Functionalization of polyhedral oligomeric silsesquioxane (POSS) via nucleophilic substitution

Article abstract of DOI:10.1055/s-0029-1216807

Octakis(3-chloropropyl)octasilsesquioxane, obtained recently by a new method, has enabled a highly efficient synthesis of a whole family of cube-like T8 silsesquioxanes by nucleophilic substitution of chlorine atom with appropriate nucleophilic agents. Fi

Full text of DOI:10.1055/s-0029-1216807

PAPER
2019
Functionalization of Polyhedral Oligomeric Silsesquioxane (POSS) via
Nucleophilic Substitution
F
unctionalization of Po
i
lyhedr
c
al
O
ligom
e
h
ric Silsesqui
a
a
Department of Organometallic Chemistry, Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznaꢀ, Poland
Fax +48(61)8291508; E-mail: marcinb@amu.edu.pl
b
Poznan Science & Technology Park, Adam Mickiewicz University Foundation, Rubieꢁ 46, 61-612 Poznaꢀ, Poland
Received 29 December 2008; revised 26 February 2009
During the last few years a number of brilliant reviews
concerning synthesis, characterization, and applications
of POSS have been published.1,2,23–27 Especially, the arti-
cle by Paul Lickiss,1 which has been published very re-
Abstract: Octakis(3-chloropropyl)octasilsesquioxane, obtained re-
cently by a new method, has enabled a highly efficient synthesis of
a whole family of cube-like T8 silsesquioxanes by nucleophilic sub-
stitution of chlorine atom with appropriate nucleophilic agents. Five
functionalized silsesquioxanes, i.e., octakis[3-(methacryloyl- cently, and references included in it, discuss all the
oxy)propyl]-, octakis(3-acetoxypropyl)-, octakis[3-(phenylami-
aspects concerning cube-like POSS in detail.
no)propyl]-, and octakis[3-(4-methylpiperazin-1-yl)propyl]octa-
silsesquioxane as well as octakis{3-[(2-hydroxyethyl)dimethyl-
About 90 POSS compounds with T8 cores have been
structurally characterized using diffraction methods and
about 50 of them are of T8R8 composition.1 The synthesis
of the majority of new T8R8 compounds is based on the
modification of a few simple precursors having such reac-
tive groups as Si–H, Si–CH=CH2, Si(CH2)3X, or Si–Ph.
High yields of functionalized POSS can be obtained by
three essential catalytic methods: (a) hydrosilylation,1,4,20
(b) nucleophilic substitution,2,20 and (c) metathesis/silyla-
tive coupling (Scheme 1).28–30
ammonio]propyl}octasilsesquioxane chloride were synthesized and
characterized by spectroscopic methods and elemental analysis.
Key words: functionalized silsesquioxanes, nucleophilic substitu-
tion, POSS, polyhedral oligosilsesquioxanes
Polyhedral oligosilsesquioxanes (POSS) are a class of
versatile building blocks for the production of inorganic–
organic hybrid materials with designed properties due to
the three-dimensional highly symmetrical nature of the
POSS core.1–7 The most important POSS materials are the
cube-like T8 derivatives, which have found a wide range
of technological application. The reasons for their domi-
nance are ease of handling and useful properties such as
thermal stability, ease of chemical modification, and
nano-sized dimension. POSS have also emerged as a new
class of nanofillers for the preparation of nanostructured
composites of higher performance.8 They have been used
extensively as catalysts,9 dendrimers,10 biocompatible
materials, and scaffolds for the development of liquids
crystals.11,12
As usual there are some limitations with each of these
methods. In some instances, direct hydrosilylation of an
olefin derivative of the intended functional group can lead
to serious side reactions. Moreover, hydrosilylation is an
exothermic reaction and can lead to an uncontrolled in-
crease in temperature, which may cause, in the case of
some functional groups (e.g., methacryloyl), undesirable
reactions. Finally, both hydrosilylation as well as meta-
thesis are catalyzed by transition metal complexes that are
very sensitive to poisoning caused by the presence of cer-
tain functional groups. The choice of functionalization
method depends also on the availability of the starting raw
material. For example, T8H8 is obtained in five weeks in
19% yield.28–30
Although the cubic T8 arrangement is achieved by the hy-
drolysis/condensation reactions of many simple silicon
compounds such as RSiCl3 or R1Si(OR2)3, only a few of
the known T8R8 derivatives can be prepared directly in
this manner.1–4
The method based on the nucleophilic substitution of
halogens in halogen derivatives of silsesquioxane is one
of the most versatile, enabling the syntheses of various
functionalized POSS. The above process is well known
and frequently applied to the synthesis of organofunction-
al silanes.31 The starting material used in this method is a
3-halopropyl-substituted silsesquioxane.
