Organometallics
Article
(d, J = 7.2 Hz, 18H). 13C NMR (CDCl3, 150.92 MHz, 25 °C): δ
134.18, 130.66, 128.24, 1.04. 29Si NMR (CDCl3, 119.22 MHz, 25 °C):
δ 10.23.
17.83, 13.84. 29Si NMR (CDCl3, 600 MHz, 25 °C): δ 35.89.
Dimethylphenylchlorosilane (Me2PhSiCl). In dichloromethane (80
mL) were dissolved dimethylphenylsilane (14.5 mL, 12.9 g, 95 mmol)
and FeCl3 (77 mg, 0.47 mmol). The reaction mixture was protected
from moisture, followed by addition of acetyl chloride (10 mL, 11.1 g,
142 mmol). The reaction mixture was stirred for 2 h while it
spontaneously refluxed. Evaporation of the solvent gave a black liquid,
which was distilled at reduced pressure to yield a colorless liquid.
Yield: 13.7 g (80 mmol, 85%). GC purity: 98%. Bp: 40 °C/1 mbar
(lit.27 76−77 °C/16 mbar). NMR data were consistent with previously
reported data.27 1H NMR (CDCl3, 600.13 MHz, 25 °C): δ 7.62 (dd, J
= 7.8, 1.8 Hz, 2H), 7.41−7.36 (m, 5 H), 0.66 (s, 6H). 13C NMR
(CDCl3, 150.92 MHz, 25 °C): δ 136.32, 133.20, 130.48, 128.22, 2.21.
29Si NMR (CDCl3, 119.22 MHz, 25 °C): δ 20.35.
tert-Butyldiphenylchlorosilane (t-BuPh2SiCl). In dichloromethane
(10 mL) were dissolved tert-butyldiphenylsilane (1.5 g, 6.3 mmol) and
FeCl3 (20 mg, 0.13 mmol). The reaction mixture was protected from
moisture, followed by addition of acetyl chloride (0.67 mL, 0.75 g, 9.5
mmol). The reaction mixture was stirred overnight until full
conversion. Evaporation of the solvent yielded a yellowish oil, which
was dissolved in hexane and passed through a thin pad of silica to
afford a colorless liquid that was evaporated to leave a colorless liquid.
Yield: 1.2 g (4.4 mmol, 69%). GC purity: ∼96%. NMR data were
consistent with previously reported data.51 1H NMR (CDCl3, 600.13
MHz, 25 °C): δ 7.75 (dd, J = 7.6, 1.2 Hz, 4H), 7.41 (tt, J = 7.6, 1.2 Hz,
2H), 7.38 (t, J = 7.6 Hz, 4H), 1.14 (s, 9H). 13C NMR (CDCl3, 150.92
MHz, 25 °C): δ 135.34, 132.62, 130.39, 128.01, 26.24, 20.84. 29Si
NMR (CDCl3, 119.22 MHz, 25 °C): δ 12.92.
Diphenylvinylchlorosilane [Ph2(vinyl)SiCl]. In dichloromethane
(10 mL) were dissolved diphenylvinylsilane (1.3 g, 6.3 mmol) and
FeCl3 (20 mg, 0.13 mmol). The reaction mixture was protected from
moisture, followed by addition of acetyl chloride (0.67 mL, 0.75 g, 9.5
mmol). The reaction mixture was stirred overnight until full
conversion. Evaporation of the solvent yielded a yellowish oil, which
was dissolved in hexane and passed through a thin pad of silica to
afford a colorless liquid that was evaporated to leave a colorless liquid.
Yield: 1.1 g (4.5 mmol, 69%). GC purity: ∼99%. NMR data were
consistent with previously reported data.53 1H NMR (CDCl3, 600.13
MHz, 25 °C): δ 7.64 (dd, J = 7.6, 1.2 Hz, 4H), 7.43 (tt, J = 7.6, 1.2 Hz,
2H), 7.38 (t, J = 7.6 Hz, 4H), 6.50 (dd, J = 20.4, 14.4 Hz, 1H), 6.30
(dd, J = 14.4, 3.0 Hz, 1H), 5.97 (dd, J = 20.4, 3.0 Hz, 1H). 13C NMR
(CDCl3, 150.92 MHz, 25 °C): δ 138.12, 134.87, 132.79, 132.66,
130.83, 128.24. 29Si NMR (CDCl3, 119.22 MHz, 25 °C): δ −1.58.
