CoFe2O4@SiO2/PrNH2 nanoparticles as highly efficient and magnetically recoverable catalyst for the synthesis of 1,3-thiazolidin-4-ones

Article abstract of DOI:10.1080/17415993.2016.1169533

An efficient three-component synthesis of 1,3-thiazolidin-4-ones is described by one-pot condensation of aldehydes, aromatic amine and thioglycolic acid with nano-CoFe₂O₄@SiO₂/PrNH₂ as a robust heterogeneous catalyst. The significant advantages of this protocol are the use of magnetically recoverable catalyst, high to excellent product yields, operational simplicity and the use of CoFe₂O₄@SiO₂/PrNH₂ nanoparticles as an environment-friendly catalyst.

Full text of DOI:10.1080/17415993.2016.1169533

Journal of Sulfur Chemistry
ISSN: 1741-5993 (Print) 1741-6000 (Online) Journal homepage: http://www.tandfonline.com/loi/gsrp20
CoFe2O4@SiO2/PrNH2 nanoparticles as highly
efficient and magnetically recoverable catalyst for
the synthesis of 1,3-thiazolidin-4-ones
Javad Safaei-Ghomi, Maryam Navvab & Hossein Shahbazi-Alavi
To cite this article: Javad Safaei-Ghomi, Maryam Navvab & Hossein Shahbazi-Alavi (2016):
CoFe2O4@SiO2/PrNH2 nanoparticles as highly efficient and magnetically recoverable
catalyst for the synthesis of 1,3-thiazolidin-4-ones, Journal of Sulfur Chemistry, DOI:
10.1080/17415993.2016.1169533
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Date: 06 May 2016, At: 09:47

JOURNAL OF SULFUR CHEMISTRY, 2016
http://dx.doi.org/10.1080/17415993.2016.1169533
CoFe2O4@SiO2/PrNH2 nanoparticles as highly efficient and
magnetically recoverable catalyst for the synthesis of
1,3-thiazolidin-4-ones
Javad Safaei-Ghomi , Maryam Navvab and Hossein Shahbazi-Alavi
Department of Organic Chemistry, Faculty of Chemistry, University of Kashan, Kashan, Iran
ABSTRACT
ARTICLE HISTORY
Received 10 December 2015
Accepted 19 March 2016
An efficient three-component synthesis of 1,3-thiazolidin-4-ones is
described by one-pot condensation of aldehydes, aromatic amine
and thioglycolic acid with nano-CoFe2O4@SiO2/PrNH2 as a robust
heterogeneous catalyst. The significant advantages of this pro-
tocol are the use of magnetically recoverable catalyst, high to
excellent product yields, operational simplicity and the use of
CoFe2O4@SiO2/PrNH2 nanoparticles as an environment-friendly cat-
alyst.
KEYWORDS
Nano-CoFe2O4@SiO2/PrNH2;
1; 3-thiazolidin-4-ones;
nanocatalyst; thioglycolic
acid; multi-component
reactions
1. Introduction
Thiazolidinones are an important class of heterocyclic compounds with a wide range of
pronounced biological activities such as HIV-reverse transcriptase inhibitor activity,[1–5]
antimicrobial activity,[6,7] H1-histamine antagonist activity,[8] anti-c (Yellow fever virus)
activity,[9] antitumor activity,[10] anti-inflammatory activity,[11] and antioxidant activity
[12] (Figure 1).
Therefore, finding efficient and simple methods for the synthesis of thiazolidinones is
an attractive challenge. The synthesis of bioactive compounds should be convenient, flex-
ible, prompt and useful in organic synthesis. Multi-component reactions (MCRs) are very
flexible, convergent, atom economic in nature and are often considered for the develop-
ment of environmentally benign synthetic methods.[13–15] The design of novel MCRs
for the synthesis of diverse groups of sulfur compounds, especially the ones that are bio-
logically active, has commanded vast attention. Development of magnetic nanoparticles
CONTACT Javad Safaei-Ghomi
safaei@kashanu.ac.ir
Department of Organic Chemistry, Faculty of Chemistry,
University of Kashan, Kashan51167, Iran
© 2016 Informa UK Limited, trading as Taylor & Francis Group

