European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown
Published: Oct. 17, 2024
Abstract A systematic mechanistic study employing rate constant ( k obs ) kinetics measurements, linear free‐energy relationship, hydrogen kinetic isotope effect and law, as well the Density Functional Theory (DFT) approach (M06‐2x/6‐311G(d,p)) for oxidation of diverse substituted benzyl alcohols with trichloroisocyanuric acid (TCCA)/H 2 O in 50 % MeCN/CH Cl at 25.0 °C is present. The results showed an autocatalytic behavior a primary (4.22). relationship σ , ρ =−1.22) indicated mechanism change 4‐CF 3 3‐NO 4‐NO fractional law (3.25) alcohol. DFT formed situ from TCCA HCl. Furthermore, calculations support high agreement through transition state that performs hydride abstraction by induction zone. In case substrates bearing strong electron withdrawing groups, changes to corresponding hypochlorite main pathway.
Language: Английский