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H.-Y. Wang et al. / Dyes and Pigments 88 (2011) 358e365
2.8. General procedure for the synthesis of the
Anal. calc. for C26H21N: C, 89.88; H, 6.09; N, 4.03%, found: C,
compounds (11, 12, 15)
89.48; H, 6.18; N, 4.34%.
4,4’-(1E,1’E)-2,2’-(1,4-phenylene)bis(ethene-2,1-diyl)bis(N,N-diphe-
These compounds were prepared according to the similar
procedure for 10.
nylaniline) (17) from (4) and (2b); m.p. 140e141 ꢁC. Yield 77%, yellow
powder, 1H NMR(300 MHz, CDCl3):
d
7.01e7.07 (m, 11H), 7.10e7.13
4-(Dibiphenyl-4-ylamino)benzaldehyde (11): m.p. 112e114 ꢁC.
(m, 10H), 7.24 (s, 3H), 7.29 (s, 3H), 7.38e7.41 (m, 5H), 7.47 (s, 4H); 13C
Yield 62%, white powder. 1H NMR(300 MHz, CDCl3):
d
9.84 (s, 1H),
NMR (100 MHz, CDCl3): d 117.9,118.4,119.4,121.5,121.5,122.2,122.75,
7.75 (d, J ¼ 8.7 Hz, 2H), 7.57e7.61 (m, 8H), 7.43e7.47 (m, 4H),
7.29e7.38 (m, 4H), 7.16 (d, J ¼ 8.4 Hz, 2H). HRMS Mþ: Calcd for
C31H23NO: 425.1780, Found: 425.1782.
124.2, 126.4, 131.5, 142.2, 142.4 ppm. IR (KBr, cmꢀ1): 1589,1492,1384,
1279, 1109, 961, 832, 752, 695. HRMS Mþ: Calcd for C46H36N2:
616.2878, Found: 616.2895.
4-((4’-(Diphenylamino)biphenyl-4-yl)(phenyl)amino)benzaldehyde
Anal. calc. for C46H36N2: C, 89.58; H, 5.88; N, 4.54%, found: C,
90.03; H, 5.63; N, 4.34%.
(12): m.p. 123e125 ꢁC. Yield 55%, white powder. 1H NMR(300 MHz,
CDCl3):
d
9.82 (s, 1H), 7.71 (d, J ¼ 8.7 Hz, 2H), 7.54 (d, J ¼ 8.7 Hz, 2H),
4,4’-(1E,1’E)-2,2’-(1,4-phenylene)bis(ethene-2,1-diyl)bis(N,N-bis
(4-(phenylethynyl)phenyl)aniline) (18) from (14) and (2b); m.p.
7.47 (d, J ¼ 8.4 Hz, 2H), 7.36 (t, J ¼ 6.9 Hz, 2H), 7.27e7.29 (m, 3H),
7.19e7.24 (m, 6H), 7.12e7.15 (m, 6H), 7.01e7.09 (m, 4H). HRMS Mþ:
Calcd for C37H28N2O: 516.2202, Found: 516.2201.
130e131 ꢁC. Yield 78%, yellow powder, 1H NMR(300 MHz, CDCl3):
d
7.03e7.14 (m, 15H), 7.29e7.34 (m, 18H), 7.39e7.43 (m, 9H),
4-(bis(4’-(Diphenylamino)biphenyl-4-yl)amino)benzaldehyde
7.50e7.53 (m, 10H); 13C NMR (100 MHz, CDCl3):
d
157.9, 157.7, 155.5,
(15): m.p. 136e137 ꢁC. Yield 50%, white powder. 1H NMR(300 MHz,
155.3, 136.9, 136.8, 135.0, 134.9, 129.4, 128.8, 128.7, 127.3, 127.2,
123.5, 123.4, 121.9, 121.8, 113.6, 113.2, 113.1, 112.8, 112.3, 112.1, 110.4,
110.2, 110.1, 109.9, 91.1 ppm. IR (KBr, cmꢀ1): 1589, 1504, 1318, 1280,
1163, 960, 829, 754, 688. HRMS Mþ: Calcd for C78H52N2: 1016.4130,
Found: 1016.4234.
