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J. Ohshita et al. / Journal of Organometallic Chemistry 689 (2004) 3258–3264
3.2. Alkoxylation of di- and trihydrosilanes
54.49; H, 11.43. Found: C, 54.25; H, 11.41%. Data for
1
PhSi(OEt)2H: b.p. 40 °C, 1 mmHg; IR 2162 cmꢀ1; H
A mixture of Hex2SiH2 (5.85 g, 29.2 mmol), EtOH
(13.38 g, 29.1 mmol), and PdCl2 (0.007 g, 0.039 mmol)
in 75 mL of benzene was stirred at room temperature
for 24 h. After the resulting black precipitates were fil-
tered, the solvent was evaporated and the residue was
fractionally distilled under reduced pressure to give
Hex2Si(OEt)H (6.22 g, 25.6 mmol; 88% yield): b.p. 75
NMR d 7.64 (dd, J = 7.7, 1.2 Hz, 2H), 7.48–7.34 (m,
3H), 4.93 (s, 1H), 3.89 (q, J = 7.0 Hz, 4H), 1.26 (br t,
J = 7.0 Hz, 6H); 13C NMR d 134.03, 133.10, 130.57,
127.94, 59.44, 18.23; GC–MS m/z 196 (M+). Anal. Calc.
for C10H16O2Si: C, 61.18; H, 8.22. Found: C, 61.06; H,
8.24%. Data for PhSi(OMe)2H: b.p. 40 °C, 1 mmHg; 1H
NMR d 7.61 (dd, J = 7.7, 1.2 Hz, 2H), 7.47–7.36 (m,
3H), 4.86 (s, 1H), 3.61 (s, 6H); 13C NMR d 133.92,
132.12, 130.75, 128.00, 51.18; GC–MS m/z 168 (M+).
Anal. Calc. for C8H12O2Si: C, 57.10; H, 7.19. Found:
C, 57.08; H, 7.23%.
1
°C, 1 mmHg; IR 2097 cmꢀ1 (Si–H); H NMR d 4.33
(quintet, J = 2.4 Hz, 1H, SiH), 3.59 (q, J = 7.0 Hz, 2H,
CH2O), 1.30–1.07 (m, 19H, CH2C2 in Hex and CH3 in
OEt), 0.76 (t, J = 7.0 Hz, 6H, CH3 in Hex), 0.55 (br t,
J = 7.2 Hz, 4H, CH2–Si); 13C NMR d 60.13 (CH2O),
32.81, 31.56, 23.09, 22.57 (Hex), 18.26 (CH3 in EtO),
14.09, 13.82 (Hex); GC–MS m/z 244 (M+). Anal. Calc.
for C14H32OSi: C, 68.77; H, 13.19. Found: C, 68.56;
H, 13.19%.
Peralkoxylation of di- and trihydrosilanes was per-
formed in a similar fashion to monoalkoxylation, using
a small excess of methanol or ethanol. Data for Hex2-
1
Si(OEt)2: b.p. 120 °C, 1 mmHg; H NMR d 3.72 (q,
J = 6.9 Hz, 4H), 1.55–1.17 (m, 22H), 0.87 (br t, J = 6.6
Hz, 6H), 0.57 (br t, J = 7.2 Hz, 4H); 13C NMR d
58.08, 33.10, 31.61, 22.88, 22.59, 18.26, 14.59, 14.09;
GC–MS m/z 288 (M+). Anal. Calc. for C16H36O2Si: C,
66.60; H, 12.58. Found: C, 66.55; H, 12.55%. Data for
Hex2Si(OMe)2: b.p. 80 °C, 1 mmHg (oven temperature
The other partial alkoxylation of di- and trihydrosi-
lanes was carried out as above. Data for Hex2Si(O-
Me)H: b.p. 65 °C, 1 mmHg (oven temperature on
Kugel-rohr distillation); IR 2098 cmꢀ1 1H NMR d
;
4.42 (quintet, J = 2.3 Hz, 1H), 3.48 (s, 3H), 1.45–1.15
(m, 16H), 0.88 (t, J = 7.0 Hz, 6H), 0.67 (br t, J = 7.0,
4H); 13C NMR d 52.20, 32.81, 31.54, 23.08, 22.55,
14.05, 13.43; GC–MS m/z 230 (M+). Anal. Calc. for
C13H30OSi: C, 67.75; H, 13.12. Found: C, 67.86; H,
13.11%. Data for Ph2Si(OEt)H: b.p. 83–85 °C, 1 mmHg;
IR 2122 cmꢀ1; 1H NMR d 7.73 (dd, J = 7.7, 1.7 Hz, 4H,
o-Ph), 7.50–7.23 (m, 6H, m- and p-Ph), 5.42 (s, 1H, SiH),
3.85 (q, J = 6.9 Hz, 2H, CH2), 1.25 (t, J = 6.9 Hz, 3H,
CH3); 13C NMR d 134.65 (CH in Ph), 134.32 (ipso-C
in Ph), 130.30, 128.01 (CH in Ph), 60.58 (CH2), 18.13
(CH3); GC–MS m/z 228 (M+). Anal. Calc. for
C14H16OSi: C, 73.63; H, 7.06. Found: C, 73.42; H,
7.07%. Data for Ph2Si(OMe)H: b.p. 63–65 °C, 1 mmHg
(oven temperature on Kugel-rohr distillation); IR 2118
1
on Kugel-rohr distillation); H NMR d 3.51 (s, 6H),
1.42–1.15 (m, 16H), 0.87 (t, J = 7.0 Hz, 6H), 0.56 (br
t, J = 7.3 Hz, 4H); 13C NMR d 50.23, 33.05, 31.50,
22.64, 22.55, 14.07, 11.92; GC–MS m/z 260 (M+). Anal.
