Ethyl ethylphosphonate, hydrolysis

Reactivity Hydrolysis products Ethyl ethylphosphonic acid, 2-(diethylamino) ethanethiol, and P,P-diethyl diethyldiphosphonate... 

Activation parameters have been calculated for alkaline hydrolysis of a range of phosphoramidates (Brown et al., 1976). Comparison of parameters for five-membered species with those for acyclic analogues indicates that in most cases the observed rate enhancement is quantitatively consistent with release of strain energy (AAH ). The entropy of activation for five-membered species is usually more negative than for acyclic analogues, but varies widely from —14.8 to -f-7.5 eu. Aksnes and Bergesen (1966) have obtained activation parameters for a series of acyclic, six-membered and five-membered phosphates, phosphonates and phosphinates. The entropy of activation for hydrolysis of ethyl propylenephosphonate [55] is strikingly more positive than for the other species studied. The difference in A5 compared to that for hydrolysis of diethyl ethylphosphonate is +17.6 eu (see Note added in Proof ). 

Theoretical studies of the hydrolysis of methyl phosphate anion have found that the dissociative mechanism involving the formation of metaphosphate is favoured over the associative mechanism involving a pentacoordinated intermediate.Phytic acid, myo-inositol hexakis(dihydrogen phosphate) (127), was completely hydrolysed to inositol in an aqueous polybasic alcohol at 150 °C a reaction mechanism was proposed. The reactions of p-nitrophenyl diethyl phosphate (128) and ethyl p-niuophenyl ethylphosphonate (129) with a wide range of oximate ions (p/(a = 7-13) in 10% aqueous ethanol at 25 °C have been studied. For oximate ions with p a 9.0, the reactivity of the oximes tends towards that of alcoholate ions and their Q -effect disappears (as had been previously shown with / -niuophenyl acetate). The reason for this is the unfavourable solvation effects of the solvent. A review (253 references) has appeared on the synthesis and reaction of Q -aminophosphonates. ° ... 

The kinetics of the basic hydrolysis of ethyl / -nitrophenyl ethylphosphonate (190) in the SDS-hexanol-water reverse micellar system has shown that at high pH and low water content the reaction occurs in the surface layer and is adequately described by a pseudo-phase model.The reactivity of ethyl aryl chloromethylphosphonates (191 X = NO2, Br, H, Et, Bu, n-octyl) in the basic hydrolysis reactions in direct micelles of cetyltrimethylammonium bromide depends on both the electronic and the hydrophobic... 

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