Facile synthesis of tris(alkoxydimethylsilyl)methane derivatives via alcoholysis under open-flask and mild conditions

Article abstract of DOI:10.1080/10426501003685783

The reactions between a variety of functionalized alcohols and tris(dimethylsilyl)methane, (HMe₂Si)₃CH, are described. Alcohols such as ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, triethylene glycol monomethyl ether, 2-chloroethanol, 1-octanol, benzyl alcohol, glycidol, and allyl alcohol were converted in the presence of Karstedts catalyst into the corresponding tris(alkoxydimethylsilyl)methanes, (ROMe ₂Si)₃CH, in a convenient one-pot operation under aerobic conditions. The appearance of the products coincides with the generation of colloidal Pt(0) species. Moreover, poly(4-chloromethyl)styrene containing tris(dimethylsilyl)methyl groups reacts with benzyl alcohol or 2-chloroethanol in the presence of Karstedts catalyst to give new macromolecules bearing tris(alkoxydimethylsilyl)methyl groups. The reaction rate is greatly influenced by the concentration of catalyst. Taylor & Francis Group, LLC.

Full text of DOI:10.1080/10426501003685783

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Phosphorus, Sulfur, and Silicon and the
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Facile Synthesis of
Tris(alkoxydimethylsilyl)methane
Derivatives via Alcoholysis Under Open-
Flask and Mild Conditions
Kazem D. Safa a , Elham Sharifi a , Shahin Tofangdarzadeh a & Akbar
Hassanpour a
a Organosilicon Research Laboratory, Faculty of Chemistry ,
University of Tabriz , Tabriz, Iran
Published online: 19 Nov 2010.
To cite this article: Kazem D. Safa , Elham Sharifi , Shahin Tofangdarzadeh & Akbar Hassanpour
(2010) Facile Synthesis of Tris(alkoxydimethylsilyl)methane Derivatives via Alcoholysis Under
Open-Flask and Mild Conditions, Phosphorus, Sulfur, and Silicon and the Related Elements, 185:12,
2433-2440, DOI: 10.1080/10426501003685783
To link to this article: http://dx.doi.org/10.1080/10426501003685783
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Phosphorus, Sulfur, and Silicon, 185:2433–2440, 2010
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426501003685783
FACILE SYNTHESIS OF
TRIS(ALKOXYDIMETHYLSILYL)METHANE DERIVATIVES
VIA ALCOHOLYSIS UNDER OPEN-FLASK AND MILD
CONDITIONS
Kazem D. Safa, Elham Sharifi, Shahin Tofangdarzadeh,
and Akbar Hassanpour
Organosilicon Research Laboratory, Faculty of Chemistry, University of Tabriz,
Tabriz, Iran
The reactions between a variety of functionalized alcohols and tris(dimethylsilyl)methane,
(HMe2Si)3CH, are described. Alcohols such as ethylene glycol monobutyl ether, ethylene
glycol monoethyl ether, triethylene glycol monomethyl ether, 2-chloroethanol, 1-octanol,
benzyl alcohol, glycidol, and allyl alcohol were converted in the presence of Karstedt’s catalyst
into the corresponding tris(alkoxydimethylsilyl)methanes, (ROMe2Si)3CH, in a convenient
one-pot operation under aerobic conditions. The appearance of the products coincides with
the generation of colloidal Pt(0) species. Moreover, poly(4-chloromethyl)styrene containing
tris(dimethylsilyl)methyl groups reacts with benzyl alcohol or 2-chloroethanol in the presence
of Karstedt’s catalyst to give new macromolecules bearing tris(alkoxydimethylsilyl)methyl
groups. The reaction rate is greatly influenced by the concentration of catalyst.
Keywords Alcoholysis reaction; Karstedt’s catalyst; poly(chloromethyl)styrene;
tris(alkoxydimethylsilyl)methane; tris(dimethylsilyl)methane
INTRODUCTION
Alcoholysis of organosilanes requires a catalyst because alcohols are not sufficiently
nucleophilic to react with Si H bonds under normal conditions. The standard method for
preparation of alkoxysilanes is to treat the organosilyl chloride with the alcohol, in the
presence of a base such as imidazole, in polar organic solvents such as DMF.1 D’Sa et al.2
have shown that organic solvents such as CH3CN and CH2Cl2 can be used with a superbase.
