C. Li et al. / Tetrahedron 70 (2014) 3909e3914
3913
sulfate and removed the solvent, and was purified by column
chromatography on silica gel with petrol ether, and then petrol
ether/CHCl3 (3:1, v/v) as eluent to give (E)-5 (0.32 g, 51%) as a yellow
product was purified by column chromatography on silica gel with
petrol ether (60e90 ꢀC)/CHCl3 (7:1, v/v) as eluent. The collected
product was dissolved in CHCl3 and precipitated with MeOH. The
precipitate was collected by filtration to afford the target molecule
as a pale yellow solid 2 (20 mg, 65%). Mp: 289e290 ꢀC. 1H NMR
solid. Mp: 187e188 ꢀC. 1H NMR (CDCl3, 400 MHz)
d (ppm) 7.39 (d,
J¼5.2 Hz, 1H), 7.37e7.33 (m, 3H), 7.30e7.25 (m, 5H), 7.17e7.10 (m,
5H), 7.07e7.02 (m, 4H), 6.86 (d, J¼16 Hz, 1H), 13C NMR (CDCl3,
(CDCl3, 400 MHz)
d
(ppm): 8.73 (s, 2H), 7.96 (d, J¼8.8 Hz, 2H), 7.81
100 MHz):
d
147.4, 145.9, 138.54, 138.48, 138.3, 137.2, 130.6, 129.3,
(d, J¼8.8 Hz, 2H), 7.75 (d, J¼8.4 Hz, 2H), 7.60 (dd, J¼8.8,1.6 Hz, 2H),
7.51e7.44 (m, 4H), 7.31e7.28 (m, 1H), 6.50 (d, J¼5.2 Hz, 2H), 6.46 (d,
127.7, 127.1, 124.5, 123.4, 123.1, 120.6, 118.8, 117.1. IR (KBr): 2919,
1590, 1384, 1331, 1274, 1175, 696 cmꢂ1. HRMS (Tesla FTMS): found
465.0674, C28H19NS3 requires 465.0661.
J¼5.6 Hz, 2H), 13C NMR (CDCl3, 100 MHz):
d 148.8, 146.9, 141.2,
140.0, 139.3, 138.5, 133.8, 130.2, 128.5, 128.1, 126.1, 125.9, 124.6,
124.0, 123.2, 121.3, 120.2, 119.4. IR (KBr): 2921, 1616, 1384, 1115,
694 cmꢂ1. HRMS (Tesla FTMS): found 680.9836, C38H19NS6 requires
680.9820.
4.2.2. Synthesis of N,N-diphenyl-N-naphtho[2,1-b]thieno[2,3-b:30,20-
d]dithiophene-5-yl-amine (1). To a solution of (E)-5 (50.0 mg,
0.11 mmol) in dry benzene (50 mL), iodine (13.7 mg, 0.05 mmol,
0.5 equiv) was added. The reaction solution was irradiated with
a 450 W unfiltered Hg medium pressure lamp. The reaction was
monitored by TLC every 20 min, and irradiation was stopped when
the (E)-5 was consumed up. After normal workup, the crude
product was purified by column chromatography on silica gel with
petrol ether (60e90 ꢀC)/CHCl3 (7:1, v/v) as eluent. The collected
product was dissolved in CHCl3 and precipitated with MeOH. The
precipitate was collected by filtration to afford pale yellow solid 1
4.2.5. Synthesis of tris[(E)-4-(2-dithieno[2,3-b: 30,20-d]thiophen-2-yl-
vinyl)phenyl] amine ((E)-7). Dithieno[2,3-b:30,20-d]thiophene-2-
carbaldehyde (4) (70 mg 0.29 mmol) and TPA-(PPh3$Br)3 (0.12 g,
0.09 mmol, 0.3 equiv) were dissolved in anhydrous tetrahydrofuran
(10 mL), a solution of potassium tert-butoxide (50 mg, 0.41 mmol,
1.4 equiv) in anhydrous tetrahydrofuran (8 mL) were added drop-
wise at 0 ꢀC, and then the reaction mixture was warmed slowly to
ambient temperature stir for 6 h. The reaction mixture was
quenched with H2O (10 mL) and extracted with CHCl3 (3ꢁ5 mL),
then washed with saturated NaHCO3 (2ꢁ20 mL) and H2O (20 mL).
