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Full-Text Articles in Physical Sciences and Mathematics
Base-Induced Decomposition Of Alkyl Hydroperoxides In The Gas Phase. Part 3. Kinetics And Dynamics In Ho + Ch3ooh, C2h5ooh, And Tert-C4h9ooh Reactions, Shuji Kato, G Barney Ellison, Veronica Bierbaum, Stephen J. Blanksby
Base-Induced Decomposition Of Alkyl Hydroperoxides In The Gas Phase. Part 3. Kinetics And Dynamics In Ho + Ch3ooh, C2h5ooh, And Tert-C4h9ooh Reactions, Shuji Kato, G Barney Ellison, Veronica Bierbaum, Stephen J. Blanksby
Stephen Blanksby
The ECO2 elimination reactions of alkyl hydroperoxides proceed via abstraction of an α-hydrogen by a base: X− + R1R2HCOOH → HX + R1R2CO + HO−. Efficiencies and product distributions for the reactions of the hydroxide anion with methyl, ethyl, and tert-butyl hydroperoxides are studied in the gas phase. On the basis of experiments using three isotopic analogues, HO− + CH3OOH, HO− + CD3OOH, and H18O− + CH3OOH, the overall intrinsic reaction efficiency is determined to be 80% or greater. The ECO2 decomposition is facile for these methylperoxide reactions, and predominates over competing proton transfer at the hydroperoxide moiety. The CH3CH2OOH …