Several variants of this method were tested by performing
reactions in aqueous or nonaqueous media using acid-
base catalysis. In most cases, however, the process re-
quires a long time (several weeks), the final yield is low
and the desired product (POSS) is accompanied by amor-
phous silsesquioxanes and those with a ladder struc-
ture.6,13–22
Very recently, we reported a new method for the synthesis
of octakis(3-chloropropyl)octasilsesquioxane (1), based
on a two-stage hydrolytic condensation of (3-chloropro-
pyl)trimethoxysilane.32,33 This approach enables selective
formation of the desired product in a shorter time (4 days),
compared to the previous methods (5 weeks), while the
yield (35%) is comparable. The process is conducted in
methanolic solution with acid hydrolysis as the first stage
SYNTHESIS 2009, No. 12, pp 2019–2024
x
x.
x
x
.
2
0
0
9
Advanced online publication: 12.05.2009
DOI: 10.1055/s-0029-1216807; Art ID: T22708SS
© Georg Thieme Verlag Stuttgart · New York

2020
M. Dutkiewicz et al.
PAPER
R
R
R
H
H
O
R
O
Si
Si
O
Si
O
O
Si
H
O
O
O
H
Si
Si
Si
Si
O
O
catalyst
O
O
R
R
+
O
O
O
O
Si
Si
Si
Si
O
O
O
Si
H
O
Si
O
O
H
Si
Si
R
O
O
H
R
H
R
a) hydrosilylation of functional olefins by hydrosilsesquioxanes1,4,20
X
R
R
X
R
O
O
X
R
Si
Si
O
O
Si
Si
O
O
O
O
Si
Si
Si
Si
O
O
catalyst
O
O
X
R
X
+
+
KX
KR
O
O
O
O
Si
Si
Si
O
Si
O
Si
O
O
Si
O
O
Si
Si
X
R
O
O
X
R
X
R
b) nucleophilic substitution of halogen in halogenopropyl-substituted. silsesquioxanes2,20
R
R
O
O
O
R
Si
Si
O
O
Si
O
Si
O
O
O
Si
Si
Si
Si
O
O
catalyst
O
O
R
R
R
+
O
O
O
O
Si
Si
Si
O
Si
O
Si
O
O
Si
Si
R
O
Si
O
O
R
R
c) metathesis and silylative coupling of vinyl-substituted silsesquioxanes28–30
Scheme 1 Most common routes for the functionalization of POSS
and condensation in the presence of dibutyltin dilaurate as two reactions, respectively, whereas in the reactions with
a catalyst in the second stage.
aniline and 1-methylpiperazine, the relevant amine hydro-
chloride was a byproduct, therefore while carrying out
these reactions, it was reasonable to use 100% amine
excess. The reaction with 2-(dimethylamino)ethanol is,
as a matter of fact, a quaternization reaction as a result
of which octakis{3-[(2-hydroxyethyl)dimethylammo-
nio]propyl}octasilsesquioxane chloride (6) was obtained.
However, it was included in the study because of the great
similarity of the reaction course.
Our method enables the product to be obtained with simi-
lar yield, but in a much shorter period of time. Moreover,
it is the optimal time, during which octakis(3-chloropro-
pyl)octasilsesquioxane (1) is selectively formed. This was
confirmed by X-ray crystal structure analysis and 29Si
NMR (only the signal at d = 67.28 is observed, which is
typical for cubic POSS). Prolonging the process would re-
sult in the formation of ladder-like and random POSS,
which are not desired in this case.
