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Kinetics and mechanism of base‐catalyzed cleavage of some bicyclo[4.2.0.]octa‐1,3,5‐trien‐7‐one (benzocyclobuten‐1(2 H )‐one) derivatives
Author(s) -
Sorial Mary A.,
Iskander George M.,
Bolton R.
Publication year - 1982
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550140808
Subject(s) - chemistry , carbanion , sodium methoxide , medicinal chemistry , kinetics , catalysis , sodium hydroxide , methoxide , substituent , cleavage (geology) , solvent , acid catalysis , base (topology) , reaction mechanism , organic chemistry , physics , geotechnical engineering , quantum mechanics , fracture (geology) , engineering , mathematical analysis , mathematics
The kinetics of cleavage of 3‐hydroxybicyclo[4.2.0]octa‐1,3,5‐trien‐7‐ones in aqueous sodium hydroxide, and of the alkoxy and acetoxy analogues in methanolic sodium methoxide solution, were examined under pseudo‐first‐order reaction conditions. The dependence of the rate upon the basicity of the solvent, whether measured by H − or by [OR − ], reflects the possible structure of the transition state. The deduced mechanism is also supported by the effects of substituents upon the reaction rate. The relative amounts of the volatile reaction products derived from o ‐toluic acid and from phenylacetic acid are understood in terms of the substituent effect upon the relative stabilities of the carbanions.