81374-84-7Relevant articles and documents
Reaction of Thiols with Phenylgyoxal To Give Thiolesters of Mandelic Acid. 2. Intramolecular Genaral-Base Catalysis and Change in Rate-Determinimg Step
Okuyama, Tadashi,Komoguchi, Shinji,Fueno, Takayuki
, p. 2582 - 2587 (1982)
Reactions of phenylglyoxal (1) with N-(2-mercaptoethyl)morpholine (2a) and -piperidine (2b) to give the thiolesters (4) of mandelic acid have been kinetically investigated at 30 deg C.The reaction proceeds through the initial formation of a hemithioacetal (3) (rapid equilibration with the equilibrium constant Kh = 400-1500 M-1) and its rearrangement via the intramolecular general-base-catalyzed proton transfers to form 4.The pH-rate profile and primary kinetic isotope effects showed that the deprotonation to form an enediol intermediate (5) is rate determining in the reaction with 2a.In the case of 2b, a change in the rate-determining step was observed.At pH 2+, Mg2+, and Ca2+ in aqueous solutions even at low ionic strength.