NON-ANOMALOUS NUCLEOPHILIC REACTIVITY OF CARBANIONS TOWARDS THE NITROSO GROUP

The reactivities of a series of carbanions (several enolate and nitron ate ions and the diethyl malonate anion) with the nitroso groups of N- methyl-N-nitrosotoluene-p-sulfonamide and a variety of alkyl nitrites have been studied. The reactivity of the carbanions correlates well wi th their basicity over 8 pK(a) units. Nitronate ions are only slightly less reactive (less than a factor of 1 0) than enolates of similar ba sicity. In general, the reactivities of the carbanions are similar to those of secondary amines of similar basicity, which contrasts with th eir anomalous behaviour in other chemical reactions (especially proton ation processes). The causes of this non-anomalous behaviour are discu ssed.