Design of a new multi-functional catalytic system Ni/SO3H?zeolite-Y for three-component synthesis of: N -benzo-imidazo- or -thiazole-1,3-thiazolidinones

Article abstract of DOI:10.1039/d0ra08237f

In this investigation, a nanoporous zeolite-NaY supported sulfonic acid was synthesized and Ni(ii) ions were successfully stabilized on SO3H?zeolite-Y (Ni/SO3H?zeolite-Y). This novel type of zeolitic nanocomposite was characterized using various techniques including FT-IR, FE-SEM, TGA, BET and EDX. Ni/SO3H?zeolite-Y was used as a multi-functional and highly active nanocatalyst for the three-component synthesis of 3-benzimidazolyl-1,3-thiazolidin-4-ones and new 3-benzthiazoleyl-1,3-thiazolidin-4-ones via cyclocondensation of 2-aminobenzimidazole or 2-aminobenzothiazole, aromatic aldehydes and thioglycolic acid in acetone-H2O at room temperature. This economical chemical procedure has advantages such as excellent yield in short reaction times, convenient manipulation and high purity of products, applicability to a broad range of substrates, and the use of a nontoxic and heterogeneous acid catalyst with good reusability.

Full text of DOI:10.1039/d0ra08237f

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Design of a new multi-functional catalytic system
Ni/SO3H@zeolite-Y for three-component synthesis
of N-benzo-imidazo- or -thiazole-1,3-
thiazolidinones†
Cite this: RSC Adv., 2020, 10, 41410
*
Mehdi Kalhor
and Soodabeh Banibairami
In this investigation, a nanoporous zeolite-NaY supported sulfonic acid was synthesized and Ni(II) ions were
successfully stabilized on SO3H@zeolite-Y (Ni/SO3H@zeolite-Y). This novel type of zeolitic nanocomposite
was characterized using various techniques including FT-IR, FE-SEM, TGA, BET and EDX. Ni/SO3H@zeolite-
Y was used as a multi-functional and highly active nanocatalyst for the three-component synthesis of 3-
benzimidazolyl-1,3-thiazolidin-4-ones and new 3-benzthiazoleyl-1,3-thiazolidin-4-ones via cyclocondensation
of 2-aminobenzimidazole or 2-aminobenzothiazole, aromatic aldehydes and thioglycolic acid in
acetone–H2O at room temperature. This economical chemical procedure has advantages such as
excellent yield in short reaction times, convenient manipulation and high purity of products, applicability
to a broad range of substrates, and the use of a nontoxic and heterogeneous acid catalyst with good
reusability.
Received 26th September 2020
Accepted 6th November 2020
DOI: 10.1039/d0ra08237f
rsc.li/rsc-advances
perimidines,6 metal loaded Y-zeolite for thermo-catalytic pyrolysis
of real end of life vehicle plastics waste,7 micro–mesoporous zeolite
catalysts for alkylation,8 Cu@zeolite/magnetic for the synthesis of
1. Introduction
In recent years, crystalline porous materials have attracted
increasing interest due to their applications in petrochemicals,
environmental technologies and chemical reactions, particu-
larly for catalytic strategies. These porous compounds include
zeolites, ordered mesoporous silica, and metal–organic frame-
works. The main features of these materials are high adsorption
capacity, active sites with different strengths, uniform channels
and cavities, and electronic properties.1 Among them, the
zeolites have recently considered as heterogeneous catalysts or
ideal supports for homogeneous catalysts due to their high
surface area, high thermos-stability, nanoporous crystalline
structure, persistence in all organic solvents, no waste or
disposal problems, less or no corrosion, easy set-up of contin-
uous processes and etc.2,3
From 1962 to now, zeolite-NaY has received considerable
concerns in uid catalytic cracking (FCC) and gasoline
production due to its high surface area, strong acidity, high
hydrothermal stability, and low cost.1 Recently, zeolite-NaY has
used as ideal supports for homogeneous catalysts such as
alkylaminopyridine-graed on HY zeolite and application in
synthesis of 4H-chromenes,4 Ni@zeolite-Y for the synthesis of 1,3-
thiazolidinones,5 nano-CuY zeolite for facile synthesis of
1,2,3-triazoles,9 Pd@zeolite-Y for Suzuki–Miyaura coupling of aryl
halides with phenylboronic acid.10
Given the importance of zeolite as a suitable mineral
support, SO3H-modied mesoporous zeolites have been
successfully applied in many catalytic reactions,11 direct meth-
anol fuel cell application12 and as temperature tolerant proton
conducting materials,13 Furthermore, Ni-based mesoporous
zeolites have been reported for catalytic synthesis for example
biomass pyrolysis,14 CO2 methanation,15 selective ring opening
of 1-methylnaphthalene,16 hydrodeoxygenation and hydro-
cracking of microalgae biodiesel17 and etc.5 Recently, zeolite-Y
has been used as the supported surface of bi-functional nano-
catalyst.18 This is very important in synthetic chemistry, that
way, the multiple types of active sites can be created on a single
nanocatalyst.19 To the best of our knowledge, there is no
example for the synthesis of activated zeolite-NaY by the
combination of Ni species and SO3H groups in its structure and
its catalytic application in the synthesis of heterocycles.
