A catalysis study of mesoporous MCM-41 supported Schiff base and CuSO4·5H2O in a highly regioselective synthesis of 4-thiazolidinone derivatives from cyclocondensation of mercaptoacetic acid

Article abstract of DOI:10.1016/j.cclet.2015.10.029

Mesoporous MCM-41 supported Schiff base and CuSO₄·5H₂O shows high catalytic activity in the cyclocondensation of mercaptoacetic acid with imines (or aldehydes and amines) to afford pharmaceutically important thiazolidinone derivatives. The catalytic reactions involving two-components or three-components afforded the desired product in high yields (up to 98% and 99%). Moreover, the catalyst works well with respect to recyclability, giving the product in 85% and 83% yields after recycling six times.

Full text of DOI:10.1016/j.cclet.2015.10.029

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CCLET-3484; No. of Pages 5
Chinese Chemical Letters xxx (2015) xxx–xxx
Contents lists available at ScienceDirect
Chinese Chemical Letters
journal homepage: www.elsevier.com/locate/cclet
Original article
A catalysis study of mesoporous MCM-41 supported Schiff base and
CuSO4ꢀ5H2O in a highly regioselective synthesis of 4-thiazolidinone
derivatives from cyclocondensation of mercaptoacetic acid
a
a
a
a
Hai-Xia Pang a, Yong-Hai Hui a, , Kui Fan , Xue-Jian Xing , Yang Wu , Jing-Hui Yang ,
*
Wei Shi b, Zheng-Feng Xie b,
*
a Key Laboratory of Oil & Gas Fine Chemicals, Ministry of Education & Xinjiang Uyghur Autonomous Region, College of Chemistry and Chemical Engineering,
Xinjiang University, Urumqi 830046, China
b Oil & Gas Field Applied Chemistry Key Laboratory of Sichuan Province, School of Chemistry and Chemical Engineering, Southwest Petroleum University,
Chengdu 610500, China
A R T I C L E I N F O
A B S T R A C T
Article history:
Mesoporous MCM-41 supported Schiff base and CuSO4ꢀ5H2O shows high catalytic activity in the
cyclocondensation of mercaptoacetic acid with imines (or aldehydes and amines) to afford
pharmaceutically important thiazolidinone derivatives. The catalytic reactions involving two-
components or three-components afforded the desired product in high yields (up to 98% and 99%).
Moreover, the catalyst works well with respect to recyclability, giving the product in 85% and 83% yields
after recycling six times.
Received 6 September 2015
Received in revised form 19 October 2015
Accepted 28 October 2015
Available online xxx
Keywords:
ß 2015 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
Published by Elsevier B.V. All rights reserved.
MCM-41
Schiff base
Cyclocondensation
Mercaptoacetic acid
Catalysis
1. Introduction
friendly, low cost, allow efficient catalyst recovery and recyclabili-
ty. To the best of our knowledge, in recent research most of the
In the recent years, thiazolidinones have been widely investi-
gated and have fascinated medicinal and organic chemists. The 4-
thiazolidinones are especially important structural units of
heterocyclic compounds exhibiting a variety of biological effects,
such as anti-inflammatory [1], antibacterial [2], antiviral [3],
antitumor [4], antimalarial [5], anti-HIV [6], tuberculostatic [7],
antihistamine [8], anticonvulsant [9], and antiarrythmic [10]. Dur-
ing the past few years, many synthetic methods have been
successfully developed to accomplish the condensation and
cyclization reaction. However, the majority of catalysts used in
these reactions are metal Lewis acid catalysts (ZnCl2, iron salts)
[11], sodium sulfate [12], coupling reagents, like DCC [13] and
HBTU [14], molecular sieves [15] and others [16] that have also
been documented for the synthesis of 2,3-disubstituted 4-
thiazolidinones. Among these, the processes catalyzed by molecu-
lar sieves are notable examples because they are environmentally
heterogeneous catalysts are mainly restricted to the discussion of
synthesis and characterization, and only a small number of
examples have been described in organic catalysis. To explore new
types of heterogeneous catalysts in available templates for organo-
catalytic reactions, we recently explored the use of defined
mesoporous siliceous material (MCM-41) on which MCM-41
supported catalysts are employed to promote the Michael addition
[17], Knoevenagel condensation reaction [18] and others
[19]. Herein, we extend the use of the MCM-41 and describe
mesoporous MCM-41 supported Schiff base and CuSO4ꢀ5H2O for
the cyclocondensation of mercaptoacetic acid with imines (or
aldehydes and amines) in high yields (up to 98% and 99%).
