Macromolecules
Article
NMR (282.4 MHz, CDCl ): δ (ppm) = −132.71, −130.59, −130.53,
catalyst (20.0 mg, 0.0235 mmol) in 2.5 mL of 1,2,4-trichlorobenzene
was then added, and the reaction mixture was kept under dynamic
vacuum while the condenser was cooled to 5 °C using a circulating
chiller. The reaction mixture was gradually heated to 90 °C over 4 h
and refluxed for 24 h. The reaction mixture was cooled down to room
temperature, 20.0 mg of Grubbs second-generation catalyst in 2.5 mL
of 1,2,4-trichlorobenzene was added, and the reaction mixture was
refluxed at 90 °C under dynamic vacuum for another 24 h. Such
process was repeated for a total of five times, and the mixture was
poured into methanol (200 mL) to precipitate the polymer, which was
purified by Soxhlet extraction with methanol, acetone, hexanes, and
3
−128.49.
3
-Chloro-4-decyl-2,5-dipropenylthiophene (TV-Cl). TV-Br (1.00 g,
2
.60 mmol), CuCl (7.37 g, 74.4 mmol), and DMF (5 mL) were
charged into a pressure vessel in an argon-filled glovebox. The mixture
was stirred at 110 °C for 72 h. The reaction mixture was poured into
water (50 mL) and extracted with diethyl ether (2 × 50 mL); the
combined organic phase was then dried over anhydrous Na SO . After
2
4
solvent removal under reduced pressure, the residue was further
purified by column chromatography over silica gel to give the title
1
compound as a clear liquid (400 mg, 45% yield). H NMR (300 MHz,
CDCl ): δ (ppm) = 0.86−0.90 (t, 3H), 1.26 (m, 14H), 1.48 (m, 2H),
chloroform to give the title compound as a black solid (637 mg, 83%
3
1
1
.85−2.01 (d, 6H), 2.51−2.63 (t, 2H), 5.68−6.16 (m, 2H), 6.43−6.69
yield). H NMR (300 MHz, CDCl ): δ (ppm) = 0.86 (t, 3H), 1.26 (m,
3
13
(
d, 2H).
-Decyl-4-iodo-2,5-dipropenylthiophene (TV-I). To a stirring
14H), 1.55 (m, 2H), 2.68 (t, 2H), 6.91 (m, 2H). C NMR (75.48
3
MHz, CDCl ): δ (ppm) = 14.13, 22.72, 29.43, 29.69, 31.94, 116.03,
3
solution of TV-Br (300 mg, 0.78 mmol) in THF (5 mL) was added
n-butyllithium (0.38 mL, 0.94 mmol) slowly at −78 °C. After 15 min,
ICH CH I (308 mg, 1.1 mmol) was added. The reaction mixture was
120.02, 134.62, 141.29. SEC (CHCl , 1 mL/min): M = 14.0 kDa, M
= 30.9 kDa, Đ = 2.2.
3
n
w
PTV-I. In a two-neck round-bottom flask equipped with a condenser
and rubber septum were added TV-I (300 mg, 0.7 mmol) and CuI
(13.3 mg, 0.07 mmol). Grubbs second-generation catalyst (5.9 mg,
0.007 mmol) in 1 mL of 1,2,4-trichlorobenzene was then added, and
the reaction mixture was kept under dynamic vacuum while the
condenser was cooled to 5 °C using a circulating chiller. The reaction
mixture was gradually heated to 90 °C over 4 h and refluxed for 24 h.
