M. Chauhan et al. / Journal of Organometallic Chemistry 645 (2002) 1–13
7
4.2.3. Phenylacetylene+phenyldichlorosilane (entry 3,
Table 1)
NMR (CDCl3): l 18.05 (Cd), 58.66 (Cc), 126.80 (Co),
128.20 (arom, Cp), 131.49 (arom, Cm), 141.91 (Cb),
143.37 (Ca); EIMS; m/z (relative intensity): 266 [M+, 7],
222 (84), 163 (39), 135 (100).
Phenyldichlorosilane (Hu¨l’s) (3.6 g, 3.0 ml, 20 mmol)
and 0.08 g of 1% Pt on carbon (4.1 mmol of Pt) were
placed in to a 25 ml flask. Phenylacetylene (2.0 g, 2.2
ml, 20 mmol) was added by addition funnel at 35 °C
over 45 min. After an additional 30 min at 45 °C,
vacuum distillation produced 5.2 g (17.8 mmol, 89%) of
E-1-phenyl-2-phenyldichlorosilylethene.
4.2.6. 1-Hexyne+trichlorosilane (entry 6 of Table 1)
1-Hexyne (1.6 g, 2.3 ml, 20 mmol) and trichlorosilane
(2.8 g, 2.1 ml, 20 mmol) were added to 0.08 g of 1% Pt
on carbon (4.1 mmol of Pt). Heating the solution for 5
h at 50 °C produced, after vacuum distillation, 4.2 g
(19 mmol, 95%) of E-1-trichlorosilylhex-1-ene [11].
Cl3ꢀSiꢀCaꢁCbꢀCcꢀCdꢀCeꢀCf (b-trans): 1H-NMR
(CDCl3): l 0.93 (t, J(H,H)=7 Hz, 3H, Hf), 1.30–1.52
(m, 4H, Hd, He), 2.24–2.32 (m, 2H, Hc), 5.81 (d of t,
J(H,H)=18.3, 1.5 Hz, 1H, Ha), 6.71 (d of t, J(H,H)=
18.3, 6 Hz, 1H, Ha); 13C-NMR (CDCl3): l 13.84 (Cf),
22.19 (Ce), 29.81 (Cd), 35.54 (Cc), 121.71 (Ca), 157.36
(Cb); EIMS; m/z (relative intensity): 216 [M+, 4], 187
(24), 174 (94), 151 (20), 133 (74), 83 (100).
PhꢀCaꢁCbꢀSiCl2Ph (b-trans): 1H-NMR (CDCl3): l
6.61 (d, J(H,H)=18.7 Hz, 1H, Hb), 7.34 (d, J(H,H)=
19.0 Hz, 1H, Ha); EIMS; m/z (relative intensity): 278
[M+, 8], 243 (1), 202 (2), 180 (100), 165 (27).
4.2.4. Phenylacetylene+triethylsilane (entry 4, Table 1)
Phenylacetylene (2.0 g, 2.2 ml, 20 mmol) and triethyl-
silane (2.3 g, 3.2 ml, 20 mmol) were added to 0.08 g of
1% Pt on carbon (4.1 mmol of Pt). Heating at 70 °C for
4.5 h produced 3.9 g (18 mmol, 91%) of a mixture of
E-1-phenyl-2-triethylsilylethene [10] and 1-phenyl-1-tri-
ethylsilylethene [10,17,21] after vacuum distillation.
4.2.7. 1-Hexyne+methyldichlorosilane (entry 7, Table
1)
1
PhꢀCaꢁCbꢀSiꢀCcꢀCd (b-trans): H-NMR (CDCl3): l
0.64 (q, J(H,H)=8 Hz, 6H, Hc), 1.00 (t, J(H,H)=8
Hz, 9 H, Hd), 6.45 (d, J(H,H)=19 Hz, 1H, Hb), 6.91
(d, J(H,H)=19.0 Hz, 1H, Ha); 13C-NMR (CDCl3): l
3.36 (Cd), 7.32 (Cc), 125.99 (Ca), 126.34 (arom, Co),
128.11 (arom, Cm), 126.68 (arom, Cp), 128.80 (arom,
ipso-Ci), 144.89 (Cb); EIMS; m/z (relative intensity):
218 [M+, 12], 189 (99), 161 (98), 131 (100). (a-isomer)
1H-NMR (CDCl3): l 0.66 (q, J(H,H)=8 Hz, 6H, Hc),
0.95 (t, J(H,H)=8 Hz, 9H, Hd), 5.60 (d, J(H,H)=3.3
Hz, 1H, Hb%), 5.89 (d, J(H,H)=3.3 Hz, 1H, Hb); 13C-
NMR (CDCl3): l 3.59 (Cc), 7.43 (Cd), 126.10 (arom,
Co), 127.90 (arom, Cp), 128.53 (arom, Cm), 138.60 (Cb),
150.40(Ca); EIMS; m/z (relative intensity): 218 [M+, 3],
189 (48), 161 (81), 133 (46), 103 (100).