Thiazolidinone heterocycles are saturated form of thiazole
that have a sulfur atom at position 1, a nitrogen atom at posi-
tion 3 and a carbonyl group at position 2, 4, or 5. The thiazo-
lidinone scaffolds are responsible for many various biologically
active heterocyclic compounds. A carbonyl group in position
four, creates 4-thiazolidinone derivatives which are used widely
in synthetic chemistry and pharmaceutical compounds. They
exhibit number of activities such as antitubercular, anti-
Department of Organic Chemistry, Payame Noor University, Tehran, 19395-4697, Iran.
E-mail: mekalhor@gmail.com; Fax: +98 2537179170; Tel: +98 2537179170
† Electronic supplementary information (ESI) available. See DOI:
10.1039/d0ra08237f
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Fig. 1 Some example of drugs containing of 1,3-thiazolidin-4-one.
Scheme 1 Synthetic method for 1,3-thiazolidin-4-ones using Ni/SO3H@zeolite-Y.
convulsant, antimicrobial, anti-inammatory, anticancer, anti- comparing the physical data with those of known samples or by
viral agents, and as anti-HIV agents.20–24 Fig. 1 shows some drug their spectral data. IR spectra were obtained with KBr disc on
structures based on thiazolidinone. This versatile applicability a JASCO FT-IR 4200-A spectrophotometer. 1H NMR and 13C
highlights the importance of access to efficient synthetic routes NMR spectra were recorded on Brucker spectrophotometer (300
to well benign the substituted thiazolidin-4-one compounds. or 500 MHz) in DMSO-d6 using Me4Si as internal standard. Field
The classical synthesis reported can be either a one-pot or a two- emission-scanning electron microscopic (FE-SEM) images were
step process through condensation of amines and aromatic performed on a Zeiss Sigma FE-SEM that it equipped with
aldehydes, and thioglycolic acid. Although various heteroge- energy dispersive X-ray spectrometer (EDX). Nitrogen adsorp-
neous and homogenous catalysts have been applied for the tion and desorption isotherms (BET analysis) were measured at
substituted 1,3-thiazolidin-4-ones,24–38 synthesis of new thiazo- 196 C by a USA Micromeritics (MicroActive for TriStar II Plus
ꢀ
lidine heterocycles and exploration for greener and cleaner Version 2.03, Serial # 283) system aer the samples were
synthetic strategies still remains as an active research.
vacuum dried at 150 ꢀC overnight. The TGA/DTA measurements
Having these facts and since today the design of new multi- were carried out by using a Bahr (Wetzlar, Germany) STA-503
functional nanocatalysts is one of the hot area of research, herein, instrument. TGA/DTA runs were recorded at a scan rate of
ꢁ1
ꢀ
we decided to report synthesis of Ni/SO3H@zeolite-Y through 10ꢀ min up to 1000 C under pure argon atmosphere.
loading nickel ions on SO3H-functionalized zeolite-NaY (SO3-
H@zeolite-Y) as a novel and very promising solid acid (Lewis and
Bronsted acid) nanocatalyst in the efficient preparation of N-
2.2. Synthesis of Ni/SO3H@zeolite-Y
benzimidazolyl-1,3-thiazolidin-4-ones (4a–j). Also, this catalytic
method was used for the synthesis of 3-benzothiazoleyl-1,3-
thiazolidin-4-ones (4k–p), as new thiazole based heterocyclic scaf-
folds (Scheme 1).