The reaction mixture was cooled down to room temperature, 5.9 mg
of Grubbs second-generation catalyst in 1 mL of 1,2,4-trichlor-
obenzene was added, and the reaction mixture was refluxed at 90 °C
under dynamic vacuum for another 24 h. Such process was repeated
for a total of five times, and the mixture was poured into methanol
(100 mL) to precipitate the polymer, which was purified by Soxhlet
extraction with methanol, acetone, hexanes, and chloroform to give the
2
2
kept at −78 °C for 45 min and then was quenched with Na S O
2
2
3
solution. The mixture was extracted with diethyl ether (2 × 20 mL);
the combined organic phase was dried over anhydrous Na SO , and
2
4
the solvent was removed under reduced pressure to give the title
1
compound as yellow liquid (300 mg, 89.1%). H NMR (300 MHz,
CDCl ): δ (ppm) = 0.86−0.90 (t, 3H), 1.26 (m, 14H), 1.43 (m, 2H),
3
=
1.84−2.02 (d, 6H), 2.56−2.69 (t, 2H), 5.66−6.21 (m, 2H), 6.46−
6
.54 (d, 2H).
PTV-F. In a two-neck round-bottom flask equipped with a
condenser and rubber septum were added TV-F (200 mg, 0.62
mmol) and CuI (11.8 mg, 0.062 mmol). Grubbs second-generation
catalyst (5.26 mg, 0.0062 mmol) in 0.8 mL of 1,2,4-trichlorobenzene
was then added, and the reaction mixture was kept under dynamic
vacuum while the condenser was cooled to 5 °C using a circulating
chiller. The reaction mixture was gradually heated to 90 °C over 4 h
and refluxed for 24 h. The reaction mixture was cooled down to room
temperature, 5.26 mg of Grubbs second-generation catalyst in 0.8 mL
of 1,2,4-trichlorobenzene was added, and the reaction mixture was
refluxed at 90 °C under dynamic vacuum for another 24 h. Such a
process was repeated for a total of five times, and the mixture was
poured into methanol (100 mL) to precipitate the polymer, which was
purified by Soxhlet extraction with methanol, acetone, hexanes, and
1
title compound as a dark black solid (47 mg, 18% yield). H NMR
(300 MHz, CDCl
2H), 2.71 (t, 2H), 6.92 (m, 2H). C NMR (75.48 MHz, CDCl
(ppm) = 14.13, 22.72, 29.44, 29.69, 31.95. SEC (CHCl , 1 mL/min):
= 4.8 kDa, M = 7.5 kDa, Đ = 1.6.
PTV-Th. PTV-Br (20 mg, 0.061 mmol) and tri-n-butyl(2-thienyl)tin
(27.4 mg, 0.073 mmol) were charged into a pressure vessel. Pd(PPh )
3 4
): δ (ppm) = 0.86 (t, 3H), 1.27 (m, 14H), 1.54 (m,
3
13
): δ
3
3
M
n
w
(7.1 mg, 0.0061 mmol), DMF (0.5 mL), and toluene (0.5 mL) were
added into the vessel in an argon-filled glovebox. The mixture was
stirred at 110 °C for 24 h. PTV-Th was isolated by precipitation into
chloroform to give the title compound as a black solid (70 mg, 42.4%
1
yield). H NMR (300 MHz, CDCl ): δ (ppm) = 0.87 (t, 3H), 1.27 (m,
1
methanol and drying under high vacuum as a black solid (8 mg,
3
13
1
4H), 1.56 (m, 2H), 2.57 (t, 2H), 6.85 (m, 2H). C NMR (75.48
39.6%). H NMR (300 MHz, CDCl
3
): δ (ppm) = 0.86 (t, 3H), 1.22
MHz, CDCl ): δ (ppm) = 14.11, 22.70, 25.12, 29.37, 29.65, 29.95,
(m, 16H), 2.57 (t, 2H), 6.98 (d, 2H), 7.15−7.43 (m, 3H). SEC
3
19
3
1.92, 115.39, 118.80, 130.33, 133.01, 152.50, 156.08. F NMR (282.4
(CHCl , 1 mL/min): M = 13.9 kDa, M = 25.7 kDa, Đ = 1.9.
