Introduction of organic/inorganic Fe3O4@MCM-41@Zr-piperazine magnetite nanocatalyst for the promotion of the synthesis of tetrahydro-4H-chromene and pyrano[2,3-d]pyrimidinone derivatives

Article abstract of DOI:10.1002/aoc.4371

Fe₃O₄@MCM-41@Zr-MNPs modified with piperazine is easily prepared and characterized using Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), N₂ adsorption–desorption, Transmission electron micr

Full text of DOI:10.1002/aoc.4371

Received: 25 November 2017
DOI: 10.1002/aoc.4371
Revised: 24 February 2018
Accepted: 2 March 2018
F U L L P A P E R
Introduction of organic/inorganic Fe3O4@MCM‐41@Zr‐
piperazine magnetite nanocatalyst for the promotion of the
synthesis of tetrahydro‐4H‐chromene and pyrano[2,3‐d]
pyrimidinone derivatives
Reyhaneh Pourhasan‐Kisomi1 | Farhad Shirini1
| Mostafa Golshekan2
1 Department of Chemistry, College of
Fe3O4@MCM‐41@Zr‐MNPs modified with piperazine is easily prepared and
characterized using Fourier transform infrared spectroscopy (FT‐IR), X‐ray
powder diffraction (XRD), N2 adsorption–desorption, Transmission electron
microscopy (TEM), Energy‐dispersive X‐ray (EDX), Vibrating sample magne-
tometry (VSM) and Thermogravimetric analysis (TGA) techniques. The charac-
terization results showed that Zr highly dispersed in the tetrahedral
environment of silica framework and piperazine is successfully attached to
the surface of the nanocatalyst in connection with zirconium. The prepared
nanosized reagent (10–30 nm), shows excellent catalytic activity in the synthe-
sis of tetrahydro‐4H‐chromene and pyrano[2,3‐d]pyrimidinone derivatives. All
reactions are performed under mild and completely heterogeneous reactions
conditions in high yields during short reaction times. On the other hand and
due to its superparamagnetic nature the catalyst can be easily separated by
the application of an external magnetic field and reused for several times.
Sciences, University of Guilan, Rasht
41335‐19141, Iran
2 Neuroscience Research Center,
Department of Pharmacology, Guilan
University of Medical Science, Rasht, Iran
Correspondence
Farhad Shirini, Department of Chemistry,
College of Sciences, University of Guilan,
Rasht, 41335‐19141, Iran.
Email: shirini@guilan.ac.ir
KEYWORDS
Fe3O4@MCM‐41@Zr‐MNPs, piperazine, pyrano[2,3‐d]pyrimidinone, superparamagnetic, tetrahydro‐
4H‐chromene
1 | INTRODUCTION
Tetrahydro‐4H‐chromenes and their derivatives are of
remarkable interest because of their wide range of
Silica mesoporous compounds are defined as natural and
synthetic compounds with a pore size of 2–50 nm, which
are classified between the two micro and macroporous
categories. The unique properties of silica mesoporous
materials like MCM‐41 such as high surface area
(~1000 m2.g−1), large pore size (2–50 nm), narrow pore
size distribution, high thermal stability and the possibility
of using them in a wide range of applications such as
catalization, isolation, photocatalysis, sensors, absorption,
etc. has focused many researchers and scientists studies
on this category of nanoporous materials.[1–7]
biological properties, such as spasmolytic, diuretic,
anti‐coagulant, anti‐cancer and anti‐anaphylactic activi-
ties.[8,9] In addition, they can be used as cognitive
enhancers, for the treatment of neurodegenerative dis-
ease, including Alzheimer's disease, amyotrophic lateral
sclerosis, Huntington's disease, Parkinson's disease, AIDS
associated dementia and Down's syndrome as well as
for the treatment of schizophrenia and myoclonus.[10,11]
4H‐Pyrans also constitute the structural unit of a series
of natural products. Finally, a number of 2‐amino‐4H‐
pyrans are useful as photoactive materials.[12] They are
Appl Organometal Chem. 2018;e4371.
