Reactions of Trichlorogermane and Trimethylgermane Etherates with 1,3-Divinyl-1,1,3,3-tetramethyldisiloxane

Article abstract of DOI:10.1134/S1070363220060067

Abstract: The effect of the reactant ratio in the reaction of tetramethyldisiloxane with germanium tetrachloride and diethyl ether on the structure and reactivity of the resulting trichlorogermane–diethyl ether complexes was studied, and the products were

Full text of DOI:10.1134/S1070363220060067

ISSN 1070-3632, Russian Journal of General Chemistry, 2020, Vol. 90, No. 6, pp. 968–976. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Obshchei Khimii, 2020, Vol. 90, No. 6, pp. 866–876.
Reactions of Trichlorogermane and Trimethylgermane Etherates
with 1,3-Divinyl-1,1,3,3-tetramethyldisiloxane
V. G. Lakhtina, A. I. Blagushinaa,*, N. V. Ushakovb,†, I. B. Sokolʼskayaa, I. A. Semyashkinaa,
D. A. Efimenkoa, I. A. Gritskovac, N. G. Komalenkovaa, and P. A. Storozhenkoa
a State Research Institute of Chemistry and Technology of Organoelement Compounds, Moscow, 105118 Russia
b Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, 199911 Russia
c MIREA—Russian Technological University, Moscow, 199454 Russia
*e-mail: n_blag@list.ru
Received January 19, 2020; revised January 19, 2020; accepted January 27, 2020
Abstract—The effect of the reactant ratio in the reaction of tetramethyldisiloxane with germanium tetrachloride
and diethyl ether on the structure and reactivity of the resulting trichlorogermane–diethyl ether complexes was
studied, and the products were reacted with 1,1,3,3-tetramethyl-1,3-divinyldisiloxane. The hydrogermylation of
1,1,3,3-tetramethyl-1,3-divinyldisiloxane with trimethylgermane in the presence of Karstedtʼs catalyst afforded
exclusively the corresponding anti-Markovnikov adducts at one and two double bonds of the substrate.
Keywords: etherate, trichlorogermane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, tetrachlorogermane, vinyl group,
siloxanes
DOI: 10.1134/S1070363220060067
Trichlorogermane is known to readily react with
unbranched olefins at normal temperature or at slightly
elevated temperature without a catalyst [1, 2]. The
reaction may take both hydrogermylation and double
germylation pathsways [3]. In the presence of ethers, a
complex of trichlorogermane with ether is formed, and it
reacts only according to the double germylation pathway
[1]. Trichlorogermane etherate reacts differently with
branched olefins, where the double bond is sterically
shielded. Olefinic substrates with a tert-butyl group
(carbon analog of trimethylvinylsilane) or four methyl
groups (tetramethylethylene) do not undergo double
germylation, and only usual germylation occurs [3].
Unlike trichlorogermane etherate, trimethylgermane
readily reacts with vinylsilanes [4].
estimating the stability of Si–O‒Si siloxane bonds in the
presence of highly reactive Ge–H bond. Symmetrical
divinyltetramethyldisiloxane 1 was used as vinyl-
substituted siloxane substrate in the hydrogermylation
with trichlorogermane etherate and trimethylgermane.
The reaction of dichlorogermylene–dioxane complex
C4H8O2·GeCl2 with methylsiloxanes follows several
pathways: (1) insertion of :GeCl2 into Si‒O bond, (2)
insertion of :GeCl2 into C‒H bond, and (3) exchange
of chlorine atoms on germanium for methyl groups
[5, 6]. Unlike the complex C4H8O2·GeCl2, which
generates dichlorogermylene, trichlorogermane etherate
(Cl3GeH·2Et2O) is capable of dissociating in two ways,
depending on the reaction medium and reactant nature;
and it can act as both source of dichlorogermylene and
hydrogermylating agent (Scheme 1).
In view of very low reactivity of unsubstituted double
bond toward hydrogermylation, in particular in the
hydrogermylation of vinylsilanes with trichlorogermane
etherate, and high reactivity of trimethylgermane
in these reactions [4], we studied the possibility of
selective hydrogermylation of vinyl groups on the
silicon atoms in siloxane structures with the goal of
The trichlorogermane–ether complex was prepared
according to the procedure described in [7], by mixing
tetramethyldisiloxane, tetrachlorogermane, and diethyl
ether at a ratio of 1:1:2. The mixture separates into layers,
where the bottom yellow oily material is trichlorogermane
Scheme 1.
GeCl3ꢀ
H+
+
† Deceased.
2
HGeCl3
:GeCl
HCl +
968

REACTIONS OF TRICHLOROGERMANE AND TRIMETHYLGERMANE ETHERATES
969
Scheme 2.
whereas addition of CDCl3 to B leads to separation of a
bright yellow solid. Therefore, the 1H NMR spectra of A
and B were recorded in DMSO-d6. When the amount of
tetramethyldisiloxane in the initial mixture was further
increased, germanium subchlorides precipitated even
during the synthesis.
Samples A and B reacted differently with compound
1. A light white suspension was formed in the reaction
with sample A, and no yellow solid separated throughout
the synthesis and subsequent fractional distillation of
the products. In contrast, bright orange germanium
subchlorides precipitated immediately after addition of
compound 1 to sample B.
etherate (2Et2O·HGeCl3)[7]. The structure of the complex
obtained directly from trichlorogermane and diethyl ether
was determined previously [8, 9].
