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  • 1
    Electronic Resource
    Electronic Resource
    Solvent effects on reactions of hydroxide ion with phosphorus(V) esters. A quantitative treatment (1996)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 9 (1996), S. 145-151 
    Details
    ISSN: 0894-3230
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Second-order rate constants of reactions of HO- with phosphate, phosphinate and thiophosphinate esters, (PhO)2PO.OC6H4NO2-p, Ph2PO.OC6H4NO2-p, Ph2PO.SPh, Ph2PO.SC6H4NO2-p and Ph2PO.SEt, go through minima with decreasing water content of H2O-MeCN or H2O-t-BuOH. The rate decrease is due to stabilization of the non-ionic ester on addition of organic solvent to H2O. This inhibition is partially offset by stabilization of the anionic transition states and in the drier solvents partial desolvation of HO- increases rates.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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    Paper (German National Licenses)
  • 2
    Electronic Resource
    Electronic Resource
    SOLVENT EFFECTS ON REACTIONS OF HYDROXIDE AND OXIMATE IONS WITH PHOSPHORUS(V) ESTERS (1997)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 221-228 
    Details
    ISSN: 0894-3230
    Keywords: solvent effects ; hydroxide ; oximates ; phosphorus(V) esters ; nucleophilicity ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---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 H2O-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.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
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