1-Hexyne (1.6 g, 2.3 ml, 20 mmol) and
methyldichlorosilane (2.3 g, 2.1 ml, 20 mmol) were
added to 0.08 g of 1% Pt on carbon (4.1 mmol Pt).
Stirring the solution at room temperature for 1.5 h
resulted in 3.8
methyldichlorosilylhex-1-ene [11,22].
CgꢀSiꢀCaꢁCbꢀCcꢀCdꢀCeꢀCf (b-trans):
g
(17.6 mmol, 88%) of E-1-
1H-NMR
(CDCl3): l 0.84 (s, 3H, Hg), 0.92 (t, J(H,H)=7 Hz,
3H, Hf), 1.27–1.48 (m, 4H, Hd, He), 2.19–2.26 (m, 2H,
Hc), 5.75 (d of t, J(H,H)=18.5, 1.5 Hz, 1H, Ha), 6.52
(d of t, J(H,H)=18.5, 6.2 Hz, 1H, Hb); 13C-NMR
(CDCl3): l 5.47 (Cg), 13.87 (Cf), 22.19 (Ce), 30.07 (Cd),
35.74 (Cc), 123.56 (Ca), 154.41 (Cb), EIMS; m/z (rela-
tive intensity): 196 [M+, 1], 181 (1), 167 (10), 154 (32),
113 (100).
4.2.5. Phenylacetylene+triethoxysilane (entry 5, Table 1)
Phenylacetylene (2.0 g, 2.2 ml, 20 mmol) and tri-
ethoxysilane (3.3 g, 3.7 ml, 20 mmol) were added to
0.08 g of 1% Pt on carbon (4.1 mmol of Pt). Heating the
solution at 55 °C for 4.5 h, provided 4–4.9 g (15–18
mmol, 75–93%) of a mixture of E-1-phenyl-2-tri-
ethoxysilylethene [10,17] and 1-phenyl-1-triethoxysi-
lylethene [10] after vacuum distillation.
4.2.8. 1-Hexyne+phenyldichlorosilane (entry 8, Table
1)
Phenyldichlorosilane (Hu¨l’s) (3.6 g, 3.0 ml, 20 mmol)
and 0.08 g of 1% Pt on carbon (4.1 mmol of Pt) were
placed in to a 25 ml flask. 1-Hexyne (1.6 g, 2.2 ml, 20
mmol) was added by addition funnel over 30 min. After
heating at 78 °C for 45 min, provided 5.0 g (19.4
mmol, 97%) of E-1-phenylldichlorosilylhex-1-ene after
vacuum distillation.
1
PhꢀCaꢁCbꢀSiꢀOꢀCcꢀCd (b-trans): H-NMR (CDCl3):
l 1.28 (t, J(H,H)=7 Hz, 9H, Hd), 3.90 (q, J(H,H)=7
Hz, 6H, Hc), 6.20 (d, J(H,H)=19.4 Hz, 1H, Hb), 7.23
(d, J(H,H)=19.4 Hz, 1H, Ha); 13C-NMR (CDCl3): l
18.19 (Cd), 58.52 (Cc), 117.7 (Ca), 126.70 (arom, Co),
128.4 (arom, Cp), 128.65 (arom, Cm), 149.04 (Cb);
EIMS; m/z (relative intensity): 266 [M+, 9], 251 (45),
222 (100), 163(15), 135 (17). (a-isomer) 1H-NMR
(CDCl3): l 1.16 (t, J(H,H)=7 Hz, 9H, Hd), 3.79 (q,
J(H,H)=7 Hz, 6H, Hc), 5.92 (d, J(H,H)=2.93 Hz,
1H, Hb%), 6.10 (d, J(H,H)=2.93 Hz, 1H, Hb); 13C-
PhꢀSiꢀCaꢁCbꢀCcꢀCdꢀCeꢀCf
(b-trans):
1H-NMR
(CDCl3): l 0.93 (t, J(H,H)=7 Hz, 3H, Hf), 1.29–1.53
(m, 4H, Hd, He), 2.24–2.32 (m, 2H, Hc), 5.91 (d of t,
J(H,H)=18.3, 1.2 Hz, 1H, Ha), 6.60 (d of t, J(H,H)=
18.3, 6.2 Hz, 1H, Hb); 13C-NMR (CDCl3): l 13.87 (Cf),
22.20 (Ce), 30.02 (Cd), 35.88 (Cc), 121.88 (arom, Co),
128.24 (arom, Cp), 131.52 (arom, Cm), 156.36 (Cb);
EIMS; m/z (relative intensity): 258 [M+, 1], 216 (26),
188 (8), 175 (100), 152 (12).