Conclusions
-
1.
The equilibrium CH-acidity (pK) of benzylphosphine oxides, as well as esters and tetraalkyl-amides of benzylphosphonic acid in diglyme (DG) and DMSO was determined by the method of transmetallation.
-
2.
The acidity in DMSO is 4–6 units of pK lower than in DG, which can be explained by supplementary stabilization in DG of the carbanions of phosphine oxides and their analogs on account of coordination of the cation with the phosphoryl group.
-
3.
A linear relationship is observed between the values of pK of phosphine oxides and amides of benzylphosphonic acid in DG and DMSO, which is not observed for compounds with alkoxyl groups at the phosphorus atom.
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4.
The linear correlations of the values of pK in the two solvents with the constants of substituents at the phosphorus atomsσ p of benzylphosphine oxides have close values of the slopes. Amides and esters of benzylphosphonic acid do not obey this dependence.
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5.
There is a linear relationship between the values of pK of derivatives of diphenylbenzylphosphine oxide with substituents in the paraposition of the benzyl group and the substituent constantsσ −.
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2497–2503, November, 1974.
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Mesyats, S.P., Tsvetkov, E.N., Petrov, É.S. et al. Equilibrium CH-acidity of organophosphorus compounds. Russ Chem Bull 23, 2406–2412 (1974). https://doi.org/10.1007/BF00922119
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DOI: https://doi.org/10.1007/BF00922119