Alkoxylation of 1,2-bis(methylchlorosilyl)ethylenes and -acetylenes

Article abstract of DOI:10.1023/A:1013225112569

Reactions of a series of 1,2-bis(methylchlorosilyl)ethylenes and -acetylenes Me_nCl_3-nSi-Z-SiCl_3-nMe_n (Z = CH=CH, C=C; n = 0-2) with ethanol and acetoxime were studied. Novel alkoxy-and isopropylideneaminooxysilanes were obtained and characterized. A relation was found between the activity of Si-Cl bonds in the reactions studied and the structure of the carbon-carbon bridge.

Full text of DOI:10.1023/A:1013225112569

Russian Journal of General Chemistry, Vol. 71, No. 8, 2001, pp. 1252 1254. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 8, 2001,
pp. 1326 1328.
Original Russian Text Copyright
2001 by Lakhtin, Nosova, Kisin, Ivanov, Chernyshev.
Alkoxylation of 1,2-Bis(methylchlorosilyl)ethylenes
and -Acetylenes
V. G. Lakhtin, V. M. Nosova, A. V. Kisin, P. V. Ivanov, and E. A. Chernyshev
Gosudarstvennyi nauchno-issledovatel’skii institut khimii i tekhnologii elementoorganicheskikh soedinenii
State Research Center of the Russian Federation, Moscow, Russia
Received April 3, 2000
Abstract Reactions of a series of 1,2-bis(methylchlorosilyl)ethylenes and -acetylenes MenCl3 nSi
Z SiCl3 nMen (Z = CH=CH, C C; n = 0 2) with ethanol and acetoxime were studied. Novel alkoxy- and
isopropylideneaminooxysilanes were obtained and characterized. A relation was found between the activity of
Si Cl bonds in the reactions studied and the structure of the carbon carbon bridge.
In our previous studies on thermal reactions
between hydrosilanes and chlorinated ethylenes [1, 2]
we obtained a series of known and novel symmetrical
1,2-bis(methylchlrosilyl)ethylenes and -acetylenes.
Replacement in such compounds of chlorine atoms
by alkoxy and isopropylideneaminooxy groups may
the reactions give as by-products the corresponding
alkyl chlorides RCl and high-boiling siloxane pro-
ducts; quantitative analysis of these by-products was
not performed because of their very low contents.
Moreover, alkyl chlorides were all the time removed
from the reaction mixtures together with CH2Cl2,
open the way to previously unknown carbofunctional which complicated their quantitative analysis. Most
alkoxy- and isopropylideneaminooxysilanes. These emphasis was given to ensuring indentical reaction
compounds are of practical interest as coupling agents, conditions (see Experimental) and determining exact
catalysts for cold curing of silicon rubbers, as well as
chain-extending agents. Hydrolysis of such monomers
may give novel polymeric materials with various
degrees of branching and containing unsaturated
fragments Si Z Si (Z = CH=CH; C C).
yields and characterizing the target products.
To gain a better insight into the relationship
between the nature of the carbon carbon bridge
between the silicon atoms and the activity of Si Cl
bonds, we studied reactions with ethanol of related
symmetrical 1,2-bis(methylchlorosilyl)ethanes. The
resulting data are listed in Table 1.
In the present work we studied reactions of 1,2-bis-
(methylchlorosilyl)ethylenes and -acetylenes with
ethanol and acetoxime, with the aim to prepare and
identify novel carbofunctional silanes. We also tried
to correlate the structure of the molecules (in parti-
cular, the nature of the carbon carbon bridge between
the silicon atoms, the number of chlorine atoms) and
their reactivity.
The data in Table 1 reveal two clearly defined
regularities: (1) increasing activity of Si Cl bonds in
the monomers studied with increasing number of
chlorine atoms in the molecules and decreasing
number of methyl groups and (2) increasing activity
of Si Cl bonds with increasing electron density on the
carbon carbon bridge between the silicon atoms.
All the reactions studied can be described by the
following general scheme:
Oximation of 1,2-bis(methylchlorosilyl)ethylenes
and -acetylenes was performed by another procedure
[3]. These reactions were performed with a double
excess of acetoxime which in this case acted both as
reagent and as HCl acceptor. The resulting data are
listed in Table 2.
MenCl3 nSi Z SiCl3 nMen + 2(3 n)ROH
CH2Cl2
Men(RO)3 nSi Z Si(OR)3 nMen
+ 2(3 n)HCl,
R = Et, Me2C=N; Z = CH=CH, C C; n = 0 2.
It is readily seen from Table 2 that hexa- and tetra-
oxime derivatives XI, XII, XIV, and XV are formed
in lower yields than dioxime derivatives X and XIII.
However, the reactions went to completion, and the
relative activities of Si Cl bonds were impossible to
The reactions with ethanol were performed in boil-
ing methylene chloride with its simultaneous distilla-
tion, which allowed us to effectively remove the HCl
formed. Gas-chromatographic analysis showed that
1070-3632/01/7108-1252$25.00 2001 MAIK Nauka/Interperiodica