While preparing trichlorogermane etherate according
to [7] we found that the yellow color of the bottom layer
is retained only at a reactant ratio of (0.5‒0.75) : 1 : 2
and that at a ratio of 1 : 1 : 2 the originally yellow color
changes to light red. The intensity ratios of the GeH,
Trichlorogermane etherate was assigned the structure
[Et2O→H←OEt2]+ GeCl3– [8, 9]. Presumably, at a
tetramethyldisiloxane‒GeCl4 ratio of >0.75 : 1, the
reduction of GeCl4 is not terminated after the first stage,
but it goes further to produce unstable dichlorogermane
etherate [Et2O→H←OEt2]GeCl2[Et2O→H←OEt2],
where GeCl2 resides in the liquid phase due to the
presence of ether; this complex rapidly decomposes
upon contact with other reagents to form germanium
subchlorides which precipitate from the mixture.
1
CH2, and CH3 signals in the H NMR spectra of both
products were approximately equal (1 : 8 : 12), which
corresponded to the complex 2Et2O·HGeCl3. In keeping
with the NMR data, the two diethyl ether molecules in
the complex are equivalent. Nevertheless, samples A and
B significantly differed from each other. In the spectrum
of A, the GeH proton resonated at δ ~10.5–10.6 ppm,
and signals of diethyl ether (CH2 quartet and CH3 triplet)
were observed at δ 3.9 and 1.6 ppm, respectively. In the
spectrum of B, the GeH signal shifted downfield to δ
13.2‒13.4 ppm, and the Et2O signals shifted upfield to
3.3 (CH2) and 1.1 ppm (CH3). Furthermore, the refractive
indices of samples A and B were nD20 = 1.491 and 1.545,
respectively. Complex A is readily soluble in CDCl3,
As we already noted, precipitation of yellow
germanium subchlorides was not observed in the reaction
of A with 1 (version a). After removal of diethyl ether
by distillation under atmospheric pressure, vacuum
distillation gave only a small amount of a liquid (~20 wt %
of the entire reaction mixture excluding diethyl ether).
According to the GC/MS data, this liquid contained
α,ω-divinyl oligodimethylsiloxane derivatives 1‒4 (from
initial disiloxane 1 to pentasiloxane 4) and compound 5
Scheme 3.
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LAKHTIN et al.
Scheme 4.
Scheme 5.
resulting from substitution of one vinyl group of 1 by
chlorine (Scheme 2).
is inserted into the Si‒O‒Si bond [5, 6] (version b,
Scheme 4). Taking into account the presence of
chloro(dimethyl)vinilsilane and disiloxane 5 in the
reaction mixture, version a seems more probable.
Presumably, complex A dissociates into germylene
chloride and hydrogen chloride, and the latter in statu
nascendi reacts at the C=C double bond (electrophilic
addition followed by β-elimination) and Si‒O‒Si bond,
leading to the formation of all identified compounds.
Scheme 3 shows reactions (1)‒(3) that are likely to
occur according to version a. Siloxane chain propagation
may be mediated by dimethylsilanone Me2Si=O which
1
The H NMR spectrum of the viscous still residue
showed signals which were assigned to methyl (δ 0‒
0.4 ppm) and methylene groups (δ 0.9‒2.7 ppm). It was
previously found that the reaction of trichlorogermane
etherate with ethylene gives a polymer which has the
structure [‒CH2CH2GeCl2‒]n [8, 9]. Judging by the
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REACTIONS OF TRICHLOROGERMANE AND TRIMETHYLGERMANE ETHERATES
971
Scheme 6.
presence of numerous signals in the 1H NMR spectrum,
the still residue obtained by us is not a regular polymer
but a mixture of oligomers and polymers containing
[‒OSiMe2CH2CH2GeCl2‒], [‒OSiMe2GeCl2OSiMe2‒],
[‒OSiMe2‒], and other units in various combinations
and at various ratios. Signals of vinylic protons at δ 5.7‒
6.2 ppm in the 1H NMR spectrum indicate formation in
the given reaction of high-molecular-weight siloxanes
with terminal vinyl groups, which cannot be separated
by distillation (signal intensity ratio Me : CH2 : CH=CH2
16.4 : 4.1 : 1).
15 products, 4 of which were obtained in a (2–5), and
two minor (<0.3%) cyclic siloxanes 16 and 17 containing
a dichlorogermylene unit in the ring. More profound
transformation of 1 in b determined predominant
formation of hexasiloxane derivatives. Scheme 5 shows
the structures of compounds which were identified
only in b. The formation of siloxanes with SiMe2H
terminal groups may be rationalized by the presence
of tetramethyldisiloxane in the reaction mixture; its
condensation products were identified previously [7].
1
Taking into account that H NMR spectrum of HCl
When analogous reaction of 1 was carried out with
sample B, a bright yellow solid (germanium subchlorides)
immediately precipitated. We failed to isolate any product
by vacuum distillation of the liquid phase obtained after
separation of the precipitate. The 1H NMR spectrum of
the viscous undistillable residue showed the same Me,
CH2, and CH=CH2 signals as in the reaction with sample
A, but with a different intensity ratio (12.1 : 6.1 : 1).
etherate in DMSO-d6 showed a signal at δ 12.8 ppm,
i.e., in the same downfield region as the GeH proton of
trichlorogermane etherate, it could be presumed that just
HCl etherate participates in the formation of siloxanes.
However, special experiments showed that no siloxanes
were formed in the reaction of 1 with 2Et2O·HCl; the
reaction of 1 with dry HCl gave only (CH2=CH)Me2SiCl
in addition to gaseous products, and only traces of high-
boiling siloxanes were detected.
No reaction occurred in the absence of diethyl
ether, i.e., on heating an equimolar mixture of GeCl4,
tetramethyldisiloxane, and compound 1. No any
transformation was observed after addition of diethyl
ether to the reactant mixture.