2
J. SAFAEI-GHOMI ET AL.
Figure 1. Biologically important 1,3-thiazolidin-4-ones.
(MNPs) for utilizations as supports and investigations of their applications represent a
significant branch of green chemistry as they enable environmentally friendly and sus-
tainable catalytic processes. The adaptation of various MNPs by coating with silica is
well known for its ability to prevent magnetic aggregation in solution and to improve
chemical stability.[16,17] To overcome the separation problems of nanocatalysts, mag-
netic materials have emerged as recoverable catalysts. Separation of MNPs is easy, con-
venient, economical and environmentally benign.[18–20] Consequently, we have used
nano-CoFe2O4@SiO2/PrNH2 for the synthesis of 1,3-thiazolidin-4-ones under reflux con-
ditions in toluene. Recently, the synthesis of 1,3-thiazolidin-4-ones has been reported using
MCRs in the presence of diverse catalysts including HClO4-SiO2,[21] ionic liquid immo-
bilized on FeNi3,[22] Fe3O4/SiO2/Salen/Mn/IL MNPs,[23] Bi(SCH2COOH)3,[24] and
Saccharomyces cerevisiae.[25] Many methods for the synthesis of 1,3-thiazolidin-4-ones
are known, but some of these methods have certain drawbacks, including long-reaction
times, utilization of toxic and non-reusable catalysts and the use of specific conditions. In
the current work, we described a novel methodology for the synthesis of 1,3-thiazolidin-
4-ones by one-pot condensation of aldehydes, aromatic amine and thioglycolic acid
with CoFe2O4@SiO2/PrNH2 nanoparticles as robust heterogeneous catalyst under reflux
conditions in toluene (Scheme 1).
Scheme 1. Synthesis of 1,3-thiazolidin-4-ones using CoFe2O4@SiO2/PrNH2 nanoparticles.

JOURNAL OF SULFUR CHEMISTRY
3
2. Results and discussion
CoFe2O4 nanoparticles were prepared according to a method reported in the literature
with some modifications.[26] Coating of a layer of silica on the surface of CoFe2O4
nanoparticles was achieved by sonication of a CoFe2O4 suspension in an alkaline
ethanol–water solution of tetraethyl orthosilicate (TEOS). The obtained CoFe2O4@SiO2
was then treated with 3-aminopropyltriethoxysilane (APTES) in refluxing toluene to afford
aminated-CoFe2O4@SiO2 NPs (Figure 2).
The particle size diameter (D) of the CoFe2O4@SiO2/PrNH2 nanoparticles has been cal-
culated by the Debye–Scherrer equation (D = Kλ/β cos θ), where β FWHM (full-width
at half-maximum or half-width) is in radian and θ is the position of the maximum of
the diffraction peak. K is the so-called shape factor, which usually takes a value of about
0.9, and λ is the X-ray wavelength. Figure 3 shows the X-ray diffraction (XRD) spec-
tra of CoFe2O4@SiO2/PrNH2 nanoparticles. According to the Debye–Scherrer equation,
the average particle sizes of the as-synthesized CoFe2O4@SiO2/PrNH2 nanoparticles were
calculated and the results show that CoFe2O4@SiO2/PrNH2 nanoparticles were obtained
with an average diameter of 11–16 nm as confirmed by XRD analysis. In order to inves-
tigate the morphology and particle size of CoFe2O4@SiO2/PrNH2 the SEM image of
CoFe2O4@SiO2/PrNH2 was obtained as shown in Figure4. The SEM image shows particles
with diameters in the range of nanometers.
Figure 2. Flow chart of the CoFe2O4@SiO2/PrNH2 nanoparticles preparation procedure.
Figure 3. The XRD pattern of CoFe2O4@SiO2/PrNH2 nanoparticles.