Since the synthesis of the starting material 1 was hitherto
difficult, nucleophilic substitution has not been frequently
applied to POSS functionalization (to octafunctionalized
POSS synthesis of chlorine in 1 in particular). A few au-
thors have reported chlorine atom substitution in 1 with I,
SCN, PPh2, and SMe.2,16,34 The reactivity of chlorine atom
in 1 was also used in the functionalization of POSS com-
pounds with silver oxide or silver nitrate to obtain hy-
droxy functionality,35,36 with 2-methyl-4,5-dihydro-
oxazole,37,38 or with N,N-dimethyloctylamine.16
The above method, due to easy access to octakis(3-chlo-
ropropyl)octasilsesquioxane (1), enables the synthesis of
a whole family of functionalized silsesquioxanes by nu-
cleophilic substitution of the chlorine atom. This is why
the present work is aimed at the synthesis of new function-
alized T8 silsesquioxanes on the basis of the reactions of
the silsesquioxane 1 with different nucleophilic agents
such as potassium methacrylate, sodium acetate, aniline,
1-methylpiperazine, and 2-(dimethylamino)ethanol as
well as at characterization of the products obtained. Func- Of all the functional groups used by us for silsesquioxane
tional groups present in the above compounds are fre- functionalization (Scheme 2), only the methacryloyl
quently employed to functionalize siloxanes.
group had been employed earlier to synthesize organo-
functional organosilicon compounds, i.e. to synthesize [3-
(methacryloyloxy)propyl]trimethoxysilane, one of the
most important silane promoters of adhesion.31
All reactions were performed in the same way, i.e. in N,N-
dimethylformamide medium, except for the reaction with
2-(dimethylamino)ethanol, where the latter operates also
as a solvent. Potassium iodide was employed as a catalyst The methacryloyl group easily undergoes free radical po-
for the reaction with potassium methacrylate and sodium lymerization. Its reactivity is frequently exploited to ob-
acetate, whereas in all other cases the amines used in the tain hybrid materials or organic-inorganic copolymers.
reactions acted autocatalytically. Moreover, potassium On the other hand, the synthesis of derivatives with meth-
chloride and sodium chloride were byproducts in the first acryloyl groups has a potentially undesirable side reac-
Synthesis 2009, No. 12, 2019–2024 © Thieme Stuttgart · New York

PAPER
Functionalization of Polyhedral Oligomeric Silsesquioxane
2021
tion, polymerization, therefore, it is necessary to carry out thermic, leading to uncontrolled polymerization. On the
this reaction in a controlled way, i.e. under relatively mild other hand, polycondensation of [3-(methacryloyl-
conditions. One of the methods that forms methacryloyl- oxy)propyl]trimethoxysilane in the presence of formic
oxy-functionalized silanes as well as silsesquioxane is acid, resulting in the formation of a mixture of oligo- and
hydrosilylation of allyl methacrylate. However, contrary polysilsesquioxanes, has also been reported in the litera-
to nucleophilic substitution, the former reaction is exo- ture.17
O
O
O
O
O
O
O
O
O
O
Si
O
O
Si
Si
O
O
Si
O
O
O
O
Si
O
O
Si
O
Si
O
Si
O
O
O
O
O
O
O
O
O
O
O
O
Si
O
Si
O
Si
O
O
O
Si
O
Si
O
O
O
O
O
O
Si
Si
Si
O
O
2
3
O
O
O
O
O
O
82%
62%
O
O
O
O
KO
KO
Cl
Cl
O
Si
O
O
Si
O
Cl
Si
Si
O
O
Cl
O
Cl
O
Si
Si
O
Cl
O
O
Si
Si
O
1
35%
NH2
HN
Cl
Cl
N
Me
Me
Me
N
N
N
N
HN
NH
Me
N
N
O
O
N
Si
O
Si
O
O
Si
Si
N
Me
O
O
Me
Me
O
N
Si
Si
Si
Si
H
N
H
O
O
N
O
O
O
O
N
O
O
Si
H
O
H
Si
Me
N
N
Si
Si
O
N
Si
O
Me
O
O
N
Si
Si
O
Si
O
O
N
HO
4
5
HN
NH
74%
79%
N
N
N
N
Me
Me
Me
N+
Me
HO
Me
OH
Me
N+
Cl–
Cl–
Cl–
N+
Me
OH
Me
N+
Cl–
O
Si
O
O
Si
HO
Me
HO
Me
O
Si
Si
O
O
Me
O
Me
O
N+
Cl–
Si
Si
O
Me
O
O
OH
Me
Si
Si
O
N+
Clv
6
82%
Cl–
N+
Cl–
N+
Me
HO
OH
Me
Me
Me
Scheme 2 General methodology for the functionalization of POSS via nucleophilic substitution
Synthesis 2009, No. 12, 2019–2024 © Thieme Stuttgart · New York

