Reaction of chloro(chlorodimethyl)dimethylsilane with O-silylurethanes and nicotinic hydrazide in the presence of hexamethyldisilazane

Article abstract of DOI:10.1023/B:RUGC.0000016017.44026.39

The reaction of chloro(chlorodimethyl)dimethylsilane and hexamethyldisilazane with O-silylurethanes and nicotinic hydrazide gives rise to products whose structure is determined by the composition, structure, and basicity of intermediate compounds. The rea

Full text of DOI:10.1023/B:RUGC.0000016017.44026.39

Russian Journal of General Chemistry, Vol. 73, No. 10, 2003, pp. 1539 1542. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 10, 2003,
pp. 1631 1634.
Original Russian Text Copyright
2003 by Kirilin, Belova, Zhvakina, Chernyshev.
Reaction of Chloro(chlorodimethyl)dimethylsilane
with O-Silylurethanes and Nicotinic Hydrazide
in the Presence of Hexamethyldisilazane
A. D. Kirilin, L. O. Belova, L. A. Zhvakina, and E. A. Chernyshev
Lomonosov Moscow State Academy of Fine Chemical Engineering, Moscow, Russia
Received April 8, 2002
Abstract The reaction of chloro(chlorodimethyl)dimethylsilane and hexamethyldisilazane with O-silyl-
urethanes and nicotinic hydrazide gives rise to products whose structure is determined by the composition,
structure, and basicity of intermediate compounds. The reaction allowed synthesis of previously unknown
linear and heterocyclic compounds.
Earlier we reported the reaction of chloro(chloro-
methyl)dimethylsilane (I) with O-silylurethanes
and silicon-containing formamides, yielding both
linear and heterocyclic compounds [1 4]. In parti-
cular [5], the reaction with silyl carbamate II [scheme
(1)] involved transacylation, isomerization, and intra-
molecular desilylation, and resulted in formation of
heterocycle IV.
With persilylated hydroxycarbamic acid II instead
of silyl carbamate II the reaction changed direction
[3], as a result of which compound IIIa underwent,
instead of intramolecular, as with III, intermolecular
desilylation [scheme (2)] to form biscarbamate VI.
Scheme 1.
O
Me3SiOCH2CH2NCOSiMe3
Me2SiCH2Cl
O
Me3SiOCH2CH2NCOSiMe3
CH2SiMe2Cl
Me3OCH2CH2
I
NCOSiMe3
Me3Si
O
II
III
Me
O
CH2CH2
I
CH2CH2
O
NCH2SiCl
Me
O
NCOSiMe3
CO2,
Me3SiCl
SiCH2
SiCH2
Me3SiCl
Me Me
Me Me
IV
Scheme 2.
O
Me3SiONCOSiMe3
SiMe3
O
O
Me Me
Me3SiONCH2SiNOSiMe3
I
Me3SiONCOSiMe3
Me2SiCH2Cl
Me3SiONCOSiMe3
CH2SiMe2Cl
Me2SiOC
O
COSiMe3
O
V
IIIa
VI
Proceeding with these studies, we found that using,
instead of chlorosilane I alone, its mixture with
hexamethyldisilazane results in a radical change in
the composition and structure of the final products.
Thus, the reaction of the preceding member of the
O-silylurethane series, trimethylsilyl N-[ -(trimethyl-
siloxy)]ethyl]carbamate (VII) which has no Si N
bond, with a mixture of chlorosilane I with hexa-
1070-3632/03/7310-1539$25.00 2003 MAIK Nauka/Interperiodica

