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Tuesday, August 4, 2020 | History

3 edition of Thermodynamic effects of fluorine as a substituent in alkenes found in the catalog.

Thermodynamic effects of fluorine as a substituent in alkenes

by Karl S. Medinger

  • 17 Want to read
  • 9 Currently reading

Published .
Written in English

    Subjects:
  • Fluorine -- Thermodynamics.,
  • Hydrocarbons -- Research.

  • Edition Notes

    Statementby Karl S. Medinger.
    The Physical Object
    Paginationxi, 115 leaves :
    Number of Pages115
    ID Numbers
    Open LibraryOL24137368M
    OCLC/WorldCa8516400

      Fluorine’s high electronegativity and small size are among the special properties that contribute to its importance in medicinal chemistry. 1 The effects of fluorine substitution on the biological behaviour of biologically active molecules have been used effectively in drug design, especially after the successful use in steroids and the anticancer drug 5-fluorouracil. 1 As a result, the. Following its well-received predecessor, this book offers an essential guide to chemists for understanding fluorine in spectroscopy. With over compounds and spectra, the second edition adds new data featuring fluorine effects on nitrogen NMR, chemical shifts, and coupling constants. Explains how to successfully incorporate fluorine into target molecules and utilize fluorine.

    Following its well-received predecessor, this book offers an essential guide to chemists for understanding fluorine in spectroscopy. With over compounds and spectra, the second edition adds new data – featuring fluorine effects on nitrogen NMR, chemical shifts, and coupling constants. contribute to the overall substituent effect of haloaromatic compounds. Inductive electron withdrawal tends to deactivate the compound toward electrophilic substitution, as noted by the general relative rate, „, of less than Since fluorine is the most electronegative element, this effect should be strongest in fluorine among the halogens.

    The unique fluorine effects in organic reactions: Recent facts and insights into fluoroalkylations Article (PDF Available) in Chemical Society Reviews 45(20) August with Reads. 6. Substituent Effects on the Thermochemistry and Electrochemistry of Free Radicals.- 7. Some Applications of ES? Spectroscopy to the Study of Substituent Effects.- 8. Substituent Effects on Absolute Rate Constants and Arrhenius Parameters for the Addition of tert-Butyl Radicals to Alkenes.- 9. Allylic Radicals-An ESR Spectroscopical Study.-


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Thermodynamic effects of fluorine as a substituent in alkenes by Karl S. Medinger Download PDF EPUB FB2

Although the effect of fluorine substit- uents is superficially similar to that of methyl, unlike methyl the overall influence of multiple fluorine substitution is pres- ently not nearly so well understood. Like methyl, a single fluorine substituent stabilizes an alkene and appears to be slightly radical by: 8.

Tetrahedron Vol. 38, No. 15, pp toPrinted in Great Britain. $ Perganron Press Ltd. THE THERMODYNAMIC EFFECT OF FLUORINE AS A SUBSTITUENT ALLYLIC CF3 AND CF2H WILLIAM R. DOLBIER, JR.* and KARL S. MEDINGER Department of Chemistry, University of Florida, Gainesville, FLU.S.A.

(Received in USA 20 Cited by: 8. A study of the effect of vinylic fluorine substituents on the 5-hexenyl radical cyclization indicates that substituents at the 6-position, or vicinal 5,6-difluoro substitution have little effect on the rate, whereas a 5-fluoro substituent slows down the rate by a factor ofand 5,6,6-trifluoro substitution enhances the rate by a factor of Cited by: 7.

rdroOron Vol. 38, No. toPrinted in Great Britain. Perpmon Press Ltd. THE THERMODYNAMIC EFFECT OF FLUORINE AS A SUBSTITUENT VINYLIC CF2 AND CFH AND ALLYLIC CF2C WILLIAM R. DOLBIER, JR.* and KARL S. MEDINGER Department of Chemistry, University of Florida, Gainesville, FLCited by: The Origin of Alkyl Substituent Effects on the Reactivity and Thermodynamic Stability of Alkenes.

A Theoretical Study on Alkene Radical Cations. Israel Journal of Chemistry23 (1), Cited by: 5. Journals & Books; Help Download full Fluorinated alkenes are crucially important ‘building- blocks’ in organofluorine chemistry and they are also fascinating models for illustrating the effect of fluorine as a substituent on reactive intermediates.

An overview of reactions of fluorinated alkenes that involve generation of intermediate. The thermodynamics of small-molecule (H2, arene, alkane, and CO) addition to pincer-ligated iridium complexes of several different configurations (three-coordinate d8, four-coordinate d8, and five-coordinate d6) have been investigated by computational and experimental means.

