Hydrocarbyltrialkoxysilanes reaction with fluoroptotatrane

Full text of DOI:10.1134/S1070363213110297

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 11, pp. 2117–2118. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © M.G. Voronkov, G.A. Kuznetsova, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83, No. 11, pp. 1927–1928.
LETTERS
TO THE EDITOR
Hydrocarbyltrialkoxysilanes Reaction with Fluoroptotatrane
M. G. Voronkov and G. A. Kuznetsova
A. E. Favorskii Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: omtrof@irioch.irk.ru
Received May 15, 2013
DOI: 10.1134/S1070363213110297
Of all 1-halogenosilatranes XSi(OCH CH ) N (XSa),
-fluorosilatrane (Х = F) is the most readily available.
and 1-methylsilatrane were fully identical to the
literature data [9–13].
2
2 3
1
Several methods of its synthesis are known [1–6].
Previously, a new simple method of 1-fluorosilatrane
Reaction of fluoroprotatrane (I) with phenyltri-
methoxysilane (II). I was obtained by heating the
mixture of 1.49 g of tris(2-hydroxyethyl)amine and
(
FSa) preparation was suggested, via the reaction of
tris(2-hydroxyethyl)ammonium fluoride (fluoropro-
tatrane, FP) with tetraethoxysilane [7]. The reaction
was performed by heating the mixture with distillating
the formed ethanol off. The yield of FSa reached 90 %.
The mechanism of that reaction was proposed based on
quantum-chemical calculations [8].
0
.37 g of ammonium fluoride during 12 h at 90–95°С
(
until the ammonia evolution ceased). 1.98 g of II was
added to the formed FP (yellow viscous liquid), and
the mixture of methanol and benzene was distilled off.
The residue was sublimed in vacuum at 1 mm Hg to
yield 1.7 g (88%) of 1-fluorosilatrane. Found, %: С
Here, we report the study of FP reactions with
3
7.26; Н 6.13; N 7.21; F 10.16; Si 14.06. C H NO FSi.
6 12 3
1
hydrocarbyltrialkoxysilanes RSi(OR ) (R = Me, Vin,
3
Calculated, %: С 37.29; Н 6.26; N 7.25; F 9.83; Si
1
–
1
or Ph; R = Me or Et). The equimolar mixture of FP (I)
1
(
4.53. IR spectrum, ν, cm : Si–F (748–802), Si–O
1
13
29
and phenyltrimethoxysilane (II) was heated upon
stirring, and the formed methanol and benzene were
distilled off and identified by chromato-mass spec-
trometry. The yield of FSa was of 88%.
790–810) and C–O (1080–1150). Н, С and Si
NMR spectra of FSa solution in CD CN: δ 2.94 and
3
H
3
.76 ppm, δ 51.6 and 57.9 ppm, δ –100.4 ppm.
C Si
Reaction of fluoroprotatrane I with vinyltri-
The reaction of I with vinyltriethoxysilane III led
ethoxysilane (III). 3.8 g of III was added to 3.38 g of
I, and ethanol was distilled off. The obtained pre-
cipitate was sublimed in vacuum (1 mm Hg). Yield of
FSa 3.5 g (91%), mp 330°С. Found, %: С 37.11; Н
to FSa with 91% yield. Both reactions proceeded via
2
splitting of the С –Si bond:
sp
1
-
+
3 2 2 3 2 2 3
RSi(OR ) + F N H(CH CH OH) → FSi(OCH CH ) N
1
+
RH + 3R OH,
6.20; N 7.13; F 10.50; Si 14.11. C
Calculated, %: С 37.29; Н 6.26; N 7.25; F 9.83; Si
4.53. Melting points, IR and NMR spectra of the
6 3
H12NO FSi.
1
R = Ph, Vin; R =Me, Et.
(1)
1
Under similar conditions, I reacted with methyl-
prepared 1-fluorosilatrane coincided with those
reported in the literature [9–13].
trimethoxysilane IV to give 1-methylsilatrane. In that
3
case, the С –Si bond remained intact:
sp
Reaction of fluoroprotatrane I with methyltri-
methoxysilane (IV). A mixture of 1.69 g of I and 1.36 g
of IV was heated with stirring until the distillation of
the formed methanol and HF ceased. The obtained
precipitate was crystallized from chloroform–heptane
(1 : 1) to give 0.75 g (40%) of 1-methylsilatrane, mp
151–152°С. Found, %: С 44.13; Н 8.12; N 7.68; Si
–
+
МеSi(OМе)
МеSi(OCH
3
+ F N H(CH
2 2 3
CH OH)
→
2
CH N +3МеОH +HF.
2
)
3
(2)
The composition and the structure of the prepared
-fluorosilatrane and 1-methylsilatrane were confirmed
1
1
13
29
by elemental analysis, Н, С, Si NMR, and IR spec-
troscopy. The IR and NMR spectra of 1-fluorosilatrane
2
117

2
118
VORONKOV, KUZNETSOVA
Russ. J. Gen. Chem., 2006, vol. 76, no. 12., P., 1968.
1
7
5.04. C H NO Si. Calculated, %: С 44.42; Н 7.99; N
.40; Si 14.84. IR spectrum, ν, cm : Si–С (619), Si–O
7
15
3
–
1
6. Voronkov, M.G., Grebneva, E.A., Trofimova, O.M.,
Albanov, A.I., Chernov, N.F., and Chipanina, N.N.,
Russ. J. Gen. Chem., 2006, vol. 76, no. 12, p. 1851.
1
13
29
(
770–817) and C–O (1080–1125). Н, С and Si
NMR spectra of the solution of 1-methylsilatrane in
CDCI : δ 2.79 and 3.75 ppm, δ 51.05 and 57.80
ppm, δ –64.4 ppm.
7
. Voronkov, M.G., Kochina, T.A., Vrazhnov, D.V., and
Litvinov, M.Yu., Russ. J. Gen. Chem., 2008, vol. 78,
no. 11, p. 2160.
3
H
C
Si
IR spectra of the synthesized compounds were
8
. Shagun, V.A., Voronkov, M.G., Vrazhnov, D.V., and
Kochina, T.A., Russ. J. Gen. Chem., 2011, vol. 81,
no. 9, p. 1792.
1
recorded with Specord IR-75 instrument in KBr. Н,
1
3
29
С and Si NMR spectra were registered with Bruker
DPX-400 spectrometer in CD CN or СDCI solutions
3
3
9. Voronkov, M.G., Shevchenko, S.G., Brodskaya, E.I.,
Baryshok, V.P., D’yakov, V.M., Frolov, Yu.L., Raikh, P.,
and Anisimova, I.L., Atlas spektrov organicheskikh
soedinenii. IK i KR spektry silatranov i model’nykh
soedinenii (Atlas of Spectra of Organic Compounds. IR
and Raman Spectra of Silatranes and Model Com-
pounds), Novosibirsk: Inst. Org. Soed. Sib. Otd. Akad.
Nauk SSSR, 1985, no. 31.
with TMS as an internal standard. Mass spectra were
recorded with gas chromatograph Agilent 6850
equipped with mass-selective detector Agilent 6973N
and capillary quartz column HP-5 MS.
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