SO3H@zeolite-Y was prepared as follows: a 500 mL suction ask
was charged with 1.5 g of zeolite-NaY and equipped with
a constant pressure dropping funnel containing 2 mL of
chlorosulfonic acid. The chlorosulfonic acid was added
dropwise manner to zeolite-NaY over a period of 30 min at
ꢀ
0 C under N2 atmosphere. Aer the addition was complete,
the mixture was shaken for 45 min. Then, the mixture was
2. Experimental
2.1. Chemicals and apparatus
washed with dichloromethane and H2O under ultrasound
ꢀ
All chemicals were purchased from the Merck and Fluka irradiation and dried at 50 C to obtain nano SO3H@zeolite-
Chemical Companies. The products were identied by Y. The loaded Ni on SO3H@zeolite-Y was prepared by ion-
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exchange process. Typically, 1.0
g SO3H@zeolite-Y in
2.4.2. 3-(1H-Benzo[d]imidazol-2-yl)-2-(2-chlorophenyl)thiazolidin-
4-one (4g). IR (KBr) (nmax): 3444, 3349 (NH), 2925 (C–H), 1683
(C]O), 1535 (C]N), 1447, 1303, 1269 (C]C), 1170 (C–N), 743,
647 (C–S–C) cmꢁ1; 1H-NMR (500 MHz, DMSO-d6) dH: 3.97 (1H, d,
J ¼ 16.50 Hz, SCH2), 4.11 (1H, d, J ¼ 16.45 Hz, SCH2), 6.85 (1H, s,
CH), 7.06–7.15 (3H, m, H–Ar), 7.24 (1H, t, J ¼ 7.55 Hz, H–Ar),
7.30 (1H, t, J ¼ 7.60 Hz, H–Ar), 7.38 (1H, d, J ¼ 7.90 Hz, H–Ar),
7.53 (2H, t, J ¼ 7.60 Hz, H–Ar), 12.52 (1H, s, NH) ppm; 13C-NMR
(125 MHz, DMSO-d6) dC: 32.1, 59.5, 112.4, 118.2, 122.0, 122.2,
125.2, 128.1, 129.9, 130.5, 131.5, 133.3, 138.3, 140.2, 144.7,
172.2 ppm; MS (m/z, %): 329 (M+, 10), 294 (100), 252 (30), 220
(94), 135 (30), 118 (20), 91 (18).
a 150 mL ask was added to an aqueous solution of NiCl2-
$2H2O (2 mM, 50 mL) at ambient temperature. The mixture
was stirred for 20 h and then it was ltered. The resulting
precipitate was washed repeatedly with water until negative
reaction of Clꢁ using AgNO3 test. The Ni/SO3H@zeolite-Y
nanocomposite was placed undꢀer ultrasound irradiations
for 30 min, and then dried at 70 C for 2 h.
2.3. General procedure for the preparation of 1,3-
thiazolidin-4-ones
2.4.3. 3-(Benzo[d]thiazol-2-yl)-2-(2-hydroxyphenyl)thiazolidin-
4-one (4k). IR (KBr) (nmax): 1700 (C]O), 1532 (C]N), 1381, 1269
(C]C), 1117 (C–N), 655 (C–S–C) cmꢁ1; 1H-NMR (300 MHz, DMSO-
d6) dH: 3.95 (1H, d, J ¼ 16.59 Hz, SCH2), 4.09 (1H, d, J ¼ 16.56 Hz,
SCH2), 6.68 (1H, t, J ¼ 7.28 Hz, CH), 6.83 (3H, q, J ¼ 8.78 Hz, H–Ar),
7.08 (1H, t, J ¼ 7.42 Hz, H–Ar), 7.28–7.40 (2H, m, H–Ar), 7.64 (1H, d,
J ¼ 7.8 Hz, H–Ar), 7.99 (1H, d, J ¼ 7.58 Hz, H–Ar), 10.12 (1H, s,
OH) ppm; 13C-NMR (75 MHz, DMSO-d6) dC: 32.3, 59.5, 115.6, 118.8,
121.2, 121.8, 124.2, 125.0, 126.2, 126.4, 128.9, 131.3, 147.7, 154.2,
156.0, 172.1 ppm; MS (m/z, %): 328.6 (M+, 48), 255.6 (100), 237.6
(9.3), 177.5 (21), 137.5 (27), 108.4 (11), 91.5 (8).
A mixture of aldehyde (1 mmol), 2-aminobenzimidazole or 2-
aminobenzothiazole (1.1 mmol), thioglicolic acid (1.2 mmol) and
5%w the Ni/SO3H@zeolite-Y (0.007 g) in 5 mL H2O/acetone (1 : 1)
was mixed at room temperature. Aer satisfactory completion of
the organic reaction (TLC monitoring using hexane and ethyl
acetate (2 : 1) as eluents), The catalyst was separated by simple
ltration and ltrate was added to 10 mL of cold water and
precipitate was ltered off and washed with cold ethanol–water
mixture. The desired product was puried by recrystallization in
ethanol–water and air dried. The known 1,3-thiazolidin-4-one
products were characterized by comparing the results of phys-
ical and spectroscopic data with those of the authentic samples.
The new N-benzothiazole-1,3-thiazolidinones were identied by
FT-IR, 1H NMR, 13C NMR and mass spectroscopy.