4
J. SAFAEI-GHOMI ET AL.
Figure 4. SEM image of CoFe2O4@SiO2/PrNH2 nanoparticles.
Figure 5 shows Fourier transform infrared (FT-IR) spectra of CoFe2O4@SiO2/PrNH2.
The bands at 464, 1079, 1628 and 3418 cm−1 are the characteristic absorptions of SiO2,
which shows evidence for the formation of a silica shell. The presence of Co–O and
Fe–O bonds in the magnetic particles is confirmed by the characteristic peak appearing
at 592 cm−1. The intense and broad peaks near 1079 and 3400 cm−1 are characteristic
absorption bands of the vibration of OH moieties, which overlap with the NH2 vibra-
tions. The enhancement of the bands at 1628 cm−1 provides direct evidence to verify the
existence of N-H deformation vibrations.[26]
Initially, we focused on systematic evaluation of different catalysts for the model reac-
tion of 4-chlorobenzaldehyde (2 mmol), aniline (2 mmol) and thioglycolic acid (2 mmol)
in different solvents. We employed various conditions and found that the reaction gave sat-
isfying result in the presence of CoFe2O4@SiO2/PrNH2 under reflux conditions in toluene
(Table 1). We examined the condensation reaction under reflux conditions in toluene with-
out catalyst, but we could not find substantial amounts of the title product. The reaction
was carried out with different amounts of CoFe2O4@SiO2/PrNH2 as catalyst. As show in
Table 1, 0.70 mol% of nano-CoFe2O4@SiO2/PrNH2 as the catalyst was suitable and the
amount of catalyst was increased to 0.90 mol %, but the yield was not improved. The
model reaction was carried out in the presence of various catalysts such as SiO2, SnO,
ZrO2, CuFe2O4, ZnFe2O4, CoFe2O4 and CoFe2O4@SiO2/PrNH2 nanoparticles. When the
reaction was carried out using CoFe2O4@SiO2/PrNH2 nanoparticles as the catalyst under
reflux conditions in toluene, the product could be obtained in good yield.
A series of aromatic aldehydes and anilines were investigated (Table 2). Interestingly, a
variety of aromatic aldehydes, including ortho, meta and para-substituted aryl aldehydes,
participated well in this reaction and gave the corresponding products in good to excellent

JOURNAL OF SULFUR CHEMISTRY
5
Figure 5. FTIR spectrum of CoFe2O4@SiO2/PrNH2 nanoparticles.
Table 1. Optimization of reaction condition using different catalysts.a
Entry
Solvent (condition)
Catalyst (mol)%
Time (min)
Yieldb (%)
1
2
3
4
5
6
7
8
PhMe (reflux)
PhMe (reflux)
PhMe (reflux)
EtOH (reflux)
DMF
PhMe (reflux)
PhMe (reflux)
PhMe (reflux)
PhMe (reflux)
PhMe (reflux)
PhMe (reflux)
PhMe (reflux)
PhMe (reflux)
PhMe (reflux)
DMF
–
500
450
450
500
350
350
300
250
250
250
220
120
120
120
120
120
trace
12
14
17
30
42
27
34
38
43
54
78
85
85
60
69
PTSA(10)
Nano-SnO (3)
Nano-ZrO2 (5)
Nano-ZrO2 (5)
Nano-ZrO2 (5)
Nano-SiO2 (3)
Nano-CuFe2O4 (2)
Nano-ZnFe2O4 (2)
Nano-CoFe2O4
9
10
11
12
13
14
15
16
Nano-CoFe2O4@SiO2
CoFe2O4@SiO2/PrNH2 (0.5)
CoFe2O4@SiO2/PrNH2 (0.7)
CoFe2O4@SiO2/PrNH2 (0.9)
CoFe2O4@SiO2/PrNH2 (0.7)
CoFe2O4@SiO2/PrNH2 (0.7)
THF
a4-chlorobenzaldehyde (2 mmol), aniline (2 mmol), thioglycolic acid (2 mmol).
bIsolated yields.
yields (Table 2). The influence of electron-withdrawing and electron-donating substituents
on the aromatic ring of aldehydes upon the reaction yields was investigated. It was shown
that aromatic aldehydes with electron-withdrawing groups reacted faster than those with
electron-releasing groups. In addition, we examined aliphatic aldehydes such as n-hexanal
instead of benzaldehydes in the reaction, but we could not find substantial amounts of the
title product from aliphatic aldehydes. Subsequently, the scope of the reaction was also
investigated with ketones, aromatic amine and thioglycolic acid. This reaction could not
be observed when ketones were used as substrates.
2.1. Proposed mechanism
Mechanistic pathways of formation of thiazolidinones are outlined in Scheme 2 and are: (i)
via initial imine formation followed by attack of the sulfur moiety of the thioglycolic acid on

