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Nitroxyl radicals chemistry

A new interesting branch of the modern antioxidant chemistry deals with the cyclic mechanisms involving acid catalysis. The first inhibiting system of this type was discovered in 1988 [44]. It consisted of an alcohol (primary or secondary), a stable nitroxyl radical TEMPO, and... [Pg.583]

The last decades have witnessed the emergence of new living Vcontrolled polymerizations based on radical chemistry [81, 82]. Two main approaches have been investigated the first involves mediation of the free radical process by stable nitroxyl radicals, such as TEMPO while the second relies upon a Kharash-type reaction mediated by metal complexes such as copper(I) bromide ligated with 2,2 -bipyridine. In the latter case, the polymerization is initiated by alkyl halides or arenesulfonyl halides. Nitroxide-based initiators are efficient for styrene and styrene derivatives, while the metal-mediated polymerization system, the so called ATRP (Atom Transfer Radical Polymerization) seems the most robust since it can be successfully applied to the living Vcontrolled polymerization of styrenes, acrylates, methacrylates, acrylonitrile, and isobutene. Significantly, both TEMPO and metal-mediated polymerization systems allow molec-... [Pg.32]

This chapter is a comprehensive overview of the progress in the field of generation, chemistry, and application of nitroxyl radicals and their precursors, for example, hindered amines of the 2,2,6,6-tetramethy1-piperidine series. Because of the importance of nitroxyl radicals to polymer stabilization, this application is discussed at length, while the others are touched upon briefly. [Pg.11]

There is no need to give a thorough description of the chemistry of hindered nitroxyl radicals as it has been fully discussed in a number of summaries including the papers written by the authors of the present communication (18,19,29-37). This paper is aimed at giving some general characteristics of the chemical properties of nitroxyl radicals and the methods for their synthesis. [Pg.18]

There has been a revolution in free radical polymerization chemistry that began in the 1980s with the seminal patent of Solomon et al. (1986). These scientists found that it was possible to obtain controlled radical polymerization of monomers such a styrene and alkyl (meth) acrylates by effecting free radical polymerization in the presence of stable nitroxyl radicals as shown below. It has been found that these controlled polymerizations carried out... [Pg.40]

Neftel, A., H. Oeschger, J. Schwander, B. Stauffer and R. Zumbrunn (1982) Ice core measurements give atmospheric CO2 content during the past 40000 yr. Nature 295, 220-223 Neftel, A., E. Moor, H. Oeschger and B. Stauffer (1985) Evidence from pwlar ice cores for the increase in atmospheric CO2 in the past two centuries. Nature 315, 45—47 Nelli, S, M. HUlen, K. Buyukafsar and W. Martin (2000) Oxidation of nitroxyl anion to nitric oxide by copper ions. British Journal of Pharmacology 131, 356-362 Neta, P. and R. E. Huie (1985) Free-radical chemistry of sulfite. Environmental Elealth Perspectives 64, 209-217... [Pg.662]

The authors argue that flavin nitroxyl radical may play a role in flavo-enzyme chemistry and suggest that the nitroxyl radical intermediate may be derived from enzyme-bound flavin 4a-hydroperoxide. [Pg.413]

Rychnovsky has reported an alternative method for the oxidation of secondary alcohols, using chiral nitroxyl radical 42 (Figure 19.14) in the presence of bleach [128]. By analogy to TEMPO oxidations [129], this chemistry is hkely to proceed via an oxoammonium ion as the active oxidant. The best substrates were found to be simple benzylic alcohols, giving S factors (= kj/kr) in the range 3.9-7.1 (Scheme 19.21). Chiral azabicyclo-N-oxyl 43 has also been used for the enantioselective electrooxidation of sec-alcohols, giving S factors of up to 21 [130]. [Pg.541]

This and some other non-radical reactions of radicals were theoretically predicted by Neiman back in the fifties. But, to obtain the starting stable radicals (5,6), it was necessary above all to obtain various sterically hindered amines. Consequently, the development of stable nitroxyl chemistry inspired great interest in hindered amines. [Pg.13]

Hindered nitroxyls have found their widest application in the spin-label method widely used in biophysical research. As has already been mentioned, this method was devised in the course of nitroxyl chemistry development when the reactions of the radicals of this class, not involving a nitroxyl group, were discovered. Several monographs and many review papers with a total number of more than one thousand pages are devoted to the spin-label method (35-39, 49, 50). These communications cover all the aspects of hindered nitroxyl application in this method. Therefore, the spin-label method is not discussed here at length. [Pg.22]


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See also in sourсe #XX -- [ Pg.18 , Pg.20 ]




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