Nitroso aromatic, radical-anions

These radical anions have been detected by ESR. This mechanism is consistent with the following result when nitrosobenzene and phenylhydroxylamine are coupled, and N labeling show that the two nitrogens and the two oxygens become equivalent. Unsymmetrical azoxy compounds can be prepared by combination of a nitroso compound with an N,N-dibromoamine. Symmetrical and unsymmetrical azo and azoxy compounds are produced when aromatic nitro compounds react with aryliminodimagnesium reagents, ArN(MgBr>2. ... 

Allyl (27, 60, 119-125) and benzyl (26, 27, 60, 121, 125-133) radicals have been studied intensively. Other theoretical studies have concerned pentadienyl (60,124), triphenylmethyl-type radicals (27), odd polyenes and odd a,w-diphenylpolyenes (60), radicals of the benzyl and phenalenyl types (60), cyclohexadienyl and a-hydronaphthyl (134), radical ions of nonalternant hydrocarbons (11, 135), radical anions derived from nitroso- and nitrobenzene, benzonitrile, and four polycyanobenzenes (10), anilino and phenoxyl radicals (130), tetramethyl-p-phenylenediamine radical cation (56), tetracyanoquinodi-methane radical anion (62), perfluoro-2,l,3-benzoselenadiazole radical anion (136), 0-protonated neutral aromatic ketyl radicals (137), benzene cation (138), benzene anion (139-141), paracyclophane radical anion (141), sulfur-containing conjugated radicals (142), nitrogen-containing violenes (143), and p-semi-quinones (17, 144, 145). Some representative results are presented in Figure 12. 

A very interesting spin-trap reaction is the reaction of paramagnetic potassium-pentacyano-cobaltate (II) 25 and aliphatic or aromatic nitroso compounds leading to pentacyano-cobalt-(III)aminyloxide radical anions 26S0 ... 

Finally mixing of aliphatic or aromatic nitroso compounds with benzene sulfinic acid leads immediately to formation of benzene-sulfonylaminyloxides75. Aminyl-oxide anion 62 was detected when nitrosobenzene was allowed to react with aqueous hydrogensulfite in presence of lead dioxide76. With nitroso trifluoromethane radical 63 was formed. With tetraphenylarsonium cation this radical anion even formed a solid, paramagnetic precipitate77. ... 

The different steps of the biotransformations that produce a primary amine from an aromatic nitro compound involve a nitro radical-anion, a nitroso derivative, a nitroxyl radical, a hydroxylamine and then the primary amine (Figure 33.15). 

Nitroarenes, on the other hand, are strong electron acceptors and easily undergo one-electron reduction (12, 13). Thus, nitrobenzene, to cite one example, has been customarily used as an effective quencher in chain reactions involving radical anion intermediates, such as in SRN1 reactions (3). Under different conditions, nitroarene radical anions are reactive species. In particular, Zinin (14) reported that treatment of nitroarenes with hot alkaline alcoholic solutions results in products of reduction, mainly the azoxy derivative (equation 2). These complex multistep processes involve nitroarene radical anion intermediates and are quite effectively inhibited by oxygen (10, 15, 16). In 1964, Russell et al. (17) wrote that apparently much of the chemistry of aromatic nitro, nitroso and azo compounds in basic solution involves electron-transfer processes . 

The anion-radicals from aromatic nitro compounds preserve the second-order axis of symmetry. The analysis of superfine structure of the ESR spectrum of the nitrobenzene anion-radical reveals equivalency of the ortho and meta protons (Ludwig et al. 1964, Levy and Myers 1965). With the anion-radical of nitrosobenzene, the situation is quite different. This was evidenced from the ESR data (Levy and Myers 1965, Geels et al. 1965). Following electron transfer, the bent nitroso group fixes in the plane of the benzene ring to a certain extent. This produces five different types of protons, since both meta and ortho protons become nonequivalent. The nonequivalence of the ortho and meta protons has also been established for the anion-radicals of acetophenone (Dehl and Fraenkel 1963) and 5-methylthiobenzoate (Debacher et al. 1982 Scheme 6.17). 

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