Cooperation of aryliminodimagnesium molecules: deoxygenation of azoxyarenes by mono- and bifunctional reagents in comparison with that by phosphorus(III) reagents

Reaction of aryliminodimagnesium [ArN(MgBr)2, IDMg] with nitrobenzene (Ar1NO2) in tetrahydrofuran (THF) gives unsymmetrical (unsym) azoxybenzene, which is deoxygenated to give unsym-azobenzene. The reaction is utilized for the independent preparation of ONN and NNO isomers of unsym-azoxy compounds. The effects of the relative value of the difference between oxidation and reduction potentials of para-substituted reactants, special effects of ortho-substituents of the substrate and also effects of structure and concentration of mono- and bis-IDMg reagents were studied previously, and ‘cooperation of their aggregate excess needed for product formation’ was proposed. This unfamiliar concept for reactions of magnesium reagents was studied further. Supporting evidence was obtained from the retarding effect of trimethylene chains of nitro [3.3] metacyclophanes and the derived azoxy [3.3] metacyclophanes and also from the effect of the length of bis-IDMg's central α,ω-polymethylenedioxy chain appropriate for azoxy deoxygenation. By comparison with deoxygenation by X3P reagents (X = EtO, Me2N), the general needs of cooperation of excess magnesium reagents were confirmed and its role in their reactions is discussed.

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