106115-17-7Relevant academic research and scientific papers
Hydrolysis of aryl N-methyl-N-arylsulfonylcarbamates
Araujo,Campelo,Iley,Norberto
, p. 494 - 497 (2007/10/03)
Tertiary sulfonylcarbamates 1 were prepared by reaction of a sulfonamide anion with aryl chloroformates. These previously unreported compounds hydrolyse in aqueous media to the parent sulfonamide and phenol. The pH-rate profile shows both spontaneous and base-catalysed processes. The reaction is also catalysed by buffers. Kinetic data for the hydrolysis of these compounds by HO- are best interpreted in terms of a mechanism involving rate-limiting formation of a tetrahedral intermediate from nucleophilic attack of hydroxide ion at the carbamate carbonyl carbon atom. For the 4-nitrophenylsulfonyl compound 1h decomposition of the tetrahedral intermediate appears to be rate-limiting with the sulfonamide anion, rather than the phenoxide, functioning as the leaving group. The buffer-catalysed process is consistent with general base-catalysed attack of water at the carbamate carbonyl carbon atom.
Alkyl Shifts in 1,4-Dipoles from Tosyl Iso(thio)cyanate and Imido(thio)carbonates or Isoureas
Schaumann, Ernst,Dietz, Joerg,Kausch, Erwin,Schmerse, Gerd C.
, p. 339 - 344 (2007/10/02)
O-->N alkyl shifts are observed in the dipoles 3, 13 from tosyl isocyanate (2a) and imido(thio)carbonates 1 (12) to give (thio)allophanates 5 (14).Similary, addition of tosyl isothiocyanate (2b) to isourea 24a leads to the product 28 of an O-->S methyl shift.A cross-over experiment involving 2a and imidothiocarbonates 12b,c gives the four products 14a-d proving the intermolecular nature of the rearrangement.However, on mixing 2a and isoureas 24a,b or 2b and imido(thio)carbonates 1 (12), the reaction stops at the stage of dipoles 8, 19, 25a,b.