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https://doi.org/10.1002/aoc.4371

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POURHASAN‐KISOMI ET AL.
often used in cosmetics, pigments and utilized as poten-
tial agrochemicals.[13]
Moreover, many zirconium salts are now commercially
available or described in the literature.[37,38] Despite its
advantages, the utility of zirconium (IV) compounds as
Lewis acids for organic reactions has not been exploited
to a greater extent largely compared to other transition
metals.[39–41] With increasing environmental concerns
and the need for efficient and green Lewis acid catalysts
for various useful organic transformations, the interest
in zirconium and its compounds has increased in last
decade.[42]
In order to increase the availability of active sites of
zirconium to compensate its low surface area, it can be
proposed to introduce zirconium into the framework of
molecular sieves pending their synthesis as co‐condensa-
tion or direct ones, by analogy with what had been made
with many other elements. In this type of mesoporous
mixed metal materials, metals are highly dispersed and
more active sites can be available.[43,44] Moreover, the
thermal and hydrothermal stability can be increased.[45]
In addition, to improve zirconium catalytic activity in
organic reactions, functionalization by organic amine
groups like piperazine as a basic functional group seems
to be a good idea.
In the other hand, to protect the environment and in
order to avoid manual attempts to filtrate and purify cat-
alysts, it is urgently needed to improve the methods that
can lead to the recovery and reuse of these nanocompos-
ites at low concentrations in complex matrices. To do
this, heterogenization of the catalyst in the form of
magnetic nanoparticles leads to catalyst recovery using
an external magnetic field and increasing the efficiency
of nanocatalysis in the next reuses.
On the basis of the previously mentioned drawbacks
on the synthesis of tetrahydro‐4H‐chromenes and
pyrano[2,3‐d]pyrimidinones, in order to introduce more
effective, useful and environmentally benign method for
the synthesis of these compounds and in continuation
of our previous reports on the application of different
acidic and basic catalysts, particularly zirconium based
and supported reagents in organic transformations,[46–49]
we were interested to prepare Fe3O4@MCM‐41@Zr‐
piperazine‐MNPs (Figure 1) and investigate its applicabil-
ity in the promotion of the synthesis of the above
mentioned target molecules.
Pyrano[2,3‐d]pyrimidinones are regular structural
subunits in a variety of important natural products,
including carbohydrates, alkaloids, polyether antibiotics,
pheromones, and iridoids. These compounds have
received considerable attention over the past years due
to their wide range of biological activities such as anti‐
tumor, anti‐bacterial, anti‐hypertensive, hepatoprotective,
cardiotonic, vasodilator, bronchodilators and anti‐allergic
activities.[14] Some of them exhibit anti‐malarial, anti‐
fungal, analgesics and herbicidal properties.[15]
Because of the aboved mentioned very important char-
acteristics, various synthetic procedures have been
reported for the synthesis of tetrahydro‐4H‐chromenes
and pyrano[2,3‐d]pyrimidinones using acidic and basic
catalysts such as metformin‐modified silica‐coated mag-
netic
nanoparticles
(MNPs)
(Fe3O4/SiO2‐Met),[16]
Fe3O4@SiO2/DABCO,[8] γ‐Fe2O3@HAp Si(CH2)3AMP,[10]
high surface area MgO,[17] N‐methylimidazole,[9]
tetrabutylammonium bromide,[18] trisodium citrate,[19] p‐
dodecylbenzenesulfonic acid,[11] poly (4‐ vinylpyridine),[20]
potassium phthalimide‐N‐oxyl,[21] [cmmim]Br and
[cmmim][BF4],[22] choline chloride (ChCl),[23] starch solu-
tion,[24] (diacetoxyiodo)benzene (DIB)[25] (for the synthesis
of tetrahydro‐4H‐chromenes), diammonium hydrogen
phosphate (DAHP),[26] L‐proline,[27] KAl(SO4)2.12H2O
(alum),[28] tetrabutylammonium bromide (TBAB),[29]
DABCO,[30] sulfonic acid nanoporous silica (SBA‐Pr‐
SO3H),[31] Al‐HMS‐20,[32] Nano‐ sawdust‐ OSO3H,[33]
ZnO‐supported copper oxide,[14] succinimidinium
hydrogensulfate ([H‐Suc] HSO4)[34] and [H2‐DABCO]
[35]
[H2PO4]2
(for the synthesis of pyrano[2,3‐d]
pyrimidinones). However, aforementioned methods suffer
from some drawbacks such as low yields, extended reaction
times, harsh reaction conditions, tedious work‐up proce-
dures, toxic solvents and application of the expensive or
unavailable catalyst. Moreover, the main disadvantages of
most of the existing methods are that the catalysts are
decomposed under aqueous work‐up conditions and their
recoveries are often impossible. Therefore, the introduction
of new catalytic systems which in them the above men-
tioned difficulties be excluded is still in demand.