6
J. SAFAEI-GHOMI ET AL.
Table 2. Synthesis of 1,3-thiazolidin-4-ones using CoFe2O4@SiO2/PrNH2 nanoparticles.
Entry
Aldehydes (1a–1o)
Anilines (2a–2o)
Product (4a–4o)
Time (min)
Yielda%
m. p °C
1
2
3
4
5
6
7
8
C6H5
2-NO2- C6H4
pyridin-2-yl
3-NO2- C6H4
pyridin-3-yl
4-Cl- C6H4
4-NO2- C6H4
thiophen-2-yl
4-isopropyl- C6H4
2-Cl-C6H4
3-NO2-C6H5
C6H5
H
H
H
H
H
H
H
H
H
4a
4b
4c
4d
4e
4f
4g
4h
4i
4j
4k
4l
4m
4n
4o
125
130
130
130
130
120
120
120
140
125
125
135
130
125
130
82
83
79
80
76
85
85
75
76
83
84
78
80
82
76
130–132 [24]
112–114
152–153 [21]
176–178 [24]
135–137
128–130 [21]
138–140 [21]
132–133 [21]
133–135
120–122
135–137
160–164 [24]
121–123 [23]
134–136 [24]
118–119 [24]
9
10
11
12
13
14
15
H
4-OMe
4-NO2
4-Cl
Me
H
C6H5
2-NO2
4-Me
aIsolated yields.
Scheme 2. Proposed reaction pathways for the synthesis of 1,3-thiazolidin-4-ones by
CoFe2O4@SiO2/PrNH2 nanoparticles.
the imine carbon catalyzed by the CoFe2O4@SiO2/PrNH2 NPs followed by intramolecular
cyclization with the expulsion of water giving rise to the cyclized product thiazolidinone
(Route A) and (ii) via the initial condensation of the amine with thioglycolic acid to form
the amide followed by cyclo-condensation of the aldehyde carbonyl group with the thiol
and NH moieties of the in situ formed amide catalyzed by the CoFe2O4@SiO2/PrNH2 NPs
giving rise to the cyclized product thiazolidinone through the expulsion of water (Route
B) (Scheme 2).
2.2. Catalyst recovery
After completion of the reaction, the catalyst was separated magnetically from the reaction
mixture and washed with Et2O, air-dried and then reused directly in the model reaction
of 4-chlorobenzaldehyde (2 mmol), aniline (2 mmol) and thioglycolic acid (2 mmol) by
0.70 mol% of CoFe2O4@SiO2/PrNH2 nanoparticles under reflux conditions in toluene.
The results demonstrated that the catalyst exhibited high but slowly decreasing activity

JOURNAL OF SULFUR CHEMISTRY
7
Figure 6. Reusability of CoFe2O4@SiO2/PrNH2 nanoparticles catalyst for the preparation of 4f.
in seven consecutive cycles, which might be attributed to the slight loss of catalyst during
the reaction and recovery processes (Figure 6)
3. Conclusions
In conclusion, we have developed a simple and highly efficient procedure for the synthe-
sis of 1,3-thiazolidin-4-ones using CoFe2O4@SiO2/PrNH2 nanoparticles as an efficient
catalyst. The remarkable advantages of this methodology are easy work-up, short reaction
times, use of magnetically recoverable catalyst, high to excellent product yields, opera-
tional simplicity and small catalyst loading. Further investigations of similar protocols are
currently underway in our laboratory.
4. Experimental
4.1. Materials and apparatus
All organic materials were purchased commercially from Sigma-Aldrich and Merck and
were used without further purification. All melting points are uncorrected and were deter-
mined in a capillary tube on a Boetius melting point microscope. FT-IR spectra were
recorded with KBr pellets using a Magna-IR, spectrometer 550 Nicolet. NMR spectra were
recorded on a Bruker 400 MHz spectrometer with DMSO as solvent and TMS as the inter-
nal standard. Powder XRD was carried out on a Philips diffractometer of X’pert Company.
Microscopic morphology of products was visualized by SEM (MIRA3 TESCAN).
4.2. Preparation of CoFe2O4@SiO2/PrNH2 nanoparticles
CoFe2O4@SiO2/PrNH2 nanoparticles were prepared according to method reported in
the literature with some modifications.[26] CoFe2O4 NPs were prepared by a chemical
co-precipitation method using FeCl3·6H2O and CoCl2·6H2O as precursors. FeCl3·6H2O

