Nickel(II) immobilized on dithizone–boehmite nanoparticles: as a highly efficient and recyclable nanocatalyst for the synthesis of polyhydroquinolines and sulfoxidation reaction

Article abstract of DOI:10.1007/s13738-018-1526-5

In this work, in the first stage, boehmite nanoparticles were easily fabricated via addition of NaOH solution to a solution of Al(NO₃)₃.9H₂O at room temperature in water. Then, nickel–dithizone catalyst was supported on bo

Full text of DOI:10.1007/s13738-018-1526-5

Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-018-1526-5
ORIGINAL PAPER
Nickel(II) immobilized on dithizone–boehmite nanoparticles:
as a highly efficient and recyclable nanocatalyst for the synthesis
of polyhydroquinolines and sulfoxidation reaction
Arash Ghorbani‑Choghamarani1 · Parisa Moradi1 · Bahman Tahmasbi1
Received: 29 April 2018 / Accepted: 11 October 2018
© Iranian Chemical Society 2018
Abstract
In this work, in the first stage, boehmite nanoparticles were easily fabricated via addition of NaOH solution to a solution
of Al(NO3)3.9H2O at room temperature in water. Then, nickel–dithizone catalyst was supported on boehmite nanoparticles
(Ni-dithizone@boehmite). Ni-dithizone@boehmite is a low-cost, nontoxic, and recoverable catalyst, which provides an
environment friendly reaction conditions. In the second stage, catalytic activity of this catalyst was studied in the synthesis
of polyhydroquinoline derivatives and selective oxidation of sulfides to sulfoxides. The reactions not require very high
temperatures or inert atmosphere. The developed heterogeneous catalyst could be easily separated by centrifugation and
recycled for several runs without leaching of Nickel from the surface of the catalyst or significant loss of its catalytic activity.
Keywords Boehmite nanoparticles · Nickel · Polyhydroquinolines · Sulfoxides · Heterogeneous catalyst
Introduction
and chemical or physical properties of boehmite [13–17].
Nevertheless, only a few application of the boehmite nano-
particles have been reported as support for the preparation
of heterogeneous catalysts [18–23]. Therefore, herein we
have used boehmite nanoparticles as support to fabricate
nickel-supported catalyst (Ni-dithizone@boehmite), then its
catalytic application was studied for synthesis of polyhyd-
roquinoline derivatives and selective oxidation of sulfides
to sulfoxides.
The heterogeneous metal catalysts supported on solid nano-
particles have acquired much interest due to their environ-
mentally friendly, recyclability and operational benefits in
comparison with their homogeneous counterparts [1–5].
Boehmite (aluminum oxide hydroxide) is one of the useful
nanomaterials for the preparation of metal-supported cata-
lysts, due to presence of high density of hydroxyl groups on
its surface [6, 7]. Moreover, boehmite nanoparticles with
high surface area and high stability compared to most nano-
particles make it as very appropriate support, which is appli-
cable in different organic reactions [8]. Boehmite has been
used in catalysis, separation, ceramics, adsorption, abra-
sives, fibers, and biomedical applications [9–11]. Boehmite
is also used as a starting material in the preparation of alu-
mina [9, 12]. Several methods such as sol–gel, hydrothermal,
precipitation, and hydrolysis of aluminum have been used
for the preparation of boehmite nanoparticles that most of
them have focused on preparation conditions, morphology,
The synthesis of sulfoxides is an important transforma-
tion in organic chemistry, because sulfoxides are useful in
the synthesis of drugs, enzyme activation, natural products,
germicides, and in medicinal chemistry [24–27]. For exam-
ple, allicin, sulindac, modafinil, garlicnin B-2, garlicnin L-1
and omeprazole are several typical examples of the sulfox-
ide derivatives with pharmaceutical and biological activities
[28, 29]. Among the various oxidants such as metal oxidants,
organic oxidant, peroxides and halogens, H2O2 was com-
monly used for this transformation as an inexpensive and
environmentally benign oxidant [30–35]. Likewise, polyhy-
droquinoline derivatives have important biological activities
such as calcium channel blockers and have been utilized for
the treatment of cardiovascular diseases such as nicardipine,
nifedipine, and amlodipine [36–39]. Therefore, the synthesis
of polyhydroquinolines and sulfoxides has remarkable atten-
tion in organic chemistry.
