Direct synthesis of 1-organylsilatranes from organyltrichlorosilanes and tris(2-hydroxyethyl)amine

Article abstract of DOI:10.1134/S1070363209050107

A direct method of synthesis of 1-organylsilatranes by the reaction of organyltrichlorosilanes with tris(2-hydroxyethyl)amine was developed. 1-Organylsilatranes RSi(OCH₂CH₂)₃N with R = Me, Et, Ph, ClCH₂, ICH₂, Cl(CH₂)₃ were prepared by this method in up to 72% yield.

Full text of DOI:10.1134/S1070363209050107

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 5, pp. 925–927. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © M.G. Voronkov, G.A. Kuznetsova, 2009, published in Zhurnal Obshchei Khimii, 2009, Vol. 79, No. 5, pp. 753–755.
Direct Synthesis of 1-Organylsilatranes
from Organyltrichlorosilanes and Tris(2-hydroxyethyl)amine
M. G. Voronkov and G. A. Kuznetsova
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: voronkov@irioch.irk.ru
Received January 29, 2009
Abstract―A direct method of synthesis of 1-organylsilatranes by the reaction of organyltrichlorosilanes with
tris(2-hydroxyethyl)amine was developed. 1-Organylsilatranes RSi(OCH2CH2)3N with R = Me, Et, Ph, ClCH2,
ICH2, Cl(CH2)3 were prepared by this method in up to 72% yield.
DOI: 10.1134/S1070363209050107
For almost half a century silatranes attract attention
due to their unusual molecular structure [1–4], high
specific biological activity [2, 5–8] and wide applica-
tions in medicine and agriculture [9].
XSi(OMe)3 + MeSi(OCH2CH2)3N
→ XSi(OCH2CH2)3N + MeSi(OMe)3,
X = ClCH2, Cl2CH, Vin, Ph, MeO, Cl.
(5)
Reactions (4) and (5) are less common but very
attractive methods for synthesis of silatranes.
The main methods of synthesis of silatranes are as
follows:
It is noteworthy that all starting Si-organyl reagents
used in the synthesis of silatranes (RSi(OR')3,
[RSiO1.5]n, [RSiO1.5–m(OH)2m]n, RSiF3) are prelimi-
narily synthesized from the isostructural Si-substituted
organyltrichlorosilanes RSiCl3. Therefore, all the
aforementioned methods of synthesis are practically
two- or even three-step processes.
Reactions of reetherification of the Si-substituted
triethoxysilanes RSi(OR')3 with tris(2-hydroxyethyl)
amine (triethanolamine, TEA) [2–4].
RSi(OR')3 + (HOCH2CH2)3N
→ RSi(OCH2CH2)3N + 3R'OH.
(1)
Reaction of the cleavage of polyorganylsilses-
quioxanes or polyorganylsioxanoles with TEA [10–12].
We have planned to work out a simplest and
economic direct method of synthesis of 1-organyl-
silatranes (RSa) starting from organyltrichlorosilanes
and TEA. So far nobody tried to synthesize 1-
organylsilatranes by this method. The only exception is
our earlier described method of synthesis of 1-
chloromethylsilatrane (ClCH2Sa) from ClCH2SiCl3
and TEA [19].
1/n [RSiO1.5–m(OH)2m]n + (HOCH2CH2)3N
→ RSi(OCH2CH2)3N + (1.5 + n) H2O.
(2)
Condensation of Si-substituted trichloro- [13, 15]
and trifluorosilanes [12, 14, 16] with tris(2-trimethyl-
siloxyethyl)amine.
RSiX3 + (Me3SiOCH2CH2)3N
On this example, we have studied the effect of the
solvent character, temperature of the reaction (from –
20 to +60°C), and the molar ratio of the reagents on
the yield of silatranes (Table 1).
→ RSi(OCH2CH2)3N + 3 Me3SiX,
(3)
X = Cl, F.
The exchange reaction of triethoxysilane and its Si-
substituted derivatives with boratrane [17].
The optimal conditions found for the synthesis of
ClCH2Sa (solvent HCCl3, the ratio of the reagents, and
the temperature of the reaction) were used for syn-
thesis of other 1-organylsilatranes by the general
scheme.
HSi(OR)3 + B(OCH2CH2)3N
→ HSi(OCH2CH2)3N + B(OR)3.
(4)
Transsilylation of silatranes with Si-substituted
trialkoxysilanes [18].
925

