Synthesis of Bis-Thiazolidinones Using Chitosan-attached Nano-CuFe2O4 as an Efficient and Retrievable Heterogeneous Catalyst

Article abstract of DOI:10.1002/jccs.201700106

The preparation of bis-thiazolidinones has been achieved by a one-pot condensation reaction of araldehydes, ethylenediamine, and 2-mercaptoacetic acid in the presence of nano-CuFe₂O₄@chitosan under reflux conditions in toluene. The c

Full text of DOI:10.1002/jccs.201700106

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Article
Synthesis of Bis-Thiazolidinones Using Chitosan-attached Nano-CuFe2O4 as an
Efficient and Retrievable Heterogeneous Catalyst
a
Javad Safaei-Ghomi, Hossein Shahbazi-Alavia,b and Seyed Hadi Nazemzadeha
*
aDepartment of Organic Chemistry, Faculty of Chemistry, University of Kashan, Kashan, Iran
bYoung Researchers and Elite Club, Kashan Branch, Islamic Azad University, Kashan, Iran
(Received: March 23, 2017; Accepted: July 6, 2017; DOI: 10.1002/jccs.201700106)
The preparation of bis-thiazolidinones has been achieved by a one-pot condensation reaction of
araldehydes, ethylenediamine, and 2-mercaptoacetic acid in the presence of nano-CuFe2O4@chito-
san under reflux conditions in toluene. The catalyst was characterized by powder X-ray diffraction
(XRD), scanning electronic microscopy (SEM), vibrating sample magnetometer (VSM) measure-
ments, thermal gravimetric analysis (TGA), and FT-IR spectroscopy. This method provides sev-
eral advantages including excellent yields, wide range of products, reusability of the catalyst, and a
low amount of the catalyst.
Keywords: Nano-CuFe2O4@chitosan; Bis-thiazolidinones; Ethylenediamine; 2-Mercaptoacetic
acid; One-pot synthesis.
magnetic nanoparticles (MNPs) can be functionalized
easily through appropriate surface modifications to ena-
ble the loading of a diverse required functionalities.18,19
Here we report the synthesis of bis-thiazolidinones by
the one-pot pseudo-five-component condensation of
araldehydes, ethylenediamine, and 2-mercaptoacetic
acid with nano-CuFe2O4@chitosan as a reusable and
robust heterogeneous catalyst under reflux conditions in
toluene (Scheme 1).
INTRODUCTION
Thiazolidinones show biological properties such as
anticancer,1 antiviral,2 antibacterial,3 antituberculosis,4
and anti-AIDS5 activities. The preparation of bioactive
compounds from readily accessible starting materials
using one-pot multicomponent reactions (MCRs) has
been attracting significant interest.6,7 Recently, reports
have appeared on synthesis of bis-thiazolidinones in the
presence of the catalysts such as HClO4-SiO2,8 zeolite,9
ChCl (choline chloride)/urea-based ionic liquid,10 and
ZnCl2.11 Despite the availability of these methods, there
remains adequate interest to find new routes for effi-
cient, high-yielding, and mild approaches to achieve
such systems. The eco-compatibility and employability
of MCRs increase when theMCRs are used in associa-
tion with a heterogeneous catalyst.12–14 Chitosan is a
biopolymer that can be used as a green catalyst in many
reactions.15–17 The presence of both hydroxyl and
amino groups in chitosan makes it useful as an efficient
catalyst. Ideally, utilizing environmental and green cat-
alysts that can be simply recycled at the end of reac-
tions has obtained significant attention in recent years.
Magnetic materials have emerged as a suitable group of
RESULTS AND DISCUSSION
In the beginning, CuFe2O4 NPs were primed using
coprecipitation, and oleic acid was used to prevent the
agglomeration among the NPs. For preparing the
chitosan-CuFe2O4 NPs, chitosan was first coated on the
surface of the NPs through physical absorption; then
glutaraldehyde was used to cross-link the chitosan, and
the CuFe2O4-chitosan NPs were obtained. A schematic
of the formation of the CuFe2O4-chitosan NPs is shown
in Scheme 2.