* Arash Ghorbani-Choghamarani
arashghch58@yahoo.com; a.ghorbani@mail.ilam.ac.ir
1
Department of Chemistry, Faculty of Science, Ilam
University, P.O. Box 69315516, Ilam, Iran
Vol.:(0123456789)
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Journal of the Iranian Chemical Society
Scheme 1 Synthesis of Ni-
dithizone@boehmite
General procedure for the synthesis
of polyhydroquinoline derivatives
Experimental
Preparation of catalyst
A mixture of aldehyde (1.0 mmol), dimedone (1.0 mmol),
ethyl acetoacetate (1.0 mmol), ammonium acetate
(1.3 mmol) and Ni-dithizone@boehmite (20.0 mg) was
stirred in PEG at 80 °C and the progress of the reaction
was monitored by TLC in n-hexane:acetone solution (vol-
ume ratio, 8:2). After completion of the reaction, catalyst
was separated by simple filtration and washed with ethyl
acetate. Products were extracted with water and ethyl ace-
tate. Then, the organic layers were dried over anhydrous
Na2SO4 (1.5 g) and then, solvent was evaporated to obtain
pure products. All products were recrystallized in ethanol.
Modified boehmite nanoparticles with (3-chloropropyl)-
trimethoxysilane (CPTMS@boehmite) was prepared
according to recent reported method [10]. The above-
mentioned solid (1.0 g) was mixed with dithizone
(2.0 mmol) and stirred at 90 °C in toluene for 48 h. The
resulting solid (dithizone@boehmite) was separated using
simple filtration, washed with ethanol and dried at room
temperature. Finally, for the preparation of catalyst, the
dithizone@boehmite (1.0 g) was dispersed in ethanol
and mixed with 2.0 mmol of Ni(NO3)2.2H2O. Then, the
obtained mixture was stirred at 80 °C for 20 h. The solid
product (Ni-dithizone@boehmite) was obtained by simple
filtration, washed with ethanol and dried at 50 °C.
Fig. 1 SEM image of Ni-dithizone@boehmite
Fig. 2 XRD pattern of Ni-dithizone@boehmite
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Fig. 3 TGA/DTA diagrams of
Ni-dithizone@boehmite
Scheme 2 Synthesis of poly-
hydroquinoline derivatives in
the presence of Ni-dithizone@
boehmite
Table 1 Optimization
Entry
Catalyst (mg)
Solvent
Temperature (ºC)
Time (min)
Yield (%)a
conditions in condensation of
benzaldehyde with dimedon,
ethyl acetoacetate, and
1
2
3
4
5
6
7
8
9
10
15
20
25
20
20
20
20
20
PEG
PEG
PEG
PEG
80
80
80
80
40
40
30
25
30
30
30
30
60
53
69
95
96
20
73
48
62
31
ammonium acetate for synthesis
of polyhydroquinolines
H2O
80
EtOH
Ethyl acetate
CH3CN
PEG
Reflux
Reflux
Reflux
60
aIsolated yield
at room temperature for the specified times (Table 4) and
the progress of the reactions was monitored by TLC in
n-hexane:acetone solution (volume ratio, 8:2). After com-
pletion of the reaction, the catalyst was separated by simple
filtration. The products were extracted with water and ethyl
acetate, and dried over anhydrous Na2SO4. Then, the solvent
General procedure for the oxidation of sulfides
to sulfoxides
0.008 g of Ni-dithizone@boehmite was added to a solu-
tion of sulfide (1.0 mmol) and 0.4 mL of H2O2 (33%). The
obtained mixture was stirred under solvent-free conditions
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Journal of the Iranian Chemical Society
Table 2 Synthesis of polyhydroquinoline derivatives in the presence of Ni-dithizone@boehmite in PEG at 80°C
Entry Aryl halide
Phenylating reagent
Time (min) Yield (%)a TOF (h−1
)
Melting point (ºC) Reported
M.P. [Refer-
ences]
1
30
95
231
217–219
216–218 [41]
2
3
130
96
54
175–178
176–178 [41]
235–238 [42]
280
240
45
96
94
93
25
28
234–237
251–253
230–233
4
5
252–253 [43]
230–232 [41]
151
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Table 2 (continued)
Entry Aryl halide
Phenylating reagent
Time (min) Yield (%)a TOF (h−1
)
Melting point (ºC) Reported
M.P. [Refer-
ences]
6
50
97
142
203–204
200–202 [41]
7
250
90
26
255–257
254–256 [41]
8
9
190
95
97
37
245–247
303–305
248–250 [44]
305–307 [44]
60
118
10
65
90
101
184–187
185–186 [43]
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Journal of the Iranian Chemical Society
Table 2 (continued)
Entry Aryl halide
Phenylating reagent
Time (min) Yield (%)a TOF (h−1
)
Melting point (ºC) Reported
M.P. [Refer-
ences]
11
180
89
36
237–239
238–240 [44]
12
240
87
26
239–242
241–244 [45]
13
14
260
200
89
95
25
34
201–204
176–178
203–205 [42]
173–175 [41]
15
160
94
43
226–228
228–230 [41]
aIsolated yield
was evaporated and pure products were obtained in high to
excellent yields.