The susceptibility of transition elements to mediate
organic synthesis constitutes one of the most efficient
strategies to attain both selectivity and efficiency in
synthetic chemistry.[36] Zirconium pertains to group IV
transition elements that can be considered as efficient
catalysts due to easy availability, low cost and low toxic-
ity. Zirconium (IV) compounds possess a high coordinat-
ing ability due to the higher charge‐to‐size value of Zr4+
compared to most of the metal ions that allows displaying
a good Lewis acid behavior and high catalytic activity.
2 | EXPERIMENTAL
2.1 | Materials
All chemicals including FeCl3·6H2O, FeCl2·4H2O,
tetraethylorthosilicate (TEOS), cetyl trimethylammonium
bromide (CTAB), NaOH, NaF, ZrOCl2.8H2O, piperazine,
benzaldehyde derivatives, dimedone, malononitrile, and

POURHASAN‐KISOMI ET AL.
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FIGURE 1 Preparation of Fe3O4@MCM‐41@Zr‐piperazine‐MNPs
barbituric acid were purchased with high purity from
Merck chemical company (Munich, Germany). All sol-
vents were prepared from Merck (Munich, Germany)
and in order to minimize the absorption of atmosphere
moisturize, in addition to getting distilled before being
used, they were kept sealed in airtight bottles as well.
via Fourier transform infrared spectroscopy (FT‐IR) mea-
surements by Perkin‐Elmer Spectrum BX series in the
range of 400–4000 cm−1. Analyzing the crystal phases
and crystallinity of synthesized MNPs were accomplished
by Philips PW1730 (Netherlands) instrument in the range
of 0.7°–80° (2Ѳ). Iron Scanning electron microphoto-
graphs (FESEM) and Energy Dispersive Spectrometer
(EDS) was performed on a TESCAN MIRA II (Czech
Republic) device to study the size and morphology of
particles. The pore volume, the BET surface area, and
the average pore size obtained before and after the mod-
ification was characterized by N2 adsorption/desorption
which was carried out at 77° K on a BELSORP‐mini II
apparatus using nitrogen. The samples were outgassed
at 393° K and 1 mPa for 12 h before adsorption measure-
ments. Thermogravimetric analysis (TGA) and differen-
tial thermal analysis (DTA) was carried out with a Q600
TGA analyzer under Argon atmosphere from 25 to
1200 °C with a heating rate of 20 °C min−1 over. The
2.2 | Characterization techniques
All products were characterized by comparing their phys-
ical constants, and IR and NMR spectroscopy with
authentic samples and those reported in the literature.
The purity determination of the substrate and reaction
monitoring was accompanied by thin‐layer chromatogra-
phy (TLC) on a silica gel Polygram SILG/UV 254 plate.
Measuring Melting points were accomplished using
electrothermal IA9100 melting point apparatus in
capillary tubes. The quality and composition of pelletized
samples of synthesized nanoparticles were characterized

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POURHASAN‐KISOMI ET AL.
magnetic properties were determined using vibrating
sample magnetometry (VSM; Lake Shore 7200 at 300
2.3.3 | Preparation of piperazine ‐func-
tionalized Fe3O4@MCM‐41@Zr‐MNPs
1
kVsm). H NMR and 13C NMR spectra were determined
For the synthesis of the functionalized Fe3O4@MCM‐
41@Zr‐MNPs with amine groups, we followed the proce-
dure reported by Yue et al.[53] and Yang et al.[52] with
minor modification. Typically, 2.186 g of piperazine was
dissolved in 10 g of methanol, and then 0.3 g of calcined
Fe3O4@MCM‐41@Zr‐MNPs was added to the solution.
The resulting slurry was continuously stirred at room
temperature for 5 h and then dried at 70 °C for the
removal of solvent, followed by further drying at 100 °C
for 1 h.
on Bruker AV‐400 using TMS (0.00 ppm) as internal
standard and DMSO‐d6 as solvent.