The X-ray diffraction (XRD) patterns of nano-
CuFe2O4@chitosan are shown in Figure 1. The crystal-
lite size diameter (D) of the nano-CuFe2O4-chitosan
was calculated using the Debye–Scherrer equation (D =
Kλ/βcosθ), where FWHM (full-width at half-maximum)
is in radians and θ is the position of the maximum of
heterogeneous catalysts owing to their numerous appli-
cations in synthesis and catalysis. The surface of
*Corresponding author. Email: safaei@kashanu.ac.ir
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Article
Safaei-Ghomi et al.
S
CHO
O
R
nano-CuFe2O4@Chitosan
O
N
H2N
+
+
O
NH2
N
OH
HS
PhMe
reflux
R
R
S
3
1
2
4
Scheme 1. Synthesis of bis-thiazolidinones using nano-CuFe2O4@chitosan.
the diffraction peak. K is the so-called shape factor,
which usually takes a value of ~0.9, and λ is the X-ray
wavelength. The pattern agrees well with the reported
Figure 3 shows the Fourier transform infrared
(FT-IR) spectrum of (a) chitosan, (b) CuFe2O4 NPs,
and (c) nano-CuFe2O4-chitosan. The FT-IR spectrum
of chitosan (Figure 3(a)) displays a broad band at
~3400 cm−1, which corresponds to the stretching vibra-
tions of O–H and N–H groups. Peaks appearing at
2923 and 2855 cm−1 are the characteristic of C–H
stretching vibrations. The band at 1634 cm−1 is
assigned to the N–H bending vibration, and bands at
1375–1450 cm−1 are assigned to the C–H bending
vibration in chitosan. The band at 1084 cm−1 displays
the stretching vibrations of the C–O bond. The bands
pattern
for
nano-CuFe2O4-chitosan
(JCPDS
no. 34–0425). The average particle size was estimated
by applying the Scherrer formula to the highest inten-
sity peak. An average size of ~35–38 nm was obtained.
In order to investigate the morphology and parti-
cle size of the nanoparticles, the scanning electron
microscopy (SEM) image of nanoparticles is presented
in Figure 2. The SEM image shows particles with dia-
meters in the range of nanometers.
OH
OH
OH
O
OH
O
R
O
O
OH
O
HO
HO
HO
O
HO
O
O
NH2
NH2
NH2
O
O
R
oleic acid
OH
= R
n
O
=
chitosan
=
O
R
O
R
O
OH
R
O
O
O
R
O
O
OH
O
O
O
O
H-O
H-O
O
glutaraldehyde
R
O
=
H-O
H-O
N
O
O
O
NH2
O
O
R
R
O
N
HO
O
OH
O
OH
Oleic acid
Chitosan
CuFe2O4
Scheme 2. Schematic illustration of the formation of CuFe2O4-chitosan NPs.
2
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Synthesis of Bis-Thiazolidinones
The magnetic properties of the nanoparticles were
characterized using a vibrating sample magnetometer
(VSM). Magnetic measurement shows that nano-
CuFe2O4 and nano-CuFe2O4-chitosan have saturation
magnetization values of 39.01 and 22.52 emu/g, respec-
tively (Figure 4). These results indicate that the catalyst
can be easily separated and recovered by an external
magnetic field.
The thermal behavior of the magnetic nanocata-
lyst was investigated by thermogravimetry analysis
(TGA). The TGA curve of the nano-CuFe2O4-chitosan
shows the mass loss of the organic materials as it
decomposes upon heating (Figure 5). The initial weight
loss from the catalyst occurs in the range 25–200ꢀC,
which could be assigned to the loss of bound water or
physically adsorbed solvent. The next TGA peak corre-
sponds to a weight loss of 14% in the range 200–700ꢀC,
which is attributed to the decomposition of the organic
species. Thus, the catalyst is stable up to 200ꢀC.
