Phosphites hydrolysis, partial

Partial hydrolysis reactions lead to a monoalkyl phosphite, but complete hydrolysis gives phosphorous acid. The hydrogen atom bound to phosphorus can also be replaced by reaction with sodium, showing that the hydrogen atom has slight acidity. 

Contact of one cm of a 0.025 molar solution of dialkyl phosphite in tetradecane at 403 K (130 C) with one gram of iron powder which had been ball milled under pentane resulted in depletion of the phosphorus in solution, as shown in Fig. 11-9. Reaction as well as adsorption took place, for soluble iron was found in the solutions of di(2-ethyIhexy1), dilauryl and distearyl phosphites. Chromatography of the solutions after contact revealed large quantities of alcohol dibutyl phosphite and di(2-ethylhexyl) phosphite yielded 92-97% of the theoretical amount of alcohol after 24 hours. Hydrolysis of the phosphite esters was ascribed to water adsorbed on the walls of the reaction tube and on the iron powder. Forbes and Battersby [46] postulated that hydrolysis is an important aspect of the mechanism of the additive action of phosphite esters. Oxidation to phosphate by the oxygen of the ambient air is deemed minor maximum augmentation of the oxygen uptake by a 6.5% solution of dibutyl phosphite over that of the tetradecane carrier fluid in the presence of iron was 20%. The easy hydrolysis of phosphites is well known. Partial... 

Isopropylideneinosine added to a cold mixture of PCI3 and trimethyl phosphate as catalyst, stirred 1 hr. at 0, the crude intermediate dissolved in ice water, treated with 6 N NaOH, and warmed at 70° inosine 5 -phosphite. Y 90% by paper chromatography. F. e., also phosphorylation by oxidation with chlorine after partial hydrolysis, s. M. Yoshikawa, M. Sakuraba, and K. Kusashio, Bull. Chem. Soc. Japan 43, 456 (1970). 

Potassium permanganate Phosphoric from phosphorous acid esters Partial hydrolysis of phosphites s. 12, 161 Arsacridone oxides from 5,10-dihydroarsacridines s. U, 989... 

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