2. Experimental
The purity of compounds was checked by thin layer chroma-
tography (TLC) using ethyl acetate/petroleum ether (1/10–1/5, v/v)
as an eluent, and IR spectrum recorded on a Bruker Equinox 55 FT-
IR spectrophotometer as KBr discs. The 1H NMR and 13C NMR
spectra were recorded on an INOVA (400 MHz) FT-NMR
*
Corresponding authors.
E-mail addresses: hyhai97@126.com (Y.-H. Hui), xiezhf@swpu.edu.cn (Z.-F. Xie).
http://dx.doi.org/10.1016/j.cclet.2015.10.029
1001-8417/ß 2015 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.
Please cite this article in press as: H.-X. Pang, et al., A catalysis study of mesoporous MCM-41 supported Schiff base and CuSO4ꢀ5H2O in a
highly regioselective synthesis of 4-thiazolidinone derivatives from cyclocondensation of mercaptoacetic acid, Chin. Chem. Lett. (2015),
http://dx.doi.org/10.1016/j.cclet.2015.10.029

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Fig. 1. The transmission electron microscope (TEM) images of ligands (L1, MCM-41; L2, amine functionalized MCM-41; L3, Schiff base supported MCM-41).
Fig. 2. The scanning electron micrograph (SEM) images of ligands (L1, MCM-41; L2, amine functionalized MCM-41; L3, Schiff base supported MCM-41).
spectrometer in DCl3 using TMS as an internal standard. The
prepared ligands were characterized by FT-IR XRD, TEM (Fig. 1) and
SEM (Fig. 2). These TEM and SEM images indicated that the
uniformity of the particle size is subsequently reduced after the
grafting of an organic moiety on the inner pore walls of MCM-41.
A mixture of ligand L3 (0.005 g, 0.01 mmol) and CuSO4ꢀ5H2O
(0.001 g, 0.05 mmol) in toluene (0.5 mL) was stirred magnetically
and then heated for 0.5 h at 110 8C reflux. Then, imine (0.018 g,
0.1 mmol) and mercaptoacetic acid (0.014 g, 0.15 mmol) were
added. The progress of the reaction was monitored by TLC using
ethyl acetate/petroleum ether (1/10–1/5). Upon completion of the
reaction, the crude mixture was purified by column chromatogra-
phy on silica gel (ethyl acetate/petroleum ether) to afford the
desired pure product (3a) in 97% yield.
Knoevenagel condensation reaction and Fridel-Crafts reaction.
Encouraged by these features, we desired to extend this catalyst
system to the synthetic of thiazolidinones.
Before examining the reaction of imines and mercaptoacetic
acid, it is reasonable to test the potential of the MCM-41-Schiff
base ligands in the reaction. The results are summarized in
Table 1. At the outset, a series of ligands catalysts, such as L1–L5,
were screened in the presence of imine/mercaptoacetic acid (1/1.5)
in toluene (entries 2–6), and the corresponding products were
identified. Ligand L3 proved to be the best ligand for the reaction
(entry 4). The sequential investigations on the metal salts, and the
result obtained with CuSO4ꢀ5H2O was superior to ZnSO4ꢀ7H2O and
NiSO4ꢀ7H2O in terms of yield, 97%, 83% and 91% yield (entries 9,
Table 1
Optimization of the reaction conditionsa.
