575
19 M. Kaneko, T. Ozawa, T. Yoneyama, S. Imazeki, A. Mukoh, M.
Sato, Eur. Pat. EP 76,633, 1982.
(570 nm) and becomes negligible around the shoulder peak
(605 nm) as shown in Figure 2.
We think the remarkable orientation of dye 1 with the
improved fluorescence intensity provides appreciable advantage
in possible applications, and anticipate much attention for this
kind of dye from researchers in related fields.
20 1: 1,4-benzoquinone (0.5 g) and 3-{4-[4-(4-butylcyclohexyl)phen-
oxy]butoxy}-4-methoxyaniline (4.3 g) were added to ethanol (50
mL) and the mixture was heated to reflux for 7 h. After cooling the
mixture to room temperature, the precipitates were filtered. The
precipitates on the filter were washed with water and dried, followed
by the purification by silica gel column chromatography with
chloroform as eluents, thereby obtaining 0.8 g of crude intermediate.
The intermediate (0.1 g) and 4-butylbenzoyl chloride (1.0 g) were
added to nitrobenzene (20 mL) and the mixture was heated at 140 °C
for 7 h. After cooling the mixture to room temperature, the resulting
precipitates were filtered and washed with methanol on the filter. The
precipitates were purified 3 times by silica gel thin layer chromatog-
raphy with chloroform as eluents, thereby obtaining 10 mg of the
final dye 1 reddish powder. IR (KBr): 2956, 2924, 2856, 1741
This work was performed by Association of Super-Ad-
vanced Electronics Technologies in the Ministry of Economy
and Industry Program of Super-Advanced Electronics Technol-
ogies supported by New Energy and Industrial Technology
Development Organization. We gratefully acknowledge Dr.
Sawada (Merck Japan Co., Ltd.) and Dr. Hasegawa (IBM Japan
Co., Ltd.) for supplying the special LC mixture with large TNI.
(C=O), 1611, 1565, 1512, 1487, 1468, 1435, 1378, 1261, 1224,
¹1
References and Notes
1179, 1129, 1056, 1017, 826, 578 cm .
1H NMR (500 MHz,
1
A. V. Ivashchenko, Dichroic Dyes for Liquid Crystal Displays, CRC
Press, New York, 1994.
a) J. V. Masi, U. S. Patent 3844637, 1974. b) L. J. Yu, M. M. Labes,
CDCl3): ¤ 8.10 (d, J = 8 Hz, 4H), 7.30 (d, J = 8.5 Hz, 4H), 7.08-
7.05 (overlapping, 6H), 6.97 (s, 2H), 6.73 (q, 4H), 6.48 (s, 2H), 4.06
(t, J = 6 Hz, 4H), 3.83 (t, J = 8.5 Hz, 4H), 2.69 (t, J = 8 Hz, 4H),
2.39 (t, J = 12.8 Hz, 2H), 1.86-1.78 (overlapping, 16H), 1.67-1.61
(m, 4H), 1.43-1.33 (m, 8H), 1.31-1.25 (m, 12H), 1.22 (s, 2H), 1.06-
0.99 (m, 4H), 0.97-0.89 (overlapping, 12H). 13C NMR (500 MHz,
CDCl3): ¤ 164.25, 156.76, 150.93, 149.30, 148.10, 147.64, 140.62,
139.80, 138.04, 130.17, 128.50, 127.34, 126.14, 114.01, 111.30,
110.27, 105.65, 77.32, 77.14, 77.09, 76.88, 76.63, 67.06, 43.67,
37.26, 37.08, 35.76, 34.55, 33.62, 33.17, 29.21, 25.72, 22.99, 22.34,
14.15, 13.90. High-resolution MS with laser desorption ionization:
m/z 1243 [M + H]+, 1265 [M + Na]+. Assignment of the 1H and
13C NMR signals was done on the basis of 1H-1H shift-correlated
2D NMR (COSY) and 13C-1H COSY.
2
3
4
5
a) P. Dyreklev, M. Berggren, O. Inganäs, M. R. Andersson, O.
M. Chikamatsu, Y. Yoshida, R. Azumi, N. Tanigaki, K. Yase,
Liedtke, M. O’Neill, A. Wertmöller, S. P. Kitney, S. M. Kelly, Chem.
