178
S. Masaoka et al. / Journal of Organometallic Chemistry 691 (2006) 174–181
for i-Pr SiCl are identical with those of the authentic sam-
ple reported previously [14].
THF was stirred at room temperature for 4 h. The organic
layer was separated and analyzed by GLC technique using
3
octadecane as an internal standard as being cyclo-Hex SiCl
3
3
.2.2. i-Pr SiOBu-n (run 2)
3
(98% yield).
A mixture of 3.46 g (15 mmol) of i-Pr SiOBu-n, 7.5 g
3
(
72 mmol) of 35% aqueous HCl, and 19 ml of THF was
3.2.8. i-Pr MeSiOMe (run 8)
2
stirred at room temperature for 4 h. The organic layer
was separated and analyzed by GLC technique using tride-
To 50.0 g (0.48 mol) of 35% aqueous HCl was added
16.0 g (0.10 mol) of i-Pr MeSiOMe at 0 °C. After the mix-
2
cane as an internal standard as being i-Pr SiCl (95% yield).
ture was stirred at 0 °C for 2 h, the organic layer was sep-
3
arated, and analyzed by GLC technique using dodecane
3
.2.3. i-Pr SiOPr-i (run 3)
3
as an internal standard as being i-Pr MeSiCl (99% yield).
2
A mixture of 2.16 g (10 mmol) of i-Pr SiOPr-i, 5.0 g
The organic layer was distilled under reduced pressure to
3
(
48 mmol) of 35% aqueous HCl, and 2.5 ml of THF was
give 14.6 g (89% yield) of i-Pr MeSiCl (b.p. 82–83 °C/
2
stirred at 50 °C for 4 h. The organic layer was separated
and analyzed by GLC technique using tridecane as an
internal standard as being i-Pr SiCl (98% yield).
35 Torr). All spectral data obtained for i-Pr MeSiCl are
2
identical with those of the authentic sample reported pre-
viously [16].
3
3
.2.4. sec-Bu SiOMe (run 4)
3
3.2.9. sec-Bu MeSiOMe (run 9)
2
A mixture of 1.15 g (5.0 mmol) of sec-Bu SiOMe, 3.8 g
To 50.0 g (0.48 mol) of 35% aqueous HCl was added
3
(
36 mmol) of 35% aqueous HCl, and 6.5 ml of THF was
18.8 g (0.10 mol) of sec-Bu MeSiOMe at 0 °C. After the
2
stirred at room temperature for 4 h. The organic layer
was separated and analyzed by GLC technique using tride-
mixture was stirred at 0 °C for 2 h, the organic layer was
separated, and analyzed by GLC technique using dodecane
cane as an internal standard as being sec-Bu SiCl (98%
as an internal standard as being sec-Bu MeSiCl (99%
3
2
yield).
yield). The organic layer was distilled under reduced pres-
sure to give 16.3 g (85% yield) of sec-Bu MeSiCl: b.p. 81–
2
+
1
3
.2.5. sec-Bu SiOBu-n (run 5)
3
82 °C/15 Torr; MS m/z 192 (M) ; H NMR d (CDCl )
3
A mixture of 27.3 g (0.10 mol) of sec-Bu SiOBu-n,
5.0 g (0.72 mol) of 35% aqueous HCl, and 150 ml of
0.30 (s, 3 H, Me–Si), 0.84–0.93 (m, 2H, HC–Si), 0.95–
1.06 (m, 12H, H C–C–C–CH ), 1.16–1.31, (m, 2H,
3
7
3
3
1
3
THF was stirred at room temperature for 4 h. The organic
layer was separated and analyzed by GLC technique using
tridecane as an internal standard as being sec-Bu SiCl (97%
–CH –), 1.56–1.76, (m, 2H, –CH –); C NMR d (CDCl3)
2 2
ꢀ3.74, ꢀ3.65, ꢀ3.6 (Me–Si), 12.8, 12.88, 12.90 (CH ), 13.1,
3
13.15, 13.17 (CH ), 21.8, 21.87, 21.91 (CH–Si), 23.8, 23.86,
3
3
9
2
yield). The organic layer was distilled under reduced pres-
23.88 (–CH –); Si NMR d (CDCl ) 35.0. Anal. Calc. for
2 3
sure to give 20.3 g (86% yield) of sec-Bu SiCl: b.p. 92–
C H ClSi: C, 56.07; H, 10.98. Found: C, 56.10; H, 10.99.