2.3 | Preparation of the catalyst
2.3.1 | Preparation of Fe3O4‐MNPs
The synthesis of Fe3O4‐MNPs was accomplished accord-
ing to our previous method with minor modification.[50]
In this way, 6.3 g FeCl3·6H2O, 4.0 g FeCl2·4H2O and
1.7 ml HCl (12 mol l−1) were dissolved in 50 ml of deion-
ized water in a beaker. Then, the solution was degassed
with argon gas and heated to 80 °C in a reactor. Concom-
itantly, 250 ml of a 1.5 mol l−1 ammonia solution was
slowly added to the solution under argon gas protection
and vigorous stirring (1000 rpm). After completion of
the reaction, the resultant black solid of Fe3O4‐MNPs
was separated from the reaction medium using an exter-
nal magnet, and after that was washed four times with
500 ml double distilled water. Finally, the obtained
Fe3O4‐MNPs were resuspended in 500 ml of degassed
deionized water. The concentration of the obtained prod-
2.4 | General procedure for the synthesis
of tetrahydro‐4H‐chromene derivatives
To prepare tetrahydro‐4H‐chromene derivatives, an
equimolar mixture of an aromatic aldehyde (1 mmol),
malononitrile (1.2 mmol), and dimedone (5,5‐dimethyl‐
1,3‐cyclohexanedione) (1 mmol), and Fe3O4@MCM‐
41@Zr‐piperazine nanocatalyst (0.03 g) was dissolved in
3 ml aqueous ethanol (7:3) and stirred at 75 °C for
appropriate time. When the reaction was completed as
indicated by TLC (n‐hexane: ethyl acetate; 6:4), the
mixture was purified with ethanol. Afterward, in the
presence of a magnetic stirrer bar, Fe3O4@MCM‐41@Zr‐
piperazine nanocatalyst was separated and the reaction
mixture turned clear. Finally, the crude product was
recrystallized from EtOH to give a pure product.
uct of Fe3O4‐MNPs was determined as 6.2 mg ml−1
.
2.3.2 | Preparation of Fe3O4@MCM‐
41@Zr‐MNPs
To synthesize Fe3O4@MCM‐41, we followed the method
described by Golshekan et al.[50] As for the introducing
of Zr in the MCM‐41 framework, we followed the
method reported by Chien et al.[51] and Yang et al.[44,52]
2.5 | General procedure for the synthesis
of pyrano[2,3‐d]pyrimidinone derivatives
Fe3O4@MCM‐41@Zr‐piperazine nanocatalyst (0.03 g)
was added to a mixture of the aromatic aldehyde
(1 mmol), malononitrile (1.2 mmol) and barbituric acid
(1 mmol) in 3 ml aqueous ethanol (1.5:1.5). Then the mix-
ture was heated at 80 °C while was monitored by TLC
(n‐hexane: ethyl acetate; 7:3). After completion of the
reaction, the mixture was recrystallized with ethanol.
The magnetic nanocomposites were then separated in
the presence of a magnetic stirring bar; the reaction mix-
ture became clear. The crude product was recrystallized
from ethanol to give a pure product.
with
a little modification. Typically, 2.186 g of
cetyltrimethylammonium bromide (CTAB), 1.461 g of
NaCl and 1.5 g of the synthesized MNPs were mixed in
130 g of H2O at room temperature, and 0.6404 g of
ZrOCl2.8H2O was then added to the above solution. The
resulting solution was stirred vigorously for 1 h, followed
by the addition of 5.2 g of tetraethyl orthosilicate (TEOS).
After being stirred for 1 day, the mixture was transferred
to an autoclave and hydrothermally treated in an oven at
100 °C for 24 h under static conditions. The solid product
was separated using an external magnetic field, washed
thoroughly with distilled water, and dried at 120 °C for
5 h. Finally, the template was removed from the as‐syn-
thesized Fe3O4@MCM‐41@Zr‐MNPs by calcination of
the synthesized particles at 550 °C for 6 h. It's notable
that based on Yang and his coworker's researches,[52] at
a Zr/Si ratio of 3/40, Zr‐MCM‐41 functionalized by the
amine group exhibits the best efficiency.
Spectral (1H and 13C NMR) data of the compounds 4o
and 4p from Table 4 are presented below:
4,4′‐(1,4‐Phenylene)bis(2‐amino‐7,7‐dimethyl‐5‐oxo‐
5,6,7,8‐tetrahydro‐4H‐chromene‐3‐carbonitrile) (4o): m.p.
266–268 °C; IR (neat) v = 3450, 3332, 3185, 2958,2933,
1
2229, 1661, 1584 cm−1; H NMR (DMSO‐d6, 400 MHz):
δ = 0.985 (s, 6H, 2CH3), 1.035 (s, 6H, 2CH3), 2.14–2.38
(m, 4H), 2.45–2.56 (m, 4H), 4.14 (s, 2H), 6.98 (s, 4H,

POURHASAN‐KISOMI ET AL.