2.4.4. 3-(Benzo[d]thiazol-2-yl)-2-(3-nitrophenyl)thiazolidin-
4-one (4l). IR (KBr) (nmax): 1690 (C]O), 1617, 1537 (C]N), 1467,
1369, 1274 (C]C), 1349, 1530 (NO2), 1228 (C–N), 658 (C–S–
C) cmꢁ1
;
1H-NMR (300 MHz, DMSO-d6) dH: 4.02 (1H, d, J ¼
16.73 Hz, SCH2), 4.32 (1H, d, J ¼ 16.71 Hz, SCH2), 7.06 (1H, s,
CH), 7.29–7.40 (2H, m, H–Ar), 7.62 (2H, t, J ¼ 7.78 Hz, H–Ar),
7.86 (1H, d, J ¼ 7.77 Hz, H–Ar), 8.00 (1H, d, J ¼ 7.45 Hz, H–Ar),
8.10 (1H, q, J ¼ 1.35 Hz, H–Ar), 8.34 (1H, s, H–Ar) ppm; 13C-NMR
(75 MHz, DMSO-d6) dC: 171.6, 155.9, 147.8, 147.5, 143.4, 131.8,
131.2, 130.3, 126.4, 124.4, 122.9, 121.9, 121.2, 120.8, 61.8,
31.8 ppm; MS (m/z, %): 357.6 (M+, 100), 315.6 (57), 284.6 (62.5),
255.6 (32.6), 237.6 (32.7), 181.5 (33.2), 135 (56).
2.4. Spectroscopic data for the new compounds
2.4.1. 3-(1H-Benzo[d]imidazol-2-yl)-2-(2-nitrophenyl)thiazolidin-
4-one (4c). FT-IR (KBr) (nmax): 3437, 3338 (NH), 2929 (C–H), 1703
(C]O), 1650, 1540 (C]N), 1520, 1338 (NO2), 1455, 1369 (C]C),
1118 (C–N), 1024, 668 (C–S–C) cmꢁ1; 1H-NMR (500 MHz, DMSO-
d6) dH: 3.39 (1H, d, J ¼ 16.55 Hz, SCH2), 4.21 (1H, d, J ¼ 16.55 Hz,
SCH2), 7.06 (3H, d br, CH and H–Ar), 7.43 (2H, s br, H–Ar), 7.47
(1H, d, J ¼ 7.90 Hz, H–Ar), 7.55 (1H, t, J ¼ 7.55 Hz, H–Ar), 8.17
(1H, d, J ¼ 8.10 Hz, H–Ar), 12.51 (1H, br, NH) ppm; 13C-NMR
(125 MHz, DMSO-d6) dC: 32.2, 58.2, 122.2, 126.0, 126.1, 129.8
(2C), 135.5, 137.2 (2C), 144.8, 146.8, 172.1 ppm; MS (m/z, %): 340
(M+, 30), 294 (32), 220 (65), 206 (30), 178 (25), 160 (100), 133 (25),
104 (18), 90 (20), 77 (18).
2.4.5. 3-(Benzo[d]thiazol-2-yl)-2-(4-nitrophenyl)thiazolidin-
4-one (4m). IR (KBr) (nmax): 1690 (C]O), 1617, 1537 (C]N),
1467, 1369, 1274 (C]C), 1349, 1530 (NO2), 1228 (C–N), 658 (C–
1
S–C) cmꢁ1; H-NMR (300 MHz, DMSO-d6) dH: 4.03 (1H, d, J ¼
16.73 Hz, SCH2), 4.28 (1H, d, J ¼ 16.67 Hz, SCH2), 7.03 (1H, s,
CH), 7.29–7.41 (2H, m, H–Ar), 7.61 (1H, d, J ¼ 7.53 Hz, H–Ar),
Scheme 2 Systematic approach for the preparation of Ni/SO3H@zeolite-Y.
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Fig. 2 FE-SEM images of (a) zeolite-NaY, (b) SO3H@zeolite-Y and (c), (d) Ni/SO3H@zeolite-Y. The EDX analysis of the Ni/SO3H@zeolite-Y is
presented in Fig. 3. The quantitative results of elemental analysis confirm presence of the S, Ni, Al, Si, Na and O elements in zeolite structure. On
the other hand, atomic absorption spectroscopy was performed to determine the concentration of Ni(II) ions loaded on SO3H@zeolite-Y which
was 3.56 mmol gꢁ1 (21%). Also, the number of acidic sites in the NZSA obtained 0.26 mmol gꢁ1 using acid–base titration method.18
7.68 (2H, d, J ¼ 8.76 Hz, H–Ar), 8.01 (1H, q, J ¼ 1.18 Hz, H–Ar), 171.6, 155.9, 147.5, 140.6, 131.5, 131.2, 127.7, 126.3, 124.4, 121.9,
8.16 (2H, d, J ¼ 8.76 Hz, H–Ar) ppm; 13C-NMR (75 MHz, DMSO- 121.2, 121.0, 62.1, 31.8 ppm; MS (m/z, %): 392.4 (M+, 58.4), 350.4
d6) dC: 171.6, 156.0, 148.5, 147.5, 147.0, 131.2, 126.7, 126.4, (42.5), 317.4 (83.2), 181.5 (49.9), 161.5 (22.4), 135.5 (100), 108.4
124.5, 124.0, 122.0, 121.2, 61.7, 31.9 ppm; MS (m/z, %): 357.1 (32.9).
