spectrometer using the FAB technique. Microanalytical data were
obtained with the use of a Perkin-Elmer 240C elemental analyzer.
Acid Amberlite (RSO3−H+, IR-120 PLUS) was regenerated
after use by washing with concentrated hydrochloric acid, water
and methanol, while basic Amberlite (IRA-400) was regenerated
after use by washing with 0.1 M NaOH solution.
stirred. While stirring, benzyltrichlorosilane (10 g, 0.044 mol) was
slowly added to the reaction mixture, stirring was maintained
overnight and a cloudy white liquid was observed. 80% of the
solvent was evaporated resulting in a white semi-liquid, which was
triturated25 to give white powder yielding 4.33 g (68%).
1H NMR (CDCl3): d 7.33 (t, C6H5), 7.72 ppm (m, C6H5); 13C
NMR (CDCl3): d 127.74, 130.66, 133.66, 134.08 ppm; 29Si NMR
(CDCl3): d −71.44 ppm (–SiCH2Ph); IR (CHCl3, CaF2, cm−1):
=
Synthesis of octavinylsilsesquioxane (H2C CH)8Si8O12
1
=
=
3083.0 (C–H), 2924.5 (C–H), 1610 (C C), 1588.7 (C C), 1141.5
(Si–O–Si); MS (FAB): 1033.0 (M+, parent ion). Elem. anal.
Calcd for C48H40Si8O12: C, 55.80; H, 3.87%; Found: C, 55.23; H,
3.34%.
Acid Amberlite of medium porosity (40 g) was washed with
concentrated hydrochloric acid, water and methanol before
charging it into a 500 mL flask, which was equipped with a
magnetic stirrer. Methanol (150 mL) was added and stirred at
◦
30 C. Vinyltrichlorosilane (4.0 mL, 0.04 mol) was added slowly
Acknowledgements
with stirring to the Amberlite methanolic solution. The stirring
continued at room temperature for 10 h during which white
microcrystals were deposited on the wall of the flask. Methanol
was decanted into a pre-prepared 500 mL flask (to be reused in
the next experiment). Dichloromethane was added to dissolve
the microcrystals and the Amberlite was filtered out for reuse
in subsequent experiments. The solvent was evaporated and the
vinyl-T8 microcrystals washed several times with methanol. The
recycled Amberlite was used 8 times, and xerogel was isolated in
The authors are thankful to the Institute of Chemistry, Academia
Sinica and the National Research Council, Taiwan, ROC, for
financial assistance granted toward this project.
References
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London, 1972, p. 218.
1
H NMR (CDCl3): d 5.69–6.15 ppm (m, H2C CH–, 24H); 13C
=
3 R. Elsaber, G. H. Mehl, J. W. Goodby and D. J. Photinos, Chem.
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NMR (CDCl3): d 128.70 ppm (C1), 136.95 ppm (C2); 29Si–
=
NMR (CDCl3): d −79.8 ppm, −80.6 ppm (–SiCH CH2); IR
−1
=
(CaF2, cm ): 3067.8 (C–H), 1604.6 (C C), 1408 (C–H) 1118.1
(Si–O–Si) 784 (Si–C); MS (FAB) : 633.2 (M+, parent ion). Elem.
anal. Calcd for C16H24Si8O12: C, 30.36; H, 3.79%; Found: C, 30.31;
H, 3.70%.
IR data for Xerogel: IR (CaF2, cm−1): 3064.3, 1603.6, 1126,
1410, 785.
The same procedure as described above was followed when
vinylmethoxysilane or vinylethoxysilane was used as a substitute
for vinyltrichlorosilane.
Synthesis of octaphenylsilsesquioxane (C6H5)8Si8O12
Base Amberlite (IRA 400, 20 g) was placed into a flask equipped
with magnetic stirrer. Ethanol (95%, 100 mL) was added and
stirred. While stirring, phenyltrichlorosilane (12.69 g, 0.06 mol)
was slowly added to the reaction mixture, and stirring was
maintained overnight. The deposited white microcrystals were
harvested and washed with small amount of dichloromethane to
give white microcrystals. Yield 5.74 g (74%).
1H NMR (C6D6): d 7.33 ppm (t, C6H5), 7.72 ppm (m, C6H5); 13
C
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Chem., 1983, 258, 277.
NMR (C6D6): d 127.74, 130.66, 133.66, 134.08 ppm; IR (C6H6,
−1
=
CaF2, cm ): 3083.0 (C–H), 2924.5 (C–H), 1610 (C C), 1588.7
+
=
(C C), 1141.5 (Si–O–Si); MS (FAB): 1033.0 (M , parent ion).
21 B. Arkes, Chem.-Tech., 1977, 7, 766.
Elem. anal. Calcd for C48H40Si8O12: C, 55.80; H, 3.87%; Found: C,
55.23; H, 3.34%.
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153.
Synthesis of octabenzylsilsesquioxane (C6H5CH2)8Si8O12
Base Amberlite (IRA 400, 30 g) was placed into a flask equipped
with magnetic stirrer. Ethanol (95%, 100 mL) was added and
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The Royal Society of Chemistry 2006
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