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
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