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2NH2), 7.04 (s, 4H, Ar‐H);13C NMR (DMSO‐d6,
100 MHz): δ = 27.4, 27.6, 28.6, 32.3, 35.4, 50.4, 58.8,
113.1, 120.2, 127.4, 143.3, 159.0, 163.1, 196.1 ppm.
4,4′‐(1,3‐Phenylene)bis(2‐amino‐7,7‐dimethyl‐5‐oxo‐
5,6,7,8‐tetrahydro‐4H‐chromene‐3‐carbonitrile) (4p): m.p.
240–242 °C; IR (neat) v = 3450, 3384, 3327, 3213, 2961,
Fe3O4@MCM‐41 nanoparticles.[58] The broad strong
bond which appears at 3230 cm−1 is related to the N–H
bond of piperazine and the bands at 2810 cm−1 and
2950 cm−1 are due to CH2 stretching vibrations.[59]
3.1.2 | Powder X‐ray diffraction (XRD)
analysis
2197, 1664, 1601, 1367 cm−1
;
1HNMR (DMSO‐d6,
400 MHz): δ = 0.955 (s, 6H, 2CH3), 1.057 (s, 6H, 2CH3),
2.045 (d, JAB = 17.4 Hz, 2H), 2.28 (d, JAB = 17.4 Hz,
2H), 2.38 (d, JAB = 17.4 Hz, 2H), 2.59 (d, JAB = 17.4 Hz,
2H), 4.113 (s, 2H), 6.80 (s, 1H, Ar), 6.92 (s, 4H, NH),
7.01 (dd, 2H, J1 = 7.6 Hz, J2 = 1.6 Hz), 7.192 (t, 1H,
J = 7.6, Ar) ppm; 13CNMR (DMSO‐d6, 100 MHz):
δ = 19, 26.9, 29.3, 32.1, 35.7, 50.3, 56.5, 58.6, 113.2,
120.1, 125.1, 126.2, 128.3, 145.5, 159, 162.9, 195.9.
X‐ray diffraction (XRD) patterns of the mesoporous
Fe3O4‐MNPs showed peaks that could be indexed both
mesoporous structure and MNPs (Figure 3). The Fe3O4‐
MNPs indicated peaks with 2Ѳ at 29.72°, 35.57°, 43.17°,
57.15° and 62.77° which are characteristic peaks of
Fe3O4 and matched well with the XRD pattern of the
standard Fe3O4 from Joint Committee on Powder Diffrac-
tion Standards (JCPDS No. 19–692).[60] The three peaks
with 2Ѳ at 1.5°–10° are characteristic peaks of MCM‐
41.[50] The peaks resemble those of magnetite, indicates
the presence of magnetite in the caves of the synthesized
nanocomposites. In low angle region, Fe3O4@MCM‐
41@Zr‐MNPs displayed an obvious diffraction peak
around 0.8°‐1°, characteristic of the Bragg plane reflection
(100), and one poorly resolved diffraction peak around 2°‐
4°, indexed as (110) reflection, which indicates the pres-
ence of ordered mesostructure and the incorporation of
Zr4+ in the framework of MCM‐41 as a sufficient evi-
dence.[60] As a more precisely description, consistent with
Yang et al. findings,[44] after incorporation of ZrOCl2 into
the gels, ordered Zr‐MCM‐41 was obtained, with the
explanation that the peak intensity of (100) plane gradu-
ally decreased and the diffraction peaks of (110) and
(200) planes gradually disappeared with introducing of
Zr, which meant that the ordering of Zr‐MCM‐41 samples
decreased when Zr was introduced into the framework of
Fe3O4@MCM‐41‐MNPs.With loading of piperazine, there
is decrease of peak intensity as well as a shift of the (100)
peak for Fe3O4@MCM‐41@Zr‐MNPs to the low angle
degree for Fe3O4@MCM‐41@Zr‐piperazine‐MNPs. The
results are similar to that observed by Xu et al.[61] upon
3 | RESULT AND DISCUSSION
3.1 | Characterization of the catalyst
3.1.1 | FT‐IR analysis
Comparison of the FT‐IR spectra of the Fe3O4‐MNPs,
Fe3O4@MCM‐41@Zr‐MNPs and Fe3O4@MCM‐41@Zr‐
piperazine‐MNPs confirm the structure of the synthesized
nanoparticles (Figure 2). For the bare MNPs, Fe3O4 usu-
ally shows bands at ~560 and 450 cm−1, from Fe–O vibra-
tions at tetrahedral and octahedral sites, respectively.[54]
In the FT‐IR spectra of the finally prepared reagent, there
are stretching vibrations of O–H bonds at ~3435 cm−1
and bending vibrations of these bonds at 1635 cm−1 [55]
.
