S. Masaoka et al. / Journal of Organometallic Chemistry 691 (2006) 182–192
191
and s-Bu2MeSiH (1% yield). The mixture was fractionally
distilled to give 124.7 g (70% yield) of s-Bu2MeSiOMe:
b.p. 78–81 ꢁC/16–18 Torr; MS m/z 189 (M + 1)+; 1H
NMR d (CDCl3) 0.02 (s, 3H, Me–Si), 0.67–0.80 (m, 2H,
HC–Si), 0.91–1.00 (m, 12H, H3CCC(CH3)–), 1.09–1.26
(m, 2H, CCH2C(C)–Si), 1.51–1.69 (m, 2H, CCH2C(C)–
Si), 3.45 (s, 3H, Me–O); 13C NMR d (CDCl3) ꢀ8.2,
ꢀ8.0, ꢀ7.8 (Me–Si), 13.1, 13.16, 13.23 (Me–C), 13.27,
13.34, 13.4 (Me–C), 20.4, 20.5, 20.6 (HC–Si), 24.21,
24.23, 24.3 (CH2–C(C)–Si), 51.1 (Me–O); 29Si NMR d
(CDCl3) 18.2. Anal. Calc. for C10H24OSi: C, 63.76; H,
12.84. Found: C, 63.70; H, 12.80%.
0.71 (m, 1H, HC–Si), 0.94 (t, 3H, Me–CC, J = 7.2 Hz),
0.95 (d, 3H, Me–CSi, J = 7.5 Hz), 1.12–1.22 (m, 1H,
–H2C–), 1.52–1.61 (m, 1H, –H2C–), 2.92 (s, 3H, Me–O);
13C NMR d (CDCl3) ꢀ4.4 (Me–Si), 13.0 (Me–CSi), 13.3
(HC–Si), 21.8 (Me–CC), 24.1 (–CH2–), 50.4 (Me–O). All
spectral data obtained for s-BuMe2SiOMe are identical
with those reported in the literature [20,21].
3.1.36. One-pot synthesis of c-HexMe2SiOMe from
Me2SiCl2 (run 38)
To 300 ml (0.71 mol) of a c-HexMgCl–THF solution
was added 7.59 g (0.24 mol) of methanol, and then 30.6 g
(0.24 mol) of Me2SiCl2. The mixture was heated to reflux
for 5 h and hydrolyzed as the usual manner, and then ana-
lyzed by GLC, as being c-HexMe2SiOMe (90% yield). The
mixture was fractionally distilled to give 34.8 g (72% yield)
of c-HexMe2SiOMe: b.p. 92–93 ꢁC/41 Torr; MS m/z 173
3.1.33. One-pot synthesis of c-Hex2MeSiOMe from
MeSiCl3 (run 32)
To 417 g (1.0 mol) of a c-HexMgCl–THF solution was
added 8.01 g (0.25 mol) of methanol, and then 37.4 g
(0.25 mol) of MeSiCl3. The mixture was heated to reflux
for 4 h and hydrolyzed as the usual manner, and then ana-
lyzed by GLC, as being c-Hex2MeSiOMe (83% yield) and
c-Hex2MeSiH (0.6% yield). The mixture was fractionally
distilled to give 35.6 g (74% yield) of c-Hex2MeSiOMe:
b.p. 129 ꢁC/7 Torr; MS m/z 241 (M + 1)+; 1H NMR d
(CDCl3) ꢀ0.01 (s, 3H, Me–Si), 0.78 (broad s, 2H, HC–
Si), 1.20 (broad s, 10H, ring protons), 1.71 (broad s,
10H, ring protons), 3.46 (s, 3H, Me–O); 13C NMR d
(CDCl3) ꢀ8.4 (Me–Si), 24.9 (HC–Si), 27.0, 27.1, 27.3,
27.9, 28.0 (CH2), 51.3 (Me–O); 29Si NMR d (CDCl3)
15.2. Anal. Calc. for C14H28OSi: C, 69.93; H, 11.74.
Found: C, 69.87; H, 11.75%.
1
(M + 1)+; H NMR d (CDCl3) 0.04 (s, 6H, Me–Si), 0.67–
0.75 (m, 1H, HC–Si), 1.06–1.21 (m, 5H, –H2C–), 1.72
(brs, 5H, –H2C–), 3.43 (s, 3H, Me–O); 13C NMR d (CDCl3)
ꢀ4.7 (Me–Si), 26.4 (HC–Si), 26.8, 26.9, 27.9 (–CH2–), 50.5
(Me–O). All spectral data obtained for c-HexMe2SiOMe
are identical with those reported in the literature [4,21,22].