ALKOXYLATION OF 1,2-BIS(METHYLCHLOROSILYL)ETHYLENES AND -ACETYLENES
1253
compare. Moreover, the hexa- and tetraoxime deriva-
tives proved crystalline substances. For isolation we
had to recrystallize them from a toluene hexane
mixture, which produced inevitable losses. Therefore,
the low yields of XI, XII, XIV, and XV may well be
associated with this recrystallization. Here one can
only note slightly better yields of acetylenic mono-
mers compared with ethylenic.
Table 1. Reaction of 1,2-bis(methylchlorosilyl)ethanes,
-ethylenes, and -acetylenes with ethanol
Reaction product
Comp.
Yield, %
no.a
Si(OR)3 nMen
Z
I
II
Si(OEt)Me2
Si(OEt)2Me
Si(OEt)3
Si(OEt)Me2
Si(OEt)2Me
Si(OEt)3
Si(OEt)Me2
Si(OEt)2Me
Si(OEt)3
CH2CH2
CH2CH2
CH2CH2
CH=CH
CH=CH
CH=CH
C C
8
67
86
32
74
92
86
89
94
Tables 3 5 list the physicochemical constants,
III
IV
V
VI
VII
VIII*
IX
1
elemental analyses, and H NMR spectra of newly
synthesized compounds.
EXPERIMENTAL
C C
C C
1
The H NMR spectra were measured on a Varian
T-60A spectrometer for neat liquids or CCl4 solutions.
The internal references were TMS and cyclohexane.
a
Here and hereinafter, stars label newly synthesized compounds.
Gas chromatography was performed on an LKhM-
72 spectrometer with a thermal conductivity detector,
column 2000 3 mm, packing 15% PMS-20000 on
Chromaton N-AW, carrier gas helium, linear tempera-
ture programming at a rate of 12 deg/min.
Table 2. Reaction of 1,2-bis(methylchlorosilyl)ethylenes
and -acetylenes with acetoxime
Reaction product
Comp.
Yield, %
no.
Si(ONCMe2)3 nMen
Z
Alkoxylations of 1,2-bis(methylchlorosilyl)ethanes,
-ethylenes, and -acetylenes were performed in identical
conditions: in a four-necked flask (50 ml) equipped
with a stirrer, a thermometer, a dropping funnel,
and a Vigreux column with a head for distillation of
CH2Cl2. To a required amount of alcohol in 20 30 ml
of CH2Cl2 we added dropwise at 50 C over the course
of 30 min a solution of 0.1 mol of a chloride in
X*
Si(ONCMe2)Me2
Si(ONCMe2)2Me
Si(ONCMe2)3
CH=CH
CH=CH
CH=CH
C C
C C
C C
73
57
52
81
63
60
XI*
XII*
XIII* Si(ONCMe2)Me2
XIV* Si(ONCMe2)2Me
XV*
Si(ONCMe2)3
Table 3. Formulas, names, and physicochemical constants of the newly synthesized compounds VIII XV
Comp.
no.
bp,
(p, mm)
C
mp,
Ca
Formula
Name
VIIIb Me(EtO)2SiC CSi(OEt)2Me
1,2-Bis(diethoxymethylsilyl)acetylene
54 (3)
92 (1 2)
Xc
Me2(Me2CNO)SiCH=CHSi(ONCMe2)Me2 1,2-Bis[(isopropylideneaminooxy)dimethyl-
silyl]ethylene
Me(Me2CNO)2SiCH=CHSi(ONCMe2)2Me 1,2-Bis[bis(isopropylideneaminooxy)methyl-
silyl]ethylene
XI
69 71
95 97
XII (Me2CNO)3SiCH=CHSi(ONCMe2)3
XIII Me2(Me2CNO)SiC CSi(ONCMe2)Me2
XIV Me(Me2CNO)2SiC CSi(ONCMe2)2Me
1,2-Bis[tris(isopropylideneaminooxy)silyl]-
ethylene
1,2-Bis[isopropylideneaminooxy)dimethyl-
silyl]acetylene
1,2-Bis[bis(isopropylideneaminooxy)methyl-
silyl]acetylene
101 (1 2) 50 52
73 75
XV
(Me2CNO)3SiC CSi(ONCMe2)3
1,2-Bis[tris(isopropylideneaminooxy)silyl]-
acetylene
93 94
a
b
20
20
c
20
20
Solvent for crystallization: toluene hexane, 1:1.
d
0.9401, n 1.4220, MR : found 78.39, calculated 78.48.
d
0.9364, n
4 D
4
D
D
1.4610, MR : found 83.80, calculated 83.87.
D
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 8 2001

