Synthesis of new monofunctional organosilicon molecules - Prospective efficient stoppers for the design of new siloxane polymers of unusual architecture

Article abstract of DOI:10.1016/j.jorganchem.2014.09.001

The work reports the synthesis and characterization of new previously unknown bulk polyfunctional organosilanes with rigid molecular structure. The molecular structures of compounds 3 and 4 were defined by X-ray data. The possibility of use of prepared co

Full text of DOI:10.1016/j.jorganchem.2014.09.001

Accepted Manuscript
Synthesis of new monofunctional organosilicon molecules – Prospective efficient
stoppers for the design of new siloxane polymers of unusual architecture
Anton A. Anisimov, Yuriy N. Kononevich, Alexander A. Korlyukov, Dmitry E. Arkhipov,
Elena G. Kononova, Alexander S. Peregudov, Olga I. Shchegolikhina, Aziz M.
Muzafarov
PII:
S0022-328X(14)00417-3
10.1016/j.jorganchem.2014.09.001
JOM 18704
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 3 June 2014
Revised Date: 26 August 2014
Accepted Date: 1 September 2014
Please cite this article as: A.A. Anisimov, Y.N. Kononevich, A.A. Korlyukov, D.E. Arkhipov,
E.G. Kononova, A.S. Peregudov, O.I. Shchegolikhina, A.M. Muzafarov, Synthesis of new
monofunctional organosilicon molecules – Prospective efficient stoppers for the design of new
siloxane polymers of unusual architecture, Journal of Organometallic Chemistry (2014), doi: 10.1016/
j.jorganchem.2014.09.001.
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ACCEPTED MANUSCRIPT
Graphical abstract
New previously unknown bulk polyfunctional organosilanes with rigid molecular structure have
been synthesized. The molecular structures of compounds 3 and 4 were defined by X-ray data.
The possibility of use of prepared compound 3 as blocking agent for preparation of
polyrotaxanes was demonstrated on model reaction.
1

ACCEPTED MANUSCRIPT
Graphical abstract
CH3
CH3
H C Si CH3
H C Si CH3
3
3
CH3
Br
H C Si CH3
3
1
. n-BuLi
1. n-BuLi
Me SiHCl
2
CH3
CH3
2. Me SiCl
2. VinSiCl3
Karstedt cat.
3
H C Si
Si
H C Si
Si
CH3
3
3
Toluene
THF
THF
CH
2
CH3
CH3
Si Cl
CH3
Br
1
Br
2
3
4
H C Si CH3
H C Si CH3
3
3
CH3
CH3
1

ACCEPTED MANUSCRIPT
Synthesis of new monofunctional organosilicon molecules – prospective efficient stoppers
for the design of new siloxane polymers of unusual architecture
a,*
a,b
a,c
Anton A. Anisimov , Yuriy N. Kononevich ,Alexander A. Korlyukov , Dmitry E.
a,c
a
a
a
Arkhipov , Elena G. Kononova , Alexander S. Peregudov , Olga I. Shchegolikhina , Aziz M.
a,b
Muzafarov
a
A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
1
19991 Moscow, Russian Federation
N.S. Enikolopov Institute of Synthetic Polymeric Materials, Russian Academy of Sciences,
17393 Moscow, Russian Federation
Pirogov Russian National Research Medical University,
b
1
c
117997 Moscow, Russian Federation
E-mail: anisimov@ineos.ac.ru
1

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1. Introduction
A preparation of polymers with a new macromolecular architecture is one of the
mainstreams of the polymer science development. From this point of view rotaxane polymers are
one of the most extraordinary structures that exist in this field. Their unusualness is in the
absence of chemical bonding between linear and cyclic units. So macrocycles are able to move
freely along the polymer chain. Rotaxanes based on cyclodextrins and polyethylene oxides are
unique example of objects of this class that are taken up to successful practical application [1-9].
This tendency has been developing very intensively. New ways of the preparation of
similar structures have been created. New components for rotaxane assembling have been
synthesized and the methods of their isolations have been improved [10-12].
Thus very interesting results were achieved in the preparation of polyrotaxanes and
polypseudorotaxanes when crown ethers were used as cyclic fragments [13-14]. Okumura and
Kawaguchi were the first who described polyrotaxanes obtained with the use of
polydimethylsiloxane as linear fragment [15-19]. These are unique examples of the preparation
of organo-inorganic polyrotaxanes.
We believe that the synthesis of pure organosilicon polyrotaxanes where both linear chain
and cycles are organosilicon compounds is a very promising task in this area. Indeed, well
controlled destruction of polyhedral metalosiloxanes is a unique source of macrocycles of
different well-defined sizes. The PDMS telehelics of different length are easily commercially
available. Thus, the most important tasks in this field that should be solved before one could start
silicone rotaxanes preparation is the synthesis of bulk blocking agents (stoppers) which prevent
sliding of cyclic molecules from linear polymer chains. It is important that such molecules have
a rigid structure.
Polyrotaxanes with polyhedral silsesquioxane blocking groups were prepared by the
group of Chinese scientists [20]. It is one of few examples of using of organosilicon compounds
as stoppers.
Our research is connected with the preparation of siloxane polyrotaxanes based on linear
olygo- or polydimethylsiloxanes and 24-unit siloxane macrocycles, tris-cis-tris-trans--
[
3
RSi(O)OSiMe ]12 (R = Ph,Me,Vi, Et) [21], so, we face the task of obtaining the molecule
stopper of required size to prevent slipping of the above cycles.
2

