Kinetic isotope effects and tunneling in cyclic double and triple proton transfer between acetic acid and methanol in tetrahydrofuran studied by dynamic proton and deuteron NMR spectroscopy

1984 ◽  
Vol 106 (4) ◽  
pp. 869-879 ◽  
Author(s):  
Detlef Gerritzen ◽  
Hans Heinrich Limbach
2013 ◽  
Vol 135 (7) ◽  
pp. 2509-2511 ◽  
Author(s):  
Michael D. Toney ◽  
Joan Nieto Castro ◽  
Trevor A. Addington

1965 ◽  
Vol 43 (8) ◽  
pp. 2254-2258 ◽  
Author(s):  
C. C. Lee ◽  
Edward W. C. Wong

endo-Norbornyl-2-d p-bromobenzenesulfonate was synthesized and the isotope effects, as measured by kH/kD, were determined over a range of temperatures for solvolyses in 30% water – 70% dioxane, acetic acid, and formic acid. Values of kH/kD are of the order of 1.20. The data appear to indicate slightly higher isotope effects as the solvents are changed from aqueous dioxane to acetic acid to formic acid, as well as somewhat higher isotope effects at lower temperatures. Possible mechanistic implications of these results are presented. Relative titrimetric acetolysis rates, kexo/kendo, at different temperatures, and enthalpies and entropies of activation for these acetolyses are evaluated and discussed.


Author(s):  
Willem Siebrand ◽  
Zorka Smedarchina ◽  
Antonio Fernández-Ramos

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