Job/Unit: I42904
/KAP1
Date: 26-11-14 14:47:52
Pages: 7
FULL PAPER
were determined by GC–MS analysis with a Varian Saturn 2100 T
equipped with a BD-5 capillary column (30 m) and a Finigan Mat
800 ion-trap detector.
Compound 13: 1H NMR (300 MHz, C6D6): δ = 0.14 (s, 6 H,
SiCH3), 0.27 (s, 6 H, SiCH3), 0.53–0.64 (m, 2 H, SiCH2), 0.75–0.85
(m, 2 H, SiCH2), 0.87–1.01 (m, 3 H, SiCH), 1.03–1.15 [m, 18 H,
SiCH(CH3)2], 7.17–7.27 (m, 3 H, Ph), 7.44–7.55 (m, 2 H, Ph) ppm.
13C NMR (75 MHz, C6D6): δ = –3.8 (SiCH3), –0.3 (SiCH3), 7.5,
10.6 (CH2), 12.8, (SiCH), 17.8 [SiCH(CH3)2], 127.8, 128.8, 133.6,
139.0 (Ph) ppm. C21H42OSi3 (394.8): calcd. C 63.88, H 10.72; found
C 63.95, H 10.68.
Synthesis of Siloxanes: A mixture that consisted of alkoxysilane
(1.0–4.0 mmol), 2-methylallylsilanes (1.0–2.5 mmol; according to
the conditions indicated in Table 1), Sc(OTf)3 (0.02 mmol), water
(1.0–4.0 mmol), and acetonitrile (15 mL) were placed in a 50 mL
one-necked round-bottomed flask and stirred at room temperature
for 1 h. After this time, the solvent was evaporated and the product
was purified by column chromatography on silica gel by eluting
with n-hexane to give the corresponding compounds (1–12) as col-
orless liquids. The synthesis of 1,1-dimethyl-3,3,3-triisopropyl-1-vi-
nyldisiloxane (1) was also performed on a larger scale under the
same reaction conditions. A mixture that consisted of ethoxytriiso-
propylsilane (10 mmol, 2.02 g), 2-methylallyldimethylvinylsilane
(25 mmol, 3.5 g), Sc(OTf)3 (0.2 mmol, 0.25 g), water (10 mmol,
0.18 g), and acetonitrile (50 mL) were placed in a 100 mL one-
necked round-bottomed flask and stirred at room temperature for
1 h. After this time, the solvent was evaporated and the product
was isolated by “bulb-to-bulb” distillation to give 2.27 g (88%) of
1 as a colorless liquid.
1,1-Dimethyl-3,3,3-triisopropyl-1-vinyldisiloxane (1): 1H NMR
(300 MHz, C6D6): δ = 0.22 (s, 6 H, SiCH3), 0.88–1.02 (m, 3 H,
SiCH), 1.03–1.12 [m, 18 H, SiCH(CH3)2], 5.70–5.78 (dd, J = 3.9,
20.4 Hz, 1 H, CH=CH2), 5.86–5.93 (dd, J = 3.9, 14.9 Hz, 1 H,
CH=CH2), 6.15–6.27 (dd, J = 14.9, 20.4 Hz, 1 H, CH=CH2) ppm.
13C NMR (75 MHz, C6D6): δ = 0.3 (SiCH3), 12.7 (SiCH), 17.7
[SiCH(CH3)2], 131.3 (CH=CH2), 139.6 (CH=CH2) ppm.
C13H30OSi2 (258.6): calcd. C 60.39, H 11.70; found C 60.55, H
11.63.
Hydrosilylation of 1,1-Dimethyl-3,3,3-triisopropyl-1-vinyldisiloxane
with 1,2-Bis(dimethylsilyl)ethane: A mixture that consisted of 1,1-
dimethyl-3,3,3-triisopropyl-1-vinyldisiloxane (0.13 g, 0.5 mmol),
1,2-bis(dimethylsilyl)ethane (0.5 or 1.0 mmol), platinum(0)-1,3-di-
vinyl-1,1,3,3-tetramethyldisiloxane
complex
(5ϫ10–4
or
1ϫ10–3 mmol), and toluene (5 mL) was placed in a 20 mL Schlenk
bomb flask fitted with a plug valve and heated at 40 °C for 1 h.
Next, after cooling the reaction mixture to room temperature, the
solvent was evaporated and the product was purified by column
chromatography on silica gel by eluting with n-hexane to give the
expected product (14 or 15) as colorless liquids in 88–94% yields.
Compound 14: 1H NMR (300 MHz, C6D6): δ = 0.08 (s, 12 H,
SiCH3), 0.21 (s, 12 H, SiCH3), 0.46–0.68 (m, 12 H, SiCH2), 0.89–
1.22 [m, 42 H, SiCH, SiCH(CH3)2] ppm. 13C NMR (75 MHz,
C6D6): δ = –4.6 (SiCH3), –0.3 (SiCH3), 6.3, 6.8, 10.7 (CH2), 12.8
(SiCH), 17.8 [SiCH(CH3)2] ppm. C32H78O2Si6 (663.5): calcd. C
57.93, H 11.85; found C 57.88, H 11.70.
Compound 15: 1H NMR (300 MHz, C6D6): δ = 0.10–0.34 (m, 18
H, SiCH3), 0.40–0.74 (m, 8 H, SiCH2), 0.80–1.44 [m, 21 H, SiCH
and SiCH(CH3)2] ppm. 13C NMR (75 MHz, C6D6): δ = –4.6, –1.1,
–0.3 (SiCH3), 6.0, 6.4, 9.8, 10.6 (CH2), 12.8 (SiCH), 17.8
[SiCH(CH3)2] ppm. C19H48OSi4 (404.9): calcd. C 56.36, H 11.95;
found C 56.41, H 11.84.
