Synthesis and photolysis of some 1-naphthyl azoxy-compounds

The photochemistry of the N-oxide function

“…A typical example is offered by pyridine IV-oxide itself. Although several studies had led to the isolation of only minute amounts of characterizable products,5 from which it was obviously difficult to reach mechanistic conclusions, it was recently shown that in basic aqueous solution the photolysis of 46 yields quantitatively the anion 47.68,69 Analogously, in the presence of secondary amines, added either before or after the photolysis of the solution, the conjugated nitriles 48 are obtained.70 Previously, it had been shown that the irradiation of pyridine IV-oxide in the presence of ^.A^-dimethyltryptamine affords analogously the nitrile 49 On the basis of these results, Buchardt suggested that, in the absence of bases, unsaturated nitriles such as 50 and 51 are formed and that the low yield of characterizable products obtained are due to the easy polymerization of these compounds.68 Indeed, in the absence of bases intractable tars containing nitrile groups (as shown by IR absorption) are obtained predominantly. It is likely that the same main photochemical process is obtained also from several pyridine IV-oxide derivatives, such as the alkyl derivatives, from which low yields of tractable products and high yield of tars also were obtained.…”

The Formation of the Azoxy-group in the Oxidation of Compounds with Nitrogen–Nitrogen Bonds

“…The oxidation of the Ν = Ν bond by peracids is widely used in practice, particularly for the synthesis of azoxyarenes (see the relevant reviews 61 178 ). Azoxidation has been used much less among aliphatic compounds.…”

Diazonium cations as intermediates in the microbial transformation of chloroanilines to chlorinated biphenyls, azo compounds, and triazenes

“…Considerable evidence has been presented on the formation of various azo compounds in soils after amendment with either aniline-based herbicides or the anilines themselves (Bartha and Pramer, 1967;Chisaka and Kearney, 1970;Sprott and Corke, 1971). The formation of azo compounds has been demonstrated to occur through the oxidation of the aniline by a peroxidase enzyme Bordeleau et al, 1972).…”

“…This aspect is under study because of its implication as a possible new route for the metabolic degradation of substituted biphenyls, (vi) Biphenyls, azobenzenes, and bis-substituted triazenes were not found in extracts of chemical controls (no bacteria present). The pH of the medium does not favor the chemical formation of the diazonium cation, and in addition it is known that azo compounds are formed from diazonium salts only in a strongly reducing medium (Bunce et al, 1976).…”