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SOLVENT EFFECTS ON REACTIONS OF HYDROXIDE AND OXIMATE IONS WITH PHOSPHORUS(V) ESTERS

✍ Scribed by Clifford A. Burton; Nicholas D. Gillitt; Anurag Kumar

Publisher
John Wiley and Sons
Year
1997
Tongue
English
Weight
138 KB
Volume
10
Category
Article
ISSN
0894-3230

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✦ Synopsis

Second-order rate constants of reactions of OH Οͺ , 2,3-butanedionemonooximate and 2-hydroxybenzaldoximate ions with aryl phosphate, phosphinate and thioarylphosphinate esters go through minima with decreasing water content of aqueous acetonitrile, tert-butyl alcohol and N-methyl-2-pyrrolidone. For reactions in H 2 O-MeCN the solvent effects are analyzed in terms of activity coefficients of the anionic nucleophiles and transition states. In the drier solvents partial desolvation of the nucleophiles increases rates. Nucleophilicities of several oximates and inorganic anions are compared in water.

πŸ“œ SIMILAR VOLUMES

OXIDATIVE HYDROLYSIS OF PHOSPHORUS(V) ES
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Peroxymonosulfate ion, HSO 5 Γ€, as Oxone in aqueous H 2 SO 4 , oxidizes sulfides [MeSC 6 H 4 X(p), X = Me, H, NO 2 ] to sulfoxides and converts aryl thiobenzoates [PhCOSC 6 H 4 X(p), X = Me, H] and thiol phosphorus(V) esters [Ph 2 POSPh, (EtO) 2 POSPh, Ph 2 POSEt, Ph(EtO)POSEt] into the acids and su

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Pseudo-first-order rate constants (k obs ) for the reaction of piperidine with phthalimide vary linearly with the total concentration of piperidine ([Pip] T ) at a constant content of CH 3 CN in H 2 O-CH 3 CN solvents within the CH 3 CN content range 2-80 % (v/v). The change in k obs with the change