To examine the effects of varying the catalyst and the
reaction time for the synthesis of bis-thiazolidinones, the
condensation reaction of 4-chlorobenzaldehyde (2 mmol),
ethylenediamine (1 mmol), and 2-mercaptoacetic acid
(2 mmol) was selected as a model. Yields were determined
in the presence of MgO NPs, CuI NPs, Fe3O4 NPs, chito-
san, and nano-CuFe2O4@chitosan, and the results are
shown in Table 1. Nano-CuFe2O4@chitosan gave the best
yields in the shortest time, and a very good yield of 86%
was obtained with 5 mg of the catalyst, which did not
improve further by increasing it to 7 mg. A reaction run in
the absence of any catalyst gave a yield of only 9%
(entry 1).
Fig. 1. XRD patterns of nano-CuFe2O4@chitosan.
at 800–900 cm−1 display the bending vibration of the
N–H bond.
From the FT-IR spectrum in Figure 3(b), two
absorption bands at ~400–600 cm−1 were observed,
which correspond to the octahedral and tetrahedral
sites of the positive ions of CuFe2O4, respectively. The
higher absorption band at 606 cm−1 corresponds to the
intrinsic vibrations of tetrahedral complexes, and the
lower absorption band at 436 cm−1 is attributed to the
vibrations of octahedral complexes.18 The broad
absorption band at 3399 cm−1 corresponds to hydroxyl
groups stretching vibrations, while that at 1628 cm−1 is
due to the bending of H2O adsorbed on the surface of
CuFe2O4 NPs.
Figure 3(c) reveals the integration of CuFe2O4
NPs and chitosan in the nano-CuFe2O4-chitosan. The
amount of loading of nano-CuFe2O4 on chitosan was
provided by inductively coupled plasma (ICP) spectros-
copy, and the loading amount of nano-CuFe2O4 on
chitosan was calculated to be 52.78 wt %.
The results show that the present catalytic method is
extendable to a wide variety of substrates to create a library
of a variety of oriented bis-thiazolidinones (Table 2).
Owing to the presence of 2 and 2’ equivalent stereo-
genic centers, bisthiazolidinones can be obtained as rac.
2R,2’R/2S,2’S and 2R,2’S-meso isomers. These bisthiazo-
lidinones have been obtained, as previously reported, by
the reaction of mercaptoacetic acid with N,N’-dibenzyli-
denethylendiamines.20,21 After work-up, the crude mix-
ture of isomers was separated by silica gel column
chromatography (diethyl ether/petroleum ether in varia-
ble ratio mixtures). In general, the meso isomers eluted
more slowly than the corresponding racemates. The race-
mate isomer 4f was obtained in higher yields than the
meso isomer 4f (81% for the rac. isomer 4f, and 19% for
Fig. 2. SEM image of nano-CuFe2O4-chitosan.
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Article
Safaei-Ghomi et al.
Fig. 5. TGA curve of nano-CuFe2O4-chitosan.
diastereotopic proton Ha (−N-CHaHb-CHaCHb-N-) of
the ethylene fragment. This last proton Ha (−N-CHaHb-
CHaCHb-N-) displayed a doublet of doublets or a multi-
plet at δ 2.675–2.634 ppm because of its interaction with
the germinal proton Hb (−N-CHaHb-CHaCHb-N-) and
the proton HB (−CO-CHAHB-S) at C-5. The Hb proton
(−N-CHaHb-CHaCHb-N-) at the aliphatic chain suf-
fered the anisotropic effect from the near amide group or
aryl substituents and it shifted down field at δ3.773–-
3.732 ppm and overlapping with HB or HA (−CO-
CHAHB-S) as a multiplet. These germinal protons of each
methylene group reside in magnetically nonequivalent
environments.20,21 H NMR of product 4f is shown in
Figure 6.
