Formation of Acrylic Acid from Lactic Acid in Supercritical Water

Article abstract of DOI:10.1021/jo00280a027

Supercritical (SC) water is an unusual medium in which fast and specific heterolytic reactions can be conducted at temperatures as high as 400 deg C.In supercritical water, lactic acid decomposes into gaseous and liquid products via three primary reaction pathways.Products of the acid-catalyzed heterolytic decarbonylation pathway are carbon monoxide, water, and acetaldehyde.Products of the homolytic, decarboxylation pathway are carbon dioxide, hydrogen, and acetaldehyde.Products of the heterolytic, dehydration pathway are acrylic acid and water.The intramolecular nucleophilic displacement of the α-hydroxyl by the carbonyl group of lactic acid, producing α-propiolactone as an unstable intermediate which subsequently rearranges to become the unsaturated acid, is a likely mechanism for acrylic acid formation, although an intramolecular E2 elimination initiated by attack of the carbonyl oxygen on a methyl hydrogen cannot be ruled out.Support for the former mechanism comes in part from the observed 100percent relative yield of acrylic acid from β-propiolactone in SC water.