Non-anomalous nucleophilic reactivity of carbanions towards the nitroso group
- 1 January 1993
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Perkin Transactions 2
- No. 6,p. 1233-1240
- https://doi.org/10.1039/p29930001233
Abstract
The reactivities of a series of carbanions (several enolate and nitronate 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 with their basicity over 8 pKa, units. Nitronate ions are only slightly less reactive (less than a factor of 10) than enolates of similar basicity. In general, the reactivities of the carbanions are similar to those of secondary amines of similar basicity, which contrasts with their anomalous behaviour in other chemical reactions (especially protonation processes). The causes of this non-anomalous behaviour are discussed.Keywords
This publication has 49 references indexed in Scilit:
- Evidence for the enol form of malonamideJournal of the Chemical Society, Chemical Communications, 1992
- Enol and enolate (carbanion) intermediates in nitrosation. Reactions of ethyl cyanoacetate, diethyl malonate and malononitrileJournal of the Chemical Society, Perkin Transactions 2, 1992
- Enol tautomers of malonic and methylmalonic acids as intermediates in nitrosationJournal of the Chemical Society, Chemical Communications, 1991
- Nitrosation of Meldrum's acid (2,2-dimethyl-1,3-dioxane-4,6-dione) and ethyl acetoacetateJournal of the Chemical Society, Perkin Transactions 2, 1991
- Carbanion nitrosation. Reaction of malononitrile with nitrous acidJournal of the Chemical Society, Perkin Transactions 2, 1989
- Kinetics and mechanism of the nitrosation of 2-nitropropane, 1-nitropropane, and nitroethaneJournal of the Chemical Society, Perkin Transactions 2, 1988
- Nitrosation of ketones: clear evidence for the involvement of the enol tautomersJournal of the Chemical Society, Perkin Transactions 2, 1988
- Involvement of the enol tautomers in the nitrosation of ketonesJournal of the Chemical Society, Chemical Communications, 1987
- Equilibrium and kinetic acidities of nitroalkanes and their relation to transition state structuresJournal of the American Chemical Society, 1970
- Broensted coefficients larger than 1 and less than 0 for proton removal from carbon acidsJournal of the American Chemical Society, 1969