M. Yasutake, T. Fujihara, A. Nagasawa, K. Moriya, T. Hirose
FULL PAPER
OCH(CH ) ] ppm. IR (KBr): ν = 3020, 2950, 2860, 2850, 1640,
˜
about 100°, and the distance of two long dimensions be-
comes ca. 23.3 Å, which well corresponds to the unit length
along the c axis, that is, d001 in Figure 9b.
The X-ray diffraction pattern of 5c suggests one-dimen-
sional ordering, which corresponds to the lamellar structure
as observed for crystalline 5e. In contrast, the measurement
of mesomorphic 4c failed because the LC structure at
192 °C was more unstable than 5c and only the crystalline
diffractions were observed at 164 °C.
3 2
1610, 1560, 1340, 1230, 830 cm–1. MS (EI): m/z = 348 [M]+.
5e: Prepared according to the general procedure. Yield 36%, m.p.
1
246–248 °C. H NMR: δ = 8.55 (s, 2 H, ArH), 8.16 (s, 2 H, ArH),
6.03 (s, 2 H, ArH), 4.52 [sext, J = 6.00 Hz, 2 H, ArOCH(CH3)2],
1.51 [d, J = 6.00 Hz, 12 H, ArOCH(CH ) ] ppm. IR (KBr): ν =
˜
3 2
2920, 2890, 1640, 1610, 1560, 1410, 1230, 830 cm–1. MS (EI): m/z
= 348 [M]+.
Supporting Information (see footnote on the first page of this arti-
cle): Characterization data of 4a,b,d and 5a,b,d; crystal data and
structure refinement for 4e and 5e; ORTEP diagram of 4e and 5e.
Conclusions
Acknowledgments
This article reports the synthesis of novel liquid crystal-
line π-acceptor pyrenediones, two anti-type derivatives, and
M. Y. is grateful for partial financial support by theIketani Science
three syn-type derivatives. In conjunction with single-crystal and Technology Foundation (0181062-A).
X-ray analyses of analogs 4e and 5e, the POM observations
of 4c, 4d and 5b–d, and the XRD analysis of 5c, it is sug-
gested that the liquid crystalline phases have terrace and
band textures, characterized as DL2. Detailed analysis of
the LC phases and the formation of quinone–hydroquinone
CT complexes are underway.
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Experimental Section
General: 1H NMR spectra were measured with Bruker DPX 400
and DRX 400 spectrometers (Molecular Analysis and Life Science
Center (MALS), Saitama University). Chemical shifts are reported
as δ values (ppm) relative to internal tetramethylsilane (TMS) in
CDCl3. Mass spectra were obtained with a JEOL JMS-700AM
mass spectrometer (EI ionization voltage of 70 eV; MALS, Saitama
University). Infrared spectra were obtained with a JASCO FTIR
125HK spectrometer.
General Procedure for the Synthesis of 4 and 5: Anhydrous iron(III)
chloride (1.25 g, 7.71 mmol) was added to a mixture of 2 and 3
(500 mg, 2.15 mmol) in decyl alcohol (250 mL) at room tempera-
ture, and the temperature was raised to 120 °C. After stirring for
12 h, about 240 mL of decyl alcohol was removed under reduced
pressure. The residue was diluted with water and extracted with
CHCl3. The organic layer was successively washed with water and
brine, dried with anhydrous Na2SO4, and then concentrated under
reduced pressure. The concentrate was chromatographed on silica
gel (Kanto N60; CHCl3/hexane, 3:1) to give 4c (25%, 293 mg,
0.54 mmol) and 5c (28%, 328 mg, 0.60 mmol). Data for 4c: M.p.
210–212 °C. 1H NMR (400 MHz, CDCl3): δ = 8.48 (d, J = 7.60 Hz,
2 H, ArH), 8.28 (d, J = 7.60 Hz, 2 H, ArH), 6.05 (s, 2 H, ArH),
4.16 (t, J = 6.40 Hz, 4 H, ArOCH2CH2CH2-), 1.95 (quint, J =
6.40 Hz, 4 H, ArOCH2CH2CH2-), 1.56–1.21 (m, 28 H, -CH2-), 0.90
[6] T. Hirose, O. Kawakami, M. Yasutake, Mol. Cryst. Liq. Cryst.