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2. Results and discussion
We developed a simple and convenient method of the preparation of a stopper molecule-
tris(4-trimethylsilylphenyl)vinylsilane 3 (Scheme 1). The compound 3 was synthesized in two
steps. The first step was a reaction of 1,4-dibromobenzene with one equivalent of n-butyllithium
at -78°C in THF which gave 4-lithiumbromobenzene. The reaction between 4-
lithiumbromobenzene and trimethylchlorosilane leads to the formation of 4-
trimethylsilylbromobenzene 2. On the second step lithiation of compound 2 with n-butyllithium
at -78°C in THF followed by addition of vinyltrichlorosilane in ratio 3:1 gave compound 3.
CH3
CH3
H C Si CH3
H C Si CH3
3
3
CH3
Br
H C Si CH3
3
1
. n-BuLi
1. n-BuLi
Me SiHCl
2
CH3
CH3
2. Me SiCl
2. VinSiCl3
Karstedt cat.
3
H C Si
Si
H C Si
Si
CH3
3
3
Toluene
THF
THF
CH3
CH
2
CH3
Si Cl
CH3
Br
1
Br
2
3
4
H C Si CH3
H C Si CH3
3
3
CH3
CH3
Scheme 1. Scheme of the synthesis of (4-trimethylsilylphenyl)vinylsilane 3 and α-(4-
trimethylsilylphenyl)-β-(dimethylchloro)-disilylethane 4.
Novel tris(4-trimethylsilylphenyl)vinylsilane 3 can be regarded not only as blocking
agent (stopper) but also as a precursor for the formation of other blocking agents which contain
various functional groups. For example, hydrosilylation reaction can be used for this purpose.
Thus, hydrosilylation of compound 3 with dimethylchlorosilane at the presence of Karstedt′s
catalyst in toluene leads to formation of tris-(4-trimethylsilylphenyl)-β-(dimethylchloro)-
disilylethane 4 (Scheme 1). It should be noted that addition occurred exclusively at β-position.
Compound 4 can be also used as a stopper for organo-silicon resins containing terminal hydroxy-
groups in the reaction of heterofunctional condensation.
To demonstrate the application of the stopper 3 to blocking the polymers the next model
reaction were carried out (Scheme 2):
3

ACCEPTED MANUSCRIPT
CH3
CH3
CH3
H C Si CH3
H C Si CH3
H C Si CH3
3
3
3
CH3 CH3
Si Si H
H
O
CH3 CH3
CH3
Karstedt cat.
CH3
H C Si
CH3
H C Si
Si
Si
CH
Si
3
CH
Si
3
Si
Si CH3
CH3
3
3
CH3
CH
2
Toluene
CH3
O
CH3
CH3
H C Si CH3
H C Si CH3
H C Si CH3
3
3
3
CH3
CH3
CH3
5
3
Scheme
2.
Scheme
of
blocking
of
tetramethyldisiloxane
with
tris(4-
trimethylsilylphenyl)vinylsilane 3.
1
13
29
All prepared compounds were fully characterized by H, C, Si NMR and elemental
analysis. Structures of compounds 3 and 4 were proved by single crystal X-ray.
Molecular
and
crystal
structure
of
α-tris-(4-trimethylsilylphenyl)-β-
(dimethylchloro)-disilylethane.
Figure 1. Molecular structure of compound 3 (atoms are represented as ellipsoids of anisotropic
displacement at 50% probability).
4

