Über Reaktionen zwischen Phosphortrichlorid und Cyclohexen unter dem Einfluß von Y-Strahlung und von Wärme

Abstract

1-chlorocyclohexyl-phosphorus dichloride is formed in a Kharasch type chain reaction when γ-rays act on mixtures of phosphorus trichloride and cyclohexene. The G-value is proportional to the reciprocal square root of the dose rate and reaches a maximum at 100°C. The activation energy of the rate determining step PCl2C6H10 · +PCl3→PCl2C6H10Cl+PCl2 · was found to amount to 6, 7 kcal/mole. At higher temperatures, the yield strongly decreases since another chain reaction predominates which produces cyclohexyl-phosphorus dichloride. The two chains have a common propagation step. 1-chlorocyclohexyl-phosphorus dichloride and cyclohexyl-phosphorus dichloride are also thermally formed at temperatures above about 150°C.