Fig. 3. FT-IR spectrum of (a) chitosan, (b) CuFe2O4
NPs, and (c) nano-CuFe2O4-chitosan.
1
the meso isomer 4f). The H NMR spectra of the com-
pounds 4a-4j displayed a doublet of doublets at δ
3.917–3.870 ppm due to the methylene proton HA at C-5
(−CO-CHAHB-S) because of its interaction with the
geminal proton HB at C-5 (−CO-CHAHB-S) and the
proton at the chiral C-2 (S-CHAr-N); doublet of doublets
at δ 3.574–3.527 ppm due to the methylene proton HB at
C-5 (−CO-CHAHB-S) because of its interaction with the
geminal proton HA (−CO-CHAHB-S) and
a
The reusability of the heterogeneous catalyst was
explored using the model reaction system under the opti-
mized conditions. After completion of the reaction, the
magnetic nanocatalyst was easily and efficiently separated
from the product by an external magnetic field. The
nano-CuFe2O4-chitosan was washed 3–4 times with etha-
nol and dried at room temperature for 5 h. The separated
catalyst could be used for five cycles. The reusability of
the nano-CuFe2O-chitosan catalyst was examined, and it
was found that product yields decreased to a small extent
on each reuse (run 1, 86%; run 2, 86%; run 3, 85%; run 4,
85%; run 5, 85%).
A probable mechanism for the synthesis of bis-
thiazolidine derivatives using nano-CuFe2O4-chitosan, is
shown in Scheme 3. The mechanism involves a primary
imine intermediate formation followed by the attack of
the sulfur atoms of the 2-mercaptoacetic acid on the acti-
vated imine groups followed by intramolecular cycliza-
tion with the elimination of H2O, giving rise to the
Fig. 4. VSM curve of (a) CuFe2O4 NPs, and
(b) nano-CuFe2O4-chitosan.
4
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Synthesis of Bis-Thiazolidinones
Table 1. Optimization of the reaction conditionsa
Entry
Solvent (reflux)
Toluene
Catalyst (amount)
Time (min)
Yield%b
1
2
3
4
5
6
7
8
No catalyst
300
250
210
240
180
200
200
200
200
100
100
100
90
9
42
54
30
55
38
50
64
65
56
65
69
82
86
86
DMF
MgO NPs (7 mol%)
CuI NPs (4 mol%)
Fe3O4 NPs (4 mol%)
CuO NPs (6 mol%)
Chitosan (15 mg)
Chitosan (15 mg)
Chitosan (15 mg)
Chitosan (20 mg)
Nnano-CuFe2O4@chitosan (5 mg)
Nano-CuFe2O4@chitosan (5 mg)
Nano-CuFe2O4@chitosan (5 mg)
Nano-CuFe2O4@chitosan (3 mg)
Nano-CuFe2O4@chitosan (5 mg)
Nano-CuFe2O4@chitosan (7 mg)
Toluene
Toluene
Toluene
EtOH
DMF
Toluene
Toluene
EtOH
CH3CN
DMF
Toluene
Toluene
Toluene
9
10
11
12
13
14
15
90
90
a Reaction conditions: a mixture of 4-chlorobenzaldehyde (2 mmol), ethylenediamine (1 mmol), 2-mercaptoacetic acid (2 mmol)
and the catalyst for various times.
b Isolated yield.
cyclized product bis-thiazolidines. In this mechanism, the
free hydroxyl and amino groups distributed on the sur-
face of chitosan-supported nano-CuFe2O4 activate the
C=O, C=N, and S–H groups through hydrogen
bonding,22 for better reaction with the nucleophiles.