The substituent para to the iridium (Y) has been varied in complexes containing the (Y-PCP)Ir unit (Y-PCP = η,3,5. In this work, five substituted 1-phenylbenzensulfonyl ethynes and the corresponding five substituted 1-phenylbenzensulfonyl ethenes were designed and synthesized as representatives of the polar alkynes and the polar alkenes.

Thermodynamic driving forces of eight elementary steps for reductions of the substituted ethynes and ethenes to the corresponding alkenes and alkanes in acetonitrile. Ionic reactions of terminal alkenes with chlorine (Cl2), bromine (Br2), and iodine monochloride (ICl) are sensitive to the alkyl substituents, and the positions and number of vinyl fluorine atoms.

These perturbations influence the symmetry of the halonium ion intermediates, which can be determined by the distribution of the Markovnikov to anti-Markovnikov products. Introduction. The reaction begins with H 2 gas and an alkene (a carbon-carbon double bond).

The pi bond in the alkene acts as a nucleophile; the two electrons in it form a sigma bond with one of the hydrogen atoms in H the pi bond broken, the other carbon (the one that did not newly receive a hydrogen) is left with a positive formal charge.

The reaction of alkenes with the disiamylborane dimer displays second-order kinetics, first-order in the dimer and first-order in the alkene. 9-borabicyclo left bracket 3. Kinetic and thermodynamic study of the substituent effect on the amino-Claisen rearrangement of para-substituted N-allyl-N-arylamine: A Hammett study via DFT (with the exception of fluorine.

Introduction Nowadays, one of the major efforts of chemists in both academia and industry is the search for “special effect” chemicals with new structures and functions. 1,2 In this context, fluorine is undoubtedly one of the elements that has attracted the highest recent research interest in several aspects of chemistry, since the judicious incorporation of the fluorine atom or the.

Gauche effect Special effects of fluorine substituent 4 Influence on reaction selectivity Reductive cyclizations Hydrogenation 5 Influence on thermodynamics Influence on equilibrium Influence on resonance structures 6 Application in asymmetric Diels–Alder reactions 7 Stereoelectronic effect versus steric clash 8 References.

The vinyl cation is a carbocation with the positive charge on an alkene carbon. Its empirical formula is C 2 H + generally, a vinylic cation is any disubstituted, trivalent carbon, where the carbon bearing the positive charge is part of a double bond and is sp the chemical literature, substituted vinylic cations are often referred to as vinyl cations, and understood to.

The substituent effects on the equilibrium constants for formation of reactive intermediates, with the pK a of the enzyme side chain to give the carbon acid pK a s reported in Scheme 74 There is a large unit effect of a single C-5 fluorine on the carbon acid pK a of enzyme-bound UMP.

alkene-forming elimination and. C Additions to Substituted Alkenes. For alkenes that have halogen or similar substituents at the doubly bonded carbons, the same principles apply as with the simple alkenes. That is, under kinetic control the preferred product will be the one derived from the more stable of the two possible intermediate carbon cations.

Wiley also publishes its books in a variety of electronic formats. Some content that appears in Solvent Effects on Fluorine Chemical Shifts / 13 Overall Summary of Fluorine Chemical Shift Ranges / 14 Alkenes with a Single Fluorine Substituent / 61 Hydrocarbon Alkenes / 62 Conjugated Alkenyl Systems / Reactions of Fluorinated Alkenes Fluorinated alkenes are typically electrophilic, and therefore they react readily with nucleophiles.

E.g. The reaction can either be nucleophilic addition or substitution. Notice that in both cases, this reaction is Regiospecific. (CH 3O- attached to the CF 2 end). Part of the NATO ASI Series book series (ASIC, volume ) Log in to check access. Buy eBook. USD Instant download Substituent Effects on Absolute Rate Constants and Arrhenius Parameters for the Addition of tert-Butyl Radicals to Alkenes.

Hanns Fischer. Pages Allylic Radicals—An ESR Spectroscopical Study. Spectroscopy to the Study of Substituent Effects -- 8. Substituent Effects on Absolute Rate Constants and Arrhenius Parameters for the Addition of tert-Butyl Radicals to Alkenes -- 9.

Allylic Radicals -- An ESR Spectroscopical Study -- ESR-Spectroscopical Investigation of Capto-dative Substituent Effects in Benzyl Radicals -- Cope rearrangements of 7,7,7-trifluoro-1,5-heptadiene and 7,7-difluoro-1,5-heptadiene were examined to gain quantitative understanding of the thermodynamic effect of allylic fluorine substitution.Fluorine substituent effects on the structure of oxirane and on the kinetic behavior of oxiranylcarbinyl radicals, as determined by DFT calculations, have been found to be similar to those.