The synthesis and structure characteristics of two novel azo-quinone derivatives

Article abstract of DOI:10.1081/SCC-100000193

The synthesis of novel LB film materials 2-(4 -hexadecyl-oxyphenylazo)anthraquinone and 2-(4-dodecyloxyphenylazo) anthraquinone is described. These materials were obtained from 2-amino-anthraquinone by azo-coupling with phenol and follwed by Williamson et

Full text of DOI:10.1081/SCC-100000193

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THE SYNTHESIS AND STRUCTURE CHARACTERISTICS
OF TWO NOVEL AZO-QUINONE DERIVATIVES
Li Hai-ying a & Lei Liang-cai a
a Petrochemical Department , Fushun Petroleum Institute , Fushun, 113001, China
Published online: 09 Nov 2006.
To cite this article: Li Hai-ying & Lei Liang-cai (2001) THE SYNTHESIS AND STRUCTURE CHARACTERISTICS OF TWO NOVEL
AZO-QUINONE DERIVATIVES, Synthetic Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 31:1, 155-158, DOI: 10.1081/SCC-100000193
To link to this article: http://dx.doi.org/10.1081/SCC-100000193
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SYNTHETIC COMMUNICATIONS, 31(1), 155–158 (2001)
THE SYNTHESIS AND STRUCTURE
CHARACTERISTICS OF TWO NOVEL
AZO-QUINONE DERIVATIVES
Li Hai-ying∗ and Lei Liang-cai
Petrochemical Department, Fushun Petroleum Institute,
Fushun 113001, China
ABSTRACT
The synthesis of novel LB film materials 2-(4-hexadecyl-
oxyphenylazo)anthraquinone and 2-(4-dodecyloxyphenylazo)
anthraquinone is described. These materials were obtained from
2-amino-anthraquinone by azo-coupling with phenol and follwed
by Williamson etherification of phenolic hydroxyl group with alkyl
bromide. The structures were confirmed by NMR, MS, FT-IR tech-
niques and elemental analysis.
The Langmuir-Blodgett (LB) method is effective for preparing organic ultra-
thin films with a fine-layered structure and specific properties (1). Thickness of
the ultra-thin films can be controlled on a molecular scale by designing the size
of the molecule. Some interesting phenomena are observed by attaching different
functionalgroups. ThestabilityoforderedLBfilmsdependsonmolecule-molecule
interaction, substrate-molecule interaction, and their relative strength (2). One
can stabilize the structures of the highly organized films through molecular-level
designing of the substrate surfaces.
∗ To whom correspondence should be addressed.
155
Copyright ꢀ 2001 by Marcel Dekker, Inc.
www.dekker.com
C

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HAI-YING AND LIANG-CAI
Scheme 1.
The highly organized LB films have attracted much attention during the past
two decades because of their prospective application in constructing molecular
electronic devices (3–5). In this study, we synthesized two novel compounds with
a long alkyl chain, an electro-chromic quinone and a photo-chromic azo region
in a conjugated system. We expect that aromatic interactions between π system
and hydrophobic interactions between alkyl chains will effectively improve the
ordered film structure and its stability. Furthermore, the azo functional group can
interconvert between the anti- and syn-form and give rise to electrochemical redox
reaction. The quinone functional group can undergo reversible red-oxidation. In
other words, the individual chemical states can be achieved and interconvert by
control of electrochemical and photochemical parameters. LB film from molecules
with an azo-quinone group has the potential of information storage and readout
process.
These two azo-quinone derivatives, 2-(4-hexadecyloxyphenylazo)anthra-
quinone and 2-(4-dodecyloxyphenylazo)anthraquinone, can be prepared from
2-aminoanthraquinone by azo-coupling with phenol, followed by Williamson
etherification of phenolic hydroxyl group with alkyl bromide.
EXPERIMENTAL
All commercially available reagents were purchased. NMR spectra were
recorded in CDCI3 solution using TMS as internal standard on an ARX-400
instrument (Bruke Co. Ltd.). IR spectra were obtained in a JASCO-FTIR-430

