New methacrylic oxazolone and thiazolidinone containing polymers for nonlinear opticalApplications

Article abstract of DOI:10.1080/15421400801926172

Oxazalone and thiazolidinone derivatives were synthesized and their physicochemical properties are determined by absorption, HNMR spectroscopies. The third order nonlinear optical properties of oxazolone and thiazolidinone containing compounds were investigated in solutions using degenerate four wave mixing (DFWM) method at 532 nm.

Full text of DOI:10.1080/15421400801926172

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New Methacrylic Oxazolone
and Thiazolidinone Containing
Polymers for Nonlinear
OpticalApplications
Vitaliy Smokal a , Aleksey Kolendo a , Oksana Krupka
a , Beata Derkowska b , Robert Czaplicki c & Bouchta
Sahraoui c
a Kyiv Taras Shevchenko National University,
Volodymyrska, Kiev, Ukraine
b Institute of Physics, N. Copernicus University,
Grudziądzka, Toruń, Poland
c Laboratory POMA, UMR CNRS, University of Angers,
Angers, France
Version of record first published: 31 Aug 2012.
To cite this article: Vitaliy Smokal , Aleksey Kolendo , Oksana Krupka , Beata
Derkowska , Robert Czaplicki & Bouchta Sahraoui (2008): New Methacrylic Oxazolone
and Thiazolidinone Containing Polymers for Nonlinear OpticalApplications, Molecular
Crystals and Liquid Crystals, 485:1, 1011-1018
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Mol. Cryst. Liq. Cryst., Vol. 485, pp. 263=[1011]–270=[1018], 2008
Copyright # Taylor & Francis Group, LLC
ISSN: 1542-1406 print=1563-5287 online
DOI: 10.1080/15421400801926172
New Methacrylic Oxazolone and Thiazolidinone
Containing Polymers for Nonlinear Optical
Applications
Vitaliy Smokal1, Aleksey Kolendo1, Oksana Krupka1,
Beata Derkowska2, Robert Czaplicki3,
and Bouchta Sahraoui3
1Kyiv Taras Shevchenko National University, Volodymyrska,
Kiev, Ukraine
2Institute of Physics, N. Copernicus University, Grudzia˛dzka,
´
Torun, Poland
3Laboratory POMA, UMR CNRS, University of Angers,
Angers, France
Oxazalone and thiazolidinone derivatives were synthesized and their physico-
chemical properties are determined by absorption, HNMR spectroscopies. The
third order nonlinear optical properties of oxazolone and thiazolidinone contain-
ing compounds were investigated in solutions using degenerate four wave mixing
(DFWM) method at 532 nm.
Keywords: aryl(meth)acrylates; NLO properties; oxazolone; radical polymerization;
thiazolidinone
INTRODUCTION
Thiazolidinone derivatives and benzene oxazolones and their analogs
are known for their biological properties [1–3]. Compounds with
oxazolones ring have exhibited antibacterial[4] as well as antifungal
activities. However, thiazolidinones have shown a wide range of phar-
maceutical properties [5]. These molecules are promising due to their
photophysical properties [6,7].
The authors would like to thank Dr. A. Garbuzova for fruitful discussion. This work
is financially supported by the Ukrainian Ministry of Research no. 0101U002162.
Address correspondence to Vitaliy Smokal, Kyiv Taras Shevchenko National Univer-
sity, Volodymyrska 60, 01033 Kiev, Ukraine. E-mail: smokal@mail.univ.kiev.ua
263=[1011]

