Mechanism of Base-Catalyzed Reactions in Phase-Transfer-Systems with Poly(ethylene glycols) as Catalysts. The Isomerization of Allylanisole

Article abstract of DOI:10.1021/jo00193a002

The mechanism of base-catalyzed reactions with poly(ethylene glycol) (PEG) as phase-transfer catalysts was studied by using the isomerization of allylanisole as a model reaction.The reaction kinetics showed the reaction to be chemical reaction controlled.The reaction system was a three-phase system consisting of an organic solvent phase, a PEG-potassium hydroxide complex phase, and a basic aqueous phase.The reaction mechanism included diffusion of the substrate from the solvent to the complex phase reaction and back diffusion of the product.The concentration of theaqueous phase is also important.When the aqueous phase is unsaturated there is no reaction.Concentrations above saturation increase rate because the basic complex becomes more potent under anhydrous conditions.The chain length and chain end moiety of the PEG catalysts have significant influence on the reaction rate.In general, short chain catalysts were more effective per gram but not per mole of catalyst.Etherification of the terminal hydroxyl group reduced activity.When alkoxide species were used as bases the trends were reversed, long chain catalysts being more effective and etherification increasing activity.