Calc. for C14H32O2Si: C, 64.55; H, 12.38%. Found: C,
63.96; H, 12.36. Data for Ph2Si(OMe)2: b.p. 110 °C, 1
mmHg; 1H NMR d 7.67 (dd, J = 7.7, 1.7 Hz, 4H),
7.41–7.38 (m, 6H), 3.64 (s, 6H); 13C NMR d 134.83,
132.27, 130.35, 127.91, 50.93; GC–MS m/z 244 (M+).
Anal. Calc. for C14H16O2Si: C, 68.81; H, 6.60. Found:
C, 68.71; H, 6.66%. Data for HexSi(OEt)3: b.p. 50 °C,
1 mmHg (oven temperature on Kugel-rohr distillation);
1H NMR d 3.80 (q, J = 7.0 Hz, 6H), 1.60–1.28 (m, 17H),
0.86 (br t, J = 7.0 Hz, 3H), 0.62 (br t, J = 7.2 Hz, 2H);
13C NMR d 58.28, 32.83, 31.48, 22.72, 22.55, 18.28,
14.07, 10.42; GC–MS m/z 248 (M+). Anal. Calc. for
C12H28O3Si: C, 57.92; H, 11.34. Found: C, 57.63; H,
11.60%. Data for PhSi(OEt)3: b.p. 70 °C, 1 mmHg (oven
temperature on Kugel-rohr distillation); 1H NMR d 7.66
(dd, J = 7.7, 1.7 Hz, 2H), 7.42–7.28 (m, 3H), 3.86 (q,
J = 6.9 Hz, 6H), 1.24 (t, J = 6.9 Hz, 9H); 13C NMR d
134.79, 130.96, 130.30, 127.82, 58.71, 18.21; GC–MS
m/z 240 (M+). Anal. Calc. for C12H20O3Si: C, 59.96;
H, 8.39. Found: C, 59.88; H, 8.37%.
1
cmꢀ1; H NMR d 7.65 (dd, J = 7.7, 1.7 Hz, 4H), 7.48–
7.37 (m, 6H), 5.41 (s, 1H), 3.63 (s, 3H); 13C NMR d
134.63, 133.60, 130.40, 128.05, 52.45; GC–MS m/z 214
(M+). Anal. Calc. for C13H14OSi: C, 72.85; H, 6.58.
Found: C, 72.87; H, 6.54%. Data for HexSi(OEt)2H:
b.p. 45 °C, 1 mmHg (oven temperature on Kugel-rohr
distillation); IR 2151 cmꢀ1 1H NMR d 4.50 (br t,
;
J = 1.7 Hz, 1H), 3.80 (q, J = 6.9 Hz, 4H), 1.28–1.17
(m, 14H), 0.87 (br t, J = 6.9 Hz, 3H), 0.65 (br t,
J = 7.2 Hz, 2H); 13C NMR d 59.32, 32.54, 31.52,
22.54, 22.07, 18.26, 14.09, 13.34; GC–MS m/z 204
(M+). Anal. Calc. for C10H24O2Si: C, 58.77; H, 11.84.
Found: C, 58.49; H, 11.89%. Data for HexSi(OMe)2H:
b.p. 80 °C, 20 mmHg (oven temperature on Kugel-rohr
3.3. Chlorination of alkoxyhydrosilanes
A mixture of Hex2Si(OEt)H (3.08 g, 12.7 mmol),
CCl4 (1.97 g, 12.8 mmol), and PdCl2 (0.0067 g, 0.038
mmol) in 25 mL of toluene was stirred at room temper-
ature for 24 h. After the resulting black precipitates were
filtered, the solvent was evaporated and the residue was
fractionally distilled under reduced pressure to give
1
distillation); H NMR (d in CDCl3) 4.44 (br t, J = 1.4
Hz, 1H), 3.54 (s, 6H), 1.39–1.18 (m, 8H), 0.86 (t,
J = 6.8 Hz, 3H), 0.67–0.63 (m, 2H); 13C NMR (d in
CDCl3) 51.25, 32.54, 31.49, 22.51, 21.88, 14.07, 12.76;
GC–MS m/z 176 (M+). Anal. Calc. for C8H20O2Si: C,