However, base-sensitive functional groups cannot be tolerated, and the production of an
ammonium hydrochloride as byproduct makes this approach unattractive. Cationic iridium
and iron catalysts have been employed for the alcoholysis of silanes.3–5 The mechanism
is believed to proceed through nucleophilic attack by the alcohol on an η2-silane adduct.
Drawbacks of these catalysts include the need for rigorously aerobic and water-free condi-
tions, slow rates, especially with bulky tertiary silanes, and poor functional group tolerance.
The highly Lewis acidic borane B(C6F5)3 has also been shown to effect the dehydrogenative
Received 15 December 2009; accepted 6 February 2010.
Address correspondence to Kazem D. Safa, Organosilicon Research Laboratory, Faculty of Chemistry,
University of Tabriz, 51664 Tabriz, Iran. E-mail: dsafa@tabrizu.ac.ir
2433

2434
K. D. SAFA ET AL.
silylation of alcohols with various silanes, albeit at very slow rates.6 Substitution reactions
of the Si-X (where X = F,Cl, Br) bond with alcohols or with water also leads to Si-O bonds.
This reaction requires bases such as amines to act as acid scavengers, in stoichiometric
amounts, making this method not very cost-effective.7,8
We have recently developed a convenient procedure for the preparation of a se-
ries of tris(alkoxydimethylsilyl)methanes from reactions of (HMe2Si)3CH with mono-
functionalized alcohols in the presence of chloroplatinic acid, [H2PtCl6.6H2O], as a cat-
alyst.9 In this article, we report the use of Karstedt’s catalyst as highly effective for the
alcoholysis of tris(dimethylsilyl)methane under open-flask conditions. Moreover, analo-
gous reactions with styrene-based polymers having Si H groups in the side chain gave
new functionalized polymers bearing silyl ether groups.
RESULTS AND DISCUSSION
Recently, we have embarked on a program directed toward the development of
reactions of tris(dimethylsilyl)methane, (HMe2Si)3CH, for the generation of syntheti-
cally useful organosilicon compounds.10–12 We have reported the preparation of some
tris(alkoxydimethylsilyl)methanes from the alcoholysis of tris(dimethylsilyl)methane in
the presence of Speier’s catalyst (H2PtCl6.6H2O) under mild aerobic conditions.9 In
ongoing efforts to exploit (HMe2Si)3CH, the alcoholysis of tris(dimethylsilyl)methane
with some functionalized alcohols in the presence of Karstedt’s catalyst [Pt2(CH2
CHSiMe2OSiMe2CH CH2)3] is examined.
The compound (HMe2Si)3CH was made in 60% yield from HMe2SiCl, CHBr3, and
Mg in THF. Alcohols, such as ethylene glycol monobutyl ether, ethylene glycol monoethyl
ether, triethylene glycol monomethyl ether, 2-chloroethanol, 1-octanol, benzyl alcohol,
glycidol, and allyl alcohol, were treated with (HMe2Si)3CH in the presence of Karstedt’s
catalyst in air under mild conditions, and the related tris(alkoxydimethylsilyl)methanes
were produced in good yields (Table I). The progress of the reactions was monitored by IR
Table I Products, yields, and reaction conditions for the alcoholysis of (HMe2Si)3CH in the presence of Karst-
edt’s catalyst
Product
Entry
ROH
Product
yield (%) Temp/time
1
2
3
4
CH3(CH2)2CH2OCH2CH2OH
CH3CH2OCH2CH2OH
CH3OCH2(CH2OCH2)3CH2OH (CH3OCH2(CH2OCH2)3CH2O Me2Si)3CH
(CH3(CH2)2CH2OCH2CH2OMe2Si)3CH
(CH3CH2OCH2CH2OMe2Si)3CH
66
76
97
55
Reflux/1 h
Reflux/3 h
Reflux/2 h
Reflux/30
min
ClCH2CH2OH
(ClCH2CH2O Me2Si)3CH
5
6
CH3(CH2)6CH2OH
(CH3(CH2)6CH2O Me2Si)3CH
64
77.
