1 research outputs found
Experimental and DFT Computational Insight into Nitrosamine Photochemistryî—¸Oxygen Matters
A nitrosamine
photooxidation reaction is shown to generate a peroxy
intermediate by experimental physical-organic methods. The irradiation
of phenyl and methyl-substituted nitrosamines in the presence of isotopically
labeled 18-oxygen revealed that an O atom was trapped from a peroxy
intermediate to trimethylphosphite or triphenylphosphine, or by nitrosamine
itself, forming two moles of nitramine. The unstable peroxy intermediate
can be trapped at low temperature in postphotolyzed solution in the
dark. Chemiluminescence was also observed upon thermal decomposition
of the peroxy intermediate, that is, when a postphotolysis low-temperature
solution is brought up to room temperature. A DFT study provides tentative
information for cyclic nitrogen peroxide species on the reaction surface