Synthesis of siloxane analogs of calixarenes

Article abstract of DOI:10.1007/s11172-015-1022-3

First siloxane analogs of calixarenes were synthesized based on the stereoregular cis-tetraphenylcyclotetrasiloxanetetrol. Different methods were used to study properties of new compounds in bulk, as well as their behavior at the water-air interface.

Full text of DOI:10.1007/s11172-015-1022-3

1
394
Russian Chemical Bulletin, International Edition, Vol. 64, No. 6, pp. 1394—1399, June, 2015
Synthesis of siloxane analogs of calixarenes
P. V. Zhemchugov,a A. S. Peregudov, Yu. N. Malakhova, A. I. Buzin, M. I. Buzin,
a
b,c
b
a,d
a
a,b
O. I. Shchegolikhina, and A. M. Muzafarov
aA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
8 ul. Vavilova, 119991 Moscow, Russian Federation.
2
Fax: +7 (499) 135 5085. Eꢀmail: zhemchugov@ineos.ac.ru
N. S. Enikolopov Institute of Synthetic Polymeric Materials, Russian Academy of Sciences,
b
7
0 ul. Profsoyuznaya, 117393 Moscow, Russian Federation
c
National Research Centre "Kurchatov Institute"
1
pl. Akademika Kurchatova, 123182 Moscow, Russian Federation
d
V. I. Lenin Moscow Pedagogical State University,
Build. 1, 1 ul. Malaya Pirogovskaya, 119991 Moscow, Russian Federation
First siloxane analogs of calixarenes were synthesized based on the stereoregular cisꢀtetraꢀ
phenylcyclotetrasiloxanetetrol. Different methods were used to study properties of new comꢀ
pounds in bulk, as well as their behavior at the water—air interface.
Key words: stereoregular organocyclosiloxanes, calixarenes, ethylenoxy groups, Langmuir
monolayer.
Calixarenes are cyclic oligomers composed of the
Results and Discussion
phenol fragments bound by the methylene bridges. Moleꢀ
cules of such compounds containing large enough cavities
and hydroxy groups play the role of the host in the
To synthesize cisꢀtetraphenylcyclotetrasiloxanetetrol (1),
we modified a known procedure for its preparation
"
guest—host"ꢀtype systems. The variation in the structure
14,15
from sodium cisꢀtetraphenylcyclotetrasiloxanolate
of such macrocycles changing their size and configuraꢀ
tion, as well as their functionalization, make it possible to
widely change the selectivity and the efficiency of binding
of different substrates. As such, calixarenes are promising
components of the sensor devices and supramolecular
structures: ionic channels, nanoparticles, and composiꢀ
tional materials with the molecular recognition funcꢀ
tions.1
(
Scheme 1).
Scheme 1
—3
The complexation properties of such compounds can
be considerably improved using Langmuir—Blodgett techꢀ
OH
Si
4
,5
nology. Earlier, calixarenes and their derivatives were
studied for the ability to form monolayers at the water—air
OH
O
OH
Si
O
OH
Si
Si
6
—9
interface,
as well as for the influence of the introducꢀ
O
O
tion of metal ions in the aqueous subphase on the characꢀ
1
0—13
ter of the Langmuir monolayer isotherms.
The active
development of chemistry of calixarenes and their analogs
is associated with the high demand for compounds and
structures of this type. Because of the serious synthetic
limitations, the problem of the preparation of such comꢀ
pounds remains a relevant issue.
In the present work, we describe the synthesis of the
first siloxane analogs of calixarene based on the stereoꢀ
regular cisꢀtetraphenylcyclotetrasiloxanetetrol (1) and the
results of the study of their behavior in monolayers at the
water—air interface.
1
n
i. NaOH, H O, Bu OH; ii. 1) toluene, EtOH, 2) HCl, H O.
2
2
The obtained tetrol (1) was used in the synthesis of
cisꢀtetra[(phenyl)(dimethylhydride)siloxy]cyclotetrasilꢀ
oxane (2) (Scheme 2).
