34512-27-1Relevant academic research and scientific papers
Electrochemical and Thermodynamic Properties of Oxygenated Nitrogen Compounds and Aromatics in Nitromethane. Application to the Energetic Aspects of the Nitration Process via Inner-sphere and/or Outer-sphere Electron-transfer Mechanisms
Boughriet, Abdel,Wartel, Michel
, p. 809 - 810 (1989)
The electrochemical and thermodynamic behaviour of oxygenated nitrogen compounds and aromatics has been studied in nitromethane (under weak solvation conditions) in order to provide energetic and mechanistic information concerning aromatic nitration compa
Reactions of carbocations with unsaturated hydrocarbons: Electrophilic alkylation or hydride abstraction?
Mayr, Herbert,Lang, Gabriele,Ofial, Armin R.
, p. 4076 - 4083 (2007/10/03)
Benzhydryl cations were used as reference electrophiles to determine the hydride donor reactivities of unsaturated hydrocarbons. The kinetics of the reactions were followed by UV-vis spectroscopy and conductivity measurements, and it was found that the second-order rate constants for the hydride transfer processes were almost independent of the solvents or counterions employed. The rate constants correlate linearly with the previously published empirical electrophilicity parameters E of the benzhydrylium ions. Therefore, the linear free energy relationship log k(20 °C) = s(E + N) could be employed to characterize the hydride reactivities of the hydrocarbons by the nucleophilicity parameters N and s. The similarity of the slopes s for hydride donors and π-nucleophiles allows a direct comparison of the reactivities of these different functional groups based on their nucleophilicity parameters N. Since nucleophilicity parameters of -5 N 0 have been found for a large variety of allylic and bisallylic hydride donors, a rule of thumb is derived that hydride transfer processes may compete with carbon-carbon bond-forming reactions when carbocations are combined with olefins of π-nucleophilicity N 0.
