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Organic & Biomolecular Chemistry
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ARTICLE
Journal Name
(100 MHz, CDCl3) δ 144.6, 142.9, 138.3, 131.4, 130.9, 129.1, 128.1,
127.5, 121.0, 120.5, 94.2, 84.5, 28.7, 21.5, 15.4; HRMS (ESI) Calcd for
[C38H32S] requires [M+H]+ 521.2303, found 521.2301.
6.98−6.94 (m, 4H), 3.85 (s, 6H), 2.60 (t, J = 7.D6OHI:z1,04.H10)3, 91/.C671O−B10.52560(m1C,
4H), 1.39−1.30 (m, 4H), 0.92 (t, J = 6.9 Hz, 6H); 13C NMR (100 MHz,
CDCl3) δ 159.6, 143.3, 142.3, 131.4, 128.9, 128.5, 126.2, 120.7, 120.4,
114.0, 94.0, 84.5, 55.3, 35.6, 33.4, 22.3, 13.9; HRMS (ESI) Calcd for
[C42H40O2S] requires [M+H]+ 609.2827, found 609.2828.
2,5-Bis(4-ethylphenyl)-3,4-bis((4-ethylphenyl) ethynyl)thiophene
(4i). The compound is obtained as yellow needles (197.2 mg, 72%);
mp 152−154 °C; 1H NMR (400 MHz, CDCl3) δ 7.91 (d, J = 7.6 Hz, 4H),
7.46 (d, J = 8.4 Hz, 4H), 7.28 (d, J = 8.4 Hz, 4H), 7.17 (d, J = 7.6 Hz, 4H),
2.73−2.64 (m, 8H), 1.30−1.23 (m, 12H); 13C NMR (100 MHz, CDCl3) δ
144.6, 142.9, 131.5, 130.9, 128.2, 127.9, 127.6, 121.0, 120.7, 94.3,
84.5, 28.9, 28.7, 15.4, 15.37; HRMS (ESI) Calcd for [C40H36S] requires
[M+H]+ 549.2616, found 549.2617.
2,5-Bis(4-methoxyphenyl)-3,4-bis((4-
methoxyphenyl)ethynyl)thiophene (4o) The compound is obtained
1
as yellow needles (216.2 mg, 78%); mp 173-175 °C; H NMR (400
MHz, CDCl3) δ 7.91−7.89 (m, 4H), 7.46−7.44 (m, 4H), 6.97−6.95 (m,
4H), 6.86−6.84 (m, 4H), 3.85 (s, 6H), 3.81(s, 6H); 13C NMR (100 MHz,
CDCl3) δ 159.6, 159.5, 141.9, 132.9, 128.8, 126.2, 120.4, 115.7, 114.0,
93.7, 83.9, 55.31, 55.28; HRMS (ESI) Calcd for [C36H28O4S] [M+H]+
557.1787, found 557.1788.
3,4-Bis((4-butylphenyl)ethynyl)-2,5-bis(4-ethylphenyl)thiophene
(4j). The compound is obtained as brown needles (211.4 mg, 70%);
mp 133−135 °C; 1H NMR (400 MHz, CDCl3) δ 7.92−7.90 (m, 4H),
7.46−7.44 (m, 4H), 7.27 (d, J = 8.2 Hz, 4H), 7.14 (d, J = 8.2 Hz, 4H),
3,4-Bis((4-ethylphenyl)ethynyl)-2,5-bis(4-fluorophenyl)thiophene
2.69 (q, J = 7.3 Hz, 4H), 2.61 (t, J = 7.8 Hz, 4H), 1.64−1.56 (m, 4H), (4p). The compound is obtained as yellow needles (195.1 mg, 74%);
1.40−1.33 (m, 4H), 1.30−1.26 (m, 6H); 13C NMR (100 MHz, CDCl3) δ mp 137−139 °C; 1H NMR (400 MHz, CDCl3) δ 7.95−7.91 (m, 4H), 7.43
144.6, 143.3, 142.9, 131.4, 130.9, 128.5, 128.1, 127.5, 121.1, 120.7,
94.3, 84.5, 35.6, 33.4, 28.7, 22.3, 15.4, 13.9; HRMS (ESI) Calcd for
[C44H44S] requires [M+H]+ 605.3242, found 605.3241.
(d, J = 8.4 Hz, 4H), 7.19−7.12 (m, 8H), 2.67 (q, J = 7.6 Hz, 4H), 1.25 (t,
J = 7.6 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 162.7 (d, J = 249.2 Hz,
1C), 145.0, 141.7, 131.5, 129.4 (d, J = 7.6 Hz, 1C), 128.0, 121.6, 120.3,
115.7 (d, J = 22.0 Hz, 1C), 94.5, 83.8, 28.9, 15.4; HRMS (ESI) Calcd for
[C36H26F2S] requires [M+H]+ 529.1802, found 529.1800.