Results and discussion
Boehmite nanoparticles were prepared and its surface was
modified by CPTMS according to the reported procedure
[10]. To synthesis of dithizone@boehmite, dithizone was
immobilized on boehmite nanoparticles. Then, dithizone@
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Journal of the Iranian Chemical Society
confirmed the crystallization of boehmite in orthorhombic
unit cells [3, 40].
TGA/DTA diagrams of Ni-dithizone@boehmite are
shown in Fig. 3. The mass loss about 10% before 250 °C
is related to the evaporation of water and adsorbed solvents
[41]. Also, the high decreasing of weight is related to immo-
bilize organic layers that are decomposed upon heating from
250 °C to 500 °C (about 15%). Final weight loss (about 5%)
which appeared above 500 °C may be related to transforma-
tion of thermal crystal phase of boehmite nanoparticles.
Scheme 3 Oxidation of sulfides to sulfoxides in the presence of Ni-
dithizone@boehmite
Application of Ni‑dithizone@boehmite
for the synthesis of polyhydroquinolines
Table 3 Optimization of reaction conditions for the oxidation of
methyl phenyl sulfides in the presence of Ni-dithizone@boehmite at
room temperature
The catalytic activity of Ni-dithizone@boehmite was stud-
ied in synthesis of polyhydroquinoline derivatives. Poly-
hydroquinolines were synthesized in the presence of Ni-
dithizone@boehmite based on concise route outlined in
Scheme 2.
Entry Catalyst (mg) Solvent
Time (min) Yield (%)a
1
2
3
4
5
6
7
8
3
5
8
10
8
8
Solvent free
Solvent free
Solvent free
Solvent free
CH3CN
Ethyl acetate
Ethanol
100
100
80
70
80
80
80
80
61
73
96
96
33
46
28
52
To optimize the reaction conditions for the synthesis of
polyhydroquinolines, condensation of benzaldehyde with
dimedone, ethyl acetoacetate, and ammonium acetate was
selected as model reaction. Several parameters such as
amount of Ni-dithizone@boehmite, effect of solvent and
temperature were examined in the selected model reac-
tion. Results of these studies are summarized in Table 1. As
shown in Table 1, the best result was obtained in the pres-
ence of 20 mg (0.82 mol %) of Ni-dithizone@boehmite in
PEG at 80 °C (Table 1, entry 3).
8
8
H2O
aIsolated yield
After optimizing of reaction conditions, the condensation
of different aldehydes with ethyl acetoacetate, dimedone,
and ammonium acetate was then tested to confirm the gen-
erality of this method and obtained results are summarized
in Table 2. Polyhydroquinoline derivatives were obtained
in high yields in the presence of Ni-dithizone@boehmite
with high TOF numbers. As shown in Table 2, a variety
of benzaldehydes bearing electron-donating and electron-
withdrawing substituents (Such as OH, CH3, OCH3, OEt,
halides, and NO2) was successfully employed for the syn-
thesis of polyhydroquinolines. Also, terephthalaldehyde was
investigated and it was afforded the desired product in good
yield (Table 2, entry 9).
boehmite was used as efficient and insoluble support for
nickel(II) (Scheme 1). Further this catalyst (Ni-dithizone@
boehmite) was characterized by thermogravimetric analy-
sis (TGA), scanning electron microscopy (SEM), X-ray dif-
fraction (XRD), atomic absorption spectroscopy (AAS), and
inductively coupled plasma (ICP-OES) techniques.
Catalyst characterizations
SEM image of Ni-dithizone@boehmite is shown in Fig. 1.
The particles size of this catalyst was studied by SEM
technique that it was found to be between 40 and 60 nm.
Also, the amount of Nickel on boehmite nanoparticles
was measured using inductively coupled plasma (ICP)
that was 0.41 × 10−3 mol g−1, which this result has good
agreement with atomic absorption spectroscopy (AAS)
(0.39×10−3 mol g−1).
Application of Ni‑dithizone@boehmite
for the oxidation of sulfides
Also, catalytic activity of Ni-dithizone@boehmite was
studied in the selective oxidation of sulfides to sulfoxides.
