Newcomb Martin, Daublain Pierre, Horner John H
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, Illinois 60607,USA.
J Org Chem. 2002 Nov 29;67(24):8669-71. doi: 10.1021/jo026218g.
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.
一系列对硝基苯亚磺酸盐酯被用于激光闪光光解（LFP）研究中，以生成会发生碎片化从而产生(2,2 - 二苯基环丙基)甲基自由基的烷氧基自由基。β - 断裂反应的速率常数随着碎片化反应中生成的羰基化合物而增加，顺序为CH₂O < MeCHO < Me₂CO < PhCHO < Ph₂CO，并且随着溶剂极性的增加而增大。对于碎片化生成苯甲醛和二苯甲酮的烷氧基自由基，当初始碳自由基与仲烷基自由基一样稳定时，β - 断裂反应比1,5 - 氢原子夺取反应更快，并且这种生成碳自由基的途径可用于LFP动力学研究。
