A new method of preparation of O-silylurethanes

Full text of DOI:10.1134/S1070363209110322

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 11, p. 2458. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © A.D. Kirilin, A.V. Gavrilova, 2009, published in Zhurnal Obshchei Khimii, 2009, Vol. 79, No. 11, p. 1932.
LETTERS
TO THE EDITOR
A New Method of Preparation of O-Silylurethanes
A. D. Kirilin and A. V. Gavrilova
Lomonosov Moscow State Academy of Fine Chemical Technology,
pr. Vernadskogo 86, Moscow, 119571 Russia
e-mail: kirilinada@rambler.ru
Received February 24, 2009
DOI: 10.1134/S1070363209110322
It was shown earlier [1, 2] that О-silylure-thanes
can be obtained via N-siloxycarbonylation of nitrogen-
containing compounds.
Carbon dioxide/hexamethyldisilasane [3] or carbon
dioxide/silane hydride [4] systems were used as an N-
siloxycarbonylating reagent.
O
HN(SiMe3)2
_NH3
RR'NCOSiMe3
RR'NH + CO2
O
HSi(OEt)3
_H2
RR'NCOSi(OEt)3
2
R = H, Alk, Ar, Me N.
2
0
We established that a novel system carbon dioxide/
N,N'-bis(trimethylsilyl)carbodiimide can be used as N-
siloxycarbonylating reagent.
tion. Yield 29.31 g (95%), bp 53°С (2 mm Hg), nD2
1.4183 (published data [1]: bp 53°С (2 mm Hg), nD
1.4189).
0
RNH + Me SiN
C
NSiMe3 + CO2
2
3
REFERENCES
O
1
2
.
.
Kirilina, N.I., Sheludyakov, V.D., Kirilin, A.D., and
Mironov, V.F., Dvuokis’ ugleroda khimii
kremniiorganicheskikh soedinenii (Carbon Dioxide in
Organosilicon Compounds Chemistry), Moscow:
NIITEKhim, 1980, p. 43.
Kirilin, A.D., Dokuchaev, А.А., Sokova, N.B.,
Patskevich, A.V., and Chernyshev, Е.А., Zh. Obshch.
Khim., 2000, vol. 70, no. 1, p. 51.
RNHCOSiMe3,
v
3 2 2
R = Me, Et, Ph, All, Me SiOCH CH .
This reaction proceeds easily and produces O-
silylurethanes in a high yield (95–98%).
Trimethylsilyl diethylcarbamate. Carbon dioxide
was bubbled through a solution of 14.8 g (0.08 mol) of
3. Sheludyakov, V.D., Kirilin, A.D., and Mironov, V.F.,
Zh. Obshch. Khim., 1975, vol. 45, no. 2, p. 479.
N,N'-bis-(trimethylsilyl)carbodiimide and 11.6
g
4. Kirilin, A.D., Dokuchaev, A.A., Menchaikina, I.N.,
Semenova, E.V., Sokova, N.B., and Chernyshev, E.A.,
Izv. Akad. Nauk Ser. Khim., 1999, no. 9, p. 2192.
о
(
0.16 mol) of diethylamine at 55 С for 2 h. Then the
liquid was filtered and subjected to fractional distilla-
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