Conclusions
-
1.
The transmetallation method has been used to measure equilibrium acidities of P(O)H-and P(S)H-acids of various structures in dimethylsulfoxide solution and relative to 9-phenyl-fluorene.
-
2.
The effect of the substituent at the P atom on the pK value for the P(O)H-acid can be described by linear correlation relations in the σφ and σ* constants. The diarylphosphinous acids cannot be fitted into such correlations because of p,π coupling in their anions.
-
3.
The acidity of the P(S)H-acids is some nine orders higher than that of the phosphoryl analogs.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Literature cited
P. R. Hammond, J. Chem. Soc., 1365 (1962).
K. Moedritzer, J. Inorg. and Nucl. Chem.,22, 19 (1961).
M. Grayson, C. E. Farley, and C. A. Streuli, Tetrahedron,23, 1065 (1967).
É. S. Petrov, E. N. Tsvetkov, S. P. Mesyats, A. I. Shatenshtein, and M. I. Kabachnik, Izv. Akad. Nauk SSSR, Ser. Khim.,1976, 782.
M. I. Terekhova, É. S. Petrov, S. P. Mesyats, and A. I. Shatenshtein, Zh. Obshch. Khim.,45, 1529 (1975).
M. I. Kabachnik, in: Chemistry and Applications of Organophosphorus Compounds (Proceedings of the First Conference) [in Russian], Izd. Akad. Nauk SSSR (1957), p. 18; M. I. Kabachnik and T. A. Mastryukova, Izv. Akad. Nauk SSSR, Otd. Khim. Nauk,1953, 163; M. I. Kabachnik and E. N. Tsvetkov, ibid.,1963, 1227; G. O. Doak and L. D. Freedman, Chem. Rev.,61, 31 (1961).
T. A. Mastryukova and M. I. Kabachnik, Usp. Khim.,38, 1751 (1969).
A. Albert and E. P. Serjeant, Ionization Constants of Acids and Bases, Methuen (1962).
M. Herlem and A. Tiebault, Bull. Soc. Chim. France,1971, 719; T. I. Lebedeva, É. S. Petrov, and A. I. Shatenshtein, Zh. Org. Khim.,13, 905 (1977); T. I. Lebedeva, V. A. Kolesova, L. L. Gerasimovich, G. A. Kefchiyan, É. S. Petrov, Yu. A. Strepikheev, and A. I. Shatenshtein, ibid.,13, 1137 (1977).
M. I. Kabachnik, T. A. Mastryukova, and T. A. Melent'eva, Zh. Obshch. Khim.,32, 267 (1962).
S. L. Manatt, G. L. Juvinall, R. I. Wagner, and D. D. Elleman, J. Am. Chem. Soc.,88, 2689 (1966).
E. Fluck and H. Binder, Z. Naturforsch.,22, 805 (1967).
O. A. Raevskii, A. N. Vereshchagin, Yu. A. Donskaya, F. G. Khalitov, I. G. Malakhova, and E. N. Tsvetkov, Izv. Akad. Nauk SSSR, Ser. Khim.,1974, 453.
M. V. Proskurnina, A. L. Chekhun, and I. F. Lutsenko, Phosphorus,4, 57 (1974).
E. N. Tsvetkov and M. I. Kabachnik, Reakts. Metody Issled. Org. Soedin.,13, 27 (1964).
R. A. Malevannaya, E. N. Tsvetkov, and M. I. Kabachnik, Izv. Akad. Nauk SSSR, Ser. Khim.,1976, 952.
Author information
Authors and Affiliations
Additional information
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1981–1984, September, 1978.
Rights and permissions
About this article
Cite this article
Tsvetkov, E.N., Terekhova, M.I., Petrov, É.S. et al. Equilibrium acidity of certain phosphoryl and thiophosphoryl PH-acids in dimethyl sulfoxide. Russ Chem Bull 27, 1743–1746 (1978). https://doi.org/10.1007/BF00929215
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF00929215