Our results lead us to suppose that just trichlorogermane
etherates contribute to siloxane chain propagation and
formation of α,ω-divinyl and other oligosiloxanes.
We then proceeded with studying the reaction of 1 with
trimethylgermane in the presence of Karstedtʼs catalyst.
The reaction of 1and Me3GeH under reflux (30‒40°C) was
very slow, and the conversion of Me3GeH in 5 h was less
than 14%. We succeeded in achieving 100% conversion of
Me3GeH by carrying out the reaction at 90°C in a sealed
ampule. The reaction mixture contained mono- and bis-
adducts 18 and 19 (52 and 22%, respectively, based on
Me3GeH; Scheme 6). The products were identified by 1H
NMR and GC/MS. The addition of trimethylgermane was
exclusively anti-Markovnikov. GLC analysis showed the
absence of Si‒O‒Si bond cleavage products. No reaction
occurred in the absence of a catalyst.
In order to find out whether compound 1 could react
with sample A in statu nascendi, compound 1 was added
to a mixture of GeCl4, tetramethyldisiloxane, and diethyl
ether immediately after the complex began to form
(version b). The results of this experiment considerably
differed from those described above for the reaction
with sample A (version a). The reaction mixture was
separated into two parts: a mixture of liquid products
distilled up to 140°C (4 mmHg) and a viscous mixture
of high-molecular-weight oligomers.
According to the GC/MS data, the liquid fraction
(~20%) was a mixture of about 20 compounds, including
dimethylsiloxanes with different combinations of
terminal groups (SiMe2CH=CH2, SiMe2H, SiMe3) and
cyclosiloxanes. Among these compounds, we identified
Like most siloxanes, the mass spectra of the synthesized
compounds lacked molecular ion peaks (except for
trisiloxane 2 whose molecular ion peak had an intensity
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LAKHTIN et al.
of 1.2%). However, it was the mass spectrum of 2 where
the [M ‒ CH3]+ ion arising from elimination of methyl
substituent was the most abundant, and it had the highest
m/z value. The intensity of the corresponding peak in the
mass spectra of 3 and 4 did not exceed 15% of the total
ion current. One of the fragmentation channels of tetra-
and pentasiloxanes 3 and 4 includes elimination of the
terminal dimethyl(vinyl)silyl group and two methyl groups
from the molecular ion to give [M ‒ Me2SiCH=CH2 ‒
2CH3]+ ion. The fragmentation of 3 gives a ion with
m/z 219 (Irel 65%) which has a favorable six-membered
structure (analog of hexamethylcyclotrisiloxane D3)
with a vinyl group. Analogous fragmentation of 4
gives a stable eight-membered cyclic ion (analog of
octamethylcyclotetrasiloxane D4) with a vinyl group,
m/z 393 (Irel 25.2%). Cyclic ions {six-membered from
3, m/z 207 (Irel 58.3%), and eight-membered from 4, m/z
281 (Irel 19.5%), [M ‒ CH=CH2 ‒ Me2SiCH=CH2]+} are
formed via elimination of the vinyl and dimethyl(vinyl)
silyl groups from the molecular ions. A low-intense ion
peak corresponding to elimination of methyl group from
hexamethylcyclotrisiloxane D3, m/z 207 (6.0%), was also
observed in the mass spectrum of 4.
of methyl group, as well as for other ions containing
the above elements, matched the experimental data.
Intensities of all isotope peaks for each ion are given
in Experimental. The mass spectra of two products of
hydrogermylation of 1 with trimethylgermane (at one
and both vinyl groups) displayed the molecular ion peaks
which were readily interpreted with account taken of the
fact that the most intense peak in the molecular ion cluster
of the adduct containing two germanium atoms had m/z
424 rather than m/z 426 corresponding to the molecular
weight calculated for 74Ge.
In summary, we have found that the ratio symmetrical
tetramethyldisiloxane‒GeCl4‒Et2O significantly affects
the structure and reactivity of trichlorogermane–ether
complexes obtained therefrom. Reactions of trichloro-
germane–ether complexes with symmetrical tetra-
methyl(divinyl)disiloxane are not selective, and they
lead to the formation of oligosiloxanes with vinyl and
other terminal groups, as well as polymeric compounds.
Trimethylgermane does not react with symmetrical
tetramethyl(divinyl)disiloxane under normal conditions in
the presence of Karstedtʼs catalyst, but hydrogermylation
products at one and both vinyl groups are formed under
autogenous pressure at 90°C with complete conversion
of trimethylgermane.
Some of similar ion peaks present in the mass
spectra of 3 and 4 had different intensities; an example
is [(CH=CH2)2SiMe]+, m/z 97, Irel 27.3 and 8.9% for
3 and 4, respectively. The relative intensity of the
[CH=CH2SiMe2]+ ion with m/z 85 in the spectrum of 4
was 15.5%, whereas the same ion in the mass spectrum
of 3 was the most abundant (Irel 100%). The [Me3Si]+
ion peak (m/z 73) had a high intensity in the mass spectra
of both 3 and 4 (Irel 91.0 and 100%, respectively). The
presence of a doublet m/z 179/181 with an intensity ratio
of 3 : 1 in the mass spectrum of 5 indicated the presence
of one chlorine atom in the molecule.
EXPERIMENTAL
Commercial germanium tetrachloride (Germanii Ltd.),
1,1,3,3-tetramethyldisiloxane (98%, Acros Organic),
1,1,3,3-tetramethyl-1,3-divinyldisiloxane (97%, Acros
Organics), and diethyl ether (Vekton JSC) were used
without further purification.
