Boratrane method of silatrane synthesis

Full text of DOI:10.1134/S1070363211010257

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 1, pp. 147–148. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © E.A. Grebneva, A.I. Albanov, O.M. Trofimova, M.G. Voronkov, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 1,
pp. 149–150.
LETTERS
TO THE EDITOR
Boratrane Method of Silatrane Synthesis
E. A. Grebneva, A. I. Albanov, O. M. Trofimova, and M. G. Voronkov
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: e-mail: omtrof@irioch.irk.ru
Received March 5, 2010
DOI: 10.1134/S1070363211010257
It has been reported earlier [1, 2] that the trans-
esterification of boratrane B(OCH2CH2)3N and its С-
derivatives with triethoxysilane in the presence of
aluminum alkoxylate affords 1-hydroxysilatran and its
С-derivative [Eq. (1)].
Magnesium propoxide [3] or AlCl3 also were used
as a catalyst [4]. In the absence of a catalyst the reac-
tion occurs more slowly. An attempt to synthesize 1-
(2-chloroethyl)silatrane through this way (1) failed [5].
We developed a simple and convenient boratrane-
based method of the synthesis of 1-organylsilatranes
RSi(OCH2CH2)3N(RSa) by the reaction of boratrane
with trialkoxy(organyl)silanes in the boiling xylene
medium in the presence of AlCl3 as a catalyst [Eq. (2)].
HSi(OEt)3 + B(OCHRCH2)3N
HSi(OCHRCH2)3 + B(OEt)3,
R = H, Me.
(1)
O
O
O
O
AlCl3
(2)
R
RSi(OR')3
+
B
N
Si
N
+ B(OR')3
O
O
I_III
R = Me, R' = Et (I); R = ClCH2, R' = Me (II); R = Ph, R' = Me (III).
Melting points, IR and NMR spectra of the
obtained silatranes I–III correspond to the published
data [6, 7].
Found, %: С 43.99; Н 8.15; Si 14.45. С17Н15NO3Si.
Calculated, %: С 44.37; Н 7.92; Si 14.84.
Silatranes II and III were prepared similarly.
1-Chloromethylsilatrane (II). Yield 2.21 g (76%),
mp 214–215°С. IR spectrum, ν, cm–1: 769, 780, 789,
914, 1087, 1123 (SiOC), 878 (CN), 614 (CCl). Н
NMR spectrum (СDCl3), δ, ppm: 3.84 (OCH2), 2.89
(NCH2), 2.64 (CH2Cl). 13C NMR spectrum (СHCl3),
δC, ppm: 57.39 (OC), 51.2 (NC), 30.96 (α-, SiCH2Cl).
Found, %: С 37.93; Н 6.62; Cl 15.41; N 6.64; Si
12.17. С7Н14ClNO3Si. Calculated, %: С 37.54; Н 6.25;
Cl 15.84; N 6.25; Si 12.55.
1-Methylsilatrane (I). A mixture of 1.88 g of
boratrane, 2.13 g of methyltriethoxysilane, and 0.03 g
of AlCl3 in 25 ml of anhydrous xylene was refluxed
with simultaneous distilling off triethyl borate over 12 h.
The colorless precipitate was filtered off and sub-
limated in a vacuum. Yield 1.94 g (86%), mp 150–
153°С. IR spectrum, ν, cm–1: 596, 619, 770, 909, 946,
1
1
1019, 1096, 1125 (SiOC), 716, 816, 1253 (SiC). Н
NMR spectrum (СDCl3), δ, ppm: 3.75 (OCH2), 2.78
(NCH2), –0.10 (CH3). 13C NMR spectrum (СDCl3), δC,
ppm: 57.76 (OC), 50.99 (NC), –0.94 (α-, SiCH3).
1-Phenylsilatrane (III). Yield 2.91 g (97%), mp
205–208°С. IR spectrum, ν, cm–1: 587, 624, 772, 912,
147

148
GREBNEVA et al.
1094 (SiOC), 487, 497, 692, 746, 1019, 1111 (SiC). 1Н
NMR spectrum (СHCl3), δ, ppm: 3.93 (OCH2), 2.94
(NCH2), 7.75 (C6H5, H 3, 4, 5), 7.26 (C6H5, H 2, 6).
13C NMR spectrum (СDCl3), δC, ppm: 57.84 (OC),
51.17 (NC), 142.00 (α-, SiC6H5), 134.11 (β-, SiC6H5),
127.37 (γ-, SiC6H5), 127.83 (δ-, SiC6H5). Found, %: С
56.89; Н 7.15; Si 10.77. С12Н17NO3Si. Calculated, %:
С 57.28; Н 6.76; Si 11.17.
4. Cradock, S., Ebsworth, E.A.V., and Muiry, I.B.,
J. Chem. Soc., Dalton Trans., 1975, no. 1, p. 25.
5. Voronkov, M.G., D’’yakov, V.M., and Baryshok, V.P.,
Zh. Obshch. Khim., 1977, vol. 47, no. 4, p. 797.
6. Birgele, I.S., Kemme, A.A., Kupche, E.L., Liepin’sh, E.E.,
Mazheika, I.B., and Shatts, V.D., Kremniiorganicheskie
proizvodnye aminospirtov (Organosilicic Derivatives of
Amino Alcohols), Riga: Zinatne, 1987.
The boratrane was prepared by the procedure
reported earlier [8].
7. 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 (Spectral Atlas of Organic Compounds. IR
and Raman Spectra of Silatranes and Model Com-
pounds), Novosibirsk: IOKh Sibir. Otd. Akad. Nauk
SSSR, 1985, no. 31, 175 p.
REFERENCES
1. Zelchan, G.I. and Voronkov, M.G., Author’s Certificate
no. 192209, 1967, Byul. Izobret., 1967, no. 5, p. 38.
2. Zelchan, G.I. and Voronkov, M.G., Khim. Geterotsikl.
Soedin., 1967, no. 2, p. 371.
3. Baryshok, V.P., Tandura, S.N., Kuznetsova, G.A., and
Voronkov, M.G., Metalloorg. Khim., 1991, vol. 4, no. 5,
p. 1150.
8. Voronkov, M.G. and Zelchan, G.I., Metody polucheniya
khimicheskikh reaktivov i preparatov (Sythesis Methods
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 1 2011