2,5-Bis(4-ethylphenyl)-3,4-bis((4-methoxyphenyl)ethynyl)
thiophene (4k) The compound is obtained as yellow needles (207.1
1
mg, 75%); mp 170−172 °C; H NMR (400 MHz, CDCl3) δ 7.90 (d, J = 3,4-Bis((4-butylphenyl)ethynyl)-2,5-bis(4-fluorophenyl)thiophene
(4q). The compound is obtained as yellow needles (210.2 mg, 72%);
4H), 3.81 (s, 6H), 2.69 (q, J = 8.0, 4H), 1.27 (t, J = 8.0 Hz, 6H); 13C NMR mp 151−153 °C; 1H NMR (400 MHz, CDCl3) δ 7.94−7.91 (m, 4H), 7.42
8.0 Hz, 4H), 7.47−7.45 (m, 4H), 7.27 (d, J = 8.0 Hz, 4H), 6.89−6.85 (m,
(100 MHz, CDCl3) δ 159.6, 144.6, 142.5, 133.0, 130.9, 128.1, 127.5,
121.1, 115.7, 114.0, 94.0, 83.9, 55.3, 28.7, 15.4; HRMS (ESI) Calcd for
[C38H32O2S] requires [M+H]+ 553.2201, found 553.2202.
(d, J = 7.6 Hz, 4H), 7.16−7.11 (m, 8H), 2.62 (t, J = 7.6 Hz, 4H),
1.64−1.56 (m, 4H), 1.38−1.31 (m, 4H), 0.97−0.91 (m, 6H); 13C NMR
(100 MHz, CDCl3) δ 162.7 (d, J = 249.2 Hz, 1C), 143.7, 141.7, 131.4,
129.5 (d, J = 7.7 Hz, 1C), 128.5, 121.6, 120.3, 115.7 (d, J = 22.0 Hz, 1C),
94.5, 83.9, 35.6, 33.4, 22.3, 13.9; HRMS (ESI) Calcd for [C40H34F2S]
requires [M+H]+ 585.2428, found 585.2429.
3,3'-((2,5-Bis(4-ethylphenyl)thiophene-3,4-diyl)bis(ethyne-2,1-
diyl))dithiophene (4l). The compound is obtained as brown needles
(191.5 mg, 76%); mp 136−138 °C; 1H NMR (400 MHz, CDCl3) δ
7.89−7.87 (m, 4H), 7.49−7.48 (m, 2H), 7.30−7.27 (m, 6H), 7.19−7.17 2,5-Bis(4-fluorophenyl)-3,4-bis((4-
(m, 2H), 2.70 (q, J = 7.8 Hz, 4H), 1.28 (t, J = 7.3 Hz, 6H); 13C NMR (100 methoxyphenyl)ethynyl)thiophene (4r). The compound is obtained
1
MHz, CDCl3) δ 144.8, 143.1, 130.7, 130.0, 128.5, 128.2, 127.5, 125.4,
122.5, 120.7, 89.2, 84.5, 28.7, 15.4; HRMS (ESI) Calcd for [C32H24S3]
requires [M+H]+ 505.1118, found 505.1116.
as yellow needles (204.8 mg, 77%); mp 160−162 °C; H NMR (400
MHz, CDCl3) δ 7.95−7.91 (m, 4H), 7.46−7.43 (m, 4H), 7.16−7.12 (m,
4H), 6.89−6.86 (m, 4H), 3.83 (s, 6H); 13C NMR (100 MHz, CDCl3) δ
162.7 (d, J = 248.2 Hz, 1C), 159.8, 141.3, 133.0, 129.4 (d, J = 7.7 Hz,
1C), 121.6, 115.7 (d, J = 22.0 Hz, 1C), 115.3, 114.1, 94.3, 83.3, 55.3;
HRMS (ESI) Calcd for [C34H22F2O2S] requires [M+H]+ 533.1387, found
533.1389.
3,4-Bis((4-ethylphenyl)ethynyl)-2,5-bis(4-
methoxyphenyl)thiophene (4m). The compound is obtained as
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yellow needles (207.2 mg, 75%); mp 99−101 °C; H NMR (400 MHz,
CDCl3) δ 7.93−7.91 (m, 4H), 7.45 (d, J = 8.4 Hz, 4H), 7.17 (d, J = 7.6 Hz,
4H), 6.98 (d, J = 8.4 Hz, 4H), 3.86 (s, 6H), 2.66 (q, J = 7.6 Hz, 4H), 1.24
(t, J = 7.6 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 159.7, 144.6, 142.3,
131.5, 128.9, 127.9, 126.2, 120.7, 120.4, 114.0, 94.0, 84.5, 55.4, 28.9,
15.4; HRMS (ESI) Calcd for [C38H32O2S] requires [M+H]+ 553.2201,
found 553.2204.
General experimental procedure for Pd-catalyzed one-pot
Suzuki/slective Sonogashira sequential 5a-d: To a solution of
tetrabromothiophene 1 (0.5 mmol) in 2 mL of DMF:EtOH (4:1), 7
mol% of Pd(PPh3)2Cl2 was added. Then, 3.5 equiv of K2CO3 and 1.2
mmol of boronic acid 2 were added to the reaction mixture. The
reaction vial was then sealed and flushed with nitrogen. The reaction
was then stirred at 65 °C until TLC revealed complete conversion of
the starting material. After the completion of the first coupling
reaction (Monitored by TLC) 5 mol% of Pd(PPh3)2Cl2, 0.52 mmol of
3,4-Bis((4-butylphenyl)ethynyl)-2,5-bis(4-
methoxyphenyl)thiophene (4n). The compound is obtained as
yellow needles (224.5 mg, 74%); mp 120−122 °C; 1H NMR (400 MHz,
6 | J. Name., 2012, 00, 1-3
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