Nitroarenes reaction with organometallic compound

To our knowledge, reactions of organometallic compounds with nitroarenes lead, as a rule, to mixtures of reduction and alkylation (or arylation) products.2 11 Only few examples have been described where the reactions proceed with the formation of N, /V-disubstituted hydroxylamine and/or secondary amines.4-6-9... 

To our knowledge, reactions of organometallic compounds with nitroarenes lead, as a... 

There are two major variants of ONSH with nucleophiles sensitive to oxidation (a) addition is an irreversible process and (b) equilibrium of the reversible addition is shifted in favor of the adducts. Nucleophilic organometallic compounds, alkyllithium and alkyl-magnesium reagents, are active enough to add irreversibly to nitroarenes in positions occupied by hydrogen to form the adducts [72]. Due to irreversibility of the addition, the SNAr reaction on treatment of ortho- and para-halonitrobenzenes with these C-nucleophiles is not observed. Further oxidation of the formed adducts with a variety of oxidants, preferably KMn04, affords products of oxidative nucleophilic alkylation. This reaction appears to be an important method for direct incorporation of alkyl substituents into aromatic rings (Scheme 14) [72, 73]. 

Yields of products obtained by electrochemical methods are comparable with those reported in the literature for similar alkylations of aromatic compounds in the presence of chemical oxidants. In spite of experimental difficulties, we have succeeded to alkylate dinitrobenzene. The reaction has to be carried out in THF (highly resistant medium) because DMF undergoes decomposition in the presence of butyl lithium. Use of butyl lithium provides higher yields of the target alkylation products, than butylmagnesium chloride. Also equivalent amounts of reactants, nitroarenes and organometallic reagents, have been found to be essential to provide the best yields of the reaction products. 

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See also in sourсe #XX -- [ , ]

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