Reactions of organochlorosilanes with chloro-and organogermanes in the presence of aluminum chloride

Article abstract of DOI:10.1134/S1070363206100100

The effect of substituents at the silicon and germanium atoms in reactions of organochlorosilanes with chloro-and organogermanes in the presence of aluminum chloride was studied. The only occurring process is the exchange of the chlorine atoms at Ge for the phenyl groups from Si; an increase in the number of methyl groups or chlorine atoms at Si promotes formation of phenyltrichlorogermane, and an increase in the number of phenyl groups or replacement of the chlorine atom at the Si atom by hydrogen leads to the formation of di-and triphenylchlorogermanes. Neither phenyl nor other radicals are transferred back from Ge to Si in the course of reactions of phenylgermanes with methylchlorosilanes in the presence of aluminum chloride; the only occurring processes are the exchange of the phenyl or methyl radicals bonded to Ge for the Cl atom bonded to Al and the disproportionation of phenylchlorogermanes. Nauka/Interperiodica 2006.

Full text of DOI:10.1134/S1070363206100100

ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 10, pp. 1564 1570.
Pleiades Publishing, Inc., 2006.
Original Russian Text V.I. Zhun’, I.V. Sbitneva, A.N. Polivanov, E.A. Chernyshev, 2006, published in Zhurnal Obshchei Khimii, 2006, Vol. 76, No. 10,
pp. 1631 1637.
Reactions of Organochlorosilanes with Chloro-
and Organogermanes in the Presence of Aluminum Chloride
V. I. Zhun’, I. V. Sbitneva, A. N. Polivanov, and E. A. Chernyshev
State Research Institute of Chemistry and Technology of Organoelement Compounds,
shosse Entuziastov 38, Moscow, 111123 Russia
e-mail: postmaster@chimex.msk.ru
Received April 21, 2006
Abstract The effect of substituents at the silicon and germanium atoms in reactions of organochlorosilanes
with chloro- and organogermanes in the presence of aluminum chloride was studied. The only occurring
process is the exchange of the chlorine atoms at Ge for the phenyl groups from Si; an increase in the number
of methyl groups or chlorine atoms at Si promotes formation of phenyltrichlorogermane, and an increase in
the number of phenyl groups or replacement of the chlorine atom at the Si atom by hydrogen leads to the
formation of di- and triphenylchlorogermanes. Neither phenyl nor other radicals are transferred back from Ge
to Si in the course of reactions of phenylgermanes with methylchlorosilanes in the presence of aluminum
chloride; the only occurring processes are the exchange of the phenyl or methyl radicals bonded to Ge for the
Cl atom bonded to Al and the disproportionation of phenylchlorogermanes.
DOI: 10.1134/S1070363206100100
The exchange of chlorine for phenyl radical on
heating a mixture of germanium tetrachloride and
methylphenyldichlorosilane in the presence of AlCl3
was discovered and studied by E.A. Chernyshev et al.
[1 4]. Later we examined the possibility of perform-
ing this reaction in the presence of not only AlCl3 but
also halides of other elements, exhibiting the proper-
ties of Lewis acids, and also the effect of substituents
at the Si atom, temperature, and amount of the cata-
lyst on the reaction course [5, 6]. A study of the effect
of substituents at Si on the direction of the reaction
formation of phenyltrichlorogermane, and a decrease
in its amount favors predominant formation of di- and
triphenylchlorogermanes. The optimal amount of the
catalyst, at which the total yield of phenylgermanes
reaches 80 90%, and the yield of diphenyldichloro-
germane (desired product) exceeds 60% is 5 10 wt %.
In the reaction of tetraphenylsilane with GeCl4, we
also detected the formation of triphenylchloroger-
mane. The replacement of chlorine atoms at Si by
methyl groups decreases the activity of phenylsilane
in the reaction under consideration. Me3SiPh appeared
to be the most inert (Table 2). With this reagent, even
at a catalyst content as high as 10 wt %, the starting
GeCl4 is not consumed. Successive replacement of the
chlorine atoms at Si by phenyl groups enhances the
activity of methylphenylsilanes (the reaction starts at
a lower content of AlCl3 in the reaction mixture) and
increases the yield of di- and triphenylchlorogermanes
from 26% with Me2SiPh2 to 55% with MeSiPh3.