1540
KIRILIN et al.
methyldisilazane would be expected [in view of
schemes (1) and (2)] to involve no transacylation by
the nitrogen atom and give compound VIII. However,
the reaction product was carbamate IX.
O
Me3SiOCH2CH2NHCOSiMe2CH2Cl
O
VIII
I
Me3SiOCH2CH2NHCOSiMe3
Me3SiCl
O
VII
Me3SiOCH2CH2NCOSiMe2CH2Cl
Si(CH3)2CH2Cl
IX
As O-silylurethanes RNHC(O)OSiMe3 are known
to fail to undergo siliconmethylation by the trimethyl-
siloxycarbonyl carbonyl and NH groups [6], we can
the starting O-silylurethane VII to give compound XI
whose transsilylation with chlorosilane I gives rise to
compound IX. The second (route b) involves initial
propose two possible routes of formation of compound N-silylation of O-silylurethane VII, yielding compound
IX [scheme (3)]. The first (route a) involves initial for-
mation of disilazane X; the latter effects N-silylation of
II, with subsequent double transsilylation of the latter
with chlorosilane I to form compound IX.
Scheme 3.
Me
ClCH2SiNHSiMe3
Me
a
VII
Me3SiCl
Me
O
HN(SiMe3)2
Me3SiOCH2CH2NHCOSiMe3 + ClCH2SiCl
Me
X
O
b
I
Me3SiOCH2CH2NCOSiMe3
SiMe3
NH3
O
I
Me3SiOCH2CH2NCOSiMe3
IX
Me2SiCH2Cl
XI
By performing the above reaction with per-
silylated hydroxycarbamic acid V which has no
N H bond we expected, like with chlorosilane I
[Scheme (2)], to obtain biscarbamate VI. Contrary
to expectations, a transsilylation product XII was
isolated.
O
O
Me3SiONCOSiMe3 + I/HN(SiMe3)2
Me3SiONCOSiMe3
Me3SiCl
MeSiMe
CH2
SiMe3
Cl
XII
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 10 2003

REACTION OF CHLORO(CHLORODIMETHYL)DIMETHYLSILANE
1541
The formation of compounds IX and XII was
proved by elemental analysis and H NMR spectral
data, as well as by the isolation of their hydrolysis
products, O-trimethylsilyl derivatives of monoethanol-
amine and hydroxylamine (compounds XIII and XIV,
respectively).
1
IX
Me3SiOCH2CH2NH2 + (ClCH2SiMe2)2O
XIII
H2O
CO2
Me3SiONH2 + (ClCH2SiMe2)2O + (Me3Si)2O
XII
XIV
The decreased reactivity of compounds V and VII
is apparently explained by fact that their basicity is
decreased by the introduction in their molecules of a
(chloromethyl)dimethylsilyl group. The decreased
basicity, in its turn, is associated with enhanced
double bonding between the oxygen atom of the tri-
methylsiloxy group and the carbonyl carbon atom in
XII compared with XI which has a Me3SiOCH2CH2
group at the nitrogen atom. This occurs because the
relative effect of silicon and carbonyl carbon atom on
oxygen unshared p electrons depends the degree of
double bonding between N and C, which in the case
of Me3SiO substituents (compound XII) that decrease
the nucleophilicity of the nitrogen atom is lower than
in the case of Me3SiOCH2CH2 (compound XI).
Me
Me
Si
O=CNHNH(CH2SiMe2Cl)2
O=CNHNH
Me
XVII
O
H2O
Si
Me
N
N
XVI
EXPERIMENTAL
The IR spectra were recorded on a Specord IR-75
instrument. The 1H NMR spectra were obtained
on a Bruker WP-80 instrument (80 MHz), solvent and
internal reference C6D6.
Gas shromatography was performed on a Shimadzu
G-8A chromatograph using a stainless-steel column
(1500 3 mm) packed with SE-30 on Chromaton
N-AW, carrier gas helium (40 cm3/min). Injector
temperature 200 C, detector temperature 180 C. The
oven temperature was linearly programmed from
50 to 150 C at a rate of 8 deg/min.
Me3Si
O
O
O
>
N
C
^
| SiMe3
ClCH2SiMe2
^
Quite a different reaction pathway with the chloro-
silane I hexamethyldisilazane system is characteristic
of isonicotinic hydrazide (XV) because of the pre-
sence in its molecule of an NH2 group and lack of
Me3SiOC(O).
(Chloromethyl)dimethylsilyl N-(chloromethyl-
dimethylsilyl)-N-[2-(trimethylsiloxy)ethyl]car-
bamate (IX). To a mixture of 23.5 g of trimethylsilyl
N-[2-(trimethylsiloxy)ethyl]carbamate and 12.16 g of
hexamethyldisilazane we added with stiring 26.96 g
of chloro(chloromethyl)dimethylsilane, and the
mixture was refluxed for 2 h. After cooling, the reac-
tion mixture was kept in a vacuum (10 mm) for 1 h at
20 C, filtered, and distilled to obtain 27.96 g (76%)
of compound IX, bp 80 81 C (4 mm), n2D0 1.4633. IR
O=CNHNH2
O=CNHNH(CH2SiMe2Cl)2
I/HN(SiMe3)2
N
XV
N
XVI
1
spectrum, cm : 1620 [ (C=O)]. Found, %: C 35.76;
H 7.79; Cl 17.56; N 4.01; Si 22.78. C12H29Cl2NO3Si3.
Calculated, %: C 36.91; H 7.49; Cl 18.16; N 3.59; Si
21.58.
This reaction, like reaction (1), involves consecu-
ive transsilylation and isomerization to give the
exhaustive siliconmethylation product XVI.
Trimethylsilyl N-[(chloromethyl)dimethylsilyl)]-
N-(trimethylsiloxy)carbamate (XII) was prepared in
a similar way from bis(trimethylsilyl) N-(trimethyl-
siloxy)carbamate. Yield 6.89 g (83%), bp 89 90 C
Taking into account that compound XVI is highly
reactive we did not attempt to isolate it pure and
hydrolyzed in situ to obtain compound XVII.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 10 2003

