Journal of the Iranian Chemical Society
to give crude product under reduced pressure. The crude
product was puriꢃed by silica gel chromatography eluting
Synthesis of (2Z, 2′Z)‑3,3′‑((9H‑ꢁuorene‑3,6‑diyl)
bis(4,1‑phenylene))bis(2‑cyanoacrylic acid) (llyu1c)
(
petroleum ether: ethyl acetate=20:1), yield 15.4%, melting
1
point 202–205 °C. HNMR (500 MHz, DMSO) δ: 10.11 (s,
Compound llyu1c (180.0 mg, 77.6%) was synthesized in
a similar way to compound llyu1a by using compound 3c,
1
H), 8.52 (s, 1H), 8.34 (s, 1H), 7.95 (d, J=3.9 Hz, 1H), 7.87
1
(
d, J=3.9 Hz, 1H), 7.75 (d, J=1.5 Hz, 1H), 4.07 (s, 1H).
melting points>350 °C. HNMR (500 MHz, DMSO) δ:8.42
(
d, J=1.1 Hz, 1H), 7.95 (s, 1H), 7.92 (dd, J=7.9, 1.4 Hz,
1
7
H), 7.75 (d, J = 7.9 Hz, 1H), 7.45 (d, J = 3.7 Hz, 1H),
Synthesis of 5, 5′‑(9H‑ꢁuorene‑3, 6‑diyl)
bis(furan‑2‑carbaldehyde) (3b)
.30 (d, J= 3.6 Hz, 1H), 4.51 (s, 3H), HRMS (ESI) m/z
−
(M-H) 487.0970, calcd for C H N O 487.0936.
29
15
2
6
Compound 3b (320.0 mg, 27.6%) was synthesized in a sim-
Synthesis of 5, 5′‑(9,9‑dimethyl‑9H‑ꢁuorene‑3,6‑diyl)
bis(thiophene‑2‑carbaldehyde) (4a)
ilar way to compound 3a by using compound 1, melting
1
point 212–214 °C. HNMR (500 MHz, CDCl ) δ: 9.66 (s,
3
1
7
H), 8.43 (d, J=1.5 Hz, 1H), 7.80 (dd, J=7.9, 1.6 Hz, 1H),
.44 (d, J=7.9 Hz, 1H), 7.34 (d, J=3.7 Hz, 1H), 6.93 (d,
To a solution of 2 (650.0 mg, 2.0 mmol),
tetrakis(triphenylphosphine)palladium (230.0 mg 0.20 mmol),
and 5-formylthiophen-2-boronic acid (1.26 g, 8 mmol) in tet-
rahydrofuran (20 mL), an aqueous 2 M potassium carbon-
ate solution (16 mL) was added at room temperature under
nitrogen. After the mixture was reꢀuxed at 75 °C for 20 h,
the reaction mixture was concentrated to give crude product
under reduced pressure. The crude product was puriꢃed by
silica gel chromatography eluting (petroleum ether: ethyl ace-
tate=20:1) to give red powder 4a(200.0 mg 15.4%), melting
J=3.7 Hz, 1H), 4.10 (s, 1H).
Synthesis of 5, 5′‑(9H‑ꢁuorene‑3,6‑diyl)
bis(benzene‑2‑carbaldehyde) (3c)
Compound 3c (250.0 mg, 26.7%) was synthesized in a simi-
lar way to compound 3a by using compound 1, melting point
1
2
8
34–236 °C. HNMR (500 MHz, CDCl ) δ 10.11 (s, 1H),
3
1
.13 (d, J=1.4 Hz, 1H), 8.02 (d, J=8.3 Hz, 2H), 7.89 (d,
point 286–288 °C. HNMR (500 MHz, DMSO) δ: 9.88 (s,
J=8.2 Hz, 2H), 7.71 (d, J=7.8 Hz, 1H), 7.65 (dd, J=7.8,
1H), 8.41 (d, J=1.5 Hz, 1H), 7.95 (dd, J=7.9, 1.6 Hz, 1H),
7.67 (d, J=7.9 Hz, 1H), 7.50 (d, J=3.7 Hz, 1H), 7.02 (d,
J=3.7 Hz, 1H), 1.60 (s, 3H).