2022
M. Dutkiewicz et al.
PAPER
The application of the reaction of nucleophilic substitu- point of view to synthesis of a variety of functionalized
tion has made it possible to obtain the product 2 with a POSS.
high yield (82%) in a relatively short time (8 h). The com-
pound 2 is a yellowish liquid of considerable viscosity.
NMR and FT-IR analyses unambiguously confirmed the
structure assumed for compound 2. Another example of
carboxy group addition to the silsesquioxane core is the
synthesis of octakis(3-acetoxypropyl)octasilsesquioxane
(3). The final yield of the latter product is the lowest
(62%), compared to all remaining silsesquioxanes, which
can be explained by the difficult isolation of the product
from sodium chloride that is formed as a byproduct.
1H NMR (300 MHz), 13C NMR (75 MHz), and 29Si NMR (59 MHz)
spectra were recorded on a Varian XL 300 spectrometer at r.t. using
CDCl3, C6D6, or D2O as solvents. FT-IR spectra were recorded on a
Bruker Tensor 27 Fourier transform spectrophotometer equipped
with a SPECAC Golden Gate diamond ATR unit. In all cases 16
scans at a resolution of 2 cm–1 were used to record the spectra. Ele-
mental analyses were made on an Elementar Analyser Vario EL III.
Melting point measurements were carried out on a Stuart Scientific
SMP3 apparatus. (3-Chloropropyl)trimethoxysilane, benzene,
CHCl3, MeOH, DMF, 1-methylpiperazine, 2-(dimethylamino)eth-
anol, dibutyltin dilaurate (DBTL), and HCl were used as received
(Aldrich) without further purification. KI was dried overnight at
120 °C and aniline was distilled under vacuum and stored over
KOH. Potassium methacrylate was synthesized from KOH and
methyl methacrylate.
The other functionalized silsesquioxanes contain amino
derivatives. Amino-functional polysiloxanes are of con-
siderable practical importance for different industrial
branches, among others the textile and cosmetic indus-
tries. The synthesis of silsesquioxanes with analogous
groups opens the possibility of expanding their applica-
tion.
Octakis(3-chloropropyl)octasilsesquioxane (1)32,33
Anhyd MeOH (119 g, 150 mL, 3.71 mol) and concd HCl (5.94 g, 5
mL) were placed in a two-necked round-bottomed flask equipped
with a condenser, addition funnel, and magnetic stirring bar. Then
(3-chloropropyl)trimethoxysilane (15 g, 13.9 mL, 75.5 mmol) was
To the best of our knowledge, compounds 4–6 have not
been previously obtained. An analogous reaction to that
with 2-(dimethylamino)ethanol (which gives product 6), added dropwise through the addition funnel over 10 min with vig-
orous stirring, which was maintained for 2 h until the soln cooled
was carried out by the use of polysiloxane substituted with
down to r.t. The mixture was allowed to stand at r.t. for an additional
chloropropyl groups to get water soluble and amphiphilic
48 h without stirring. After 2 d, DBTL as a condensation catalyst
silicone.39 Significant practical importance of compounds
(150 mg, 140 mL, 0.24 mmol) was added with stirring. Then the
mixture was left for a further 2 d to give a white crystalline precip-
of this type has encouraged us to perform the synthesis of
analogous silsesquioxanes. Quaternization of tertiary hy-
droxyalkylamine [2-(dimethylamino)ethanol] with 3-
chloropropyl groups attached to POSS gave quaternary
(hydroxyalkylammonio)alkyl-substituted silsesquioxane
6, well soluble in water, with high yield (82%).
itate. The supernatant liquid was filtered off and the collected crys-
tals were washed several times with MeOH and dried in a vacuum
to give 1 (3.68 g, 35%); mp 206–208 °C.
