Formation of radicals

Homolytic cleavage of most a bonds may be achieved if the compound is subjected to a sufficiently high temperature, typically about 200 °C. However, some weak bonds will undergo homolysis at temperatures little above room temperature. Bonds of peroxy and azo compounds fall in this category, and such compounds may be used to initiate a radical process. Di-tert-butyl peroxide, dibenzoyl peroxide 

Essentials of Organic Chemistry Paul M Dewick 2006 John Wiley Sons, Ltd 

At increased temperatures, the peroxide bond is cleaved homolytically, giving radicals. Dibenzoyl peroxide is a diacyl peroxide and cleaves rather more readily than the dialkyl peroxide, but further decomposition then occurs in which carbon dioxide 

Homolytic cleavage of diazo compounds such as AIBN is also driven by the stability of a neutral molecule, this time molecular nitrogen, and two alkyl radicals are produced. 

An alternative approach to homolytic cleavage is photolysis, the absorption of light energy, especially 

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The rate of formation of radicals will depend on a number of features, including the concentration of initiator, temperature and the presence of other agents. Since subsequent stages of polymer growth occur almost instantaneously it is the relative slowness of this stage which causes the overall conversion times in most polymerisations to be at least 30 minutes and sometimes much longer. 

Preventive antioxidants which prevent the formation of radicals by reactions (7.1) and (7.3). 

Any agent which functions to prevent the formation of radicals by these processes may be considered as a preventive antioxidant. In practice three classes are generally recognised ... 

Xenon difluoride [4, 5, 7, 8,10] is a white crystalline material obtained through the combination of fluorine and xenon m the presence of light The reagent is commercially available and possesses a relatively long shelf-life when stored cold (freezer) Xenon difluoride is very effective for small-scale fluormation of alkenes and activated nucleophilic substrates. The reactions are usually conducted between 0 °C and room temperature in chloroform or methylene chloride solutions Hydrogen fluoride catalysis is sometimes helpful Xenon difluoride reacts in a manner that usually involves some complexation between the substrate and reagent followed by the formation of radical and radical cation intermediates... 

A photochemical variant, the so-called photo-Fries rearrangement, proceeds via intermediate formation of radical species. Upon irradiation the phenyl ester molecules (1) are promoted into an excited state 11. By homolytic bond cleavage the radical-pair 12 is formed that reacts to the semiquinone 13, which in turn tautomerizes to the p-acylphenol 3. The corresponding ort/zo-derivative is formed in an analogous way ... 

At present, high-temperature stabilization of polyolefins is still misunderstood besides, this problem presents serious difficulties. Stabilization of thermal oxidation and photoinduced destruction with the use of stabilizers in this case is inefficient, since at high temperatures these stabilizers are easily evaporated out of the polyolefin melt and decomposed with the formation of radicals capable of initiating additional kinetic chains of destruction. 

The rate of formation of radical from the photoinitiator molecule (the only light-absorbing molecule in the system) Vr- is generally given by Eq. (4) ... 

Crano191 has investigated the reaction between diisopropyl peroxydicarbonate and tertiary amines. These experiments indicate the formation of radicals by loss of a hydrogen from the a-CH2 of the amine. It seems likely that the mechanism of... 

The identification of both phenylethyl and 1-phenyl-1,2,3,4-lelrahydronaphthalenyl end groups in polymerizations of styrene retarded by FeCl3/DMP provides the most compelling evidence for the Mayo mechanism.316 The 1-phenyl-1.2,3,4-tetrahydronaphthalenvl end group is also seen amongst other products in the TEMPO mediated polymerization of styrene,317318 However, the mechanism of formation of radicals 96 in this case involves reaction of the nitroxide with the Diels-AIder dimer (Scheme 3.63). The mechanism of nitroxide mediated polymerization is discussed further in Section 9.3.6. 

Rao and Symons49 studied the formation of radicals in y-radiolysis of dilute solutions of dimethyl sulfoxide in fluorotrichloromethane. By ESR studies they found the radical cation (CH3)2SOt whose ESR spectrum show considerable g anisotropy and small methyl proton hyperfine coupling. 

This sequence of formation of radical cation which is followed by a C—S bond scission into alkyl radical and alkyl sulfonyl cation was previously suggested by the same authors for the radiolysis of polyfolefin sulfonefs in the solid state72 and was confirmed by scavenger studies73. Scavengers are ineffective in crystalline solids such as dialkyl sulfones and hence could not be used in this study. 

Ce4+ is a versatile one-electron oxidizing agent (E° = - 1.71 eV in HC10466 capable of oxidizing sulfoxides. Rao and coworkers66 have described the oxidation of dimethyl sulfoxide to dimethyl sulfone by Ce4+ cation in perchloric acid and proposed a SET mechanism. In the first step DMSO rapidly replaces a molecule of water in the coordination sphere of the metal (Ce v has a coordination number of 8). An intramolecular electron transfer leads to the production of a cation which is subsequently converted into sulfone by reaction with water. The formation of radicals was confirmed by polymerization of acrylonitrile added to the medium. We have written a plausible mechanism for the process (Scheme 8), but there is no compelling experimental data concerning the inner versus outer sphere character of the reaction between HzO and the radical cation of DMSO. 

Since the n bonds of allenes are orthogonal, the rates of formation of radicals resulting... 

A particular case of a [3C+2S] cycloaddition is that described by Sierra et al. related to the tail-to-tail dimerisation of alkynylcarbenes by reaction of these complexes with C8K (potassium graphite) at low temperature and further acid hydrolysis [69] (Scheme 24). In fact, this process should be considered as a [3C+2C] cycloaddition as two molecules of the carbene complex are involved in the reaction. Remarkable features of this reaction are (i) the formation of radical anion complexes by one-electron transfer from the potassium to the carbene complex, (ii) the tail-to-tail dimerisation to form a biscarbene anion intermediate and finally (iii) the protonation with a strong acid to produce the... 

Loss of electrons from the polymer chain with the formation of radical cations (polarons) and dications (bipolarons). 

Some physical techniques can be classified into flame treatments, corona treatments, cold plasma treatments, ultraviolet (UV) treatment, laser treatments, x-ray treatments, electron-beam treatments, ion-beam treatments, and metallization and sputtering, in which corona, plasma, and laser treatments are the most commonly used methods to modify silicone polymers. In the presence of oxygen, high-energy-photon treatment induces the formation of radical sites at surfaces these sites then react with atmospheric oxygen forming oxygenated functions. 

Oxidation is initiated by formation of radicals which may be the result of enzyme catalysed reactions like oxygen activation by xanthine oxidase in... 

Fig. 16.1 Progression of oxidation in a food system from formation of radicals through primary and secondary lipid oxidation products to protein damage.

Dimerization of a number of arylalkenes catalyzed by vitamin Bj2 and Ti(III) as reductant has been examined (Shey et al. 2002). Mechanisms were examined including the requirement of a reductant, and a reaction was proposed that involved the formation of radicals at the benzylic carbon atoms. 

As in reduction reactions, two possible mechanisms exist for substitution reactions (1) electron-radical, involving the intermediate formation of radicals and their reaction with nucleophiles X ... 

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