801. The radiolysis of tri-n-alkyl phosphates

Abstract

Electron irradiation of trialkyl phosphates leads to the corresponding dialkyl hydrogen phosphate as a major product, the absolute yield decreasing in the series trimethyl to tripentyl ester. Yields of the respective monoalkyl dihydrogen phosphates are less by ten-fold and formation of phosphoric acid is negligible. Hydrocarbon products include alkenes and alkanes, but the yields do not account quantitatively for the loss of organic fragments in acid formation. Yields of hydrogen generally increase with molecular weight of the ester. These results are lnterpreted in terms of reactions involving the parent moleculeion. There is mass-spectral evidence that organic phosphate ions can undergo simple rearrangement accompanied by fragmentation of the alkyl chain; in the liquid state the latter reaction leading to formation of acid phosphate is assumed to compete with other ionic processes leading to hydrogen production. (auth)