Substituent Dependence of the ?-Acceptor Induced Bond Cleavage Reactions of Benzyl Phenyl Ethers

Article abstract of DOI:10.1021/jo00292a033

The relative C-O bond cleavage reaction rates (k_rel) of eight substituted benzyl phenyl ethers (BPE's) have been measured.These C-O bond cleavage reactions were thermally initiated by 2,3-dichloro-5,6-dicyanoquinone (DDQ).The equilibrium constants (K) for charge-transfer complex formation of these BPE's with the electron acceptors DDQ and TCNE in the solvent methylene chloride have also been determined at room temperature.The best correlation of log k_rel for DDQ reactions has been observed in these reactions.From this data, hydride transfer to DDQ is the rate-determining step of the reaction.