1
.7 Hz, 1H), 4.05 (s, 1H).
Synthesis of (2Z, 2′Z)‑3,3′‑((9H‑ꢁuorene‑3,6‑diyl)
bis(thiophene‑5,2‑diyl))bis(2‑cyanoacrylic acid) (llyu1a)
Synthesis of 5, 5′‑(9, 9‑dimethyl‑9H‑ꢁuorene‑3, 6‑diyl)
bis(furane‑2‑carbaldehyde) (4b)
A solution of 3a (150 mg, 0.39 mmol), cyanoacetic acid
Compound 4b (350.0 mg, 32.0%) was synthesized in a similar
(
270 mg, 2.52 mmol), and piperidine (90.0 g, 1.1 mmol)
way to compound 3a by using compound 2, melting point,
in 1,2-dichloroethane (10 mL) was reꢀuxed under nitro-
gen atmosphere for 9 h. The resulted red precipitate was
ꢃltered and recrystallized with ethanol to give red powder
llyu1a (170.0 mg, 83.8%), melting points 343–346 °C.
1
2
63-265 °C. H NMR (500 MHz, CDCl ) δ:9.72 (s, 1H), 8.31
3
(
d, J=1.5 Hz, 1H), 7.85 (dd, J=7.9, 1.6 Hz, 1H), 7.54 (d,
J=7.9 Hz, 1H), 7.40 (d, J=3.7 Hz, 1H), 6.98 (d, J=3.7 Hz,
H), 1.56 (s, 3H).
1
1
HNMR (500 MHz, DMSO) δ:8.50 (s, 1H), 8.31 (s, 1H),
7
.92 (d, J=3.9 Hz, 1H), 7.83 (d, J=3.9 Hz, 1H), 7.73 (d,
Synthesis of 4, 4′‑(9,9‑dimethyl‑9H‑ꢁuorene‑3,6‑diyl)
dibenzaldehyde (4c)
J=1.5 Hz, 1H), 7.71 (s, 1H), 4.05 (s, 1H); HRMS (ESI) m/z
−
5
19.0405(M-H) , calcd for C H N O S 519.0479.
2
9
15
2
4 2
Compound 4c (360.0 mg, 31.3%) was synthesized in a simi-
Synthesis of (2Z, 2′Z)‑3,3′‑((9H‑ꢁuorene‑3,6‑diyl)
bis(furan‑5,2‑diyl))bis(2‑cyanoacrylic acid) (llyu1b)
lar way to compound 3a by using compound 2, melting
1
point 227–230 °C. H NMR (500 MHz, CDCl ) δ: 10.10 (s,
3
1
H), 8.07 (d, J=1.3 Hz, 1H), 8.01 (d, J=8.4 Hz, 2H), 7.87
Compound llyu1b (250.0 mg, 82.8%) was synthesized in
(d, J=8.2 Hz, 2H), 7.65 (dd, J=7.8, 1.7 Hz, 1H), 7.59 (d,
J=7.8 Hz, 1H), 1.60 (s, 3H).
a similar way to compound llyu1a by using compound
1
3
b, melting points > 350 °C. HNMR (500 MHz, DMSO)
δ:8.42 (d, J = 1.1 Hz, 1H), 7.95 (s, 1H), 7.92 (dd, J = 7.9,
1
1
.4 Hz, 1H), 7.75 (d, J = 7.9 Hz, 1H), 7.45 (d, J = 3.7 Hz,
H), 7.30 (d, J=3.6 Hz, 1H), 4.51 (s, 3H); HRMS (ESI) m/z
−
(
M-H) 487.0970, calcd for C H N O 487.0936.
2
9
15
2
6
1
3