Solvolytic reactivity of 1-trifluoromethyl-1-phenylethyl tosylate. Correlation of substituent effects in the formation of highly destabilized carbonium ions

Autor:	Annette D. Allen, Thomas T. Tidwell, Michael P. Jansen, Nevindra N. Mangru, K. M. Koshy
Rok vydání:	1982
Předmět:	Trifluoromethyl Chemistry General Chemistry Reaction intermediate Biochemistry Medicinal chemistry Catalysis chemistry.chemical_compound Colloid and Surface Chemistry Reaction rate constant Nucleophile Carbonium ion Kinetic isotope effect Reactivity (chemistry) Solvolysis
Zdroj:	Journal of the American Chemical Society. 104:207-211
ISSN:	1520-5126 0002-7863
Popis:	The solvolytic rate constants of 1-trifluoromethyl-1-phenylethyl toxylate (2) in solvents of widely different ionizing power and nucleophilicity are linearly related with slope mlt. slashsub OTslt. slash = 1.01 to the rates of 2-adamantyl tosylate in the same solvents. The rate ratio k(PhCHMeOTs)/k(2) is 2 x 10/sup 5/ in 100% EtOH. Added salts cause modest increases in the rate of solvolysis of 2 in 80% EtOH independent of the nucleophilicity or basicity of the salts. The isotope effect k(CH/sub 3/)/k(CD/sub 3/) on the rate of solvolysis of 2 ranges from values around 1.6 in the less ionizing solvents to values around 1.3 in more ionizing solvents. The product from 2 is mainly that of substitution in all solvents studied, with increasing amounts of elimination in the less ionizing solvents. These results are interpreted in terms of rate-limiting ionization of 2 to form a carbonium ion intermediate.
Databáze:	OpenAIRE
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