2006, 451, 65–74.
[7] A. J. Fatiadi, J. Chromatography 1965, 20, 319–324.
[8] V. S. Chesnovskii, V. A. Shigalevskii, Zh. Org. Kim. 1986, 22,
1159–1163.
[9] M. Al-Ibramhim, H.-K. Roth, U. Zhokhavets, G. Gobsch, S.
Sensfuss, Solar Energy Material & Solar Cells 2005, 85, 12–20.
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2006, 128, 8549–8558; b) D. M. de Leeuw, M. M. J. Simenon,
A. R. Brown, R. E. F. Einerhand, Synth. Met. 1997, 87, 53–59.
[11] a) The computations were performed with CAChe programs;
b) M. J. S. Dewar, E. G. Zoebisch, E. F. Healy, J. J. P. Stewart,
J. Am. Chem. Soc. 1985, 107, 3902–3909; c) J. J. P. Stewart,
WinMOPAC (version 2), Fujitsu Ltd., Tokyo, Japan, 1998.
[12] The measurements for 4e and 5e were performed with a Bruker
SMART APEX (Saitama University, MALS Center) with Mo-
Kα radiation (λ = 0.71073 Å) at 123 K. The structure was
solved by direct methods and SHELXS-97 and refined by using
SHELXL-97. Hydrogen atoms were located at calculated posi-
tions. Absorption correction was applied by using SADABS;
(t, J = 6.4 Hz, 6 H, -CH CH ) ppm. IR (KBr): ν = 2950, 2920,
˜
2
3
2850, 1640, 1610, 1560, 1340, 1230, 830 cm–1. MS (EI): m/z = 544
[M]+. Data for 5c: M.p. 156–158 °C. 1H NMR (400 MHz, CDCl3):
δ = 8.55 (s, 2 H, ArH), 8.21 (s, 2 H, ArH), 6.03 (s, 2 H, ArH), 4.16
(t, J = 6.40 Hz, 4 H, ArOCH2CH2-), 1.95 (quint, J = 6.40 Hz, 4
H, ArOCH2CH2CH2-), 1.56–1.21 (m, 28 H, -CH2-), 0.90 (t, J =
¯
a) 4e: C22H20O4, Fw 348.38, triclinic, space group P1 (#2), a =
4.3861(2) Å,
79.9992(19)°,
b
β
=
=
8.9381(5) Å,
87.0184(18)°,
c
=
10.9735(7) Å,
77.680(3)°,
α
V
=
=
6.40 Hz, 6 H, -CH CH ) ppm. IR (KBr): ν = 3060, 2920, 1640,
˜
γ
=
2
3
413.85(4) Å3, T = 123(2) K, Z = 1, Dcalcd. = 1.398 gcm–3,
µ(Mo-Kα) = 0.096 mm–1, R = 0.0456 and Rw = 0.1308 for 1821
observed reflections with I Ͼ 2σ from 1448 unique reflections;
b) 5e: C22H20O4, Fw 348.38, triclinic, space group C2/c (#19),
a = 19.452(4) Å, b = 16.127(3) Å, c = 13.725(3) Å, β =
1610, 1560, 1410, 1230, 830 cm–1. MS (EI): m/z = 544 [M]+.
4e: Prepared according to the general procedure. Yield 38%, m.p.
1
254–255 °C. H NMR: δ = 8.47 (d, J = 7.60 Hz, 2 H, ArH), 8.29
(d, J = 7.60 Hz, 2 H, ArH), 6.04 (s, 2 H, ArH), 4.77 [sext, J =
6.00 Hz, 2 H, ArOCH(CH3)2], 1.51 [d, J = 6.00 Hz, 12 H, Ar-
121.88(3)°, V = 3655.9(13) Å3, T = 123(2) K, Z = 8, Dcalcd.
=
4124
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Eur. J. Org. Chem. 2008, 4120–4125