Mayr, Herbert and Gonzalez, Jose L. and Lüdtke, Kerstin
Comparison of the Nucleophilicities of Alkynes and Alkenes. Quantitative Determination of the Nucleophilicities of Alkynes toward Carbenium Ions.
In: Chemische Berichte, Vol. 127, No. 3: pp. 525-531
Relative reactivities of alkenes and alkynes toward diarylmethyl cations have been determined by direct rate measurements and by competition experiments in dichloromethane. At -70°C alkynes are found to be one to two orders of magnitude less reactive than analogously substituted alkenes (e.g. phenylacetylene/styrene), but the reactivity difference reduces strongly as the temperature is raised. The stereochemistry of the vinyl chlorides produced by addition of benzhydryl chlorides to alkynes is characterized.