To prepare the first siloxane analogs of calixarenes
(3a—c), the methyl allyl ethers of monoꢀ, diꢀ, and triethylꢀ
ene glycol, obtained according to the procedure described
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1394—1399, June, 2015.
066ꢀ5285/15/6406ꢀ1394 © 2015 Springer Science+Business Media, Inc.
1

Synthesis of siloxane analogs of calixarenes
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 6, June, 2015
1395
Scheme 2
Residue weight (wt.%)
1
00
7
5
2
5
0
5
1
2
3
2
00
400
600
800 T/С
i. Pyridine/toluene, reflux, 1.5 h.
Fig. 1. The TGA curves for compounds 3a (1), 3b (2), and 3c (3)
in air at 10 C min– heating rate.
1
earlier,16 were silylated in the presence of a Karsted cataꢀ
lyst (Scheme 3).
Residue weight (wt.%)
100
Scheme 3
7
5
2
5
0
5
3
2
1
2
00
400
600
T/С
Fig. 2. The TGA curves for compounds 3a (1), 3b (2), and 3c (3)
in the flow of argon at 10 C min– heating rate.
1
of compounds 3a—c in air, which is observed in the
200—400 C temperature range (see Fig. 1). It should be
noted that the amount of the mass loss increases in paralꢀ
lel with the length of the ethylenoxy fragment. As a conseꢀ
quence, after the thermooxidation transformations stopped
in the region of 700 C, the decrease in the weight of the
solid residue is observed in the following order 3a < 3b < 3c.
Differential scanning calorimetry (DSC) was used to
determine glass transition temperature for compounds 3a—c
(Fig. 3). We found that the glass transition temperature
increases with the length of the ethylenoxy fragment and
is equal to –80 (3a), –77 (3b), and –74 C (3c), approꢀ
aching the glass transition temperature of highꢀmolecuꢀ
X =
Ct is the Karsted catalyst.
3
: n = 1 (a), 2 (b), 3 (c)
The structure and purity of new compounds were conꢀ
1
29
firmed by the GPC data, GLCꢀMS, H and Si NMR
spectroscopy, and elemental analysis.
Thermogravimetric analysis (TGA) showed that the
destruction in air (Fig. 1) of compounds 3a—c began at
about 200 C, whereas the destructive processes in argon
(
Fig. 2) developed at considerably higher temperatures,
around 350 C. It is obvious that such a significant differꢀ
ence in the thermal behavior is related to the presence of
the ethylenoxy groups (X) in the chemical structure of the
synthesized compounds, which tend to undergo early
thermooxidation transformations.1 This is the reason
which leads to the presence of the first decomposition step
1
8
larꢀweight poly(ethylene oxide), –67 C.
To characterize the behavior of the molecules at the
water—air interface, we studied the surface pressure (—A)
and surface potential (U—A) isotherms. The isotherms
of compression of Langmuir monolayers (—A and U—A)
7

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Russ.Chem.Bull., Int.Ed., Vol. 64, No. 6, June, 2015
Zhemchugov et al.
1
2
3
Table 1. Characteristics of —A and U—A isoꢀ
therms of compounds 3a—c
endo
exo
Parameters
3a
3b
3c
2
–1
–1
А /Å (molecule)
185
122
122
405
165
126
220
130
1128.5
445
165
131
280
140
132
475
—
0
2
А /Å (molecule)
1
1
1
U/mV
/mN m–

2
–1
А /Å (molecule)
–
125
–100
–75
–50
–25
0 T/С
2
2
/mN m–
1
—
Fig. 3. The DSC curves for compounds 3a (1), 3b (2), and 3c (3)
–
1
at 10 C min heating rate.
2
area per one molecule of 122 Å . Supposedly, a conformaꢀ
tional rearrangement occurs in this region, when the ethylꢀ
enoxy groups immerse in water, and the morphology of
the surface film becomes irregular (see Fig. 5, b). Upon
completion of this transition, the growth of the surface
pressure resumes to 26 mN m , and a second plateau is
observed in the —A isotherm of the compression of a thin
surface film of compound 3a. The bright round domains
are seen on the microphotograph of the surface film shown
in Fig. 5, c.
