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SOLVENT EFFECTS ON REACTIONS OF HYDROXIDE AND OXIMATE IONS WITH PHOSPHORUS(V) ESTERS
Author(s) -
Burton Clifford A.,
Gillitt Nicholas D.,
Kumar Anurag
Publication year - 1997
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/(sici)1099-1395(199704)10:4<221::aid-poc868>3.0.co;2-b
Subject(s) - chemistry , phosphinate , nucleophile , hydroxide , solvent , acetonitrile , aqueous solution , solvent effects , alcohol , ion , inorganic chemistry , aryl , reaction rate constant , tetrabutylammonium hydroxide , medicinal chemistry , organic chemistry , kinetics , alkyl , catalysis , physics , fire retardant , quantum mechanics
Second‐order rate constants of reactions of OH − , 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. © 1997 John Wiley & Sons, Ltd.