CDCl3): d 9.83 (s, 1H), 7.71 (s, 2H), 7.54 (s, 3H), 7.46 (s, 4H), 7.26 (m,
11H), 6.97e7.18 (m, 20H). HRMS Mþ: Calcd for C55H41N3O:
759.3250, Found: 759.3253.
Anal. calc. for C78H52N2: C, 92.09; H, 5.15; N, 2.75%, found: C,
92.41; H, 4.76; N, 2.82%.
2.9. 4-(Bis(4-(phenylethynyl)phenyl)amino)benzaldehyde (14)
N,N0-(4,40-(1E,10E)-2,20-(1,4-phenylene)bis(ethene-2,1-diyl)bis(4,1-
phenylene))bis(N-phenylbiphenyl-4-amine) (19) from (10) and (2b);
m.p. 160e161 ꢁC yield 75%, yellow powder, 1H NMR(300 MHz,
4-(bis(4-Iodophenyl)amino)benzaldehyde 5 (5.25 g, 10 mmol),
ethynylbenzene 13 (2.10 g, 21 mmol), copper (I) iodine (47 mg,
0.25 mmol), bis(triphenylphosphine) dichloropalladium(II)
(0.18 mg, 0.25 mmol) and triethylamine (25 mL) in dry toluene
(25 mL) were placed in a sealed flask under an argon atmosphere.
The mixture was stirred at room temperature for 0.5 h and then
heated to 80 ꢁC. After stirring for 24 h at this temperature, the
mixture was filtered and the filtrate concentrated under reduced
pressure. The residue was purified by silica gel column chroma-
tography (ethyl acetate/petroleum ether, 1/10, v/v) (3.55 g, 75%).
CDCl3):
d
7.03e7.24 (m, 20H), 7.29e7.32 (m, 5H), 7.42e7.51 (m, 14H),
123.1, 123.3,
7.56e7.59 (m, 5H); 13C NMR (100 MHz, d6-DMSO):
d
123.4,123.9,124.1,124.2, 124.6,126.3, 126.3,127.8,127.8,129.0,129.7,
129.8,130.1,134.2,134.6,139.7,139.7,146.8,146.9,147.2 ppm. IR (KBr,
cmꢀ1): 1592, 1488, 1325, 1280, 1174, 1103, 962, 832, 759, 695. HRMS
Mþ: Calcd for C58H44N2: 768.3504, Found: 768.3478.
Anal. calc. for C58H44N2: C, 90.59; H, 5.77; N, 3.64%, found: C,
90.35; H, 5.53; N, 4.12%.
M.p. 110e112 ꢁC. Yellow solid, 1H NMR(400 MHz, CDCl3):
d 9.87 (s,
N,N0-(4,40-(1E,10E)-2,20-(1,4-phenylene)bis(ethene-2,1-diyl)bis(4,1-
phenylene))bis(N-(biphenyl-4-yl)biphenyl-4-amine) (20) from (11)
and (2b); m.p. 165e166 ꢁC. Yield 77%, yellow powder, 1H NMR
1H), 7.76 (d, J ¼ 8.4 Hz, 2H), 7.48e7.54 (m, 8H), 7.34e7.36 (m, 6H),
7.12e7.14 (m, 6H). HRMS Mþ: Calcd for C35H23NO: 473.1780, Found:
473.1777.
(300 MHz, CDCl3):
d
7.41e7.61 (m, 31H), 7.29e7.35 (m, 4H), 7.15e7.24
141.8,
(m, 13H), 6.99e7.08 (m, 4H); 13C NMR (100 MHz, CDCl3):
d
2.10. General procedure for the synthesis of the
compounds (16e22)
141.5, 135.4, 131.5, 130.6, 126.8, 123.6, 122.7, 122.6, 122.3, 121.8, 121.5,
119.4, 118.9 ppm. IR (KBr, cmꢀ1): 1597, 1511, 1323, 1284, 1107, 958,
833, 762, 694. HRMS Mþ: Calcd for C70H52N2: 920.4130, Found:
920.4080.
