AbstractThe kinetic results (from DSC and1H NMR) of the thermolysis of symmetric azochloroalkanes and azoalkyl acetates with the general structure R1R2(X) C—N=N—C(X) R1R2(X=OCOCH3, Cl; R1, R2=CH3, C6H5) and of asymmetric phenylazoalkyl acetates with the general structure R1R2(H3COCO) C—N=N—C6H5(R1R2=CH3, C6H5) are described. The suitability of the asymmetric compounds as initiators for radical polymerization is demonstrated with (diphenyl)phenylazomethyl acetate (7c). Quantitative measurements of the thermolysis products from 1,1′‐azo(methylethyl) diacetate (4a) showed that the ratio for the disproportionation to combination reaction of the resulting substituted alkyl radi