926
VORONKOV, KUZNETSOVA
Table 1. Optimization of the conditions of synthesis of
ClCH2Sa by the reaction of ClCH2SiCl3 with TEA
Our numerous attempts to synthesize XSa with X =
H, Cl from HSiC13 and SiC14 and TEA failed.
However, similar methods of synthesis of FSa from
TEA and SiF4 we described earlier [20].
ClCH2SiCl3:N
(CH2CH2OH)3
Yield of
ClCH2Sa, %
Solvent
Temperature, °C
HCCl3
HCCl3
HCCl3
HCCl3
HCCl3
HCCl3
HCCl3
H2CCl2
H2CCl2
MeCN
1:1
1:1
1:2
1:4
1:4
1:2
1:4
1:2
1:2
1:1
–20
0 to –5
0 to –5
0 to –5
20
62
EXPERIMENTAL
66
70a
66a
68a
63a
45a
72a
68a
46
IR spectra were taken on a Specord IR 75
1
13
instrument from KBr pellets. Н and С NMR spectra
were recorded on a Bruker 400 spectrometer at
working frequencies 400 and 100 MHz respectively,
with HMDS as an internal standard.
61
61
0 to –5
20
General procedure for the synthesis of RSa. To a
stirred solution of organyltrichlorosilane in HCCl3 at
0–5°С in an inert atmosphere a solution of TEA in
HCCl3 was slowly added dropwise. The reaction
mixture was stirred until warming to room
temperature, HCCl3 and hydrogen chloride were
distilled off, the solid residue was heated under a
vacuum (1–2 mm Hg) at 110–120°С, and the formed
1-organylsilatrane was extracted with an appropriate
solvent.
–5
a Recalculated to the starting silane.
RSiCl3 + (HOCH2CH2)3N → RSi(OCH2CH2)3N + 3 HCl,
R = Me, Et, Ph, ClCH2, ICH2, Cl(CH2)3.
The above reaction of organyltrichlorosilanes with
TEA in HCCl3 at the temperature of 0–5°С results in
the corresponding 1-organylsilatranes in up to 66%
yield (Table 2). The order of mixing has practically no
effect on the yield of RSa. The low yield of ICH2Sa
(33%) and PhSa (40%) is probably due to splitting of
the Si–C bond by the liberated HCl.
ACKNOWLEDGMENTS
This work was performed with a financial support
from the Council of grants of the President of RF
(NSh-255.2008.3).
Table 2. Yield, mp, and elemental analysis of RSa synthesized from RSiCl3 and TEA
Found, %
Cl(I)
Calculated, %
Cl(I)
Yield,
(%)
R
mp, °С
Formula
C
H
N
Si
C
H
N
Si
151–152
Me
Et
50
55
40
66
33
50
44.47 7.94
47.15 8.27
56.87 7.04
7.40 15.10 C7H15NO3Si
7.22 13.80 C8H17NO3Si
5.76 10.72 C12H17NO3Si
44.42 7.99
7.40 14.84
6.89 13.82
5.57 11.17
(chloroform–heptane)
132–133
(heptane)
47.26 8.43
57.34 6.82
209–210
(xylene)
Ph
215–217
ClCH2
ICH2
37.43 6.25 15.72 6.21 12.37 C7H14ClNO3Si 37.58 6.31 15.85 6.26 12.55
(chloroform–heptane)
190–191
27.10 4.93 40.00 4.44
9.05 C7H14INO3Si
26.68 4.48 40.26 4.35 8.91
(chloroform–heptane)
130–131
Cl(CH2)3
43.26 7.80 14.54 5.68 11.20 C9H18ClNO3Si 42.93 7.21 14.08 5.56 11.16
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 5 2009
(chloroform–heptane)

DIRECT SYNTHESIS OF 1-ORGANYLSILATRANES
927
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