(M+, 3.4), 108 (22.9), 69 (23.6), 46 (100).
2.4.7. 3-(Benzo[d]thiazol-2-yl)-2-(4-methoxyphenyl)thiazolidin-
2.4.6. 3-(Benzo[d]thiazol-2-yl)-2-(4-bromophenyl)thiazolidin-
4-one (4o). IR (KBr) (nmax): 1690 (C]O), 1617, 1537 (C]N), 1467,
1
4-one (4n). IR (KBr) (nmax): 1690 (C]O), 1617, 1537 (C]N), 1467, 1369, 1274 (C]C), 1228 (C–N), 658 (C–S–C) cmꢁ1; H-NMR (300
1
1369, 1274 (C]C), 1228 (C–N), 658 (C–S–C) cmꢁ1; H-NMR (300 MHz, DMSO-d6) dH:: 3.69 (3H, s, OMe), 3.98 (1H, d, J ¼ 16.81 Hz,
MHz, DMSO-d6) dH: 3.99 (1H, d, J ¼ 16.76 Hz, SCH2), 4.26 (1H, d, J SCH2), 4.26 (1H, d, J ¼ 16.79 Hz, SCH2), 6.85 (1H, s, CH), 6.85 (2H, d,
¼ 16.73 Hz, SCH2), 6.89 (1H, s, CH), 7.30–7.41 (4H, m, H–Ar), 7.50 J ¼ 7.51 Hz, H–Ar), 7.29–7.42 (4H, m, H–Ar), 7.65 (1H, d, J ¼ 7.97 Hz,
(2H, d, J ¼ 8.41 Hz, H–Ar), 7.63 (1H, d, J ¼ 8.75 Hz, H–Ar), 8.00 H–Ar), 7.99 (1H, d, J ¼ 7.69 Hz, H–Ar) ppm; 13C-NMR (75 MHz,
(1H, d, J ¼ 7.74 Hz, H–Ar) ppm; 13C-NMR (75 MHz, DMSO-d6) dC: DMSO-d6) dC: 171.6, 158.9, 155.9, 147.6, 132.9, 131.2, 127.0, 126.3,
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Fig. 3 EDX spectrum of the Ni/SO3H@zeolite-Y.
124.3, 121.8, 121.2, 113.9, 62.5, 55.0, 31.9 ppm; MS (m/z, %): 342.6 SO3H@zeolite-Y nanocomposite is similar to that of the bare
(M+, 99.9), 300.6 (71.6), 267.6 (80.5), 208.5 (68.8), 181.5 (59.6), 151.5 zeolite aer functionalization with –SO3H organic group. Also,
(54.7), 135.5 (100), 108.4 (32.8).
Fig. 2c and d show aer stabilization of Ni(II) ions, the crystal-
2.4.8. 3-(Benzo[d]thiazol-2-yl)-2-(4-methylphenyl)thiazolidin-
line and layer and layer structure with too pores for Ni/SO3-
4-one (4p). IR (KBr) (nmax): 1690 (C]O), 1617, 1537 (C]N), H@zeolite-Y is still preserved. The average nanoparticles size is
1467, 1369, 1274 (C]C), 1228 (C–N), 658 (C–S–C) cmꢁ1 1H- 26–29 nm, respectively.
NMR (300 MHz, DMSO-d6) dH: 2.23 (3H, s, Me), 3.98 (1H, d, J The FT-IR spectra of zeolite-NaY, SO3H@zeolite-Y and Ni/
;
¼ 16.78 Hz, SCH2), 4.23 (1H, d, J ¼ 16.75 Hz, SCH2), 6.86 (1H, s, SO3H@zeolite-Y are illustrated in Fig. 4. In the spectrum of
CH), 7.10 (2H, d, J ¼ 7.99 Hz, H–Ar), 7.25–7.42 (4H, m, H–Ar), zeolite-NaY, in Fig. 4a, the broad peak in 3459 cmꢁ1 region is
7.64 (1H, d, J ¼ 7.81 Hz, H–Ar), 7.99 (1H, q, J ¼ 0.68 Hz, H– related to the O–H stretching of hydrogen bonded internal
Ar) ppm; 13C-NMR (75 MHz, DMSO-d6) dC: 171.7, 155.9, 147.6, silanol groups and hydroxyl stretching of water, while the peak
138.1, 137.3, 131.2, 129.2, 126.3, 125.3, 124.3, 121.9, 121.2, 62.6, at 1635 cmꢁ1 corresponds to the O–H group bending mode of
31.8, 20.6 ppm; MS (m/z, %): 326.5 (M+, 93.2), 284.5 (50.5), 251.5 water. Moreover, the peaks at 1021 and 792 cmꢁ1 are attributed
(85), 181.5 (32.1), 135.5 (100), 91.5 (24.3), 69.4 (25.8).
to the symmetric and asymmetric stretching vibrations of the
Si–O–Si groups, respectively.18 In the spectrum of SO3-
H@zeolite-Y in Fig. 4b, the broad peak at 3407 cmꢁ1 may be
attributed to the –OH stretching vibration of the –SO3H groups.
