Spin trapping chemistry of acyl radicals

Abstract

AbstractThe EPR spectra of a variety of different acyl radical adducts of PBN (C‐phenyl N‐tert‐butyl nitrone) and MNP (2‐methyl‐2‐nitrosopropane) were measured and their hyperfine splitting constants determined. Included are benzoyl, acetyl and other alkylacyl, alkoxyacyl, aminoacyl and alkylaminoacyl adducts. All examples gave relatively large β‐hydrogen hyperfine splittings ranging from 2.71 to 5.93 G in the PBN spin adducts. Long‐range hyperfine splitting was found to both nitrogen and amino‐hydrogen atoms in the aminoacyl adducts, indicating specific preferred conformations of the spin adducts. The MNP adducts have the well known 7‐8 G nitrogen hyperfine splitting with little else. The existence of hydrogen atom abstraction from benzaldehyde by nitroxides was established, indicating that nitroxides cannot be considered as inert reagents when sent to probe systems containing aldehydes. For example, the EPR signal due to a nitronyl nitroxide was rapidly quenched in the presence of benzaldehyde in benzene. Also, a surprising increase in intensity of benzoyl PBN adduct was noted after photolysis when the light was turned off. Double acyl adduct formation is proposed.