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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
Author(s) -
Trachsel Alain,
Govoni Alexandra,
de Saint Laumer JeanYves,
Frérot Eric,
Herrmann Andreas
Publication year - 2008
Publication title -
chemistry and biodiversity
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.427
H-Index - 70
eISSN - 1612-1880
pISSN - 1612-1872
DOI - 10.1002/cbdv.200890217
Subject(s) - chemistry , tertiary alcohols , reaction rate constant , hydrolysis , propane , intramolecular force , group (periodic table) , organic chemistry , medicinal chemistry , alcohol , kinetics , physics , quantum mechanics
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.