NDLI: Thermodynamic Origin of the Increased Rate of Hydrolysis of Phosphate and Phosphorothioate Esters in DMSO/Water Mixtures

Content Provider	PubMed Central
Author	Sorensen-stowell, Kerensa Hengge, Alvan C.
Abstract	The hydrolysis rates of the dianions of phosphate and phosphorothioate esters are substantially accelerated by the addition of polar aprotic solvents such as DMSO and acetonitrile. The activation barrier ΔG‡ is smaller due to a lower enthalpy of activation. The enthalpy of transfer of p-nitrophenyl phosphate (pNPP) and p-nitrophenyl phosphorothioate (pNPPT), from water to 0.6 (mol) aq DMSO (60 mol-percent water in DMSO) were measured calorimetrically. The enthalpies of activation for the hydrolysis reactions in the two solvents permitted the calculation of the enthalpy of transfer of the transition states. This transfer is thermodynamically favorable for both the reactants and the transition states, but is more favorable for the transition states. In the case of pNPP, the enthalpy of transfer of the reactant is -23.9 kcal/mol, compared to -28.3 for the transition state. The difference is greater for pNPPT, where the enthalpy of transfer of the reactant is -23.2 kcal/mol, and that for the transition state is -35.3. The results show that the reduced enthalpies of activation in both hydrolysis reactions arise not from a destabilization of the reactants in the mixed solvent, but from the fact that the enthalpy of transfer of the transition states to the mixed solvent is significantly more negative than the enthalpy of transfer of the reactants.
Related Links	http://dx.doi.org/10.1021/jo060896b
Ending Page	7184
Page Count	5
Starting Page	7180
File Format	PDF
ISSN	00223263
e-ISSN	15206904
Journal	The Journal of organic chemistry
Issue Number	19
Volume Number	71
Language	English
Publisher Date	2006-09-01
Access Restriction	Open
Subject Keyword	Organic Chemistry Research in Higher Education
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry

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