The yield of Ph3GeCl in the reaction with MeSiPh3
reaches 13%. Methylphenylchlorosilanes are more
active in the reaction than chlorine-free methylphenyl-
silanes (Table 2); diphenyldichlorogermane is formed
in a yield of up to 70%.
of organochlorosilanes RnR1kSiCl4
(R, R1 = H,
n
k
methyl, chloromethyl, vinyl, allyl, phenyl; n, k = 1 3)
with germanium tetrachloride in the presence of alu-
minum chloride showed that the activity of organo-
silanes and the reaction direction are determined not
only by the amount of AlCl3 in the reaction mixture
[5, 6], but also by the substituents at Si. For example,
the reaction of PhSiCl3 with GeCl4 gave phenyltri-
chlorogermane as the only Ge-containing product
(yield up to 90%), irrespective of the reactant ratio
and the catalyst amount, which was varied in a wide
range. Diphenyldichlorogermane was formed in the
reaction of GeCl4 with diphenyldichlorosilane, tri-
phenylchlorosilane, and tetraphenylsilane (Table 1).
With an increase in the molar ratio of phenylchloro-
silane to GeCl4, the yield of diphenyldichlorogermane
increases, but the trend noted in [5] is preserved:
An increase in the amount of the catalyst leads to the
Replacement of the Cl atom at Si by the ethoxy
group suppresses the exchange of substituents bet-
ween the Si and Ge atoms. At the same time, replace-
ment of the Cl atom at Si by the H atom enhances the
1564

REACTIONS OF ORGANOCHLOROSILANES
1565
Table 1. Reaction of phenylchlorosilanes with GeCl4 in the presence of AlCl3 (110 120 C, 3 h)
Starting
silane
Silane: GeCl4
molar ratio
AlCl3,
wt%
GeCl4
conversion, %
PhGeCl3
yield, %
Ph2GeCl2
yield, %
Ph2SiCl2
Ph2SiCl2
Ph2SiCl2
Ph2SiCl2
Ph2SiCl2
Ph2SiCl2
Ph2SiCl2
Ph2SiCl2
Ph3SiCl
Ph3SiCl
Ph3SiCl
Ph3SiCl
Ph3SiCl
Ph3SiCl
Ph3SiCl
Ph3SiCl
Ph3SiCl
Ph3SiCl
Ph4Si a
1
1
1
1
2
2
2
2
1
1
1
1
1
1
2
2
3
3
1
1
1
1
2.5
5
10
20
2.5
5
7.5
10
5
7.5
10
15
20
30
5
44
81
87
92
54
84
88
86
4
67
84
87
80
89
50
72
58
91
42
74
97
97
16
74
79
90
25
7
4
54
67
50
34
7
64
60
49
21
3
49
72
55
88
11
45
33
14
14
36
51
23
33
57
80
10
5
10
15
20
25
30
3
28
64
83
Ph4Si
Ph4Si
Ph4Si
a
Ph GeCl is also formed (yield 26%).
3
Table 2. Reaction of methylphenyl- and methylphenylchlorosilanes with GeCl4 in the presence of AlCl3 (110 120 C,
3 h, molar ratio silane : GeCl4 = 1 : 1)
Starting
silane
AlCl3,
wt%
GeCl4
conversion, %
PhGeCl3
yield, %
Ph2GeCl2
yield, %
Ph3GeCl
yield, %
Me3SiPh
15
10
15
20
7.5
10
15
20
25
30
1
16
29
50
65
25
90
88
81
86
91
35
49
59
65
75
83
89
15
80
97
80
0.1
6
22
41
0.18
6
22
21
6
71
59
57
55
52
26
31
35
34
25
19
1
0.22
11
4
0.4
8
Me2SiPh2
Me2SiPh2
Me2SiPh2
MePh2SiCl
MePh2SiCl
MePh2SiCl
MePh2SiCl
MePh2SiCl
MePh2SiCl
MePhSiCl2
MePhSiCl2
MePhSiCl2
MePhSiCl2
MePhSiCl2
MePhSiCl2
MePhSiCl2
MeSiPh3
18
22
24
29
36
3
16
23
26
44
62
86
1
2.5
5
7.5
10
15
20
15
20
25
30
13
2
MeSiPh3
MeSiPh3
MeSiPh3
15
42
56
53
26
24
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 10 2006

1566
ZHUN’ et al.