IR (ATR): 2996–2875, 1457–1274, 1230–940, 552 cm–1.
1H NMR (300 MHz, CDCl3): d = 0.78 (t, 16 H, SiCH2), 1.84 (quint,
16 H, CH2), 3.53 (t, 16 H, CH2Cl).
The application of other amine derivatives in the nucleo-
philic substitution of the chlorine atom in 1 gave an effec-
tive synthesis of products 4 and 5 with high yields (74%
and 79%, respectively). The reactions were conducted in
the same way by using 100% excess of amine in order to
combine HCl (released during the reactions) by forming
amine hydrochloride that can be easily separated from the
desirable product by washing with appropriate solvents.
In both cases, products 4 and 5 form solids and NMR and
FT-IR analyses fully confirmed their structures.
13C NMR (75 MHz, CDCl3): d = 9.9, 26.4, 47.1.
29Si NMR (59 MHz, CDCl3): d = –67.28.
Octakis[3-(methacryloyloxy)propyl]octasilsesquioxane (2);
Typical Procedure
All functionalized silsesquioxanes 2–6 were synthesized in a simi-
lar way. Syntheses were carried out in a two-necked round-
bottomed flask equipped with condenser, thermometer, magnetic
stirring bar, and heater. Octakis(3-chloropropyl)octasilsesquioxane
(1, 300 mg, 0.27 mmol) was dissolved in DMF (5.68 g, 6 mL, 77.6
mmol) and placed in the reaction flask. Next potassium methacry-
late (261 mg, 2.12 mmol) and KI (28 mg, 0.169 mmol) were added
to this soln. The reaction was carried out at 100 °C for 8 h with stir-
ring. Then the mixture was filtered in order to remove KCl that pre-
cipitated during the reaction and the obtained filtrate was subjected
to concentration by vacuum evaporation of DMF. The remaining
viscous liquid was filtered again, washed with distilled H2O to re-
move all residual potassium salts and dissolved in CHCl3. The or-
ganic layer was then separated and evaporated under vacuum to
give 2 (330 mg, 82%).
In conclusion, octakis(3-chloropropyl)octasilsesquioxane
(1) obtained according to the new effective method,32,33 is
a very important and attractive precursor for synthesis of
a wide range of functionalized silsesquioxanes, prepared
by nucleophilic substitution of the chlorine atoms in 1
with appropriate organic groups. This reaction enables
highly efficiently syntheses of five functionalized silses-
quioxanes: octakis[3-(methacryloyloxy)propyl]silsesqui-
oxane (2), octakis(3-acetoxypropyl)octasilsesquioxane
(3), octakis[3-(phenylamino)propyl]silsesquioxane (4),
octakis[3-(4-methylpiperazin-1-yl)propyl]silsesquioxane
(5), and octakis{3-[(2-hydroxyethyl)dimethylammo-
nio]propyl}octasilsesquioxane chloride (6). The reaction
proceeded under considerably milder conditions than
those needed when using other well-known methods and
therefore, it can be applied from synthetic and economic
IR (ATR): 2957, 2896, 1716, 1639, 1454–1297, 1250–939 cm–1.
1H NMR (300 MHz, CDCl3): d = 0.68 (t, 16 H, SiCH2), 1.74 (s, 24
H, CH3), 1.92 (quint, 16 H, CH2), 4.08 (t, 16 H, CH2O), 5.53 (s, 8
H, CH2=C), 6.07 (s, 8 H, CH2=C).
13C NMR (75 MHz, CDCl3,): d = 8.2, 18.3, 22.3, 66.3, 125.3, 136.4,
167.3.
29Si NMR (59 MHz, CDCl3): d = –68.69.
