Macromolecules, Vol. 37, No. 7, 2004
Polythiophene Derivatives 2355
-OCO-), 7.51 (d, 2ArH, J ) 8.5 Hz, meta to -OCH2CH2-),
7.58 (d, 2ArH, J ) 8.4 Hz, meta to -OCO-), 8.16 (d, 2ArH, J
) 8.7 Hz, meta to -COO-).
-PhOCH2CHF-), 4.58 (dd, 1H, J ) 4.4 Hz, cylic, -OCH-
OCH2-), 4.70-4.84 (dm, 1H, -OCH2CHF-), 6.87-6.89 (dd,
4ArH, J ) 8.7, 8.8 Hz, ortho to -OCH2CHF-, ortho to -OCH2-
CH2-), 7.38-7.40 (dd, 4ArH, J , 8.7 Hz, meta to -OCH2CHF-,
meta to -OCH2CH2-).
4-(4′-(10-Hyd r oxyd eca n yloxy))bip h en yl-4-(2-flu or ooc-
ta n yloxy)ben zoa te (7). PPTS (80 mg) was added to a solution
of compound 3 (4.00 g, 5.9 mmol) in 120 mL of ethanol and
refluxed at 80 °C for 2 h under an argon atmosphere. TLC
indicated completion of the reaction. After evaporation of the
solvent, the residue was thoroughly washed with water and
extracted with ether. The ether layer was dried over anhydrous
MgSO4 overnight. The solution was evaporated and purified
by column chromatography (silica gel, CH2Cl2/acetone ) 40/
1) and recrystallized from ethanol to give 3.48 g (yield ) 99.4%)
of 7 as white solid.1 IR (cm-1): 3323, 2927, 2853, 1727, 1607,
1498, 1258, 1221, 1086, 802. H NMR (CDCl3, δ from TMS,
ppm): 0.90 (t, 3H, J ) 6.9 Hz, -CH3), 1.19-1.88 (m, 26H,
-OCH2CHF(CH2)5CH3; -OCH2(CH2)8CH2 OH), 3.64 (t, 2H, J
) 6.6 Hz, -CH2CH2OH), 4.00 (t, 2H, J ) 6.5 Hz, -PhOCH2-
CH2-), 4.11-4.22 (m, 2H, -PhOCH2CHF-), 4.80-4.94 (dm,
1H, -OCH2CHF-), 6.97 (d, 2ArH, J ) 8.7 Hz, ortho to -OCH2-
CH2-), 7.01 (d, 2ArH, J ) 8.9 Hz, ortho to -OCH2CHF-), 7.25
(d, 2ArH, J ) 8.7 Hz, ortho to -OCO-), 7.51 (d, 2ArH, J )
8.7 Hz, meta to -OCH2CH2-), 7.58 (d, 2ArH, J ) 8.5 Hz, meta
to -OCO-), 8.18 (d, 2ArH, J ) 8.8 Hz, meta to -COO-).
2,5-Dibr om oth ioph en e-3-car boxylic Acid (8). Thiophene-
3-carboxylic acid (5 g, 39 mmol) was very slowly added to a
solution of N-bromosuccinimide, NBS (15.1 g, 86 mmol), in 80
mL of DMF by a pressure-equalized dropping funnel. After
the addition was complete, 10 mL of DMF was added to the
reaction mixture, refluxed for 20 h at 50 °C under an argon
atmosphere. The reaction vessel was wrapped with aluminum
foil to shield the reaction from light. TLC indicated completion
of the reaction. Then the reaction mixture was allowed to warm
to room temperature. The solution was poured into large
amount of saturated sodium sulfate cooled by ice water. The
yellow precipitate was filtered off and recrystallized from an
ethanol:water mixture to yield 7.98 g of 8 as white needlelike
crystal. Yield ) 71.2%. IR (cm-1): 3095, 2989, 2924, 2871,
2623, 2561, 2481, 1677, 1526, 1443, 1253, 1003, 905. 1H NMR
(CDCl3, δ from TMS, ppm): 7.43 (s, 1ArH, BrCCHC-), 13.34
(sb, 1H, -COOH).
2,5-Dibr om oth iop h en e-3-a cetic Acid (9). Thiophene-3-
acetic acid (10 g, 70.3 mmol) was very slowly added to a
solution of N-bromosuccinimide, NBS (30.2 g, 172 mmol), in
50 mL of DMF by a dropping funnel. After the addition, 10
mL of DMF was further added to the reaction mixture and
refluxed at 50 °C for 20 h under an argon atmosphere. The
reaction vessel was wrapped by aluminum foil to shield the
reaction from light. TLC indicated completion of the reaction.