Table 3. Reaction of phenylhydrosilanes with GeCl4 in the presence of AlCl3 (110 120 C, 3 h, molar ratio silane : GeCl4 =
1 : 1)
Starting
silane
AlCl3,
wt%
GeCl4
conversion, %
PhGeCl3
yield, %
Ph2GeCl2
yield, %
Ph3GeCl
yield, %
Me2PhSiH
Me2PhSiH
Me2PhSiH
Me2PhSiH
MePhSiHCl
MePhSiHCl
MePhSiHCl
MePh2SiH
MePh2SiH
MePh2SiH
MePh2SiH
Ph3SiH
2.5
5
10
20
5
10
20
2.5
5
10
20
1
40
50
50
51
46
56
60
55
60
62
64
5
13
26
29
45
8
38
43
8
15
17
21
6
31
9
7
3
9
42
30
34
45
0.6
60
62
52
35
2
11
7
17
18
19
3
6
8
5
Ph3SiH
Ph3SiH
Ph3SiH
Ph3SiH
2.5
5
10
20
89
90
94
94
5
6
15
58
reactivity of the silane: Exchange starts at a lower
amount of the catalyst in the mixture.
ClCH2SiPhnClkMe3 n + GeCl4
1 15% AlCl3
PhGeCl3 + Ph2GeCl2 + Ph3GeCl,
PhnClkMe3 n+kSiH + GeCl4
n = 1 3.
AlCl3
PhGeCl3 + Ph2GeCl2 + Ph3GeCl,
The reaction of (chloromethyl)dimethylphenylsilane
with GeCl4 yields exclusively phenyltrichloroger-
mane, irrespective of the AlCl3 content. At the same
time, with chloromethyltriphenylsilane, diphenyldi-
chlorogermane and triphenylchlorogermane are also
formed (Table 4). We found that the reactivity of
ClCH2SiPh3 toward GeCl4 is comparable to that of
Ph3SiCl. This fact suggests that the reaction of
ClCH2SiPh3 with GeCl4 initially involves its decom-
position to the corresponding phenylchlorosilane
which is the actual reactive species in the reaction
with GeCl4 in the presence of AlCl3:
n = 1 3, k = 0 2.
An increase in the activity of phenylhydrosilanes
is also manifested in the fact that, whereas the reac-
tion of GeCl4 with phenyldichlorosilane yields phen-
yltrichlorogermane irrespective of the amount of
AlCl3 in the reaction mixture, in the reactions of
MePhClSiH and Me2PhSiH with the system GeCl4
AlCl3, the reaction products also contain Ph2GeCl2
and even Ph3GeCl (Table 3). These products were
formed in the reactions of GeCl4 with phenylchloro-
silanes only when the starting phenylchlorosilane con-
tained two or more phenyl groups. Apparently, the
hydrogen atom at Si exerts an activating effect on the
exchange PhSi/ClGe.
AlCl3
ClCH2SiPh3
ClSiPh3.
To assess the applicability of this method to the
synthesis of alkenyl- and alkylgermanes, we studied
the behavior in this reaction of silanes with other
substituents containing -electron systems (vinyl and
allyl groups) and p-electron pairs capable of interac-
tion with the electron system of the aluminum atom,
e.g., chloromethyl groups.
Methyldiphenylsilane and triphenylsilane are the
most active in the reaction with GeCl4. As seen from
Table 3, in the reaction of Ph3SiH with GeCl4, at an
AlCl3 content of 2.5%, the yield of Ph2GeCl2 reaches
60%, and with methyldiphenylsilane it reaches 40%.