Synthesis 2009, No. 12, 2019–2024 © Thieme Stuttgart · New York

PAPER
Functionalization of Polyhedral Oligomeric Silsesquioxane
2023
Anal. Calcd for C56H88O28Si8: C, 46.90; H, 6.19. Found: C, 46.83;
H, 6.18.
Anal. Calcd for C64H136N16O12Si8: C, 49.70; H, 8.86; N, 14.49.
Found: C, 49.74; H, 8.87; N, 14.50.
Octakis(3-acetoxypropyl)octasilsesquioxane (3)
Octakis{3-[(2-hydroxyethyl)dimethylammonio]propyl}octasil-
sesquioxane Chloride (6)
DMF (6.63 g, 7 mL, 90.5 mmol), octakis(3-chloropropyl)octasilses-
quioxane (1, 300 mg, 0.27 mmol), NaOAc (174 mg, 2.12 mmol) and
KI (28 mg, 0.169 mmol) were placed in a reaction flask. The reac-
tion was carried out at 100 °C for 24 h with stirring. After cooling
to r.t., the mixture was filtered in order to remove NaCl that precip-
itated during the reaction and the obtained filtrate was subjected to
concentration by vacuum evaporation of DMF. The solid residue
was washed with distilled H2O to remove all residual potassium and
sodium salts and dissolved in benzene. The organic layer was then
separated and evaporated under vacuum to give 3 (200 mg, 62%) as
a light yellow oil
Octakis(3-chloropropyl)octasilsesquioxane (1, 300 mg, 0.27 mmol)
and 2-(dimethylamino)ethanol with 100% excess (380 mg, 427 mL,
4.3 mmol) of were placed in a reaction flask. The reaction was car-
ried out at 100 °C for 24 h with stirring. The excess of 2-(dimethyl-
amino)ethanol was removed from the postreaction mixture by
vacuum evaporation to give 6 (380 mg, 82%) as a white solid; the
melting point of the obtained material is much higher then its de-
composition temperature. The product changed its color from white
to dark red during the measurement at about 230 °C.
IR (ATR): 3222, 2944–2775, 1469–1300, 1230–900, 698 cm–1.
IR (ATR): 2950–2880, 1738, 1457–1350, 1238, 1114–1000, 519
cm–1.
1H NMR (300 MHz, C6D6): d = 0.85 (t, 16 H, SiCH2), 1.35 (quint,
1H NMR (300 MHz, D2O): d = 0.59 (t, 16 H, SiCH2), 1.86 (quint,
16 H, CH2), 2.84 (t, 16 H, CH2N), 3.11 (s, 48 H, CH3), 3.37 (t, 16
H, NCH2), 3.47 (s, 8 H, OH), 3.75 (t, 16 H, CH2O).
16 H, CH2), 1.82 (s, 24 H, CH3), 4.05 (t, 16 H, CH2O).
13C NMR (75 MHz, D2O): d = 9.5, 16.5, 51.4, 55.3, 64.9, 67.3.
29Si NMR (59 MHz, D2O): d = –67.31.
13C NMR (75 MHz, C6D6): d = 11.1, 20.5, 22.7, 65.9, 170.2.
29Si NMR (59 MHz, C6D6): d = –69.49.
Anal. Calcd for C56H136Cl8N8O20Si8: C, 38.43; H, 7.83; N, 6.40.
Found: C, 38.50; H, 7.85; N, 6.42.
Anal. Calcd for C40H72O28Si8: C, 39.20; H, 5.92. Found: C, 39.15;
H, 5.91.
Acknowledgment
Octakis[3-(phenylamino)propyl]octasilsesquioxane (4)
Octakis(3-chloropropyl)octasilsesquioxane (1, 400 mg (0.35 mmol)
was dissolved in DMF (7.57 g, 8 mL, 103 mmol) and placed togeth-
er with almost 100% excess of aniline (500 mg, 489 mL, 5.37 mmol)
in a reaction flask. The reaction was carried out at 110 °C for 24 h
with stirring. The mixture was filtered in order to remove aniline hy-
drochloride and the obtained filtrate was subjected to concentration
by vacuum evaporation of DMF. The solid residue was washed with
benzene several times to remove all remaining amine and byproduct
(amine hydrochloride) followed by drying under vacuum to give 4
(410 mg, 74%); mp 100–103 °C.
