J.-Y. Balandier et al. / Tetrahedron 66 (2010) 9560e9572
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4.2.3. 5,500-Dioctyl-3,4,300,400-tetracyano-2,20:50,200-terthiophene
(2a). A mixture of 2,5-bis(tributylstannyl)thiophene (23) (0.172 g,
0.26 mmol), Pd(PPh3)4 (0.05 g, 0.04 mmol), and 2-bromo-5-octyl-
115.0, 114.0, 110.7, 110.5 (C3, C30, C4, C40, C6, C60, C7, C70), 40.9
(eCOeCH2e), 31.5, 29.0, 28.8, 23.7, 22.6 (e(CH2)5eCH3),14.0 (eCH3).
Mp: 216e218 ꢁC. Rf (CH2Cl2)¼0.70. UVevis (nm): labs¼342.
C28H30N4O2S2: EI-HRMS (Mþꢂ): calcd: 518.1810; found: 518.1808.
ꢁ
3,4-dicyanothiophene (18) (0.166 g, 0.5 mmol) was heated over-
night at 105 ꢁC in dry toluene (10 mL) under argon. After cooling,
the reaction mixture was directly purified by column chromatog-
raphy on silica gel (CH2Cl2) to afford a yellow solid (0.025 g,
0.044 mmol). Yield: 17%.
4.2.7. 5,5000-Dioctyl-3,4,3000,4000-tetracyano-2,20:50,200:500,2000-quaterthio-
phene (4a). A mixture of bithiophene 29 (375.0 mg, 0.92 mmol), Pd
(OAc)2 (94.8 mg, 0.42 mmol), and i-Pr2EtN (119.0, 158
mL,
1H NMR (CDCl3): 7.63 (s, 2H, H30, H40), 3.02 (t, 4H, J¼7.56 Hz,
eCH2eC7H15), 1.76 (m, 4H, eCH2eCH2eC6H12), 1.34 (m, 20H,
e(CH2)5eCH3), 0.89 (t, 6H, J¼6.96 Hz, CH3). 13C NMR (CDCl3): 157.8
(C5, C500), 143.4 (C2, C200), 134.2 (C20, C50), 129.0 (C30, C40), 112.6,
111.6, 111.0, 106.5 (C3, C300, C4, C400, C6, C600, C7, C700), 31.7, 31.0, 29.9,
29.1, 29.0, 28.9 22.6 (e(CH2)7eCH3), 14.1 (eCH3). Mp: 194e196 ꢁC.
Rf (CH2Cl2)¼0.70. UVevis (nm): labs¼392. C32H36N4S3: MALDI-
HRMS (MNaþ): calcd: 595.2000; found: 595.1989.
0.92 mmol) in toluene (20 mL) was refluxed under argon for 4.5 h.
After cooling to room temperature, the solvent was evaporated in
vacuo. The residue was then dissolved in dichloromethane and
purified by chromatography on silica gel (CH2Cl2) to give an orange
solid (153 mg, 0.23 mmol). Yield: 51%.
1H NMR (CDCl3): 7.54 (d, 2H, J¼3.97 Hz, H30, H400), 7.27 (d, 2H,
J¼3.97 Hz, H40, H300), 3.00 (t, 4H, J¼7.54 Hz, eCH2eC7H15), 1.76 (m,
4H, eCH2eCH2eC6H12), 1.30 (m, 20H, e(CH2)5eCH3, 0.90 (t, 6H,
J¼6.97 Hz, CH3). 13C NMR (CDCl3): 156.7 (C5, C5000), 144.6 (C2, C2000),
138.9 (C20, C500), 131.5 (C50, C200), 129.2, 125.9 (C30, C300, C40, C400),
112.9, 111.8, 110.7, 105.1 (C3, C3000, C4, C4000 C6, C6000, C7, C7000), 31.7,
31.0, 29.8, 29.1, 29.1, 28.9, 22.6 (CH2)7eCH3), 14.1 (CH3). Mp: 202 ꢁC.
Rf (CH2Cl2)¼0.71. UVevis (nm): labs¼421. C36H38N4S4: MALDI-
HRMS (Mþꢂ): calcd: 654.1979; found: 654.1965.