264=[1012]
V. Smokal et al.
In the present work, we chose oxazolone and thiazolidinone deriva-
tives, synthesized the methacrylic monomers containing the model
fragments, polymers, co-polymers with methyl methacrylate investi-
gated their spectral characteristics. The third order nonlinear optical
properties of oxazolone and thiazolidinone derivatives have been
investigated in solutions using degenerate four wave mixing (DFWM)
method at 532 nm.
EXPERIMENT
Materials and Characterization Methods
N,N-dimethylformamide (DMF) were vacuum-distilled off from
calcium hydride just prior to use. 2,20-Azobis(isobutyronitrile) (AIBN)
was recrystallized twice from absolute methanol. Methacrylic anhy-
dride and methacryloyl chloride were vacuum-distilled, immediately
before use. Methylmethacrylate (MMA) was dried by distillation under
argon. All other reagents and solvents were commercially available
and used as received.
1H NMR (400 MHz) spectra were recorded on a ‘‘Mercury-400’’ spec-
trometer using DMSO-d6 as solvent. Chemical shifts are in ppm from
the internal standard tetramethylsilane (TMS).
UV-VIS measurements in the 210–600 nm spectral regions were
performed at room temperature in ethanol in quartz cuve
(C ¼ 10ꢀ5 mol=L) with a Perkin-Elmer UV=VIS=NIR Lambda 19
spectrometer.
Synthesis
Oxazolone derivatives were prepared by condensation of different
arylaldehydes with hippuric acid in acetic anhydride, in the presence
of anhydrous sodium acetate as a homogeneous basic catalyst as was
describe previously (Fig. 1) [9].
2-phenyl-4-[[4-acetyloxyphenyl]methylene]-5(4H)-oxazolone (p-1b):
m.p. 168ꢁC, yield: 80%. 1H NMR (400 MHz, DMSO-d6), % (ppm):
=
7.36 (s, 1H, ꢀCH ), 2.44 (s, 3H, CH3), 8.26–8.18 (m, 4H, PhꢀH),
7.3–7.65 (m, 5H, PhꢀH). UV-VIS (ethanol) kmax: 225, 261, 366 nm.
2-phenyl-4-[[3-acetyloxyphenyl]methylene]-5(4H)-oxazolone (m-1b):
ꢁ
1
m.p. 140 C (lemon coloured crystals from AcOH), yield 75%. H NMR
=
(400 MHz, DMSO-d6), % (ppm): 7.32 (s, 1H, ꢀCH ), 2.3 (s, 3H, CH3),
7.21–8.04 (m, 4H, PhꢀH), 7.70–8.15 (m, 5H, PhꢀH). UV-VIS (ethanol)
k
max: 223, 260, 361 nm.

