Mechanisms of Organic Reactions

Organic Chemistry An Intermediate Text, Second Edition, by Robert V. Hoffman ISBN 0-47T45024-3 Copyright 2004 John Wiley Sons, Inc. 

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In nature, oxygen occurs in three stable isotopic species oxygen-16 [14797-70-7] O, 99.76% oxygen-17 [13968-48-4], 0.038% and oxygen-18 [14797-71-8], 0.20% (7). Commercial fractional distillation of water produces concentrations of as high as 99.98% concentrations up to 55% are also produced. The isotope has been used to trace mechanisms of organic reactions. 

Quantitative structure-reactivity analysis is one of the most powerful tools for elucidating the mechanisms of organic reactions. In the earliest study, Van Etten et al. 71) analyzed the pseudo-first-order rate constants for the alkaline hydrolysis of a variety of substituted phenyl acetates in the absence and in the presence of cyclodextrin. The... 

Comprehensive Chemical Kinetics , edited by Bamford and Tipper, 1969—, Elsevier, Amsterdam, is a multivolume treatise covering the area of reaction kinetics. Six of these volumes (not all published at the time of writing) deal with the kinetics and mechanisms of organic reactions in a thorough and comprehensive manner. 

The several theoretical and/or simulation methods developed for modelling the solvation phenomena can be applied to the treatment of solvent effects on chemical reactivity. A variety of systems - ranging from small molecules to very large ones, such as biomolecules [236-238], biological membranes [239] and polymers [240] -and problems - mechanism of organic reactions [25, 79, 223, 241-247], chemical reactions in supercritical fluids [216, 248-250], ultrafast spectroscopy [251-255], electrochemical processes [256, 257], proton transfer [74, 75, 231], electron transfer [76, 77, 104, 258-261], charge transfer reactions and complexes [262-264], molecular and ionic spectra and excited states [24, 265-268], solvent-induced polarizability [221, 269], reaction dynamics [28, 78, 270-276], isomerization [110, 277-279], tautomeric equilibrium [280-282], conformational changes [283], dissociation reactions [199, 200, 227], stability [284] - have been treated by these techniques. Some of these... 

Cambridge University Press, 1954) 146. On Ingold s move to UCL, J. W. Baker was appointed "Reader in the Mechanism of Organic Reactions" and F. Challenger was appointed "Professor of Organic Chemistry" at Leeds. Baker s book is Tautomerism (London Routledge, 1934), with an appendix by Ingold. 

Lapworth, A. J. J. Chem. Soc. 1903, 83, 995. Arthur Lapworth (1872—1941) was bom in Scotland. He was one of the great figures in the development of the modem view of the mechanism of organic reactions. Lapworth investigated the Benzoin condensation at the Chemical Department, The Goldsmiths Institute, New Cross, UK. 

EXAMPLES OF COMPLEX APPROACHES TO DISCERNMENT OF ION-RADICAL MECHANISM OF ORGANIC REACTIONS... 

Use of curved-arrow notation to depict die mechanisms of organic reactions requires that appropriate mechanistic principles be superimposed on the correct use of curved arrows to denote movement of electrons. The mechanism of a reaction is the stepwise process by which reactants are converted to products, and generally each step involves bond making and/or bond breaking that can readily be depicted by curved-arrow notation. 

Differences in reactivities of the hydroxyl groups of carbohydrates have been recognized for some time. Certain of these differences are understandable from the point of view of classical organic chemistry in this respect the differences in reactivity of primary and secondary alcohols may be cited. The advent of a much better knowledge of mechanisms of organic reactions, in many cases initiated and promoted in the area of carbohydrate chemistry, has clarified some of the complex properties of the polyfunctional carbohydrates. Further impetus and stimulus in this direction should be of material value in clarifying the reactions and possibilities of carbohydrate chemistry. 

Molecular dynamics simulations and mechanism of organic reactions non-TST behaviors... 

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