SYNTHESIS OF ALKYL- AND ARYLPHOSPHONIC ACID MONOESTERS BY DIRECT ESTERIFICATION OF DIBASIC PHOSPHONIC ACIDS IN THE PRESENCE OF AN ARSONIC ACID CATALYST

Abstract

Partial hydrolysis of a diester, hydrolysis of the monochloro monoester, or alcoholysis of a phosphonic acid anhydride generally is used to prepare monoesters of alkyl- and arylphosphonic acids. Limited cases have been reported for the esterification of a dibasic phosphonic acid to yield the monoester, and none of these methods are as simple as the analogous method for preparing carboxylic acid esters, in which the carboxylic acid is esterified with an alcohol in the presence of an acid catalyst. Described is a method for preparing monoesters of alkyl- and arylphosphonic acids by direct esterification with an alcohol in the presence of a catalytic amount of phenylarsonic acid. The water formed during the reaction is removed azeotropically. For example, methylphosphonic acid was esterified in good yield to give its isopropyl, butyl, cyclohexyl, bornyl, and octadecyl monoesters. Similarly prepared are the ethyl, butyl, hexyl, and 2-(ethylthio)ethyl monoesters of phenylphosphonic acid, as well as 2-isopropoxyethyl hydrogen ethylphosphonate and 2-methoxyethyl hydrogen benzylphosphonate.

Keywords:

• Alkylphosphonic acid monoester
• arylphosphonic acid monoester
• catalysis
• esterification
• phenylarsonic acid

NMR spectra were acquired by Sue Harsh. Exact mass measurements were obtained by Edwin Quinones and Dr. Aaron Frank.