Then the reaction mixture was allowed to warm to room
temperature. The solution was poured into a large amount of
saturated sodium sulfate cooled by ice water. The yellow
precipitate was filtered off and recrystallized from an ethanol:
water mixture to yield 13.2 g of 9 as white needlelike crystal.
Yield ) 63.0%. IR (cm-1): 3101, 2918, 1702, 1417, 1235, 1016,
829, 634, 474. 1H NMR (CDCl3, δ from TMS, ppm): 3.63 (s,
2H, CH2), 6.95 (s, 1ArH, BrCCHC).
4-(2-F lu or oocta n yloxy)-(4′-(10-h yd r oxyd eca n yloxy))bi-
p h en yl (11). A mixture of compound 10 (0.60 g, 1.2 mmol)
and PPTS (15 mg) in ethanol was refluxed for 2 h at 80 °C
under an argon atmosphere. TLC indicated completion of the
reaction. Then the solvent was removed by evaporation. The
crude product was washed with water thoroughly and ex-
tracted with ether. The organic layer was filtered and dried
over anhydrous MgSO4 overnight. The solvent was evaporated,
and purification by column chromatography (silica gel, CH2-
Cl2/acetone ) 40/1) followed by recrystallization from ethanol
afforded 0.51 g of 10 in 99.8% yield. IR (cm-1): 3301, 2920,
1
2851, 1609, 1503, 1276, 1253, 1178, 1049, 824, 808. H NMR
(CDCl3, δ from TMS, ppm): 0.83 (t, 3H, J ) 6.8, -CH3), 1.16-
1.80 (m, 26H, -OCH2(CH2)8CH2O-; -CH2CHF(CH2)5CH3),
3.29-3.45 (dm, 2H, -OCH2CH2-), 3.56 (q, 2H, J ) 6.5 Hz,
-CH2OH), 3.91 (t, 2H, J ) 6.6 Hz, -PhOCH2CH2-), 3.97-
4.08 (m, 2H, -PhOCH2CHF-), 4.70-4.84 (dm, 1H, -OCH2-
CHF-), 6.87-6.90 (dd, 4ArH, J ) 8.7 Hz, ortho to -OCH2-
CHF-, ortho to-OCH2CH2-), 7.38-7.40 (dd, 4ArH, J ) 8.6
Hz, meta to -OCH2CHF-, meta to -OCH2CH2-).
10-(4-(4′-(4′′-(2-F lu or ooct yloxy)p h en ylca r b on yloxy))-
bip h en oxy)d ecyl 2,5-Dibr om oth iop h en e-3-ca r boxyla te
(M1). Compound 4 (593 mg, 1.0 mmol) was added to a mixture
of 2,5-dibromothiophene-3-carboxylic acid (5) (343 mg, 1.2
mmol), (dimethylamino)pyridine, DMAP 147 mg (1.2 mmol),
and dicyclohexylcarbodiimide, DCC (246 mg, 1.2 mmol), in 15
mL of absolute CH2Cl2 and further stirred for 24 h at room
temperature under an argon atmosphere. TLC indicated
completion of the reaction. Then the solution was filtered to
remove the urea crystals, and the solvent was removed by
evaporation. The crude product was purified by column chro-
matography (n-hexane/ethyl acetate ) 2/1) and recrystallized
from n-hexane/ethanol solution () 2/1) to afford 904 mg of M1
as colorless crystal. Yield > 99.9 %. IR (cm-1): 2925, 2852,
1716, 1605, 1498, 1215, 1171, 1086, 800, 763. 1H NMR (CDCl3,
δ from TMS, ppm): 0.91 (t, 3H, J ) 6.9, -CH3), 1.21-1.89
(m, 26H, -OCH2CHF(CH2)5CH3; -OCH2(CH2)8CH2O-), 4.00
(t, 2H, J ) 6.6 Hz, -PhOCH2CH2-), 4.09-4.22 (m, 2H,
-PhOCH2CHF-), 4.27 (t, 2H, J ) 6.7 Hz, -COOCH2CH2-),
4.80-4.94 (dm, 1H, -OCH2CHF-), 6.97 (d, 2ArH, J ) 8.7 Hz,
ortho to -OCH2CH2-), 7.01 (d, 2ArH, J ) 8.9 Hz, ortho to
-OCH2CHF-), 7.24 (d, 2ArH, J ) 8.7 Hz, ortho to -OCO-),
7.35 (s, 1ArH, -SBrCCHC-), 7.51 (d, 2ArH, J ) 8.7 Hz, meta
to -OCH2CH2-), 7.58 (d, 2ArH, J ) 8.6 Hz, meta to
-OCO-), 8.18 (d, 2ArH, J ) 8.9 Hz, meta to -COO-).