9 21
3
+
1
9
0
3 °C/5 Torr; MS m/z 234 (M) ; H NMR d (CDCl3)
.95–1.08 (m, 3H, HC–Si), 0.97 (t, 9H, H C–C–Si,
3
3.2.10. cyclo-Hex MeSiOMe (run 10)
2
J = 7.3 Hz), 1.07 (d, 9H, H C–C–C, J = 6.2 Hz), 1.17–
3
1
3
To 50.0 g (240 mol) of 35% aqueous HCl was added
1
.31, (m, 3H, –CH –), 1.65–1.78, (m, 3H, –CH –);
C
2
2
1
2.0 g (50 mmol) of cyclo-Hex MeSiOMe at 0 °C. After
2
NMR d (CDCl ) 13.4 (CH ), 13.5 (CH ), 21.3 (CH–Si),
3
3
3
2
9
the mixture was stirred at 0 °C for 2 h, the organic layer
was separated, and analyzed by GLC technique using
tetradecane as an internal standard as being cyclo-Hex2-
MeSiCl (99% yield). The organic layer was distilled un-
der reduced pressure to give 10.2 g (83% yield) of
2
4.3 (–CH –); Si NMR d (CDCl ) 33.1. Anal. Calc. for
2 3
C H ClSi: C, 61.36; H, 11.59. Found: C, 61.33; H,
1
2
27
1
3
3
1.60.
.2.6. cyclo-Hex SiOMe (run 6)
3
cyclo-Hex MeSiCl: b.p. 138 °C/6 Torr; MS m/z 244
2
A mixture of 15.4 g (50 mmol) of cyclo-Hex SiOMe,
7.5 g (360 mmol) of 35% aqueous HCl, and 85 ml of
3
+
1
(
M) ; H NMR d (CDCl ) 0.27 (s, 3H, Me–Si), 0.87–
3
0
1
.96 (m, 2H, HC–Si), 1.22–1.25 (m, 10H, –CH –),
2
THF was stirred at room temperature for 4 h. The organic
layer was separated and analyzed by GLC technique using
1
3
.72–1.79, (m, 10H, –CH –); C NMR d (CDCl ) ꢀ4.2
2
3
(
(
Me–Si), 25.9 (CH–Si), 26.6, 26.66, 26.72, 27.65, 27.69
–CH –); Si NMR d (CDCl ) 34.0. Anal. Calc. for
octadecane as an internal standard as being cyclo-Hex SiCl
3
29
2
3
(
99% yield). The organic layer was recrystallized from hex-
C H ClSi: C, 63.76; H, 10.29. Found: C, 63.80; H,
1
1
25
ane to give 14.1 g (90% yield) of cyclo-Hex SiCl: m.p. 101–
3
10.32.
1
02 °C. All spectral data obtained for cyclo-Hex SiCl are
3
identical with those of the authentic sample reported previ-
ously [15].
3.2.11. i-PrMe SiOMe (run 11)
2
To 25.0 g (240 mmol) of 35% aqueous HCl was added a
3
.2.7. cyclo-Hex SiOBu-n (run 7)
3
solution of 1.32 g (10 mmol) of i-PrMe SiOMe in 5.8 ml of
2
A mixture of 1.75 g (5.0 mmol) of cyclo-Hex SiOBu-n,
.75 g (36 mmol) of 35% aqueous HCl, and 8.6 ml of
xylene at 0 °C over a period of 1 h. After the mixture was
stirred for 1 h, the organic layer was separated and
3
3