An intense peak at 1000–1250 cm−1 corresponded to the
Si‐O stretching vibrations in the amorphous silica
shell.[50] Also, the external vibrations of SiO4 chains can
be observed at ~1200 and 800 cm−1 [55]
In this spectra,
.
the angular bending of Si–O units (450 cm−1) is over-
lapped with the Fe–O vibrations.[56,57] The band at
980 cm−1 shows the fundamental vibrations of Zr–O–Si
which overlaps with the Si–OH vibrations of
FIGURE 2 The FT‐IR spectra of a)
Fe3O4‐MNPs b) Fe3O4@MCM‐41@Zr‐
MNPs and c) Fe3O4@MCM‐41@Zr‐
Piperazine‐MNPs

6 of 18
POURHASAN‐KISOMI ET AL.
FIGURE 3 The XRD patterns of a)
Fe3O4@MCM‐41@Zr‐MNPs and b)
Fe3O4@MCM‐41@Zr‐piperazine‐MNPs
the loading of polyethyleneimine (PEI) onto MCM‐41.
Accordingly, The diffraction patterns of MCM‐41 did
not change after the piperazine was loaded, which indi-
cated that the structure of MCM‐41 was preserved. How-
ever, the intensity of the diffraction peaks of MCM‐41 did
change. After loading of piperazine, the intensity of the
pores were filled with piperazine, restricting the access of
nitrogen into the pores at the liquid nitrogen tempera-
ture.[61] The surface area was estimated to be 219.57 m2.
g−1 and the residual pore volume of the Fe3O4@MCM‐
41@Zr‐piperazine‐MNPs is only 0.3072 cm3.g−1. These
results correlate with the pore filling effect of the pipera-
zine which was also reflected by the XRD characteriza-
tion. As we can see, the adsorption curve is identical to
the desorption curve, which indicates that materials
possess broad mesoporous structure.[63] Although after
piperazine impregnation, the BET surface and total pore
volume area were reduced, high surface areas and total
pore volume were observed in Fe3O4@MCM‐41@Zr
supported materials. Consequently, it could be concluded
that well‐organized mesoporous Fe3O4@MCM‐41@Zr‐
piperazine‐MNPs catalyst with a high surface area could
be obtained in the present study.
diffraction
peaks
of
Fe3O4@MCM‐41@Zr‐MNPs
decreased, which was possibly caused by the pore filling
by piperazine.
3.1.3 | BET analysis
The nitrogen adsorption/desorption isotherms of
Fe3O4@MCM‐41@Zr‐MNPs before and after modifica-
tion with piperazine are shown in Figure 4. The iso-
therms correspond to type IV (in the IUPAC
classification), which is typical of mesoporous mate-
rials,[62] and further confirm that the piperazine was
loaded into the pore channels of the MCM‐41 support.
The Brunauer‐Emmet‐Teller (BET) surface areas, total
pore volume and Barret‐Joyne‐Halendu (BJH) pore diam-
eter were 597.42 m2.g−1, 0.3912 cm3.g−1, and 2.6196 nm,
respectively. After loading of piperazine, the mesoporous
3.1.4 | Transmission electron microscopy
(TEM) analysis
The TEM images of the prepared functionalized
Fe3O4@MCM‐41@Zr‐MNPs are shown in Figure 5. The
FIGURE 4 The N2 adsorption/desorption isotherm of a) Fe3O4@MCM‐41@Zr‐MNPs and b) Fe3O4@MCM‐41@Zr‐piperazine‐MNPs

POURHASAN‐KISOMI ET AL.
7 of 18
FIGURE 5 The TEM images of Fe3O4@MCM‐41@Zr‐piperazine‐MNPs
TEM images disclosed the spherical‐like particles of all
samples including agglomeration of dark MNPs cores
surrounded by lighter amorphous silica shells bearing
metals nanoparticles.[50,64]
3.1.5 | EDX analysis
The EDX results of Fe3O4@MCM‐41@Zr‐piperazine‐
MNPs are depicted in Figure 6 indicating the presence
of all expected elements (Fe, Si, Zr, N and O). The exis-
tence of Zr and N elements demonstrates the successful
loading of Zr and piperazine in the next step, onto the
surface of the materials.
