Radical mechanisms quinones

Efforts to achieve a retardation of cross-linking in elastomers are based on the general assumption of a radical mechanism for retardation cross-linking and the possibility of its inhibition by a deactivation of the reactive macromolecular radical [33]. These compounds generally contain one or more labile hydrogen atoms, which after, donation of this atom, will form relatively inactive radicals. Typical antirad agents are quinones, hydroquinones, and aromatic amines (phenyl and napthylamines). 

Each ion-radical reaction involves steps of electron transfer and further conversion of ion-radicals. Ion-radicals may either be consnmed within the solvent cage or pass into the solvent pool. If they pass into the solvent pool, the method of inhibitors will determine whether the ion-radicals are prodnced on the main pathway of the reaction, that is, whether these ion-radicals are necessary to obtain the hnal prodnct. Depending on its nature, the inhibitor may oxidize the anion-radical or reduce the cation-radical. Thns, quinones are such oxidizers whereas hydroquinones are reducers. Because both anion and cation-radicals are often formed at the first steps of many ion-radical reactions, qninohydrones— mixtures of quinones and hydroquinones—turn out to be very effective inhibitors. Linares and Nudehnan (2003) successfully used these inhibitors in studies on the mechanism of reactions between carbon monoxide and lithiated aromatic heterocycles. 

A radical mechanism has been proposed involving an initial electron transfer (ET) from the silyl telluride to the quinone followed by the formation of a phenoxy radical as precursor of the product. 

The addition of hydrogen halides to simple olefins, in the absence of peroxides, takes place by an electrophilic mechanism, and the orientation is in accord with Markovnikov s rule.116 When peroxides are added, the addition of HBr occurs by a free-radical mechanism and the orientation is anti-Markovnikov (p. 751).137 It must be emphasized that this is true only for HBr. Free-radical addition of HF and HI has never been observed, even in the presence of peroxides, and of HCI only rarely. In the rare cases where free-radical addition of HCI was noted, the orientation was still Markovnikov, presumably because the more stable product was formed.,3B Free-radical addition of HF, HI, and HCI is energetically unfavorable (see the discussions on pp. 683, 693). It has often been found that anti-Markovnikov addition of HBr takes place even when peroxides have not been added. This happens because the substrate alkenes absorb oxygen from the air, forming small amounts of peroxides (4-9). Markovnikov addition can be ensured by rigorous purification of the substrate, but in practice this is not easy to achieve, and it is more common to add inhibitors, e.g., phenols or quinones, which suppress the free-radical pathway. The presence of free-radical precursors such as peroxides does not inhibit the ionic mechanism, but the radical reaction, being a chain process, is much more rapid than the electrophilic reaction. In most cases it is possible to control the mechanism (and hence the orientation) by adding peroxides... 

A concerted electron transfer mechanism, with formation of an alkyl radical and quinone radical anion, has been proposed to account for the products of reaction of benzophenone with alkyllithium or Grignard reagents 92 the ratio of addition to reduction products is dependent on the alkyl group and not on the metal. 

Despite the ionic reactions, other reactions (presented in Scheme 44) show that free-radical mechanisms can also take place. Catalyzed by ebselen, TBHP oxidation of alkylarenes to alkyl aryl ketones (141) [240], anthracene to anthraquinone (142), 1,4-dimethoxyarenes to 1,4-quinones (e.g., menadione 143) [244], and oxidative coupling of 2-aminophenol to phenoxazinone (144) [245] gave results similar to these when one-electron oxidants such as Ce(IV), Ag(II), or Mn(III) were the reagents. Moreover, oxidation of azine derived from 2-acetylpyridine gave a mixture of ketone (145) and condensed triazole (146) [240], The same result was found when cerium ammonium nitrate was used as the reagent. This suggests that the... 

Direct evidence for the formation of radical o-quinone (and sometimes p-qui-none) complexes was established in the studies quoted above. Various synthetic techniques starting from elemental metals, nonmetals, metal salts, and complexes have been developed for obtaining these coordination compounds. The peculiarities of their thin structure and physical-chemical properties were investigated. The obtained products have practical applications, in particular for medical purposes. Quinone-based metal complexes have a potential applicability as cocatalysts in a wide range of reactions involving electron exchange between substrate and catalysts. Further studies in this field and on mechanisms of electron mobility between the metal center and the o-quinone ligands are still necessary to understand the vast and complex redox chemistry of these compounds. 

Radical mechanisms account for the stoichiometry for reduction of triketohydrindane by N(5)-ethyldihydroflavin and reduction of triphenylmethyl carbonium ion species by dihydroflavin, (24). One-electron reduction of quinone by N(5)-ethyldihydroflavin also has been shown. These results are not surprising since the substrates and flavin support reasonably stable radical states. Radical species also can be established as intermediates in the oxidation of 9-hydroxyfluorene and methyl mandelate by Flox (Equations 28 and 29, respectively). The reactions of Equations 28 and 29 are facile when carried out in... 

Aromatically substituted enols are easily autoxidized to the keto-hydroperoxide form (4, 5, 6, 10, 11, 12, 16), which, we postulate, would then initiate a radical polymerization. A radical mechanism is proved by the inhibiting effect of quinone and a,polymer yield is directly proportional to the square root of the initiator concentration (7). 

Hydrides of tin and germanium also reduce quinones, ultimately to the hydroquinones. The detailed mechanism of hydrogen transfer between four stannanes and four quinones has been studied which suggested a radical mechanism in which hydrogen transfer was the first step. ... 

The polycyclic aromatic hydrocarbon carcinogens, which are very ubiquitous, are metabolized by the microsomal mixed-function oxidase system of target tissues to a variety of metabolites such as phenols, quinones, epoxides, dihydrodiols and dihydrodiol-epoxides ( ). The mqjor pathway of activation of benzo(a)pyrene (BP) leads to the formation of dihydrodiol-epoxide of BP which interacts predominantly with the 2-amino of guanine of DNA. The dihydrodiol-epoxide of BP appears to be the major ultimate electrophilic, mutagenic, and carcinogenic metabolite of BP ( ). Nevertheless, other metabolites such as certain phenols, epoxides and quinones may contribute to the overall carcinogenic activity of BP. In addition, a free radical mechanism may also be partly involved in its carcinogenic activity. 

Examples of I), 2), and 3) are given above. Addition to nitrogen was described for azoben-zenc. Addition to carbonyl oxygen may be seen for example in the addition of /-butylmagnesium chloride to benzophenone 65). For tr-diketones and ortho quinones, 0-alkylation may be the main product as de.scribed for benzil 59] and quinones [102,103,104). 5-alkylation has been seen in the addition to thiobenzophenone [105]. Addition to nitrogen is seen with nitrobenzene 1106] and with pyridazinium salts [107]. The products mentioned are produced via a radical mechanism, sometimes in signilicant amounts but often as unimportant by-products. 

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