Energy Sufficient α-Amino Peroxides as Potential Sources of Excited- State Carbonyls

Article abstract of DOI:10.1021/jo01290a020

Products from the thermolysis of α-amino peroxides 2 and 3 reveal a normal di-sec-alkyl peroxide decomposition route rather than an intramolecular base-catalyzed elimination.With peroxide 2, N-phenyl-N-methylformamide and benzophenone were produced in 92 and 97percent yield, respectively.Peroxide 3 gave N-phenyl-N-methylformamide and 1-mesityl-3,3-diphenylpropane-1,2-dione in yields of 82 and 89percent, respectively.From thermochemical calculations, it was deduced that peroxides 2 and 3 are energy sufficient to generate excited-state products upon thermolysis.Extremely low chemiluminescence quantum yields (Φ_CL) were observed for 3, in both the absence and the presence of acceptors (9,10-dibromoanthracene, 9,10-diphenylanthracene, and rubrene).Luminescence from the thermolysis of 2 was too weak to obtain Φ_CL values.The lack of efficient excited-state product formation in these energy sufficient reactions is discussed.A proposed mechanism for bioluminescence in the flavin system is also considered in relationship to the thermolyses of 2 and 3.