51788-72-8Relevant academic research and scientific papers
Convenient criterion for the distinction between electrophilic and electron transfer reactions of electron-rich alkenes
Bauld, Nathan L.,Aplin, J. Todd,Yueh, Wang,Endo, Stephanie,Loving, Angie
, p. 15 - 24 (2007/10/03)
Both experimental and theoretical studies confirm that the formation of aryl vinyl ether and aryl vinyl sulfide cation radicals from the corresponding neutral substrates correlates with the Brown σ+ parameters as opposed to Hammett σ values. Peak oxidation potentials for both classes of substrates correlate preferentially with σ+, as do gas-phase ionization energies calculated by both semi-empirical and ab initio methods. In contrast, the protonation energies of the same substrates, which relate to carbocation formation, correlate preferentially with σ values, as do rates of protonation and other electrophilic additions. These observations permit a sharp distinction between electrophilic and electron transfer reactions of these two common classes of electron-rich substrates. Using this criterion, the cycloadditions of tetracyanoethylene to these substrates are found to proceed via an electrophilic mechanism, rather than by a previously proposed electron transfer mechanism.
REACTIONS OF THIIRANES. X. REGIOSELECTIVITY OF RING-OPENING IN METHYL- AND VINYLTHIIRANES BY PHENOLS
Tverdokhlebov, V. P.,Polyakova, N. Yu.,Tselinskii, I. V.
, p. 1258 - 1261 (2007/10/02)
The effects of substituents in the phenol on the regioselectivity of the ring opening of methyl- and vinylthiiranes with phenols in the presence of 3-chloro-1-propene have been studied.Increasing the electron-donating properties of the substituent in the phenol increases the amount of the isomer corresponding to cleavage of the ring in accordance with Krasurskii's rule.The reaction rate was increased considerably when carried out in highly polar aprotic solvents.