8
J. SAFAEI-GHOMI ET AL.
(5.4 g) and CoCl2·6H2O (2.38 g) were dissolved in 100 mL distilled water. Then, the mix-
ture solution was transferred into a three-necked flask equipped with a mechanical stirrer.
Fifty milliliters of 3 mol/L NaOH solution were added into the flask under vigorous stir-
ring. The mixture was heated to reflux for 1 h to yield a black dispersion. When the reaction
had finished, the black product was washed with double-distilled water several times until
the pH value of the solution became neutral. The black precipitate was separated by a per-
manent magnet, followed by washing three times with ethanol and drying at 100°C in a
vacuum for 24 h.
Coating of a layer of silica on the surface of the CoFe2O4 NPs was achieved by pre-
mixing (ultrasonic) a dispersion of the purified CoFe2O4 NPs (1 g) obtained previously
with distilled water (80 mL) for 1 h at 40°C. A concentrated ammonia solution (1.5 mL) was
added and the resulting mixture stirred at 40°C for 30 min. Subsequently, TEOS, 1.0 mL
was charged to the reaction vessel and the mixture continuously stirred at 40°C for 24 h.
The silicacoated NPs were collected using a permanent magnet, followed by washing three
times with ethanol, diethyl ether and drying at 100°C in a vacuum for 24 h.
CoFe2O4@SiO2 (1 g) was added to the solution of 3-aminopropyltriethoxysilane
(2 mmol, 0.44 g) in dry toluene (20 mL) and refluxed for 24 h. After the reaction had fin-
ished, the aminated-CoFe2O4@SiO2 were separated by a permanent magnet, washed with
double-distilled water and anhydrous ethanol, and dried at 80°C for 8 h to give the surface
bound amino group CoFe2O4@SiO2/PrNH2.
4.3. General procedure for the preparation of 1,3-thiazolidin-4-ones
A mixture of aldehydes (2 mmol), aromatic amine (2 mmol), thioglycolic acid (2 mmol)
and 0.70 mol% of CoFe2O4@SiO2/PrNH2 nanoparticles in PhMe (15 mL) was refluxed.
The reaction was monitored by TLC. After completion of the reaction, the catalyst was
separated magnetically. The precipitate was filtered and recrystallized with n-hexane/ethyl
acetate to get pure product.
4.3.1. 2,3-diphenylthiazolidin-4-one (4a)
White solid; m.p 132–134°C, IR (KBr) cm−1: 1672, 1594, 1521, 1521, 1455, 1346; 1H NMR
(400 MHz, DMSO-d6): δ (ppm) 3.89 (d, 1 H, 2J = 15 Hz), 4.09 (d, 1 H, 2J = 15 Hz), 6.50
(s, 1H), 7.25 (t, 1 H, J = 7.2 Hz), 7.27–7.34 (m, 9H); 13C NMR (100 MHz, DMSO-d6): δ
(ppm) 33.08, 59.78, 124.62, 126.24, 128.12, 128.90, 129.92, 135.91, 136.92, 147.25, 171.52;
Anal. calcd for C15H13NOS: C, 70.56; H, 5.13; N, 5.49; S, 12.56. Found: C, 70.47; H, 5.02;
N, 5.36; S, 12.49.
4.3.2. 2-(2-Nitrophenyl)-3-phenylthiazolidin-4-one (4b)
1
Cream solid; m.p 112–114°C, IR (KBr) cm−1: 1686, 1595, 1521, 1449, 1343; H NMR
(400 MHz, DMSO-d6): δ (ppm) 3.84 (d, 1 H, 2J = 16 Hz), 3.97 (d, 1 H, 2J = 16 Hz), 6.78 (s,
1H), 7.12 (m, 1H, J = 7.2 Hz), 7.16–7.27 (m, 4H), 7.47–7.49 (t, 1 H, J = 8 Hz), 7.53–7.70
(m, 2 H), 7.98–8.00 (d, 1H, J = 8 Hz); 13C NMR (100 MHz, DMSO-d6): δ (ppm) 32.29,
59.74, 125.53, 127.04, 127.10, 128.05, 129.36, 129.98, 135.02, 135.89, 137.73, 147.40, 171.36;
Anal. calcd for C15H12N2O3S: C, 59.99; H, 4.03; N, 9.33; S, 10.68. Found: C, 59.87; H, 3.94;
N, 9.41; S, 10.56.

