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J. G. Rodrıguez et al. / Tetrahedron 62 (2006) 3355–3361
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sodium sulfate and after filtration; the solvent was removed
to give a residue, which was purified by silica gel column
chromatography (hexane/dichloromethane, 2:1). Compound
8 was isolated as a pale-yellow solid, mp 237–239 8C
(lit. 239–241 8C),2 290 mg (98%) yield.
1H NMR (CDCl3): d 7.63 (d, 2H, JZ8.1 Hz), 7.12 (d, 2H,
JZ8.1 Hz), 1.60 (s, 6H).
4.1.12. 4-[p-(Trimethylsilylethynyl)phenyl]-2-methyl-3-
butyn-2-ol (12). Following the general method used for
the synthesis of 7, a mixture of Cl2Pd(PPh3)2 (400 mg,
0.73 mmol), Cu2I2 (14 mg, 0.073 mmol), compound 11
(2.1 g, 7.32 mmol), trimethylsilylacetylene (718 mg,
7.31 mmol), and NEt3 (100 mL) was stirred at room
temperature for 12 h. By silica gel column chromatography
(hexane/dichloromethane, 2:1) was obtained 12 as a white
solid, mp 108–109 8C, 1.8 g (98%) yield.
UV–vis (CH2Cl2), lmax (nm): 269 (3, 134,800), 279
(3, 242,300), 308 (3, 24,100), 321 (3, 31,200), 334 (3,
21,800). Fluorescence (CH2Cl2), lmax (nm): 523 (fZ0.03).
4.1.9. 9-(p-Methoxyphenyl)-9-methyl-2,7-bis(trimethyl-
silylethynyl)fluorene (9). Following the general method
used for the synthesis of 7, a mixture of Cl2Pd(PPh3)2
(16 mg, 0.02 mmol), Cu2I2 (0.4 mg, 0.002 mmol), com-
pound 6 (50 mg, 0.11 mmol), trimethylsilylacetylene
(24 mg, 0.24 mmol), and NEt3 (30 mL) was stirred for
16 h at 50 8C. By silica gel flash column chromatography
(hexane/dichloromethane, 2:1) was isolated 9 as a white
solid, mp 195–196 8C, 50 mg (94%) yield.
1
IR (KBr, cmK1): 3286, 2157, 1497, 1250, 833, 759. H
NMR (CDCl3): d 7.40 (d, 2H, JZ8.6 Hz), 7.33 (d, 2H, JZ
8.6 Hz), 1.6 (s, 6H), 0.24 (s, 9H). 13C NMR (CDCl3): d
131.7, 131.4, 122.8, 122.7, 104.5, 96.0, 95.6, 81.7, 65.5,
31.3, K0.1.
4.1.13. p-(Trimethylsilylethynyl)phenylacetylene (13).
General procedure. To a solution of 4-[p-(trimethylsilyl-
ethynyl)phenyl]-2-methyl-3-butyn-2-ol (12) (204 mg,
0.8 mmol) in dry toluene (40 mL) was added finely
powdered sodium hydroxide (3.2 mg, 0.08 mmol), under
argon atmosphere, and the mixture was warmed at the
reflux temperature for 2 h, and then filtered. The solvent
was removed at reduced pressure and the solid residue
was purified by silica gel column chromatography (hexane/
dichloromethane, 1:1) giving 13 as a white solid, mp
52–53 8C, 158 mg (99%) yield.
UV–vis (CH2Cl2), lmax (nm): 301 (3, 35,400), 311 (3, 56,800),
328 (3, 50,800), 344 (3, 83,000). Fluorescence (CH2Cl2), lmax
(nm): 351 and 363 (fZ0.79). IR (KBr, cmK1): 2959, 2154,
1253, 1250, 1061, 893, 859, 760. 1H NMR (CDCl3): d 7.66 (d,
2H, JZ7.9 Hz), 7.47 (dd, 2H, JZ7.9, 1.4 Hz), 7.31 (d, 2H,
JZ1.4 Hz), 7.04 (d, 2H, JZ8.9 Hz), 6.77 (d, 2H, JZ8.9 Hz),
3.76 (s, 3H), 1.82 (s, 3H), 0.24 (s, 18H). 13C NMR (CDCl3):
d 158.3, 154.4, 139.2, 135.7, 131.4, 127.7, 127.6, 122.4,
120.1, 113.8, 105.6, 94.6, 55.2, 54.0, 25.1, K0.1. C31H34OSi2
(478.77). Anal. Calcd: C 77.77, H 7.16. Found: C 77.95,
H 7.02.
