Understanding and Control of Dimethyl Sulfate in a Manufacturing Process: Kinetic Modeling of a Fischer Esterification Catalyzed by H2SO4

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• 作者：John P. Guzowski ; Jr. ; Edward J. Delaney ; Michael J. Humora ; Erwin Irdam ; William F. Kiesman ; Albert Kwok ; Amy D. Moran
• 刊名：Organic Process Research & Development
• 出版年：2012
• 出版时间：February 17, 2012
• 年：2012
• 卷：16
• 期：2
• 页码：232-239
• 全文大小：399K
• 年卷期：v.16,no.2(February 17, 2012)
• ISSN：1520-586X

文摘

The formation and fate of monomethyl sulfate (MMS) and dimethyl sulfate (DMS) were studied by proton NMR for a sulfuric acid catalyzed esterification reaction in methanol. The kinetic rate constants for DMS and MMS were determined at 65 掳C by fitting time-dependent experimental data to a model using DynoChem. In refluxing methanol, sulfuric acid was converted to monomethyl sulfate (MMS) in nearly quantitative yield within 45 min. Once formed, the MMS underwent a reversible esterification reaction to form DMS. Dimethylsulfate reacted with methanol to regenerate MMS and form dimethyl ether. A byproduct of the esterification reaction was water, which further consumed DMS through hydrolysis. On the basis of derived rate constants, in refluxing methanol, DMS would not be expected to exceed 4 ppm in the reaction mixture at equilibrium. In the presence of the carboxylic acid substrate, DMS was not detected in the reaction mixture. The reaction pathways of this system have been systematically investigated, and the results of this study will be presented.