Synthesis of trimethylsilyl β-(2,2-dimethylhydrazino)propionate

Full text of DOI:10.1023/B:RUJO.0000034921.07201.c2

Russian Journal of Organic Chemistry, Vol. 40, No. 1, 2004, pp. 127-128. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 1, 2004,
pp. 136-137.
Original Russian Text Copyright Ó 2004 by Rakhlin, Gostevskii, Fomina, Mirskov, Makarova, Lopyrev, Voronkov.
SHORT
COMMUNICATIONS
Synthesis of Trimethylsilyl b-(2,2-Dimethylhydrazino)propionate
V. I. Rakhlin, B. A. Gostevskii, A. N. Fomina, R. G. Mirskov, O. S. Makarova,
V. A. Lopyrev, and M. G. Voronkov
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences
ul. Favorskogo 1, Irkutsk, 664033 Russia
fax: (3952) 419 346
Received May 6, 2003
Aliphatic esters of b-(2,2-dimethylhydrazino)propionic
acid were synthesized by reaction of 1,1-dimethylhydra-
zine with the corresponding alkyl acrylates [1, 2]. Methyl
acrylate is known to react with 1,1-dimethylhydrazine in
polar solvents (water, alcohol), affording a cyclic adduct,
1,1-dimethyldihydro-pyrazol-1-ium-3-olate [1]. In the re-
action of an organosilicon acrylate, 1,3-bis(acrylo-
yloxymethyl)-1,1,3,3-tetramethyldisiloxane with 1,1-dim-
ethylhydrazine, product of addition at the double bond is
formed in a poor yield (26.6%) [3].
1,1-dimethylhydrazine and trimethylsilyl acrylate. The
subsequent addition of 1,1-dimethylhydrazine at the double
bond of trimethylsilyl acrylate leads to the final product in
high yield.
Trimethylsilyl acrylate was prepared by reaction
of 13.5 g (0.19 mol) of acrylic acid with 43 g (0.27 mol)
of hexamethyldisilazane. Yield 22.6 g (84%), bp 35°C (15
mm), nD20 = 1.4092; published data [8]: bp 52–54°C (57
mm), nD20 = 1.4109.
Trimethylsilyl b-(2,2-dimethylhydrazino)pro-
pionate (I). (a) A flask was charged with a few crystals
of hydroquinone and 14.4 g (0.1 mol) of trimethylsilyl acry-
late, and 6 g (0.1 mol) of 1,1-dimethylhydrazine was added
dropwise under stirring. The mixture was stirred for 4 h
at 60°C. Yield of ester I 4.5 g (23.5%), bp 74°C (3 mm),
nD20 = 1.4331. 1H NMR spectrum (CDCl3), d, ppm: 0.13 s
(9H, MeSi), 2.27 s (6H, MeN), 2.36 t (2H, CCH2), 2.83 t
(2H, NCH2).
2Me2NNH2 + (CH2=CHCOOCH2SiMe2)2O
g(Me2NNHCH2CH2COOCH2SiMe2)2O
Trimethylsilyl b-(2,2-dimethylhydrazino)propionate (I)
is a starting compound in the synthesis of Mildranat, which
is an efficient cardiotropic drug [4–7]. With the goal of
preparing compound I we examined the reaction of
trimethylsilyl acrylate with 1,1-dimethylhydrazine.
(b) Acrylic acid, 99.4 g (1.38 mol), was added
dropwise at 7°C to a mixture of 187 g (1.3 mol) of
trimethyl(2,2-dimethylhydrazino)silane and 500 ml of dry
diethyl ether, and the mixture was heated for 2 h under
Me2NNH2 + CH2=CHCOOSiMe3
gMe2NNHCH2CH2COOSiMe3
I
reflux. Yield of ester I 236 g, bp 62–62°C (2 mm), nD20
=
However, heating of an equimolar mixture of the re-
actants for 4 h at 60°C gave only 24% of ester I. We
succeeded in obtaining compound I in 85% yield by reac-
tion of trimethyl(2,2-dimethylhydrazino)silane with acrylic
acid in boiling diethyl ether (reaction time 2 h).
1.4300. Found, %: C 47.21; H 9.76; Si 13.81.
C8H20N2O2Si. Calculated, %: C 47.02; H 9.87; Si 13.74.
1
The H NMR spectra were recorded on a Bruker
DPX-400 spectrometer from 10–20% solutions in CDCl3
using tetramethylsilane as internal reference. The chemi-
cal shifts were measured with an accuracy of ±0.01 ppm.
Me3SiNHNMe2 + CH2=CHCOOH
gMe2NNHCH2CH2COOSiMe3
This study was performed under financial support
by the Interdisciplinary Integration Project no. 104, Sibe-
rian Division, Russian Academy of Sciences.
The reaction involves cleavage of the Si–N bond in
trimethyl(2,2-dimethylhydrazino)silane with formation of
1070-4280/04/4001-0127Ó2004 MAIK “Nauka/ Interperiodica”

RAKHLIN et al.
naukhova, R.V., Efremov, V.G.,Arutyunov, G.P., Poryadin, G.V.,
128
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 1 2004