Reactions of cyclopropyl radicals in the methyl-initiated decomposition of cyclopropanecarbaldehyde

Abstract

The decomposition of di-t-butyl peroxide in the presence of cyclopropanecarbaldehyde has been studied between 138 and 186°. The following expressions for the logarithms of the rate constants have been found (where C₃H₅= cyclopropyl): CH₃+ C₃H₅·CHO = CH₄+ C₃H₅·CO; 12·4 –(9000/2·3RT), C₃H₅·+ C₃H₅·CHO = C₃H₆+ C₃H₅·CO; 12·5 –(8600/2·3RT), C₃H₅·CO = C₃H₅·+ CO; 11·7 –(17,900/2·3RT), C₃H₅·=·CH₂·CH:CH₂; 10·4 –(19,100/2·3RT) The first two rate constants are in mole^–1 c.c. sec.^–1; the second two are in sec.^–1 and refer to a system pressure of 50 torr.