The importance of polarity, bond strength and steric effects in determining the site of attack and the rate of free radical substitution in aliphatic compounds

Tedder, J. M.

doi:10.1016/0040-4020(82)80168-3

Cited by 99 publications

(40 citation statements)

References 21 publications

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“…Over the past century, an enormous body of literature has provided a foundation for "peering into the eyes" of C À H bonds. [4][5][6][7][8] If C À H bonds could talk, what stories would they tell? The purpose of this Minireview is to compile some of those stories inferred from the literature.…”

Section: Introductionmentioning

confidence: 99%

If CH Bonds Could Talk: Selective CH Bond Oxidation

2011

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C–H oxidation has a long history and an ongoing presence in research at the forefront of chemistry and interrelated fields. As such, numerous highly useful texts and reviews have been written on this subject. Logically, these are generally written from the perspective of the scope and limitations of the reagents employed. This minireview instead attempts to emphasize chemoselectivity imposed by the nature of the substrate. Consequently many landmark discoveries in the field of C–H oxidation are not discussed, but hopefully the perspective taken herein will allow for the more ready incorporation of C–H oxidation reactions into synthetic planning.

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Section: Introductionmentioning

confidence: 99%

If CH Bonds Could Talk: Selective CH Bond Oxidation

2011

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“…We note, however, that alkyl radical additions to olefins generally exhibit activation energies below 20 kJ/ mole, with the addition of tert-butyl radicals to VTEOS having a reported activation energy of just 16.0 kJ/mole [24]. Hydrogen atom transfers can present more substantial activation energy barriers, reaching 42.4 kJ/mole for the gas-phase reaction of methyl radicals with propane [30]. Based on these approximate values, one would expect VTEOS graft yields to decline with temperature, which is not consistent with our experimental findings.…”

Section: Discussionmentioning

confidence: 76%

Radical mediated graft modification of polyolefins: Vinyltriethoxysilane addition dynamics and yields

Parent

Parodi

2006

Polymer Engineering & Sci

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The dynamics and yields of peroxide-initiated grafting of vinyltriethoxysilane (VTEOS) to tetradecane and linear low density polyethylene (LLDPE) are described. VTEOS grafting kinetics at 160°C abide by the basic tenets of radical-mediated additions in terms of the influence of initiator loading and homolysis rate. However, reaction yields recorded for both the model and polymer systems are surprisingly insensitive to temperature, in apparent conflict with conventional models of free radical addition chemistry. These experimental observations are used to identify the predominant reactions within a general kinetic scheme, and to support the assumptions required to develop a rate expression that captures the effect of reagent concentrations on the dynamics of graft-modification.

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“…It is believed that a change in the reactivity of a substratum RH with a variation in R is associated with the three main structural factors, i.e., the energy, polar, and spatial effects [33,34]. The degree of manifestation of these effects and their relative significance depend on the substratum structure.…”

Section: Ch 3 C (+) Hphbmentioning

confidence: 98%