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Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

Organophosphorus intermediates. VI. The acid-catalysed reaction of trialkyl orthoformates with phosphinic acid

MJ Gallagher and H Honegger

Australian Journal of Chemistry 33(2) 287 - 294
Published: 1980

Abstract

Trialkyl orthoformates react with phosphinic acid to give the corresponding alkyl phosphinate and alkyl mono- or bis- (dialkoxymethyl)phosphinates; dialkyl phosphonites and phosphine, PH3, are also formed. The formation of P-alkylated products is acid- catalysed and is believed to proceed by alkylation of the trivalent tautomer of phosphinic acid (or its ester) by the dialkoxymethyl carbonium ion arising from the ortho ester in the presence of acid. A comparison with the corresponding reactions of phosphonic acid suggests that the trivalent tautomer of phosphinic acid [HP(OH)2] is formed much more readily than the trivalent form of phosphonic acid [P(OH)3] and this is accounted for by proposing that the equilibria

RPH(O)OR′ +H+ ↔ RP+H(OH)OR' ↔ RP(OH)OR'+H+ (R = H, OH; R' = H, alkyl)

lie further to the right for R = H than for R = OH because of inductive effects. 31P and 1H n.m.r. data are reported.

https://doi.org/10.1071/CH9800287

© CSIRO 1980

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