By Rees Ch.
Content material: Arenium ions: constitution and reactivity / by means of V.A. Koptyug
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Additional resources for Contemporary Problems in Carbonium Ion Chemistry I-II
53, Brown has shown the data on the solvolysis of secondary and tertiary 2-exo- and 2-endo-substituted norbornanes to correlate well with log k (~+ for aryl groups is equivalent to o +) without any "break" of the curves (Fig. 3). From this fact Brown has excluded a o-participation in the solvolysis of secondary 2-exo-norbornanes. Criticizing Peters' method Schleyer notes 13) that the accuracy of determining the rate constants of secondary substrates from the data on tertiary analogues is rather low and the error may amount to 102.
But the solvolysis via a classical ion implies such a fast interconversion of classical ions that Corey, for chemical purposes, takes the ion as symmetrical. -%s -0zeJ or -o2c,. so; If a reaction, as pointed out by Bethel and Gold ~), proceeds via a classical 2-norbornyl ion, then the rate of conversion of the initially formed ion into an enantiomer must exceed the rate of its interaction with the solvent by more than 2000. The latter interaction is characterized by a constant of about 109-101° see-l; hence the interaction rate constant of classical ions must be of the order of 1013 sec-1.
E. just when the nonclassical ion is formed; for tertiary exo and endo epimers the 13-isotope effect is practically the same. 11. In the nonclassical ion the 3-exo-H(D) atom is situated ideally for interacting with the vacant p-orbital o f C 2 while 3-endo-H(D) has a dihedral angle of 60 ° with the p-orbital axis. If the ionization of 2-exo-norbornyl brosylate resulted in a classical ion, then the effects of 3-exo- and 3-endo-deuterium would be equal. 31 Murr has noted that the y-isotope effect for compounds 74 and 75 is practically the same 142); even if ionization of 2-endo-norbornyl brosylate does involve steric hindrances they are not effective enough to affect the value of kn/k D during solvotysis of compound 75.
Contemporary Problems in Carbonium Ion Chemistry I-II by Rees Ch.