Hydroxylamines reactions with organometallic compounds

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... 

Related amination reactions of organometallic compounds RM have been performed with )V,)V dimethyl-0-(mesityl-sulfonyl)hydroxylamine (20), )V,)V-dimethyl-0-(phenylsul-fonyl)hydroxylamine (21), and )V,)V-dimethyl-O-(j0-tolylsul-fonyl)hydroxylamine (22). Stmctures (23)-(26) provide exanples of A(jV-dimethylamines formed by reactions of RM with the mesitylsulfonyl species (20). ... 

Miscellaneous reactions of thiocyanogen have been reported, but their study has been too limited for a proper evaluation of their usefulness. Thiocyanogen has been shown to react with a variety of organometallic compounds and to replace the hydrogen on sulfur in mercaptans and thiophenols and the hydrogen on nitrogen of aliphatic amines and di-substituted hydroxylamines. These reactions doubtless are capable of further development. 

Addition of organometallic reagents to nitro compounds is possible but is sparingly used. Reaction of aromatic nitro compounds with large excess of phenyl magnesium bromide produces hydroxylamines in moderate yield . Similar addition of Grignard compounds to nitromethane proceeds in low yield ° while addition of excess methyllithium to tertiary nitro compound 113 results in formation of hydroxylamine 114 (equation 83) . ... 

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