Reflux/4 h
Rt/10 h
CH OH
2
(
CH2OMe2Si)3CH
7
8
71
75
Rt/2 h
O
O
(
CH2OMe2Si)3CH
CH2OH
CH2 CHCH2OH
(CH2 CHCH2O Me2Si)3CH
Reflux/18 h

SYNTHESIS OF TRIS(ALKOXYDIMETHYLSILYL)METHANES
2435
spectroscopy until the Si H absorbance in the IR spectrum disappeared. The colorless re-
action mixture gradually turned to a homogeneous black solution, indicating the generation
of colloidal Pt(0) particles.
In all cases, reaction times are significantly shorter than those with Speier’s catalyst,
even for larger alcohols. Furthermore, good yields (Table I, entries 6 and 7) were obtained
in reactions of benzyl alcohol and glycidol at room temperature. The alcoholysis in the
presence of Karstedt’s catalyst was carried out under aerobic conditions, unlike those in
previous work.13,14
Benzyl alcohol in the presence of Speier’s catalyst gave dibenzyl ether,
PhCH2OCH2Ph, instead of the expected (PhCH2OSiMe2)3CH.9 The reaction of
benzyl alcohol with (HMe2Si)3CH in the presence of Karstedt’s catalyst at room
temperature led to (PhCH2OMe2Si)3CH, but at higher temperature, coupling took place
(Scheme 1). In the case of glycidol (Table I, entry 7), alcoholysis was successful at room
temperature, but under reflux, polymerization instead of alcoholysis was observed.
PhH2COMe2Si
PhH2COMe2Si
HMe2Si
HMe2Si
HMe2Si
PhCH OH
2
PhCH2OH
C
H
C
H
PhCH2OCH2Ph
Karstedt/R.T
Karstedt / reflux
PhH2COMe2Si
Scheme 1 The alcoholysis of (HMe2Si)3CH with benzyl alcohol.
The amount of Karstedt’s catalyst has a significant effect on the alcoholysis rate. The
optimum amount was determined by experiments with ethylene glycol monoethyl ether.
Table II shows that increasing amounts of catalyst leads to faster reactions and shorter
alcoholysis times. For instance, by increasing the amount of catalyst from [Pt◦]/[Si H] =
1.10 × 10−4 to [Pt◦]/[Si H] = 2.21 × 10−4, we were able to reduce the reaction time from
3 h to 30 min.
The attachment of organosilyl groups to macromolecules leads to important modifi-
cations in polymer properties, such as gas permeability and permaselectivity parameters;
mechanical, thermal, and surface properties; and photochemical reactivity; and constitutes
an important research field in its own right. Alcoholyses of polymeric silicon compounds
such as polysiloxanes and polysilanes, or copolymers containing such polymeric units,
have been reported,15–17 but to our knowledge there are a few references in the literature
to alcoholysis of groups attached to polystyrene side chains in the presence of Karstedt’s
catalyst.18 Alkoxy groups were attached to polymer side chains under the same conditions
as those used for monomeric compounds, but the reactions were heterogeneous since the
polymers were insoluble in alcohols.
4-Chloromethylstyrene (4-CMS) was homopolymerized at 70◦C with AIBN as rad-
ical initiator. Then the homopolymer P1 (0.5 g) was treated with an optimized amount
of (HMe2Si)3CLi (25 mmol) in THF. The replacement of chlorine atoms by (HMe2Si)3C
groups was easily followed by the appearance of the Si H absorption at 2110–2130 cm−1
.
A FTIR spectrum of the resulting polymer P1-SiH exhibits the following characteristics.
Table II Effect of the amount of Karstedt’s catalyst on the alcoholysis of glycol monoethyl ether
(Pt/Si H)
Time
0.55 × 10−4
1.10 × 10−4
1.65 × 10−4
2.21 × 10−4
2.75 × 10−4
5.52 × 10−4
4 h
3 h
100 min
30 min
10 min
10 min

2436
K. D. SAFA ET AL.
Pt
(HMe2Si)3CLi
THF
(
CH2
CH2
CH
CH
)
n
CH2
)
CH
(
)
(
n
n
ROH
Cl
Me2Si
H
SiMe2
SiMe2
Me2Si
SiMe2
SiMe2
H
OR
OR
H
OR
P
1
P
H2C
CH2CH2Cl
R=
2
R=
P
3
Scheme 2 Alcoholysis of polymer P1 with benzyl alcohol or 2-chloroethanol.
