Conclusions
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1.
For a study of the electronic effects of phosphorus-containing substituants, the rate constants of protophilic isotopic exchange of deuterium in the ortho-, meta-, and para-positions of deuterated phenyl rings of triphenylphosphine, triphenylamine, triphenylphosphine oxide, as well as in the metal- and para-positions of dimethylphenylphosphine, were determined.
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2.
The rate constants of protophilic isotopic exchange in deuteromethyl groups of diphenyl-m- and diphenyl-p-tolylphosphines, their oxides, and methyldiphenylphosphine were determined.
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3.
On the basis of the data obtained, it was concluded that trivalent phosphorus has an electron-acceptor character; it is similar to pentavalent phosphorus, and it differs qualitatively from trivalent nitrogen, which is apparently due to the presence of pπ-dπ interaction and the absence of a negligible effect of pπ-conjugation.
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Literature cited
E. N. Tsvetkov, D. I. Lobanov, and M. I. Kabachnik, Teor. i Éksperim. Khimiya,1, 729 (1965).
E. N. Tsvetkov, D. I. Lobanov, and M. I. Kabachnik, Teor. i Éksperim. Khimiya,2, 457 (1966).
E. N. Tsvetkov, D. A. Bochvar, and M. I. Kabachnik, Teor. i Éksperim. Khimiya,3, 3 (1967).
E. N. Tsvetkov, M. M. Makhamatkhanov, and M. I. Kabachnik, Teor. i Éksperim. Khimiya,3, 824 (1967).
G. P. Schiemenz, Angew. Chemie. Internat. Edit.,5, 129, 595, 731 (1966).
R. A. Baldwin, M T. Cheng, and G. D. Homer, J. Organ. Chem.,32, 2176 (1967).
J. J. Monagle, J. V. Mengenhauser, and D. A. Jones, Jr., J. Organ. Chem.,32, 2477 (1967).
V. I. Stepanov, A. I. Bokanov, and B. A. Korolev, ZhOKh,37, 2139 (1967).
M. I. Kabachnik, E. N. Tsvetkov, and Chang Chung Yu, Tetrahedron Letters, 5 (1962); M. I. Kabachnik, E. N. Tsvetkov, and Chang Chung-Yu, ZhOKh,32, 3340 (1962); D. J. Peterson, J. Organ. Chem.,31, 950 (1966).
H. Gilman and G. E. Brown, J. Amer. Chem. Soc.,67, 824 (1945).
E. A. Yakovleva, E. N. Tsvetkov, D. J. Lobanov, M. I. Kabachnik, and A. I. Shatenshtein, Tetrahedron Letters, 4161 (1966); E. A. Yakovleva, E. N. Tsvetkov, D. I. Lobanov, M. I. Kabachnik, and A. I. Shatenshtein, DAN SSSR,170, 1103 (1966).
D. I. Lobanov, E. N. Tsvetkov, E. V. Saltanova, E. A. Yakovleva, A. I. Shatenshtein, and M. I. Kabachnik, Izv. AN SSSR, Ser. Khim., 2050 (1968).
A. I. Shatenshtein, Isotopic Exchange and Replacement of Hydrogen in Organic Compounds [in Russian], Izd-vo AN SSSR (1960).
A. I. Shatenshtein, Tetrahedron,18, 95 (1962).
A. I. Shatenshtein and Yu. I. Ranneva, ZhOKh,31, 1423 (1961); A. I. Shatenshtein, Yu. I. Ranneva, and T. T. Kovalenko, Ibid.,32, 967 (1962).
J. J. Daly, J. Amer. Chem. Soc., 3799 (1964).
Y. Sasaki, K. Kimura, and M. Kubo, J. Chem. Phys.,31, 477 (1959).
S. E. Cremer and R. J. Chorvat, Tetrahedron Letters, 419 (1966).
D. P. Craig and K. A. R. Mitchell, J. Chem. Soc., 4682 (1965).
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2012–2019, September, 1968.
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Yakovleva, E.A., Tsvetkov, E.N., Lobanov, D.I. et al. Protophilic deutero-exchange of certain tertiary arylphosphines and their oxides. Russ Chem Bull 17, 1917–1922 (1968). https://doi.org/10.1007/BF00904983
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DOI: https://doi.org/10.1007/BF00904983