Thexyldimethylchlorosilane (thexMe2SiCl). In dichloromethane
(10 mL) were dissolved thexyldimethylsilane (0.9 g, 6.3 mmol) and
FeCl3 (20 mg, 0.13 mmol). The reaction mixture was protected from
moisture followed by addition of acetyl chloride (0.67 mL, 0.75 g, 9.5
mmol). The reaction mixture was stirred overnight until full
conversion. Evaporation of the solvent yielded a brown oil, which
was dissolved in hexane and passed through a thin pad of silica to
afford a colorless liquid that was evaporated to leave a colorless liquid.
Yield: 0.65 g (3.6 mmol, 58%). GC purity: ∼95%. NMR data were
consistent with previously reported data.54 1H NMR (CDCl3, 600.13
MHz, 25 °C): δ 1.73 (m, J = 6.9 Hz, 1H), 0.94 (s, 6H), 0.92 (d, J = 6.9
Hz, 6H), 0.41 (s, 6H). 13C NMR (CDCl3, 150.92 MHz, 25 °C): δ
34.17, 26.06, 20.12, 18.75, 1.25. 29Si NMR (CDCl3, 119.22 MHz, 25
°C): δ 36.38.
Methyldiphenylchlorosilane (MePh2SiCl). In dichloromethane (10
mL) were dissolved methyldiphenylsilane (1.2 g, 6.3 mmol) and FeCl3
(20 mg, 0.13 mmol). The reaction was protected from moisture
followed by addition of acetyl chloride (0.67 mL, 0.75 g, 9.5 mmol).
The reaction mixture was stirred overnight until full conversion.
Evaporation of the solvent gave a brown oil, which was suspended in
hexane and passed through a thin pad of silica to afford a colorless
liquid that was evaporated to leave a colorless liquid. Yield: 0.91 g (3.9
mmol, 61%). GC purity: ∼98%. NMR data were consistent with
previously reported data.27 1H NMR (CDCl3, 600.13 MHz, 25 °C): δ
7.63 (tt, J = 7.2, 1.8 Hz, 4H), 7.41 (tt, J = 7.2, 1.8 Hz, 2 H), 7.38 (tt, J
= 7.2, 1.8 Hz, 4H). 13C NMR (CDCl3, 150.92 MHz, 25 °C): δ 134.63,
1,4-Bis(chlorodimethylsilyl)benzene (ClMe2Si-C6H4-SiMe2Cl). In
ice-cooled dichloroethane (10 mL) were dissolved 1,4-bis-
(dimethylsilyl)benzene (1.4 mL, 1.2 g, 6.3 mmol) and FeCl3 (20
mg, 0.13 mmol). The reaction mixture was protected from moisture,
followed by addition of acetyl chloride (1.3 mL, 1.5 g, 18.9 mmol).
The reaction mixture was warmed to room temperature with stirring
for 1 h, followed by addition of acetyl chloride (0.04 mL, 0.05 g, 0.6
mmol). After an additional 1 h full conversion was achieved.
Evaporation of the solvent yielded a brown oil, which was dissolved
in hexane and left at −15 °C overnight during which a brown slurry
separated. The obtained colorless liquid was passed through a thin pad
of silica and evaporated to yield colorless semisolid crystals. Yield: 1.49
g (5.7 mmol, 90%). GC purity: ∼98%. NMR data were consistent with
previously reported data.55 1H NMR (C6D6, 600.13 MHz, 25 °C): δ
7.50 (s, 4H), 0.44 (s, 12H). 13C NMR (C6D6, 150.92 MHz, 25 °C): δ
138.69, 132.88, 1.83. 29Si NMR (C6D6, 119.22 MHz, 25 °C): δ 20.29.
Methylphenylchlorosilane (MePhSiHCl). In a flame-dried vessel
under argon, methylphenylsilane (1.1 mL, 1.0 g, 8.2 mmol) and
Fe(acac)3 (56 mg, 1.6 mmol) were dissolved in dichloromethane (15
mL). Next, acetyl chloride (0.65 mL, 0.72 g, 9.2 mmol) was added into
the reaction mixture in six portions, upon which a color change from
red to light yellow was observed. The reaction mixture was stirred
overnight. Evaporation of the solvent gave a yellowish oil, which was
dissolved in hexane and passed through a thin pad of silica and
evaporated to yield a colorless liquid. Yield: 0.76 g (4.9 mmol, 59%).