Sulfoxides were synthesized through oxidation of sulfides
in the presence of Ni-dithizone@boehmite based on con-
cise route outlined in Scheme 3. Oxidation of methyl phenyl
sulfide using hydrogen peroxide was selected as model reac-
tion for optimize reaction conditions. Obtained results of
The XRD pattern of Ni-dithizone@boehmite is shown
in Fig. 2. As shown in Fig. 2, the boehmite phase was
confirmed from the XRD pattern by the peak positions,
which are in close agreement with standard XRD pattern
of boehmite nanoparticles [12, 40] and all the peaks can be
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Journal of the Iranian Chemical Society
Table 4 Selective oxidation of sulfides to sulfoxides in the presence of Ni-dithizone@boehmite
Entry Sulfide
Product
Time (min) Yield (%)a TOF (h−1
)
Melting point (ºC) Reported
M.P. [Ref-
erences]
1
80
15
96
97
218
30–32
30–32 [26]
2
1175
Oil
Oil [46]
3
4
5
15
5
95
97
80
1151
3527
40
Oil
Oil
Oil
Oil [34]
Oil [34]
Oil [46]
360
6
7
40
88
90
400
136
Oil
Oil [47]
120
84–87
85–89 [34]
8
9
20
75
93
90
845
218
Oil
Oil [46]
60–64
61–64 [26]
10
20
95
863
Oil
Oil [46]
aIsolated yield
Table 5 Comparison of Ni-dithizone@boehmite in the oxidation of
97% 97%
95%
94%
92%
91%
100
80
60
40
20
0
90%
89%
methyl phenyl sulfide with previously reported catalysts
Entry Catalyst
Time (min) Yielda (%) [References]
1
2
DSA@MNPs
360
180
98 [34]
90 [48]
Polymer-anchored
Cu(II)
3
4
5
6
7
8
Cu-SPATB/Fe3O4
Cd-salen-MCM-41
TsOH
Ni-salen-MCM-41
VO2F (dmpz)2
95
150
240
156
300
80
98 [49]
98 [50]
88 [51]
95 [50]
95 [52]
96 [this work]
1
2
3
4
5
6
7
8
Run number
Ni-dithizone@boe-
hmite
Fig. 4 Recycling of Ni-dithizone@boehmite in oxidation of tetahy-
drothiophen
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Journal of the Iranian Chemical Society
optimization conditions in model reaction are summarized in
Table 3. As shown in Table 3, the best results were obtained
in the presence of 0.008 g (0.33 mol%) of catalyst at room
temperature under solvent-free conditions using 0.4 mL of
H2O2.
boehmite can be recovered and recycled over than eight
times without any significant loss of its catalytic activity.
Acknowledgements Authors thank Ilam University and Iran National
Science Foundation (INSF) for financial support of this research
project.
In obtained optimum conditions, the various aliphatic
and aromatic sulfides were successfully converted to their
corresponding sulfoxides in the presence of Ni-dithizone@
boehmite and all products were obtained in good yields
without any byproduct from over oxidation such as sulfone.
The result of these studies is shown in Table 4. To show the
chemoselectivity of present methodology, sulfides including
other functional groups such as olefin or hydroxyl groups
were subjected to sulfoxidation reaction, that these func-
tional groups remained intact during the oxidation condi-
tions (Table 4, entries 2, 6 and 8).
References
1. D. Wang, D. Astruc, Fast-growing field of magnetically recy-
clable nanocatalysts. Chem. Rev. 114, 6949–6985 (2014). https
://doi.org/10.1021/cr500134h
2. D. Astruc, F. Lu, J.R. Aranzaes, Nanoparticles as recyclable
catalysts: the frontier between homogeneous and heterogeneous
catalysis. Angew. Chem. Int. Ed. 44, 7852–7872 (2005). https
://doi.org/10.1002/anie.200500766
3. B. Tahmasbi, A. Ghorbani-Choghamarani, Pd(0)-Arg-boehmite:
as reusable and efficient nanocatalyst in Suzuki and Heck reac-
tions. Catal Lett 147, 649–662 (2017). https://doi.org/10.1007/
s10562-016-1927-y
Reusability of the catalyst
4. G.R. Patzke, Y. Zhou, R. Kontic, F. Conrad, Oxide nanomateri-
als: synthetic developments, mechanistic studies, and techno-
logical innovations. Angew. Chem. Int. Ed. 50, 826–859 (2011).
https://doi.org/10.1002/anie.201000235
Recovering and recycling are major advantages of het-
erogeneous catalysts compared to homogeneous catalysts.
Therefore, the reusability of Ni-dithizone@boehmite was
confirmed in the oxidation of tetrahydrothiophen (Fig. 4).
After completion of each reaction, the catalyst was recovered
by centrifugation, washed with ethyl acetate and reused up
to eight times without any significant loss of its catalytic
activity. The average isolated yield for eight runs was 93.5%,
which clearly indicate the practical reusability of Ni-dithi-
zone@boehmite.