The shape of the —A and U—A isotherms of the
expansion of a thin surface film of compound 3a is similar
to that of the corresponding compression isotherms. Upon
the film expansion, the formed domains undergo destrucꢀ
tion and the aggregates can be observed on the surface
(see Fig. 5, d), which then spread with the formation of
a monolayer. The —A isotherm completely reproducꢀ
es upon repeated compression of the monolayer of comꢀ
pound 3a.
of compounds 3a—c are shown in Fig. 4, their principal
parameters are given in Table 1. The changes in the morꢀ
phology of the surface film of compound 3a in the comꢀ
pression—expansion cycle are illustrated in the microphoꢀ
tographs obtained by microscopy at the Brewster angle
–
1
(
Fig. 5). A monotonous growth is observed in the —A
and U—A isotherms upon the compression of the Langꢀ
muir monolayer of compound 3a. In this case, the growth
of the surface potential began long before the surface presꢀ
sure started to grow. A continuous uniform monolayer is
seen on the water surface at the Brewster angle in the early
stage (see Fig. 5, a). We assume that in this region the
hydrophobic (phenyl) groups in the molecules of comꢀ
pound 3a are oriented toward the air phase, whereas
the hydrophilic (siloxane and ethylenoxy) groups lie
on the surface of water. The latter suggestion is supportꢀ
ed by the fact that poly(ethylene oxide), despite its soluꢀ
bility in water,1 can form monolayers at the water—air
interface. The collapse of the poly(ethylene oxide) monoꢀ
layer, according to the literature data,2 is accompanied
by a gradual immersion of the ethylenoxy units in water,
which is reflected by a plateau in the —A and U—A
isotherms.
9
For compounds 3b and 3c, the behavior on the water
surface in the compression—expansion cycle, as well as
the —A and U—A isotherms, are similar to those obꢀ
served for compound 3a. From the data in Table 1, it
follows that in the order of compounds 3a, 3b, and 3c
a growth of the area values per one molecule in both the
sparse (A ) and the maximally compressed (A ) monoꢀ
0
The further compression of a thin surface film of comꢀ
pound 3a leads to the appearance of a plateau in the —A
0
1
(
22 mN m–1) and U—A isotherms (405 mV) with the
layers is observed, that indicates that in the initial state the
ethylenoxy units lie on the surface of water. It should be
noted that in this series the elongation of the ethylenoxy
substituent by one ethylenoxy unit results in the increase

/mN m–1
U/mV
5
4
3
00
–1
6
in the stability of the monolayers ( ) by 4—6 mN m
1
4
3
2
1
0
0
0
0

U1
and the maximal value of the surface potential (U) by
5
00
00
3
0—40 mV.
4
A2; 
2
For the benzyl ether monodendrones with an oligoꢀ
3
ethylenoxy chain in the focal point, a contribution of the
hydrophobic and the hydrophilic moieties to the increase
in the stability of monolayers was evaluated, and the
increase in the monolayer collapse pressure was found
A1; 
1
2
200
100
1
A0
–1
to be 3—4 mN m with the elongation of the sequence
2
–1
21
2
00
400
600
800 A/Å (molecule)
by one ethoxy group. Earlier, such a behavior was
observed for the monolayers of carbosilane dendrimers
of third and sixth generation with the ethylenoxy units in
the shell.
Fig. 4. —A (1—3) and U—A (4—6) isotherms upon compresꢀ
sion of the Langmuir monolayers of compounds 3a (1, 4), 3b (2, 5),
and 3c (3, 6). Т = 20 C.
2
2

Synthesis of siloxane analogs of calixarenes
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 6, June, 2015
a
1397
b
5
0 m
50 m
c
d
5
0 m
50 m
Fig. 5. Microphotographs of the thin surface film of compound 3a at the Brewster angle for compression at the pressure of 10 (a),
3 (b), and 25 mN m–1 (c) and expansion at the pressure of 23 mN m (d). T = 20 C.