The Si H bond is associated with the strong absorption at 2115 cm−1 and the Si CH3
bonds with absorptions at 1255 and 830 cm−1. As shown in Scheme 2, the Si H func-
tional groups of the homopolymer were converted to alkoxy groups with benzyl alcohol or
2-chloroethanol in heterogeneous reactions in the presence of Karstedt’s catalyst. The IR
and NMR spectroscopic results indicated that under optimal conditions, replacement of H
by OR at the silicon center was complete, as shown by the disappearance of both the Si H
peak at 2115 cm−1 and the signal ascribed to Si H at 4.0 ppm in the 1H NMR spectrum
(see Figures 1 and 2).
Figure 1 FT-IR spectrum of P3.

SYNTHESIS OF TRIS(ALKOXYDIMETHYLSILYL)METHANES
2437
Figure 2 The 1H NMR spectrum of P3.
EXPERIMENTAL
Materials
For the preparation of (HMe2Si)3CH,19 bromoform (CHBr3), THF, and Mg were
all obtained from Merck and dried by standard methods. HMe2SiCl (Aldrich) was used
as received. All alcohols such as ethylene glycol monobutyl ether, ethylene glycol mo-
noethylether, triethylene glycol monomethyl ether, 2-chloroethanol, glycidol, 1-octanol,
benzyl alcohol, and allyl alcohol were obtained from Merck. The monomer CMS (Merck
99%) was distilled under reduced pressure to remove inhibitors before use. Toluene was
stirred over calcium hydride for 24 h and distilled under a dry argon atmosphere. The ini-
tiator α,αꢁ-azobis(isobutyronitrile) (Merck) was purified by crystallization from methanol.
Platinum divinyltetramethyldisiloxane complex (Karstedt’s catalyst, 0.10 M solution in
xylenes) was purchased from Aldrich.
Measurements
Infrared spectra were recorded on KBr pellets with a 4600 Unicam FT-IR spectopho-
tometer. 1H NMR and 13C NMR spectra were recorded on a Bruker 400 MHz spectrometer
at room temperature with CDCl3 as a solvent. The mass spectra were obtained with a
GC-Mass Agilent quadrupole mode 5973N spectrometer operating at 70 eV. Elemental
analyses were made with an Elementar, Vario EL III mode instrument.
General Procedures for Synthesis of (ROMe2Si)3CH (1–5)
Karstedt’s catalyst (40 µL) was added to a solution of (HMe2Si)3CH (2.0 g,
10.6 mmol) in ROH (40 mL). The mixture was heated under reflux, the solvent was
evaporated off, and the residue was distilled to give the products (ROMe2Si)3CH.

2438
K. D. SAFA ET AL.
Synthesis of (CH3CH2CH2CH2OCH2CH2OMe2Si)3CH (1). The general pro-
cedure gave (CH3CH2CH2CH2OCH2CH2OMe2Si)3CH after 1 h, (1.32 g, 66.4%), bp
90◦C/3 mmHg; FT-IR (KBr, cm−1) 2958, 2868 (C H), 1253, 836 (Si C), 1094 (Si O),
1
1011 (C O); H NMR (CDCl3, 400 MHz): δ 0.02 (s, 1H, CH), 0.10 (s, 18H, SiMe2),
3
0.81 (t, 9H, CH2CH3, J = 7.5 Hz), 1.21–1.30 (m, 6H, CH3CH2CH2), 1.40–1.47 (m,
3
6H, CH2CH2CH2,), 3.57 (t, 6H, CH2OSi, J = 5.7 Hz), 3.30–3.41 (overlapped, 12H,
CH2CH2OCH2CH2); 13C NMR (CDCl3, 100 MHz): δ 0.0 (SiMe2), 9.5 (CH), 12.7
(CH2CH3), 18.0 (CH2CH3), 30.6 (CH3CH2CH2), 60.3 (CH2OSi), 69.7 (CH2CH2CH2), 70.9
(CH2O); MS (EI) m/z (%) 523 (5, [M − Me]+), 305 (90, [M − 3BuO − Me]+), 205 (100,
[M − 3BuOEtO − 2Me]+), 189 (40, [M − 3BuOEtO]+), 57 (36, [CH3CH2CH2CH2]+).