5. H. Hassani, B. Zakerinasab, A. Nozarie, Sulfonic acid sup-
ported on Fe2O3/VO2 nanocatalyst: a highly efficient and reus-
able nanocatalyst for synthesis of spirooxindole derivatives.
Asian J. Green Chem. 3, 59–69 (2018). https://doi.org/10.22631
/ajgc.2017.101572.1032
6. P. Moradi, A. Ghorbani-Choghamarani, Efficient synthesis of
5-substituted tetrazoles catalysed by palladium–S-methyliso-
thiourea complex supported on boehmite nanoparticles. Appl
Organometal Chem 31, e3602 (2017). https://doi.org/10.1002/
aoc.3602
7. M. Bakherad, R. Doosti, M. Mirzaee, K. Jadidi, A.H. Amin,
O. Amiri, Palladium-free and phosphine-free sonogashira cou-
pling reaction of aryl halides with terminal alkynes catalyzed
by boehmite nanoparticle-anchored Cu(I) diethylenetriamine
complex. Res. Chem. Intermed. 43, 7347–7363 (2017). https://
doi.org/10.1007/s11164-017-3079-0
Comparison of the catalyst with previously reported
catalysts
To show the activity and accessibility of Ni-dithizone@
boehmite in comparison with previously reported cata-
lysts, the results for the oxidation of methyl phenyl sulfide
in the presence of Ni-dithizone@boehmite have been
compared with previous catalysts and the results are sum-
marized in Table 5. As shown in Table 5, Ni-dithizone@
boehmite is more effective catalyst in selected reaction,
which product was obtained in higher yields at shorter
reaction time.
8. M. Ghalkhani, M. Salehi, Electrochemical sensor based on
multi-walled carbon nanotubes–boehmite nanoparticle compos-
ite modified electrode. J. Mater. Sci. 52, 12390–12400 (2017).
https://doi.org/10.1007/s10853-017-1361-6
9. S.P. Dubey, A.D. Dwivedi, M. Sillanpaa, H. Lee, Y.N. Kwon,
C. Lee, Adsorption of As(V) by boehmite and alumina of dif-
ferent morphologies prepared under hydrothermal conditions.
Chemosphere 169, 99–106 (2017). https://doi.org/10.1016/j.
chemosphere.2016.11.052
10. A. Ghorbani-Choghamarani, P. Moradi, B. Tahmasbi, Ni–S-meth-
ylisothiourea complexes supported on boehmite nanoparticles and
their application in the synthesis of 5-substituted tetrazoles. RSC
Adv. 6, 56638–56646 (2016). https://doi.org/10.1039/c6ra08026j
11. D. Xu, H. Jiang, M. Li, A novel method for synthesizing well-
defined boehmite hollow microspheres. J. Colloid Interface Sci.
504, 660–668 (2017). https://doi.org/10.1016/j.jcis.2017.05.021
12. A. Ghorbani-Choghamarani, B. Tahmasbi, P. Moradi, Synthesis
of a new Pd(0)-complex supported on boehmite nanoparticles
and study of its catalytic activity for Suzuki and Heck reac-
tions in H2O or PEG. RSC Adv 6, 43205 (2016). https://doi.
org/10.1039/c6ra02967a
Conclusion
Ni-dithizone@boehmite was synthesized by a simple pro-
cedure as an efficient and reusable heterogeneous catalyst
and characterized by SEM, XRD, TGA, AAS and ICP
techniques. This catalyst was successfully applied for the
synthesis of polyhydroquinoline derivatives and selective
oxidation of sulfides to sulfoxides. Also Ni-dithizone@
13. T. Fujii, S. Kawasaki, M. Kanakubo, Differences in crystal
growth behaviors of boehmite particles with octanoic acid and
1 3

Journal of the Iranian Chemical Society
sodium octanoate under supercritical hydrothermal conditions.
J. Supercrit. Fluids 119, 81–87 (2017). https://doi.org/10.1016/j.
supflu.2016.09.011
J Porous Mater 24, 1461–1472 (2017). https://doi.org/10.1007/
s10934-017-0386-1
28. M.M.D. Pramanik, N. Rastogi, Visible light catalyzed methyl-
sulfoxidation of (het)aryl diazonium salts using DMSO. Chem.
Commun. 52, 8557–8560 (2016). https://doi.org/10.1039/C6CC0
4142F
14. Y. Ohta, T. Hayakawa, T. Inomata, T. Ozawa, H. Masuda, Novel
nano boehmite prepared by solvothermal reaction of aluminum
hydroxide gel in monoethanolamine. J. Nanopart. Res. 19, 232
(2017). https://doi.org/10.1007/s11051-017-3918-3
29. K.G.M. Koua, V.M. Dong, Tandem rhodium catalysis: exploiting
sulfoxides for asymmetric transition-metal catalysis. Org. Biomol.