3.1.37. One-pot synthesis of t-BuMe2SiOMe from Me2SiCl2
(run 40)
To a solution prepared from 9.3 g (0.072 mol) of Me2-
SiCl2 and 2.31 g (0.072 mol) of methanol was added
100 ml (0.18 mol) of a t-BuMgCl–THF solution at 20–
25 ꢁC for 30 min. The mixture was heated to reflux for
6 h and hydrolyzed as the usual manner, and then analyzed
by GLC, as being t-BuMe2SiOMe (62% yield). The mixture
was fractionally distilled to give 5.6 g (54% yield) of t-Bu-
Me2SiOMe: b.p. 117–118 ꢁC/760 Torr. All spectral data
obtained for t-BuMe2SiOMe are identical with those re-
ported in the literature [23].
3.1.34. One-pot synthesis of i-PrMe2SiOMe from Me2SiCl2
(run 34)
To 250 ml (0.6 mol) of an i-PrMgCl–THF solution was
added 7.69 g (0.24 mol) of methanol, and then 31.0 g
(0.24 mol) of Me2SiCl2. The mixture was heated to reflux
for 4 h and hydrolyzed as the usual manner, and then ana-
lyzed by GLC, as being i-PrMe2SiOMe (90% yield). The
mixture was fractionally distilled to give 24.6 g (77% yield)
of i-PrMe2SiOMe: b.p. 104–105 ꢁC/760 Torr; MS m/z 133
References
[1] (a) A. Shirahata, Jpn. Tokkyo, JP 2069791;
(b) N. Sakamoto, H. Taniguchi, A. Inada, M. Fujikawa, Jpn.
Tokkyo, JP 2854832.
[2] H. Gilman, R.N. Clark, J. Am. Chem. Soc. 69 (1947) 1499–1500.
[3] A. Funatsu, T. Kubota, M. Endo, Jpn. Kokai Tokkyo Koho, JP
2001-039990.
1
(M + 1)+; H NMR d (CDCl3) 0.05 (s, 6H, Me–Si), 0.80–
0.97 (m, 1H, HC–Si), 0.96 (d, 6H, Me–C, J = 6.2 Hz),
3.43 (s, 3H, Me–O); 13C NMR d (CDCl3) ꢀ5.0 (Me–Si),
14.2 (HC–Si), 16.8 (Me–C), 50.5 (Me–O). All spectral data
obtained for i-PrMe2SiOMe are identical with those re-
ported in the literature [19].
[4] I.I. Lapkin, R.G. Mukhina, N.F. Kirillov, Zh. Obshch. Khim. 57
(1987) 146–151.
[5] (a) A.F. Reid, C.J. Wilkins, J. Chem. Soc. (1955) 4029–4034;
(b) R. Corriu, G. Royo, J. Organomet. Chem. 40 (1972) 229–249;
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(d) M.C. Harvey, W.H. Nebergall, J.S. Peake, J. Am. Chem. Soc. 79
(1957) 2762–2764;
3.1.35. One-pot synthesis of s-BuMe2SiOMe from Me2SiCl2
(run 36)
To 500 g (1.35 mol) of a s-BuMgCl–THF solution was
added 14.3 g (0.45 mol) of methanol, and then 57.4 g
(0.45 mol) of Me2SiCl2. The mixture was heated to reflux
for 6 h and hydrolyzed as the usual manner, and then ana-
lyzed by GLC, as being s-BuMe2SiOMe (90% yield). The
mixture was fractionally distilled to give 46.2 g (71% yield)
of s-BuMe2SiOMe: b.p. 128 ꢁC/760 Torr; MS m/z 147
(e) N.S. Marans, L.H. Sommer, F.C. Whitmore, J. Am. Chem. Soc.
73 (1951) 5127–5130;
(f) L.H. Sommer, C.L. Frye, G.A. Parker, J. Am. Chem. Soc. 86
(1964) 3276–3279;
(g) L.H. Sommer, G.A. Parker, C.L. Frye, J. Am. Chem. Soc. 86
(1964) 3280–3282.
[6] L. Horner, J. Mathias, J. Organomet. Chem. 282 (1985) 155–174.
[7] R.F. Cunico, L. Bedell, J. Org. Chem. 45 (1980) 4797–4798.
1
(M + 1)+; H NMR d (CDCl3) 0.07 (s, 6H, Me–Si), 0.65–