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KIRILIN et al.
(13 mm), n2D0 1.4443. IR spectrum, cm : 1650
1H NMR spectrum, , ppm: 0.2 s (12H, SiCH3),
2.48 s (4H, SiCH2). Found,%: C 48.65; H 6.99; N
14.26; Si 19.38. C12H21N3O2Si1. Calculated,%: C
48.78; H 7.16; N 14.22; Si 19.01.
1
1
[ (C=O)]. H NMR spectrum, , ppm: 0.058 s [6H,
Si(CH3)2], 0.079 s [9H, Si(CH3)3], 2.59 s (2H, SiCH2).
Found, %: Cl 10.63; Si 25.59. C10H26ClNO3Si3.
Calculated, %: Cl 10.81; Si 25.68.
REFERENCES
2-(Trimethylsiloxy)-1-ethanamine (XIII). To
4.65 g of O-silylurethane IX we added with stirring
a mixture of 0.51 g of water and 1.65 g of acetone,
and the reaction mixture was heated for 2 h at 60 C.
The organic layer was fractionated to isolate 1.76 g
(93%) of compound XIII, bp 134 135 C, n2D0 1.4166.
1. Kirilin, A.D., Belova, L.O., Lakhtin, V.G., and Cherny-
shev, E.A., Zh. Obshch. Khim., 2002, vol. 72, no. 12,
p. 2025.
2. Sheludyakov, V.D., Shukyurov, A.Kh., Kirilina, N.I.,
Sokova, N.B., and Kirilin, A.D., Zh. Obshch. Khim.,
1988, vol. 58, no. 1, p. 93.
1
IR spectrum, cm : 3320 and 1600 [ (NH2)] (publi-
shed data [7]: bp 132 133 C, n2D0 1.4170).
3. Sheludyakov, V.D. Lebedeva, A.B., Shukyurov, A.Kh.,
and Kirilin, A.D., Zh. Obshch. Khim., 1986, vol. 56,
no. 6, p. 1308.
O-(Trimethylsilyl)hydroxylamine (XIV) was ob-
tained in a similar way from O-silylurethane XII.
Yield 3.45 g (91%), bp 98 100 C, n2D0 1.4051 (pub-
lished data [8]: bp 98 100 C, n2D0 1.4050).
4. Sheludyakov, V.D., Kirilina, N.I., Kuznetsova, M. G.,
Kisin, A.V., and Kirilin, A.D., Zh. Obshch. Khim.,
1981, vol. 51, no. 8, p. 1824.
N-(2,2,6,6-Tetramethyl-1,4,2,6-oxazadisilynan-4-
yl)isonicotinamide (XVII). To a mixture of 7.10 g of
isonicotinic hydrazide, 7.10 g of hexamethyldisilazane,
and 50 ml of absolute toluene we added with stirring
15.67 g of chloro(chloromethyl)dimethylsilane, and
the mixture was refluxed for 2 h. The reaction mixture
was treated (with cooling with water) with a solution
of sodium hydrocarbonate in 200 ml of water and
stirred for 1 h. Yield 15.49 g (95%), mp 113 115 C.
5. Sheludyakov, V.D., Kotrikadze, E.L., and Kirilin, A.D.,
Zh. Obshch. Khim., 1984, vol. 54, no. 5, p. 1134.
6. Kirilin, A.D., Doctoral (Chem.) Dissertation, Moscow,
1991, p. 46.
7. Andrianov, K.A. and Volkova, L.M., Izv. Akad. Nauk
SSSR, Ser. Khim., 1957, no. 5, p. 577.
8. Duboudin, F., Frainnet, E., Vincon, G., and Dabscat, F.,
1
IR spectrum, cm : 1640 [ (C=O)] and 3350 [ (NH)].
J. Organomet. Chem., 1974, vol. 82, no. 1, p. 41.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 10 2003