Cyclotrimerization of butyl and cyclohexyl isocyanate—catalysis and kinetics

Abstract

AbstractThe cyclotrimerization of model aliphatic and cycloaliphatic isocyanates (butyl and cyclohexyl isocyanate) was carried out using an ammonium carboxylate and a salicylaldehyde‐potassium complex as catalysts. The kinetics of the cyclotrimerization of butyl isocyanate in both 2‐ethoxyethyl acetate and dimethylformamide (DMF) using the 2‐ethylhexanoate salt of trimethylaminopropanol‐2 was found to be of first order with respect to the isocyanate and also of first order with respect to the catalyst. The reaction rate in DMF was considerably greater than in 2‐ethoxyethyl acetate, as could be expected. Employing the salicylaldehyde‐potassium catalyst, the cyclotrimerization of butyl isocyanate followed second‐order kinetics with respect to the isocyanate and first order with regard to the catalyst. Due to the fact that the cyclotrimerization of cyclohexyl isocyanate was found to be slower than that of butyl isocyanate, the cyclotrimerization of this isocyanate was carried out only in DMF using the 2‐ethylhexanoate salt of trimethylaminopropanol‐2 as the catalyst. The kinetics of this reaction was found to follow second order with respect to the isocyanate and first order with regard to the catalyst. The products of the reactions were identified by IR, 1H‐NMR, and mass spectrometry.