93551-87-2Relevant academic research and scientific papers
KINETICS AND MECHANISM OF HYDROLYSIS OF BENZHYDRYL N-ARYLTHIOCARBAMATES AND STUDY OF THEIR IR SPECTRA
Mindl, Jaromir,Sterba, Vojeslav,Kaderabek, Vladimir,Klicnar, Jiri
, p. 1577 - 1591 (2007/10/02)
The hydrolysis of benzhydryl N-arylthiocarbamates proceeds by the E1cB mechanism.The reaction mechanism of S-benzhydryl N-arylthiocarbamates has been determined by trapping the reactive intermediate phenyl isocyanate (as N-phenyl-N'-morpholinourea) and by following the substituent effects in benzene ring of the benzhydryl group.The hydrolysis mechanism of O-benzhydryl N-arylthiocarbamates has been confirmed by spectral and kinetic determination of phenyl isothiocyanate.The hydrolysis of the primary formed phenyl isothiocyanate is almost 10 times slower than that ofthe starting thiocarbamate.With O-benzhydryl N-arylthiocarbamates at pH below 9 there takes place, at first, a rapid rearrangement to S-benzhydryl N-arylthiocarbamates, and benzhydrol is the reaction product.The rearrangement rate is pH independent.At pH above 11.5 the hydrolysis of O-benzhydryl N-arylthiocarbamates is much faster than the rearrangement, and thiobenzhydrol is the reaction product.Using the deuterated derivatives, the IR spectra of carbamates and thiocarbamates have been interpreted with respect to coupled vibrations of carbamic, thiocarbamic, and dithiocarbamic groups.
