76946-77-5Relevant academic research and scientific papers
Effect of Dimethyl Sulfoxide Solvent in the Thermolysis of Alkyl Nitrates Elucidated by the Temperature Dependence of a Kinetic Isotope Effect
Kwart, H.,Brechbiel, M. W.
, p. 461 - 463 (1982)
The cyclic, bent TS* of gas-phase thermolytic decomposition of benzyl nitrate has been compared to the analogous thermal elimination of amine oxides in diglyme solution.The use of Me2SO solvent in amine oxide thermolysis has been shown to alter the TS* to one which accommodates linear H transfer.Me2SO solvent in the case of benzyl nitrate is now found to afford a nearly quantitative conversion to benzaldehyde.Other alkyl nitrates show a similarly facile reaction to produce good yields of the carbonyl product.However, through measurement of the temperature dependence of kH/kD with benzyl-α-d nitrate it is found that the TS* for decomposition is little altered by comparison with the gas-phase thermolysis reaction.The differences in behavior of the amine oxide and alkyl nitrate reactions in Me2SO and the possible origins of these differences are discussed briefly.
Regarding the Mechanism of the Carbonyl-Forming Elimination Reaction of Alkyl Nitrates
Kwart, H.,George, T. J.,Horgan, A. G.,Lin, Y. T.
, p. 5143 - 5147 (2007/10/02)
The temperature dependence of kH/kD for the formation of benzaldehyde through base-catalyzed HNO2 elimination from benzyl nitrate is indicative of a tunneling pathway of linear proton transfer.The same criterion applied to the uncatalyzed, gas-phase reaction reveals a cyclic transition state of nonlinear proton transfer.From these and other considerations it has been deduced that the base-catalyzed reaction is best formulated as a cyclic process of linear H transfer and is consistent with an ECO1cb rather than the ECO2 mechanism previously claimed.
The Transition State in the Carbonyl-Forming Elimination Reaction of Alkyl Nitrates
Kwart, H.,George, T. J.,Horgan, A. G.,Lin, Y. T.
, p. 1970 - 1972 (2007/10/02)
The title reaction, now found to involve proton tunneling with base catalysis and a cyclic, nonlinear proton transfer in the uncatalyzed gas-phase process, cannot have (as previously formulated) an ECO2 mechanism.