JOURNAL OF SULFUR CHEMISTRY
9
4.3.3. 3-phenyl-2-(pyridin-2-yl)thiazolidin-4-one (4c)
White solid; m.p 150–152°C, IR (KBr) cm−1: 1673, 1587, 1524, 1497, 1432; H NMR
(400 MHz, DMSO-d6): δ (ppm) 3.80 (d, 1 H, 2J = 15.6 Hz), 4.03 (d, 1 H, 2J = 15.6 Hz),
6.47 (s, 1H), 7.04 (d, 1H, J = 7.2 Hz), 7.15–7.40 (m, 5H), 7.52 (m, 1H), 7.72–7.74 (d,
J = 7.4 Hz, 1H), 8.49 (d, 1H, J = 7.00 Hz 1H); 13C NMR (100 MHz, DMSO-d6): δ (ppm)
33.15, 60.21, 124.69, 127.04, 128.02, 129.30, 130.25, 135.05, 135.93, 147.40, 157.30, 171.36;
Anal. calcd for C14H12N2OS: C, 65.60; H, 4.72; N, 10.93; S, 12.51. Found: C, 65.54; H, 4.61;
N, 10.98; S, 12.42.
1
4.3.4. 2-(3-Nitrophenyl)-3-phenylthiazolidin-4-one (4d)
Cream solid; m.p 179–181°C, IR (KBr) cm−1: 1676, 1596, 1529, 1521, 1497, 1386, 1348; 1H
NMR (400 MHz, DMSO-d6): δ (ppm) 3.89 (d, 1 H, 2J = 15 Hz), 4.08 (d, 1H, 2J = 15 Hz),
6.72 (s, 1H), 7.11 (m, 1 H, J = 7.2 Hz), 7.19–7.29 (m, 4H), 7.41–7.52 (t, 1 H, J = 8 Hz),
7.51–7.72 (d, J = 7.2 Hz, 1 H), 7.80 (d, J = 7.2 Hz, 1H),7.98–8.00 (s, 1H); 13C NMR
(100 MHz, DMSO-d6): δ (ppm) 33.09, 60.14, 125.62, 127.22, 127.26, 128.15, 129.33, 129.93,
135.15, 135.93, 137.82, 147.42, 171.35; Anal. calcd for C15H12N2O3S: C, 59.99; H, 4.03; N,
9.33; S, 10.68. Found: C, 59.81; H, 3.92; N, 9.42; S, 10.51.
4.3.5. 3-phenyl-2-(pyridin-3-yl)thiazolidin-4-one (4e)
White solid; m.p 135–137°C, IR (KBr) cm−1: 1673, 1582, 1495, 1431; 1H NMR (400 MHz,
2
2
DMSO-d6): δ (ppm) 3.88 (d, 1 H, J = 15.6 Hz), 4.05 (d, 1 H, J = 15.6 Hz), 6.57 (s,
1H), 7.13 (d, 1H, J = 6.4 Hz), 7.29–7.60 (m, 5H), 7.83–7.85 (d, J = 8 Hz, 1H), 7.38–7.40
(d, J = 4 Hz, 1H), 8.53 (s, 1H);13C NMR (100 MHz, DMSO-d6): δ (ppm) 33.19, 60.28,
124.72, 127.05, 128.09, 129.35, 130.29, 135.14, 135.91, 147.47, 157.33, 171.35; Anal. calcd
for C14H12N2OS: C, 65.60; H, 4.72; N, 10.93; S, 12.51. Found: C, 65.52; H, 4.64; N, 10.97;
S, 12.41.
4.3.6. 2-(4-chlorophenyl)-3-phenylthiazolidin-4-one (4f)
1
White solid, m.p 125–127°C, IR (KBr) cm−1: 1675, 1595, 1520, 1453, 730; H NMR
(400 MHz, DMSO-d6): δ (ppm) 3.94 (d, 1 H, 2J = 15 Hz), 4.02 (d, 1 H, 2J = 15 Hz), 6.58
(s, 1H), 7.04–7.45 (m, 7 H), 7.60–7.68 (m, 2 H); 13C NMR (100 MHz, DMSO-d6): δ (ppm)
33.10, 59.95, 124.45, 125.22, 126.64, 129.12, 129.60, 135.10, 137.23, 146.81, 171.08; Anal.
calcd for C15H12ClNOS: C, 62.17; H, 4.17; N, 4.83; S, 11.07. Found: C, 62.08; H, 4.04; N,
4.71; S, 10.86.
4.3.7. 2-(4-Nitrophenyl)-3-phenylthiazolidin-4-one (4g)
Yellow solid; m.p 133–134°C, IR (KBr) cm−1: 1686, 1598, 1521, 1521, 1455, 1346; 1H NMR
(400 MHz, DMSO-d6): δ (ppm) 3.89 (d, 1 H, 2J = 15 Hz), 4.09 (d, 1 H, 2J = 15 Hz), 6.69
(s, 1H), 7.12–7.15 (t, 1 H, J = 7.2 Hz), 7.27–7.35 (m, 4H), 7.66–7.68 (d, 2 H, J = 8 Hz),
8.10–8.12 (d, 2 H, J = 8 Hz); 13C NMR (100 MHz, DMSO-d6): δ (ppm) 33.11, 60.18,
125.65, 127.26, 128.15, 129.33, 129.93, 135.93, 137.82, 147.42, 171.35 Anal. calcd for
C15H12N2O3S: C, 59.99; H, 4.03; N, 9.33; S, 10.68. Found: C, 59.85; H, 3.93; N, 9.40; S,
10.54.

