Russian Chemical Bulletin, International Edition, Vol. 64, No. 4, pp.

965—966, April, 2015 965

Synthesis of N[chloro(dimethyl)silyl]Nmethylacetamide
N. F. Lazareva and A. Yu. Nikonov

A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences,
1 ul. Favorskogo, 664033 Irkutsk, Russian Federation.
Email: nataly_lazareva@irioch.irk.ru

A transsilylation reaction of bis[(Nmethyl)acetamido]dimethylsilane with chloro(chloro

methyl)(dimethyl)silane leads to the formation of two products: N[chloro(dimethyl)
silylmethyl]Nmethylacetamide (1) and N[chloro(dimethyl)silyl]Nmethylacetamide (2).

Key words: bis[(Nmethyl)acetamido]dimethylsilane, chloro(chloromethyl)(dimethyl)

silane, N[chloro(dimethyl)silyl]Nmethylacetamide, transsilylation.

Carboxylic acid N(triorganylsilyl)amides RC(O)
NMeSiR1R2R3 are widely used in synthetic organic and
organoelement chemistry as silylating agents (see Refs 1—4
and references cited therein), their structure and reactivity
are well studied. There are synthesized representatives of
carboxylic acid N(silyl)amides, which contain OR, OAr,
and RC(O)N(R´) functional groups at the silicon atom.5—13
However, these compounds are few and their reactivity is
studied little. To the best of our knowledge, the literature
information about carboxylic acid N[(halo)silyl]amides
is absent. The transsilylation reaction of carboxylic acid
N(trimethylsilyl)amides and related compounds with
chloro(chloromethyl)(dimethyl)silane (ClCH2SiMe2Cl)
leads to the liberation of chlorotrimethylsilane and the
formation of the corresponding N[chloro(dimethyl)
silylmethyl]amides, the (O—Si)chelated compounds of
pentacoordinated silicon (Scheme 1; see Refs 14 and 15
and references cited therein).
methylsilane reacted with an equimolar amount of chloro
(chloromethyl)(dimethyl)silane with the formation of two
products: N[chloro(dimethyl)silylmethyl]Nmethyl
acetamide (1), the synthesis of which by other methods
was described earlier, and whose structure was confirmed
by multinuclear NMR spectroscopy16 and Xray diffrac
tion study,17 and N[chloro(dimethyl)silyl]Nmethyl
acetamide (2) (Scheme 2). It should be noted that com
pound 2 can be also involved in the transsilylation reac
tion with ClCH2SiMe2Cl, and after addition of the second
equivalent of ClCH2SiMe2Cl to the reaction mixture or if
the ratio of reagents is 1 : 2, only dichlorodimethylsilane
and compound 1 are formed in the yields close to quanti
tative.
Scheme 2

Scheme 1

R1 = Alk, Ar, RR´N; R2 = Alk, Me3Si, NRR´, RC(O)

We assumed that the reaction of diorganyldiamido

silanes RR´Si[N(R)C(O)R´]2 with ClCH2SiMe2Cl, to
gether with the formation of (O—Si)chelated pentacoor
dinated compound, can also give an N[(chloro)silyl]
amide of the corresponding carboxylic acid. In this work, When the reaction was carried out in pentane solution
we studied the reaction of the simplest bis[(Nmethyl) with the equimolar ratio of reagents at –5 C (±3 C), the
acetamido]dimethylsilane Me2Si[N(Me)C(O)Me]2 with product 2 was isolated in the pure form. Compound 2 is
ClCH2SiMe 2Cl. In fact, bis[(Nmethyl)acetamido]di a colorless liquid, extremely easily hydrolysable by air

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 0965—0966, April, 2015.
10665285/15/64040965 © 2015 Springer Science+Business Media, Inc.
966 Russ.Chem.Bull., Int.Ed., Vol. 64, No. 4, April, 2015
moisture: the process is so rapid, that it is impossible to
accurately determine its refractive index. Nonetheless, the
spectral characteristics of compound 2 sealed in a tube
under inert dry atmosphere do not change after storage of
the tube for a week at –78 C (a Dewar flask with dry ice),
that indicates its stability under these conditions. Attempt
ed distillation of compound 2 led to its intensive resinifi
cation and decomposition. The structure of compound 2
was confirmed by multinuclear NMR spectroscopy, its
composition by elemental analysis. Note that for com
pound 2, a possibility of existence of the Nsilyl tautomer 2
in the equilibrium with the Osilylimidate Me2Si(Cl)O
C(Me)=NMe cannot be excluded (see Refs. 18 and 19
and references cited therein).
Experimental
The reaction was carried out in thoroughly dried glassware
under dry argon. Pentane was distilled over sodium and stored
over 4 Å molecular sieves. Bis[(Nmethyl)acetamido]dimethyl
silane was synthesized according to the procedure described ear
lier.20 NMR spectra of 20% solutions of compounds in CDCl3
were recorded on a Bruker 400 spectrometer (1H, 400.1 MHz;
13C, 100.6 MHz; 29Si, 79.5 MHz) using cyclohexane as an inter
nal standard.
Synthesis of N[chloro(dimethyl)silyl]Nmethylacetamide
(2). A solution of freshly distilled ClCH2SiMe 2Cl (0.29 g,
2 mmol) in pentane (10 mL) was added dropwise with a syringe
to a cooled (to –5 C) solution of bis[(Nmethyl)acetamido]
dimethylsilane (0.4 g, 2 mmol) in pentane (20 mL) with vigorous
stirring. The solution was stirred at this temperature for 1 h,
then, the temperature was raised to ambient, and the mixture
was allowed to stand for 16 h. A precipitate of N[chloro
(dimethyl)silylmethyl]Nmethylacetamide (1) was filtered and
dried in vacuo. The yield was 0.34 g (94%). The 1H, 13C, and 29Si
NMR spectral data of this compound agreed with those reported
in the literature.16 Pentane was evaporated on a rotary evapora
tor, the residue was dried in vacuo and analyzed. The yield of
compound 2 was 0.32 g (97%). 1H NMR, : 0.64 (s, 6 H, MeSi);
2.12 (s, 3 H, MeC(O)); 2.95 (s, 3 H, MeN). 13C NMR, : 3.86
(MeSi); 22.93 (MeC(O)); 30.76 (MeN); 179.90 (C=O). 29Si NMR,
: 3.05. Found (%): C, 36.86; H, 7.76; N, 8.17. C5H12ClNOSi.
Calculated (%): C, 36.24; H, 7.30; N, 8.45.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 140331462).
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Received December 12, 2014;
in revised form January 22, 2015