Organophosphorus compounds, which are most toxic components of agricultural chemicals, have generally phosphoester bond (X = P (YR)
3, X, Y = O, S; R = alkyl group) . In this study, the reactivity for hydrolysis of phosphoester linkage was investigated by estimating the activation energies (Δ E
≠) for the step of nucleophilic attacking of H
2O to P = X (X = O or S) double bond in phosphoester linkage, because that this step is the rate-determining step for hydrolysis.
The clarified points are as follows:
(1) The Δ E
≠ values for the hydrolysis of compounds having P = O double bond are relatively smaller than those having P = S double bond, owing to larger electrophilicity of phosphorus atom in P = O than P = S (sulfur atom (S) is less electronegative than O) .
(2) The sulfur atom in phosphoester linkage generally raises Δ E
≠ value (and therefore, makes less reactive) .
(3) The electron-donating (such as phenyl group) and electron-withdrawing substituents (such as F) on phosphorus atom raise and lower Δ E
≠, which are attributable to larger and smaller electrophilicity of P because of the offset and the increase of positive charge (δ
+) on P originated in the polarization of P
δ+ = X
δ- double bond, respectively.
(4) The activation energy for intramolecular rearrangement of methyl group converting two ester skeletons (for example, between thiolate and thionate) is extremely larger than that for hydrolysis.
The calculation suggested that the reactivity for the hydrolysis of organophosphorus compounds corresponds to the electrophilicity of phosphorus atom on P = X and the ΔE
≠value consistently changes depending on the electronegativity of X atom (X =O or S) (and consequently, the electrophilicity of P on P = X) and the electron-donating or withdrawing nature of substituents on P
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