While the peak at 1635 cmꢁ1 corresponds to bending mode of
O–H of water. Beside those, the broad band at around
1080 cmꢁ1 corresponds to the Si–O stretching vibration and the
asymmetric and symmetric stretching of S]O bond. The bands
at 944 and 794 cmꢁ1 maybe assigned to the S–O bond. The
displacement of IR bands to lower frequencies (red-shi) in the
spectrum of Ni/SO3H@zeolite-Y in Fig. 4c, as compared with
SO3H@zeolite-Y, conrm the exchange of a number of Ni2+
(heavier cation) with Na+ ion.5
The N2 adsorption–desorption isotherm of zeolitic nano-
composites are shown in Fig. 5. The isotherms exhibit nitrogen
types I isotherms which represents the microporous materials.
Also, by looking at their hysteresis type, it can be seen that zeolitic
structures have slits (layer and layer with high pores) structure and
the initial nanostructure aer the functionalize is still retained.18,39
3. Results and discussion
3.1. Synthesis and characterization of nanocatalyst
In this research, zeolite-NaY was functionalized with organic
and inorganic species. As shown in Scheme 2, SO3H@zeolite-Y
was synthesized by the reaction of chlorosulfonic acid with
zeolite-NaY under solvent-free conditions. Then, Ni(II) ions were
stabilized on the SO3H@zeolite-Y to produce a multi-functional
nanohybrid with strong acidity. A systematic study was carried
out for the characterization of the synthesized Ni/SO3-
H@zeolite-Y. Then the catalytic activity of SO3H@zeolite-Y
supported Ni was investigated for the synthesis of N-
heterocyclic-1,3-thiazolidin-4-one. The number of acidic sites
in the SO3H@zeolite-Y obtained 0.26 mmol gꢁ1 using acid–base
titration 18.
Fig. 2 shows the FE-SEM photographs of the zeolitic nano-
structures. In Fig. 2a, it can be seen clearly that the zeolite-NaY
has a crystalline structure. Fig. 2b shows that structure of
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Fig. 4 The FT-IR spectra of (a) zeolite-NaY, (b) SO3H@zeolite-Y and (c) Ni/SO3H@zeolite-Y.
The hybrid inorganic–organic nanostructure shows a pore size 185 ꢀC is attributed to desorption of physical and chemical
distribution in the range of 2–5.13 nm (Fig. 5c). water molecules through endothermic process. The weight loss
The textural properties of zeolitic frameworks are summa- of 9.56% observed in the temperature range of 200–850 ꢀC
rized in Table 1. Comparison of SBET from 419 m2 gꢁ1 for zeolite- might be attributed to the removal of SO3H groups in the zeolite
NaY to 285 m2 gꢁ1 for SO3H@zeolite-Y shows decrease in framework.
specic surface aer modication with –SO3H and Ni func-
tional groups.40 The data at this table reveals that the SBET of
Ni/SO3H@zeolite-Y (298 m2 gꢁ1) had increased slightly to its
3.2. Catalytic properties of catalyst
former modied structure. Furthermore, the SO3H@zeolite-Y
has a lower pore volume in comparison with zeolite-NaY,
which might be due to the presence of SO3H groups on the
pore surface. Also, this means that the SO3H groups are
graed onto the pore wall surface of zeolite-NaY. This
decrease of pore volume was also observed for the Ni/SO3-
H@zeolite-Y.
3.2.1. Optimization of reaction conditions. To determine
the optimized reaction conditions, a one-pot reaction of 4-
nitrobenzaldehyde, 2-aminobenzimidazole and thioglycolic
acid was performed as the model reaction at room tempera-
ture in the presence of Ni/SO3H@zeolite-Y. The results are
listed in Table 2 which indicate the Ni/SO3H@zeolite-Y as
a powerful nanocatalyst acted at ambient temperature so that
5wt% of the nanocatalyst in acetone/H2O (1 : 1) was optimum
conditions (Table 2, entry 6). Comparing the zeolite-NaY,
TGA curve of Ni/SO3H@zeolite-Y is presented in Fig. 6. The
weight loss of 12.39% between the temperature intervals of 50–
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Fig. 5 N2 adsorption/desorption isotherms of (a) zeolite-NaY and SO3H@zeolite-Y, (b and c) N2 ads./des. isotherm and BJH pore size distri-
butions of Ni/SO3H@zeolite-Y.