1254
LAKHTIN et al.
Table 4. Elemental analyses of the newly synthesized compounds VIII XV
Found, %
Calculated, %
N
Comp.
Formula
no.
C
H
N
O
Si
C
H
O
Si
VIII 49.60
8.88
9.12
7.95
7.51
8.38
7.48
7.11
22.23
11.16
12.70
18.31
11.57
15.77
18.96
19.45
19.54
14.26
10.65
19.58
14.10
10.68
C12H26O4Si2
49.66
50.35
50.00
46.69
50.70
48.24
46.87
8.96
9.09
8.33
7.39
8.45
7.54
7.03
22.07
11.19
12.50
18.67
11.27
16.08
18.75
19.31
19.58
14.58
10.89
19.72
14.07
10.93
X
XI
XII
50.38
49.10
46.39
9.80
14.47
16.10
9.65
14.36
16.55
C12H26N2O2Si2
C16H32N4O4Si2
C20H38N6O6Si2
C12H24N2O2Si2
C16H30N4O4Si2
C20H36N6O6Si2
9.79
14.58
16.34
9.86
14.07
16.40
XIII 49.82
XIV
XV
47.29
46.70
1
Table 5. H NMR chemical shifts ( , ppm) of compounds
VIII and X XVa
of toluene we added at 55 60 C a solution of 0.1 mol
of chlorosilane in 10 20 ml of toluene. The reaction
mixture was left to stand for 2 h at that temperature,
and the precipitate of acetoxime hydrochloride was
filtered off. Gaseous ammonia was barboted through
the filtrate to alkaline reaction. The mixture was
filtered, and the fitrate was fractionated to isolate the
final products. Compounds XI XV were obtained by
recrystallization from a 1:1 toluene hexane mixture.
Comp.
no.
CH=
Me2CN=O
MeSi
X
XI
XII
XIII
XIV
XV
6.74
6.68
6.75
1.78
1.83
1.83, 1.87
1.87
0.21
0.33
0.30
0.40
1.87
1.83
REFERENCES
1. Sheludyakov, V.D., Lakhtin, V.G., Zhun’, V.I., Shcher-
binin, V.V., and Chernyshev, E.A., Zh. Obshch. Khim.,
1981, vol. 51, no. 8, pp. 1829 1833.
a
Compound VIII, , ppm: 3.65 (CH O), 1.04 (Me), 0.03 (MeSi).
2
10 15 ml of CH2Cl2. The solvent was simultaneously
distilled off. The reaction mixture was fractionated to
isolate the final products.
2. Sheludyakov, V.D., Zhun’, V.I., Lakhtin, V.G., Turkel’-
taub, G.N., Bochkarev, V.N., Slyusarenko, T.F., No-
sova, V.M., Kisin, A.V., and Polyakova, M.V.,
Available from ONIITEKhim, Cherkassy, 1983,
no. 1060KhP D82.
Oximation of 1,2-bis(methylchlorosilyl)ethylenes
and -acetylenes with acetoxime was performed by the
following procedure. To a mixture of a required
amount of acetoxime (double excess) and 50 100 ml
3. USSR Inventor’s Certificate 724514, 1979, Byull.
Isobret., 1979, no. 12.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 8 2001