ACCEPTED MANUSCRIPT
Figure 2. Molecular structure of compound 4 (atoms are represented as ellipsoids of anisotropic
displacement at 50% probability).
In the structure of compound 3 the silicon atoms can be divided in to two types. The first
type is Si1 atom linking to vinyl group while the second type represented by the silicon atoms of
terminal trimethylsilyl moieties. In the same fashion, in the case of compound 4 there are three
types of chemically non-equivalent silicon atoms – the central Si1 atom, the atom of SiClMe
moiety and SiMe groups, respectively. In spite of different chemical environment, bond lengths
and angles at these atoms differ from each other only marginally. The Si-C bonds are about 1.86-
2
3
1.88 Å that corresponds to the standard values for bonds of this type.
In the structure of molecule of compound 3 there are no atoms characterized by the
notable electron-acceptor properties. Thus basic intermolecular interactions responsible for the
stability of crystalline package of compound 3 are the same as in the case of hydrocarbons. To
analyze intermolecular interactions we used Hirshfeld surface analysis (HSA) [22] and atom-
atom potentials (force field UNI [23]). HSA method is related to comparative analysis of
curvature of electron densities of spherical atoms in molecules and crystal. The differences
between molecule and crystal shows the regions of accumulation and depletion of electron
density thus giving possibility of visualization of areas correspond to intermolecular contacts of
5

ACCEPTED MANUSCRIPT
various types. According to the results of HSA, about 82% of surface area (Fig.3) of molecule 3
is covered by H…H contacts. The rest of surface is related to contribution of C…H contacts and
C-H…π interactions between methyl, vinyl, and phenyl groups. The energy of crystal packing of
3
(heat of sublimation at 0 K) was estimated with force field UNI is 210.2 kJ/mol. Such a large
value of sublimation energy is not surprising, taking into consideration the volume and surface
2
area of 3 determined by HSA (748.3 Å и 612.6 Å
,
respectively).
Figure 3. The surface of molecule of compound 3 in the frame of HSA method. Projection is
analogous to Fig. 1.Red color marks area of C…H type contacts. Light-blue, blue and green
colors mark areas of the shortest contacts of H…H types.
6

ACCEPTED MANUSCRIPT
Figure 4. The surface of molecule of compound 4 in terms of HSA method. Projection is
analogous to Fig.1. Red color marks area of C…H contact types. Light-blue, blue and green
colors mark the areas of the shortest contacts of H…H types.
2 2 2
The replacement of vinyl group with (CH ) SiMe Cl leads to noticeably increase of sublimation
energy to 269.46 kJ/mol. This value, however, was increased partly as a result of intermolecular
bonding between compound 4 and solvated toluene molecule. The volume of molecule 4 and
3
2
2 2 2
respective surface are 884.24 A and 716.93 Å . The presence of (CH ) SiMe Cl group in
molecule of compound 4 demonstrate weak effect on the nature of intermolecular interactions in
crystal compared to the crystal structure of compound 3. The H…H contacts in 4 cover the
78.7% of molecular surface area. Chlorine atom in molecule 4 forms weak intermolecular bonds
C-H…Cl mainly with toluene molecule (4.1% of surface area). Most probably, the contribution
of the intermolecular interaction of the latter type in the sublimation energy is insignificant.
7

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3. Conclusion
New previously unknown bulk polyfunctional organosilanes with rigid molecular structure have
been synthesized. The molecular structures of compounds 3 and 4 were defined by X-ray data.
The possibility of use of prepared compound 3 as blocking agent for preparation of
polyrotaxanes was demonstrated on model reaction.
4. Experimental
4.1. General methods and materials
All solvents were purified before use. Tetrahydrofurane (THF) was distilled from
sodium/benzophenone, and toluene from calcium hydride under argon. 1,4-Dibromobenzene, n-
2
BuLi (1.6 M solution in hexane) and calcium hydride (CaH ) were purchased from Acros
Organics. Chlorotrimethylsilane, chlorodimethylsilane and trichlorovinylsilane were purchased
from Acros Organics and distilled before use. Karstedt′s catalyst (Platinum(0)-1,3-divinyl-
1,1,3,3-tetramethyldisiloxane complex solution in xylene, Pt ~2 %) was purchased from Aldrich.
The 4-trimethylsilylbromobenzene 2 was prepared using the method described in the literature
[
24].The reactions were monitored by thin-layer chromatography (TLC) using Fluka silica gel
(60 F 254) plates (0.25 mm). Column chromatography was carried out using Merck 60 (230–400
–1
mesh) silica gel. Visualization was made with UV light. Infrared spectra in the 50–3500 cm
region were obtained for KBr pellets and nujol mulls on Bruker Tensor 37 FTIR spectrometer.
TM
NMR spectra were recorded on a Bruker Avance
600 spectrometer operating at 600.22,
1
13
29
1
13
1
50.93 and 119.26 MHz for H, C and Si respectively. The chemical shifts for H and C
29
were indirectly referenced TMS via the solvent signals. The chemical shifts for Si were
1
13
measured with TMS as an external standard. The assignment of the signals in H and С NMR
spectra has been performed by use of 2D COSY, HMQC and HMBC techniques on the basis of
1
13
the Bruker program standard library.The signals in NMR H and C spectra were assigned by
D experiments (COSY, HMQS, HMBC).
2
4.2. Molecular and crystal structure determination of compounds 3 and 4
All measurements were carried out with Bruker Smart APEX DUO difractometer. The
structures were solved by direct methods and refined in full matrix anisotropic approximation
2
againt F . All calculations were carried out with programs SHELXTL 5.0 [26] and OLEX 2 [27].
8

