caa a22 4500 46905672X CHVBK 20180323132845.0 cr unu---uuuuu 170328e19920301xx s 000 0 eng 10.1163/156856792X00191 doi (NATIONALLICENCE)springer-10.1163/156856792X00191 EPR studies on electron transfer reactions between O-benzoyl-N-alkylhydroxylamines and perfluoroacyl peroxides. Generation of n - and sec -alkyl perfluoroacyl nitroxides and sec - and tert -alkyl perfluoroalkyl nitroxides [Elektronische Daten] [C. Zhao, Y. Peng, Y. Qu] Both EPR studies and product analysis have disclosed that the oxidation of O-benzoyl-N-alkylhydroxylamines (1, 4, 7) by perfluoroacyl peroxides (2) is an electron transfer-initiated process. Depending on the nature of the alkyl groups in the substrates, the caged radical pair CP1 (RN OCOPh, RfCOO) may react through different radical pathways resulting in different nitroxides along with the neutral products. With primary, benzyl and secondary alkyl groups, a 1,2-acyl shift becomes the predominant pathway resulting in acyl nitroxides (3, 5). With tert-alkyl groups such as tert-butyl, tert-alkyl perfluoroalkyl nitroxides (8) are formed via β-scission of both RN*OCOPh and RfCOO*. A general mechanistic pathway is proposed for the titled reactions generating the quite useful fluorinated nitroxides. Springer, 1992 Zhao C. Department of Chemistry, Huazhong University of Science and Technology, 430074, Wuhan, China aut Peng Y. Department of Chemistry, Huazhong University of Science and Technology, 430074, Wuhan, China aut Qu Y. Department of Chemistry, Huazhong University of Science and Technology, 430074, Wuhan, China aut Research on Chemical Intermediates Springer Netherlands 18/1(1992-03-01), 1-17 0922-6168 18:1<1 1992 18 11164 https://doi.org/10.1163/156856792X00191 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1163/156856792X00191 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Zhao C. Department of Chemistry, Huazhong University of Science and Technology, 430074, Wuhan, China aut NATIONALLICENCE 700 1- Peng Y. Department of Chemistry, Huazhong University of Science and Technology, 430074, Wuhan, China aut NATIONALLICENCE 700 1- Qu Y. Department of Chemistry, Huazhong University of Science and Technology, 430074, Wuhan, China aut NATIONALLICENCE 773 0- Research on Chemical Intermediates Springer Netherlands 18/1(1992-03-01), 1-17 0922-6168 18:1<1 1992 18 11164 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer