title: Hydroxylamine as an oxygen nucleophile: substitution of sulfonamide by a hydroxyl group in benzothiazole-2-sulfonamides.
abstract: Benzothiazole-2-sulfonamides react with an excess of hydroxylamine in aqueous solutions to form 2-hydroxybenzothiazole, sulfur dioxide, and the corresponding amine. Mechanistic studies that employ a combination of structure-reactivity relationships, oxygen labeling experiments, and (in)direct detection of intermediates and products reveal that the reaction proceeds via oxygen attack, and that oxygen incorporated in the 2-hydroxybenzothiazole product derives from hydroxylamine. The reaction, which is performed under mild conditions, can be used as a deprotection method for cleavage of benzothiazole-2-sulfonyl-protected amino acids.
authors.affiliation: Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands.
authors.forename: Jos J A G
authors.initials: JJ
authors.lastname: Kamps
authors.forename: Roman
authors.initials: R
authors.lastname: Belle
authors.forename: Jasmin
authors.initials: J
authors.lastname: Mecinović
mesh_terms: D000588:Amines / Q000138:chemical synthesis / Q000737:chemistry; D052160:Benzothiazoles / Q000138:chemical synthesis / Q000737:chemistry*; D006878:Hydroxides / Q000737:chemistry*; D019811:Hydroxylamine / Q000737:chemistry*; D015394:Molecular Structure; D010100:Oxygen / Q000737:chemistry*; D013449:Sulfonamides / Q000737:chemistry*; D013458:Sulfur Dioxide / Q000138:chemical synthesis / Q000737:chemistry
chemical_list: D000588:Amines; D052160:Benzothiazoles; D006878:Hydroxides; D013449:Sulfonamides; D013458:Sulfur Dioxide; D019811:Hydroxylamine; C031356:hydroxide ion; C005465:benzothiazole; D010100:Oxygen