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Table 1
Crystallographic and experimental parameters for the structures 3 and 4.
3
4
Brutto formula
C
29
H42Si
4
34.50 5
C H53ClSi
Formula weight
502.99
100
P-1
643.67
120
T, K
Space group
Z
P-1
2
2
A, Å
B, Å
C, Å
α, °
12.1716(14)
12.5150(15)
12.5257(14)
103.734(2)
113.209(2)
108.122(2)
1518.5(3)
1.100
12.411(3)
12.807(3)
14.563(3)
66.275(4)
74.409(4)
69.033(4)
1957.6(8)
1.092
β, °
Γ, °
3
V, Å
-3
dcalc, gЧcm
-1
M, см
2.11
2.72
F(000)
544
694
2qmax, °
61
61
Reflections collected
Independent reflections
Independent reflections
20968
26137
11929
9290
7
206
7395
(
I>2s(I))
Parameters
[for refl. With I>2s(I)]
307
397
R
1
0.0429
0.0558
9

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wR
2
0.1213
1.032
0.1548
1.020
GOF
Residual electron density,
0.572/-0.302
1.252/-0.797
-3
eЧÅ (ρmin/ρmin
)
Atom coordination, thermal parameters and experimental conditions are deposited in
Cambridge structural database [26] (CCSD numbers are 959176).
4.3. Synthesis of tris(4-trimethylsilylphenyl)vinylsilane (3)
1.6 M solution of n-BuLi in hexane (24.5 mL, 0.039 mol) was added dropwise to solution
of 4-trimethylsilylbromobenzene 2 (9 g, 0.039 mol) in absolute THF (90 mL) at -78°С in argon
under stirring. The reaction mixture was stirred at -78°С for 1 h. A solution of
trichlorovinylsilane (1.65 mL, 0.013 mol) in THF (5 mL) was added, and the mixture was stirred
at -78 °С for 1 h. After allowing the reaction mixture to warm up to room temperature 150 mL of
water was added under stirring. The aqueous layer was extracted twice with ethylacetate and
2 4
washed by water. After drying over Na SO the solvent was evaporated in vacuo to yield
compound 3 as colorless solid. The product was purified by recrystallization from hexane. As a
result 4.91 g of white powder with 75% yield was obtained. IR (KBr): 850, 1134, 1248, 1680-
-1
1
2
1
3
640, 3047 cm . H NMR (δ ppm, J Hz, CDCl ): 7.58 (broad singlet, 12H, ArH), 6.75 (dd, J =
3
3
3
2
2
0.2, J = 14.6, 1H, =CH-trans), 6.36 (dd, J = 14.6, J = 3.6, 1H, SiCH-), 5.88 (dd, J = 20.2,
3
13
J = 3.6, 1H, =CH-cis), 0.33 (s, 27H, SiCH
36.78 (1C, =CH
3
). C NMR (δ ppm, CDCl
3
): 141.85 (3C, C-SiMe
3
),
1
2
), 135.12 (6C, HCCSiMe
3
), 134.57 (3C, CSiAr Vin), 133.77 (1C,
2
29
SiCH=CH ), 132.64 (6C, HCCSiAr Vin), 1.19 (9C, SiCH ). Si NMR ((δ ppm, CDCl )): -4.0
2
2
3
3
(3Si, Me
3
Si), -17.7 (1Si, Ar
3
SiVin). Anal. Calc. (%) for C29
4
H42Si : C, 69.25; H, 8.42; Si, 22.34.
Found: C, 69.19; H, 8.41; Si, 22.40.
.4. Synthesis of α-tris-(4-trimethylsilylphenyl)-β-(dimethylchloro)-disilylethane (4)
4
To a solution of tris-(4-trimethylsilylphenyl)vinylsilane (2g, 0.004 mol) and
dimethyldichlorosilane (1.46 mL, 0.012 mol) in toluene (60 mL) Karstedt’s catalyst was added
(60 ꢀL, solution in xylene 2.1-2.4 % Pt) under stirring. The reaction mixture was stirred at 35 °C
for 8 hours. After the reaction was complete platinum was precipitated on centrifuge and solvent
with exess of dimethyldichlorosilane were evaporated in vacuo. The residual product was
purified by recrystallization from toluene. As a result 2.39 g of white powder with 96 % yield
1
0