On the contrary, replacement of the Cl atom at Si by
the chloromethyl group decreases the reactivity of
phenylsilanes toward GeCl4. With chloromethylphen-
ylsilanes, only phenylgermanes are formed:
We found that, in the reaction of chloroalkylchloro-
silanes with the system GeCl4 AlCl3, the radicals are
not transferred from the Si to Ge atom; only products
of decomposition of chloromethyl group are formed:
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 10 2006

REACTIONS OF ORGANOCHLOROSILANES
1567
atom for chlorine, occurring apparently under the ac-
tion of AlCl3:
0.5 10% AlCl3
ClCH2SiR3 + GeCl4
ClSiR3
AlCl3
GeCl4/ClCH2SiR3
1
Yield of ClSiR3, %
0.4 8
Me2PhSiVin + GeCl
Me2PhSiCl,
Yield of Me2PhSiCl, %
11 15
GeCl4/Me2PhSiVin
0
0.2 3
1
0
0.6 39
ClCH2Me2SiCl appeared to be the most active in
this reaction, and ClCH2SiCl3, the least active.
(C7H15)3SiVin + GeCl4
15 50% AlCl3
(C7H15)3SiCl + (C7H15)2SiCl2.
In the presence of the system GeCl4 AlCl3 or of
AlCl3 only, chloromethyltriethoxysilane formed ap-
preciable amounts of bis(triethoxysilyl)ethane:
11 54%
79 15%
Also we detected products of exchange of the or-
ganic radicals at Si (Vin/Ph and Me/Ph exchange):
(EtO)3SiCH2Cl + GeCl4
1 15% AlCl3
(EtO)3SiCH2CH2Si(EtO)3.
AlCl3
Me2PhSiVin + GeCl4
MeSiPh3
0.2 19%
GeCl4/Me2PhSiVin
Yield of MeSiPh3, %
1
0
0 9
2 3
Apparently, the presence of AlCl3 rather than
GeCl4 is the major factor governing the transforma-
tions of chloromethylorganosilanes.
Allylsilanes, like vinylsilanes, react with the sys-
tem GeCl4 AlCl3. However, with allylphenylsilanes,
we have not detected even products of exchange of the
phenyl group at Si for the Cl atom from Ge, as was
observed with vinylphenylsilanes. Allylgermanes were
not detected either. The major products detected pre-
sumably originate from the following reactions.
Experiments on reactions of vinyl- [VinPhSiCl2,
Vin4Si, Vin2SiPh2, Me2PhSiVin, (C7H15)3SiVin] and
allylsilanes (Me2VinSiAll, MePh2SiAll, Ph2SiAll2,
MeSiAll3, PhSiAll3, VinSiAll3) with GeCl4 showed
that the exchange of substituents between the Si and
Ge atoms occurs only with vinylphenyldichlorosilane,
and only the phenyl group is transferred. The yield of
phenyltrichlorogermane decreased with an increase in
the AlCl3 content. Vinylgermanes were not detected.
(1) Exchange of the allyl and vinyl groups at Si
for chlorine:
VinPhSiCl2 + GeCl4
AlCl3
AlCl3
PhGeCl3 + VinSiCl3.
Ph2SiAll2 + GeCl
Ph2SiAllCl
Yield of Ph2SiAllCl, %
18 69
60 25%
GeCl4/Ph2SiAll2
1
0
In addition, the reaction mixture contained products
of exchange of the phenyl or vinyl group at the Si
21 23
Table 4. Reaction of vinylphenylchlorosilane and chloromethyltriphenylsilane with GeCl4 in the presence of AlCl3
(110 120 C, 3 h, molar ratio silane : GeCl4 = 1 : 1)
Starting
silane
AlCl3,
wt%
GeCl4
conversion, %
PhGeCl3
yield, %
Ph2GeCl2
yield, %
Ph3GeCl
yield, %
ClCH2SiPh3
ClCH2SiPh3
ClCH2SiPh3
ClCH2SiPh3
ClCH2SiPh3
ClCH2SiPh3
VinPhSiCl2
VinPhSiCl2
VinPhSiCl2
VinPhSiCl2
2.5
5
16
63
91
100
91
100
71
27
36
36
2
50
56
29
56
29
11
3
7
35
71
35
71
60
25
27
27
10
15
10
15
5
15
25
25
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 10 2006

1568
ZHUN’ et al.
We noted that the vinyl group is eliminated more
readily than the allyl group. With vinyltriallylsilane,
the major reaction product is triallylchlorosilane:
react with methylchlorosilanes in the presence of
AlCl3; only the starting reactants are detected in the
reaction mixture.