1a ((bromomethyl)benzene) (1 mmol) or 1b (1,4-bis(bromo-
methyl)benzene) (1 mmol) and triethyl phosphite (3 mmol) were
heated to reflux at 185 ꢁC for 3 h with stirring. Excess triethyl
phosphite was collected under reduced pressure at 69 ꢁC (1.5 mm
Hg) and the phosphonium salt 2 (2a ¼ diethyl benzylphosphonate,
2b ¼ tetraethyl 1,4-phenylenebis(methylene)diphosphonate) was
obtained. The corresponding triphenylamine aldehyde in dry DMF
(5 mL) was added dropwise. NaOEt (0.34g, 5 mmol) was then added
and the mixture heated to 60 ꢁC for 2 h. The ensuing mixture was
filtered and the solids washed with EtOH. Solids were dissolved in
dichloromethane, washed in distilled H2O, dried over MgSO4 and
the solvent was removed. The residue was chromatographed on
a silica gel column (petroleum ether/dichloromethane, 4/1, v/v) to
afford the pure product. The following compounds were obtained
in this fashion:
Anal. calc. for C70H52N2: C, 91.27; H, 5.69; N, 3.04%, found: C,
90.64; H, 5.96; N, 3.40%.
N4,N40-(4,40-(1E,10E)-2,20-(1,4-phenylene)bis(ethene-2,1-diyl)bis
(4,1-phenylene))bis(N4,N40,N40-triphenylbiphenyl-4,40-diamine) (21)
from (12) and (2b); m.p. 187e188 ꢁC. Yield 75%, yellow powder, 1H
NMR(300 MHz, CDCl3):
7.12e7.17 (m, 22H), 6.97e7.08 (m, 12H),; 13C NMR (100 MHz,
CDCl3): 147.9, 147.7, 147.4, 147.1, 146.6, 136.9, 135.4, 134.9, 131.9,
d 7.39e7.48 (m, 18H), 7.24e7.28 (m, 10H),
d
129.6, 129.5, 128.1, 127.6, 127.6, 126.9, 126.9, 124.9, 124.7, 124.6,
124.3, 123.9, 123.4, 123.1 ppm. IR (KBr, cmꢀ1): 1618, 1490, 1328,
1277, 1176, 1103, 961, 845, 768, 693. HRMS Mþ: Calcd for C82H62N4:
1102.4974, Found: 1102.4924.
Anal. calc. for C82H62N4: C, 89.26; H, 5.66; N, 5.08%, found: C,
90.04; H, 5.36; N, 4.60%.
(E)-N,N-diphenyl-4-styrylaniline (16) from (4) and (2a); m.p.
N4,N40-(4,40-(1E,10E)-2,20-(1,4-phenylene)bis(ethene-2,1-diyl)bis
(4,1-phenylene))bis(N4-(40-(diphenylamino)biphenyl-4-yl)-N40,N40-
diphenylbiphenyl-4,40-diamine) (22) from (15) and (2b); m.p.
189e190 ꢁC. Yield 70%, yellow powder, 1H NMR(300 MHz,
204e206 ꢁC. Yield 78%, white powder, 1H NMR(300 MHz, CDCl3):
d
7.48e7.50 (m, 3H), 7.32e7.39 (m, 5H), 7.24e7.26 (m, 3H), 7.04e7.12
(m, 10H); 13C NMR (100 MHz, CDCl3):
d
142.4, 142.2, 132.5, 126.4,
124.2, 123.5, 123.0, 122.2, 122.1, 121.9, 121.2, 119.4, 118.5, 117.9 ppm.
IR (KBr, cmꢀ1): 1587, 1491, 1326, 1278, 1173, 963, 822, 751, 694.
HRMS Mþ: Calcd for C26H21N: 347.1674, Found: 347.1674.
CDCl3):
(m, 35H), 7.01e7.07 (m, 11H); 13C NMR(100 MHz, CDCl3):
147.9, 147.3, 147.1, 146.5, 136.9, 135.5, 134.8, 132.1, 129.5, 128.1,
d
7.42e7.50 (m, 29H), 7.24e7.29 (m, 13H), 7.12e7.21
d
148.0,