Mechanisms of lactone hydrolysis in neutral and alkaline conditions

Rafael Gomez-Bombarelli, Emilio Calle, Julio Casado

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25 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)6868-6879
Number of pages12
JournalJournal of Organic Chemistry
Volume78
Issue number14
DOIs
Publication statusPublished - 19 Jul 2013

Keywords

  • CARBOXYLIC-ACID ESTERS
  • FREE-ENERGY PROFILE
  • ETHYL-ACETATE
  • METHYL FORMATE
  • THEORETICAL-ANALYSIS
  • REACTION PATHWAYS
  • AQUEOUS-SOLUTION
  • HYDROXIDE ION
  • GENERAL BASE
  • WATER

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