Financial support from the Ministry of Science and Higher Educa-
tion (Poland); Grant 05 0005 04/2008 is gratefully acknowledged.
References
(1) Lickiss, P. D.; Ratabont, F. Adv. Organomet. Chem. 2008,
57, 1.
(2) Baney, R. H.; Itoh, M.; Sakakibara, A.; Suzuki, T. Chem.
Rev. 1995, 95, 1409.
(3) Feher, F. J.; Budzichowski, T. A. Polyhedron 1995, 14,
3239.
(4) Brick, C. M.; Tamaki, R.; Kim, S. G.; Asuncion, M. Z.; Roll,
M.; Nemoto, T.; Ouchi, Y.; Chujo, Y.; Laine, R. M.
Macromolecules 2005, 38, 4655.
(5) Hybrid Materials; Kickelbick, G., Ed.; Wiley-VCH:
Weinheim, 2006.
(6) Voronkov, M. G.; Lavrent’ev, V. I. Top. Curr. Chem. 1982,
102, 199.
(7) Loy, D. A.; Shea, K. J. Chem. Rev. 1995, 95, 1431.
(8) Sanchez, C.; Julian, B.; Belleville, P.; Popall, M. J. Mater.
Chem. 2005, 15, 3559.
(9) Feher, F. J.; Blanski, R. L. J. Chem. Soc., Chem. Commun.
1990, 1614.
(10) Feher, F. J.; Wyndham, K. D. Chem. Commun. 1998, 323.
(11) Feher, F. J.; Wyndham, K. D.; Sciadome, M. A.; Hamuro, Y.
Chem. Commun. 1998, 1469.
(12) Saez, I. M.; Goodby, J. W. Liq. Cryst. 1999, 26, 1101.
(13) Murugavel, R.; Bhattacharjee, M.; Roesky, H. W. Appl.
Organomet. Chem. 1999, 13, 227.
(14) Yuan, C.; Hu, C. Chem. J. Internet 2000, 2(5), 025026pc;
http://www.chemistrymag.org/.
(15) Roꢂciszewski, P.; Kazimierczuk, R.; Sołtysiak, J. Polimery
2006, 51, 1.
(16) Chojnowski, J.; Fortuniak, W.; Roꢂciszewski, P.; Wercel,
W.; Łukasiak, J.; Kamysz, W.; Hałasa, R. J. Inorg.
Organomet. Polym. Mater. 2006, 16, 219.
(17) Eisenberg, P.; Erra-Balsells, R.; Ishikawa, Y.; Lucas, J. C.;
Naomi, H.; Williams, R. J. J. Macromolecules 2002, 35,
1160.
1H NMR (300 MHz, CDCl3): d = 0.76 (t, 16 H, SiCH2), 1.84 (quint,
16 H, CH2), 3.13 (NH), 3.53 (t, 16 H, CH2NH), 7.12–7.32 (m, 40
Harom).
13C NMR (75 MHz, CDCl3): d = 9.3, 26.2, 47.0, 113.1, 115.2,
129.2, 146.1.
29Si NMR (59 MHz, CDCl3): d = –67.11.
Anal. Calcd for C72H96N8O12Si8: C, 58.03; H, 6.49; N, 7.52. Found:
C, 58.05; H, 6.50; N, 7.53.
Octakis[3-(4-methylpiperazin-1-yl)propyl]octasilsesquioxane
(5)
Octakis(3-chloropropyl)octasilsesquioxane (1, 400 mg, 0.35 mmol)
was dissolved in DMF (7.57 g, 8 mL, 103 mmol) and placed togeth-
er with 100% excess of 1-methylpiperazine (570 mg, 631 mL, 5.7
mmol) in a reaction flask. The reaction was carried out at 100 °C for
48 h with stirring. Then the mixture was filtered in order to remove
amine hydrochloride that was formed during the reaction and the
obtained filtrate was subjected to concentration by vacuum evapo-
ration of DMF. The solid residue was washed with CHCl3 several
times to remove the product from the remaining amine and its hy-
drochloride. All CHCl3 portions were collected together. In the next
step CHCl3 was removed by vacuum evaporation to give 5 (460 mg,
79%).