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TWO NOVEL AZO-QUINONE DERIVATIVES
157
spectrometer with potassium bromide plates. MS data were measured with a VG
ZAB-HS instrument and the ultimate analysis data was given from a CARLO
ERDA 1106 instrument (Italy). Melting point was recorded in a WRS-1 digital
melting point apparatus (China).
2-(4-Dodecyloxphenylazo)anthraquinone
Conc. Sulfuric acid (12 mL) was added dropwise to 2-aminoantraquinone
(2.3 g) in a 100-mL Erlenmeyer flask. The mixture was stirred for 15 min at room
temperature. Then sodium nitrite (0.83 g) in water (5 mL) was added dropwise
and the mixture stirred for 45 min. The reaction mixture was poured slowly to a
solution of phenol (0.94 g) and sodium hydroxide (9.5 g) in distilled water (50 mL).
The mixture was stirred for 1 h, acidified with acetic acid (50%), and the formed
precipitate collected by filtration. The filter cake was washed with water and dried
in vacuo to give 2-(4-hydroxyphenylazo)anthraquinone (2.7 g). Yield: 82%. 2-(4-
Hydroxyphenylazo)-anthraquinone (1.64 g) in THF (10 mL) was added dropwise
to the mixture of 1-bromododecane (2.5 g) and sodium hydroxide (0.4 g) and THF
(25 mL). The mixture was refluxed until complete reaction. After cooling to room
temperature, the mixture was extracted with either (3 × 100 mL) and the combined
extracts washed with saturated brine. The solvent was evaporated under reduced
pressure and the residue was crystallized from the mixture of ether and THF (5:1),
obtaining 2-(4-dodecyloxypbenylazo)anthraquinone (1.9 g) as a reddish brown
solid. Yield: 76.6%. mp: 88.8◦–89.5◦C. MS (EI) m/e: 496(M+). Anal. calcd: C,
1
77.38; H, 7.31; N, 5.64. Found: C, 77.39; H, 7.25; N, 5.58. H NMR (CDCI3)
δ: 0.87–0.90 (t, 3H, J = 6.8, -CH3); 1.27–1.37 (m, 16H, -(CH2)-8); 1.47–1.51
(m, 2H, -CH2CH2CH2O-); 1.82–1.87 (m, 2H, -CH2CH2O-); 4.06–4.09 (t, 2H,
ꢁ
J = 6.5, -CH2O-); 7.03–7.05 (dd, 2H, J = 7.0 and J = 2.0, Hββ ); 7.82–7.84 (m,
ꢁ
ꢁ
2H, HAA ); 7.99–8.02 (dd, 2H, J = 7.0 and J = 2.0, Hαα ); 8.22–8.25 (dd, 1H,
ꢁ
J = 8.2 and J = 2.0, H3); 8.34–8.38 (m, 2H, HBB ); 8.44–8.47 (d, 1H, J = 8.3,
H4); 8.75 (d, 1H, J = 1.95, H1).
2-(4-Hexadecyloxyphenylazo)anthraquinone
Prepared similarly as described above. mp: 93.2◦–94.4◦C. MS (EI) m/e:
552 (M+). Anal. calcd: C, 78.22; H, 8.02; N, 5.07. Found: C, 78.11; H, 8.07; N,
4.99. 1H NMR (CDCI3) δ: 0.90–0.86 (t, 3H, J = 6.8, -CH3); 1.26–1.37 (m, 26H,
-(CH2)-13); 1.80–1.85 (m, 2H, -CH2CH2O-); 4.06–4.09 (t, 2H, J = 6.5, -CH2O-);
ꢁ
ꢁ
7.03–7.05 (2H, dd, J = 7.0 and J = 2.0, Hββ ); 7.82–7.84 (m, 2H, HAA ); 7.99–8.02
ꢁ
(dd, 2H, J = 7.0 and J = 2.0, Hαα ); 8.22–8.25 (dd, 1H, J = 8.3 and J = 2.0, H3);
ꢁ
8.34–8.38 (m, 2H, HBB ); 8.44–8.47 (d, 1H, J = 8.3, H4); 8.75 (d, 1H, J = 1.95,

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158
HAI-YING AND LIANG-CAI
H1). IR (KBr) cm−1: 2917 (νC-H), 2855 (νC-H), 1673 (νC O), 1590 (νφ), 1472
=
(δH-C-H ), 1300 (νas,-φ-O-C), 1250 (νs,-φ-O-C), 1147 (νφ-N), 708 (νφ-H).
REFERENCES
1. Buchel, M.; Sekkat, Z.; Paul, S.; Weichart, B.; Menzel, H., Knoll, W. Langmuir
1995, 11, 4460.
2. Miller, C.J.; Cuendet, P.; Gratzel, M. J. Phys. Chem. 1991, 95, 877.
3. Schildkraut, J.S.; Penner, T.L.; Willand, C.S.; Ulman, A. Opt. Lett. 1988, 13,
134.
4. Li, H.; Liu, Z. Synthetic Comm. 1998, 20, 3779.
5. Yamada, S.; Nedano, T.; Matsuo, T. Thin Solid Film 1994, 245, 196.
Received April 2, 2000

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