1
The H NMR spectra were recorded on a Bruker
AM-360 at 360 MHz using tetramethylsilane as internal
standard. Low-boiling products were analyzed by GLC
on an LKhM-72 chromatograph equipped with a thermal
conductivity detector [2-m column packed with 5%
SE-30 on Chromaton N-AW (0.250–0.315 mm); oven
temperature programming from 50 to 280°C at a rate
of 12 deg/min; detector temperature 290°C, injector
temperature 300‒320°C; carrier gas helium, flow rate
40 mL/min]. The mass spectra (electron impact, 70 eV)
were recorded on a Hewlett-Packard HP 5971 mass-
selective detector; DB-5 capillary column 25 m×0.32 mm,
film thickness 25 μm; oven temperature programming
from 40 to 280°C at a rate of 7 deg/min; carrier gas
helium, flow rate 0.8 mL/min.
The mass spectra of 6–15 (version b) showed some
similarity to the spectra of 2–5 (version a): there was
no molecular ion peak, and the [M ‒ Me]+ ion had the
largest m/z value. The differences are mainly related to
the terminal groups; for example, [M ‒ H]+ ion appears
due to the presence of a Si(Me2)H group. Identification
of isomeric organogermanium compounds 16 and 17
involved some difficulties since their molecules contain
three multi-isotope elements, one germanium atom,
two silicon atoms, and two chlorine atoms. To interpret
mass spectra of 16 and 17, we used Isotope Distribution
Calculator and Mass Spec Plotter. The calculated intensity
distribution for ion peaks formed as a result of elimination
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REACTIONS OF TRICHLOROGERMANE AND TRIMETHYLGERMANE ETHERATES
973
Trichlorogermane–diethyl ether complex. Sample
A. A mixture of tetramethyldisiloxane, germanium
tetrachloride, and diethyl ether at a ratio of (0.5‒0.75) :
1 : 2 was heated to ~50°C without stirring. When the
mixture began to boil, external heating was removed,
and strong gas evolution was observed through a U-tube
filled with polymethylsiloxane and connected to a reflux
condenser. The mixture gradually separated into two
layers. After settling down, the bottom light yellow oily
layer of trichlorogermane etherate A was separated. Yield
70–80%.
Me2SiCH2=CH]+ (19.5/6.0/2.6), 207/208/209 [D3 ‒ CH3]+
(6.0/1.0/0.6), 159/160/161 [Me2SiOSiMe2CH2=CH]+
(51.0/7.7/3.8), 147/148/149 [Me2SiOSiMe3]+
(26.4/4.7/2.2), 85/86/87 [Me2SiCH2=CH]+ (65.5/6.1/3.4),
73/74/75 [Me3Si]+ (100.0/9.3/4.7), 59/60/61 [MeSiO]+
(49.7/3.3/1.6), 32 [O2] (20.2), 28 [C2H4]+∙ (32.5), 18
[H2O]+∙ (9.0).
1-Chloro-1,1,3,3-tetramethyl-3-vinyl-1,3-di-
siloxane (5). Mass spectrum, m/z (Irel, %): 179/181 [M ‒
CH3]+ (100.0/35.3), 167/169 [M ‒ CH2=CH]+ (17.2/7.5),
159/160/161 [M ‒ Cl]+ (24.0/5.0/2.3), 153/155 [M ‒ CH3 ‒
C2H4]+ (21.3/7.5), 137/139 [CH2=CH(H)OSi(Me2)Cl]+
(8.1/8.4), 133(9.5), 73 [Me3Si]+ (30.9), 59 [MeSiO]+
(21.0), 45 [MeSiH2]+ (7.0), 32 [MeOH]+∙ (8.2), 28
[C2H4]+∙ (23.9), 27 [CH2=CH]+ (8.7).
When the ratio tetramethyldisiloxane–germanium
tetrachloride–diethyl ether was 1 : 1 : 2, the originally
yellow bottom layer changed to light red (sample B).
Reaction of trichlorogermane–diethyl ether
complex with 1,1,3,3-tetramethyl-1,3-divinyldisiloxane
(1). Sample A was slowly added with stirring to
an equimolar amount of compound 1. The mixture
spontaneously warmed up to 43‒45°C and was stirred
for 5 h at 50°C. Ether was distilled off under atmospheric
pressure, and the products were isolated by fractional
distillation under reduced pressure. The still residue was
analyzed by NMR.
b. Compound 1 was added to a mixture of tetra-
methyldisiloxane–GeCl4–Et2O (0.5 : 1 : 2) immediately
after complex A began to form.
1,1,3,3,5,5,5-Heptamethyl-1-vinyltrisiloxane (6).
Mass spectrum, m/z (Irel, %): 233 [M ‒ Me]+ (2.2),
219/220/221 [M ‒ C2H5]+ (100/28.6/15.7), 207 [D3 ‒
Me]+ (13.0), 191/192/193 [M ‒ CH2=CH ‒ 2Me]+
(70.2/19.1/10.2), 190 [M ‒ CH2=CH ‒ 2H2 ‒ H]+ (22.5),
147 [Me2SiOSiMe3]+ (9.9), 133/134/135 [HSi(Me2)
OSiMe2]+ (19.8/3.7/1.0), 119 (3.3), 103 [HSi(Me)
OSiMe2]+ (12.2), 102 [MeSiOSiMe]+ (12.3), 89
[Me3SiO]+ (27.1), 85 [CH2=CHSiMe2]+ (38.0), 73/74/75
[Me3Si]+ (69.8/10.0/12.0), 72 [CH2SiMe2]+ (25.5),
59/60/61 [HSiMe2]+ (47.2/3.8/4.1), 45 [MeSiH2]+ (28.0),
44 [MeSiH]+ (6.7), 43 [MeSi]+ (9.3), 32 [OH]+. (4.0), 28
[C2H4]+∙ (13.6), 27 [CH2=CH]+ (6.2), 18 [H2O]+∙ (8.7).
a. Light yellow oily sample Awas added to compound 1.