–1
2
The second plateau (at  ) in the —A isotherms of
based on cisꢀtetraphenylcyclotetrasiloxanetetrol with
2
compounds 3a,b is observed at practically the same area
monoꢀ, diꢀ, and triethylene glycols. The influence of
molecular parameters of compounds obtained on the
quantitative characteristics of Langmuir monolayers was
demonstrated. The presence of the hydrophilic (ethylenꢀ
oxy and siloxane) and hydrophobic (arene, methyl,
and methylene) fragments in the composition of moleꢀ
cules provides the selforganization on the interphase
surfaces and confirms their pronounced amphiphilic
nature.
2
per one molecule equal to 65 Å (A ). Assuming that the
2
ethylenoxy substituents are immersed in water, tetrapheꢀ
nylcyclosiloxane remains on the surface. The area per one
2
2
siloxane unit is ~17 Å , that correlates with 16 Å per one
2
3
unit for dimethylꢀ or methylphenylꢀsubstituted linear
and cyclolinear2 polyorganosiloxanes.
4
The height of the second step in the surface pressure
decreases on going from monoꢀ (see Fig. 4, curve 1) to
diethylene glycolꢀsubstituted cyclotetrasiloxane (see Fig. 4,
curve 2). For triethylene glycolꢀsubstituted derivative, the
second step of the surface pressure is indistinguishable
Experimental
(
see Fig. 4, curve 3).
All the organic solvents were dried and distilled over CaH2,
except dimethylchlorosilane (Aldrich) and pyridine (Aldrich),
which were used as purchased. A Karsted catalyst (1,3ꢀdivinylꢀ
In conclusion, we suggested a convenient method
for the synthesis of the siloxane analogs of calixarenes

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Russ.Chem.Bull., Int.Ed., Vol. 64, No. 6, June, 2015
Zhemchugov et al.
1
,1,3,3ꢀtetramethyldisiloxane)platinum(0) as a 2% (Pt) solution
solved in a mixture of toluene (66 mL) and ethanol (2.5 mL),
then, the solution was added dropwise to a solution of concenꢀ
trated HCl (10 mL) in water (653 mL) with vigorous stirring.
The reaction mixture was stirred for 2—3 min. The crystals
formed were separated on a Schott funnel, washed with water,
until the test on the presence of Cl– ions was negative, and
toluene. The product 1 was dried in vacuo in the presence of
in xylene (Aldrich) was used for catalysis.
Products were isolated by preparative HPLC using a Shiꢀ
madzu LCꢀ8A chromatograph, a Smartline RI 2400 refractoꢀ
metric detector (KNAUER, Germany), a Kromasil 300ꢀ5Sil,
E96811 column (250×30 mm), eluent THF.
GPC analysis was carried out on a chromatographic installaꢀ
tion consisting of a STAIER, series 2 highꢀpressure pump
CaCl for 24 h. The yield was 3.3 g (93.2%). Found (%): C, 52.25;
2
(
Akvilon, Russia), a RIDK 102 refractometric detector (Czech
H, 4.19; Si, 20.24. C H Si O . Calculated (%): C, 52.14;
2
4
24
4
8
1
Republic), and a JETSTREAM 2 PLUS column termostat
H, 4.38; Si, 20.33. H NMR ((CD ) O), : 7.36 (d, 8 H, oꢀC H ,
3
2
6
5
(
(
(
KNAUER, Germany). The thermostatic temperature was 40 C
±0.1 C), eluent THF, the flow rate 1.0 mL min–1. The column
J = 6 Hz); 7.26 (t, 4 H, pꢀC H , J = 12 Hz); 7.18 (t, 8 H, mꢀC H ,
6 5 6 5
29
J = 18 Hz); 6.25 (s, 4 H, OH). Si NMR ((CD ) O), : –69.9.