Anal. Calc. for C25H58Si3O6: C, 55.7; H, 10.8. Found: C, 55.3; H, 10.7%.
Synthesis of (CH3CH2OCH2CH2OMe2Si)3CH (2). The general procedure gave
(CH3CH2OCH2CH2OMe2Si)3CH after 3 h, (3.6 g. 76.5%), bp 70◦C/3 mmHg; FT-IR
(KBr, cm−1) 2969, 2867 (C H), 1254, 850 (Si C), 1106 (Si O), 1016 (C O); 1H NMR
(CDCl3, 400 MHz): δ 0.09 (s, 1H, CH), 0.14 (s, 18H, SiMe2), 1.12 (t, 9H, CH3CH2, 3JHH
=
3
7 Hz), 3.61 (t, 6H, CH2OSi, J-5.5Hz), 3.39–3.48 (overlapped, 12H, CH3CH2OCH2);
13C NMR (CDCl3, 100 MHz): δ 0.0 (SiMe2), (CH), 14.0 (CH3CH2), 60.5 (CH2OSi),
65.4 (CH3CH2), 70.7 (CH3CH2OCH2); MS (EI) m/z (%) 439(100, [M − Me]+), 365
(68, [M − CH3CH2OCH2CH2 − Me]+), 147 (79, [M − 2CH3CH2OCH2CH2]+), 73 (54,
[CH3CH2OCH2CH2]+). Anal. Calc. for C19H46Si3O6: C, 50.2; H, 10.2. Found: C, 49.9; H,
10.5%
Synthesis of (CH3OCH2CH2OCH2CH2OCH2CH2OMe2Si)3CH (3). The gen-
eral procedure gave (CH3OCH2CH2OCH2CH2OCH2CH2OMe2Si)3CH after 2 h, (6.8 g,
96.9%), bp 152◦C/0 mmHg; FT-IR (KBr, cm−1) 2872 (C H), 1253, 853 (Si C), 1108
1
(Si O), 1018(C O); H NMR (CDCl3, 400 MHz): δ −0.26 (s, 1H, CH), −0.14 (s,
18H, SiMe2), 3.34 (t, 6H, CH2OSi, 3J = 5 Hz), 3.10–3.30 (overlapped, 30H, CH2OCH2);
13C NMR (CDCl3, 100 MHz): δ 0.0 (SiMe2), 9.4 (CH), 57.7 (CH3), 60.1 (CH2OSi),
69.2–69.3 (CH2OCH2CH2), 70.6 (CH3OCH2), 71.2 (CH2CH2OSi); MS (EI) m/z (%)
367(,[M − 3CH3OCH2CH2OCH2CH2]+), 225 (30, [CH3OCH2CH2O] +), 205 (50, [2
CH3OCH2CH2OCH2CH2]+), 147 (28, [CH3OCH2CH2OCH2CH2OCH2CH2]+), 103 (100,
[CH3OCH2CH2OCH2CH2]+), 59 (96, [CH3OCH2CH2] +). Anal. Calc. for C28H64Si3O12:
C, 49.6; H, 9.5. Found: C, 49.2; H, 9.3%.
Synthesis of (ClCH2CH2OMe2Si)3CH (4). The general procedure gave
(ClCH2CH2OMe2Si)3CH after 30min, (2.25 g, 54.7%), bp 80◦C/3 mmHg; FT-IR (KBr,
1
cm−1) 2971 (C H), 1255, 863 (Si C), 1096 (Si O), 1006(C O); H NMR (CDCl3,
400 MHz): δ 0.05 (s, 1H, CH), 0.23 (s, 18H, SiMe2), 3.52 (t, 6H, CH2Cl, 3J = 6 Hz), 3.78
3
(t, 6H, CH2O, J = 6 Hz); 13C NMR (CDCl3, 100 MHz): δ 0.0 (SiMe2), 9.7 (CH), 44.1
(CH2Cl), 61.9 (CH2O); MS (EI) m/z (%) 411 (100, [M − Me]+), 345 (25, [M − CH2Cl
− Me]+), 279 (30, [M − 3CH2Cl](+, 223 (89, [M − 3CH2Cl − Me]+), 189 (10, [M −
3CH2CH2Cl]+), 63 (10, [CH2CH2Cl]+). Anal. Calc. for C17H43Si3O3Cl3: C, 38.3; H, 7.5.
