Mechanisms of Polymer-Supported Catalysis. 1. Reaction of 1-Bromooctane with Aqueous Sodium Cyanide Catalyzed by Polystyrene-Bound Benzyltri-n-butylphosphonium Ion

Article abstract of DOI:10.1021/ja00403a032

The rate of reaction of 1-bromooctane with aqueous sodium cyanide catalyzed by insoluble polystyrene-bound benzyltri-n-butylphosphonium salts has been studied as a function of the method of mixing of the triphase system, catalyst particle size, degree of polymer cross-linking, solvent, and temperature.Reaction rates increase as the speed of mechanical stirring increases to a maximum rate at 600 rpm.Turbulent vibromixing and ultrasonic mixing do not cause any additional reaction rate increase.Reaction rates increase as catalyst particle sizes decrease, even at the maximum stirring speed.Reaction rates decrease as percent of divinylbenzene cross-linking in the polymer increases from 2percent to 10percent.Reaction rates increase with increasing swelling power of the solvent in the order decane < toluene < chlorobenzene.The results are discussed in terms of mass transfer and intraparticle diffusion limitations on the reaction rates.The polymer-bound benzyltri-n-butylphosphonium ion gives reaction rates >/= 28 times faster than polymer-bound benzyltrimethylammonium when mass transfer and intraparticle diffusion do not limit the rates.