244
B.R. Yoo et al. / Journal of Organometallic Chemistry 605 (2000) 240–245
1
3
were employed in all reactions. Aluminum chloride and
benzene were purchased from Aldrich Chemical and all
C-NMR (150 MHz): l 23.63, 23.95 (CH ), 37.65
2
(benzylic-CH ), 126.22, 128.41, 128.50, 140.64 (ipso-C)
(phenyl-carbons). Data for 2g%: H-NMR (600 MHz): l
1.53 (d, J=7 Hz, 3H, CH ), 1.88 (dd, J=7, 15 Hz)
1.96 (dd, J=7, 15 Hz) (1H, SiCH ), 3.32 (sex, J=7
2
1
(
v-chloroalkyl)silanes from Gelest. Reagents were used
without purification except for benzene. Benzene was
dried by distillation from sodium benzophenone ketyl
prior to use. The reaction products were analyzed by
GLC using a packed column (10% SE-30 or SE-54 on
3
2
Hz, 1H, benzylic-CH), 7.27–7.42 (m, 5H, phenyl-H).
13
C-NMR (150 MHz): l 25.65 (SiCH ), 33.92 (CH ),
2
3
8
0–100 mesh Chromosorb W/AW, 1/8%%×1.5 m) or a
35.20 (benzylic-CH), 126.63, 126.68, 128.65, 146.43
(ipso-C) (phenyl-carbons). Anal. Calc. for C H Cl Si:
capillary column (SE-30, 30 m) with a Varian 3300 gas
chromatograph, thermal conductivity detector, and Hi-
tachi D-2500 integrator. Product yields were deter-
mined chromatographically with n-dodecane as an
internal standard, unless otherwise stated. Samples for
characterization were purified by a preparative GLC
using a Donam system series DS 6200 gas chro-
matograph with a thermal conductivity detector and a 4
m×1/8%% stainless steel column packed with 20% OV-
9
11
3
C, 42.62; H, 4.37. Found for an 89:2 mixture of 2g and
1
2g%: C, 42.59; H, 4.38%. Data for 2h: H-NMR (600
MHz): l 0.76 (s, 3H, SiCH ), 1.15 (t, 2H, SiCH ), 1.86
3
2
(sex, J=8 Hz, 2H, CH ), 2.71 (t, J=8 Hz, 2H, ben-
2
13
zylic-CH ), 7.18–7.31(m, 5H, phenyl-H). C-NMR
2
(150 MHz): l 5.18 (CH ), 21.21 (SiCH ), 24.24 (CH ),
3
2
2
38.34 (benzylic-CH ), 126.06, 128.44, 128.50, 141.39
2
1
(ipso-C) (phenyl-carbons). Data for 2h%: H-NMR (600
101 on 80–100 mesh Chromosorb P/AW. NMR spec-
MHz): l 0.50 (s, 3H, SiCH ), 1.47 (d, J=7 Hz, 3H,
3
tra were recorded on a Varian Unity Plus 600 (FT, 600
CH ), 1.65 (m, 2H, SiCH ), 3.23 (t, J=7 Hz, 1H,
3
2
1
13
13
MHz, H; 150 MHz, C) spectrometer in CDCl sol-
benzylic-CH), 7.27–7.39 (m, 5H, phenyl-H). C-NMR
(150 MHz): l 5.80 (CH ), 25.46 (SiCH ), 31.80 (CH ),
3
vent. Mass spectra were obtained using a Hewlett–
Packard 6890 GC–MS. HRMS (high-resolution mass
3
2
3
35.34 (benzylic-CH), 126.53, 126.65, 128.62, 147.10
(ipso-C) (phenyl-carbons). Anal. Calc. for C H Cl Si:
(
70 eV, EI) spectra) were performed by the Korea Basic
10
14
2
Science Institute, Seoul, Korea. Elemental analyses
were performed by the chemical analysis laboratory of
the Korea Institute of Science and Technology. The
structures of products 2a–f were confirmed by compari-
son with purchased samples.
C, 51.50; H, 6.05. Found for an 80:13 mixture of 2h
and 2h%: C, 51.49; H, 6.07%.
3.4. Reaction of 2 with hydrogen chloride in the
presence of aluminum chloride
3
.2. Reaction of benzene with 1a
Into a 100 ml flask were charged 2c (2.03 g, 11.0
mmol), aluminum chloride (0.29 g, 2.2 mmol), and
n-dodecane (0.4 g) as an internal standard. Gaseous
HCl was bubbled to the stirred reaction solution at
room temperature for 10 min. The reaction mixture was
then analyzed by GLC. Compound 2b (12%), toluene
(23%), and dimethyldichlorosilane (23%) were observed
along with 62% of unreacted 2c.
Using the same procedure described for 2c with HCl,
compound 2d reacted with bubbling gaseous HCl in the
presence of aluminum chloride for 10 min. The decom-
posed products, toluene (62%), trimethylchlorosilane
(62%), and 2c (12%) were observed along with 8% of
unreacted 2d by GLC.
To a 25 ml stainless steel bomb was charged alu-
minum chloride (0.29 g, 2.2 mmol), 1a (2.0 g, 10.9
mmol), benzene (8.5 g, 109.0 mmol), and dodecane (0.5
ml, 0.38 g). The reactions were carried out at 80 and
2
00°C for 20 h, respectively. The progresses of the
reactions were monitored by GLC. Product 2a (31%)
was observed with a 45% consumption of 1a in a 20 h
reaction at 200°C, but not in a 20 h reaction at 80°C.
3.3. General procedure for the reaction of benzene with
compounds 1b–g
To a suspension of AlCl (0.4 g, 3.0 mmol) under
3
nitrogen atmosphere at 0°C was charged a mixture of 1
3.5. Aluminum chloride-catalyzed reaction of 1d
(
15.0 mmol) and benzene (150 mmol). The reaction
mixtures were stirred at 0 or 80°C. The progresses of
the reactions were monitored by GLC. After 1 was
consumed, trichlorophosphine oxide was added. The
complex of aluminum chloride and phosphine oxide
was filtered off. The filtrate was distilled to give reac-
tion products. The reaction products are summarized in
Using the procedure described for 2c with HCl, 1d (1
g, 8.2 mmol) was stirred with and without bubbling
gaseous HCl in the presence of AlCl (0.2 g, 1.5 mmol)
3
at room temperature for 30 min. With the 36% con-
sumption of 1d in the absence of gaseous HCl,
ethyldimethylchlorosilane (34%) was observed predomi-
nantly along with a trace of trimethylchlorosilane by
GLC analysis. The reaction of 1d in the presence of
gaseous HCl gave the similarity to the results from the
reaction in the absence of HCl.
1
Tables 1 and 3. Data for 2g: H-NMR (600 MHz): l
1
2
2
.58–1.63 (m, 2H, SiCH ), 2.11–2.16 (m, 2H, CH ),
2
2
.71 (t, J=7 Hz, 2H, benzylic-CH ), 7.38 (d, J=7 Hz,
2
H), 7.42 (t, 7 Hz, 1H), 7.51 (t, 7 Hz, 2H) (phenyl-H).