1H NMR (300 MHz, CDCl3): d = 0.82 (t, 16 H, SiCH2), 1.25 (t, 16
H, CH2N), 2.33 (quint, 16 H, CH2), 2.43 (m, 24 H, NCH3), 3.74 (s,
64 H, NCH2).
13C NMR (75 MHz, CDCl3): d = 10.0, 19.0, 44.4, 50.5, 52.9, 59.7.
29Si NMR (59 MHz, CDCl3): d = –67.50.
Synthesis 2009, No. 12, 2019–2024 © Thieme Stuttgart · New York

2024
M. Dutkiewicz et al.
PAPER
(18) Gültek, A.; Seçkin, T.; Adigüzel, H. Ì. Turk. J. Chem. 2005,
29, 391.
(29) Itami, Y.; Marciniec, B.; Kubicki, M. Chem. Eur. J. 2004,
10, 1239.
(19) Bassindale, A. R.; Liu, Z.; MacKinnon, I. A.; Taylor, P. G.;
Yang, Y.; Light, M. E.; Horton, P. N.; Hoursthouse, M. B.
Dalton Trans. 2003, 2945.
(20) Dittmar, U.; Hendan, B. J.; Florke, U.; Marsmann, H. C.
J. Organomet. Chem. 1995, 489, 185.
(21) Bassindale, A. R.; Gentle, T. E. J. Mater. Chem. 1993, 12,
1319.
(22) Agaskar, P. A. Inorg. Chem. 1991, 30, 2707.
(23) Provatas, A.; Matisons, J. G. Trends Polym. Sci. 1997, 5,
327.
(30) Waehner, J.; Marciniec, B.; Pawluć, P. Eur. Inorg. Chem.
2007, 18, 2975.
(31) Deschler, U.; Kleinschmit, P.; Panster, P. Angew. Chem., Int.
Ed. Engl. 1986, 25, 236.
(32) Marciniec, B.; Maciejewski, H.; Dutkiewicz, M. PL 383291,
2007.
(33) Marciniec, B.; Dutkiewicz, M.; Maciejewski, H.; Kubicki,
M. Organometallics 2008, 27, 793.
(34) Handen, B. J.; Marsmann, H. C. Appl. Organomet. Chem.
1999, 13, 287.
(24) Laine, R. M. J. Mater. Chem. 2005, 15, 3725.
(25) Baney, R. H.; Cao, X. In Silicon-Containing Polymers;
Jones, R. G.; Ando, W.; Chojnowski, J., Eds.; Kluwer
Academic Press: Dordrecht, 2000.
(26) Li, G.; Wang, L.; Li, H.; Pittman, C. U. Jr. J. Inorg.
Organomet. Polym. 2001, 11, 123.
(35) Liu, Y.; Yang, X.; Zhang, W.; Zheng, S. Polymer 2006, 47,
6814.
(36) Feher, F. J.; Wyndham, K. D.; Soulivang, D.; Nguyen, F.
J. Chem. Soc., Dalton Trans. 1999, 1491.
(37) Kim, K. M.; Ouchi, Y.; Chudo, Y. Polym. Bull. (Berlin)
2003, 49, 341.
(27) Marciniec, B.; Maciejewski, H.; Pietraszuk, C.; Pawluć, P.
Hydrosilylation. A Comprehensive Review on Recent
Advances, In Advances in Silicon Science, Vol. 1; Marciniec,
B., Ed.; Springer: Heidelberg, 2009.
(38) Sgen, J.; Zheng, S. J. Polym. Sci., Part B: Polym. Lett. 2006,
44, 942.
(39) Fortuniak, W.; Rózga-Wijas, K.; Chojnowski, J.; Labadens,
F.; Sauvet, G. React. Funct. Polym. 2005, 61, 315.
(28) Marciniec, B. Coord. Chem. Rev. 2005, 249, 2374.
Synthesis 2009, No. 12, 2019–2024 © Thieme Stuttgart · New York