171. A criterion for the mechanism of the reaction between alkyl halides and hydroxylic solvents. Reactions of tert.-butyl chloride

Author(s):  
Leslie C. Bateman ◽  
Edward D. Hughes ◽  
Christopher K. Ingold
1973 ◽  
Vol 31 (10) ◽  
pp. 831-834 ◽  
Author(s):  
Toshiyuki MIYATA ◽  
Takahiro HAMADA ◽  
Tsuneaki HIRASHIMA ◽  
Osamu MANABE ◽  
Hachiro HIYAMA

1979 ◽  
Vol 57 (5) ◽  
pp. 500-502 ◽  
Author(s):  
Joaquim Jose Moura Ramos ◽  
Jacques Reisse ◽  
M. H. Abraham

A new treatment of the solvent effect on the solvolysis of tert-butyl chloride is proposed. This treatment is based on activation free energy measurements and on transfer free energy measurements of the reactant (R) on the one hand and of a model (M) of the activated complex (AC) on the other hand. Solute–solvent interaction free energies for the reactant, the activated complex and the model compound are estimated. This estimation involves the calculation of the free energy of cavity formation of these various solutes (R, AC, and M) in all the solvents. These cavity terms, which are a function of the cohesive properties of the solvent and of the surface of the cavity do not reflect the electronic structure of the solute whereas the interaction free energy term does. The method we propose can be described as a new 'experimental' approach for the study of the charge separation in an activated complex.


1979 ◽  
Vol 83 (11) ◽  
pp. 1488-1491 ◽  
Author(s):  
Jose M. Riveros ◽  
Peter W. Tiedemann ◽  
Bartolomeu C. De Melo ◽  
J. Fernando. Faigle

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