p-Nitrobenzenesulfenate esters as precursors for laser flash photolysis studies of alkyl radicals. 2002

Martin Newcomb, and Pierre Daublain, and John H Horner
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, Illinois 60607,USA. men@uic.edu

A series of p-nitrobenzenesulfenate esters was used in laser flash photolysis (LFP) studies to generate alkoxyl radicals that fragmented to give the (2,2-diphenylcyclopropyl)methyl radical. Rate constants for the beta-scission reactions increased as a function of the carbonyl compound produced in the fragmentation reaction in the order CH2O < MeCHO < Me2CO < PhCHO < Ph2CO and increased with increasing solvent polarity. For alkoxyl radicals that fragment to produce benzaldehyde and benzophenone, the beta-scission reactions are faster than 1,5-hydrogen atom abstractions when the incipient carbon radical is as stable as a secondary alkyl radical, and this entry to carbon radicals can be used in LFP kinetic studies.

UI MeSH Term Description Entries

Related Publications

Martin Newcomb, and Pierre Daublain, and John H Horner
October 2000, Organic letters,
Martin Newcomb, and Pierre Daublain, and John H Horner
July 2002, The Journal of organic chemistry,
Martin Newcomb, and Pierre Daublain, and John H Horner
January 1991, Biochemistry,
Martin Newcomb, and Pierre Daublain, and John H Horner
March 2003, Organic & biomolecular chemistry,
Martin Newcomb, and Pierre Daublain, and John H Horner
September 2017, Organic & biomolecular chemistry,
Martin Newcomb, and Pierre Daublain, and John H Horner
July 1986, Photochemistry and photobiology,
Martin Newcomb, and Pierre Daublain, and John H Horner
March 1977, Photochemistry and photobiology,
Martin Newcomb, and Pierre Daublain, and John H Horner
November 2003, Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology,
Martin Newcomb, and Pierre Daublain, and John H Horner
January 1973, Anais da Academia Brasileira de Ciencias,
Copied contents to your clipboard!