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J. SAFAEI-GHOMI ET AL.
4.3.8. 3-phenyl-2-(thiophen-2-yl)thiazolidin-4-one (4h)
White solid; m.p 130–131°C, IR (KBr) cm−1: 1686, 1598, 1521, 1521, 1455, 1346;1H NMR
(400 MHz, DMSO-d6): δ (ppm) 3.86 (d, 1 H, 2J = 15.6 Hz), 3.98 (d, 1 H, 2J = 15.6 Hz),
6.82 (s, 1H), 7.12–7.55 (m, 8 H); 13C NMR (100 MHz, DMSO-d6): δ (ppm) 33.55, 59.27,
123.64, 125.52, 127.26, 128.15, 129.33, 129.93, 130.99, 139.42, 171.35; Anal. calcd for
C13H11NOS2: C, 59.74; H, 4.24; N, 5.36; S, 24.54. Found: C, 59.64; H, 4.32; N, 5.42; S,
24.61.
4.3.9. 2-(4-isopropyl-phenyl)-3-phenylthiazolidin-4-one (4i)
1
White solid; m.p 133–135°C, IR (KBr) cm−1: 1685, 1595, 1521, 1496, 1455, 1346; H
NMR (400 MHz, DMSO-d6): δ (ppm) 1.07 (2 CH3, 6 H), 2.60 (m, 1H, CH), 3.81 (d,
1 H, 2J = 15 Hz), 4.03 (d, 1 H, 2J = 15 Hz), 6.49 (s, 1H), 7.12–7.15 (t, 1 H, J = 7.2 Hz),
7.20–7.25 (m, 4H), 7.42–7.44 (d, 2 H, J = 8 Hz), 7.45–7.46 (d, 2 H, J = 8 Hz); 13C NMR
(100 MHz, DMSO-d6): δ (ppm) 22.54, 33.16, 35.50, 60.19, 126.65, 127.29, 127.95, 129.24,
129.62, 135.90, 137.80, 147.30, 171.22 Anal. calcd for C18H19NOS: C, 72.69; H, 6.44; N,
4.71; S, 10.78. Found: C, 72.74; H, 6.48; N, 4.54; S, 10.68.
4.3.10. 2-(2-chlorophenyl)-3-phenylthiazolidin-4-one (4j)
1
White solid, m.p 120–124°C, IR (KBr) cm−1: 1683, 1598, 1521, 1455, 732; H NMR
2
2
(400 MHz, DMSO-d6): δ (ppm) 3.89 (d, 1H, J = 15.6 Hz), 3.96 (d, 1 H, J = 15.6 Hz),
6.76 (s, 1H), 7.12 (m, 1H, J = 7.2 Hz), 7.16–7.45 (m, 4 H), 7.47–7.54 (m, 3 H), 7.61 (d,
1H, J = 7.00 Hz); 13C NMR (100 MHz, DMSO-d6): δ (ppm) 33.20, 60.02, 124.50, 125.20,
126.53, 128.02, 129.10, 129.60, 135.12, 135.72, 137.25, 146.83, 171.10; Anal. calcd for
C15H12ClNOS: C, 62.17; H, 4.17; N, 4.83; S, 11.07. Found: C, 62.12; H, 4.08; N, 4.72; S,
10.88.
4.3.11. 3-(4-methoxyphenyl)-2-(3-nitrophenyl)thiazolidin-4-one (4k)