1,1,3,3,5,5-Hexamethyl-1,5-divinyltrisiloxane (2).
Mass spectrum, m/z (Irel, %): 260 [M]+∙ (1.2), 245/246/247
[M ‒ CH3]+ (100/23.0/12.0), 205/206/207 (38.8/8.0/5.0),
101/102/103 (19/14.6/10.0), 97/98/99 (36.5/5.0/5.2),
73/74/75 [Me3Si]+ (81.0/7.9/9.0), 59 [MeOSi]+(60.8).
Hereinafter, noninformative peaks with a relative
intensity of less than 5% are not given.
1,1,3,3.5,5,7,7,7-Nonamethyl-1-vinyltetrasiloxane
(7). Mass spectrum, m/z (Irel, %): 281/282/283 [M ‒
Me]+ (100/21.0/14.7), 265 [M ‒ 2Me ‒2H]+ (11.6), 249
[M ‒ 3Me ‒ 2H]+ (10.0), 207 [D3 ‒ Me]+ (4.3), 193
[D3 ‒ Me ‒ CH2]+ (17.2), 191 [D3 ‒ Me ‒ CH2 ‒ 2H]+
(10.0), 133 [HSi(Me2)·OSiMe2]+ (16.0), 103 [HSi(Me)
OSiMe]+ (2.0), 73 [Me3Si]+ (20.4), 59 [HSiMe2]+ (2.0),
45 [MeSiH2]+ (2.1), 32 [MeOH]+∙ (1.6), 28 [C2H4]+∙ (7.8),
18 [H2O]+∙ (1.2).
1,1,3,3,5,5,7,7-Octamethyl-1,7-divinyltetrasiloxane
(3). Mass spectrum, m/z (Irel, %): 319/320/321 [M ‒
CH3]+ (13.0/4.0/2.2), 231/232/233 [M ‒Me2SiOSiH]+
(12.0/3.1/2.0), 219/220/221 [M ‒ Me2SiCH2=CH ‒
2CH3]+ (65.0/12.0/7.0), 207/208/209 [M ‒ CH2=CH ‒
Me2SiCH2=CH]+ (58.3/10.8/6.5), 203 (10.0), 193
(12.0), 191 (11.0), 177 (6.0), 133 (10.0), 112 (8.5),
97/98/99 [(CH2=CH)2SiMe]+ (27.3/2.8/2.4), 85/86/87
[CH2=CHSiMe2] (100.0/8.6/5.0), 73/74/75 [Me3Si]+
(91.0/7.1/4.9), 71(9.6), 59/60/61 [MeOSi]+ (53.3/4.1/2.5),
45 [SiOH]+ (11.7), 28 [C2H4]+∙ (19.5), 18 [H2O]+ (5.0).
1,1,3,3,5,5,7,7-Octamethyl-1-vinyltetrasiloxane
(8). Mass spectrum, m/z (Irel, %): 307 [M ‒ H]+ (0.12),
293/294/295 [M ‒ CH3]+ (45.1/18.0/10.0), 219/220/221
[M ‒ Me3SiO]+ (37.8/11.2/6.0), 207/208/209 [M ‒
O(Me)2SiVin]+ (61.8/8.5/5.2), 193/194/195 [M ‒
Me2SiCH2=CH ‒ 2Me]+ (33.7/6.1/3.3), 133/134/135
[H(Me2)SiOSi(Me2)]+ (12.0/1.2/0.7), 85/86/87
[CH2=CHSi(Me2)]+ (61.8/8.5/5.2), 73/74/75 [Me3Si]+
1,1,3,3,5,5,7,7,9,9-Decamethyl-1,9-divinyl-
pentasiloxane (4). Mass spectrum, m/z (Irel, %):
393/394/395 [M ‒ CH3]+ (6.7/1.6/0.9), 305 [M ‒ Me2SiO ‒
SiH]+(5.6), 293/294/295 [M ‒ Me2SiCH2=CH ‒
2CH3]+(25.2/8.3/3.7), 281/282/283 [M ‒ CH2=CH ‒
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LAKHTIN et al.
(100/9.3/5.1), 59/60/61 [HSiMe2]+ (34.3/3.3/3.0), 45
[H2SiMe]+ (13.7), 44 [HSiMe]+ (2.2), 27 [CH2=CH]+∙
(4.2), 18 [H2O]+∙ (2.5).
(OH)2]+ (6.2), 281/282/283 [M ‒ OSi(Me2)OSiMe3]+
(17.2/4.3/1.7), 265 [MeO(Me2)SiOSi(Me2)O]+ (2.2),
233/234/235 [(CH2)3Si(Me2)OSi(Me2)OSiMe]+
(26.2/4.3/0.7), 221(7.5), 219(6.0), 207/208/209 [D3 ‒
Me]+ (35.8/7.6/2.3), 159 [Me3SiOSiC3H6]+ (6.7),
147/148/149 [Me3SiOMe2]+ (20.0/2.6/0.9), 146 (5.1),
133/134/135 [HSi(Me2)OSiMe2]+ (11.0/0.5/0.15),
85/86/87 [Me2SiC2H3]+ (25.0/2.6/0.3), 73/74/75
[Me3Si]+ (100/9.6/4.0), 59 [Me2SiH]+ (10.0), 46 (4.3),
45 [Me2SiH]+ (5.0), 18 [H2O]+∙ (3.9), 15 [Me]+ (3.5).
