Th. A. J. W. Wajer

C-nitroso compounds—VI : Acyl-alkyl-nitroxides from acyl radicals and nitroso compounds as studied by ESR☆

Abstract Acryl radicals combine with nitroso compounds to give acyl-alkyl-nitroxides, which are identified by their ESR spectra. The acyl radicals are generated by oxidation of aldehydes with suitable hydrogen-acceptors such as t-butoxy radicals or by intermediates obtained int he photochemical and thermal decomposition of nitroso compounds. During photolysis of alkyl nitrites in hydrocarbon solvents the acyl-alkyl-nitroxides appear also and this is explained on the basis of known reactions of alkyl nitrites and their decomposition products.Abstract Acryl radicals combine with nitroso compounds to give acyl-alkyl-nitroxides, which are identified by their ESR spectra. The acyl radicals are generated by oxidation of aldehydes with suitable hydrogen-acceptors such as t-butoxy radicals or by intermediates obtained int he photochemical and thermal decomposition of nitroso compounds. During photolysis of alkyl nitrites in hydrocarbon solvents the acyl-alkyl-nitroxides appear also and this is explained on the basis of known reactions of alkyl nitrites and their decomposition products.

C-nitroso compounds—II : On the photochemical and thermal formation of nitroxides from nitroso compounds, as studied by E.S.R.

Abstract It is demonstrated that nitroxides can be generated by photochemical or thermal decomposition of C-nitroso compounds. The nitroxide-formation takes place in both cases via the nitroso monomer. The influence of the wavelength on the photochemical reaction is discussed.

C-Nitroso compounds—VII: An ESR study of alkylnitroxides

Abstract It is demonstrated that alkylnitroxides can be generated from nitrosoalkanes by thermal reduction with hydroxylamines or by photoreduction with thiophenol. The solvent dependence of the ratio of the nitrogen and hydrogen splitting constants in t-butylnitroxide is explained on the basis of mesomeric contributions to the structure of the radical.