丙硫菌唑重要中间体的合成、提纯及动力学研究

发布时间：2018-01-28 05:58

本文关键词： 丙硫菌唑 1 2 4-三氮唑中间体相转移催化剂提纯动力学　出处：《吉林大学》2017年硕士论文　论文类型：学位论文

【摘要】：三唑类杀菌剂由于其具有广谱、低毒、离散、残效长和较好的内吸传导性能并兼具保护和治疗作用等特性而备受亲睐,是农药研究开发中的热点之一。丙硫菌唑是德国拜耳公司研制开发的一款新型广谱三唑类杀菌剂,相较于传统三唑类杀菌剂,丙硫菌唑具有内吸性好,持效期长,杀菌谱更广的特点。化学结构中硫酮结构的引入,赋予了丙硫菌唑独特的人生魅力。丙硫菌唑除对所有麦类病害都有很好的防治效果外,对油菜、花生等作物的传统病害防效同样突出。随着丙硫菌唑市场价格的逐渐稳定,开发丙硫菌唑生产新工艺的研究,以提高丙硫菌唑的收率和产量,满足它在防治禾谷类作物和豆类作物等众多病害中的广泛应用,具有十分重要的意义。中间体的合成成为阻碍丙硫菌唑原药生产的最大障碍,本文的主要思路就是对重要中间体1-(1-氯环丙基)-2-(1,2,4-三唑基)乙酮的合成工艺进行探讨和研究,进而为丙硫菌唑的合成及工业化做好铺垫。以提高丙硫菌唑收率、缩短生产工艺流程、减少能耗为目标,本文开展了丙硫菌唑中间体1-(1-氯环丙基)-2-(1,2,4-三唑基)乙酮的合成研究,主要研究内容如下:1、本文在后格氏法的基础上对丙硫菌唑合成路线进行了设计改进。实验设计以1-氯-1-氯乙酰基环丙烷和1,2,4-三氮唑为起始原料,经过三步反应制取丙硫菌唑。2、研究了中间体1-(1-氯环丙基)-2-(1,2,4-三唑基)乙酮的合成、提纯新方法。实验中采用了单因素实验和正交实验,以确定最佳工艺条件,优化工艺过程。对中间体粗产品的后处理进行了实验分析,确定最佳提纯方法。在合成过程中,确定了影响1-(1-氯环丙基)-2-(1,2,4-三唑基)乙酮收率的主要因素。通过单因素实验和正交实验确定了最优操作条件,得到1-(1-氯环丙基)-2-(1,2,4-三唑基)乙酮的最高收率为98.28%。通过极差和方差分析,确定各因素影响力的大小顺序为缚酸剂用量反应温度原料配比反应时间。在提纯过程中,选取了合适的成盐强酸、成盐溶剂和盐解离溶剂,确定影响提纯收率的主要因素有三种,即成盐温度、成盐后冷却温度和浓硝酸用量。在确保1-(1-氯环丙基)-2-(1,2,4-三唑基)乙酮高纯度以及粗产品损失少的前提下,通过单因素实验确定了最佳提纯实验条件,提纯后收率能达到95.95%,纯度在99%以上,该实验过程无论对缩短工艺流程还是对降低消耗定额都具有实际意义。3、本文探讨了1-(1-氯环丙基)-2-(1,2,4-三唑基)乙酮合成反应动力学,建立了动力学模型,根据实验数据确定了该合成反应为二级反应,反应速率常数的指前因子为k0=3.67×107 L·mol-1·h-1,反应活化能为Ea=46.63 kJ/mol,反应宏观动力学方程为:(?),所得动力学方程经实验验证准确。4、研究了准确可靠的化学分析方法,以便于快速地检测实验情况及质量。实验采用气相色谱分析法,解决研究过程中的化学分析难题,进行实验产品的定性定量分析,通过傅里叶红外光谱仪、气相色谱质谱联用仪和核磁共振仪对实验产品进行了定性分析与表征,对所得谱图进行了解析,测定数据表明所测化合物与预期目标物结构相同,判定产品为中间体1-(1-氯环丙基)-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.

【学位授予单位】：吉林大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ455.4

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