Application of Yttrium Iron Garnet as a Powerful and Recyclable Nanocatalyst for One-Pot Synthesis of Pyrano[2,3-c]pyrazole Derivatives under Solvent-Free Conditions

Article abstract of DOI:10.1134/S1070428019110186

The application of yttrium iron garnet (YIG) superparamagnetic nanoparticles as a new recyclable and highly efficient heterogeneous magnetic catalyst for one-pot synthesis of pyrano[2,3-c]pyrazole derivatives under solvent-free conditions, as well as etherification and esterification reactions are described. The advantages of the proposed method include the lack of organic solvents, clean reaction, rapid removal of the catalyst, short reaction times, excellent yields, and recyclability of the catalyst.

Full text of DOI:10.1134/S1070428019110186

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2019, Vol. 55, No. 11, pp. 1755–1763. © Pleiades Publishing, Ltd., 2019.
Application of Yttrium Iron Garnet as a Powerful and Recyclable
Nanocatalyst for One-Pot Synthesis
of Pyrano[2,3-c]pyrazole Derivatives
under Solvent-Free Conditions
E. Sedighiniaa, R. Badria,*, and A. R. Kiasatb
a Department of Chemistry, Khouzestan Science and Research Branch, Islamic Azad University, Ahvaz, Iran;
Department of Chemistry, Ahvaz Branch, Islamic Azad University, Ahvaz, Iran
b Department of Chemistry, College of Science, Shahid Chamran University, Ahvaz 61357-4-3169, Iran
*e-mail: rashidbadri@scu.ac.ir; rashidbadri@yahoo.com
Received June 19, 2019; revised August 17, 2019; accepted September 3, 2019
Abstract––The application of yttrium iron garnet (YIG) superparamagnetic nanoparticles as a new recyclable
and highly efficient heterogeneous magnetic catalyst for one-pot synthesis of pyrano[2,3-c]pyrazole derivatives
under solvent-free conditions, as well as etherification and esterification reactions are described. The
advantages of the proposed method include the lack of organic solvents, clean reaction, rapid removal of the
catalyst, short reaction times, excellent yields, and recyclability of the catalyst.
Keywords: nanoparticle, yttrium iron garnet, pyrano[2,3-c]pyrazole, etherification, esterification, one-pot
synthesis, sol–gel
DOI: 10.1134/S1070428019110186
INTRODUCTION
group of natural active compounds. Among them
polyfunctional heterocyclic compounds have emerged
as the most important class of nitrogenous heterocycles
in the field of organic, combinatorial and pharmacolo-
gical chemistry because of their presence as efficient
core structures in many biologically active compounds
[13]. Pyrano[2,3-c]pyrazole derivatives, which belong to
this class of heterocycles, exhibit a broad spectrum of
biological activities, both natural and synthetic, and play
a special role in the design of anticancer, anti HIV,
antitumor, anti-inflammatory, analgesic, bronchodila-
tor, antiviral, antipyretic, anti-fungal, antibacterial,
antiprotozoal, and anticoagulant drugs [14–20].
Search for new catalysts with excellent activity,
high selectivity, low toxicity, high surface area, high
stability and, more important, allowing easy removal is
among the main aims of chemical research and
industry [1–3]. These properties are characteristic of
magnetic nanoparticles (MNPs), among which ferrites
MNPs are have by far been the most used type of
MNPs. The application of ferrites MNPs in a wide range
of sensors, imaging agents, storage media, adsorbents,
microelectronics, and catalysts and catalyst supports in
chemistry and biomedicine have been reported [4–9].
In the present study we demonstrated the utility of
YIG superparamagnetic nanoparticles as a catalyst for
mild and efficient synthesis of pyrano[2,3-c]pyrazole
derivatives. The YIG catalyst showed such advantages
as simple work up, clean reaction, short reaction times,
excellent yields, as well as easy removability and
recyclability.
Garnets are interesting ferrites, and many studies
have been devoted to their magnetic properties. Since
its discovery in 1956, yttrium iron garnet (YIG) has
attracted a lot of attention due to its applications in
magneto-optical domains and microwave devices [10–
12]. Despite of the great utility of ferrites in chemical
synthesis, as well as higher scores of garnet than other
ferrites, it has not yet been used as a catalyst in
chemistry.
RESULTS AND DISCUSSION
Recently, significant attention has been paid to
nitrogenous heterocycles as the largest and important
The take nanoparticles discovered in other sciences
and test their catalytic properties in chemistry allows
1755

SEDIGHINIA et al.
