Synthesis and X-Ray Structure of OPE
J. Chin. Chem. Soc., Vol. 51, No. 6, 2004 1415
82.37, 113.16, 117.60, 153.89 ppm; IR (CHCl3) n 2106,
1269, 1015 cm-1. MS (m/z) 326.3 (M+); HRMS calc. for
C22H30O2 326.2246, found 326.2254.
4H), 7.67 (d, J = 8 Hz, 4H) ppm; 13C NMR (75 MHz, CDCl3)
d 14.05, 22.63, 25.72, 29.25, 31.57, 69.56, 87.35, 94.00,
94.16, 113.80, 116.74, 122.92, 133.01, 137.49, 153.61 ppm;
IR (CHCl3) n 2199, 1274, 1212, 1051 cm-1; MS (m/z) 730
(M+); HRMS calc. for C34H36O2I2 730.0805, found 730.0811.
1,4-Bis-(4-bromo-phenylethynyl)-2,5-bis-hexyloxybenzene
(IV)
To a dried round-bottomed flask were added compound
(III) (5.0 g, 15.31 mmol), 1-bromo-4-iodo-benzene (8.67 g,
30.64 mmol), bis(triphenylphosphine)palladium dichloride
(0.43 g, 0.61 mmol), copper iodide (0.23 g, 1.21 mmol), and
triphenylphosphine (0.63 g, 2.40 mmol). The system was
evacuated and flushed with nitrogen (3 ´); the dry piperidine
(60 mL) was degassed with nitrogen and then added into the
reaction mixture. The mixture was stirred at rt for 8 h. The
solvent was evaporated, and chloroform was added. The or-
ganic phase was washed with a saturated solution of NH4Cl
(3 ´ 50 mL), a solution of NaCl (3 ´ 50 mL), and dried over
anhydrous MgSO4. The solvent was removed in a vacuum,
and the residue was purified by column chromatography (sil-
ica gel, hexane/chloroform, 10:0.5) to give compound (IV) as
a faint yellow solid (7.89 g, 81% yield). M.p. 112-113 °C. 1H
NMR (300 MHz, CDCl3) d 0.89 (t, J = 7 Hz, 6H), 1.33-1.37
(m, 8H), 1.51-1.56 (m, 4H), 1.79-1.86 (m, 4H), 4.02 (t, J = 7
Hz, 4H), 6.70 (s, 2H), 7.39 (d, J = 8 Hz, 4H), 7.49 (d, J = 8
Hz, 4H) ppm; 13C NMR (75 MHz, CDCl3) d 14.02, 22.62,
25.70, 29.24, 31.56, 69.54, 87.05, 93.82, 113.78, 116.72,
122.35, 122.49, 131.57, 132.92, 153.60 ppm; IR (CHCl3) n
2209, 1274, 1186, 1067 cm-1; MS (m/z) 634 (M+); HRMS
calc. for C34H36O2Br2 634.1082, found 634.1096.
