P. Shen et al. / Organic Electronics 12 (2011) 125–135
129
was added in a 50 mL three-necked flask. When the mix-
ture was heated up to 60 °C, Pd(PPh3)4 (115 mg,
0.1 mmol) was added into the mixture solution quickly,
and then the mixture was stirred at 100 °C for 48 h. After
cooling to 70 °C, the mixture was treated with dilute
aqueous HCl (10 mL) solution and stirred for 30 min. Then
the resulting mixture was changed into a yellow-green
color and extracted with dichloromethane at room tem-
perature. The combined organic layer was washed with
brine several times, dried over anhydrous MgSO4, filtered
and evaporated under vacuum. The crude product was
purified by silica gel column chromatograph eluted with
petroleum ether/dichloromethane (5/1, v/v) to obtain 11
as a yellow sticky oil. Yield: 43% (0.37 g). FT-IR (KBr,
6H), 6.98 (s, 1H), 6.80 (d, 1H, J = 7.6 Hz), 2.95 (t, 2H,
J = 7.7 Hz), 1.67–1.63 (m, 2H), 1.54–1.26 (m, 6H), 0.88 (t,
3H, J = 7.8 Hz). Elem. Anal. Calcd. for
C55H47NOS: C,
85.79; H, 6.15; N, 1.82; S, 4.16. Found: C, 85.66; H,
6.43; N, 1.80; S, 4.61.
2.4.8. 3-(5-(2-(4-(Diphenylaminephenyl)-9,9-diethylfluorene-
7-yl)-3-hexylthiophene-2-yl)-2-cyanoacrylic acid (SD6)
Under nitrogen atmosphere, a mixture of compound 11
(0.40 g, 0.61 mmol), cyanoacetic acid (0.1 g, 1.22 mmol),
piperidine (0.5 mL), toluene (15 mL) and CH3CN (5 mL)
was refluxed at 80 °C for 12 h. After cooling, the solution
was extracted with dichloromethane and 0.1 M aqueous
solution of HCl. The organic layer was dried over anhy-
drous MgSO4, filtered and evaporated under vacuum. The
crude product was purified by silica gel column chromato-
graph eluted with chloroform/methanol (15/1, v/v) to ob-
tain SD6 as a red solid. Yield: 68% (0.30 g). FT-IR (KBr,
cmÀ1): 1667 ( C@O). 1H NMR (400 MHz, CDCl3): d (ppm)
m
10.04 (s, 1H), 7.76–7.71 (m, 2H), 7.70–7.68 (m, 2H),
7.62–7.56 (m, 6H), 7.31–7.28 (m, 3H), 7.19–7.17 (m,
6H), 7.10–7.05(m, 2H), 2.99 (t, 2H, J = 7.8 Hz), 2.12–2.10
(m, 4H), 1.80–1.76 (m, 2H), 1.56–1.36 (m, 6H), 0.88 (t,
3H, J = 6.5 Hz), 0.40 (t, 6H, J = 7.3 Hz). 13C NMR
(100 MHz, CDCl3): d (ppm) 182.6, 156.4, 148.6, 148.3,
147.6, 147.3, 144.2, 141.1, 140.8, 139.9, 135.9, 133.3,
130.9, 130.6, 130.1, 129.8, 128.9, 128.7, 127.3, 125.9,
125.5, 123.2, 122.6, 50.1, 35.8, 32.0, 31.9, 29.1, 24.7,
cmÀ1): 2216 ( C@O). 1H NMR (400 MHz, CDCl3):
m„), 1682 (m
d (ppm) 8.50 (s, 1H), 7.79–7.76 (m, 3H), 7.65(s, 1H), 7.62–
7.57 (m, 4H), 7.38 (s, 1H), 7.32–7.28 (m, 4H), 7.20–7.06 (m,
6H), 7.08–7.04 (m, 2H), 2.86 (t, 2H, J = 8.1 Hz), 2.15–2.14
(m, 4H), 1.72 (br, 2H), 1.43–1.28 (m, 6H), 0.93 (br, 3H),
0.39 (t, 6H, J = 7.2 Hz). MALDI-TOF: m/z 726.169.
22.8, 14.2, 8.9. Elem. Anal. Calcd. for
C46H45NOS: C,
83.72; H, 6.87; N, 2.12; S, 4.86. Found: C, 83.86; H,
6.53; N, 2.01; S, 5.02.
2.4.9. 3-(5-(3-(4-(Diphenylaminephenyl)-9-ethylcarbazole-6-
yl)-3-hexylthiophene-2-yl)-2-cyanoacrylic acid (SD7)
2.4.6. 5-(3-(4-(Diphenylaminephenyl)-9-ethylcarbazole-6-
yl)-3-hexylthiophene-2-carbaldehyde (12)
SD7 was synthesized according the same procedure as
that of SD6, except that compound 12 (0.2 g, 0.32 mmol)
was used instead of 11. The crude product was purified
by silica gel column chromatograph eluted with chloro-
form/methanol (10/1, v/v) to obtain SD7 as a red solid.
