- Gas-Phase Nucleophilic Displacement Reactions
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Displacement reactions of each of a variety of anionic nucleophiles reacting with each of a variety of neutrals have been studied by pulsed ion cyclotron resonance (ICR) spectroscopy.Rate constants for these reactions are interpreted in terms of a three-step reaction sequence.RRKM calculations are used to obtain information about the energy of transition states.The origin of the barrier to reaction in solution is discussed.
- Olmstead, William N.,Brauman, John I.
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p. 1653 - 1662
(2007/10/03)
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- Characterization of Monomeric Thiopivaldehyde
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The title compound is the first aliphatic thioaldehyde to be observed under odinary laboratory conditions.Its spectral data and chemical characterization are described, including 2+3 cycloadditions with nitronate ester 6, 2+4 cycloaddition with reactive dienes, thiophilic addition with phenyllithium, carbophilic addition with butyllithium, conversion to episulfide 15 by the Wittig reagent, and oxidation to sulfine 17 with MCPBA.Independent generation of thiopivaldehyde from tert-butyllithium + ethyl thionoformate followed by heating 9 in xylene or by cycloreversion of 2-tert-butyl-1,2-dithiolane with butyllithium are also described.
- Vedejs, Edwin,Perry, David A.,Wilde, Richard G.
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p. 2985 - 2989
(2007/10/02)
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