0.2 1% AlCl3
The reactions of Ph2GeCl2 and Ph3GeCl with
methylchlorosilanes result in elimination of the phenyl
group from the Ge atom and formation of the corre-
sponding chlorogermanes (see example below):
VinSiAll3
AllSiCl.
(3 8%)
(2) Disproportionation of phenylchlorosilanes
formed by elimination of the allyl group:
1 20% AlCl3
Ph2GeCl2 + MeSiCl3
PhGeCl3 + GeCl4.
12 93% 1 7%
AlCl3
MePh2SiAll2
MePh2SiCl
MeSiPh3 + MePhSiCl2.
Apparently, the phenyl group at Ge is exchanged
for the Cl atom from Al, because an increase in the
AlCl3 content in the reaction mixture results in in-
creased content of chlorogermanes.
(3) Formation of bissilylethanes:
Me2VinSiAll
A similar but more complex pattern is observed in
the reaction of dimethyldiphenylgermane with methyl-
chlorosilanes and SiCl4 (Table 5). In its reaction with
(Me2AllSiXH2)2 + (MeAll2SiCH2)2 + (All3SiCH2)2,
PhSiAll3
(Me2AllSiCH2)2 + (AllSiCH2)2.
MekSiCl4
or SiCl4, only the disproportionation
k
The products of similar transformations were de-
tected in reactions of methylphenylchlorosilanes with
GeCl4 in the presence of AlCl3 (see examples below).
products of methylphenylchlorogermanes are formed
(exchange Me/Cl, Ph/Cl, Me/Ph):
Me2GePh + MekSiCl4 k
(1) Ph/Cl exchange in chlorosilanes:
1 20% AlCl3
GeCl4 + Me2GePhCl + MePhGeCl2
AlCl3
MeSiPh3
MeSiPh2Cl + MePhSiCl2.
+ PhGeCl3 + Ph2GeCl2 + Ph3GeCl
+ MeGePh3 + Ph4Ge.
(2) Me/Ph exchange at the Si atom:
These products are formed by replacement of the
phenyl and methyl groups at Ge with Cl. However,
neither methylchloro- nor phenylchlorosilanes were
detected in the reaction mixture; therefore, apparently,
the phenyl group at Ge is exchanged for the Cl atom
from Al. This is confirmed by the fact that an increase
in the AlCl3 content leads to increased content of
chlorogermanes. It should be noted that the phenyl
and methyl groups are eliminated with approximately
equal probability, and the conversion depends only on
the catalyst amount. The exchange of radicals is more
pronounced at small amounts of AlCl3 (up to 10%).
At a higher content of AlCl3, the content of products
formed by replacement of the methyl and phenyl
groups at Ge by Cl increases.
AlCl3
Me3SiPh
Me2SiPh2.
(3) Exchange of H atom in hydrosilane for Cl:
AlCl3
Me2PhSiH
Me2PhSiCl.
(4) Exchange of H atom in hydrosilane for phenyl
group:
2MePh2SiH
MeSiPh3 + MePhSiH2.
Comparison of the compositions of the product
mixtures from the reactions of methylphenylchloro-,
vinyl-, and allylsilanes with the system GeCl4 AlCl3
and from the reactions of these compounds with AlCl3
in the absence of GeCl4 under similar conditions
shows that, as a rule, GeCl4 affects the degree of
conversion of the reactants, i.e., it affects the reaction
course.
Thus, the study of the reaction of phenylchloroger-
manes with silicon tetrachloride and methylchloro-
silanes in the presence of AlCl3 showed that the back
transfer of phenyl or other radicals from the Ge atom
to the Si atom does not occur. No phenyl derivatives
of silicon were detected in the reaction mixture. In the
reactions of phenylchlorogermanes or dimethyldi-
phenylgermane with methylchlorosilanes and SiCl4,
the final products contained only compounds formed
by the exchange of the phenyl or methyl radical at Ge
Thus, only phenyl group at Si is capable of replac-
ing Cl at Ge. Therefore, it was interesting to examine
the possibility of back transfer of substituents from Ge
to Si.