Chem. 13, 5844–5847 (2015). https://doi.org/10.1039/C5OB0
0083A
15. S.M. Kim, Y.J. Lee, K.W. Jun, J.Y. Park, H.S. Potdar, Synthesis
of thermo-stable high surface area alumina powder from sol–gel
derived boehmite. Mater Chem Phys 104, 56–61 (2007). https
://doi.org/10.1016/j.matchemphys.2007.02.044
30. G. Chehardoli, M.A. Zolfigol, Melamine-(H
2SO4)3/melamine-
16. X.Y. Chen, H.S. Huh, S.W. Lee, Hydrothermal synthesis of
boehmite (Γ-Alooh) nanoplatelets and nanowires: ph-controlled
morphologies. Nanotechnology 18, 285608 (2007). https://doi.
org/10.1088/0957-4484/18/28/285608
(HNO3)3 Instead of H2SO4/HNO3: a safe system for the fast
oxidation of thiols and sulfides under solvent-free. J. Sulfur
Chem. 36, 606–612 (2015). https://doi.org/10.1080/17415
993.2015.1074688
17. M. Thiruchitrambalam, V.R. Palkar, V. Gopinathan, Hydrolysis
of aluminium metal and sol–gel processing of nano alumina.
Mater Lett 58, 3063–3066 (2014). https://doi.org/10.1016/j.matle
t.2004.05.043
31. Y. Liu, H. Wang, C. Wang, J.P. Wan, C. Wen, Bio-based green
solvent mediated disulfide synthesis via thiol couplings free of
catalyst and additive. RSC Adv 3, 21369–21372 (2013). https://
doi.org/10.1039/C3RA42915F
18. A. Ghorbani–Choghamarani, M. Hajjami, B. Tahmasbi, N. Noori,
Boehmite silica sulfuric acid: as a new acidic material and reus-
able heterogeneous nanocatalyst for the various organic oxidation
reactions. J. Iran. Chem. Soc. 13, 2193–2202 (2016). https://doi.
org/10.1007/s13738-016-0937-4
32. M.A. Zolfigol, A. Khazaei, M. Safaiee, M. Mokhlesi, R. Rosta-
mian, M. Bagheri, M. Shiri, H.G. Kruger, Application of silica
vanadic acid as a heterogeneous, selective and highly reusable
catalyst for oxidation of sulfides at room temperature. J Mol
Catal A Chem 370, 80–86 (2013). https://doi.org/10.1016/j.molca
ta.2012.12.015
19. M. Hajjami, A. Ghorbani-Choghamarani, R. Ghafouri-Nejad,
B. Tahmasbi, Efficient preparation of boehmite silica dopamine
sulfamic acid as a novel nanostructured compound and its appli-
cation as a catalyst in some organic reactions. New J Chem. 40,
3066–3074 (2016). https://doi.org/10.1039/C5NJ03546E
20. A. Mohammadinezhad, B. Akhlaghinia, Fe3O4@boehmite-NH2-
CoII NPs: an inexpensive and highly efficient heterogeneous mag-
netic nanocatalyst for the Suzuki–Miyaura and Heck–Mizoroki
cross-coupling reactions. Green Chem. 19, 5625–5641 (2017).
https://doi.org/10.1039/C7GC02647A
33. A. Shaabani, A.H. Rezayan, Silica sulfuric acid promoted selec-
tive oxidation of sulfides to sulfoxides or sulfones in the presence
of aqueous H2O2. Catal. Commun. 8, 1112–1116 (2007). https://
doi.org/10.1016/j.catcom.2006.10.033
34. D. Habibi, M.A. Zolfigol, M. Safaiee, A. Shamsian, A. Ghorbani-
Choghamarani, Catalytic oxidation of sulfides to sulfoxides using
sodium perborate and/or sodium percarbonate and silica sulfu-
ric acid in the presence of KBr. Catal. Commun. 10, 1257–1260
(2009). https://doi.org/10.1016/j.catcom.2008.12.066
21. M. Mirzaee, B. Bahramian, J. Gholizadeh, A. Feizi, R. Gholami,
Acetylacetonate complexes of vanadium and molybdenum sup-
ported on functionalized boehmite nano-particles for the catalytic
epoxidation of alkenes. Chem. Eng. J. 308, 160–168 (2017). https
://doi.org/10.1016/j.cej.2016.09.055
35. A. Ghorbani-Choghamarani, H. Rabiei, B. Tahmasbi, B. Ghasemi,
F. Mardi, Preparation of DSA@MNPs and application as hetero-
geneous and recyclable nanocatalyst for oxidation of sulfides and
oxidative coupling of thiols. Res. Chem. Intermed. 42, 5723–5737
(2016). https://doi.org/10.1007/s11164-015-2399-1
22. M. Bakherad, R. Doosti, M. Mirzaee, K. Jadidi, Synthesis of
pyrazolopyranopyrimidines catalyzed by caffeine supported on
boehmite nanoparticles and their evaluation for anti-bacterial
activities. Iran J Catal 7, 27–35 (2017)
36. S.M. Vahdat, F. Chekin, M. Hatami, M. Khavarpour, S. Baghery,
Z. Roshan-Kouhi, Synthesis of polyhydroquinoline derivatives via
a four-component Hantzsch condensation catalyzed by tin diox-
ide nanoparticles. Chin. J. Catal. 34, 758–763 (2013). https://doi.