1,1,3,3,5,5-Hexamethyl-7-(trimethylsilyloxy)-
cyclotetrasiloxane (9). Mass spectrum, m/z (Irel, %):
341/342/343 [M ‒ Me]+ (64/1.6/0.9), 281/282/283 [M ‒
Me3Si ‒ 2H]+ (50.0/14.3/7.5), 280 (10.4), 267/268/269
[M ‒ Me3SiO]+ (92.7/20.0/11.4), 251 (5.5), 249 (6.2),
207/208/209 [D3 ‒ Me]+ (16.2/1.7/0.5), 193 (8.1), 191
(8.1), 147/148/149 [Me3SiOSiMe2]+ (23.8/1.1/0.5),
133/134/135 [Me2SiOSi(Me2)H]+ (47.5/6.0/2.0),
73/74/75 [Me3Si]+ (100/7.5/4.6), 59/60/61 [Me2SiH]+
(44.0/1.7/1.3), 45/46 [MeSiH2]+ (14.8/0.6).
1,1,3,3,5,5,7,7,9,9,11,11-Dodecamethyl-1-
vinylhexasiloxane (14). Mass spectrum, m/z (Irel,
%): 441 [M ‒ Me]+ (1.2), 367 [M ‒ Me2SiO ‒ Me]+
(1.5), 341/342/343 [M ‒ CH2=CH ‒ Me2Si ‒ OCH2]+
(6.4/1.2/0.4), 325 [M ‒ OSiMe2 ‒ CH2=CH ‒ 2Me]+
(3.7), 307 [CH2=CH(Me2SiO)3SiMe2]+ (6.1), 267
(3.9), 233/234/235 [CH2=CH(Me2)Si(OSiMe2)2]+
(65.6/10.7/6.3), 221/222/223 [Me2SiOSi(Me2)·OSiMe3]+
(12.7/2.4/1.7), 207/208/209 [D3 ‒ Me]+ (11.7/1.4/0.8),
159/160/161 [CH2=CH(Me2)Si-OSiMe2]+ (23.7/1.6/0.6),
147/148/149 [Me2SiOSiMe3]+ (25.7/2.5/1.4), 133
[Me2SiOSi(Me2)H]+ (6.0), 97 (7.3), 85/86/87
[CH2=CHSiMe2]+ (65.7/5.8/2.1), 73/74/75 [Me3Si]+
(100/10.0/3.7), 59/60/61 [Me2SiH]+ (27.5/1.8/0.3), 45
[Me2SiH2]+ (7.0), 27 [CH2=CH]+ (4.3), 18 [H2O]+∙ (5.0).
1,1,3,3,5,5,7,7,9,9-Decamethylcyclopentasiloxane
(10). Mass spectrum, m/z (Irel, %): 355/356/357 [M ‒
CH3]+ (21.3/9.6/5.8), 339 [M ‒ 2Me ‒ H]+ (2.3), 323
[M ‒ MeSiH2 ‒ 2H]+ (1.1), 281 [M ‒ Me3SiO]+ (0.4),
267/268/269 [M ‒ H(Me)SiOSiMe]+ (31.8/8.0/2.0),
251/252/253 [M ‒ Me2Si(Et)O]+ (4.2/2.0/0.6), 73/74/75
[Me3Si]+ (100/9.4/4.3), 59 [C3H7O]+ (6.0), 45 [H2SiMe]+
(9.7), 44 [SiMe]+ (2.3), 28 [C2H4]+∙ (1.6), 15 [CH3]+∙ (0.6).
1,1,3,3,5,5,7,7,9,9-Decamethyl-1-vinyl-1,3,5,7,9-
pentasiloxane (11). Mass spectrum, m/z (Irel, %): 367
[M ‒ Me]+ (2.1), 355 [M ‒ CH2=CH]+ (5.6), 341 [M ‒
CH2=CH ‒ CH2]+ (5.6), 325 [M ‒ CH2=CH ‒ 2Me]+ (3.6),
293 [M ‒ Me2SiO ‒ Me]+ (7.0), 281 [M ‒ CH2=CH(Me2)·
SiO]+ (8.1), 233 [M ‒ H(Me2)·SiOSi(Me2)O]+
(21.2), 207/208/209 [D3 ‒ Me]+ (33.1/6.1/3.0), 159
[CH2=CH(Me2)SiOSi(Me2)]+ (7.0), 147 [(Me2)
SiOSiMe3]+ (14.2), 133 [(Me2)SiO·Si(Me2)H]+ (9.1),
85 [CH2=CH(Me2)Si]+ (27.0), 73/74/75 [Me3Si]+
(100/6.1/3.7), 59 [Me2SiH]+ (19.0), 45 [MeSiH2]+ (6.0),
27 [CH2=CH]+ (3.6), 18 [H2O]+∙ (3.8).