The organic layer was dried over anhydrous MgSO4. After the sol-
vent was removed under vacuum, the collected product was dis-
solved in CHCl3 and precipitated in MeOH. The precipitate was
collected by filtration to afford the target molecule as a pale yellow
solid (E)-7 (0.06 g, 68%). Mp: >300 ꢀC. 1H NMR (CDCl3, 400 MHz)
(20 mg, 38%). Mp: 173e174 ꢀC. 1H NMR (400 MHz, CDCl3):
d 8.56 (d,
J¼2.0 Hz, 1H), 7.86 (d, J¼8.8 Hz, 1H), 7.73 (d, J¼8.8 Hz, 1H), 7.69 (d,
J¼8.8 Hz, 1H), 7.45 (dd, J¼8.8, 2.4 Hz, 1H), 7.36 (t, J¼7.8 Hz, 4H),
7.28e7.25 (m, 4H), 7.15 (t, J¼7.4 Hz, 2H), 7.04 (d, J¼5.6 Hz, 1H), 6.63
(d, J¼5.6 Hz, 1H), 13C NMR (CDCl3, 100 MHz):
d 148.1, 146.6, 141.2,
139.8, 139.3, 138.7, 133.9, 130.1, 129.7, 129.5, 128.3, 127.6, 126.1,
125.3, 124.6, 123.5, 122.1, 121.5, 119.6, 117.7. IR (KBr): 3030, 2922,
1618, 1585, 1368, 1358, 1175, 697, 623 cmꢂ1. HRMS (Tesla FTMS):
found 463.0518, C28H17NS3 requires 463.0503.
d
(ppm): 7.41e7.39 (m, 9H), 7.34 (d, J¼5.2 Hz, 3H), 7.30 (s, 3H), 7.19
(d, J¼16.0 Hz, 3H), 7.11 (d, J¼8.4 Hz, 6H), 6.88 (d, J¼16.0 Hz, 3H), 13
C
NMR (pyridine-d5, 100 MHz):
d 147.4, 146.9, 140.2, 139.5, 139.4,
4.2.3. Synthesis of (E)-4,40-bis[(2-(dithieno[2,3-b:30,20-d]thiophene)-
139.0, 132.8, 129.4, 128.4, 128.3, 125.1, 122.4, 119.8, 118.7. IR (KBr):
2922, 1595, 1384, 1322, 696, 663 cmꢂ1. HRMS (Tesla FTMS): found
904.9624, C48H27NS9 requires 904.9631.
