重要中间体及目标化合物经IR、1HNMR、LC-MS等进行了结构表征,并对各步的反应机理及影响产率的主要因素进行了探讨。该合成工艺以30.9%的总收率(以起始原料4-氯-2-氟苯胺计),纯度为99.3%(HPLC归一含量)成功完成了目标化合物的合成。该工艺优化了反应条件(反应温度、溶剂、催化剂种类及用量),提高了反应产率,缩短了反应时间。此路线技术成熟、操作简便、原料易得、适合工业化生产。噻吩类衍生物是一类重要的杂环化合物,存在于许多药物分子及天然产物中。虽然有很多关于噻吩化合物合成的方法被报道,但其大部分有引入硫元素、反应条件苛刻、催化剂昂贵、多步合成以及提纯麻烦等诸多缺点,因此开发普遍、高效、快速的合成方法具有十分重要的意义。第二章基于β-羰基二硫代羧酸酯和乙烯基叠氮独特的结构和优良的反应类型,构建了一种路易斯酸催化合成噻吩类衍生物的方法。讨论了不同溶剂、催化剂、温度和时间等条件对反应的影响,并确定了合成噻吩类化合物的最佳反应条件为:以甲苯为溶剂,通过InCl3催化合成噻吩类衍生物,所合成的化合物均经IR、1H NMR、13C NMR、HRMS进行了表征,并通过化合物a-1单晶确定了目标化合物的精确分子结构,提出了反应可能的机理。
[Abstract]:Azolone, three zazolone herbicides, developed by FMC company in 1990 and reported. Because of their low toxicity, strong potency and suitable crops, it has aroused great interest in pesticide synthesis workers and major manufacturers. However, the synthesis technology of azolone is not mature and many difficult points have not been solved. We explore and condition through the route. A process route for synthesis of azazolone suitable for industrial production was found. In the first chapter, zazazone was synthesized from 4- chloro -2- Fluoroaniline by nine steps. This method uses one pot method to synthesize the key intermediate phenyl three zolidone, Meerwein aryl into acylomides, and finally the synthesis of zazoone from amides, for the first time. The important intermediates and target compounds were characterized by IR, 1HNMR, LC-MS and so on. The reaction mechanism of each step and the main factors affecting the yield were discussed. The synthetic process with the total yield of 30.9% (the initial raw material 4- chloride -2- fluoraniline) and the purity of 99.3% (HPLC normalization) successfully completed the synthesis of the target compound. The process optimizes the reaction conditions (reaction temperature, solvent, type and amount of catalyst) to improve the yield of the reaction and shorten the reaction time. This route is mature, easy to operate, easy to obtain and suitable for industrial production. Thiophene derivatives are a kind of important heterocyclic compounds, which exist in many drug molecules and natural products. Many methods for the synthesis of thiophene compounds have been reported, but most of them have the disadvantages of introducing sulfur elements, harsh reaction conditions, expensive catalysts, multistep synthesis and purification trouble. Therefore, the development of universal, efficient and rapid synthesis methods is of great significance. The second chapter is based on beta carbonyl two thiocarboxylate and vinyl superposition. A method of catalytic synthesis of thiophene derivatives by Lewis acid was constructed by the unique structure of nitrogen and the excellent type of reaction. The effects of different solvents, catalysts, temperature and time on the reaction were discussed, and the optimum reaction conditions for the synthesis of thiophene were determined by the catalytic synthesis of thiophene through InCl3 in toluene as the solvent. The compounds were characterized by IR, 1H NMR, 13C NMR, HRMS, and the exact molecular structure of the target compounds was determined by the single crystal of the compound A-1, and the possible mechanism of the reaction was proposed.

【学位授予单位】：青岛科技大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：TQ457.2;O626.12

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