L I T E 1 1 A T U 1 1 E C I T E D
1.
2.
3.
A . N . Vereshchagin, S. G. Vul'fson, A . I. Donskova, and V. I. Savtn, Dokl. Akad. Nauk SSSB, 215,
339 (1974).
S.G. Vul'fson, A . I. Donskova, A. N. Vereshchagin, and V. I. Savin, Izv. Akad. Nauk SSS11, Ser.
Khim., 76 (1975).
B . A . Arbuzov, A. I. Donskova, S. G. Vul'fson, and A . N. Vereshchagin, Izv. Akad. Nauk SSS11,
Set. Khim., 1498 (1975).
4.
5.
6.
7.
8.
A . H . Cowley and T. O. Furth, J. Am. Chem. Soc., 91, 39 (1969).
L. S. Bartell, 11. L. Carrol, and J. P. Gullory, Tetrahedron Lett., 705 (1964).
L. S. Bartell and J. P. GuUory, J. Chem. Phys., 43, 647 (1965).
J . P . Pi e rre and P. Arnoud, Bull. Soc. Chtm. France, 1690 (1966).
M . J . Aronsy, K. E. Calderbank, and H. J. Stootman, J. Chem. Soc. P e r k i n Trans., 2 (1973), 1365.
A. de MeiJere and W . Iuttke, Tetrahedron Lett., 2047 (1969).
9.
10.
11.
12.
13.
14.
15.
16.
L. S. BarteIl, J. P. Gullory, and A. T. Parks, J. Phys. Chem., 69, 3043 (1965).
M . T . Rogers and J. D. Roberts, J. Am. Chem. Soc., 68, 843 (1946).
W . H . Flygare, A. Narath, and W. D. Gwinn, J. Chem. Phys., 36, 200 (1962).
A . N . Vereshchagin and S. G. Vul'fson, T e o r . Eksp. Khim., 4, 548 (1968).
C. -Y. Chen and 1t. J. W. LeFewre, J. Chem. Soc., B, 40 (1966).
O. E x n s r and V. Jehli~ka, Collect. Czech. Chem. Commun., 30, 639 (1965).
L . A . Yanovskaya, V. A . Dombrovskii, G. V. Kryshtal', L. G. Vorontsova, M . O. Dekarptlevtch, and
I. P. Yakovlev, Application of Conformationsl Analysis to the Synthesis of New Organic Compounds [in
Russian], Izd. Odessk. Univ. (1975), p. 167.
17.
18.
M . J . Aroney, M. G. Corfleld, and 1t. J . W . LeFevre, J. Chem. Soc., 1964, 648.
P . H . Gore, P. A . Hopkins, 1t. J. W . LeFevre, L. Random, and G. L. 111tchie, J. Chem. Soc., B,
120 (1971).
19.
I.G. Tishchenko, O. G. Kultnkovtch, and Yu. V. Glazkov, Zh. OrE. Khim., 11, 581 (1975).
C O N F O R M A T I O N S O F C E R T A I N
D I A L K Y L A 1 1 Y L P H O S P H I N E S
A N D T H E I R O X I D E S
O. A . 1 1 a e v s k i i , A . N. V e r e s h c h a g i n ,
Y u . A . D o n s k a y a , I. G. M a l a k h o v a ,
Y u . I. S u k h o r u k o ¢ , E. N. T s v e t k o v ,
and M. I. K a b a c h n i k
UDC 541.63:547.1'i18
The energy of p-- ~" coupling in 112EAr aromatic compounds containing an unshared electron pair CUSP) is
determined by two geometrical factors: 1) the valence angles at the hetero atom, which, in turn, are fixed by
the unshared pair hybridization and the energy of pair interaction with the aromatic ring • system [1], and 2)
the spatial ortentstion of the aryl r i n g .
In the course of a study of the dimethyl- and di(tert-butyl)-p-tolylphosphinss
[3], we have shown that both
the f i r s t and the second of t h e s e factors are unfavorable for p-- • coupling in the dialkylarylphosphines, the
situation here being different from that met with the aromatic amines. In fact the unshared pair of the phos-
phorous is coplansr with the benzcyl ring, and accordingly orthogonal to the r system of the latter, a situation
in which the second-power cosine law predicts zero possibility of p-- • interaction.
The present paper will report the results of a study of.~he geometrical structures of dimethylphenylphos-
phine 6), digert-butyl)phenylphosphine (II), dimethyt-p-cyanophenylphosphine C[II), dimethyl-p-tolytphosphine
A . E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Branch of the Academy of Sciences of
the USSR. Translated from Izvestiya Akademit Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2243-2246,
October, 1976. Origiml article submitted August 7, 1975.
o[ this i ~ b ~ t ~
~
be ee~Woduced, stored tn • eetvf~NI xyUem, or mms~itted, in cny [orm or by any magns, ¢~¢¢~mc, mecn~aau, photocopying, I
txavc~bicfrom the publlxt~.for $7.30.
enJoofllveu~ e ~ , ~ l n for otkcewt~, without ~ t t m p~m~lon of'thel~bli~w. A ¢o1~ of th~
~
]
2092