FIGURE
6
The EDX profiles of Fe3O4@MCM‐41@Zr‐
piperazine‐MNPs
3.1.6 | TGA analysis
zirconium, so there will be no particular weight loss in
this range of temperature and the observed change can
be related to the desorption of the physically adsorbed
water and removal of OH groups of the MCM network.
Hoewer, in the case of Fe3O4@MCM‐41@Zr‐piperazine‐
MNPs, due to the addition of piperazine as an organic
Thermogravimetric analysis (TGA) was performed
for characterization of Fe3O4@MCM‐41@Zr‐MNPs in
comparison with Fe3O4@MCM‐41@Zr‐piperazine‐MNPs
[Figure 7 (a,b)].
Since more than 90% of the structure of
Fe3O4@MCM‐41@Zr‐MNPs consists of iron, silica, and

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POURHASAN‐KISOMI ET AL.
superparamagnetic behavior, as evidenced by a zero rem-
anence and coercively on the magnetization loop.[55]
The large saturation magnetization values of
Fe3O4@MCM‐41@Zr‐MNPs and Fe3O4@MCM‐41@Zr‐
piperazine‐MNPs were 27.85 emu/g and 35.21 emu/g,
respectively, which is sufficiently high for magnetic sepa-
ration using a conventional magnet. It is deduced that the
decrease in saturation magnetization of Fe3O4@MCM‐
41@Zr‐piperazine‐MNPs is due to the grafted nonmag-
netic organic group, piperazine.
3.2 | Catalytic activity
After identification of the prepared MNPs, the synthe-
sized magnetic catalysts were used to promote the
synthesis of tetrahydro‐4H‐chromene and pyrano[2,3‐d]
pyrimidinone derivatives. At first, the efficiency of
Fe3O4@MCM‐41@Zr in the synthesis of 2‐amino‐4‐(4‐
chlorophenyl)‐7,7‐dimethyl‐5‐oxo‐5,6,7,8‐tetrahydro‐4H‐
chromene‐3‐carbonitrile, 7‐amino‐5‐(4‐bromophenyl)‐
2,4‐dioxo‐1,3,4,5‐tetrahydro‐2H‐pyrano[2,3‐d]pyrimidine‐
6‐carbonitrile and some other derivatives was surveyed
under optimized conditions tabulating in Table 1. Due
to the weak obtained results of these reactions that were
lower than expected and in order to improve the men-
tioned reactions to proceeding more efficiently, we
decided to investigate the influence of Fe3O4@MCM‐
41@Zr functionalized with piperazine in the aforemen-
tioned first two syntheses. In this regard, to prepare these
products in a more efficient way with minimum amount
of the catalyst and generally for optimization of the reac-
tion conditions, the reaction of 4‐chlorobenzaldehyde 1
(1 mmol), malononitrile 2 (1.2 mmol), and dimedone 3
(1 mmol) or barbituric acid 5 (1 mmol) was selected as
a model reaction and the various conditions including
amounts of the catalyst, solvent and temperature were
examined. Finally, the best conditions are selected on
the basis of these results as represented in Schemes 1
and 2. Any further increase of the catalyst or temperature
did not improve the reactions times and yields. The
obtained results were tabulated in Tables 2 and 3.
FIGURE 7 The TGA curves of a) Fe3O4@MCM‐41@Zr‐MNPs
and b) Fe3O4@MCM‐41@Zr‐piperazine‐MNPs
compound, a larger weight loss is observed, which con-
firms the catalyst structure.
3.1.7 | VSM analysis
Figure 8 represents the obtained magnetic hysteresis
curves of MNPs. Both Fe3O4@MCM‐41@Zr‐MNPs and
Fe3O4@MCM‐41@Zr‐piperazine‐MNPs exhibit typical
In order to generalize the best conditions, different
derivatives of tetrahydro‐4H‐chromene (4a‐p) and
pyrano[2,3‐d]pyrimidinone (6a‐j) were prepared and the
results were summarized in Table 4. After ending the
reaction, a small amount of products wasted through
the work‐up process and percentage yields got less than
conversion yields. By comparison of the mass of pure
product, we got from the chemical reaction (actual yield)
and the theoretical maximum (predicted) yield which was
calculated from the balanced equation, the percentage of
product efficiency (percentage yield) was calculated.