org/10.1016/S1872-2067(11)60518-4
23. K. Bahrami, M.M. Khodaei, M. Roostaei, The preparation and
characterization of boehmite nanoparticles-TAPC: a tailored and
reusable nanocatalyst for the synthesis of 12-Aryl-8,9,10,12-
tetrahydrobenzo[A]xanthen-11-ones. New J Chem 38, 5515–5520
(2014). https://doi.org/10.1039/C4NJ01128G
37. M. Nasr-Esfahani, S.J. Hoseini, M. Montazerozohori, R. Meh-
rabi, H. Nasrabadi, Magnetic Fe
3O4 nanoparticles: efficient and
recoverable nanocatalyst for the synthesis of polyhydroquinolines
and Hantzsch 1,4-dihydropyridines under solvent-free condi-
tions. J. Mol. Catal. A: Chem. 382, 99–105 (2014). https://doi.
org/10.1016/j.molcata.2013.11.010
24. N.G. Afzaletdinova, E.R. Ibatova, Y. Murinov, Extraction of
iridium (IV) by dihexyl sulfoxide from hydrochloric acid solu-
tions. Russ. J. Inorg. Chem. 51, 971–976 (2006). https://doi.
org/10.1134/S0036023606060209
38. A. Ghorbani-Choghamarani, M.A. Zolfigol, M. Hajjami, H.
Goudarziafshar, M. Nikoorazm, S. Yousefi, B. Tahmasbi, Nano
aluminium nitride as a solid source of ammonia for the prepara-
tion of Hantzsch 1,4-dihydropyridines and bis-(1,4-dihydropyri-
dines) in water via one pot multicomponent reaction. J Braz Chem
Soc 22, 525–531 (2011). https://doi.org/10.1590/S0103-50532
011000300016
25. R.V. Kupwade, S.S. Khot, U.P. Lad, U.V. Desai, P.P. Wadgaonkar,
Catalyst-free oxidation of sulfides to sulfoxides and diethylamine
catalyzed oxidation of sulfides to sulfones using oxone as an oxi-
dant. Res. Chem. Intermed. 43, 6875–6888 (2017). https://doi.
org/10.1007/s11164-017-3026-0
26. L. Shiri, B. Tahmasbi, Tribromide ion immobilized on magnetic
nanoparticles as an efficient catalyst for the rapid and chemoselec-
tive oxidation of sulfides to sulfoxides. Phosphorus Sulfur Silicon
192, 53–57 (2017). https://doi.org/10.1080/10426507.2016.12248
78
39. P.N. Kalaria, S.P. Satasia, D.K. Raval, Synthesis, characterization
and pharmacological screening of some novel 5-imidazopyrazole
incorporated polyhydroquinoline derivatives. Eur. J. Med. Chem.
78, 207–216 (2014). https://doi.org/10.1016/j.ejmech.2014.02.015
40. B. Tahmasbi, A. Ghorbani-Choghamarani, First report of the
direct supporting of palladium–arginine complex on boehmite
nanoparticles and application in the synthesis of 5-substituted
tetrazoles. Appl Organometal Chem 31, e3644 (2017). https://
doi.org/10.1002/aoc.3644
27. M. Hajjami, Z. Shirvandi, Z. Yousofvand, Zr (IV)-ninhydrin sup-
ported MCM-41 and MCM-48 as novel nanoreactor catalysts for
the oxidation of sulfides to sulfoxides and thiols to disulfides.