1
IR (KBr, cmK1): 3302, 2162, 1580, 1413, 1250, 760. H
NMR (CDCl3): d 7.45 (s, 4H), 3.20 (s, 1H), 0.30 (s, 9H). 13
C
4.1.10. 2,7-Diethynyl-9-(p-methoxyphenyl)-9-methyl-
fluorene (10). Following the general method used for the
synthesis of 8, a mixture of potassium carbonate (304 mg,
NMR (CDCl3): d 131.8, 131.7, 123.5, 122.1, 104.3, 96.4,
83.1, 78.9, K0.1. C13H14Si (189.34). Anal. Calcd: C 78.72,
H 7.11. Found: C 78.86, H 7.04.
2.2 mmol), compound
9 (50 mg, 0.11 mmol), and
THF–MeOH (16 mL/4 mL) was stirred at room temperature
for 3 h. By silica gel flash column chromatography (hexane/
dichloromethane, 2:1) was isolated 10 as a white solid, mp
183–184 8C, 37 mg (99%) yield.
4.1.14. 2,7-Di[(p-trimethylsilylethynylphenyl)ethynyl]-
fluoren-9-one (14). Following the general method used
for the synthesis of 7, a mixture of Cl2Pd(PPh3)2 (35 mg,
0.05 mmol), Cu2I2 (1 mg, 0.005 mmol), compound 3
(100 mg, 0.25 mmol), compound 13 (99 mg, 0.5 mmol),
and NEt3 (30 mL) was stirred for 12 h at 50 8C. By silica gel
flash column chromatography (hexane/dichloromethane,
5:1), was obtained 14 as an orange solid, mpO300 8C,
104 mg (73%) yield.
UV–vis (CH2Cl2), lmax (nm): 293 (3, 42,700), 304 (3,
61,500), 321s (3, 34,200), 332 (3, 58,100). Fluorescence
(CH2Cl2), lmax (nm): 355 (fZ0.52). IR (KBr, cmK1): 2103,
1
2934, 2103, 1263, 894, 825. H NMR (CDCl3): d 7.69 (d,
2H, JZ7.9 Hz), 7.49 (d, 2H, JZ7.9 Hz), 7.35 (s, 2H), 7.04
(d, 2H, JZ8.9 Hz), 6.77 (d, 2H, JZ8.9 Hz), 3.76 (s, 3H),
3.08 (s, 2H), 1.84 (s, 3H). 13C NMR (CDCl3): d 158.3,
154.4, 139.4, 135.5, 131.5, 127.9, 127.5, 121.5, 120.3,
113.8, 84.1, 77.6, 55.2, 54.0, 25.2. MS (70 eV): 334 (MC,
75), 319 (100), 276 (20), 250 (6), 226 (9), 159 (15).
C25H18O (334.41). Anal. Calcd: C 89.79, H 5.43. Found: C
89.88, H 5.68.
IR (KBr, cmK1): 3012, 2157, 1592, 1473, 1254, 759. UV–
vis (CH2Cl2), lmax (nm): 310 (3, 11,200), 358 (3, 15,800).
Fluorescence (CH2Cl2), lmax (nm): 531 (fZ0.03). 1H NMR
(CDCl3): d 7.80 (dd, 2H, JZ6.2, 1.6 Hz), 7.64 (dd, 2H, JZ
6.2, 1.6 Hz), 7.53 (m, 8H), 7.35 (d, 2H, JZ6.2 Hz), 0.26 (s,
18H). 13C NMR (CDCl3): d 189.7, 141.2, 135.4, 132.5,
132.0, 131.1, 127.5, 123.5, 122.3, 121.8, 120.7, 103.8, 97.4,
85.1, 78.3, K0.1. C39H32OSi2 (572.84). Anal. Calcd: C
81.77, H 5.63. Found: C 81.50, H 5.85.
4.1.11. 4-(p-Iodophenyl)-2-methyl-3-butyn-2-ol (11).
Following the general method used for the synthesis of
7, a mixture of Cl2Pd(PPh3)2 (21 mg, 0.03 mmol), Cu2I2
(0.6 mg, 0.003 mmol), 1,4-diiodobenzene (1 g, 3.03 mmol),
2-methyl-3-butyn-2-ol (255 mg, 3.03 mmol), and NEt3
(100 mL) was stirred at room temperature for 12 h. By
silica gel flash column chromatography (hexane/ethyl
acetate, 4:1) was obtained 11 as a white solid, mp
89–90 8C, 676 mg (78%) yield.
4.1.15. 4-[p-(p-{Trimethylsilylethynyl}phenylethynyl)-
phenyl]-2-methyl-3-butyn-2-ol (15). Following the
general method used for the synthesis of 7, a mixture of
Cl2Pd(PPh3)2 (35 mg, 0.05 mmol), Cu2I2 (1.2 mg,
0.005 mmol), compound 11 (143 mg, 0.5 mmol), compound
13 (100 mg, 0.5 mmol), and NEt3 (100 mL) was stirred at