1756
one to save time and money for the synthesis and
identification of new materials. Yttrium iron garnet
Y3Fe5O12 (YIG) is an example of ferrimagnetic cera-
mics used in passive microwave devices. It contains
Fe3+ and Y3+ ions distributed between different sites of
the compound [21]. Nanoparticles of YIG were
prepared according to the reported procedure [22] with
a minor modification. The surface-to-volume ratios of
nanoparticles are very high and crucial in their
catalytic effect in organic synthesis, and, therefore, the
increase of this ratio with decreasing particle size
enhances the catalytic activity of the nanoparticles.
is an effective synthetic tool with excellent advantages
widely accepted in industry and organic synthesis (see
Supplementary materials). The catalytic performance
of YIG nanoparticles was first tested in simple etherifi-
cation (Table 1) and esterification (Table 2). Reactions
and the catalyst showed good activity in both reactions.
After successful testing with excellent results, YIG nano-
particles was used for the one-pot multicomponent
synthesis of pyrano[2,3-c]pyrazole derivatives (Table 3).
In summary, in the present study, super
paramagnetic nanoparticles of YIG were used as a
green, an efficient, and an easy-to-handle catalyst for
etherification and esterification reactions and synthesis
of pyrano[2,3-c]pyrazole derivatives. This method
Superparamagnetic YIG nanoparticles of about 40–
50 nm were prepared using the sol–gel method, which
Table 1. Solvent-free etherification of alcohols in the presence of YIG nanoparticles
YIG (0.005 g)
2R_OH
ROR
Solvent-free, 80°C
Entry no.
R–OH
Product
Time, min
Yield, %
91
H3C CH CH2 OH
CH3
1
2
ROR
ROR
15
15
93
H3C
OH
OH
3
4
5
6
7
8
ROR
ROR
ROR
ROR
ROR
ROR
15
15
15
15
15
15
93
91
95
93
91
87
OH
CH2OH
MeO
CH2OH
CH2OH
CH2
CH2OH
Cl
9
ROR
ROR
20
20
87
89
CH2OH
CH2OH
NO2
10
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APPLICATION OF YTTRIUM IRON GARNET AS A POWERFUL AND RECYCLABLE
1757
Table 2. Solvent-free acetylation of alcohols with acetic acid in the presence of YIG nanoparticles
YIG (0.005 g)
R_OH
CH3COOR
Acetic acid, 80°C
Entry no.
R–OH
Product
Time, min
Yield, %
1
2
CH3CH2OH
CH3COOR
CH3COOR
15
15
93
94
H3C
OH
C2H5
CH OH
H3C
3
CH3COOR
15
94
4
5
6
7
OH
OH
CH3COOR
CH3COOR
CH3COOR
CH3COOR
15
15
20
20
93
94
94
91
CH2OH
CH2
CH2OH
CH3
CH3
H3C
CH2OH
8
CH3COOR
20
93
MeO
CH2OH
9
CH3COOR
CH3COOR
20
20
93
91
CH2OH
10
Cl
11
12
CH3COOR
CH3COOR
20
89
87
CH2OH
NO2
20
CH2OH
offers some advantages, including high yields and
short reaction times. The catalyst could be reused more
than eight reaction cycles with significant loss in
catalytic activity (Fig. 1, for the first cycle 96% and for
the Eighth cycle 91% yield). The proposed interesting
concept of using garnet MNPs as a catalyst can
extended to other organic syntheses.
EXPERIMENTAL
All solvents and reagents purchased from
Sigma–Aldrich and Merck and were of high-grade
quality used as received. Products were separated,
purified by different chromatographic techniques,
and identified by comparing their IR and NMR
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SEDIGHINIA et al.
1758
Table 3. One-pot three-component synthesis of pyrano[2,3-c]pyrazole derivatives in the presence of YIG nanoparticles
X
CHO
O
H3C
N
NH2
Y3Fe5O12
+
NC
CN
+
+
CN
YIG, solvent-free, 80°C
NHR
O
X
EtO
N
O
NH2
R
R = H, Ph.
Entry no.
Aldehyde
R
Product
Time, min
Yield, %
NO2
CHO
H3C
1
H
H
H
20
20
20
94
91
90
CN
N
NO2
N
O
NH2
H
CHO
H3C
N
2
3
CN
N
O
NH2
H
Cl
CHO
H3C
CN
N
Cl
N
O
NH2
Cl
H
CHO
H3C
N
4
5
H
H
20
20
90
89
CN
Cl
N
O
NH2
H
CHO
NO2
CN
H3C
N
O2N
N
O
NH2
H
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APPLICATION OF YTTRIUM IRON GARNET AS A POWERFUL AND RECYCLABLE
Table 3. (Contd.)
