REACTION OF TETRAFLUOROSILANE WITH TRIS(2-HYDROXYETHYL)AMINE
1853
teraction and stereochemical rigidity of the quasisila-
trane heterocycle VI and VII.
(47%) of compound VI with mp 180 C was ob-
tained.
The 15N chemical shift in the 15N NMR spectrum
of 1,1-difluoroquasisilatranes VI and VII are slightly
(by 1 and 3 ppm, respectively) shifted downfield as
compared to the 15N chemical shifts in the spectra of
the starting bis(2-hydroxyethyl)amine ( 349.1 ppm)
and methyl-bis(2-hydroxyethyl)amine ( 348.4 ppm)
[14] under the same conditions [10]. This small dif-
ference of the 15N chemical shifts is apparently
caused by slight deshielding of the nitrogen atom
upon its protonation in alkyl amines [10] and op-
positely directed (shielding) contribution of the
cyclization effect [11].
1,1-Difluoro-5-methylquasisilatrane VII was
synthesized similarly in the yield of 1.04 g (35%),
mp 162 C.
ACKNOWLEDGMENTS
This work was supported by the Council on grants
of the President of Russian Federation (NSh-4575.
2006.3) and INTAS (Grant No. 03-51-4164).
REFERENCES
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IR spectrum of 1-fluorosilatrane III is identical to
that given in the atlas of spectra [6]. It was reported
earlier that the stretching vibrations of the Si F bonds
in compounds of pentacoordinate silicon containing
one or two Si F bonds and intramolecular bond
=O Si are mixed and are observed in relatively
narrow frequency intervals [12]. In the spectra of 1,1-
difluoroquasisilatranes VI and VII having coordina-
tion bond N Si stretching vibrations (Si F) cor-
4. Voronkov, M.G. and D’yakov, V.M., Silatranes
(Silatrany), Novosibirsk: Nauka, 1978.
5. Voronkov, M.G., Dyakov, V.M., and Kirpichen-
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1
respond to the bands at 770 and 900 cm .
EXPERIMENTAL
IR spectra of the synthesized compounds were
registered on a Specord IR-75 spectrometer in pellets
1
with KBr. H, 13C, 15N, 19F, and 29Si NMR spectra
were recorded on a Bruker Dތ-400 spectrometer (at
400.13, 100.61, 40.56, 376.50, and 79.5 MHz, respec-
tively) in DMSO-d6, internal standard TMS.
1-Fluorosilatrane III. a. Gaseous tetrafluorosilane
obtained by the reaction of 2 ml of conc. H2SO4 with
powder-like mixture of 4.7 g of Na2SiF6 and 1.5 g of
SiO2 was passed into the solution of 4.28 g of tris(2-
hydroxyethyl)amine in benzene during 3 h at 3 to
0 C. The precipitate formed was filtered, washed with
dry ether and sublimed under vacuum. 0.84 g (75%)
of compound III was obtained.
9. Voronkov, M.G., Boyarkina, E.V., Gebel’, I.A., Al-
banov, A.I., and Basenko, S.V., Zh. Obshc. Khim.,
2005, vol. 75, no. 12, p. 2018.
10. Witanowski, M. and Stefaniak, L., in: Annual Reports
on NMR Spectroscopy, Webb, G.A., Ed., London:
Academic Press, 1981.
b. Tetrafluorosilane obtained as above was passed
into the hexane solution of 15.66 g of tris(2-trimethyl-
siloxyethyl)amine during 3 4 h at 5 0 C. The
yellowish precipitate formed was filtered, washed
with dry ether and sublimed under vacuum. 3.78 g
(53%) of compound III was obtained.
11. Birgele, I.S., Kemme, A.A., Kupchee, E.L., Lie-
pin’sh, E.E., Mazeika, I.B., and Shats, V.D.,
Kremniiorganicheskie
proizvodnye
aminospirtov
1,1-Difluoroquasisilatrane VI. Through the solu-
tion of 4.36 g of bis(2-trimethylsiloxyethyl)amine in
10 ml of hexane gaseous tetrafluorosilane was passed
during 3 h at 5 0 C. The white precipitate formed
was filtered and sublimed under vacuum. 1.39 g
(Organosilicon Derivatives of Alkanolamines),
Lukevics, E.Ya., Riga: Zinatne, 1987.
12. Frolov, Yu.L., Voronkov, M.G., Gavrilova, G.A.,
Chipanina, N.N., Gubanova, L.I., and Dyakov, V.M.,
J. Organometal. Chem., 1983, vol. 244, p. 107.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 12 2006