SO3H@zeolite-Y and Ni/SO3H@zeolite-Y, it can be concluded efficiency. Looking at Table 2 shows that the reaction yields
that as a nanoporous Ni/SO3H@zeolite-Y is the best catalyst increases in the aprotic-protic polar solvent mixture (water/
due to reduced reaction time and increased product acetone). This may be due to the type of mechanism
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Table
structures
1 Porosimetery values for zeolite-NaY and its modified
5 that is followed by catalytic oxidation process and remove
a H2O molecule to produce the Schiff base I. In second catalytic
activating stage, the nucleophilic attack of thioglicolic acid
takes place to form the third intermediate II. Finally, aer
intermolecular nucleophilic attack and the loss of the another
H2O molecule, cyclization of the 1,3-thiazolidin-4-one products
4a–p can be done.
a
b
c
d
e
SBET
VBJH
DBJH
DAap
PAPS
Samples
(m2 gꢁ1
)
(cm3 gꢁ1
)
(nm)
(nm)
(nm)
Zeolite-NaY
SO3H@zeolite- 285
Y
441
0.032
0.053
6.73
5.15
2.21
2.35
13.6
21.1
3.2.3. Catalytic potential. To study the reusable ability of
the catalyst, the Ni/SO3H@zeolite-Y was recovered from the
reaction mixture at the end of each run by simple ltration,
Ni/
298
0.049
5.14
2.37
20.7
SO3H@zeolite-
Y
ꢀ
and then washed with ethyl acetate and dried at 80 C. The
a
b
c
Specic surface area. Pore volume. Pore size (calculated from the
d
recycled Ni/SO3H@zeolite-Y was tested for more runs under
optimized reaction conditions, and its activity showed that
catalyst has a good reusability even aer ve runs (Table 4).
Also, the Ni content in the nanocatalyst was 21% w/w (atomic
absorption analysis) before the catalytic run, while aer the
h reaction cycle, was marginally decreased to 20.4% w/w
(this reduction can be due to the error in experimental
chemical analysis).
adsorption branch). Adsorption average pore diameter (4V/A by
BET). e Average particle size (estimated using the Temkin method).
proposed (Scheme 3) and the better performance of the
multi-functional nanocatalyst in the water-acetone solvent
mixture.
To demonstrate the versatility and uniqueness of this cata-
lytic transformation, a variety of aromatic aldehydes were con-
verted into corresponding N-benzimidazolyl(thiazolyl)-1,3-
thiazolidin-4-ones in term of low reaction times and high
yields at room temperature. As shown in Table 3, in all cases,
aromatic aldehydes with substituents carrying either electron-
donating (OH, OMe) or electron-withdrawing groups (Cl, Br,
NO2) reacted successfully and gave the expected products in
excellent yields and short reaction times.
3.2.2. Reaction mechanism in the presence of catalyst. The
suggested mechanism of formation of 1,3-thiazolidin-4-ones
catalyzed by the Ni/SO3H@zeolite-Y is shown in Scheme 3. At
the beginning of this catalytic reaction, nano-Ni/SO3H@zeolite-
Y activates the carbonyl group of the aldehyde by the SO3H
functional group and Ni2+ on the surface of zeolite to produce
intermediate 20a–j.
The basic structure of the reused catalyst was also conrmed
with FT-IR spectra. Fig. 7 has indicated that there is no differ-
ence in the FT-IR the fresh and the recovered zeolitic cata-
lysts, approximately. As a result, the heterogeneous nature of
the nanocatalyst is conrmed in this reaction and no
noticeable leaching of amount of Ni or –SO3H groups has
occurred. Also, this minimal reduction in nanocatalyst
activity may be due to the nature and textural properties of
the nanocomposite, such as reducing the specic surface
area or lling a number of cavities.
The catalytic activity of Ni/SO3H@zeolite-Y was compared
with previously reported various catalysts for the preparation of
1,3-tiazolidin-4-one derivatives. The results are listed in Table 5.
The good catalytic performance of the Ni/SO3H@zeolite-Y
nanocatalyst in comparison with other previously reported
procedures, could be due to the fact that the acidic and metal
sites existed on the catalyst.
Aerwards, 2-aminobenzimidazole (2-aminobenzothiazole)
as a nucleophile attacks activated aldehyde to afford the species
Fig. 6 TGA curve of the Ni/SO3H@zeolite-Y.
