Conclusions
-
1.
The equilibrium CH acidity of esters of phosphinylacetic acids was determined relative to 9-phenylfluorene in diglyme and in DMSO by the method of transmetallation.
-
2.
The values of pK of ethylphosphinyl acetates in diglyme (Li+ cation) are 6–8 units of pK lower than in DMSO (K+ cation). This is explained by the chelate coordination of the metal cation with the phosphoryl and carbethoxyl groups of the carbanion in the contact ion pair, formed in diglyme.
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3.
A correlation of the values of pK of ethylphosphinyl acetates in both solvents with the σP constants of alkyl and aryl substituents at the phosphorus atom was established.
-
4.
There is no single correlation between the values of pK of ethylphosphinyl acetates in diglyme and the ionization constants of phosphinylacetic acids in water.
-
5.
The diethoxyphosphinyl group is inferior to its analog — the carbethoxyl group, with a value of the acidifying effect in dimethyl sulfoxide approximately 2.5 units of pK lower.
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For the preceding communications of this series, see [1, 2].
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 534–540, March, 1976.
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Petrov, É.S., Tsvetkov, E.N., Terekhova, M.I. et al. Equilibrium CH acidity of organophosphorus compounds. Russ Chem Bull 25, 517–522 (1976). https://doi.org/10.1007/BF01106644
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DOI: https://doi.org/10.1007/BF01106644