Radical oxidations

In the intermediate complexe of free radical arylation, it is necessary to oxidize the reaction intermediate to avoid dimerization and disporportio-nation (190-193, 346) In this case isomer yield and reactivity will be highest with radical sources producing very oxidative radicals or in solvents playing the role of oxidants in the reaction. The results are summarized in Tables III-29 and III-30. 

Like most other engineering thermoplastics, acetal resins are susceptible to photooxidation by oxidative radical chain reactions. Carbon—hydrogen bonds in the methylene groups are principal sites for initial attack. Photooxidative degradation is typically first manifested as chalking on the surfaces of parts. 

One characteristic of chain reactions is that frequentiy some initiating process is required. In hydrocarbon oxidations radicals must be introduced and to be self-sustained, some source of radicals must be produced in a chain-branching step. Moreover, new radicals must be suppHed at a rate sufficient to replace those lost by chain termination. In hydrocarbon oxidation, this usually involves the hydroperoxide cycle (eqs. 1—5). 

Nitroxides are iV, iV-disubsdnited nitric oxide radicals, the unpaired electron being delocalized between the nitrogen and oxygen The reduction of 2-methyl-2-nitropropane with sodium or electrochemically yields di-r-butyl nitroxide as the final product " Such nitroxide radicals are important for the snidy of a organic ferromagnet... 

This statement does not mean, however, that the mechanism of diazotization was completely elucidated with that breakthrough. More recently it was possible to test the hypothesis that, in the reaction between the nitrosyl ion and an aromatic amine, a radical cation and the nitric oxide radical (NO ) are first formed by a one-electron transfer from the amine to NO+. Stability considerations imply that such a primary step is feasible, because NO is a stable radical and an aromatic amine will form a radical cation relatively easily, especially if electron-donating substituents are present. As discussed briefly in Section 2.6, Morkovnik et al. (1988) found that the radical cations of 4-dimethylamino- and 4-7V-morpholinoaniline form the corresponding diazonium ions with the nitric oxide radical (Scheme 2-39). 

Figure 8. Photoelectron spectrum (PES) and Penning ionization electron spectrum (PIES) of nitric oxide radical. Average vibrational energy spacing of the first band amounts to 285 and 284 cm", respectively (104).

Lu, C. Y. Lui, Y.Y. (2002). Electron transfer oxidation of tryptophan and tyrosine by triplet states and oxidized radicals of flavin sensitizers a laser flash photolysis study. Biochimica et Biophysica Acta (BBA) - General Subjects, Vol. 1571, No.l, (May 2002), pp. 71-76, ISSN 0304-4165... 

Oxidation — Oxidizing radicals with high redox potential can remove one electron from the carotenoid molecule to yield a radical cation CAR - e- CAR+ (e.g. CAR H- R CAR + R). 

TABLE 4. Hyperfine splitting constants (gauss) of thioxanthone S-(mono or di)oxide radical anions as free or tight contact ion-pair ... 

Ru(bipy)3 formed in this reaction is reduced by the sacrificial electron donor sodium ethylenediaminetetra-acetic acid, EDTA. Cat is the colloidal catalyst. With platinum, the quantum yield of hydrogenation was 9.9 x 10 . The yield for C H hydrogenation was much lower. However, it could substantially be improv l by using a Pt colloid which was covered by palladium This example demonstrates that complex colloidal metal catalysts may have specific actions. Bimetalic alloys of high specific area often can prepared by radiolytic reduction of metal ions 3.44) Reactions of oxidizing radicals with colloidal metals have been investigated less thoroughly. OH radicals react with colloidal platinum to form a thin oxide layer which increases the optical absorbance in the UV and protects the colloid from further radical attack. Complexed halide atoms, such as Cl , Br, and I, also react... 

Long SR, Christesen SD. 1989. Laser ionization studies of organophosphonates and phosphorus oxide radicals. Journal of Physical Chemistry 93(18) 6625-6628. 

Halogen oxide radicals such as CIO and BrO are important reactive intermediates in the catalytic cycles of ozone destruction in the middle and upper stratosphere. The first absorption band CIO(/l211 <— X2 I) starts from 318 nm and has a series of vibronic bands that converge to a broad continuum at wavelengths shorter than 264nm (Fig. 8).98-101 In this continuum region four dissociation pathways are thermodynamically possible,33... 

Oxidaton of heme goes through the biliverdin species. Octaethylbiliverdin can exist in coordinated form as the fully reduced trianion (OEB)3-, as the two-electron-oxidized monoanion (OEBox), or as the one-electron-oxidized radical (OEB-)2-. Nickel forms complexes with all three moieties, [Nin(OEB)]ra with n I 1, 0, and -1 (689).1787 The most highly oxidized species [Ni(OEBox)]I3 could be crystallized. The structure shows a helical coordination of the linear tetrapyrrole ligand around nickel with Ni—N distances of 1.867 A and 1.879 A. 