3
2
300×7.8 mm) was filled with Phenogel sorbent (Phenomenex,
cisꢀTetra[(phenyl)(dimethylhydride)siloxy]cyclotetrasiloxane
(2). A mixture of compound 1 (1.7 g, 3.08 mmol) and pyridine
(1.08 g, 12.3 mmol) in toluene (40 mL) was added to a solution
of chlorodimethylsilane (1.74 g, 12.3 mmol) in toluene (10 mL)
with vigorous stirring. The reaction mixture was refluxed for
1.5 h, then filtered from the precipitate of pyridine hydrochloride.
The resulting solution was washed with distilled water until the
test on the presence of Cl– ions was negative and dried with
sodium sulfate. After evaporation of the solvent on a rotary evapꢀ
orator, the product 2 was concentrated in vacuo of an oil pump
with heating in a water bath (60—70 C). The yield was 1.64 g
(68%). Found (%): C, 49.18; H, 6.15; Si, 28.35. C H O Si .
3
USA) with particle size 5 m, pore size 10 Å (the passport
separation range to 75000 Da). The registration and processing
of the measurement results were carried out using the Multiꢀ
Khrom 1.6 GPKh program (Ampesand, Russia).
1
29
H and Si NMR spectra were recorded on a Bruker Avanꢀ
ceTM 600 spectrometer (600.22 and 119.26 MHz, respectively).
Chemical shifts for H were measured relative to the signal of
residual proton CHCl ( 7.27). Chemical shifts for Si were
measured relative to the external Me Si.
Thermogravimetric studies were carried out on a Derivatoꢀ
graphꢀC instrument (MOM, Hungary) in air and under argon at
1
1
2
9
3
4
3
2
48
8
8
–
1
1
0 C min heating rate.
Calculated (%): C, 48.94; H, 6.16; Si, 28.61. H NMR (CDCl ),
3
Studies by DSC were carried out on a DSCꢀ822e (Mettler—
: 7.38 (d, 8 H, oꢀC H , J = 6 Hz); 7.33 (t, 4 H, pꢀC H , J = 12 Hz);
6
5
6
5
Toledo, Switzerland) at 10 C min–1 heating rate.
7.18 (t, 8 H, mꢀC H , J = 18 Hz,); 4.92—4.90 (m, 4 H, Si—H);
6 5
2
9
Formation of Langmuir monolayers and studies of their propꢀ
0.32—0.31 (d, 24 H, CH , J = 6 Hz). Si NMR (CDCl ),
3
3
erties upon compression between two movable barriers at the
: –17.3 (4 Si, O—Si—(CH ) ), –78.1 (4 Si, Si—O—Si).
3
2
2
–1
rate 15 cm min was carried out using a Minitrough Extended
Langmuir trough (KSV, Finland). The subphase was the water
with specific resistivity of 18.2 M cm–1 (at 25 C), which was
purified and demineralized using a MilliꢀQ Integral Water Puriꢀ
fication System apparatus (Millipore, USA). The subphase was
termostated at 20 C. Twice distilled chloroform was used as
a solvent. The surface pressure was determined with the accuracy
cisꢀTetra{(phenyl)[(dimethyl)(methylpropylmonoethylene
glycol)siloxy]}cyclotetrasiloxane (3a). A Karsted catalyst (3 L,
0.1 L per 1 mL of the reaction mixture) was added to a solution
of monoethylene glycol methyl allyl ether (1.95 g, 16.68 mmol)
in benzene (10 mL). Then, a solution of compound 2 (2.88 g,
3.67 mmol) in benzene (15 mL) was added slowly dropwise with
vigorous stirring, and the reaction mixture was stirred for 2 days
at 65 C. After evaporation of the solvent the product 3a was
isolated by preparative HPLC. The yield was 1.56 g (34%).
