Direct esterification of phosphinic acids under microwave conditions: extension to the synthesis of thiophosphinates and new mechanistic insights

被引：25

作者：

Keglevich, Gyoergy ^{[1
]}

Kiss, Nora Zsuzsa ^{[1
]}

Drahos, Laszlo ^{[2
]}

Koertvelyesi, Tamas ^{[3
]}

机构：

[1] Budapest Univ Technol & Econ, Dept Organ Chem & Technol, H-1521 Budapest, Hungary

[2] Hungarian Acad Sci, Chem Res Ctr, H-1525 Budapest, Hungary

[3] Univ Szeged, Dept Phys Chem & Mat Sci, H-6701 Szeged, Hungary

来源：

TETRAHEDRON LETTERS | 2013年 / 54卷 / 06期

关键词：

Phosphinic acids; Thiophosphinates; Esterification; Microwave; Theoretical calculations; Mechanism; ASSISTED ESTERIFICATION;

D O I：

10.1016/j.tetlet.2012.11.054

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The direct esterification of phosphinic acids has been extended to the preparation of thiophosphinates using thiols, but the conversions are only ca. 50%. The outcome is in agreement with the unexpectedly high enthalpy of activation and endothermicity suggested by quantum chemical calculations. At the same time, formation of the thiophosphinates confirms the A(AC)2 (phosphinylation) mechanism and excludes the S-N reaction paths. Formation of an olefinic intermediate under the reaction conditions is also excluded experimentally. (C) 2012 Elsevier Ltd. All rights reserved.

引用

页码：466 / 469

页数：4

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