4.2.4. 5,500-Dioctanoyl-3,4,300,400-tetracyano-2,20:50,200-terthiophene
(2b). A mixture of 2,5-bis(tributylstannyl)thiophene (23) (0.219 g,
0.33 mmol), Pd(PPh3)4 (0.110 g, 0.09 mmol), and 2-bromo-5-(2-
heptyl-1,3-dioxolan-2-yl)-3,4-dicyanothiophene (22) (0.253 g,
0.66 mmol) was heated overnight at 105 ꢁC in dry toluene (10 mL)
underargon. Aftercooling, the mixturewasdirectly filtratedon silica
gel (CH2Cl2) to afford 45 mg of the corresponding protected ter-
thiophene together with triphenylphospine oxide. This mixture was
then solubilized in 10 mL of CH2Cl2 and 1 gof amberlystÒ A15 dry ion
exchange resin was added and the mixture was stirred overnight.
The resin was removed by filtration and washed with 30 mL of
CH2Cl2. The filtrate was evaporated to dryness and the solid residue
was dispersed in methanol, filtered, washed with methanol, and
dried to afford an orange solid (16 mg, 0.03 mmol). Yield: 10%.
1H NMR (CDCl3): 7.85 (s, 2H, H30, H40), 3.11 (t, 4H, J¼7.21 Hz,
eCOeCH2e), 1.79 (m, 4H, eCOeCH2eCH2e), 1.32 (m, 16H,
e(CH2)4eCH3), 0.89 (t, 6H, J¼6.85 Hz, eCH3). 13C NMR (CDCl3):
190.1 (C]O), 149.5 (C5, C500), 148.6 (C2, C200), 134.9 (C20, C50), 130.9
(C30, C40), 113.9, 111.7, 111.3, 109.6 (C3, C300, C4, C400, C6, C600, C7, C700),
40.7 (eCOeCH2e), 31.6, 29.0, 28.9, 23.9, 22.6 (e(CH2)5eCH3), 14.1
(eCH3). Mp: 224e226 ꢁC. UVevis (nm): labs¼413. C32H32N4O2S3:
MALDI-HRMS (MNaþ): calcd: 623.1585; found: 623.1609.
4.2.8. 5,5000-Bis(octanoyl)-3,4,3000,4000-tetracyano-2,20:50,200:500,2000-qua-
terthiophene(4b). Quaterthiophene 25 (30.0 mg, 0.039 mmol) was
dissolved in 10 mL of CH2Cl2. Then 1.0 g of amberlystÒ A15 dry ion
exchange resin was added and the mixture was stirred overnight.
The resin was removed by filtration and washed with 30 mL of
CH2Cl2. The filtrate was concentrated and then purified by column
chromatography on silica gel (CH2Cl2) to afford a red solid (22 mg,
0.032 mmol). Yield: 81%.
1H NMR (CDCl3): 7.75 (d, 2H, J¼4.07 Hz, H30, H400), 7.38 (d, 2H,
J¼4.07 Hz, H300, H40), 3.1 (t, 4H, J¼7.13 Hz, COeCH2e), 1.78 (m, 4H,
eCOeCH2eCH2e), 1.35 (m, 16H, e(CH2)4eCH3), 0.90 (t, 6H,
J¼7.01 Hz, eCH3). 13C NMR (CDCl3): solubility is too low for 13C
NMR measurements. Mp: 274e278 ꢁC. Rf (CH2Cl2)¼0.42. UVevis
(nm): labs¼454.
4.2.9. 5,5000-Dioctyl-30,40,300,400-tetracyano-2,20:50,200:500,2000-quater-
thiophene (5a). A mixture of 5-bromo-50-octyl-3,4-dicyano-2,20-
bithiophene (33) (75.0 mg, 0.18 mmol), Pd(OAc)2 (20 mg,
4.2.5.
5,50-Dioctyl-3,30,4,40-tetracyano-2,20-bithiophene (3a). A
mixture of 2-bromo-5-octyl-3,4-dicyanothiophene (18) (361.0 mg,
1.11 mmol), Pd(OAc)2 (70 mg, 0.31 mmol), and i-Pr2EtN (143.4 mg,
190 mL, 1.11 mmol) in toluene (15 mL) was refluxed under argon for
2 h. After cooling to room temperature, the mixture was purified by
column chromatography on silica gel (CH2Cl2) to give a white solid
(150 mg, 0.31 mmol). Yield: 56%.
0.09 mmol), and i-Pr2EtN (24.0 mg, 32 mL, 0.18 mmol) in toluene
7 mL under argon was refluxed for 1.5 h. After cooling to room
temperature, the mixture was directly purified by column chro-
matography on silica gel (CH2Cl2) to afford the desired quater-
thiophene 5a as an orange solid (36.0 mg, 0.06 mmol). Yield: 60%.