2-yl)vinylphenyl]-N-phenylamine
((E)-6). Dithieno[2,3-b:30,20-d]
thiophene-2-carbaldehyde (4) (0.33 g, 1.47 mmol) and TPA-
(PPh3$Br)2 (0.64 g, 0.7 mmol, 0.48 equiv) were dissolved in anhy-
drous tetrahydrofuran (15 mL), solution of potassium tert-butoxide
(0.38 g, 3.34 mmol, 2.3 equiv) in anhydrous tetrahydrofuran
(10 mL) were added dropwise at 0 ꢀC, and then the reaction mixture
was warmed slowly up to ambient temperature stir for 6 h. The
reaction mixture was quenched with H2O (10 mL) and extracted
with CHCl3 (3ꢁ5 mL), then washed with saturated NaHCO3
(2ꢁ30 mL) and H2O (30 mL). The organic layer was dried over
anhydrous MgSO4. After the solvent was removed under vacuum,
the dry solid was dissolved in 20 mL THF, and then refluxed in
presence of catalysis amount iodine for 6 h. Then the mixture was
added diluted solution sodium hydroxide to remove iodine, after
that extracted it with CHCl3 (3ꢁ10 mL). Organic layer was dried
with anhydrous sodium sulfate and removed the solvent, and was
purified by column chromatography on silica gel with petrol ether,
and then petrol ether/CHCl3 (3:1, v/v) as eluent to give (E)-6 (0.21 g,
46%) as a yellow solid. Mp: 252e253 ꢀC. 1H NMR (CDCl3, 400 MHz)
4.2.6. Synthesis of N,N,N-tri(naphtho[2,1-b]thieno-[2,3-b:30,20-d]di-
thiophene-5-yl)amine (3). To a solution of (E)-7 (30 mg, 0.03 mmol)
in dry benzene (30 mL), iodine (4.2 mg, 0.02 mmol, 0.5 equiv) was
added. The reaction solution was irradiated with a 450 W unfiltered
Hg medium pressure lamp. The reaction was monitored by TLC
every 20 min, and irradiation was stopped when the (E)-7 was
consumed up. After normal workup, the crude product was purified
by column chromatography on silica gel with petrol ether
(60e90 ꢀC)/CHCl3 (3:1, v/v) as eluent. The collected product was
dissolved in CHCl3 and precipitated with MeOH. The precipitate
was collected by filtration to afford the target molecule as a pale
yellow solid 3 (10 mg, 34%). Mp: >300 ꢀC. 1H NMR (CDCl3,
400 MHz)
d
(ppm): 8.86 (s, 3H), 8.10 (d, J¼8.8 Hz, 3H), 7.93 (d,
J¼8.8 Hz, 3H), 7.85 (d, J¼8.4 Hz, 3H), 7.81 (dd, J¼8.0, 2.0 Hz, 3H),
6.20 (d, J¼5.2 Hz, 3H), 5.76 (d, J¼5.2 Hz, 3H). IR (KBr): 2921, 1611,
1508, 1384, 1360, 1331, 1267, 692, 652 cmꢂ1. HRMS (Tesla FTMS):
found 898.9155, C48H21NS9 requires 898.9172.
d
(ppm): 7.41e7.34 (m, 8H), 7.32e7.28 (m, 4H), 7.19e7.13 (m, 4H),
7.08 (d, J¼8.0 Hz, 5H), 6.87 (d, J¼16 Hz, 2H), 13C NMR (pyridine-d5,
100 MHz):
d 148.0, 147.7, 146.9, 140.2, 139.5, 139.3, 138.9, 132.4,
Acknowledgements
130.4, 129.4, 128.34, 128.3, 125.6, 124.7, 124.4, 122.2, 119.8, 118.7. IR
(KBr): 2924, 2853, 1621, 1593, 1360, 1324, 696, 667 cmꢂ1. HRMS
(Tesla FTMS): found 685.0149, C38H23NS6 requires 685.0161.
We thank Mr. Pengtao Ma for crystal measurements. This re-
search was supported by National Natural Science Foundation of
China (21270255, U1304207, 20972041), Program for SRFDP
(20124103110004) and Program of Henan University (SBGJ090506).
4.2.4. Synthesis of N-phenyl-N,N-dinaphtho[2,1-b]thieno[2,3-b:30,20-
d]dithiophene-5-yl-amine (2). To a solution of (E)-6 (30.0 mg,
0.04 mmol) in dry benzene (30 mL), iodine (6.0 mg, 0.02 mmol,
0.5 equiv) was added. The reaction solution was irradiated with
a 450 W unfiltered Hg medium pressure lamp. The reaction was
monitored by TLC every 20 min, and irradiation was stopped when
the (E)-6 was consumed up. After normal workup, the crude
Supplementary data
Supplementary data associated with this article can be found in