p-Nitrobenzenesulfenate esters as precursors for laser flash photolysis studies of alkyl radicals.
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.
Newcomb
Martin
M
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, Illinois 60607,USA. men@uic.edu
Daublain
Pierre
P
Horner
John H
JH