261. b) C. Weder, A. Montali, C. Sarwa, C. Bastiaansen, P. Smith,
New Photoluminescent Display Devices in Semiconducting Poly-
mers, ACS Symposium Series 735, ed. by B. R. Hsieh, Y. Wei,
American Chemical Society, Washington DC, 1999, Chap. 16,
R. A. Palmans, J. Bras, B. Pepin-Donat, S. Guillerez, P. Smith, C.
a) V. I. Kopp, B. Fan, H. K. M. Vithana, A. Z. Genack, Opt. Lett.
1998, 23, 1707. b) S. M. Morris, A. D. Ford, M. N. Pivnenko, H. J.
Nishimura, T. Toyooka, F. Araoka, K. Ishikawa, J. W. Wu, H.
10, 394. e) C. Mowatt, S. M. Morris, M. H. Song, T. D. Wilkinson,
21 2: Chloranyl (0.5 g), 3-{4-[4-(4-butylcyclohexyl)phenoxy]butoxy}-
4-methoxyaniline (1.7 g), and sodium acetate (0.32 g) were added to
ethanol (20 mL) and the mixture were heated to reflux for 5 h. After
cooling the mixture to room temperature, the precipitates were
filtered. The reactant left on the filter was washed with water and
dried, thereby obtaining 1.8 g of crude intermediate. The intermedi-
ate (0.1 g) and 4-butylbenzoyl chloride (1.0 g) were added to
nitrobenzene (20 mL) and the mixture was heated at 160 °C for 4 h.
After cooling the mixture to room temperature, the resulting
precipitates were filtered. The precipitates were purified 3 times by
silica gel thin layer chromatography with chloroform as eluents,
thereby obtaining 10 mg of the final dye 2 reddish powder. IR (KBr):
2956, 2920, 2851, 1744 (C=O), 1610, 1585, 1558, 1512, 1487,
6
7
1467, 1433, 1287, 1260, 1181, 1134, 1055, 1017, 911, 824,
¹1
582 cm
.
1H NMR (500 MHz, CDCl3): ¤ 8.10 (d, J = 8 Hz, 4H),
7.30 (d, J = 8.5 Hz, 4H), 7.26 (overlapping), 7.16 (s, 2H), 7.08 (d,
J = 9 Hz, 4H), 6.74 (d, J = 9 Hz, 4H), 4.09 (t, J = 6 Hz, 4H), 3.84 (t,
J = 6.3 Hz, 4H), 2.69 (t, J = 7.5 Hz, 4H), 2.39 (t, J = 11.8 Hz, 2H),
1.87-1.79 (m, 16H), 1.67-1.61 (m, 4H), 1.41-1.36 (m, 8H), 1.31-
1.28 (m, 12H), 1.25 (s, 12H), 1.22 (br, 2H), 1.06-1.01 (m, 4H), 0.97-
0.89 (overlapping, 12H). High-resolution MS with laser desorption
ionization: m/z 1311 [M + H]+, 1333 [M + Na]+. Assignment of
8
9
1
11 X. Zhang, R. Yamaguchi, K. Moriyama, M. Kadowaki, T.
the H signals was done on the basis of those from dye 1.
22 E7: 4-n-pentyl-4¤-cyanobiphenyl 51%, 4-n-heptyl-4¤-cyanobiphenyl
25%, 4-n-octyl-4¤-cyanobiphenyl 16%, 4-n-pentyl-4¤¤-cyanoterphen-
yl 8%.
13 M. Salamonczyk, A. Kovarova, J. Svoboda, D. Pociecha, E.
23 E9: 4-n-propyloxy-4¤-cyanobiphenyl 15%, 4-n-pentyloxy-4¤-cyano-
biphenyl 38%, 4-n-heptyloxy-4¤-cyanobiphenyl 38%, 4-n-pentyl-4¤¤-
cyanoterphenyl 9%.
14 M. Matsui, M. Suzuki, K. Mizuno, K. Funabiki, S. Okada, T.
16 a) N. S. Sariciftci, U. Lemmer, D. Vacar, A. J. Heeger, R. A. J.
Tanaka, C. Sekine, T. Ashida, M. Ishitobi, N. Konya, M. Minai, K.
24 A. Sawada et al., Annual Report of Association of Super-Advanced
Electronics Technologies on Low Power Super-Advanced LCD
Development, Association of Super-Advanced Electronics Technol-
ogies, Tokyo, 2001, p. 76.
25 W. A. Huffmann, British. Pat. GB 2,024,844A, 1980.
27 L. Pauling, General Chemistry, Dover Publications, New York,
1988, p. 197.
Chem. Lett. 2011, 40, 573-575
© 2011 The Chemical Society of Japan