3. Results and discussion
Entry
Catalyst
Solvent
Time (h)
Temp (8C)
Yield (%)b
Recently, we disclosed an interesting heterogeneous catalyst
1
None
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
CH2Cl2
EtOH
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
6/8
12
12
12
12
110
110
110
110
110
110
110
110
110
110
40
27
generated
from
MCM-41,
3-(triethylsilyl)propan-1-amine
2
L1
35
3
L2
26
(NH2CH2CH2CH2Si(OEt)3), and heterocyclic aldehyde, in which
the surface area and pore of MCM-41 would exhibit high reactivity
during the catalyst formation (Scheme 1). As the catalytic property
could be facilely tuned by altering organic functional groups on the
mesoporous, this catalyst system proved generally efficient for the
4
L3
55
5
L4
53
6
L5
32
7
L3/ZnSO4ꢀ7H2O
L3/NiSO4ꢀ7H2O
L3/CuSO4ꢀ5H2O
CuSO4ꢀ5H2O
L3/CuSO4ꢀ5H2O
L3/CuSO4ꢀ5H2O
L3/CuSO4ꢀ5H2O
L3/CuSO4ꢀ5H2O
L3/CuSO4ꢀ5H2O
L3/CuSO4ꢀ5H2O
L3/CuSO4ꢀ5H2O
L3/CuSO4ꢀ5H2O
L3/CuSO4ꢀ5H2O
L3/CuSO4ꢀ5H2O
83
8
91
9
97
10
11
12
13
14
15
16
17
18c
19d
20e
75
72
78
51
THF
78
62
DMF
150
100
110
25/80
110
110
110
35
H2O
38
Toluene
Toluene
Toluene
Toluene
Toluene
71/75
36/68
76
80
76/84
a
Reaction conditions: all reactions were performed with imine (0.1 mmol),
mercaptoacetic acid (0.15 mmol), catalyst (10 mol%) in toluene (0.5 mL) at 110 8C for
12 h.
b
Isolated yield.
c
Use 15 mol% catalyst.
d
Use 5 mol% catalyst.
e
Scheme 1. The cyclocondensation of imine with mercaptoacetic acid.
The molar ratio of imine/mercaptoacetic acid is 1/1.1 or 1/1.2.
Please cite this article in press as: H.-X. Pang, et al., A catalysis study of mesoporous MCM-41 supported Schiff base and CuSO4ꢀ5H2O in a
highly regioselective synthesis of 4-thiazolidinone derivatives from cyclocondensation of mercaptoacetic acid, Chin. Chem. Lett. (2015),
http://dx.doi.org/10.1016/j.cclet.2015.10.029

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3
Scheme 2. The cyclocondensation of two-component.
Scheme 3. The cyclocondensation of three-component.
aldehydes and amines were also evaluated (Scheme 3), giving the
corresponding 4-thiazolidinones with good results (up to 99%). As
shown in Table 3, the reactivity was found to be insensitive to the
electronic properties of the substituent of amines (entries 1–9 and
21–22), and electron-donating groups on the phenyl ring or
aliphatic amines provided results with high yields (ꢁ90%).
Consequently, the cyclohexanone was subjected to the reaction
and yielded 3w with good result (89%). Notably, the diamino-
benzene was also tested under the reaction conditions of an
aldehydes:amines:mercaptoacetic acid ratios of 2:1:2. The thia-
zolidinone product could not be detected with the o-diamino-
benzene, but 1-benzyl-2-phenyl-1H-benzo[d]imidazole 3x was
obtained with 84% yield. The p- and m-diaminobenzenes could be
converted into the di-thiazolidinones 3y and 3z (Scheme 4) [20].
To further exploit the synthetic potential of the current catalytic
system, a scaled-up synthesis of the product 3a was performed by
the two-component and three-component reactions. As shown in
Scheme 5, by treatment of 10 mmol of imine under the optimized
reaction conditions, 2.43 g of the product 3a was obtained in the
two-component reaction. And in the three-component reaction,
the 100-fold amount of 4a also reacted well to deliver the desired
product in 93% yield without any significant loss in yield.