KBr plates. Powder XRD was carried out on a Philips dif-
fractometer (X’pert) with monochromatized Cu Kα radia-
tion (λ = 1.5406 Å). Microscopic morphology of products
was visualized by SEM (QBSD). TGA curves are recorded
using a V5.1A DUPONT 2000 instrument. The magnetic
property of magnetite nanoparticles was measured with a
VSM (Meghnatis Daghigh Kavir Co.; Kashan Kavir;
Iran) at room temperature.
EXPERIMENTAL
Materials and methods
1H NMR and 13C NMR spectra were recorded on a
Bruker Avance-400 MHz spectrometer in the presence of
tetramethylsilane as internal standard. The IR spectra were
recorded on an FT-IR Magna 550 apparatus using with
General procedure for the preparation
of nano-CuFe2O4@chitosan
For preparation of nano-CuFe2O4@chitosan, chit-
osan (0.5 g) in 100 mL of 2.0 wt % acetic acid solution,
Table 2. Yields of a series of bis-thiazolidinones (racemate as major product) 4a–ja
Entry
Aldehyde
Product
Time (min)
Yield%b
m.p. (ꢀC)Ref
m.p. (ꢀC )
1
2
3
4
5
6
7
8
9
4-Cl-C6H4
2-Cl-C6H4
C6H5
4-NO2-C6H4
3-NO2-C6H4
Pyridin-2-yl
Pyridin-3-yl
Pyridin-4-yl
4-CH3-C6H4
4-Isopropyl-C6H4
4a
4b
4c
4d
4e
4f
4g
4h
4i
90
93
94
90
90
93
95
93
98
100
86
84
82
87
83
83
78
80
77
75
285–28820
150–152
143–145
155–157
164–166
222–224
170–172
191–193
221–223
158–160
163–165
210–21120
152–1558
–
–
167–16921
198–20021
224–22521
–
10
4j
–
a Reaction conditions: a mixture of araldehyde (R = various) (2 mmol) and ethylenediamine (1 mmol), 2-mercaptoacetic acid
(2 mmol) and nano-CuFe2O4@chitosan (5 mg) in toluene (5 mL) was refluxed for various times.
b Isolated yield.
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Safaei-Ghomi et al.
General procedure for the preparation
of bis-thiazolidinones
A mixture of aldehydes (2 mmol), ethylenediamine
(1 mmol), 2-mercaptoacetic acid (2 mmol), and 5 mg of
nano-CuFe2O4@chitosan in toluene (5 mL) was
refluxed. The reaction was monitored by TLC. After
completion of the reaction, the nanocatalyst could be
easily separated using an external magnet. The solvent
was evaporated, and the crude mixture was separated
by silica gel column chromatography (diethyl ether/
petroleum ether) to get the pure product.
Spectral data of new products
3,3’-(Ethane-1,2-diyl)bis(2-(4-nitrophenyl)thiazoli-
din-4-one) (4d). Yellow solid; m.p164–166ꢀC, IR (KBr)
Fig. 6. 1H NMR of product 4f.
1
cm−1: 2932, 1672, 1523; H NMR (400 MHz, DMSO-
d6): 2.65–2.74 (m, 2H), 3.51–3.63 (m, 2H), 3.65–3.74
(m, 2H), 3.93 (dd, J = 1.9, 16 Hz, 2H), 6.04 (d,
J = 1.9 Hz, 2H), 7.45 (d, J = 8 Hz, 4H), 8.09 (d,
J = 8 Hz, 4H);13C NMR (100 MHz, DMSO-d6): 32.6,
41.5, 63.7, 123.5, 130.1, 147.3, 150.5, 171.7; Anal. calcd
for C20H18N4O6S2: C, 50.62; H, 3.82; N, 11.81; S,
13.51; Found: C, 50.52; H, 3.75; N, 11.65; S, 13.44.
