文献类型：专利

英文题名：Chlorinating carboxylic acid to corresponding acyl chloride comprises e.g. adding organic carboxylic acid, carbon tetrachloride, ferric trichloride and N,N-dimethylformamide to kettle, sealing, agitating, adding alcohol and refluxing

作者：LIU R;CHU C

机构：[1]UNIV EAST CHINA SCI&TECHNOLOGY

申请号：CN101973865-A

申请日：2010-09-14

公开日：2011-02-16

语种：英文

收录：DERWENT

摘要：NOVELTY - Chlorinating carboxylic acid into corresponding acyl chloride using carbon tetrachloride comprises: providing substituted benzoic acid compound (I) or carboxylic acid compound (II) as a reaction substrate and e.g. adding (I), carbon tetrachloride, ferric trichloride and N,N-dimethylformamide into a kettle, sealing, agitating, cooling, adding alcohol, refluxing, collecting the acyl chloride, evaporating the alcohol, neutralizing by saturated sodium bicarbonate solution, leaching by diethyl ether, combining the organic phases and drying by anhydrous sodium sulfate to obtain ethyl benzoate. USE - The method is useful for chlorinating carboxylic acid into corresponding acyl chloride using environmental pollutant carbon tetrachloride. ADVANTAGE - The method: utilizes the environmental pollutant carbon tetrachloride as the chlorinating agent, thus reducing the environmental pollution; utilizes low cost and easily available ferric trichloride catalyst, which activates carbon tetrachloride for the process of transforming carboxylic acid into acyl chloride; is suitable for large scale industrial production; and provides a new chlorination process and relatively safe chlorine source for the mass production of agricultural and pharmaceutical intermediates. DETAILED DESCRIPTION - Chlorinating carboxylic acid into corresponding acyl chloride using environmental pollutant carbon tetrachloride comprises either: providing substituted benzoic acid compound of formula (I) as a reaction substrate, carbon tetrachloride as a chlorinating reagent and a reaction solvent, ferric trichloride as a catalyst and N,N-dimethylformamide as an auxiliary catalyst, where the molar ratio of carboxylic acid, ferric trichloride and N,N-dimethylformamide is 1:0.1-10:0-0.05, and the amount of carbon tetrachloride is 1-50 ml/mmol of carboxylic acid, sequentially adding (I), carbon tetrachloride, ferric trichloride and N,N-dimethylformamide into a high-pressure kettle, sealing the high-pressure kettle, agitating, and controlling temperature at 100-800 degrees C and reaction time as 3-72 hours, cooling the kettle, relieving pressure, adding alcohol, refluxing for half an hour, collecting the generated acyl chloride, relieving the pressure and evaporating the alcohol, neutralizing the solution in the kettle using saturated sodium bicarbonate solution and leaching using diethyl ether, combining the organic phases and drying by anhydrous sodium sulfate to obtain ethyl benzoate; or taking carboxylic acid compound of formula (CH(R4)(R5)-COOH) (II) as a reaction substrate, carbon tetrachloride as a chlorinating reagent and a reaction solvent and ferric trichloride as a catalyst, where the molar ratio of the carboxylic acid and ferric trichloride is 1:0.1-10, and the amount of carbon tetrachloride is 1-50 ml/mmol of carboxylic acid, sequentially adding (II), carbon tetrachloride and ferric trichloride into the high-pressure kettle, sealing the high-pressure kettle, agitating, and controlling temperature within 100-800 degrees C and reaction time within 3-72 hours, cooling the kettle, relieving the pressure, adding dichloromethane, after completing the reaction, adding 4 M dilute hydrochloric acid, leaching using dichloromethane, combining the organic phases, drying by anhydrous ferric trichloride and concentrating the organic phases to obtain the corresponding acyl chloride. R1-R3 = H, Cl, Br, F, I, NO2, CH3, C2H5 or substituted phenyl; and R4, R5 = H, F, Cl, I, alkyl or optionally substituted phenyl.