Found (%): C, 53.60; H, 7.69; Si, 17.78. C H O Si . Calcuꢀ
–
1
up to 0.1 mN m by the Wilhelm method using a roughened
platinum plate. The surface potential was measured by the viꢀ
brating electrode technique, using a SPOT sensor (KSV, Finꢀ
land) with the accuracy up to 1 mV. The morphology of the
Langmuir films directly on the water surface was visualized
using a BAM300 Brewster microscope (KSV, Finland). The
microphotographs shown in this work are geometrically correctꢀ
ed with allowance for the observation at the Brewster angle of
5
6
96 16
8
1
lated (%): C, 53.81; H, 7.74; Si, 17.96. H NMR (CDCl ), : 7.32
3
(d, 4 H, oꢀC H , J = 6 Hz); 7.28 (t, 8 H, pꢀC H , J = 18 Hz);
6
5
6
5
7.11 (t, 8 H, mꢀC H , J = 18 Hz); 3.53 (t, 10 H, O—CH —CH ,
6
5
2
2
J = 6 Hz); 3.41 (t, 6 H, O—CH —CH , J = 12 Hz,); 3.38 (s, 12 H,
2
2
O—CH ); 3.37—3.34 (m, 8 H, CH —CH —CH ); 1.68—1.63
3
2
2
2
5
2
3.1 and correspond to the section of the interphase surface of
00×200 m.
(m, 8 H, CH —CH —CH ); 0.65—0.63 (m, 8 H, Si—CH );
2 2 2 2
2
9
0.24 (s, 24 H, Si—(CH ) ). Si NMR (CDCl ), : 11.1 (4 Si,
3
2
3
Sodium cisꢀtetraphenylcyclotetrasiloxanolate. The preparaꢀ
O—Si—CH ); —79.5 (4 Si, Si—O—Si).
2
tion of sodium cisꢀtetraphenylcyclotetrasiloxanolate was carried
out according to the modified procedure,1 by the mixing of
tributoxyphenylsilane (23.04 g, 0.071 mol) in nꢀbutanol (80 mL)
and NaOH (3.00 g, 0.075 mol) (with allowance for the substance
purity) in water (1.28 mL, 0.071 mol). The crystals formed over
time after the cooling were filtered and washed with hexane on
a Schott funnel. To remove excessive solvents (hexane and
nꢀbutanol), the crystals were dried in vacuo of a waterꢀjet pump
for 1 h to obtain a white crystalline compound (10.25 g) containing
solvent molecules of butanol. Found (%): C, 54.93; H, 9.15; Na, 6.05;
Si, 7.09. [PhSi(O)ONa] •12(hꢀC H OH), C H Na O Si .
cisꢀTetra{phenyl[(dimethyl)(methylpropyldiethylene glycꢀ
ol)siloxy]}cyclotetrasiloxane (3b). The reaction and the workꢀup
were carried out similarly to the preparation of compound 3a.
Compound 2 (2 g, 3.25 mmol) in benzene (10 mL) was added to
a mixture of diethylene glycol methyl allyl ether (2.39 g, 14.9 mol)
in benzene (8 mL) and a Karsted catalyst (2 L, 0.1 L per 1 mL
of the reaction mixture), and the mixture was stirred at 65 C for
2 days. After evaporation of the solvent, the product 3b was
isolated by preparative HPLC. The yield was 1.49 g (41%).
Found (%): C, 53.68; H, 7.75; Si, 15.46. C H O Si . Calcuꢀ
4
6
4
112 20
8
1
lated (%): C, 53.90; H, 7.92; Si, 15.75. H NMR (CDCl ),
4
4
9
72 140
4
24
4
3
Calculated (%): C, 54.24; H, 8.85; Na, 5.77; Si, 5.77.
: 7.32—7.26 (m, 12 H, oꢀC H ); 7.11—7.07 (m, 8 H, pꢀC H );
6
5
6
5
cisꢀTetraphenylcyclotetrasiloxanetetrol (1). The sodium cisꢀ
3.66—3.61 (m, 18 H, O—CH —CH ); 3.57 (t, 14 H, O—CH —
2 2 2
tetraphenylcyclotetrasiloxanolate (10.25 g, 6.4 mmol) was disꢀ
CH , J = 12 Hz); 3.40 (s, 12 H, O—CH ); 3.38—3.37 (m, 8 H,
2 3

Synthesis of siloxane analogs of calixarenes
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 6, June, 2015
1399
CH —CH —CH ); 1.62—1.57 (m, 8 H, CH —CH —CH );
10. L. Dei, A. Casnati, P. Lonostro, Langmuir, 1995, 11,
1268—1272.
