D.E. Jung et al. / Journal of Organometallic Chemistry 696 (2011) 3687e3692
3691
determined according to standard material: Si(CH3)4 0.0 ppm. GC/
MS data were obtained with an HP6890/5973 system (70 eV, EI).
products (3aed) are plotted against reaction time in Fig. 2. Similar
results were obtained when three runs of this reaction were carried
out for reproducibility test.
4.2. General procedure for synthesis of 3a
4.7. Effect of temperature on hydrosilylation of 2a with 1a
A 25 mL dried stainless steel tube with a valve was charged with
1a (7.9 g, 58.3 mmol), 2a (2.0 g, 29.3 mmol), and n-dodecane (1.0 g)
as an internal standard under a dry nitrogen atmosphere. After the
tube was sealed with a cap, the reaction was carried out at 250 ꢀC.
The progress of the reaction was monitored by GLC. The yield of 3a
is based on the amount of 2a used and was determined by GLC with
use of an internal standard. In a 10-fold scaled-up reaction, the
reaction of 2a (19.9 g, 292.1 mmol) with 1a (79.0 g, 583.2 mmol) in
a 250-mL dried stainless steel tube with a valve was carried out at
250 ꢀC for 6 h. Then, the reaction mixture was fractionally distilled
to give 3a (56.5 g, 277.5 mmol; CAS no. 14579-03-4) in 95% isolated
yield. The results are summarized in Table 1.
In a typical experiment, the reactions of 1a (7.9 g, 58.3 mmol)
with 2a (2.0 g, 29.3 mmol) were carried out at temperatures
ranging from 150 ꢀC to 270 ꢀC. The progress of the reaction was
monitored by GLC. The yields of 3a obtained at various tempera-
tures are plotted against reaction time in Fig. 3.
4.8. Effect of the molar ratio of reactants on hydrosilylation of 2a
with 1a
In a typical experiment, reactions were carried out using
a variety of molar ratios of 1a to 2a: 1a 11.9 g (87.8 mmol), 8.0 g
(58.8 mmol), 6.0 g (44.2 mmol), and 4.8 g (35.4 mmol) were used
with respect to 2a (2.0 g, 29.3 mmol). All reactions were carried out
at 250 ꢀC and monitored by GLC. Yields are on the basis of the
amount of 2a used and were determined by GLC with the use of an
internal standard and are plotted against reaction time in Fig. 4.
4.3. Synthesis of 3be3d
Following the same procedure and scale described in the
general procedure for the synthesis of 3a, the reactions of cyclo-
alkenes 2bed with 1a were carried out. The yields of 3b (CAS no.
98-12-4), 3c (CAS no. 135225-23-9) and 3d (CAS no. 18290-59-0)
are based on the amount of 2 used and was determined by GLC with
use of an internal standard. These results are summarized in
Table 1. In addition, a 10-fold scaled-up reaction of 2b (24.0 g,
292.1 mmol) with 1a (79.0 g, 583.2 mmol) was carried out at 250 ꢀC
4.9. Thermal hydrosilylation of 2e with 1a
In a typical experiment, the reaction of 2e (2.4 g, 28.5 mmol)
with 1a (7.9 g, 58.3 mmol) was carried out at temperatures ranging
from 150 ꢀC to 250 ꢀC. The progress of the reaction was monitored
by GLC. Yields are on the basis of the amount of 2e used and were
determined by GLC with the use of an internal standard. The
distributions of the products [3k (CAS no. 928-65-4), 3l (CAS no.
18151-52-5), and 3m (CAS no. 875288-11-2)] and reactants are
plotted against reaction time in Figs. 5 and 6.
for 6 h in
a 250-mL dried stainless steel tube, 3b (59.8 g,
274.8 mmol) was obtained in a 94% isolated yield.
4.4. Synthesis of 3ee3h
Following the similar procedure and scale described in the
general procedure for the synthesis of 3a, the reactions of cyclo-
alkenes 2aed with 1b instead of 1a were carried out. The yields of
3e (CAS no. 14579-04-5), 3f (CAS no. 5578-42-7), 3g, and 3h (CAS
no. 117314-86-6) are based on the amount of 2 used and was
determined by GLC with the use of an internal standard. These
results are summarized in Table 1. In addition, a 10-fold scaled-up
reaction of 2c (28.1 g, 292.1 mmol) with 1b (67.1 g, 583.3 mmol)
was carried out at 250 ꢀC for 40 h in a 250-mL dried stainless steel
tube, 3g (50.6 g, 239.5 mmol) was obtained in a 82% isolated yield.
4.10. Thermal hydrosilylation of 2g with 1a
In a typical experiment procedure, the reaction of 2g with 1a
was carried out. The distribution of products and reactants are
plotted against reaction time in Fig. 7.
Acknowledgements
This research was supported by a grant from the Fundamental
R&D Program for Core Technology of Materials funded by the
Ministry of Knowledge Economy and partially by the Korea Insti-
tute of Science and Technology.
Data for 3g: 1H NMR (CDCl3)
SiCH), 1.34e1.70 (m, 8H, CH2CH2CH2CH2), 1.74e1.89 (m, 2H),
d 0.75 (s; 3H, SiCH3), 1.08e1.25 (m, 1H,
1.90e2.05 (m, 2H); 13C NMR
d 3.24 (SiCH3), 27.17, 28.10, 29.12,
31.14(SiCH); 29Si NMR 28.23; mass spectrum (70 eV, EI), m/z (rel
intensity) 210 (12, Mþ), 182 (5), 167 (8), 154 (19), 113 (59,
(Cl2CH3Si)þ), 97 (100), 81 (30), 67 (19), 55 (80). Anal. Calcd for
C8H16Cl2Si: C, 45.49; H, 7.64. Found: C; 45.12, H; 7.68.
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Reaction of 1a (31.6 g, 233.2 mmol) with mixture of 2a (2.0 g,
29.3 mmol), 2b (2.4 g, 29.2 mmol), 2c (2.8 g, 29.1 mmol), 2d (3.2 g,
29.0 mmol) and n-dodecane (1.0 g) in a 100-mL dried stainless steel
tube with a valve was carried out at 250 ꢀC. The yields of the