1H NMR (CDCl3): 7.60 (d, 2H, J¼3.79 Hz, H3, H3000), 6.88 (d, 2H,
J¼3.79 Hz, H4, H4000), 2.88 (t, 4H, J¼7.51 Hz, eCH2eC7H15), 1.73 (m,
4H, eCH2eCH2eC6H13), 1.35 (m, 20H, e(CH2)5eCH3), 0.89 (t, 6H,
J¼6.93 Hz, CH3). 13C NMR (CDCl3): 153.5 (C5, C5000), 149.4 (C2, C2000),
135.9 (C50, C200), 130.3 (C4, C4000), 127.6 (C20, C500), 126.4 (C3, C3000),
112.3, 112.0, 111.8, 105.8 (C30, C40, C60, C70, C300, C400, C600, C700), 31.8,
31.4, 30.4, 29.2, 29.1, 29.0, 22.6 (e(CH2)7e), 14.1 (CH3). Mp:
201e203 ꢁC. Rf (CH2Cl2)¼0.88. UVevis (nm): labs¼432. C36H38N4S4:
MALDI-HRMS (Mþꢂ): calcd: 654.1979; found: 654.1968.
1H NMR (CDCl3): 3.07 (t, 4H, J¼7.59 Hz, eCH2eC7H15), 1.79 (m,
4H, eCH2eCH2eC6H12), 1.29 (m, 20H, e(CH2)5eCH3, 0.89 (t, 6H,
J¼6.95 Hz, CH3). 13C NMR (CDCl3): 160.4 (C5, C50), 138.0 (C2, C20),
111.7, 111.4, 111.1, 110.7 (C3, C30, C4, C40, C6, C60, C7, C70), 31.7, 31.0,
30.0, 29.0, 29.0, 28.9, 22.6 (CH2)7eCH3), 14.0 (CH3). Mp: 74e76 ꢁC. Rf
(CH2Cl2)¼0.82. UVevis (nm): labs¼339. C28H34N4S2: EI-HRMS
(MNaþ): calcd: 513.2123; found: 513.2100.
4.2.6. 5,50-Bis(octanoyl)-3,30,4,40-tetracyano-2,20-bithiophene (3b).
0
0
0
0
5 -Bis(heptyl-1,3-dioxolan-2-yl)-3,3 ,4,4 -tetracyano-2,2 -bithio-
phene (28) (60 mg, 0.099 mmol) was dissolved in 10 mL of CH2Cl2.
Then 1 g of amberlystÒ A15 dry ion exchange resin was added and
the mixture was stirred overnight. The resin was removed by fil-
tration and washed with 20 mL of CH2Cl2. The filtrate was con-
centrated and then purified by column chromatography on silica
gel (CH2Cl2) to afford a white solid (45 mg, 0.077 mmol). Yield: 88%.
1H NMR (CDCl3): 3.13 (t, 4H, J¼7.14 Hz, eCOeCH2e), 1.81 (m, 4H,
eCOeCH2eCH2e),1.35 (m,16H, e(CH2)4eCH3), 0.89(t, 6H, J¼6.93 Hz,
eCH3). 13C NMR (CDCl3): 189.6 (C]O), 153.0 (C5, C50),142.2 (C2, C20),
4.2.10. 5,5000-Dioctanoyl-30,40,300,400-tetracyano-2,20:50,200:500,2000-qua-
terthiophene (5b). A mixture of 5-bromo-50-octanoyl-3,4-dicyano-
2,20-bithiophene (37) (83.0 mg, 0.20 mmol), Pd(OAc)2 (20 mg,
ꢀ
0.09 mmol), and i-Pr2EtN (25.9 mg, 34 mL, 0.20 mmol) in toluene
(6 mL) was refluxed under argon for 1.5 h. After cooling to room
temperature, the mixture was directly purified on column chro-
matography on silica gel (CH2Cl2) to afford the desired quater-
thiophene as an orange solid (36.0 mg, 0.05 mmol). Yield: 53%.
1H NMR (CDCl3): 7.78 (d, 2H, J¼4.06 Hz, H4, H4000), 7.73 (d, 2H,
J¼4.06 Hz, H3, H3000), 2.93 (t, 4H, J¼7.31 Hz, eCH2eCOe), 1.77 (m,