Nitrosobenzene oxidant

Nitrosobenzene may be obtained by the oxidation of P pheiiylhydroxylamine with acid dichromate solution at 0° ... 

Oxidation. Aromatic amines can undergo a variety of oxidation reactions, depending on the oxidizing agent and the reaction conditions. For example, oxidation of aniline can lead to formation of phenyUiydroxylamine, nitrosobenzene, nitrobenzene, azobenzene, azoxybenzene or -benzoquinone. Oxidation was of great importance in the early stages of the development of aniline and the manufacture of synthetic dyes, such as aniline black and Perkin s mauve. 

Phenazine mono-N-oxides have also been prepared from nitrobenzene derivatives. Condensation of nitrobenzene with aniline using dry NaOH at 120-130 °C results in modest yields of phenazine 5-oxide, although the precise mechanism of this reaction is not well understood (57HC(ll)l) with unsymmetrical substrates it is not possible to predict which of the isomeric fV-oxides will be produced. Nitrosobenzene derivatives also function as a source of phenazine mono-fV-oxides thus, if 4-chloronitrosobenzene is treated with sulfuric acid in acetic acid at 20 °C the fV-oxide is formed (Scheme 21). 

Isoxazolin-5-imines were produced by nitrile oxide addition to cyanoacetates (62HC(17)l,p.7), by the reaction of nitrones with phenylacetonitrile (74CB13), and by base addition of nitrosobenzene to nitriles (Scheme 148) (72LA(762)154). 

Azetidine N-oxides produce isoxazolidines by a thermal ring expansion (77AHC(21)207, 75GEP2365391), and nitrosobenzenes react with alkenes to provide isoxazolidines (77AHC(21)207, 79IZV1059). 

Cleavage of the heterocycle is observed when oxepin reacts with l-chloro-4-nitrosobenzene to give 4-chloro-AL(6-oxohexa-2,4-dienylidene)aniline iV-oxide (6) in 62% yield.215... 

Rate law and activation energy. The oxidation of nitrosobenzene by terf-butyl hydroperoxide is catalyzed by di-terf-butyl peroxyoxalate (TBO) and by a cobalt(II) chelate complex. 

This type of method has been used to prepare l,2,4-thiadiazolo[2,3- ]pyridine derivatives. The oxidative hetero-cyclization is exemplified by the formation of compound 86 from thioacetamide 85 using nitrosobenzene (Equation 24) <2004S2975>. 

The reaction in Eq. (15) is under the control of C-6-PDH, that in Eq. (16) is catalyzed by MHbR, while that in reaction (17) is non-enzymatic. It is remarkable that nitrosobenzene is reduced enzymatically to phenylhydroxylamine which oxidizes Hb to MHb and is, by this, reoxidized to nitrosobenzene (L5) the latter substance acts catalyti-cally and not stoichiometrically when forming MHb from Hb by the fact of its regeneration during reaction (17). 

The oxidation of aniline by Caro s acid to nitrosobenzene, which proceeds in a quite different way, may be recalled here (p. 179). 

Addition of carbanions (which may be electrochemically generated), derived from active methylene compounds (such as fluorene or indene193), to nitrosobenzene produces the intermediate181 70, which is dehydrated to the azomethine 71 or may be oxidized to the nitrone derivative 72, as illustrated by Scheme 8. 

As can be seen from the preceding discussion, the existence of nitroso compounds as intermediates in the electrochemical reduction of nitro compounds is mostly inferential nitroso compounds are easier to reduce than nitro compounds. Hence, they should be reduced as quickly as they are formed and would not be expected to be isolable. However, nitroso compounds have occasionally been isolated in unusual structural cases54 and the nitrosobenzene radical anion has been identified by ESR spectroscopy in at least one instance64. It is possible to prepare nitroso compounds by a two-step sequence one reduces the nitro compound electrochemically to the hydroxylamine, then electrochemi-cally oxidizes the hydroxylamine to the nitroso compound65. 

Formation of phenylhydronitroxide radicals, DMPO (5,5-dimethyl-l-pyrroline-7V-oxide)/glutathiyl and DMPO/hemoglobin thiyl free radical adducts has been detected in erythrocytes of rats in vivo after administration of nitrosobenzene and phenylhydroxylamine, respectively92,94. The data, however, could also be interpreted in a different way ... 

Atomic charges, effective charges at reacting centres, and HOMO and LUMO energies have been calculated for nitrobenzene, nitrosobenzene, A-phenylhydrazine, diphenyldiazine, A,A -diphenyldiazine-A-oxide, and A,A -diphenyUiydrazine, compared with kinetic data for the hydrogenation of these compounds, and used to propose a mechanism for the hydrogenation of nitrobenzene. 

The pH-rate profile for reaction of nitrosobenzene with A-methylhydroxylamine (to form only 1-methyl 2-phenyldiazene-2-oxide) has been found to exhibit a negative break between pH 0.5 and 3.0. This has been ascribed to a change in ratedetermining step from nucleophilic attack on nitrosobenzene at low pH to dehydration of the A,iV -dihydroxy intermediate at higher pH the dehydration is subject to general-acid catalysis a = 0.34) and specific and general-base catalysis (f) = 0.20). The pH-rate profile is similar to that for reaction of A-methylhydroxylamine with... 

Reduction by Fe(ll) results in an increase in the amount of iron oxides, which favor further reaction. Such autocatalytic behavior characterizes the oxidation of Fe(II) by and explains C Cl NO reduction by Fe(ll) in the absence of an iron mineral phase. Generalizing this behavior, it can be assumed that Fe(III) colloids derived from Fe(ll) oxidation in subsurface anoxic systems, together with other colloids, affect the environmental persistence of nitroaromatic contaminants. Colon et al. (2006), for example, elucidate factors controlling the transformation of nitrosobenzenes and N-hydroxylanilines, which are the two intermediate... 

The catalytic preparation of esters and amides under mild and waste free reaction conditions using readily available starting materials is a desirable goal. The first redox process of this type using heterocyclic carbenes was reported by Castells and co-workers in 1977 in which aldehydes were oxidized to esters in one-pot in the presence of nitrobenzene [104], Furfural 169 is converted into methyl 2-furoate 170 in 79% yield Eq. 15. Nitrobenzene is the presumed stoichiometric oxidant for the oxidation of the nucleophilic alkene XXX to the acyl azolium XXXI by successive electron transfer events. The authors observe nitrosobenzene as a stoichiometric byproduct. This type of reactivity is also observed when cyanide is used as the catalyst. Miyashita has expanded the scope of this transformation using imida-zolylidene carbenes [105-107]. 

Although electrochemical oxidation of Al-cyclohexyl-Al-hydroxylamine in the presence of pyridine afforded the corresponding dimeric nitroso compound with a low yield, A-hydroxy t-alkylamines were transformed into the corresponding nitroso compounds (equation 8) . Similarly, A-phenylhydroxylamine was transformed into nitrosobenzene under similar reaction conditions. ... 

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