Yellow solid; m.p 135–137°C, IR (KBr) cm−1: 3068, 20923, 1677, 1524, 1346;1H NMR
2
(400 MHz, DMSO-d6): δ (ppm) 3.73 (s, OCH3), 3.91 (d, 1H, J = 16 Hz), 4.10 (d, 1H,
2J = 16 Hz), 6.66 (s, 1H), 7.07–7.09 (d, 2H, J = 8 Hz), 7.18–7.20 (d, 2H, J = 8 Hz), 7.58 (t,
1H, J = 8 Hz), 7.87–7.89 (d, 1 H, J = 8 Hz), 8.06–8.08 (d, 1 H, J = 8 Hz), 8.21 (s, 1H);13C
NMR (100 MHz, DMSO-d6): δ (ppm) 33.08, 55.84, 60.08, 122.45, 125.67, 127.27, 128.16,
129.94, 133.14, 134.83, 136.84, 147.42, 154.20, 171.35; Anal. calcd for C16H14N2O4S: C,
58.17; H, 4.27; N, 8.48; S, 9.71. Found: C, 58.28; H, 4.36; N, 8.40; S, 9.62.
4.3.12. 3-(4-nitrophenyl)-2-phenylthiazolidin-4-one (4l)
Yellow solid; m.p 154–156°C, IR (KBr) cm−1: 2394, 2852, 2356, 1693, 1592, 1512, 1328,
1263; 1H NMR (400 MHz, DMSO-d6): δ (ppm) 3.94 (d, 1H, 2J = 15.6 Hz), 4.14 (d, 1H,
2J = 15.6 Hz), 6.75 (s, 1H), 7.36–7.44 (m, 5H), 7.86–7.88 (d, 2H, J = 8.0 Hz), 8.19–8.21
(d, 2H, J = 8.0 Hz); Anal. calcd for C15H12N2O3S: C, 59.99; H, 4.03; N, 9.33; S, 10.68.
Found: C, 59.85; H, 4.08; N, 9.48; S, 10.54.
4.3.13. 3-(4-chlorophenyl)-2-phenylthiazolidin-4-one (4m)
White solid; m.p 120–122°C, IR (KBr) cm−1: 2955, 2858, 1679, 1478, 1385, 1278, 1255,
1
2
742; H NMR (400 MHz, DMSO-d6): δ (ppm) 3.98 (d, 1 H, J = 16 Hz), 4.21 (d, 1 H,
2J = 16 Hz), 6.69 (s, 1H), 7.04–7.24 (m, 5 H), 7.34–7.36 (d, 2H, J = 8 Hz), 7.86–7.88 (d,

JOURNAL OF SULFUR CHEMISTRY
11
2H, J = 8 Hz); Anal. calcd for C15H12ClNOS: C, 62.17; H, 4.17; N, 4.83; S, 11.07. Found:
C, 62.12; H, 4.11; N, 4.73; S, 10.97.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
The authors gratefully acknowledge the financial support of this work by the Research Affairs Office
of the University of Kashan, Kashan, I. R. Iran [grant number 159196/IV].
ORCID
Javad Safaei-Ghomi http://orcid.org/0000-0002-9837-4478
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