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Journal of the Iranian Chemical Society
41. A. Ghorbani-Choghamarani, B. Tahmasbi, N. Noori, R. Ghafouri-
nejad, A new palladium complex supported on magnetic nanopar-
ticles and applied as an catalyst in amination of aryl halides, Heck
and Suzuki reactions. J. Iran. Chem. Soc. 14, 681–693 (2017).
https://doi.org/10.1007/s13738-016-1020-x
for oxidation reactions. RSC Adv. 6, 56458–56466 (2016). https
://doi.org/10.1039/c6ra09950e
48. P. Gogoi, M. Kalita, T. Bhattacharjee, P. Barman, Copper–Schiff
base complex catalyzed oxidation of sulfides with hydrogen
peroxide. Tetrahedron Lett. 55, 1028–1030 (2014). https://doi.
org/10.1016/j.tetlet.2013.12.073
42. A. Ghorbani-Choghamarani, B. Tahmasbi, Z. Moradi, S-Benzyli-
sothiourea complex of palladium on magnetic nanoparticles: a
highly efficient and reusable nanocatalyst for synthesis of poly-
hydroquinolines and Suzuki reaction. Appl Organometal Chem.
31, e3665 (2017). https://doi.org/10.1002/aoc.3665
49. S.M. Islam, A.S. Roy, P. Mondal, K. Tuhina, M. Mobarak, J. Mon-
dal, Selective oxidation of sulfides and oxidative bromination of
organic substrates catalyzed by polymer anchored Cu(II) complex.
Tetrahedron Lett. 53, 127–131 (2012). https://doi.org/10.1016/j.
tetlet.2011.10.138
43. M.A. Bodaghifard, M. Solimannejad, S. Asadbegi, S. Dolatab-
adifarahani, Mild and green synthesis of tetrahydrobenzopyran,
pyranopyrimidinone and polyhydroquinoline derivatives and DFT
study on product structures. Res. Chem. Intermed. 42, 1165–1179
(2016). https://doi.org/10.1007/s11164-015-2079-1
50. A. Ghorbani-Choghamarani, B. Tahmasbi, P. Moradi, N. Havasi,
Cu–S-(propyl)-2-aminobenzothioate on magnetic nanoparticles:
highly efficient and reusable catalyst for synthesis of polyhydro-
quinoline derivatives and oxidation of sulfides. Appl Organometal
Chem. 30, 619–625 (2016). https://doi.org/10.1002/aoc.3478
51. M. Nikoorazm, A. Ghorbani-Choghamarani, H. Mahdavi, S.M.
Esmaeili, Efficient oxidative coupling of thiols and oxidation of
sulfides using UHP in the presence of Ni or Cd salen complexes
immobilized on MCM-41 mesoporous as novel and recoverable
nanocatalysts. Microporous Mesoporous Mater. 211, 174–181
(2015). https://doi.org/10.1016/j.micromeso.2015.03.011
52. B. Yu, C.X. Guo, C.L. Zhong, Z.F. Diao, L.N. He, Metal-free che-
moselective oxidation of sulfides by in situ generated Koser’s rea-
gent in aqueous media. Tetrahedron Lett. 55, 1818–1821 (2015).
https://doi.org/10.1016/j.tetlet.2014.01.116
44. G.B. Dharma Rao, S. Nagakalyan, G.K. Prasad, Solvent-free syn-
thesis of polyhydroquinoline derivatives employing mesoporous
vanadium ion doped titania nanoparticles as a robust heterogene-
ous catalyst via the Hantzsch reaction. RSC Adv 7, 3611–3616
(2017). https://doi.org/10.1039/C6RA26664A
45. O. Goli-Jolodar, F. Shirini, M. Seddighi, Introduction of a novel
nanosized N-sulfonated brönsted acidic catalyst for the promotion
of the synthesis of polyhydroquinoline derivatives via Hantzsch
condensation under solvent-free conditions. RSC Adv. 6, 26026–
26037 (2016). https://doi.org/10.1039/C6RA04148E
46. G. Mohammadi Ziarani, A.R. Badiei, Y. Khaniania, M. Haddad-
pour, One pot synthesis of polyhydroquinolines catalyzed by
sulfonic acid functionalized SBA-15 as a new nanoporous acid
catalyst under solvent-free conditions. Iran J Chem Chem. Eng.
29, 1–10 (2010)
53. S. Hussain, D. Talukdar, S.K. Bharadwaj, M.K. Chaudhuri,
VO
2F(dmpz)2: a new catalyst for selective oxidation of organic
sulfides to sulfoxides with H2O2. Tetrahedron Lett. 53, 6512–6515
(2012). https://doi.org/10.1016/j.tetlet.2012.09.067
47. A. Ghorbani-Choghamarani, P. Moradi, B. Tahmasbi, Ni-
SMTU@boehmite: as an efficient and recyclable nanocatalyst
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