1,1,3,3,5,5,7,7,9,9,11,11-Dodecamethyl-1,11-
divinylhexasiloxane (15). Mass spectrum, m/z (Irel, %):
467 [M‒Me]+ (4.1), 367/368/369 [M‒CH2=CH(Me2)Si ‒
O‒CH2]+ (8.8/4.0/2.0), 293/294/295[M‒Me3SiOSi(Me)·
(CH2=CH)OCH2]+ (7.7/3.5/2.2), 267 (7.0), 245 [M ‒
OSi(Me2)OSi(Me2)·OSi(Me2) ‒ Me]+ (13.7), 233/234/235
[CH2=CH(Me)2SiOSi(Me2)OSiMe2]+ (49.3/8.4/5.0),
221/222/223 [Me2SiO ‒ Si(Me2)OSiMe3]+ (10.4/2.4/1.7),
205 (6.0), 191 (5.0), 159/160/161 [CH2=CH(Me2)Si ‒
OSi(Me2)]+ (32.1/6.2/2.0), 147/148/149 [Me2SiOSiMe3]+
(27.7/4.1/1.8), 133 [HSi(Me2)OSiMe2]+ (8.1), 131 (4.2),
97 (7.6), 85/86/87 [CH2=CHSi(Me2)]+ (74.3/8.0/3.8),
73/74/75 [Me3Si]+ (100/9.0/2.3), 59/60/61 [HSiMe2]+
(39.8/3.8/1.1), 45 [Me2SiH2]+ (11.5), 27 [CH2=CH]+
(5.5), 18 [H2O]+∙ (5.5).
1,1,3,3,5,5,7,7,9,9,9-Undecamethyl-1-vinylpenta-
siloxane (12). Mass spectrum, m/z (Irel, %): 381 [M ‒ Me]+
(0.35), 353 [M ‒ C3H7]+ (0.42), 307 [M ‒ Me3SiO]+ (5.3),
233/234/235 [M ‒ Me3SiOSi(Me2)O]+ (36.0/6.1/3.7),
221 [CH2=CHSi(Me2)OSi(Me2)O]+ (7.8), 207 [D3 ‒
Me]+ (18.1), 159 [CH2=CH(Me2)SiOSMe2]+ (14.7),
147 [Me2SiOSiMe3]+ (5.8), 85/86/87 [CH2=CHSiMe2]+
(41.9/4.8/2.4), 73/74/75 [Me3Si]+ (100/8.0/3.0), 59
[HSiMe2]+ (14.1), 45 [Me2SiH2]+ (4.1).
6,6-Dichloro-1,1,3,3-tetramethyl-2-oxa-1,3-
disila-6-germacycloheptane (16). Mass spectrum,
m/z (Irel, %): 313/315/316/317/318/319/320/321
[M ‒ Me]+ (7.7/16.2/8.3/23.7/6.0/14.1/5.1/
6.0), 299/301/302/303/304/305/306/307 [M ‒
Et]+ (5.6/10.2/(13.8/9.7/11.5/14.5/3.0/13.8/
9.0/9.3), 285/287/288/289/290/291/292/293 [M ‒
C3H7]+ (11.8/24.5/12.0/31.6/15.7/19.5/4.1/9.2),
1,3,3,5,5,7,7,9,9-Nonamethyl-1-(trimethylsilyloxy)-
cyclopentasiloxane (13). Mass spectrum, m/z (Irel, %):
429 [M ‒ Me]+ (0.6), 367 [M ‒ MeSiO2 ‒ 2H]+ (1.8),
355/356/357 [M ‒ Me3SiO]+ (4.1/0.4/0.1), 341/342/343
[M ‒ Me3SiOCH2]+ (4.1/0.4/0.1), 307 [M ‒ H(Me)·
SiOSi(Me2)·(OH)2]+ (6.0), 293 [M ‒ Me2SiOSi(Me)·
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REACTIONS OF TRICHLOROGERMANE AND TRIMETHYLGERMANE ETHERATES
975
257/259/260/261/262/263/264/265 [MeSiCH2CH2]+ (5.4/
10.0/4.5/16.0/4.1/10.1/1.7/2.4), 207/208/209 [D3 ‒ Me]+
(8.7/2.0/0.4), 179/181 [ClGe(C2H3)C3H7)]+ (11.0/4.7),
165/167/168/169 [ClGe(CH2)2SiH2]+ (8.6/18.3/3.6/5.8),
160/161/162 [CH2(Me2)SiO·Si(Me2)CH2]+ (36.0/6.2/2.0),
151/152/153/154/155/156/157[ClGeCH2SiH2]+ (13.8/9.7/
22.2/5.8/6.0/2.6/6.7), 145146/147 [CH2(Me2)SiOSi(Me)·
CH2]+ (100/19.5/10.0), 144 [Me2SiOSi(CH2CH)Me]+
(24.0), 143 [CH2(Me)SiOSi(CH2CH)Me]+ (15.0), 137/139
[ClGeC2H3]+ (32.8/15.1), 129/130/131/132/133/135
[GeCH2SiMe]+ (11.0/20.5/73.7/26.0/26.3/5.5),
117/118/119 [GeCH2SiH]+ (44.0/10.4/16.0), 116(20.8),
115(9.8), 103/105/107/108/109/110/111 [Cl2Ge]+ (14.0/
18.1/27.5/6.8/28.3/5.2/8.4), 93/95 [Me2SiCl]+ (31.8/9.5),
85/86 [Me2SiCH2=CH]+ (21.8/9.0), 87/88/89 [Me2SiEt]+
(14.8/4.4/6.0), 73/74/75 [Me3Si]+ (98.0/10.0/11.0), 72
[Me2SiCH2]+ (49.9), 71 [CH2SiCH2]+∙ (11.2), 59/60/61
[Me3SiO]+ (46.0/4.8/2.8), 45 [MeSiH2]+ (39.8), 44
[MeSiH]+ (15.8), 43 [MeSi]+ (17.1), 31 [MeO]+ (6.0),
28 [C2H4]+∙ (15.3), 27 [C2H3]+ (23.0), 18 [H2O]+∙ (17.1).
Reaction of compound 1 with HCl etherate.