Strong oxidizing radicals (such as peroxyl radicals R02 ) generate CAR + via electron transfer and, because the radical CAR are themselves strong oxidizing agents (see Section 14.4.3.2 and Table 14.12), this species may well be the most important of the CAR radicals formed. 

Reported redox potentials of laccases are lower than those of non-phenolic compounds, and therefore these enzymes cannot oxidize such substances [7]. However, it has been shown that in the presence of small molecules capable to act as electron transfer mediators, laccases are also able to oxidize non-phenolic structures [68, 69]. As part of their metabolism, WRF can produce several metabolites that play this role of laccase mediators. They include compounds such as /V-hvdi oxvacetan i I ide (NHA), /V-(4-cyanophenyl)acetohydroxamic acid (NCPA), 3-hydroxyanthranilate, syringaldehyde, 2,2 -azino-bis(3-ethylben-zothiazoline-6-sulfonic acid) (ABTS), 2,6-dimethoxyphenol (DMP), violuric acid, 1-hydroxybenzotriazole (HBT), 2,2,6,6-tetramethylpipperidin-iV-oxide radical and acetovanillone, and by expanding the range of compounds that can be oxidized, their presence enhances the degradation of pollutants [3]. 

The isolation of calycanthine (9) in 1888 by Eccles [28] and the subsequent proposition for its origins in the oxidative dimerization of tryptamine by Woodward [29] and Robinson [30] had prompted several key synthetic studies based on a biomimetic approach. Hendrickson was the first to experimentally verify the plausibility of forming the C3-C3 linked dimers through an oxidative radical dimerization strategy (Scheme 9.2a). He demonstrated that the sodium enolate of a tryptamine-derived oxindole could be oxidized with iodine to afford a mixture of three possible stereoisomers. The racemic product was isolated in 13 % yield, while the meso product was isolated in 8 % yield. Global reduction of the oxindole and carbamates afforded the first synthetic samples of chimonanthine (7) [9a],... 

Various authors have studied the ageing of triterpenoid resins to understand and possibly slow their deterioration [3, 4, 12, 13, 17 36]. The main degradation pathway is autoxida-tion, an oxidative radical chain reaction [37, 38] after formation of radicals, oxygen from the air is inserted, leading to peroxides. The peroxides can be homolytically cleaved, resulting in new radicals that continue the chain reaction. The cleavage of peroxide bonds can be induced thermally or photochemically. 

An oxidative radical coupling promoted by tetra-ra-butylammonium cerium(IV) nitrate (TB ACN) between P-aminocinnamate 22 and enamine 23 provided pyrrole-3,4-dicarboxylate 24 <06T2235>. Dimerization of the P-aminocinnamates provided symmetrical pyrroles. 

A Sml2-induced reductive cyclization of (V-(alkylketo)pyrroles provided an entry into medium ring 1,2-annelated pyrroles <06EJO4989>. An oxidative radical alkylation of pyrroles with xanthates promoted by triethylborane provided access to a-(pyrrol-2-yl)carboxylic acid derivatives <06TL2517>. An oxidative coupling of pyrroles promoted by a hypervalent iodine(III) reagent provided bipyrroles directly <060L2007>. 

L. Campanella, L. Persi, and M. Tomassetti, A new tool for superoxide and nitric oxide radicals determination using suitable enzymatic sensors. Sens. Actuators B. 68, 351-359 (2000). 

Polasek M, Skala P, Opletal L and Jahodar, L. 2004. Rapid automated assay of anti-oxidation/radical-scavenging activity of natural substances by sequential injection technique (SIA) using spectrophotomet-ric detection. Anal Bioanal Chem 379(5—6) 754—758. 

Oxidative radical cyclization of fi-keto esters. Radical cyclizations of unsaturated 0-keto esters initiated by Mn(III) acetate (1) can be terminated by oxidative 0-hydride elimination by Cu(OAc)2 (equation I). This radical reaction can... 

The photoreactivity of the involved catalyst depends on many experimental factors such as the intensity of the absorbed light, electron-hole pair formation and recombination rates, charge transfer rate to chemical species, diffusion rate, adsorption and desorption rates of reagents and products, pH of the solution, photocatalyst and reactant concentrations, and partial pressure of oxygen [19,302,307], Most of these factors are strongly affected by the nature and structure of the catalyst, which is dependent on the preparation method. The presence of the impurities may also affect the photoreactivity. The presence of chloride was found to reduce the rate of oxidation by scavenging of oxidizing radicals [151,308] ... 

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