Entry no.
1759
Aldehyde
R
Product
Time, min
Yield, %
OMe
CHO
H3C
N
6
H
20
92
CN
OCH3
N
O
O
O
NH2
CF3
H
CHO
H3C
N
7
8
9
H
H
H
20
20
20
89
91
90
CN
CF3
N
NH2
NO2
H
CHO
H3C
CN
N
NO2
N
NH2
H
OMe
CHO
H3C
N
CN
OMe
N
O
NH2
H
NO2
CHO
H3C
10
PH
20
95
CN
N
NO2
CHO
N
O
NH2
Ph
H3C
N
11
PH
20
90
CN
N
O
NH2
Ph
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SEDIGHINIA et al.
R
1760
Table 3. (Contd.)
Entry no.
Aldehyde
Product
Time, min
Yield, %
Cl
CHO
H3C
12
PH
20
90
CN
N
N
Cl
O
NH2
Cl
Ph
CHO
H3C
13
14
PH
CN
20
30
92
90
N
N
Cl
O
NH2
Ph
CHO
H3C
NO2
CN
O2N
PH
N
N
O
NH2
Ph
OCH3
CHO
OMe
H3C
15
PH
20
92
CN
N
N
O
NH2
CF3
Ph
CHO
H3C
16
17
PH
20
20
93
94
CN
N
N
CF3
O
NH2
Ph
CH3
CHO
CH3
H3C
PH
CN
N
N
O
NH2
Ph
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APPLICATION OF YTTRIUM IRON GARNET AS A POWERFUL AND RECYCLABLE
1761
Table 3. (Contd.)
Entry no.
Aldehyde
R
Product
Time, min
Yield, %
OCH3
CHO
H3C
N
18
PH
20
89
CN
OMe
N
NH2
O
Ph
spectra and melting points with respective
characteristics of authentic samples. Yttrium iron
garnet was prepared according to [24] with minor
modifications.
Fe (NO3)3·9H2O (2.74 g) were dissolved in deionized
water (50 mL). After stirring at room temperature (1 h),
citric acid (6.83 g) was added to the solution, and it
was refluxed at 80°C for 60 min until to allow
formation of a gel which was then dried at 115°C for
24 h. The dry powder was ground and annealed at
1000°C for 4 h (Fig. 2). The product was characterized
by XRD, FT-IR spectroscopy, SEM, TEM and TGA.
(For detailed information, see Supplementary materials).
1
13
The H and C NMR spectra were measured on a
Bruker DPX-400 AVANCE spectrometer in CDCl3
against internal TMS. The IR spectra were obtained on
a Perkin–Elmer LXI85256 spectrometer. The melting
points were determined on an electrothermal capillary
melting point apparatus and are uncorrected. The
reaction progress was monitored by TLC (on silica gel
polygram SILG/UV 254 plates) given in Supplemen-
tary materials through scanning electron microscopy,
transmission electron microscopy (TEM), thermos
gravimetric analysis (TGA).
Typical procedure for etherification of alcohols
in the presence of YIG nanoparticles. 2 mmol of
alcohol and 0.005 g of catalyst was heated at 80°C.
The progress of the reactions was monitored by TLC
(acetone–n-hexane, 1 : 2). After completion of the
reaction, the catalyst was easily removed from the
product by turning off the stirrer without using any
external magnet. The product was removed and dried
Synthesis of nano yttrium iron garnets Y3Fe5O12.
Weighed amounts of Y(NO3)3·6H2O (1.56 g) and
Table 4. Comparison of different catalysts in the synthesis of pyrano[2,3-c]pyrazole
Reference
Entry no.
Catalyst
Time, min
Yield, %
[25]
[26]
1
2
3
4
5
6
7
SPPyNsa
DBSAb
30–60
180
50–92
82–94
85–90
89–92
93–97
79–82
89–95
[27]
Palladium nanoparticles
PVPyc
4–43
[28]
18–65
25–60
30–60
15–20
SB-DABCOd
NMPyTSe
[29]
[30]
This work
YIG nanoparticles
a
b
c
d
e
Sulfonated polypyrrolenanospheres.
p-Dodecylbenzenesulfonic acid.
Poly(4-vinylpyridine).
Silica bonded n-propyl-4-aza-1-azoniabicyclo[2.2.2]octane chloride.
