Autoxidation of Biologically Active Amines
Final rept. Jun 1964-Jun 1970
CASE WESTERN RESERVE UNIV CLEVELAND OH DEPT OF CHEMISTRY
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The copper-catalyzed oxidation of amines was investigated using peresters as oxidants. Rather random cleavage of alkyl groups was found. The autoxidation of N-alkyl isoindolines was found to be markedly enhanced by hydrogen donor solvents. A mechanism involving oxidative dehydrogenation to isoindoles followed by further rapid oxidation to phthalimidines was proposed. The photochemical decomposition of benzylamine and a seres of N-substituted benzylamines and benzylammonium salts was studied. Substituents included primary, secondary, and tertiary alkyl groups. Both the initial cleavage reaction and the primary dark reactions following bond cleavage were investigated. The primary, secondary, and tertiary amines were found to yield a benzyl radical and an amino radical during photolysis. No competition was observed for any alkyl group or hydrogen, leading to the conclusion that the photochemical reaction was a result of absorption inthe aromatic chromophore. Product studies and labeling techniques showed the primary dark reaction for secondary amines to be one involving hydrogen atom abstraction by the amino radical from the N-H bond of a substrate molecule. Reactions involving these secondary amino radicals and benzyl radicals account for the majority of the other products.
- Organic Chemistry
- Radiation and Nuclear Chemistry