Optically active 4-(4-{4-[(2S)-(2-methylbutoxy)]benzoyloxy}-phenyldiazenyl)benzaldehyde

Article abstract of DOI:10.1134/S1070428015020098

4-(4-{4-[(2S)-(2-methylbutoxy)]benzoyloxy}phenyldiazenyl)benzaldehyde was synthesized and its structure was identified.

Full text of DOI:10.1134/S1070428015020098

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2015, Vol. 51, No. 2, pp. 195–197. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © S.A. Kuvshinova, V.A. Burmistrov, I.V. Novikov, V.V. Aleksandriiskii, O.I. Koifman, 2015, published in Zhurnal Organicheskoi
Khimii, 2015, Vol. 51, No. 2, pp. 207–209.
Optically Active 4-(4-{4-[(2S)-(2-Methylbutoxy)]benzoyloxy}-
phenyldiazenyl)benzaldehyde
S. A. Kuvshinovaa, V. A. Burmistrova,b, I. V. Novikova,
V. V. Aleksandriiskiia,b, and O. I. Koifmana,b
a Ivanovo State University of Chemistry and Technology, Research Institute of Macroheterocyclic Compounds,
Sheremetevskii pr. 7, Ivanovo, 153000 Russia
e-mail: sofya.kuv@yandex.ru
b Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia
Received October 24, 2014
Abstract—4-(4-{4-[(2S)-(2-methylbutoxy)]benzoyloxy}phenyldiazenyl)benzaldehyde was synthesized and its
structure was identified.
DOI: 10.1134/S1070428015020098
Among the multitude of compounds exhibiting me-
somorphism the class of thermotropic liquid crystals of
cholesteric type is especially interesting. A unique
property of these crystals to reflect selectively the light
in the visible region makes them indispensable in
designing modern temperature sensors for electronics
and medicine [1, 2]. The possibility of local changes in
optical properties of cholesteric mesogens under the
action of light or electric field provides the opportunity
to use them as photoactive materials for reversible (and
irreversible) colored information storage in the systems
possessing optical memory for display technology,
photonics, optoelectronics, and holography [3]. A
promising application of the mesophase of the chole-
steric type is the analysis of the optical isomers of organic
compounds by Gas Liquid Chromatography method [4].
Besides the individual compounds the chiral ne-
matic phase may be formed of nematic mixtures either
with cholesterol and chiral nematics or with optically
active non-mesogenic additive. The number of chiral
additives already synthesized for inducing helically
stranded mesophase is fairly large [5–7].
We formerly synthesized, characterized supramole-
cular mesogenic 4-[4-(ω-hydroxyalkoxy)phenyldia-
zenyl]benzaldehydes, and investigated their mesomor-
phic properties [8]. 4-[4-(3-Hydroxypropoxy)phenyl-
diazenyl]benzaldehyde (1) exhibits polymorphism
(Fig. 1) and is a highly efficient stationary phase for the
gas chromatography [9].
In order to induce the chiral nematic phase in the
mesophase of compound 1 we prepared optically
HO
O
N
O
N
C
H
C
Sc
N
1
136.3ºC
96.3ºC
145.0ºC
Fig. 1. Phase transition temperature of 4-[4-(3-hydroxypropoxy)phenyldiazenyl]benzaldehyde 1.
195

KUVSHINOVA et al.
196
Scheme 1.
KOH,
CH3
CH3
H2O
COOH
*
*
CH3 CH2 CH CH2
O
COOH
CH2
HO
CH3
CH CH2Br +
EtOH
CH3
*
SOCl2
CH3 CH2 CH CH2
O
COCl
+
HO
N
N
CHO
CH3
*
O
CH2Cl2,
Py
CH2 CH CH2
O
C
CH3
O
N
N
CHO
2
active 4-(4-{4-[(2S)-(2-methylbutoxy)]benzoyloxy}-
phenyldiazenyl)benzaldehyde (2) by the condensation
of 4-[(S)-2-methylbutoxy]benzoyl chloride [10] and 4-
[4-(hydroxy)phenyldiazenyl]benzaldehyde [11] in
dichloromethane in the presence of pyridine. The
Note that mesogens 1 and 2 contain in their
structure a reactive aldehyde group providing a
possibility to perform the condensation of these
compounds with pyrrole in order to prepare
tetraphenylporphins for designing multipurpose
functional materials underlain by macroheterocycles.
1
structure of compound 2 was established from Н
NMR spectrum and elemental analysis (Scheme 1).
(a)
The polarization thermomicroscopic study was
carried out on the optically active aldehyde 2 and the
mixture containing 90 wt % of compound 1 and 10 wt %
of aldehyde 2 obtained by stirring the components
mixture in the isotropic liquid state over 1 h. It
demonstrated that the synthesized aldehyde
2
possessed no liquid-crystalline properties; the mixture
of aldehydes 1 and 2 at the mentioned components
ratio melted at 91.0°С forming a smectic phase that at
121.8°С transformed into chiral nematic phase with
a characteristic “finger prints” texture (Fig. 2). The
transition of the binary system into the isotropic
liquid state was observed at 143.0°С. Thus optically
active aldehyde 2 induced a chiral nematic phase
in the mesophase of the supramolecular liquid-
crystalline compound 1 in a sufficiently wide tem-
perature range.
(b)
EXPERIMENTAL
Recording of 1Н NMR spectra and measuring of the
chemical shifts was performed on a high resolution
spectrometer Bruker Avance III at operating frequency
500 МHz. The proton stabilization was carried out by
CDCl3. The chemical shifts were measured with
respect to HMDS. The phase state of the synthesized
mesogen and the binary mixture was studied using a
microscope Polam Р211 equipped with a heating
block. The microscope was also equipped with a video
camera KPC-S230CWX (3.6 mm) that made it pos-
Fig. 2. Photo of textures of smectic (а) and chiral nematic
(b) phases of the binary mixture of 90 wt % of
supramolecular mesogen 1 and 10 wt % of optically active
aldehyde 2.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 2 2015