Compound 12 was synthesized according the same pro-
cedure as that of 11, except that compound 9 (0.67 g,
1.3 mmol) was used instead of 8. Yield: 42% (0.34 g). FT-
IR (KBr, cmÀ1): 1665 ( C@O). 1H NMR (400 MHz, CDCl3): d
m
Yield: 59% (0.13 g). FT-IR (KBr, cmÀ1): 2210 (
m
„), 1679
(ppm) 10.02 (s, 1H), 8.43 (s, 1H), 8.33 (s, 1H), 7.85 (d, 1H,
J = 8.4 Hz), 7.78 (d, 1H, J = 8.4 Hz), 7.60 (d, 2H, J = 8.5 Hz),
7.47 (d, 1H, J = 8.4 Hz), 7.43 (d, 1H, J = 8.5 Hz), 7.31–7.26
(m, 4H), 7.21–7.16 (m, 7H), 7.05–7.04 (m, 2H), 4.41 (q,
2H, J = 7.2 Hz), 2.99 (t, 2H, J = 8.2 Hz), 1.78–1.72 (m, 2H),
1.48 (t, 3H, J = 7.0 Hz), 1.43–1.26 (m, 6H), 0.86 (t, 3H,
J = 6.8 Hz). 13C NMR (100 MHz, CDCl3): d (ppm) 182.5,
157.0, 148.9, 147.6, 147.5, 144.3, 143.8, 140.8, 136.6,
132.3, 130.9, 129.8, 129.7, 128.7, 127.2, 125.3, 123.2,
122.8, 119.4, 119.2, 116.7, 111.6, 106.3, 48.5, 32.1, 31.9,
29.1, 24.8, 22.8, 15.8, 14.2. Elem. Anal. Calcd. for
(m
C@O). 1H NMR (400 MHz, CDCl3): d (ppm) 8.49 (s, 1H),
8.47 (s, 1H), 8.40 (s, 1H), 7.85 (d, 1H, J = 7.7 Hz), 7.74 (d,
1H, J = 7.9 Hz), 7.64 (d, 2H, J = 8.1 Hz), 7.49–7.45 (m, 3H),
7.38 (s, 1H), 7.17–7.13 (m, 9H), 7.05–7.04 (m, 2H), 4.42
(br, 2H), 2.86 (t, 2H, J = 7.6 Hz), 1.72–1.65 (m, 2H), 1.50
(t, 3H, J = 7.3 Hz), 1.41–1.26 (m, 6H), 0.89 (t, 3H,
J = 6.4 Hz). MALDI-TOF: m/z 699.093.
2.4.10. 3-(5-(2-(4-(Diphenylaminephenyl)-9,9-
spirobifluoren-7-yl)-3-hexylthiophene-2-yl)-2-cyanoacrylic
acid (SD8)
C43H40N2OS: C, 81.61; H, 6.37; N, 4.43; S, 5.07. Found: C,
81.76; H, 6.53; N, 4.64; S, 5.61.
SD8 was synthesized according the same procedure as
that of SD6, except that compound 13 (0.16 g, 0.21 mmol)
was used instead of 11. The crude product was purified by
silica gel column chromatograph eluted with chloroform/
methanol (20/1, v/v) to obtain SD8 as a red solid. Yield:
2.4.7. 5-(2-(4-(Diphenylaminephenyl)-9,9-spirobifluoren-7-
yl)-3-hexylthiophene-2-carbaldehyde (13)
Compound 13 was synthesized according the same
procedure as that of 11, except that compound 10
(0.71 g, 1.1 mmol) was used instead of 8. The crude prod-
uct was purified by silica gel column chromatograph
eluted with petroleum ether/dichloromethane (8/1, v/v)
to obtain 12 as a yellow solid. Yield: 33% (0.27 g). FT-IR
75% (0.13 g). FT-IR (KBr, cmÀ1): 2214 (
m„), 1689 (mC@O).
1H NMR (400 MHz, CDCl3): d (ppm) 8.40 (s, 1H), 7.92–
7.90 (m, 4H), 7.78 (d, 1H, J = 7.4 Hz), 7.65 (d, 1H,
J = 7.4 Hz), 7.45–7.40 (m, 2H), 7.28–7.21 (m, 6H), 7.17–
7.14 (m, 2H), 7.09–7.00 (m, 9H), 6.88 (s, 1H), 6.81 (d, 2H,
J = 7.6 Hz), 2.73 (t, 2H, J = 7.6 Hz), 1.69–1.55 (m, 2H),
1.34–1.27 (m, 6H), 0.87 (t, 3H, J = 7.9 Hz). MALDI-TOF: m/
z 820.267.
(KBr, cmÀ1): 1665 ( C@O). 1H NMR (400 MHz, CDCl3): d
m
(ppm) 10.03 (s, 1H), 7.89–7.88 (m, 4H), 7.72 (d, 1H,
J = 7.4 Hz), 7.63 (d, 1H, J = 7.4 Hz), 7.48–7.45 (m, 2H),
7.40–7.20 (m, 10H), 7.14–7.12 (m, 2H), 7.06–6.99 (m,