本文選題：除草劑 + 唑草酮��； 參考：《青島科技大學(xué)》2016年碩士論文

【摘要】：唑草酮,三唑啉酮類除草劑,1990年由FMC公司研發(fā)并報(bào)道。由于其毒性低,藥力強(qiáng),適合作物較廣,因而引起農(nóng)藥合成工作者及各大廠家的巨大興趣。但是目前唑草酮的合成技術(shù)不成熟,很多合成難點(diǎn)還沒有解決,我們通過路線探索以及條件優(yōu)化,找到一條適合工業(yè)化生產(chǎn)的合成唑草酮的工藝路線。第一章以4-氯-2-氟苯胺為原料,經(jīng)九步單元反應(yīng)合成產(chǎn)物唑草酮。此法采用“一鍋法”合成關(guān)鍵中間體苯基三唑啉酮,Meerwein芳基化合成酰胺物,最后由酰胺物合成唑草酮,為首次報(bào)道。重要中間體及目標(biāo)化合物經(jīng)IR、1HNMR、LC-MS等進(jìn)行了結(jié)構(gòu)表征,并對(duì)各步的反應(yīng)機(jī)理及影響產(chǎn)率的主要因素進(jìn)行了探討。該合成工藝以30.9%的總收率(以起始原料4-氯-2-氟苯胺計(jì)),純度為99.3%(HPLC歸一含量)成功完成了目標(biāo)化合物的合成。該工藝優(yōu)化了反應(yīng)條件(反應(yīng)溫度、溶劑、催化劑種類及用量),提高了反應(yīng)產(chǎn)率,縮短了反應(yīng)時(shí)間。此路線技術(shù)成熟、操作簡(jiǎn)便、原料易得、適合工業(yè)化生產(chǎn)。噻吩類衍生物是一類重要的雜環(huán)化合物,存在于許多藥物分子及天然產(chǎn)物中。雖然有很多關(guān)于噻吩化合物合成的方法被報(bào)道,但其大部分有引入硫元素、反應(yīng)條件苛刻、催化劑昂貴、多步合成以及提純麻煩等諸多缺點(diǎn),因此開發(fā)普遍、高效、快速的合成方法具有十分重要的意義。第二章基于β-羰基二硫代羧酸酯和乙烯基疊氮獨(dú)特的結(jié)構(gòu)和優(yōu)良的反應(yīng)類型,構(gòu)建了一種路易斯酸催化合成噻吩類衍生物的方法。討論了不同溶劑、催化劑、溫度和時(shí)間等條件對(duì)反應(yīng)的影響,并確定了合成噻吩類化合物的最佳反應(yīng)條件為:以甲苯為溶劑,通過InCl3催化合成噻吩類衍生物,所合成的化合物均經(jīng)IR、1H NMR、13C NMR、HRMS進(jìn)行了表征,并通過化合物a-1單晶確定了目標(biāo)化合物的精確分子結(jié)構(gòu),提出了反應(yīng)可能的機(jī)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.

【學(xué)位授予單位】：青島科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：TQ457.2;O626.12

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