Alternatively, in a flame-dried vessel under argon, methylphenylsilane
(11 mL, 10 g, 82 mmol) and Fe(acac)3 (0.56 mg, 1.6 mmol) were
dissolved in dichloromethane (150 mL) followed by dropwise addition
of acetyl chloride (6.5 mL, 7.2 g, 92 mmol), upon which a similar color
change from red to light yellow was observed. The reaction mixture
was stirred overnight followed by evaporation of the solvent, leaving a
yellowish oil which was distilled at reduced pressure to give a colorless
liquid. Yield: 7.5 g (48 mmol, 58%). GC purity: ∼85%. Bp: 92 °C/50
mbar (lit.27 76−78 °C/28 mbar). NMR data were consistent with
previously reported data.27 1H NMR (CDCl3, 600.13 MHz, 25 °C):
7.62 (d, J = 7.2 Hz, 2H), 7.43 (t, J = 7.2 Hz, 1H), 7.38 (t, J = 7.2 Hz,
2H), 5.30 (q, J = 3.0 Hz, 1H), 0.73 (d, J = 3.0 Hz, 3H). 13C NMR
(CDCl3, 150.92 MHz, 25 °C): δ 133.76, 133.70, 131.01, 128.38, 0.25.
29Si NMR (CDCl3, 199.22 MHz, 25 °C): δ 3.06.
Methyl(1-naphthyl)chlorosilane (MNHSiCl). In a flame-dried vessel
under argon, methyl(1-naphthyl)silane (14 g, 82 mmol) and Fe(acac)3
(0.28 g, 0.8 mmol) were dissolved in dichloromethane (150 mL),
followed by dropwise addition of acetyl chloride (5.9 mL, 6.5 g, 83
mmol), upon which a color change from red to light yellow was
observed. The reaction mixture was stirred overnight until reaching full
conversion. Evaporation of the solvent yielded a yellowish oil, which
was distilled at reduced pressure to give a colorless liquid. Yield: 12.5 g
1
(60 mmol, 74%). GC purity: ∼80%. Bp: 90 °C/0.7 mbar. H NMR
(CDCl3, 600.13 MHz, 25 °C): 8.15 (d, J = 7.8 Hz, 1H), 7.90 (d, J =
8.4 Hz, 1H) 7.83 (m, 2H), 7.53 (ddd, J = 8.4, 6.6, 1.2 Hz, 1H) 7.47
(ddd, J = 7.8, 6.6, 1.2 Hz), 7.44 (dd, J = 7.8, 6.6 Hz, 1H), 5.66 (q, J =
3.0 Hz, 1H), 0.87 (d, J = 3.0 Hz, 3H). 13C NMR (CDCl3, 150.92
MHz, 25 °C): δ 135.98, 134.30, 133. 23, 131.80, 131.24, 129.07,
126.99, 126.65, 126.02, 125.02, 0.73. 29Si NMR (CDCl3, 119.22 MHz,
25 °C): δ 2.25.
Chlorination of Alkoxysilanes. Triphenylchlorosilane
(Ph3SiCl). In dichloroethane (10 mL) were dissolved triphe-
nylmethoxysilane (1.8 g, 6.3 mmol) and FeCl3 (5 mg, 0.03
mmol). The reaction mixture was protected from moisture,
followed by addition of acetyl chloride (0.67 mL, 0.74 g, 9.5
mmol). The reaction mixture was stirred overnight until full
conversion. Evaporation of the solvent left a yellowish oil,
which was dissolved in hexane and passed through a thin pad of
silica to afford a colorless liquid that was evaporated and
crystallized from hexane to yield white crystals. Yield: 1.7 g (5.8
mmol, 90%). For characterization data, vide supra.
Triisopropylchlorosilane (i-Pr3SiCl). In dichloroethane (10 mL)
were dissolved triphenylmethoxysilane (1.2 g, 6.3 mmol) and FeCl3 (5
3204
dx.doi.org/10.1021/om300066v | Organometallics 2012, 31, 3199−3206