Methacrylic Oxazolone and Thiazolidinone for NLO
265=[1013]
FIGURE 1 Chemical structures of oxazolone and thiazolidine derivatives.
2-phenyl-4-[(4-hydroxyphenyl)methylene]-5(4H)-oxazolone
(p-1a):
m.p. 218ꢁC, yield: 35%. 1H NMR (400 MHz, DMSO-d6), % (ppm):
=
7.22 (s, 1H, ꢀCH ), 10.27 (s, 1H, ꢀOH), 6.88–8.14 (m, 4H, PhꢀH),
7.60–8.13 (m, 5H, PhꢀH). UV-VIS (ethanol) kmax: 258, 383 nm.
2-phenyl-4-[(4-methacryloyloxyphenyl)methylene]-5(4H)-oxazolone
(p-1c): m.p. 170ꢁC, yield 55%. 1H NMR (400 MHz, DMSO-d6), %
=
=
(ppm): 5.89 (s, 1H, CH2 ), 6.34 (s, 1H, CH2 ), 2.06 (s, 3H, ꢀCH3),
7.28–8.18 (m, 4H, PhꢀH), 7.70–8.35 (m, 5H, PhꢀH).
2-phenyl-4-[(3-methacryloyloxyphenyl)methylene]-5(4H)-oxazolone
(m-1c): m.p.: 138ꢁC, yield 76%. 1H NMR (400 MHz, DMSO-d6), %
=
=
(ppm): 5.90 (s, 1H, CH2 ), 6.37 (s, 1H, CH2 ), 2.08 (s, 3H, ꢀCH3),
7.25–8.16 (m, 4H, PhꢀH), 7.67–8.15 (m, 5H, PhꢀH).
(4-hydroxyphenyl)methylene-2-thioxo-4-thiazolidinone (p-2a): 2-thioxo-
4-thiazolidinone (1 g, 0.0075 mol.) in isopropyl alcohol was added to
4-hydroxybenzaldehyde (0.91 g). The reaction mixture was heated
for 2 h on a steam bath 80–90ꢁC and then poured into water. The
resultant solid product was collected, washed with cold ethanol, hot
water, ethanol and then small amount of hexane and then dried to
afford compound p-2a as yellow solid m.p. 283–285ꢁC, yield 80%.
1
=
H NMR (400 MHz, DMSO-d6), % (ppm): 7.49 (s, 1H, ꢀCH ), 10.26
(s, 1H, ꢀOH), 13.52 (s, 1H, ꢀNH), 6.87–7.70 (m, 4H, PhꢀH). UV-VIS
(ethanol) kmax: 242, 292, 395 nm.
(3-hydroxyphenyl)methylene-2-thioxo-4-thiaꢁzolidinone (m-2a) was
1
obtained as described for p-2a, m.p. 250–252 C, yield 75%. H NMR
=
(400 MHz, DMSO-d6), % (ppm): 7.47 (s, 1H, ꢀCH ), 9.68 (s, 1H,
ꢀNH), 6.85–7.27 (m, 4H, PhꢀH). UV-VIS (ethanol) kmax: 252, 276,
380 nm.
(4-acetyloxyphenyl)methylene-2-thioxo-4-thiazolidinone (p-2b): (p-2a)
(1 g) in acetic anhydride (3 ml) was heated on a steam bath 80–90ꢁC.
After 2 h, the mixture was cooled and then poured into water. The
resultant solid product that formed were filtered off, washed with
water and dried. Recrystallization from ethanol alcohol gave yellow

266=[1014]
V. Smokal et al.
ꢁ
1
crystals m.p. 238–240 C, yield 70%. H NMR (400 MHz, DMSO-d6),
=
% (ppm): 7.61 (s, 1H, ꢀCH ), 2.29 (s, 3H, ꢀCH3), 13.75 (s, 1H,
ꢀNH), 7.25–7.50 (m, 4H, PhꢀH). UV-VIS (ethanol) kmax: 240, 266,
377 nm.
(3-acetyloxyphenyl)methylene-2-thioxo-4-thiazolidinone (m-2b) was
obtained as described for (p-2b), m.p. 175–177ꢁC, yield 60%. 1H
=
NMR (400 MHz, DMSO-d6), % (ppm): 7.58 (s, 1H, ꢀCH ), 2.30 (s, 3H,
CH3), 13.73 (s, 1H, ꢀNH), 7.22–7.53 (m, 4H, PhꢀH). UV-VIS (ethanol)
k
max: 239, 264, 374 nm.
4-(methacryloyloxy)benzaldehyde: 4.9 g (0.04 mol) 4-hydroxybenzal-
dehyde and 11.4 ml (0.08 mol) triethylamine in 150 ml of diethyl ether
was cooled to 0ꢁC. To the solution 8.4 g (0.08 mol) of methacryloyl
chloride in 8 ml of diethyl ether was added dropwise in 40 min while
stirring. The precipitated triethylammonium chloride was filtered off
and the filtrate was allowed to stand for 12 h at 4ꢁC. The suspended
matter formed in the solution was separated by filtration. Then the
solvent was evaporated and the residue was dried to give 7.0 g
(90%) of a pale yellow solid.
4-(methacryloyloxyphenyl)methylene-2-thioxo-4-thiazolidinone (p-2c):
(2 g)
4-(methacryloyloxy)benzaldehyde,
2-thioxo-4-thiazolidinone
(2.5 g), anhydrous sodium acetate (0.3 g; 0.2 mol) in 50 ml isopraponol
was heated on a steam bath 80–90ꢁC. After 2 h, the mixture was cooled
and then was poured on ice. The resultant solid product that formed
were filtered off, washed with water and dried. Recrystallization from
ethanol alcohol gave yellow crystals m.p. 195ꢁC, 65%. 1H NMR
=
(400 MHz, DMSO-d6), % (ppm): 5.86 (s, 1H, CH2 ), 6.31 (s, 1H,
=
CH2 ), 2.03 (s, 3H, ꢀCH3), 7.28–7.66 (m, 4H, PhꢀH), 7.62 (s, 1H,
=
ꢀCH ), 13.69 (s, 1H, ꢀNH).
3-(methacryloyloxyphenyl)methylene-2-thioxo-4-thiazolidinone (m-2c)
was obtained as described for (p-2c), m.p. 155ꢁC, yield 60%. 1H
=
NMR (400 MHz, DMSO-d6), % (ppm): 5.87 (s, 1H, CH2 ), 6.33
=
(s, 1H, CH2 ), 2.05 (s, 3H, ꢀCH3), 7.28–7.54 (m, 4H, PhꢀH), 7.6 (s,
=
1H, ꢀCH ), 13.75 (s, 1H, ꢀNH).
Polymerization
The synthesis of homo- and copolymers based on methacrylic mono-
mers and methylmethacrylates (MMA), as a typical polymerization
procedure [8], is discussed below. The polymerization ability of the
new monomer was investigated kinetically for radical homo- and
copolymerization using the dilatometric method. The process was
conducted in 10% DMF solution at 80ꢁC (argon atmosphere, initiator –
AIBN 1%); contractions were measured by KM-6 cathetometer.

