Gao R, Ho D G, Dong T, Khuu D, Franco N, Sezer O, Selke M
Department of Chemistry and Biochemistry, California State University, Los Angeles, Los Angeles, California 90032, USA.
Org Lett. 2001 Nov 15;3(23):3719-22. doi: 10.1021/ol010195v.
[reaction--see text] The chemistry of singlet oxygen with all three isomers of tris(methoxyphenyl)phosphine has been studied. For the severely hindered ortho isomer, intramolecular rearrangement to form phenyl diphenyl phosphinate is preferred to formation of phosphine oxide at low concentration in aprotic solvents. In protic solvents, no intramolecular reactivity is observed. A detailed kinetic analyses has been undertaken. There is no physical quenching, regardless of solvent. Mechanistic implications of these findings are discussed.
[反应——见正文] 已经研究了单线态氧与三（甲氧基苯基）膦的三种异构体的化学反应。对于位阻严重的邻位异构体，在非质子溶剂中低浓度时，分子内重排形成苯基二苯基次膦酸酯比形成氧化膦更占优势。在质子溶剂中，未观察到分子内反应活性。已进行了详细的动力学分析。无论溶剂如何，均不存在物理猝灭。讨论了这些发现的机理意义。
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