Mechanistic Studies on the Basic Hydrolysis of 2,2,2-Trichloro-1-arylethanones

Article abstract of DOI:10.1021/jo00233a009

The basic hydrolysis of 2,2,2-trichloro-1-phenylethanone (1a), 2,2,2-trichloro-1-(p-methoxyphenyl)ethanone (1b), and 2,2,2-trichloro-1-(p-chlorophenyl)ethanone (1c) has been studied in the pH range 5.5-13.2.In all cases the reaction products were chloroform and the corresponding benzoate.The reaction is first order toward both the ethanone and hydroxide ion and proceeds via an addition-elimination-type mechanism.The initial addition step forms the corresponding ethanone hydrates, which, depending on the pH, will form the mono- and dianionic intermediates, the elimination of CCl3 from the mono- and/or dianionic species being the rate-limiting step of the reaction.