On the reactivity of organophosphorus compounds: Part IV. The alkaline hydrolysis of some O‐phosphylated 2‐pyridine oximes
- 1 January 1968
- journal article
- research article
- Published by Wiley in Recueil des Travaux Chimiques des Pays-Bas
- Vol. 87 (6) , 673-686
- https://doi.org/10.1002/recl.19680870607
Abstract
The rates of alkaline hydrolysis of a number of O‐phosphylated 2‐pyridine oximes, C5H4NC(R1)NOP(O)R2R3, at different temperatures have been determined. The second‐order rate constants and the values of ΔH* and ΔS* are reported. Two parallel pathways of hydrolysis are observed: a nucleophilic substitution reaction on phosphorus (SN2P) generating the oxime and the parent acid and an elimination reaction of the Beckmann type (E2 or ElcB) producing the nitrile and the parent acid. The effects of the groups R1, R2 and R3 on the rates of substitution and elimination are discussed.Keywords
This publication has 16 references indexed in Scilit:
- 682. Stability of N-heterocyclic oxime derivatives. Part I. Decomposition of N-methylpyridinium 3-and 4-O-acetyladoxime iodides in aqueous solutionJournal of the Chemical Society, 1965
- 683. Stability of N-heterocyclic oxime derivatives. Part II. Decomposition of N-methylacetylpyridinium O-acetylketoxime iodides in aqueous solutionJournal of the Chemical Society, 1965
- Mechanisms of Nucleophilic Substitution in Phosphate EstersChemical Reviews, 1964
- The Preparation of Diethyl PhosphateBulletin of the Chemical Society of Japan, 1961
- The Dehydration Reactions by Means of Esters of Phosphoric AcidBulletin of the Chemical Society of Japan, 1961
- 371. The mechanism of hydrolysis of phosphonochloridates and related compounds. Part I. The effect of substituentsJournal of the Chemical Society, 1960
- Oximes of the Pyridine Series1Journal of the American Chemical Society, 1957
- INFRARED STUDY OF THE N—OH GROUP IN ALPHA AND BETA OXIMESCanadian Journal of Chemistry, 1954
- 101. Kinetic studies in the phosphinyl chloride and phosphorochloridate series. Part I. Solvolytic reactionsJournal of the Chemical Society, 1953
- The Anhydrides of Dimethyl- and Diethylphosphinic AcidsJournal of the American Chemical Society, 1951