1-n-Butyl-1,1-dimethyl-3,3,3-triisopropyldisiloxane (2): 1H NMR
(300 MHz, C6D6): δ = 0.16 (s, 6 H, SiCH3), 0.57–0.68 (m, 2 H,
SiCH2), 0.87–1.02 (m, 6 H, SiCH and CH3), 1.03–1.14 [m, 18 H,
SiCH(CH3)2], 1.31–1.45 (m, 4 H, CH2CH2) ppm. 13C NMR
(75 MHz, C6D6): δ = 0.3 (SiCH3), 12.8 (SiCH), 13.7 (SiCH3), 17.8
[SiCH(CH3)2], 18.4 (SiCH2), 25.7 (CH2), 26.5 (CH2) ppm.
C15H36OSi2 (288.6): calcd. C 62.42, H 12.57; found C 62.50, H
12.69.
Hydrosilylation of Vinyltriethoxysilane with 15: A mixture that con-
sisted of 15 (0.2 g, 0.5 mmol), vinyltriethoxysilane (0.11 g,
0.6 mmol),
platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane
complex (5ϫ10–4 mmol), and toluene (5 mL) was placed in a
20 mL Schlenk bomb flask fitted with a plug valve and heated at
40 °C for 1 h. Next, after cooling the reaction mixture to room
temperature, the solvent was evaporated and 0.28 g of the product
(16) was afforded as a colorless liquid in 94% yield.
1,1,1,5,5-Pentamethyl-5-vinyl-3,3-bis(trimethylsiloxy)trisiloxane (4):
1H NMR (300 MHz, C6D6): δ = 0.23 (s, 27 H, OSiCH3), 0.29 (s, 6
H, SiCH3), 5.81–5.90 (dd, J = 4.0, 20.2 Hz, 1 H, CH=CH2), 5.93–
6.00 (dd, J = 4.0, 14.9 Hz, 1 H, CH=CH2), 6.21–6.33 (dd, J = 14.9,
20.2 Hz, 1 H, CH=CH2) ppm. 13C NMR (75 MHz, C6D6): δ = 0.3
(SiCH3), 1.8 (OSiCH3), 132.2 (CH=CH2), 139.2 (CH=CH2) ppm.
C13H36O4Si5 (396.9): calcd. C 39.34, H 9.14; found C 39.44, H 9.08.
Compound 16: 1H NMR (300 MHz, C6D6): δ = 0.02–0.12 (m, 12
H, SiCH3), 0.15–0.28 (m, 6 H, SiCH3), 0.48–0.87 (m, 12 H, SiCH2),
0.92–1.02 (m, 3 H, SiCH), 1.03–1.15 [m, 18 H, SiCH(CH3)2], 1.16–
1.27 (t, 9 H, CH3CH2O), 3.77–3.91 (q, 6 H, CH3CH2O) ppm. 13C
NMR (75 MHz, C6D6): δ = –4.7, –4.6, –0.3 (SiCH3), 3.0, 5.9, 6.2,
6.7, 6.8, 10.6 (CH2), 12.8 (SiCH), 17.8 [SiCH(CH3)2], 18.3
(CH3CH2O), 58.2 (CH3CH2O) ppm. C27H66O4Si5 (595.3): calcd. C
54.48, H 11.18; found C 54.39, H 11.04.
1
1-n-Butyl-1,1,3,3,3-pentamethyldisiloxane (7): H NMR (300 MHz,
C6D6): δ = 0.06–0.19 (m, 15 H, SiCH3), 0.53–0.63 (m, 2 H, SiCH2),
0.86–0.96 (m, 3 H, CH3), 1.30–1.42 (m, 4 H, CH2CH2) ppm. 13C
NMR (75 MHz, C6D6): δ = 0.16 (SiCH3), 1.75 (SiCH3), 13.7
(SiCH3), 18.1 (SiCH2), 25.6 (CH2), 26.4 (CH2) ppm. C9H24OSi2
(204.5): calcd. C 52.87, H 11.83; found C 52.96, H 11.92.
Acknowledgments
Experimental Procedure for the Hydrosilylation Reaction of 1,1-Di-
methyl-3,3,3-triisopropyl-1-vinyldisiloxane with Dimethylphenylsi-
This work was made possible by the Ministry of Science and
lane: A mixture that consisted of 1,1-dimethyl-3,3,3-triisopropyl-1- Higher Education (Poland) (grant number IP2011 017771).
vinyldisiloxane (0.13 g, 0.5 mmol), dimethylphenylsilane (0.075 g,
0.55 mmol), platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane
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Schlenk bomb flask fitted with a plug valve and heated at 60 °C
for 1 h. Next, after cooling the reaction to room temperature, the
solvent was evaporated, and the product was purified by column
chromatography on silica gel by eluting with n-hexane to give the
product (13) as a colorless liquid in 97% yield.
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2008097877; S. K. Lee, J. B. Seon, EP 1498443.
[2] M. A. Brook, Silicon, in: Organic, Organometallic and Polymer
Chemistry, Wiley, 2000, p. 257–308 and 466–472.
[3] Z. M. Michalska, Transition Met. Chem. 1980, 5, 125–129.
Eur. J. Inorg. Chem. 0000, 0–0
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