N-Methyl pyridinium tosylate.
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SEDIGHINIA et al.
1762
Fig. 2. Preparation of nano yttrium iron garnets Y3Fe5O12.
SUPPLEMENTARY MATERIALS
Fig. 1. Recyclability of YIG in the synthesis of pyrano[2,3-
c]pyrazole derivatives under solvent- free conditions.
Supplementary materials are available for this
article at https://doi.org/10.1134/S1070428019110186
and are accessible for authorized users.
under vacuum. For the reaction times and the
structures and yields of the products, see Table 1.
ACKNOWLEDGMENTS
Typical procedure for acetylation of alcohols
with acetic acid in the presence of YIG
nanoparticles. Mixture of 0.005 g and glacial
acetic acid was placed in a 50-mL round bottom
flask, and was stirred for 5 min. Then, alcohol
(1 mmol) was added to the solution, and reaction
solution was stirred under reflux condition for
specified time. The progress of reaction was monitored
by TLC (acetone–n-hexane, 1 : 2). After completion
of the reaction, catalyst was easily removed by
shutting down the stirrer without using any external
magnet. The product was purified by recrystalliza-
tion in hot ethanol. For the reaction times and
the structures and yields of the products, see
Table 2.
The authors are grateful to the Ahvaz Branch, Islamic
Azad University, for financial support.
CONFLICT OF INTEREST
The authors declare no conflict of interest
REFERENCES
1. Avelino, C., and Hermenegildo, G., Top. Catal., 2008,
vol. 48, p. 8.
https://doi.org/10.1007/s11244-008-9056-5
2. Weckhuysen, B.M., Nat. Chem., 2009, vol. 1, p. 690.
https://doi.org/10.1038/nchem.453
3. Graham, J.H., Mater. Chem., 2009, vol. 19, p., 1222.
https://doi.org/10.1039/B812300B
Typical procedure used for preparation of
4. Kiasat, A.R. and Nazari, S., J. Incl. Phenom. Macrocycl.
Chem., 2013, vol. 6, p. 363.
https://doi.org/10.1007/s10847-012-0207-8
5. Pyun, J., Polym. Rev., 2008, vol. 47, p. 231.
https://doi.org/10.1007/978-3-319-08446-6
6. Kassaee, M.Z., Masrouri, H., and Movahedi, F., Appl.
Catal. A, 2011, vol. 395, p. 28.
pyrano[2,3-c]pyrazole derivatives.
A
mixture
containingethyl acetoacetate (1 mmol), hydrazine/phe-
nylhydrazine (1 mmol), aromatic aldehyde (1 mmol),
malononitrille (1 mmol), and nanopowders of yttrium
iron garnet (0.005 g) was heated at 80°C under well-
mixed conditions for appropriate time. Completion of
the reaction was indicated by TLC (acetone–n-hexane,
1 : 2). After completion of the reaction, the stirrer was
turned off, and the entire catalyst was readily collected
by the internal magnet, and was washed by 10 mL of
water–ethanol solution (1 : 1), and then was dried in
air for further use. Insoluble crude product was
dissolved in hot ethanol, and the product was purified
by recrystallization in ethanol to afford a pure product.
For the reaction times and the structures and yields of
the products, see Table 3.
https://doi.org/10.1016/j.apcata.2011.01.018
7. Badruddoza, A.Z.M., Tay, A.S.H., Tan, P.Y., Hidajat, K.,
and Uddin, M.S., J. Hazard. Mater., 2011 vol. 185,
p. 1177.
8. Akoz, E., Erdemir, S., and Yilmaz, M., J. Inclusion.
Phenom. Macrocycl. Chem., 2012, vol. 73, p. 449.
https://doi.org/10.1007/s10847-011-0083-7
9. Movlaee, K., Ganjali, M.R., Norouzi, P., and Giovanni, N.,
Nanomat. (Basel), 2017, vol. 7, p. 406.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 11 2019

APPLICATION OF YTTRIUM IRON GARNET AS A POWERFUL AND RECYCLABLE
1763
20. Rostamizadeh, Sh., Nojavan, M., Aryan, R., Isapoor, E.,
and Azad, M., J. Mol. Catal. A-Chem., 2013,
vols. 374–375, p. 102.
https://doi.org/10.3390/nano7120406
10. Sankaranarayanan, V.K. and Gajbhiye, N.S., J. Am.
Cer. Soc., 1990, vol. 73, p. 1301.