7 and 8, respectively). Then, the solvent effects on reactivity were
examined in the presence of 0.005 g L3 and 10 mol% CuSO4ꢀ5H2O.
And it determined that among the screened solvents, toluene was
superior to other solvents. Furthermore, when the reaction was
performed in polar solvents, the formation of 3a was detected in
ethanol or H2O with low yields. Additional optimization of the
reaction system revealed that 12 h, 110 8C and an imine/
mercaptoacetic acid ratio of = 1/1.5 were the optimal choices.
Therefore, the optimal conditions were as follows: imine
(0.10 mmol), mercaptoacetic acid (0.15 mmol), L3 (0.005 g),
CuSO4ꢀ5H2O (10 mol%) in toluene (0.5 mL) at 110 8C for 12 h.
Under optimized conditions, the substrate range of imines was
investigated using 0.005 g L3 and 10 mol% CuSO4ꢀ5H2O as catalyst
(Scheme 2). As shown by the results in Table 2, the catalytic
cyclocondensation reaction proceeded well for many differently
substituted imines, independent of the electron-withdrawing or
electron-donating character of the substituent (up to 97% yield).
Notably, an excellent result of 98% yield was obtained when the R2
is a benzyl group, (entry 9). Moreover, the R1 substituents
containing electron-attracting groups had
a slightly higher
reaction activity than these with electron-donating groups (entries
10–12 and 15 vs. 13–14 and 16). In addition, fused ring and
heteroaromatic substituted imines also reacted well with mer-
captoacetic acid to deliver the desired product in 88% and 90%
yields, respectively (entries 17–18).
We then turned our attention to the three component reactions
in the presence of 0.005 g L3 and 10 mol% CuSO4ꢀ5H2O. Various
As recyclability is important for the applications of
a
heterogeneous catalyst, reuse performance of mesoporous
MCM-41 supported Schiff base and CuSO4ꢀ5H2O is investigated
in the two-component and three-component cyclocondensation
(Table 4). Upon completion of reaction, the catalyst is recovered by
Table 3
Substrates investigated range for the cyclocondensation reaction of three-componenta.
Table 2
Substrates investigated range for the cyclocondensation reaction of two-componenta.
Entry
R1
R2
Products
Yield (%)b
1
C6H5
C6H5
3a
3b
3c
3d
3e
3f
93
83
88
86
88
93
77
80
99
89
86
93
88
90
89
83
88
Entry
R1
R2
Products
Yield (%)b
2
C6H5
p-FC6H4
p-ClC6H4
p-BrC6H4
p-OCH3C6H4
p-CH3C6H4
p-NO2C6H4
m-NO2C6H4
PhCH2
1
C6H5
C6H5
3a
3b
3c
3d
3e
3f
97
88
80
83
80
79
79
83
98
90
93
95
83
79
93
77
88
3
C6H5
2
C6H5
p-FC6H4
p-ClC6H4
p-BrC6H4
p-CH3OC6H4
p-CH3C6H4
p-NO2C6H4
m-NO2C6H4
PhCH2
4
C6H5
3
C6H5
5
C6H5
4
C6H5
6
C6H5
5
C6H5
7
C6H5
3g
3h
3i
6
C6H5
8
C6H5
7
C6H5
3g
3h
3i
9
C6H5
8
C6H5
10
11
12
13
14
15
16
17
p-FC6H4
p-ClC6H4
p-BrC6H4
p-OCH3C6H4
p-CH3C6H4
p-NO2C6H4
m-OCH3C6H4
C6H5
3j
9
C6H5
C6H5
3k
3l
10
11
12
13
14
15
16
17
p-FC6H4
p-ClC6H4
p-BrC6H4
p-CH3OC6H4
p-CH3C6H4
p-NO2C6H4
m-CH3OC6H4
C6H5
3j
C6H5
C6H5
3k
3l
C6H5
3m
3n
3o
3p
3q
C6H5
C6H5
C6H5
3m
3n
3o
3p
3q
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
18
C6H5
3r
92
18
C6H5
3r
90
19
20
21
22
p-ClC6H4
p-ClC6H4
C6H5
m-NO2C6H4
p-OCH3C6H4
(CH2)3CH3
3s
3t
84
90
93
90
19
20
p-ClC6H4
p-ClC6H4
m-NO2C6H4
p-CH3OC6H4
3s
3t
96
94
3u
3v
C6H5
(CH2)11CH3
a
a
Reaction conditions: all reactions were performed with imine (0.1 mmol)
mercaptoacetic acid (0.15 mmol), L3 (0.005 g), CuSO4ꢀ5H2O (10 mol%) in toluene
(0.5 mL) at 110 8C for 12 h.
