The Reaction of Nitriles under High Pressure. IV. The Replacement of the Substituents of Trialkyl-1,3,5-triazines

Abstract

Abstract It was found that, when some symmetrically 2,4,6-tri-substituted 1,3,5-triazines are kept with an iminoether or an amidine under high pressures and at elevated temperatures, unsymmetrically 2,4,6-tri-substituted 1,3,5-triazines are produced by way of the replacement of one or two (Remark: Graphics omitted.) groups of the triazines with the (Remark: Graphics omitted.) group of the iminoether or that of the amidine. Several mixtures of nitriles and methanol can be used for this replacement reaction in place of iminoethers or amidines at 4000–8000 atm and 100–150 °C. In these mixtures, equilibrium amounts of methyl iminoethers are rapidly formed. Increases in the size of the substituents of the original triazine and in their electron-releasing power inhibit this replacement reaction. Nitriles with an electron-releasing moiety give tri-substituted triazines replaced selectively by one of the original substituents.