Synthesis and properties of zwitterionic phosphonioglycolates

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• 作者：Kaleswara Rao Basvani ; Olga S. Fomina ; Dmitry G. Yakhvarov ; Joachim Heinicke
• 关键词：P compounds ; Phosphonium ; Glycolates ; Zwitterionic compounds
• 刊名：Polyhedron
• 出版年：8 January, 2014
• 年：2014
• 卷：67
• 期：Complete
• 页码：306-313
• 全文大小：460 K

文摘

Reaction of diphenylphosphane with glyoxylic acid hydrate in diethyl ether furnished diphenylphosphanylglycolic acid 1 and in a 1:2 molar ratio almost quantitatively the zwitterionic phosphonioglycolic acid glycolate 2. Tertiary phosphanes with aryl or alkyl groups (phenyl, m/p-tolyl, p-anisyl, n-butyl, tert-butyl) react similarly to triorganylphosphonioglycolates 3a-h, which like 2 precipitate from the etheral solutions of the reactants. Tri-n-butylphosphonioglycolate (3e) forms an ionic liquid and tri-tert-butylphosphonioglycolate (3f) a viscous product whereas the other phosphonioglycolates are solids. Yields and stabilities of 3a-e increase with the P-basicity of the starting phosphane whereas bulky groups like tert-butyl cause destabilization. Compound 2 is the most stable phosphonioglycolate with only minor amounts of 1 in the solvolysis equilibrium in D₂O. The triaryl and tributylphosphonioglycolates 3a-f decompose in protic solvents with recovery of tertiary phosphanes. On heating at 100 掳C the compounds decompose to the corresponding phosphine oxides, minor amounts of glycolic acid and unidentified products.