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Table 2 Optimizing the model reaction conditions at room temperature
Entry
Catalyst loading (w/wt%)
Solvent
Time (min)
Yielda (%)
1
2
3
4
5
6
7
8
5
10
10
10
10
5
3
5
EtOH
EtOH
30
25
45
30
25
15
35
60
35
60
50
15
30
30
240
80
90
72
87
89
97
75
30
73
43
67
42
75
Trace
—
EtOH/H2O (1 : 1)
Acetone
Acetone/H2O (1 : 1)
Acetone/H2O (1 : 1)
Acetone/H2O (1 : 1)
H2O
MeOH
CHCl3
MeCN
Acetone/H2O (1 : 1)
Acetone/H2O (1 : 1)
Acetone/H2O (1 : 1)
Acetone/H2O (1 : 1)
9
5
5
5
10
11
12
13
14
15
5 (NiCl2$2H2O)
5 (SO3H@ZY)
5 (zeolite-Y)
—
a
Isolated yield.
Scheme 3 Proposed mechanism for the synthesis of compounds 4a–p.
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Table 3 Synthesis of compounds 4a–p in the presence of Ni/SO3H@zeolite-Y at room temperature
Entry
Ar-CHO
Product
Time (min)
Mp (ꢀC)
Yielda (%)
1
20
209–210 (208–210)b
85
90
2
3
22
15
245–246 (245–246)
265–267
92
4
5
18
15
147–148 (146–148)
208–210 (207–210)
90
95
6
20
244–246 (244–246)
94
7
20
221–223
89
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Table 3 (Contd.)
Entry
Ar-CHO
Product
Time (min)
Mp (ꢀC)
Yielda (%)
8
25
216 (215–217)
84
9
25
22
21
220 (221–223)
167–169 (167–170)
252–253
87
89
93
10
11
2b
12
13
2d
20
15
171–172
95
97
2e
176
14
2f
20
161–162
95
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Table 3 (Contd.)
Entry
15
Ar-CHO
Product
Time (min)
Mp (ꢀC)
Yielda (%)
2h
25
177–178
90
16
2i
25
194–195
88
a
Isolated yields. b Melting points in parentheses are reported in the literature.37
Table 4 Catalyst recovery study in the model reaction under opti- Table
5 Comparison of the activity of various catalysts for the
mized conditions
synthesis of 1,3-tiazolidin-4-ones
Entry
Time (min)
Yielda (%)
Time
(min)
Entry Catalyst
Condition
Yield (%)
1
2
3
4
5
15
15
15
15
15
97
97
93
92
89
1
2
3
DCC
Ni@zeolite
Pd NPs
THF, RT
60
25–35
60
(59–95) (ref. 36)
(80–95) (ref. 5)
(71–90) (ref. 28)
EtOH, RT
Solvent-free,
100 ꢀ
C
4
5
6
7
Alum
Silica gel
DIPEA
CoFe2O4@SiO2/
Pr-NH2
MW, 100 ꢀC
THF, RT
4–5
(86–98) (ref. 33)
a
Isolated yields.
240–420 (77–96) (ref. 29)
Toluene, reux 180–240 (65–85) (ref. 31)
PhCH3, reux 120–480 (75–85) (ref. 35)
8
9
Catalyst-free
HClO4–SiO2
H2O, RT
PhCH3,
240–420 (79–96) (ref. 32)
180–360 (70–88) (ref. 30)
100 ꢀ
C
10
11
La(NO3)3
MCM-41@Si-L,
CuSO4
EtOH, RT
PhCH3,
24
720
(77–90) (ref. 37)
(77–99) (ref. 41)
110 ꢀ
C
12
Fe3O4@SiO2/
APTPOSS
Solvent-free,
30
(90–94) (ref. 42)
60 ꢀ
C
13
Ni/SO3H@zeolite-Y H2O–acetone, 15–25
85–97 (This
work)
RT
4. Conclusion
In conclusion, the SO3H@zeolite-Y supported Ni has been
synthesized successfully and found to be a highly efficient and
multi-functionalized nanocatalyst for the three-component
Fig. 7 FT-IR spectra of (a) the fresh catalyst and (b) the five-times
reused catalyst.
synthesis
of
3-benzimidazolyl
or
benzthiazoleyl-1,3-
thiazolidin-4-ones under green conditions. This procedure
offers several advantages, including improving the reaction
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performance, operational simplicity without high temperature, 19 (a) D. Jagadeesan, Appl. Catal., A, 2016, 511, 59–77; (b)
exceptionally fast, high yields, low cost, non-toxic nature of the
nanocatalyst, and reusability of the catalyst.
H. Zhang, Y. Zhang, Y. Zhou, C. Zhang, Q. Wang, Y. Xua
and M. Zhang, RSC Adv., 2016, 6, 18685–18694.
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Conflicts of interest
There are no conicts to declare.
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R. M. Hindley, S. A. Smith and P. L. Thurlby, Bioorg. Med.
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Acknowledgements
We are grateful to the research commute of Payame Noor
University for providing nancial and technical supports for
this work.
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