期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 78, 期 14, 页码 6868-6879出版社
AMER CHEMICAL SOC
DOI: 10.1021/jo400258w
关键词
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资金
- Spanish Ministerio de Ciencia e Innovacion and European Regional Development Fund [CTQ2010-18999]
- Spanish Ministerio de Educacion for a PhD scholarship [AP2006-01976]
The neutral and base-catalyzed hydrolysis of nine carboxylic acid esters was studied using a hybrid supermolecule-PCM approach including six explicit water molecules. The molecules studied included two linear esters, four beta-lactones, two gamma-lactones, and one delta-lactone: ethyl acetate and methyl formate, beta-propiolactone, beta-butyrolactone, beta-isovalerolactone, diketene (4-methyleneoxetan-2-one), gamma-butyrolactone, 2(5H)-furanone, and delta-valerolactone. DFT and ab initio methods were used to analyze the features of the various possible hydrolysis mechanisms. For all compounds, reasonable to very good qualitative and quantitative agreement with experimental work was found, and evidence is provided to support long-standing hypotheses regarding the role of solvent molecule as a base catalyst. In addition, novel evidence is presented for the existence of an elimination-addition mechanism in the basic hydrolysis of diketene. A parallel work addresses the acid-catalyzed hydrolysis of lactones.
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