1,4-Bis-hexyloxy-2,5-bis(4-trimethylsilanylethynylphenyl-
ethynyl)benzene (VI)
To a dried round-bottomed flask were added compound
(V) (5.0 g, 6.85 mmol), bis(triphenylphosphine)palladium
dichloride (0.11 g, 0.16 mmol), copper iodide (0.06 g, 0.32
mmol), and triphenylphosphine (0.16 g, 0.61 mmol). The sys-
tem was evacuated and flushed with nitrogen (3 ´); the dry
piperidine (30 mL) was degassed with nitrogen and then
added into the reaction mixture. Under stirring, trimethylsi-
lylacetylene (1.37 g, 14 mmol) was added to the solution. The
mixture was stirred at rt for 3 h. The solvent was evaporated,
and chloroform was added. The organic phase was washed
with a saturated solution of NH4Cl (3 ´ 50 mL), a solution of
NaCl (3 ´ 50 mL), and dried over anhydrous MgSO4. The sol-
vent was removed in a vacuum, and the residue was separated
by column chromatography (silica gel, hexane/chloroform,
10:0.5~1) to give 4.4 g of compound (VI) in 96% yield. Com-
1
pound (VI): yellow solid. M.p. 156-157 °C. H NMR (300
MHz, CDCl3) d 0.26 (s, 18H), 0.90 (t, J = 7 Hz, 6H), 1.34-
1.38 (m, 8H), 1.52-1.54 (m, 4H), 1.82-1.87 (m, 4H), 4.02 (t, J
= 7 Hz, 4H), 7.00 (s, 2H), 7.45 (s, 8H) ppm; 13C NMR (75
MHz, CDCl3) d -0.10, 14.03, 22.63, 25.73, 29.26, 31.58,
59.57, 87.91, 94.60, 96.29, 104.66, 113.87, 116.77, 122.85,
123.47, 131.31, 131.85, 153.63 ppm; IR (CHCl3) n 2147,
1409, 1378, 1020 cm-1; MS (m/z) 670.4 (M+); HRMS calc. for
C44H54O2Si2 670.3662, found 670.3652.
1,4-Bis-hexyloxy-2,5-bis(4-iodo-phenylethynyl)-benzene
(V)
To a dried two-neck round-bottomed flask was added
compound (IV) (10 g, 15.72 mmol); the system was evacu-
ated and flushed with nitrogen. Dry ether (200 mL) was
added, and a solution of n-Buli (2.5 M, 12.6 mL) in ether (100
mL) was then added droplwise at 0 °C. After stirring at 0 °C
for 3 h, the solution of 1,2-diiodoethane (8.90 g, 31.56 mmol)
in 20 mL of ether was added, the reaction mixture was stirred
at rt for 12 h. The solution was then washed with a saturated
solution of Na2S2O3 (2 ´ 50 mL), a solution of NaCl (3 ´ 50
mL), and dried over anhydrous MgSO4. The solvent was re-
moved under vacuum; the crude product was purified by col-
umn chromatagrophy (silica gel, hexane/CHCl3 = 5:0.5) to
give compound (V) as a light yellow solid (6.5 g, 57% yield).
M.p. 110-111 °C. 1H NMR (300 MHz, CDCl3) d 0.88 (t, J = 7
Hz, 6H), 1.29-1.36 (m, 8H), 1.47-1.54 (m, 4H), 1.78-1.97 (m,
4H), 4.01 (t, J = 7 Hz, 4H), 6.98 (s, 2H), 7.24 (d, J = 8 Hz,
1,4-Bis-(4-ethynyl-phenylethynyl)-2,5-bis-hexyloxy-ben-
zene (VII)
Compound (VI) (2.0 g, 2.98 mmol) was dissolved in
CHCl3 (50 mL), CH3OH (10 mL), and a solution of NaOH
(0.96 g, 24.0 mol) in 10 mL of water was added. The mixture
was stirred at rt for 12 h, and then washed with a saturated so-
lution of NaCl (3 ´ 50 mL), and dried over anhydrous MgSO4.
The solvent was removed in a vacuum, and the residue was
recrystallized from CHCl3/hexane to provide pure compound
(VII) as a yellow solid (1.50 g, 96% yield). M.p. 112-114 °C.
1H NMR (300 MHz, CDCl3) d 0.90 (t, J = 7 Hz, 6H), 1.31-
1.36 (m, 8H), 1.50-1.58 (m, 4H), 1.80-1.87 (m, 4H), 3.18 (s,
2H), 4.03 (t, J = 7 Hz, 4H), 7.01 (s, 2H), 7.47 (s, 8H) ppm; 13
C
NMR (75 MHz, CDCl3) d 14.01, 22.62, 25.72, 29.25, 31.57,
69.55, 78.93, 83.28, 87.97, 94.39, 113.84, 116.76, 121.83,
Xue, Cuihua