10-(4-(4′-(4′′-(2-F lu or ooct yloxy)p h en ylca r b on yloxy))-
biph en oxy)decyl (2,5-Br om o-3-th ien yl)acetate (M2). Com-
pound 7 (1.36 g, 2.3 mmol) was added to a mixture of 9 (1.02
g, 3.4 mmol), DMAP (145 mg, 3.4 mmol), and DCC (702 mg,
3.4 mmol) in 50 mL of absolute CH2Cl2, and the solution was
stirred for 24 h at room temperature under an argon atmo-
sphere, TLC indicated completion of the reaction. Then the
solution was filtered to remove the urea crystals, and the
solvent was removed under reduced pressure. The crude pro-
duct was purified by column chromatography (n-hexane/ethyl
acetate ) 2/1) and recrystallized from a n-hexane:ethanol
mixture ()9/1) to give 1.70 g of M2 as colorless crystal in 85.0%
yield. IR (cm-1): 2924, 2854, 1731, 1608, 1497, 1254, 1207,
1168, 1078, 801, 763. 1H NMR (CDCl3, δ from TMS, ppm): 0.91
(t, 3H, J ) 6.9 Hz, -CH3), 1.20-1.82 (m, 26H, -OCH2CH-
F(CH2)5CH3; -OCH2(CH2)8CH2O-), 3.56 (s, 2H, -CCH2C-
OO-), 4.00 (t, 2H, J ) 6.5 Hz, -PhOCH2CH2-), 4.11-4.22
(m, 2H, -COOCH2CH2-; -PhOCH2CHF-), 4.80-4.94 (dm,
1H, -OCH2CHF-), 6.94 (s, 1ArH, -SBrCCHC-), 6.97 (d,
2ArH. J ) 8.8 Hz, ortho to -OCH2CH2-), 7.01 (d, 2ArH, J )
8.9 Hz, ortho to -OCH2CHF-), 7.24 (d, 2ArH, J ) 8.6 Hz,
ortho to -OCO-), 7.51 (d, 2ArH, J ) 8.7 Hz, meta to -OCH2-
CH2-), 7.58 (d, 2ArH, J ) 8.6 Hz, meta to -OCO-), 8.18 (d,
2ArH, J ) 8.9 Hz, meta to -COO-).
4-(10-(2-Tetr a h yd r op yr a n yloxy))-4′-(2-flu or ooctyloxy)-
bip h en yl (10). A solution of 1 (467 mg, 3.1 mmol) and DEAD
(1.60 g, 3.6 mmol, 40 wt % in toluene) in 7 mL of THF was
added dropwise to a stirred mixture of 5 (1.28 g, 3.0 mmol)
and TPP (944 mg, 3.6 mmol) in THF (5 mL). The resulting
reaction mixture was stirred for a further 24 h under an argon
atmosphere; TLC indicated completion of the reaction. The
colored reaction mixture was then evaporated to remove
solvent. The solid was washed with water thoroughly and
extracted with ether. Then the organic layer was evaporated
to remove solvent. Purification by column chromatography
(silica gel, n-hexane/ethyl acetate ) 2/1) afforded 0.732 g of
10 in 44.0% yield. IR (cm-1): 2932, 2854, 1608, 1503, 1275,
1252, 1037, 823, 807. 1H NMR (CDCl3, δ from TMS, ppm): 0.93
(t, 3H, J ) 6.9, -CH3), 1.18-1.77 (m, 32H, cylic, -OCH2(CH2)3;
-OCH2(CH2)8CH2O-; -OCH2CHF(CH2)5CH3), 3.29-3.45 (dm,
2H, -OCH2CH2-), 3.64-3.82 (dm, 2H, cylic, -OCH2(CH2)3),
3.91 (t, 2H, J ) 6.6 Hz, -PhOCH2CH2-), 3.97-4.08 (m, 2H,