3,3’-(Ethane-1,2-diyl)bis(2-(3-nitrophenyl)thiazoli-
1.5 g of oleic acid-modified CuFe2O4 NPs were added
into a three-necked flask. The mixture was subjected
with ultrasonic waves for 15 min and stirred for
10 min. Then, 2 mL of glutaraldehyde solution (25 wt
%) was added into the mixture at 40ꢀC, and the cross-
linking reaction was carried out for 180 min. After the
reaction, the composites were collected through mag-
netic separation and washed by deionized water and
ethanol several times. The products were dried under
vacuum.
din-4-one) (4e). Cream-colored solid; m.p. 222–224ꢀC,
1
IR (KBr) cm−1: 2922, 1665, 1514; H NMR (400 MHz,
DMSO-d6): 2.62–2.67 (m, 2H), 3.54–3.57 (m, 2H),
3.63–3.66 (m, 2H), 3.87 (dd, J = 1.7, 15 Hz, 2H), 5.94
(d, J = 1.9 Hz, 2H), 7.55–7.76 (m, 4H), 8.02–8.08 (m,
4H);13C NMR (100 MHz, DMSO-d6): 32.5, 41.6, 63.5,
126.4, 129.6, 130.7, 134.3, 143.8, 148.6, 171.6; Anal.
calcd for C20H18N4O6S2: C, 50.62; H, 3.82; N, 11.81; S,
13.51; Found: C, 50.74; H, 3.66; N, 11.78; S, 13.42.
3,3’-(Ethane-1,2-diyl)bis(2-(p-tolyl)thiazolidin-4-
one) (4i). White solid; m.p.158–160ꢀC, IR (KBr) cm−1
:
1
2928,1665; H NMR (400 MHz, CDCl3): 2.27 (s, 6H),
2.65–2.74 (m, 2H), 3.52–3.63 (m, 4H), 3.65 (dd,
J = 1.8, 16 Hz, 2H), 5.47 (d, J = 1.5 Hz, 2H), 7.12 (s,
8H);13C NMR (100 MHz, CDCl3): 20.5, 32.3, 39.4,
63.2, 126.8, 129.3, 135.2, 138.7, 171.2; Anal. calcd for
C22H24N2O2S2: C, 64.05; H, 5.86; N, 6.79; S, 15.54;
Found: C, 63.91; H, 5.92; N, 6.88; S, 15.37.
3,3’-(Ethane-1,2-diyl)bis(2-(4-isopropylphenyl)thia-
zolidin-4-one) (4j). White solid; m.p.163–165ꢀC, IR
(KBr) cm−1: 2954, 1665; H NMR (400 MHz, CDCl3):
1.14 (d, J = 7 Hz, 12H), 2.68–2.75 (m, 2H), 2.82–2.88
(m, 2H), 3.55–3.64 (m, 4H), 3.67 (dd, J = 1.8, 16 Hz,
1
Scheme 3. Schematic mechanism for the catalytic
activity of nano-CuFe2O4@chitosan for
the synthesis of the titled compound.
6
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Synthesis of Bis-Thiazolidinones
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2H), 5.47 (d, J = 1.4 Hz, 2H), 7.13 (d, J = 8 Hz, 4H),
7.15 (d, J = 8 Hz, 4H);13C NMR (100 MHz, CDCl3):
23.4, 32.2, 33.4, 39.6, 63.1, 126.67, 126.75, 135.6, 149.8,
171.1; Anal. calcd for C26H32N2O2S2:C, 66.63; H,
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In conclusion, we have developed a simple and
highly efficient protocol for the synthesis of bis-
thiazolidinones by one-pot pseudo-five-component con-
densation of araldehydes, ethylenediamine, and 2-
mercaptoacetic acid with nano-CuFe2O4-chitosan as a
reusable and robust heterogeneous catalyst under reflux
conditions in toluene. Atom economy, the wide range
of products, excellent yields, reusability of the catalyst,
and little catalyst loading are some of the important
features of this protocol.
ACKNOWLEDGMENTS
The authors are grateful to the University of
Kashan, Iran, for supporting this work (Grant No:
159196/XXII).
Supporting information
Additional supporting information is available in
the online version of this article.
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