A new route to 1-chlorosilatrane

Article abstract of DOI:10.1134/S1070363210100075

A method for the synthesis of 1-chlorosilatrane by the reaction of organyltrichlorosilanes RSiCl₃ (R = Vin, Ph) and tetrachlorosilane with triethanolamine or its hydrochloride was developed. This simple and economical method allows obtaining 1-chlorosilatrane in 60% yield.

Full text of DOI:10.1134/S1070363210100075

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 10, pp. 1926–1928. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © M.G. Voronkov, G.A. Kuznetsova, V.P. Baryshok, 2010, published in Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 10, pp. 1615–
1617.
A New Route to 1-Chlorosilatrane
M. G. Voronkova, G. A. Kuznetsovaa, and V. P. Baryshokb
a Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: omtrof@irioch.irk.ru
b Irkutsk State Technical University, Irkutsk, Russia
Received June 17, 2010
Abstract―A method for the synthesis of 1-chlorosilatrane by the reaction of organyltrichlorosilanes RSiCl3
(R = Vin, Ph) and tetrachlorosilane with triethanolamine or its hydrochloride was developed. This simple and
economical method allows obtaining 1-chlorosilatrane in 60% yield.
DOI: 10.1134/S1070363210100075
RCl + CH2=CHCH2Si(OCH2 CH2)3N → ClSi(OCH2CH2)3N
1-Chlorosilatrane ClSi(OCH2CH2)3N (ClSa) is used
as a precursor in the synthesis of many 1-substituted
silatranes, as well as in theoretical studies of molecular
and stereoelectronic structure of chelate silicon
compounds [1–4]. For the synthesis of ClSa and its
analog, 1-chloro(3,7,10-trimethyl)silatrane, the follow-
ing methods have been used.
+ CH2=CHCH2R,
R = CCl3, CF3, C3F7.
(6) Reaction of tetrachlorsilane with tris(2-tri-
methylsiloxyethyl)amine [11]:
SiCl4 + (Me3SiOCH2CH2)3N
→ ClSi(OCH2CH2)3N + 3Me3SiCl.
(1) The reaction of 1-hydrosilatrane with elemental
chlorine in the presence of an acceptor of hydrogen
chloride [5]:
(7) The reaction of C-substituted tris(2-hydroxy-
alkyl)amines or related hydrochlorides with organyl-
trichlorosilanes [12]:
Cl2 + HSi (OCH2 CH2)3N → ClSi (OCH2 CH2)3N + HCl.
RSiCl3 + (HOCHMeCH2)n(HOCH2CH2)3–nN·(HCl)m
→ ClSi (OCHMeCH2)n(OCH2CH2)3–nN + RH
+ (2 + m)HCl,
By the same way 1-chloro-3,7,10-trimethylsilatrane
was obtained, in the absence of the HCl acceptor [5].
R = CH2=CH, C6H5, ClCH2CH2, Cl3P; n = 1 – 3; m = 0, 1.
(2) 3,7,10-Trimethylsilatrane reaction with N-chloro-
succinimides [5]:
We have shown that ClSa is formed easily in the
reaction of triethanolamine or its hydrochloride (chloro-
protatrane) with tetrachlorosilane according to the
equation:
(CH2CO)2NCl + HSi(OCHMeCH2)3N
→ ClSi (OCHMeCH2)3N + (CH2CO)2NH.
(3) The reaction of 1-ethoxysilatrane with phos-
phorus or sulfur chlorides [6]:
SiCl4 + (HOCH2CH2)3N·nHCl
→ ClSi(OCH2CH2)3N + (3 + n) HCl,
n = 0, 1.
R(O)Cl2 + 2C2H5OSi(OCH2CH2)3N → 2ClSi(OCH2CH2)3N
+ R(O)(OC2H5)2,
Of particular interest is the unusual formation ClSa
in the reaction of chloroprotatrane with the organyl-
trichlorosilanes containing a π-electron system con-
nected to the silicon atom (CH2=CH, C6 H5). This
process proceeds with the cleavage of the C(sp2)–Si
bond by the liberated HCl along the equation:
R = ClP, CH3P, S.
(4) 1-Hydrosilatrane chlorination by organic or
organosilicon chlorides [7–9]:
