Nature of N‐S bond cleavage of 2,3‐dihydro‐2,2‐dimethyl‐7‐benzofuranyl (di‐n‐butylaminosulfenyl) (methyl)carbamate

Abstract

The cleavage of the N‐S bond in 2,3‐dihydro‐2,2‐dimethyl‐7‐benzofuranyl (di‐n‐butylaminosulfenyl) (methyl)carbamate was examined in different buffer solutions (hydrolysis), in buffer solution containing sulfhydryl reagents (thiolysis) and on thin‐layer chromatographic plates. In buffer solution and on thin‐layer plates, N‐S bond cleavage readily occurred to give carbofuran as a major product, with minor amounts of bis‐carbofuran‐N,N’‐disulfide and ‐trisulfide. The hydrolysis reaction in buffer proceeded with first‐order kinetics. Significant amounts of an unknown polar compound were obtained in buffer solution and on thin‐layer plates. In the presence of excess cysteine and glutathione at pH 7.0, thiolytic N‐S bond cleavage occurred with first‐order kinetics to give carbofuran as the sole identifiable product. At pH 5.0, three minor products were obtained along with carbofuran.