Methacrylic Oxazolone and Thiazolidinone for NLO
267=[1015]
SCHEME 1 Synthesis of oxazolone and thiazolidinone derivatives.
The resulting viscous solution was added dropwise into ethanol to
precipitate polymeric materials. Polymers were repeatedly purified
by centrifugal separation from ethanol. The conversion rate was con-
trolled gravimetrically. Monomers conversion during the homopoly-
merization process of (m-1c) was 37% in 260 minutes with
resulting homopolymer (m-1d); (m-2c) was 63% in 240 minutes with
homopolymer (m-2d); (p-2c) was 67% in 261 minutes with homo-
polymer (p-2d). The conversion rate during the copolymerization pro-
cess of (m-1c) with methylmethacrylates was 67% in 390 minutes.
The structure of oxazolone containing copolymer (m-1e) calculated
from 1H NMR data is approximately the same as the structure of
the initial mixture 1:3. (cf. Scheme 1).
RESULTS AND DISCUSSION
Nonlinear optical properties of studied compounds were investigated
using nonlinear transmission and degenerate four wave mixing
(DFWM) measurements at 532 nm in solutions [10,11]. In this experi-
ment, three optical pulses (two pump beams and a probe beam), each
of 30 ps duration produced by Nd:YAG laser and 1 Hz repetition rate,
were obtained by using two beam splitters. The pulses were aligned so
as to coincide within the sample, both temporally and spatially. The
angle between the pump beams and weak-probe beam was about
12ꢁ. Two of these beams interfere inside the sample to form a grating
from which the third beam diffracts to form a phase-conjugate
signal that retraces the probe path. The photodetector and photomul-
tiplier tube, which were fed to a digital storage oscilloscope and linked
to the computer, recorded the incident and phase-conjugate energies,
respectively.
The studied compounds were dissolved in DMF. The solvent produced
signals under the experimental conditions. Third order nonlinear optical
susceptibility of DMF was estimated to be v<3> ¼ 1:28 ꢂ 10ꢀ12 ½esuꢃ.
Carbon disulfide (CS2) was used as reference to calibrate the measure-
<3>
CS2
ment system in DFWM (v
¼ 1:26 ꢄ 10ꢀ12 ½esuꢃ). The thiazolidinone

