2024-03-28T19:26:40Z
https://soar-ir.repo.nii.ac.jp/oai
oai:soar-ir.repo.nii.ac.jp:00017433
2023-03-31T05:46:46Z
1702:1703:1706
KINETICS OF THE REACTION OF trans-3- METHYLTHIOACRYLOPHENONE WITH HYDROXIDE ION. DETECTION OF CARBANION INTERMEDIATE BY THE DIFFERENCE SPECTRUM.
KAWASAKI, Atsushi
Reaction of trans-3-methylthioacrylophenone (MeSAcr) with hydroxide ion was followed spectrophotometric ally in aqueous solution. The reaction was found to be a typical series reaction : MeSAcr → benzoylacetaldehyde enolate → acetophenone. A carbanion intermediate, the enolate ion, was detected by the coincidence of difference spectra between the spectra in basic reaction solutions and in their acidified solutions with those between the spectra of benzoylacetaldehyde enolate and of the parent aldehyde. The first step of reaction in eq. (3) was kinetically first order in MeSAcr and first order in hydroxide ion. The second-order rate constants were obtained for MeSAcr-hydroxide ion combination reactions. The first-order rate coefficients for the second step of reaction in eq. (3) were obtained at the later stage of reaction where almost all MeSAcr was consumed. The rate coefficients are expressed as: k_<obs> = K₀ + k_<OH>⁻[OH⁻]. This is completely consistent with a mechanism for the hydrolysis of enolates of dicarbonyl compounds.
Article
信州大学教養部紀要. 27: 249-256(1993)
departmental bulletin paper
信州大学教養部
1993-03-25
application/pdf
信州大学教養部紀要.
27
249
256
1340-9972
AN10176022
https://soar-ir.repo.nii.ac.jp/record/17433/files/Liberal_arts27-14.pdf
eng