title: Controlled release of volatile secondary and tertiary alcohols by neighboring group participation: stepwise cyclization and re-opening of 2,2'-bis(carbamoyl)dibenzoates at neutral pH.
abstract: Bioactive, volatile, secondary and tertiary fragrance alcohols are efficiently released by intramolecular neighboring-group-assisted hydrolysis of 2,2'-bis(carbamoyl)dibenzoates at neutral pH. The stepwise cyclization of 2,2'-[(methylimino)bis(propane-3,1-diylcarbamoyl)]dibenzoates is followed by the re-opening of the intermediately formed diphthalimide and proceeds in an overall four-step consecutive reaction sequence. Kinetic rate constants for all four reaction steps could be determined pairwise by reversed-phase HPLC. At neutral pH, secondary alcohols were released by one order of magnitude faster than the tertiary alcohols, and the rate constants for the re-opening of the diphthalimides were found to be in the same order of magnitude as the release of the tertiary alcohols. Dynamic headspace analysis on a dry cotton surface finally confirmed the efficient release of tertiary alcohols under mild reaction conditions generally encountered for applications in functional perfumery.
authors.affiliation: Firmenich SA, Division Recherche et Développement, 1 Route des Jeunes, Genève 8.
authors.forename: Alain
authors.initials: A
authors.lastname: Trachsel
authors.forename: Alexandra
authors.initials: A
authors.lastname: Govoni
authors.forename: Jean-Yves
authors.initials: JY
authors.lastname: de Saint Laumer
authors.forename: Eric
authors.initials: E
authors.lastname: Frérot
authors.forename: Andreas
authors.initials: A
authors.lastname: Herrmann
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D001565:Benzoates / Q000138:chemical synthesis / Q000737:chemistry*; D002851:Chromatography, High Pressure Liquid; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D013056:Spectrophotometry, Ultraviolet
chemical_list: D000438:Alcohols; D001565:Benzoates