268=[1016]
V. Smokal et al.
and oxazolone derivatives were contained in 1 mm and 2 mm thick
quartz cuvettes, respectively.
We used the nonlinear transmission measurement to check if stud-
ied compounds possess the two-photon absorption. The coefficient (b)
that corresponds to the imaginary parts of the third order nonlinear
optical susceptibility at 532 nm. For studied compounds we obtained
the transmission curves constant with the incident intensity, the
transmission value being lower than unity, which favors a one-photon
contribution to the absorption. This means that the molecules exhib-
ited only linear absorption at the excitation wavelength, showing that
the third order nonlinear optical susceptibility of these materials has a
real number at 532 nm, so the imaginary parts of the third order
nonlinear optical susceptibility equal zero.
The third order nonlinear optical susceptibilities of studied com-
pounds dissolved in DMF were obtained from the degenerate four
wave mixing measurements. The experimental and theoretical results
of DFWM reflectivity (R) of studied compounds dissolved in DMF are
presented in Figure 2. The DFWM reflectivity (R) was calculated from
the propagation equation of the four beams in interaction taking into
account linear absorption (a) coefficient. The intensity of generated
beam is proportional to the product of intensities of interacting beams.
FIGURE 2 DFWM reflectivity (R) of studied compounds as a function of input
pump intensity.

Methacrylic Oxazolone and Thiazolidinone for NLO
269=[1017]
TABLE 1 The Values of the Linear Absorption Coefficient (a) and
the Absolute Values of the Third Order Nonlinear Optical Sus-
ceptibility (v<3>) of Studied Compounds Dissolved in DMF
Compounds
a ½cmꢀ1
ꢃ
v<3> ½esuꢃ
m-1e
m-1d
p-2d
m-2d
p-2b
m-2b
1.70
1.70
2.23
2.11
2.61
2.48
1.11 ꢄ 10ꢀ12
0.75 ꢄ 10ꢀ12
2.16 ꢄ 10ꢀ13
1.28 ꢄ 10ꢀ13
2.24 ꢄ 10ꢀ13
1.92 ꢄ 10ꢀ13
The DFWM reflectivity (R) can be expressed as follows [10,11]:
ꢀ
ꢁ
2
I4ð0Þ
I3ð0Þ
48p3
n2ck
I1ð0ÞI2ð0Þ expðꢀaLÞ
R ¼
¼
v<3>
ð1Þ
Â
Ã
2
a
p cothðpLÞ þ 2
ꢂ
ꢃ
2
a2
4
48p3 <3>
where p2 ¼
ꢀ
n2ck v
I1ð0ÞI2ð0Þ and a, L, k, and n are the linear
absorption coefficient, the thickness of the sample, wavelength of the
used laser beam and the linear refractive index of the considered
material, respectively.
The best fit of experimental variations of R given by Eq. (1) versus I,
represented by solid lines in Figure 2, led to the estimation of the
absolute value of v<3> (see Table 1).
We can see that the value of third order nonlinear optical suscept-
ibilities for copolymer m-1e is bigger than for homopolymer m-1d
(see Table 1) due to steric factor. We notice that the values of the third
order nonlinear optical susceptibility (v<3>) of p-2b and p-2d are
almost the same. We can also see that the third order nonlinear optical
susceptibility (v<3>) values of the para thiazolidine derivatives p-2b
and p-2d are larger than m- substituent compounds m-2b and
m-2d. We supposed that the behaviour come from different photoi-
somerization processes of investigated compounds.
CONCLUSIONS
We synthesized the novel NLO polymer containing oxazalone and
thiazolidinone moiety. The polymerization ability of the new mono-
mers were investigated kinetically for radical homopolymerization
and copolymerization using the dilatometric method. The NLO effect
of copolymer is higher than the corresponding homopolymer, and
for modeling compounds of methacrilic monomers higher than for

270=[1018]
V. Smokal et al.
polymers due to steric factor. New polymers are great promise for
practical device applications.
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