Amidinoquinoxaline N-oxides as novel spin traps

Abstract

A novel type of spin traps 1 derived from the pyrimidoquinoxaline N-oxide heterocyclic core is reported. EPR technique was used to evaluate their ability to trap methyl radicals generated in a Fenton reaction in the presence of DMSO. All the synthesized nitrones showed spin trapping properties and the corresponding nitroxides 2 were characterized by EPR. The novel spin traps showed remarkably persistent signals, as confirmed in a competition experiment with DMPO. The addition rate constants leading to the spin adducts (kadd) were determined, and very good correlations were found with steric and electronic parameters of the parent nitrones. The spin adducts decomposition rate constants (kdec) and the corresponding half-life times (t1/2) were also determined. DFT and MP2 calculations were used in order to rationalize the adducts hfcc and the structural factors influencing their addition and decomposition rates.