3
n
w
MHz, CDCl ): δ (ppm) = −126.79. SEC (CHCl , 1 mL/min): M =
2-(5-Bromothiophen-2-yl)-1,3-dioxolane. 5-Bromo-2-thiophene-
carboxaldehyde (5.00 g, 43.8 mmol), ethylene glycol (17.3 mL,
109.6 mmol), and a catalytic amount of p-toluenesulfonic acid (25 mg,
0.13 mmol) were dissolved in 35 mL of toluene in a 100 mL round-
bottom flask equipped with a Dean−Stark apparatus. The reaction
mixture was refluxed at 140 °C for 20 h. The reaction mixture was
extracted by ethyl ether and followed by washing with saturated
3
3
n
1
7.8 kDa, M = 35.8 kDa, Đ = 2.0.
w
PTV-Cl. In a two-neck round-bottom flask equipped with a
condenser and rubber septum were added TV-Cl (200.0 mg, 0.59
mmol) and CuCl (5.9 mg, 0.059 mmol). Grubbs second-generation
catalyst (5.0 mg, 0.0059 mmol) in 1 mL of 1,2,4-trichlorobenzene was
then added, and the reaction mixture was kept under dynamic vacuum
while the condenser was cooled to 5 °C using a circulating chiller. The
reaction mixture was gradually heated to 90 °C over 4 h and refluxed
for 24 h. The reaction mixture was cooled down to room temperature,
Na
CO , DI H
O, and saturated brine solution. The combined organic
SO . After solvent removal under
2
3 2
phase was dried with anhydrous Na
2
4
reduced pressure, the residue was further purified by distillation to give
1
5
.0 mg of Grubbs second-generation catalyst in 1 mL of 1,2,4-
trichlorobenzene was added, and the reaction mixture was refluxed at
0 °C under dynamic vacuum for another 24 h. Such process was
the title compound as a yellow liquid (5.0 g, 81.3% yield). H NMR
(300 MHz, CDCl
6.90−6.95 (d, 2H).
): δ (ppm) = 3.97−4.13 (t, 4H), 6.02 (s, 1H),
3
9
repeated for a total of five times, and the mixture was poured into
methanol (200 mL) to precipitate the polymer, which was purified by
Soxhlet extraction with methanol, acetone, hexanes, and chloroform to
(5-(1,3-Dioxolan-2-yl)thiophen-2-yl)trimethylstannane (2). To a
stirring solution of 2-(5-bromothiophen-2-yl)-1,3-dioxolane (2 g,
8.507 mmol) in dry THF (5 mL) at −78 °C was added 5.1 mL of
1
n
give the title compound as a black solid (120 mg, 71.9% yield). H
BuLi (2.5 M in THF, 12.8 mmol) solution dropwise through a
NMR (300 MHz, CDCl ): δ (ppm) = 0.86 (t, 3H), 1.27 (m, 14H),
degassed syringe. After 15 min, Me SnCl solution (2.2 M in THF, 5
3
3
13
1
.54 (m, 2H), 2.59 (t, 2H), 6.87 (m, 2H). C NMR (75.48 MHz,
mL, 11.01 mmol) was added. The reaction mixture was warmed up
and kept under room temperature for 4 h. The resulting reaction
mixture was extracted with diethyl ether (2 × 40 mL), followed by
washing with saturated brine solution. The combined organic phase
was dried over anhydrous Na SO . After solvent removal under
CDCl ): δ (ppm) = 14.12, 22.72, 29.42, 29.70, 31.94, 118.77, 119.40,
3
1
26.37, 133.42, 139.16. SEC (CHCl , 1 mL/min): M = 12.2 kDa, M
3 n w
=
20.1 kDa, Đ = 1.7.
PTV-Br. In a two-neck round-bottom flask equipped with a
2
4
condenser and rubber septum were added TV-Br (900 mg, 2.347
mmol) and CuI (35.7 mg, 0.187 mmol). Grubbs second-generation
reduced pressure, the crude compound was further dried under high
vacuum and used for next step without further purification (2.57 g,
H
Macromolecules XXXX, XXX, XXX−XXX