11. Y. Zhifeng, S. Pang, W. He, X. Shi, Z. Guo, L. Zhu, Spectroꢀ
chim. Acta, Part A, 2001, 57, 1443—1447.
2
2
2
2
2
2
0
.60—0.57 (m, 8 H, Si—CH ); 0.20 (s, 24 H, Si—(CH ) ).
2 3 2
2
9
Si NMR (CDCl ), : 11.1 (4 Si, O—Si—CH ); —79.6 (4 Si,
3
2
Si—O—Si).
cisꢀTetra{phenyl[(dimethyl)(methylpropyltriethylene glycol)ꢀ
siloxy]}cyclotetrasiloxane (3c) was obtained similarly from comꢀ
pound 2 (2.5 g, 3.18 mmol) in benzene (14 mL), triethylene
glycol methyl allyl ether (3 g, 14.6 mmol) in benzene (12 mL),
and a Karsted catalyst (3 L, 0.1 L per 1 mL of the reaction
mixture), the yield was 2.14 g (42%). Found (%): C, 52.54;
H, 7.69; Si, 14.32. C H O Si . Calculated (%): C, 53.97;
12. H. Weijiang, L. Fang, Y. Zhifeng, Y. Zhang, Z. Guo, L. Zhu,
Langmuir, 2001, 17, 1143—1149.
13. D. Vollhardt, J. Gloede, G. Weidemann, R. Rudert, Langꢀ
muir, 2003, 19, 4228—4234.
14. O. Shchegolikhina, Yu. Pozdniakova, M. Antipin, D. Katꢀ
soulis, N. Auner, H. Herrshaft, Organometallics, 2000,
19, 1077—1082.
15. O. Shchegolikhina, Y. Pozdnyakova, Y. Molodtsova, S. Koꢀ
rkin, S. Bukalov, L. Leites, K. Lyssenko, A. Peregudov,
N. Auner, D. Katsoulis, Inorg Chem., 2002, 41, 6892—6904.
16. J. Light, R. Breslow, Org. Synth., 1995, 72, 199—208.
17. R. S. Goglev, M. B. Neiman, Vysokomolekulyarnye soꢀ
edineniya. Khimicheskie svoistva i modifikatsiya polimerov
[Highꢀmolecularꢀweight Compounds. Chemical Properties and
Modification of Polymers], Nauka, Moscow, 1964, 156 pp.
(in Russian).
7
2
128 24
8
1
H, 8.05; Si, 14.02. H NMR (CDCl ), : 7.28—7.05 (m, 12 H,
3
C H ); 7.09—7.06 (m, 8 H, 4ꢀmꢀC H ); 3.66—3.61 (m, 26 H,
6
5
6
5
OCH CH ); 3.56—3.55 (m, 22 H, OCH CH ); 3.38 (s, 12 H,
2
2
2
2
OCH ); 3.36—3.34 (m, 8 H, CH CH CH ); 1.61—1.56 (m, 8 H,
3
2
2
2
CH CH CH ); 0.59—0.56 (m, 8 H, Si—CH ); 0.19 (s, 24 H,
2
2
2
2
2
9
Si(CH ) ). Si NMR (CDCl ), : 11.1 (4 Si, O—Si—CH );
3
2
3
2
—
79.6 (4 Si, Si—O—Si).
This work was financially supported by the Presidium
of the Russian Academy of Sciences (Program OKhꢀ6)
and the Russian Foundation for Basic Research (Project
No. 13ꢀ03ꢀ00932).
18. D. W. Van Krevelen, Properties of Polymers: Their Estimation
and Correlation with Chemical Structure, Elsevier, Amsterꢀ
dam, 1972, p. 439.
1
9. D. J. Kuzmenka, S. Granick, Macromolecules, 1988, 21,
79–782.
7
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Received March 19, 2015;
in revised form May 5, 2015
2