Reactions of 1-hydrosilatrane with 2-hydroxyethylamines [5]

Full text of DOI:10.1023/A:1020731606372

Russian Journal of General Chemistry, Vol. 72, No. 7, 2002, pp. 1148 1149. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 7, 2002,
pp. 1227 1228.
Original Russian Text Copyright
2002 by Voronkov, Kuznetsova, Baryshok.
LETTERS
TO THE EDITOR
Reactions of 1-Hydrosilatrane with 2-Hydroxyethylamines
M. G. Voronkov, G. A. Kuznetsova, and V. P. Baryshok
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, Russia
Received May 28, 2001
Among silatranes, 1-hydrosilatrane (I, SaH) is of
considerable theoretical and practical interest, which
is due to high and specific reactivity of the Si H bond
[1 7]. This compound readily reacts with alcohols and
phenols [1], alkanediols [2, 3], and carboxylic acids
[4]. Dehydrocondensation of I with glucose and man-
nose yields silatranyl derivatives of monosaccharides
[5]. Silatrane I was suggested as an effective reductant
[6 13].
1-[2-(dimethylamino)ethoxy]silatrane IIIa, mp 117
118 C (published data [14, 15]: yield 55%, mp 114
115 C). Found, %: C 45.34; H 8.83; N 10.57; Si
10.52. C10H22N2O4Si. Calculated, %: C 45.78; H
8.45; N 10.68; Si 10.70.
Reaction of 1-hydrosilatrane with N,N-diethyl-
aminoethanol. A mixture of 3.5 g of 1-hydrosilatrane
and 2.4 g of N,N-diethylaminoethanol in 40 ml of
chloroform was heated for 4 h. The solvent was dis-
tilled off, and the residue was treated with pentane;
4.1 g (70%) of IIIb was obtained, mp 98 99 C (pub-
lished data [14, 15]: yield 59%, mp 94 95 C). Found,
%: C 49.70; H 9.18; N 9.57; Si 9.40. C12H26N2O4Si.
Calculated, %: C 49.64; H 9.02; N 9.65; Si 9.67.
We have studied dehydrocondensation of alkyl(2-
hydroxyethyl)amines IIa IIc with silatrane I.
R3 nN(CH2CH2OH)n + nHSi(OCH2CH2)3N
IIa IIc
I
1-Silatranol IV. A 0.09-g portion of water was
added to a solution of 1.45 g of IIIb in 10 ml of
chloroform, and the mixture was refluxed for 3.5 h.
The precipitate was filtered off; yield 0.7 g (74%),
mp 205 207 C (published data [9]: yield 57%,
mp 205 210 C). Found, %: C 37.90; H 7.15; N 7.45;
Si 14.44. C6H13NO4Si. Calculated, %: C 37.68;
H 6.85; N 7.32; Si 14.69.
R3 nN(CH2CH2OSa)n + nH2
IIIa IIIc
n = 1, R = Me (a), Et (b); n = 3 (c).
This reaction readily occurs under mild conditions
without a catalyst. Amino alcohols II with R = H or
n = 2 under similar conditions react to give polymers.
(N-Diethylaminoethoxy)silatrane IIIb is smoothly
hydrolyzed to give 1-silatranol IV in 96% yield.
Reaction of 1-hydrosilatrane with triethanol-
amine. A solution of 1.49 g of triethanolamine in
15 ml of chloroform was added dropwise over a pe-
riod of 1 h to a refluxing solution of 5.25 g of I in
30 ml of chloroform. The mixture was refluxed for
an additional 0.5 h, and the solvent was distilled off
at reduced pressure (10 15 mm Hg). The creamy
white finely crystalline residue was mixed with 30 ml
of hexane and then filtered off; yield 6.45 g (96%),
mp 258 260 C (published data [9]: yield 54%, mp
260 C). Found, %: C 43.11; H 7.27; N 12.88; Si 8.16.
C24H48N4O12Si3. Calculated, %: C 43.09; H 7.23;
N 12.60; Si 8.38.
IIIb + H2O
HOSi(OCH2CH2)3N + Et2NCH2CH2OH
IV
This reaction is a simple and convenient route to
1-silatranol IV. Previously compound IV was prepared
in a lower yield by hydrolysis of N(CH2CH2OSa)3 [9].
Reaction of 1-hydrosilatrane with N,N-dimethyl-
aminoethanol. A mixture of 3.1 g of 1-hydrosilatrane
and 1.6 g of N,N-dimethylaminoethanol in 40 ml of
anhydrous chloroform was heated for 7 h until hydro-
gen evolution ceased. The solvent was distilled off,
and the residue was sublimed to give 3.5 g (75%) of
The IR spectra were recorded with a Specord IR-75
spectrometer (KBr pellets).
1070-3632/02/7207-1148$27.00 2002 MAIK Nauka/Interperiodica

REACTIONS OF 1-HYDROSILATRANE WITH 2-HYDROXYETHYLAMINES
1149
ACKNOWLEDGMENTS
8. Voronkov, M.G., Petukhov, L.P., Vakul’skaya, T.I.,
Baryshok, V.P., Tandura, S.N., and Pestunovich, V.A.,
Izv. Akad. Nauk SSSR, Ser. Khim., 1979, no. 7, p. 1665.
The study was financially supported by the Russian
Foundation for Basic Research (project no. 00-15-
97395).
9. Frye, C.L., Vincent, G.A., and Finzel, W.A., J. Am.
Chem. Soc., 1971, vol. 93, no. 25, p. 6805.
10. Attar Bashi, M.T., Eaborn, C., Vencl, J., and Wal-
ton, D.R.M., J. Organomet. Chem., 1976, vol. 117,
no. 4, p. 87.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 7 2002