Found: C, 38.0; H, 7.1%.
Synthesis of (CH3CH2CH2CH2CH2CH2CH2CH2OMe2Si)3CH (5). The gen-
eral procedure gave (CH3CH2CH2CH2CH2CH2CH2CH2OMe2Si)3CH after 4 h (3.8 g,
63.6%), bp 130◦C / 0 mm Hg; FT-IR (KBr, cm−1) 2927, 2856 (C H), 1253, 858 (Si C),
1
1094 (Si O), 1014 (C O); H NMR (CDCl3, 400 MHz): δ −0.19 (s, 1H, CH), 0.21
3
(s, 18H, SiMe2), 0.90 (t, 9H, CH3CH2, J = 7 Hz), 1.29 (s, 30H, CH3(CH2)4CH2),
1.49–1.53 (m, 6H, CH2CH2CH2O), 3.53 (t, 6H, CH2OSi, 3J = 6.5 Hz); 13C NMR (CDCl3,
100 MHz): δ 2.0 (SiMe2), 9.5 (CH), 13.1 (CH3), 21.7 (CH3CH2), 24.9 (CH3CH2CH2), 24.9

SYNTHESIS OF TRIS(ALKOXYDIMETHYLSILYL)METHANES
2439
(CH3(CH2)2CH2), 28.3 (CH3(CH2)3CH2); 30.8 (CH2CH2CH2O), 31.7 (CH2CH2O), 64.3
(CH2O); MS (EI) m/z (%) 445 (29, [M − CH3(CH2)6CH2O]+), 317 (24), 207 (23), 205 (100,
[M − 2CH3(CH2)6CH2O − CH3(CH2)6CH2]+), 203 (22), 57 (23, [CH3CH2CH2CH2]+).
Anal. Calc. for C31H70Si3O3: C, 64.7; H, 12.2. Found: C, 64.9; H, 12.3%.
Reaction Between (HMe2Si)3CH and Benzyl Alcohol (6)
Karstedt’s catalyst (40 µL) was added to a solution of (HMe2Si)3CH (2 g, 10.6 mmol)
in benzyl alcohol (40 mL). The mixture was stirred at room temperature for 10 h. The solvent
was evaporated off, and the residue was distilled to give (C6H5CH2OMe2Si)3CH, (4.06 g,
77.1%), bp 120◦C/3 mmHg; FT-IR (KBr, cm−1) 3064, 3031 (Ar-H), 2956, 2898 (C H),
1604 (C = C), 1255, 862 (Si C), 1065 (Si O), 1014 (C O); 1H NMR (CDCl3, 400 MHz):
δ 0.12 (s, 1H, CH), 0.44 (s, 18H, SiMe2,), 4.85 (s, 6H, ArCH2), 7.41–7.52 (m, 15H, Ar);
13C NMR (CDCl3, 100 MHz): δ 0.4 (SiMe2), 10.1 (CH), 63.4 (CH2O), 14.0 (C-CH2),
125.8–127.0 (Ar); MS (EI) m/z (%) 493 (22, [M − Me]+), 401 (43, [M − PhCH2O]+), 309
(58, [M − PhCH2O − PhCH2]+), 295 (43), 203 (44),181 (100, [2PhCH2]+). Anal. Calc.
