W. Storck, Georg Mancke
May 1, 1985
Citations
0
Influential Citations
11
Citations
Journal
Journal of Molecular Catalysis
Abstract
Abstract The reaction of the hydroxy group of 4-[N-(3-hydroxypropyl)-N-methylamino]pyridine with p-bromomethylstyrene produces a monomer in which the catalytically active 4-dialkylaminopyridine function is bound via a spacer arm. This monomer (15 mol%) may be copolymerized with styrene and p-divinylbenzene (6 mol%) in an n-octanol/n-octane mixture as a solvent to form a resin with good mechanical and swelling properties. The rates of the dimerization of phenyl isocyanate into l,3-diphenyl-l,3-diazetidine-2,4-dione and of the decomposition of this dimer have been measured in dioxane at 25 δC by IR techniques in the presence of this resin or 4-dimethylamino-pyridine (4-DMAP). For the heterogeneous polymer system, the rate constant for the forward reaction was found to be greater than that for the reverse reaction by a factor of two. The reaction of phenyl isocyanate with phenylacetic acid in dioxane at room temperature yielded phenylacetanilide in virtually similar amounts irrespective of whether 4-DMAP or the polymeric resin was used as the catalyst. The catalytic properties of these pyridines are ascribed to their ability to decarboxylate the mixed anhydride of phenylacetic acid and phenylcarbamic acid which exist in equilibrium with each other in a mixture of phenyl isocyanate and the carboxylic acid.