Hydrogen chloride etherate was slowly added with
stirring to an equimolar amount of compound 1. No
evolution of heat was observed. The mixture was stirred
for 3 h at 30°C, diethyl ether was distilled off under
reduced pressure, and the products were isolated by
fractional distillation under reduced pressure.
Reaction of compound 1 with dry hydrogen
chloride. Gaseous hydrogen chloride was passed using
a capillary through a required amount of compound 1
at 30°C without stirring, and the mixture was analyzed
by GLC.
Reaction of trimethylgermane with compound 1.
A glass ampule was charged with an equimolar mixture
of trimethylgermane and compound 1, one drop of
Karstedtʼs catalyst was added, and the ampule was sealed
and heated for 5 h at 90°C. The ampule was opened,
and the mixture was analyzed by GLC and subjected
to fractional distillation under reduced pressure. The
products were identified by 1H NMR and GC/MS.
5,5-Dichloro-1,1,3-trimethyl-3-vinyl-2,4-dioxa-
1,3-disila-5-germacycloheptane (17). Mass spectrum,
m/z (Irel, %): 317 [M ‒ Me]+ (2.5), 302/304/306
[M ‒ C2H4]+ (2.8/3.2/2.6), 285/287/289/291 [M ‒
C3H7]+ (1.0/3.8/5.0/0.8/3.0), 261 [M ‒ HSiC2H4]+ (0.8),
167/168/169/171 [ClGeOSiCH2]+ (100/13.6/36.1/3.0),
160 [CH2(Me2)SiOSi(:CH2)OCH2]+∙ (9.3), 145/146/147
[CH2(Me)SiOSi(:CH2)OCH2]+∙ (51.5/9.0/4.0),
103/105/107/109/111 [GeCl]+ (5.0/10.1/11.0/12.1/4.0),
102 (4.0), 101 (4.2), 93/95 [Me2SiCl]+ (13.7/4.5),
85/86 [Me2SiCH2=CH]+ (7.8/3.2), 87/88/89 [Me2SiEt]+
(8.0/1.0/2.0), 73/74/75 [Me3Si]+ (67.0/5.7/4.9), 72
[Me2SiCH2]+∙ (19.1), 43 [MeSi]+ (17.1), 32 [MeOH]+
(3.5), 28 [C2H4]+∙ (5.0), 27 [C2H3]+ (11.1), 18 [H2O]+∙
(8.5).
1,1,3,3-Tetramethyl-1-[2-(trimethylgermyl)-
ethyl]-3-vinyldisiloxane (18). Yield 52% (based on
trimethylgermane), bp 210‒212°C, nD20 = 1.4320. 1H NMR
spectrum, δ, ppm: 0.08 s, 0.12 s, and 0.16 s (21H, CH3Si,
CH3Ge); 0.48‒0.54 m (2H, CH2Si), 0.62‒0.68 m (2H,
CH2Ge), 5.71‒6.20 m (3H, CH=CH2). Mass spectrum,
m/z (Irel, %): 306 [M]+· (2.3), 291 [M ‒ Me]+ (12.1),
159/160/161 [CH2=CH(Me2)SiOSiMe2]+ (100/18.2/8.6),
147 /148/149 [Me2SiOSiMe3]+ (12.3/2.1/0.4), 145 (10.0),
133/134/135 [H(Me2)SiOSiMe2]+ (20.3/3.4/1.7), 131
[Me2GeVin]+ (28.1), 119 [GeMe3]+ (57.3), 105 (6.0),
103 (7.5), 85 [CH2=CHSiMe2]+ (8.0), 73/74/75 [Me3Si]+
(23.5/3.0/3.2), 59/60/61 [Me2SiH]+ (23.8/2.1/1.6), 45
[MeSiH2]+ (4.1), 32 [O2]+∙ (1.3), 28 [C2H4]+∙ (6.3), 18
[H2O]+∙ (1.3).
c. The yellow solid precipitated in the reaction of
sample B with compound 1 was separated, but no liquid
products were isolated from the residue by vacuum
distillation.
1,1,3,3-Tetramethyl-1,3-bis[2-(trimethylgermyl)-
ethyl]disiloxane (19). Yield 22% (based on
20
trimethylgermane), bp 240‒243°C, nD = 1.4441.
1H NMR spectrum, δ, ppm: 0.6 s (12H, CH3Si),
0.11 s (18H, CH3Ge), 0.45‒0.51 m (4H, CH2Si),
0.60‒0.66 m (4H, CH2Ge). Mass spectrum, m/z (Irel, %):
424/426 [M]+· (1.1/0.4), 409/411 [M ‒ Me]+ (1.3/1.0),
277/279 [M ‒ Me2SiOSiMe3]+ (17.2/3.6), 147/148/149
[Me2SiOSiMe3]+ (13.6/1.7/0.9), 145 (13.1), 133 [H(Me2)
SiOSiMe2]+ (6.1), 131 [Me2GeCH2=CH]+ (6.0), 119
[GeMe3]+ (100), 73 [Me3Si]+ (21.0), 59 [Me2SiH]+ (3.9),
45 [MeSiH2]+ (1.2), 28 [C2H4]+∙ (1.7).
Hydrogen chloride–diethyl ether complex.Athree-
necked flask was charged with a required amount of
diethyl ether, and gaseous hydrogen chloride was passed
through a capillary without stirring or external heating.
The mixture spontaneously warmed up by 11°C. When
evolution of heat was no longer observed, bubbling of
HCl was terminated, and the product was identified by
1H NMR.
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976
LAKHTIN et al.
https://doi.org/10.1134/S1070363208050101
CONFLICT OF INTEREST
No conflict of interest was declared by the authors.
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