RCl + HSi(OCH2CH2)3N → ClSi(OCH2CH2)3N + RH,
R = PhCO, Ph3C, Me3Si.
RSiCl3 + (HOCH2CH2)3N·HCl → ClSi(OCH2 CH2)3N
+ RH + 3HCl,
(5) Homolytic reaction of haloalkanes with 1-
allylsilatrane [7, 10]:
R = CH2=CH, C6 H5.
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1927
A NEW ROUTE TO 1-CHLOROSILATRANE
Noteworthy that in the reaction of triethanolamine
with C6H5SiCl3 phenylsilatrane is formed [13],
whereas the product of the reaction of triethanolamine
hydrochloride with phenyltrichlorosilane is 1-chloro-
silatrane. Reactions of vinyltrichlorosilane and tetra-
chlorosilane with triethanolamine were carried out in
an argon atmosphere in chloroform at a temperature
from –5 to 0°C. Reactions of vinyl- and phenyl-
trichlorosilanes, and tetrachlorosilane with triethanol-
amine hydrochloride were carried out in the absence of
a solvent with a gradual increase in temperature to
130–150°C. The yield of 1-chloro-silatrane in all cases
was ~60%.
Reaction of phenyltrichlorosilane with triethanol-
amine hydrochloride. A mixture of 1.06 g of phenyl-
trichlorosilane with 0.93 g of triethanolamine hydro-
chloride was heated in argon at atmospheric pressure at
150–160°C for 2 h, then 2 h in a vacuum (5–8 mm Hg)
at the same temperature. The solid reaction product
was extracted with methylene chloride. From the
extract 0.58 g (56%) of 1-chlorosilatrane was isolated
with the decomposition temperature above 200°C.
Found, %: C 34.26, H 5.53, Cl 17.02, N 7.00, Si 12.95.
C6H12ClNO3Si. Calculated, %: C 34.36, H 5.77, Cl
16.90, N 6.68, Si 13.39.
Reaction of viniltrichlorosilane with triethanol-
amine hydrochloride. Similarly from 0.41 g of vinil-
trichlorosilane and and 0.47 g triethanolamine hydro-
chloride 0.32 g (60%) of 1-chlorosilatrane was ob-
tained. Found, %: C 34.55, H 5.80, Cl 16.83, N 6.84,
Si 13.20. C6 H12ClNO3Si. Calculated, %: C 34.36, H
5.77, Cl 16.90, N 6.68, Si 13.39.
EXPERIMENTAL
The IR spectra were recorded on a Specord IR-75
instrument from the tablets with KBr. The H and 13C
1
NMR spectra were recorded on a Bruker-400
spectrometer at the operating frequencies 400 and
100 MHz, respectively. As an internal reference was
used HMDS.
Reaction of tetrachlorosilane with triethanol-
amine hydrochloride. Similarly from 0.85 g of tetra-
chlorosilane and 0.93 g of triethanolamine hydro-
chloride 0.45 g (43%) of 1-chlorosilatrane was obtained.
Reaction of viniltrichlorosilane with triethanol-
amine. To a solution of 0.8 g of vinyltrichlorosilane in
20 ml of CHCl3 cooled to –5–0°C at stirring in an
argon atmosphere was added dropwise a solution of
0.75 g of triethanolamine in 20 ml of CHCl3. Then
chloroform was distilled off from the reaction mixture,
the resulting solid residue was heated in a vacuum (2–
3 mm Hg) at 110–120°C for 2 h to decompose the
complex of ClSa with HCl, and extracted with
methylene chloride. From the extract 0.63 g (61%) of
1-chlorosilatrane was isolated with the decomposition
point above 200°C. Found, %: C 34.68, H 6.11, Cl
17.34, N 6.31, Si 13.29. C6H12ClNO3Si. Calculated, %:
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obtained. Found, %: C 34.38, H 5.90, Cl 17.22, N
6.53, Si 13.56. C6H12ClNO3Si. Calculated, %: C 34.36,
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