發(fā)布時(shí)間：2018-01-28 05:58

  本文關(guān)鍵詞： 丙硫菌唑 1 2 4-三氮唑 中間體 相轉(zhuǎn)移催化劑 提純 動(dòng)力學(xué)　出處：《吉林大學(xué)》2017年碩士論文　論文類(lèi)型：學(xué)位論文

【摘要】：三唑類(lèi)殺菌劑由于其具有廣譜、低毒、離散、殘效長(zhǎng)和較好的內(nèi)吸傳導(dǎo)性能并兼具保護(hù)和治療作用等特性而備受親睞,是農(nóng)藥研究開(kāi)發(fā)中的熱點(diǎn)之一。丙硫菌唑是德國(guó)拜耳公司研制開(kāi)發(fā)的一款新型廣譜三唑類(lèi)殺菌劑,相較于傳統(tǒng)三唑類(lèi)殺菌劑,丙硫菌唑具有內(nèi)吸性好,持效期長(zhǎng),殺菌譜更廣的特點(diǎn)�；瘜W(xué)結(jié)構(gòu)中硫酮結(jié)構(gòu)的引入,賦予了丙硫菌唑獨(dú)特的人生魅力。丙硫菌唑除對(duì)所有麥類(lèi)病害都有很好的防治效果外,對(duì)油菜、花生等作物的傳統(tǒng)病害防效同樣突出。隨著丙硫菌唑市場(chǎng)價(jià)格的逐漸穩(wěn)定,開(kāi)發(fā)丙硫菌唑生產(chǎn)新工藝的研究,以提高丙硫菌唑的收率和產(chǎn)量,滿(mǎn)足它在防治禾谷類(lèi)作物和豆類(lèi)作物等眾多病害中的廣泛應(yīng)用,具有十分重要的意義。中間體的合成成為阻礙丙硫菌唑原藥生產(chǎn)的最大障礙,本文的主要思路就是對(duì)重要中間體1-(1-氯環(huán)丙基)-2-(1,2,4-三唑基)乙酮的合成工藝進(jìn)行探討和研究,進(jìn)而為丙硫菌唑的合成及工業(yè)化做好鋪墊。以提高丙硫菌唑收率、縮短生產(chǎn)工藝流程、減少能耗為目標(biāo),本文開(kāi)展了丙硫菌唑中間體1-(1-氯環(huán)丙基)-2-(1,2,4-三唑基)乙酮的合成研究,主要研究?jī)?nèi)容如下:1、本文在后格氏法的基礎(chǔ)上對(duì)丙硫菌唑合成路線進(jìn)行了設(shè)計(jì)改進(jìn)。實(shí)驗(yàn)設(shè)計(jì)以1-氯-1-氯乙�；h(huán)丙烷和1,2,4-三氮唑?yàn)槠鹗荚?經(jīng)過(guò)三步反應(yīng)制取丙硫菌唑。2、研究了中間體1-(1-氯環(huán)丙基)-2-(1,2,4-三唑基)乙酮的合成、提純新方法。實(shí)驗(yàn)中采用了單因素實(shí)驗(yàn)和正交實(shí)驗(yàn),以確定最佳工藝條件,優(yōu)化工藝過(guò)程。對(duì)中間體粗產(chǎn)品的后處理進(jìn)行了實(shí)驗(yàn)分析,確定最佳提純方法。在合成過(guò)程中,確定了影響1-(1-氯環(huán)丙基)-2-(1,2,4-三唑基)乙酮收率的主要因素。通過(guò)單因素實(shí)驗(yàn)和正交實(shí)驗(yàn)確定了最優(yōu)操作條件,得到1-(1-氯環(huán)丙基)-2-(1,2,4-三唑基)乙酮的最高收率為98.28%。通過(guò)極差和方差分析,確定各因素影響力的大小順序?yàn)榭`酸劑用量反應(yīng)溫度原料配比反應(yīng)時(shí)間。在提純過(guò)程中,選取了合適的成鹽強(qiáng)酸、成鹽溶劑和鹽解離溶劑,確定影響提純收率的主要因素有三種,即成鹽溫度、成鹽后冷卻溫度和濃硝酸用量。在確保1-(1-氯環(huán)丙基)-2-(1,2,4-三唑基)乙酮高純度以及粗產(chǎn)品損失少的前提下,通過(guò)單因素實(shí)驗(yàn)確定了最佳提純實(shí)驗(yàn)條件,提純后收率能達(dá)到95.95%,純度在99%以上,該實(shí)驗(yàn)過(guò)程無(wú)論對(duì)縮短工藝流程還是對(duì)降低消耗定額都具有實(shí)際意義。3、本文探討了1-(1-氯環(huán)丙基)-2-(1,2,4-三唑基)乙酮合成反應(yīng)動(dòng)力學(xué),建立了動(dòng)力學(xué)模型,根據(jù)實(shí)驗(yàn)數(shù)據(jù)確定了該合成反應(yīng)為二級(jí)反應(yīng),反應(yīng)速率常數(shù)的指前因子為k0=3.67×107 L·mol-1·h-1,反應(yīng)活化能為Ea=46.63 kJ/mol,反應(yīng)宏觀動(dòng)力學(xué)方程為:(?),所得動(dòng)力學(xué)方程經(jīng)實(shí)驗(yàn)驗(yàn)證準(zhǔn)確。4、研究了準(zhǔn)確可靠的化學(xué)分析方法,以便于快速地檢測(cè)實(shí)驗(yàn)情況及質(zhì)量。實(shí)驗(yàn)采用氣相色譜分析法,解決研究過(guò)程中的化學(xué)分析難題,進(jìn)行實(shí)驗(yàn)產(chǎn)品的定性定量分析,通過(guò)傅里葉紅外光譜儀、氣相色譜質(zhì)譜聯(lián)用儀和核磁共振儀對(duì)實(shí)驗(yàn)產(chǎn)品進(jìn)行了定性分析與表征,對(duì)所得譜圖進(jìn)行了解析,測(cè)定數(shù)據(jù)表明所測(cè)化合物與預(yù)期目標(biāo)物結(jié)構(gòu)相同,判定產(chǎn)品為中間體1-(1-氯環(huán)丙基)-2-(1,2,4-三唑基)乙酮。
[Abstract]:Three triazole fungicide because of its broad-spectrum, low toxicity, discrete, long residual effect and good absorption within the conduction performance and both protective and therapeutic effect and other characteristics is very popular, is one of the hot research and development of pesticide. Prothioconazole is a new type of broad-spectrum Bayer company developed three azole compared with the conventional fungicides, three triazole fungicide, prothioconazole with suction, long duration, wide bactericidal spectrum characteristics. Introduce the sulfur ketone structure and chemical structure, gives life charm of prothioconazole unique. Prothioconazole except for all wheat disease and have a good control effect on rape, peanut and other crops, the traditional disease prevention effect is also prominent. With prothioconazole market prices gradually stabilized, new technology research development and production of prothioconazole, in order to improve prothioconazole yield and yield, meet it in the prevention and treatment of cereal crops and Widely used in legume crops and many other diseases, it has very important significance. The synthesis of intermediates become the biggest obstacle to prothioconazole technical production, the main idea of this paper is an important intermediate for 1- (1- chlorine cyclopropyl) -2- (1,2,4- three