Reaction conditions: all reactions were performed with aldehydes (0.1 mmol),
amines (0.12 mmol) and mercaptoacetic acid (0.15 mmol), L3 (0.005 g), CuSO4ꢀ5H2O
(10 mol%) in toluene (0.5 mL) at 110 8C for 12 h.
b
b
Isolated yield.
Isolated yield.
Please cite this article in press as: H.-X. Pang, et al., A catalysis study of mesoporous MCM-41 supported Schiff base and CuSO4ꢀ5H2O in a
highly regioselective synthesis of 4-thiazolidinone derivatives from cyclocondensation of mercaptoacetic acid, Chin. Chem. Lett. (2015),
http://dx.doi.org/10.1016/j.cclet.2015.10.029

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Scheme 6. Proposed catalytic mechanism.
Scheme 4. The cyclocondesation of thioglycolic acid with ketone or diamines.
4. Conclusion
In summary, the efficient synthesis of thiazolidinones derived
from two-component and three-component cyclocondensation
with the catalyst mesoporous MCM-41 supported Schiff base and
CuSO4ꢀ5H2O is described. The results are illustrative of the ligands
in the catalytic system that plays a key role in the cyclocondensa-
tion reaction. In particular, this method has the advantages of a
high atomic efficiency and high yields of products (up to 98% and
99%), mild reaction conditions, simple operation, environmentally
friendly and wide range of applicable substrates. Further
investigations of cyclocondensation catalyzed by mesoporous
MCM-41 supported Schiff base and CuSO4ꢀ5H2O are in progress.
Acknowledgments
Scheme 5. Scaled-up version of the cyclocondensation in the two-component and
We acknowledge the National Natural Science Foundation of
China (Nos. 21162026, 21262034 and 21362036) and Doctoral
Fund of Xinjiang University (No. BS110111) for financial support,
Xinjiang University Analytical & Testing Center for instrumental
analyses, and Adamas-beta Chemical Co., for all chemical reagents.
three-component reaction.
centrifugal separation, washed and dried and the loss of catalyst
refilled and reused for next cycle. It was found that the catalyst L3/
CuSO4ꢀ5H2O exhibited good catalytic activity with 85% and 83%
yields after the sixth recycle.
References
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group by forming O–Cu bonding (A) with carbonyl oxygen, and
then accelerate to enhance nucleophilicity of mercapto group of
thioglycolic acid causing its facile addition on the imine (B). This
then facilitates the intramolecular cyclocondensation to form
intermediate C. Finally, the loss of H2O affords the desired
thiazolidinones (Scheme 6) [20].
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highly regioselective synthesis of 4-thiazolidinone derivatives from cyclocondensation of mercaptoacetic acid, Chin. Chem. Lett. (2015),
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Please cite this article in press as: H.-X. Pang, et al., A catalysis study of mesoporous MCM-41 supported Schiff base and CuSO4ꢀ5H2O in a
highly regioselective synthesis of 4-thiazolidinone derivatives from cyclocondensation of mercaptoacetic acid, Chin. Chem. Lett. (2015),
http://dx.doi.org/10.1016/j.cclet.2015.10.029