Vinyl hydrogen acidities of two stereoisomers.
The gas-phase acidities of the vinyl hydrogens of cis- and trans-2-butene were measured by the silane kinetic method in a Fourier-transform ion cyclotron resonance spectrometer. The acidities of ethene and the secondary vinyl hydrogen of propene were measured by the same method. The method was calibrated using the known acidities of methane and benzene. The vinyl hydrogens of trans-2-butene are more acidic than the vinyl hydrogens of cis-2-butene by 4.5 kcal/mol; the acidities of ethene and the secondary vinyl hydrogen of propene are between those of the two butenes. The acidity of cis-2-butene is 409 +/- 2 kcal/mol, and the acidity of trans-2-butene is 405 +/- 2 kcal/mol. Density functional theory calculations are in good agreement with the experiments. The results are discussed in terms of steric interactions, polarizabilities, dipole-dipole interactions, and charge-dipole interactions.
Walthall
David A
DA
Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA.
Brauman
John I
JI