ACCEPTED MANUSCRIPT
-1 1
was obtained. IR (KBr): 538-516, 850, 1134, 1248, 2960-2850, 3047 cm . H NMR (δ ppm, J
3
Hz, CDCl
Ar SiCH
3
): 7.56 (AB-system, J = 7.7, 12H, Ar), 1.43 (m, 2H, Me
2
ClSi-CH
Si). C NMR (δ ppm, CDCl
), 134.9 (6C, HCCSiMe ), 132.8 (6C, HCCSiAr
SiCH ), 1.1 (2C, CH Si(CH Cl), -1.2 (9C, SiCH
SiCl), -4.0 (3Si, Me Si), -9.9 (1Si, CH SiAr). Anal. Calcd.
: C, 62.30; H, 8.26; Cl, 5.93; Si, 23.50. Found: C, 62.75; H, 8.79; Cl, 5.44;
2
), 0.95 (m, 2H,
): 141.9
CH ),
13
3
2
), 0.45 (s, 6H, (CH
3
)
2
SiCl), 0.32 (s, 27H, (CH
CH
Cl), 4.6 (1C, Ar
): 33.1 (1Si, Me
3
)
3
3
(
3C, C-SiMe
1.7 (1C, CH
NMR (δ ppm, CDCl
%) for C31
3
), 135.1 (3C, CSiAr
2
2
3
2
2
29
1
2
SiMe
2
3
2
2
3
)
2
3
). Si
3
2
3
2
(
H49ClSi
5
Si, 23.02
4.5 Reaction of compound (3) with tetramethyldisiloxane
To a solution of tris-(4-trimethylsilylphenyl)vinylsilane (2.8g, 0.0056 mol) and
tetramethyldisiloxane (0.19 mL, 0.0014 mol) in toluene (60 mL) Karstedt’s catalyst was added
(60 ꢀL, solution in xylene 2.1-2.4 % Pt) under stirring. The reaction mixture was stirred at 25 °C
for 24 hours. After the reaction was complete solvent was evaporated in vacuo. The residual
product was purified by column chromatography. As a result 3.19 g of white powder with 95%
-1 1
yield was obtained. IR (KBr): 850, 1052, 1134, 1248, 2960-2850, 3047 cm . H NMR (δ ppm, J
3
Hz, CDCl
3
): 7.53 (AB-system, J = 7.7, 12H, Ar), 1.33 (m, 4H, CH
2
SiO), 0.63 (m, 4H,
13
Ar SiCH ), 0.30 (s, 54H, Me Si), 0.06 (s, 12H, CH Si(CH ) O). C NMR (δ ppm, CDCl3):
3
2
3
2
3 2
1
41.5 (6C, C-SiMe
3
), 135.7 (6C, CSiAr
2
CH
2
), 134.9(12C, HCCSiMe
SiCH ), -0.2 (4C, CH
18C, SiCH3). Si NMR (δ ppm, CDCl ): 8.2 (2Si, Me SiO), -4.1 (6Si, Me SiAr), -9.9 (2Si,
3
), 132.8 (12C,
HCCSiAr CH
2
2
), 10.6 (2C, CH
2
SiMe
2
O), 4.5 (2C, Ar
3
2
2
Si(CH O), -1.2
3 2
)
29
(
3
2
3
2
ArSiCH ). Anal. Calcd. (%) for C62H98OSi10: C, 65.30; H, 8.66; Si, 24.63. Found: C, 65.12; H,
8.75; Si, 24.53.
Acknowledgements
This work financially was supported by the Presidium of RAS (project ОХ-3) and the
Russian Foundation for Basic Research (Project 13-03-00932 ).
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ACCEPTED MANUSCRIPT
The new bulk organosilanes with rigid molecular structure were synthesized.
The molecular structures of compounds 3 and 4 were defined by X-ray data.
The possibility of use compound 3 as blocking agent was demonstrated.