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A Study on the Rearrangement of Dialkyl 1-Aryl-1-hydroxymethylphosphonates to Benzyl Phosphates

[ Vol. 24 , Issue. 4 ]

Author(s):

Zita Rádai, Réka Szabó, Áron Szigetvári, Nóra Zsuzsa Kiss, Zoltán Mucsi and György Keglevich*   Pages 465 - 471 ( 7 )

Abstract:


The phospha-Brook rearrangement of dialkyl 1-aryl-1-hydroxymethylphosphonates (HPs) to the corresponding benzyl phosphates (BPs) has been elaborated under solid–liquid phase transfer catalytic conditions. The best procedure involved the use of triethylbenzylammonium chloride as the catalyst and Cs2CO3 as the base in acetonitrile as the solvent at room temperature. The substrate dependence of the rearrangement has been studied, and the mechanism of the transformation under discussion was explored by quantum chemical calculations. The key intermediate is an oxaphosphirane. The one-pot version starting with the Pudovik reaction has also been developed. The conditions of this tandem transformation were the same, as those for the one-step HP→BP conversion.

Keywords:

α-hydroxyphosphonate, benzyl phosphate, phospha-Brook rearrangement, mechanism.

Affiliation:

Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, 1521 Budapest, Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, 1521 Budapest, Spectroscopy Research Department, Gedeon Richter Plc., 1103 Budapest, Gyömrői út 19-21, Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, 1521 Budapest, Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, 1521 Budapest, Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, 1521 Budapest



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