for C28H40Si3O3: C, 66.1; H, 7.9. Found: C, 65.9; H, 7.8%
Reaction Between (HMe2Si)3CH and Glycidol (7)
Karstedt’s catalyst (40 µL) was added to a solution of (HMe2Si)3CH (2 g, 10.6 mmol)
in glycidol (40 mL). The mixture was stirred at room temperature for 2 h. The solvent
was evaporated off, and the residue was distilled to give the product, (5.2 g, 71.1%), bp
35◦C/0 mmHg; FT-IR (KBr, cm−1) 2927, 2877 (C-H), 1258, 848 (Si-C), 1099 (Si-O),
1
1041 (C-O); H NMR (CDCl3, 400 MHz): δ − 0.14 (s, 1H, CH), 0.07 (s, 18H, SiMe2),
42.43–2.61 (m, 6H, CH2O), 3.30–3.42 (m, 3H, CH-CH2), 3.61–4.15 (m, 6H, (CH2OSi);
13C NMR (CDCl3, 100 MHz): δ 2.5 (SiMe2), 16.8 (CH), 43.0 (CH2O), 56.65 (C-CH2), 69.5
(CH2OSi); MS (EI) m/z (%) 205(100, [M − (3RCH2+Me)]+), 189(77, [M − (3RCH2O)]+),
131(45, [RCH2OSiMe2]+), 73(22, [RCH2O]+). Anal. Calc. for C23H58Si3O6: C, 47.2; H,
8.4. Found: C, 46.8; H, 8.8%.
Reaction Between (HMe2Si)3CH and Allyl Alcohol (8)
Karstedt’s catalyst (40 µL) was added to a solution of (HMe2Si)3CH (2 g, 10.6 mmol)
and allyl alcohol (40 mL) in toluene as a solvent. The mixture was stirred at room tempera-
ture for 18 h. The solvent was evaporated off, and the residue was distilled to give (CH2 =
CHCH2OMe2Si)3CH (1.24 g, 74.7%), bp 110◦C/3 mm Hg; FT-IR (KBr, cm−1) 2952, 2862
1
(C H), 1252, 862 (Si C), 1093 (Si O), 1013 (C O); H NMR (CDCl3, 400 MHz): δ
3
0.04 (s, 1H, CH), 0.21 (s, 18H, SiMe2), 4.08 (d, 6H,CH2O, J = 3 Hz), 5.00–5.05 (dd,
3H,HHC = CH), 5.17–5.23 (dd, 3H, HHC = CH), 5.82–5.91 (m, 3H, CH2 = CHCH2); 13
C
NMR (CDCl3, 100 MHz): δ 0.1 (SiMe2), 17.4 (CH), 62.3 (CH2O), 133.5 (CH2 = CHCH2),
136.1 (CH2 = CHCH2); MS (EI) m/z (%) 343 (100, [M − Me]+), 245(26, [M − 2CH2
= CHCH2O − 2Me]+), 203 (24), 189 (63, [M − 3CH2 = CHCH2O]+). Anal. Calc. for
C17H36Si3O3: C, 54.8; H, 9.7. Found: C, 54.6; H, 9.6%.
Synthesis of Polymers P2 and P3 Bearing −SiMe2OR Groups
in the Side Chain
Karstedt’s catalyst (40 µL) was added to a solution of polymer P1 (0.5 g) in benzyl
alcohol or 2-chloroethanol (40 mL). The heterogeneous mixture was heated under reflux,

2440
K. D. SAFA ET AL.
and the progress of the alcoholysis was monitored by FT-IR spectroscopy. The resulting
polymer was filtered off and washed several times with cold methanol. It was dissolved in
chloroform (10 mL), the solution was filtered to remove Pt particles, and the polymer was
precipitated from methanol to give P2 or P3.
Spectroscopic Results for New Homopolymers
P2: FT-IR (KBr, cm−1) 3022, 2980, (C H), 1255, 850 (Si C),1654, 1450(C C),
1010 (Si O), 988 (C O); 1H NMR (CDCl3, 400 MHz): δ 0.10 (SiMe2), 1.3, 1.8 (CH2CH),
4.91 (PhCH2), 7.20–8.12 (Ph); 13C NMR (CDCl3, 100 MHz): δ − 5.0 (SiMe2), −3.2(CH),
70.9 (CH2Ph), 126.1–140.0 (Ph).
P3: FT-IR (KBr, cm−1) 3024, 2959 (C H), 1250, 850 (Si C), 1010 (Si O), 980
1
(C O); H NMR (CDCl3, 400 MHz): δ 0.10 (SiMe2), 1.3, 1.8 (CH2CH), 3.57 (ClCH2),
3.95 (CH2O); 13C NMR (CDCl3, 100MHz): δ −0.5 (SiMe2), −3.6 (CH), 42.7 (CHCl), 63.4
(CH2O).
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