benzimidazolyl) to investigate and research the synthesis of acetophenone, and for the synthesis and industrialization of prothioconazole pave the way. In order to improve the yield of prothioconazole, shorten the production process, reduce the energy consumption as the goal, this paper carried out the prothioconazole intermediate 1- (1- chlorine Huan Bingji) -2- (1,2,4- three pyrazolyl) synthesis of acetophenone, the main research contents are as follows: 1. In this paper based on the Grignard method prothioconazole synthetic route was designed to improve. The experimental design with 1- chloro -1- chloracetyl cyclopropane and 1,2,4- three triazole as starting material through three steps of preparing propylene reaction of sulfur bacteria was.2, the research of intermediate 1- (1- chloride Huan Bingji -2- (1,2,4-) three benzimidazolyl) ethanone synthesis, a new method of purification. The experiment with single factor and orthogonal experiments, to determine the optimal technological conditions, optimize the process of intermediates of crude product postprocessing were analyzed. The optimum purification method. In the synthesis process, to determine the impact of 1- (1- chlorine cyclopropyl) -2- (1,2,4- three benzimidazolyl) ethanone main factors. The optimal operating conditions were determined by single factor experiment and the orthogonal experiment, 1- (1- chlorine cyclopropyl) -2- (1,2,4- three benzimidazolyl) highest yield of acetophenone was 98.28%. Through the analysis of range and variance, determination various factors influence the size of the order of the amount of acid binding agent and reaction temperature and reaction time. The ratio of raw materials in the purification process, select the appropriate acid salt, salt solvent and salt dissociation solvent, determine the primary factors affecting the purification yield of three kinds, namely salt into temperature. Salt after cooling temperature and nitric acid dosage. In order to ensure the 1- (1- chlorine cyclopropyl) -2- (1,2,4- three benzimidazolyl) ethanone premise of high purity and less loss of the crude product under the optimum experimental conditions of purification were determined by single factor experiment, the yield could reach 95.95% after purification, the purity was above 99%, the experimental process whether to shorten the process still has the practical significance to reduce the consumption of.3, this paper discusses 1- (1- chlorine cyclopropyl) -2- (1,2,4- three pyrazolyl) ethanone synthesis reaction kinetics, dynamics model was established based on the experimental data, the synthesis reaction is two grade reaction were determined, the reaction rate constant of a factor of k0=3.67 * 107 L - mol-1 - H-1, the activation energy was Ea=46.63 kJ/mol, the reaction kinetic equations: (?), the kinetic equation is verified by experiments and accurate study of chemical.4, accurate and reliable analysis method for rapid detection of experiment The situation and quality. Experiments by gas chromatography analysis method, solve the problem of chemical analysis in the process of research, qualitative and quantitative analysis of experimental products, by means of Fourier transform infrared spectroscopy, gas chromatography mass spectrometry on experimental products were analyzed and characterized by qualitative instrument and NMR, the spectrum analysis, determination the data showed that the target compounds and expected the same structure, determine the product for the intermediate 1- (1- chlorine cyclopropyl -2- (1,2,4-) three benzimidazolyl) ethanone.

【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：TQ455.4

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