OPTICALLY ACTIVE 4-(4-{4-[(2S)-(2-METHYLBUTOXY)]BENZOYLOXY}...
197
sible to follow the dynamics of the phase transitions
and to photograph the phase textures at any given
moment. The temperature was measured with the
accuracy ±0.1°С.
the Ministry of Education and Science of the Russian
Federation.
REFERENCES
4-(4-{4-[(2S)-(2-Methylbutoxy)]benzoyloxy}-phe-
nyldiazenyl)benzaldehyde (2). A solution of 1.31 g
(5.8 mmol) of 4-[(2S)-2-butoxy]benzoyl chloride in
15 mL of dichloromethane was added dropwise to a
solution of 1.3 g (5.8 mmol) of 4-[4-(hydroxy)phenyl-
diazenyl]benzaldehyde in 30 mL of dichloromethane
and 5 mL of pyridine. The mixture was boiled for 12 h,
cooled, then filtered, and the filtrate was evaporated.
The residue was transferred into 150 mL of 3%
solution of sodium hydrogen carbonate, the mixture
was stirred for 1 h, then filtered, and the precipitate
was washed with water. The reaction product was
purified by recrystallization from hexane and ethanol.
Yield 2.1 g (87%), orange-red bright crystals, mp
110.8°С (EtOH). 1Н NMR spectrum, δ, ppm: 0.99 t (3Н,
СН3, J 7.48 Hz), 1.08 d (3Н, СН3, J 6.90 Hz), 1.32 q
(1Н, СН2, J 6.90 Hz), 1.62 q (1Н, СН2, J 6.90 Hz),
1.93 m (1Н, СН), 3.86 m (1Н, ОСН2), 7.02 d (2НAr, J
8.70 Hz), 7.43 d (2НAr, J 8.70 Hz), 8.06 s (4НAr), 8.07
d (2НAr, J 7.50 Hz), 8.17 d (2НAr, J 8.70 Hz), 10.13 s
(1Н, СНО). Found, %: C 71.31; H 5.06; N 6.18.
C25H24N2O4. Calculated, %: C 72.12; H 5.77; N 6.73.
1. Gautherie, M., J. Phys., 1969, vol. 30, p. 4.
2. Moller, U. and Bosjen, J., Cancer Res., 1975, vol. 35,
p. 3116.
3. Bobrovsky, A.Yu. and Shibaev, V.P., J. Mater. Chem.,
2009, vol. 19, p. 366.
4. Onuchak, L.A., Arutyunov, Yu.I., Kuraeva, Yu.G.,
Burmatnova, T.S., Burmistrov, V.A., Kuvshinova, S.A.,
and Litov, K.M., RF Patent 2528126, 2014; Byull.
Izobret., 2014, no. 25.
5. Fukuda, K., Suzuki, H., and Ni, J., Jpn. J. Appl. Phys.,
2007, vol. 46, p. 5208.
6. Thompson, M.P. and Lemieux, R.P., J. Mater. Chem.,
2007, vol. 17, p. 5068.
7. Witkiewicz, Z., Oszczudłowski, J., and Repelewicz, M.,
J. Chrom. A., 2005, vol. 1062, p. 155.
8. Kuvshinova, S.A., Zav’yalov, A.V., Koifman, O.I.,
Aleksandriiskii, V.V., and Burmistrov, V.A., Russ. J. Org.
Chem., 2004, vol. 40, p. 1113.
9. Kuvshinova, S.A., Burmistrov, V.A., Fokin, D.S.,
Blokhina, S.V., and Koifman, O.I., Russ. J. Anal. Chem.,
2009, vol. 64, p. 505.
10. Hu, J.-Shi, Zhang, B.-Y., and Zhou, A.-J., J. Appl.
Polymer. Sci., 2006, vol. 100, p. 4234.
11. Burmistrov, V.A., Kareev, V.Yu., Korzhenevskii, A.B.,
and Koifman, O.I., Izv. Vuzov, Ser. Khim. i Khim.
Tekhnol., 1986, vol. 29, p. 34.
The study was carried out under the financial
support of the Russian Scientific Foundation (contract
no. 14-23-00204). The thermomicroscopic studies
were performed in the framework of State Contract of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 2 2015