https://doi.org/10.1016/j.molcata.2013.04.002
21. Mallmann, E.J.J., Sombra, A.S.B., Goes, J.C., and
Fechine, P.B.A., Solid State Phenom., 2013, vol. 202, p. 65.
https://doi.org/10.4028/www.scientific.net/SSP.202.65
22. Zhanxing, S., Minghaoa, F., Dehua, Ch., Lixian, W.,
Yangai, L., and Zhaohui, H., Key Eng. Mater.,
2008, vols. 368–372, p. 582.
https://doi.org/10.4028/www.scientific.net/KEM.368-
372.582
23. Niznansky, D., Lancok, A., Hutlova, A., and Bursık, J.,
Int. J. Inorg. Mat., 2001, vol. 3, p. 479.
https://doi.org/10.1016/s1466-6049(01)00063-0
24. Sedighinia, E., Badri, R., and Kiasat, A.R., Org. Chem.
Res., 2018, vol. 4, p. 110.
https://doi.org/10.22036/org.chem.2018.60464.1077
25. Fadovipoor, E., Nazari, S., Zarei Ahmady, A.,
Gorjizadeh, M., Afshari, M., and Keshavarz, M., Orient.
J. Chem., 2015, vol. 31, p. 733.
https://doi.org/10.1111/j.1151-2916.1990.tb05195.x
11. Gheiratmand, T., Madaah Hosseini, H.R., Shalbaf, F.,
Mohhebali, M., Mozaffari, M.A., Arabi, S.H., and
Farzanegan, F., J. Supercond. Novel Magn., 2017,
vol. 30, p. 3085.
https://doi.org/10948-017-4115-4
12. Hosseini Vajargah, S., Madaah Hosseini, H.R., and
Nemati, Z.A., J. Alloys Compd., 2007, vol. 430, p. 339.
https://doi.org/10.1016/j.jallcom.2006.05.023
13. Yancheng, H., Xiaoyi, X., and Boshun, W., Tetrahedron
Lett., 2015, vol. 56, p. 32.
https://doi.org/10.1016/j.tetlet.2014.11.061
14. Vigorita, M.G., Ottana, R., Monforte, F., Maccari, R.,
Trovato, A., Monforte, M.T., and Taviano, M.F., Bio.
Org. Med. Chem. Lett., 2001, vol. 11, p. 2791.
https://doi.org/10.1016/j.jscs.2012.09.001
15. Rawal, R.K., Tripathi, R., Katti, S.B., Pannecouque, C., and
De Clercq, E., Bio. Org. Med. Chem., 2007, vol. 15, p. 31.
https://doi.org/10.13005/ojc/310215
https://doi.org/10.1016/j.bmc.2006.12.003
16. Adib, M., Sheibani, E., Zhu, L-G., Mirzaei, P.,
Tetrahedron Lett., 2008, vol. 49, p. 5108.
17. Palekar, V.S., Damle, A.J., and Shukla, S.R., Eur.
J. Med. Chem., 2009, vol. 44, p. 5112.
26. Jin, T-Sh., Zhao, R-Q., and Li, T-Sh., Arkivoc, 2006, p. 176.
https://doi.org/10.3998/ark.5550190.0007.b18
27. Saha, M. and Kumar Pal, A., Adv. Nanopart., 2012,
p. 61.
https://doi.org/10.4236/anp.2012.13009.
28. Albadi, J. and Mansournezhad, A., Curr. Chem.
Lett., 2014, vol. 3, p. 221.
https://doi.org/10.1016/j.2009.07.023
18. Mironov, M.A., QSAR Comb. Sci., 2005, vol. 25, p. 423.
https://doi.org/10.1002/qsar.200540190
https://doi.org/10.5267/j.ccl.2014.10.001
29. Hasaninejad, A., Shekouhy, M., Golzar, N., Zare, A., and
Doroodmand, M.M., Appl. Catal. A, 2011, vol. 402,
p. 11.
https://doi.org/10.1016/j.apcata.2011.04.012
30. Giribala, M.B., Vinod, T.K., and Sandeep, T.A., Iran.
Chem. Commun., 2017, vol. 5, p. 268.
19. Sala, M., Chimento, A., Saturnino, C., Gomez-
Monterrey, I.M., Musella, S., Bertamino, A., Milite, C.,
Sinicropi, M.S., Caruso, A., Sirianni, R., Tortorella, P.,
Novellino, E., Campiglia, P., and Pezzi, V., Bio. Org.
Med. Chem. Lett., 2013, 23, p. 4990.
https://doi.org/10.1016/j.bmcl.2013.06.051
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 11 2019