We found that phenyltrichlorogermane does not
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REACTIONS OF ORGANOCHLOROSILANES
1569
Table 5. Reaction of dimethyldiphenylgermane with methylchlorosilanes of the general formula MekSiCl4 (k = 0 3) in
k
the presence of AlCl3 (110 120 C, 3 h, molar ratio MekSi4 k/Me2GePh2 = 1 : 1)
Reaction mixture composition, wt %
MekSiCl4 k
k = 0 3
,
AlCl3,
wt%
LB*a GeCl4 Me2GePh2
Me2PhGeCl MePhGeCl2
PhGeCl3
MePh3GeCl
2.3
MeSiCl3
1
27.8
36.4
38.3
24.5
32.5
28.7
34.9
28.8
24.3
37.4
35.2
41.8
1.1
35.5
35.9
6.7
14.4
23.2
11.2
9.4
8.4
4.1
9.4
21.6
8.8
0.8
7.4
10.3
MeMeSiCl3
MeMeSiCl3
MeMe2SiCl2
MeMe2SiCl2
MeMe2SiCl2
MeMe3SiCl
Me3SiCl
Me3SiCl
SiCl4
SiCl4
SiCl4
10
20
1
10
20
1
10
20
1
10
20
2.7
6.7
5.1
6.1
4.8
1.7
3.5
4.1
10.6
11.7
18.2
22.8
29.7
16.4
10.8
3.0
6.2
2.8
23.9
12.1
2.3
31.3
4.2
4.6
1.1
0.4
2.2
11.0
Reaction mixture composition, wt %
MekSiCl4 k
k = 0 3
,
AlCl3,
wt%
Ph2GeCl2
Ph3GeMe
Ph4Ge
Ph3GeCl
4.9
MeSiCl3
MeSiCl3
MeSiCl3
Me2SiCl2
Me2SiCl2
Me2SiCl2
Me3SiCl
Me3SiCl
Me3SiCl
SiCl4
1
10
20
1
10
20
1
10
20
1
10
20
54.9
0.3
1.3
4.6
10.2
9.8
1.7
7.2
39.3
19.2
9.8
3.8
1.6
4.6
2.1
8.0
6.1
5.1
18.3
4.0
23.0
0.5
2.1
18.0
SiCl4
SiCl4
14.4
22.8
8.6
a
Low-boiling products, including benzene.
for the Cl atom from AlCl3, and also the products of
disproportionation of phenylchlorogermanes.
A 50-ml reaction flask was charged with 0.1 mol of
the starting chlorosilane and calculated amount of
phenylchlorogermane or dimethyldiphenylgermane.
The reactant ratio was 1 : 1. Then the calculated
amount of AlCl3 was added. The mixture was heated
at 110 120 C for 3 h. After cooling, the mixture was
analyzed by GLC. The products were identified by
retention times using authentic samples.
EXPERIMENTAL
Reaction of organochlorosilanes with tetrachlo-
rogermane in the presence of aluminum chloride.
A 50-ml reaction flask was charged with 0.1 mol of
the starting organosilane, 0.1 mol (molar ratio 1 : 1)
or 0.05 mol (2 : 1) of tetrachlorogermane, and the
calculated amount of AlCl3. The mixture was heated
at 110 120 C for 3 h. After cooling, the mixture was
analyzed by GLC. The products were identified by re-
tention times using authentic samples.
The reaction mixtures and products were analyzed
by gas liquid chromatography on an LKhM-80 chro-
matograph under the following conditions: metallic
column (1000 3 mm), stationary phase 5% SE-30
on Chromosorb G/AW-DMCS (particle size 0.15
0.18 mm), programmed heating from 50 to 290 C at
1
Reaction of phenylgermanes with chlorosilanes.
a rate of 8 deg min , injector temperature 320 C,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 10 2006

1570
ZHUN’ et al.
thermal conductivity detector (detector temperature
300 C, current 90 mA), carrier gas He (flow rate
30 ml min ).
3. Lakhtin, V.G., Yakovleva, M.V., and Chernyshev, E.A.,
Available from VINITI, Moscow, 2002, no. 2071-
V2002.
1
4. Lakhtin, V.G., Kurakaeva, N.A., Mit’ko, A.A., Pyato-
va, Yu.I., and Chernyshev, E.A., Available from
VINITI, Moscow, 2003, no. 1850-V2003.
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