Solvolytic displacements

A. Streitwieser, Jr., Solvolytic Displacement Reactions, McGraw-Hill, New Tfcrk, 1962 J. F. Bunnett, Annu. Rev. Phys. Chem. 14 271 (1963). 

A Strdtwieser, Jt, Solvolytic Displacement Reactions, McGraw-Hill, New York, 1962. 

Spieth. F.. quoted by Streitwieser, A., Jr. Solvolytic Displacement Reactions McGraw-Hill New York, 1962 p 53. 

A number of reports on the investigation of the stereochemistry of solvolytic displacement at vinyl carbon have appeared. Rappoport and Apeloig (173) have studied the solvolytic behavior, under a variety of conditions, of cis and trans 1,2-dianisyl-2-phenylvinyl halides, 178. 

For reviews, see L. Melander, Isotope Effects on Reaction Rates, Ronald Press, New York, 1960 F.W. Westheimer, Chem. Rev., 61, 265 (1961) Streitwieser, A., Jr., Solvolytic Displacement Reactions, McGraw-Hill, New York, 1962 E. H. Halevi,Prog Phys. Org. Chem., 1, 109 (1963) C. J. Collins and N. S. Bowman, eis.. Isotope Effects in Chemical Reactions, Van Nostrand Reinhold Co., New York, 1970. 

The second series of data on protic solvent effects in bromination that are related to transition states comprises the m-values of solvent-reactivity correlations. First, it is important to underline that 7-parameters, the solvent ionizing powers, established from solvolytic displacements, work fairly well in this electrophilic addition. This is expected since bromination, like SN1 reactions, leads to a cation-anion pair by heterolytic dissociation of the bromine-olefin CTC, a process similar to the ionization of halogenated or ether derivatives (Scheme 14). 

The rigorous analogy between electrophilic halogenation and solvolytic displacements was recognized only recently (Ruasse et al., 1991). Consequently, for most of the previously published solvent effects, the above procedure has not been applied systematically. Winstein Grunwald, YW G, parameters have... 

Streitwieser, A, jr. Solvolytic displacement reactions at saturated carbon atoms. Chem. Reviews 56, 675 (1956). 

A. Streitwieser, Solvolytic Displacement Reactions at Saturated Carbon Atoms," Chem. Rev. 56, 571 (1956). 

Comprehensive reviews of S 2 substitution can be found in (a) S. R. Hartshorn, Aliphatic Nucleophilic Substitution, Cambridge University Press, London, 1973 (b) A. Streitwieser, Solvolytic Displacement Reactions, McGraw-Hill, New York, 1962 (c) C. K. Ingold, Structure and Mechanism in Organic Chemistry, 2nd ed., Cornell University Press, Ithaca, N.Y., 1969. 

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