Insights into a surprising reaction: The microwave-assisted direct esterification of phosphinic acids

被引:97
|
作者
Keglevich, Gyoergy [1 ]
Kiss, Nora Zsuzsa [1 ]
Mucsi, Zoltan [1 ]
Koertvelyesi, Tamas [2 ]
机构
[1] Budapest Univ Technol & Econ, Dept Organ Chem & Technol, H-1521 Budapest, Hungary
[2] Univ Szeged, Dept Phys Chem & Mat Sci, H-6701 Szeged, Hungary
关键词
PHASE-TRANSFER CATALYSIS; EFFICIENT SYNTHESIS; ACTIVE METHYLENE; ALKYLATION; IRRADIATION; DERIVATIVES; PHENOLS; OXIDES;
D O I
10.1039/c2ob06972e
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
It is well-known that phosphinic acids do not undergo direct esterifications with alcohols under thermal conditions. However, the esterifications take place under microwave (MW) irradiation due to the beneficial effect of MW. As a comparison, maximum 12-15% conversions were observed on traditional heating. It was proved experimentally that the MW-assisted esterifications are not reversible under the conditions applied that may be the consequence of the hydrophobic medium established by the long chain alcohol/phosphinic ester. Neither the thermodynamic, nor the kinetic data obtained by high level quantum chemical calculations justify the direct esterification of phosphinic acids under thermal conditions. The thermodynamic data show that there is no driving force for the reactions under discussion. As a consequence of the relatively high values of activation enthalpy (102-161 kJ mol(-1)), these esterifications are controlled kinetically. Comparing the energetics of the esterification of phosphinic acids and the preparative results obtained under MW conditions, one can see the potential of the MW technique in the synthesis of phosphinates. During our study, a series of new cyclic phosphinates with lipophilic alkyl groups was synthesized.
引用
收藏
页码:2011 / 2018
页数:8
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