Importantly, note that the superparamagnetic nature of
FIGURE 8 The Magnetic hysteresis curves of Fe3O4@MCM‐
41@Zr‐MNPs and Fe3O4@MCM‐41@Zr‐piperazine‐MNPs

POURHASAN‐KISOMI ET AL.
9 of 18
TABLE 1 Preparation of tetrahydro‐4H‐chromene and pyrano[2,3‐d]pyrimidinone derivatives by using Fe3O4@MCM‐41@Zr‐MNPs as the
catalyst
Entry
Aldehyde
Product
Time (min)
Yield (%)a
1
C6H5CHO
4ab
40
74
2
3
4‐ClC6H4CHO
4bbv
30
25
85
82
4‐NO2C6H4CHO
4gb
4
5
C6H5CHO
6ac
35
20
70
78
4‐ClC6H4CHO
6bc
6
4‐NO2C6H4CHO
6gc
30
80
aPercentage yield = [actual yield (e.g. in grams)/ predicted theoretical yield (same mass units as above)] x 100.
bThe reaction was done via condensation of aldehyde (1 mmol), malononitrile (1.2 mmol), dimedone (1 mmol), and Fe3O4@MCM‐41@Zr nanocatalyst (0.03 g)
in 3 ml aqueous ethanol (3:7) at 75 °C.
cThe reaction was done via condensation of aldehyde (1 mmol), malononitrile (1.2 mmol), barbituric acid (1 mmol), and Fe3O4@MCM‐41@Zr nanocatalyst
(0.03 g) in 3 ml aqueous ethanol (1.5:1.5) at 80 °C.
SCHEME 1 Synthesis of tetrahydro‐4H‐chromene derivatives catalyzed by Fe3O4@MCM‐41@Zr‐piperazine‐MNPs in aqueous ethanol
(3:7) at 75 °C

10 of 18
POURHASAN‐KISOMI ET AL.
SCHEME 2 Synthesis of pyrano[2,3‐d]pyrimidinone derivatives catalyzed by Fe3O4@MCM‐41@Zr‐piperazine‐MNPs in aqueous ethanol
(1:1) at 80 °C
TABLE 2 Optimization of the amount of the catalyst, temperature and solvent in the synthesis of tetrahydro‐4H‐chromene derivative of 4‐
chlorobenzaldehyde
Entry
Amount of catalyst (g)
Solvent
Temp. (°C)
Time (min)
Conversion
1
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.02
0.03
0.04
H2O
75
75
75
75
75
r.t
r.t
r.t
75
90
75
60
30
20
30
10
60
60
100
25
32
5
100
100
100
100
100
70
2
C2H5OH
3
C2H5OH: H2O (1:1)
C2H5OH: H2O (3:7)
C2H5OH: H2O (7:3)
CH3COCH3: H2O (1:1)
H2O
4
5
6
7
50
8
C2H5OH
100
98
9
C2H5OH
10
11
C2H5OH: H2O (2:1)
C2H5OH: H2O (7:3)
100
98
TABLE 3 Optimization of the amount of the catalyst, temperature and solvent in the synthesis of pyrano[2,3‐d]pyrimidinone derivative of
4‐chlorobenzaldehyde
Entry
Amount of catalyst (g)
Solvent
Temp. (°C)
Time (min)
Conversion
1
2
3
4
5
6
0.03
0.03
0.03
0.03
0.04
0.02
H2O
80
80
80
r.t
80
80
35
25
5
100
97
C2H5OH
C2H5OH: H2O (1:1)
C2H5OH: H2O (3:7)
C2H5OH: H2O (7:3)
CH3COCH3: H2O (1:1)
100
70
60
20
60
90
50
the synthesized nanocatalyst, as a beneficial and valuable
feature, made the isolation and reuse of this catalyst very
easy. As is shown in Figure 9, in the presence of an exter-
nal magnet, Fe3O4@MCM‐41@Zr‐piperazine‐MNPs was
easily separated from its aqueous suspension in a few
minutes.
However, as indicated in Table 4, aromatic aldehydes
with electron‐withdrawing groups reacted as well as aro-
matic aldehydes with electron‐releasing groups. So the
different group substitution of the aldehydes with the
same groups located at different positions of the aromatic
ring has been shown not to have much effect on the for-
mation of the final product.
It's notable that after completion of the reaction, as
indicated by TLC (n‐hexane: ethyl acetate; 6:4 (the
mixture was dissolved in sufficient amount of ethanol
in order to dissolve all of the chemical product which
results in the presence of insoluble solid catalyst
particles. Then in the presence of a magnetic stirrer
bar, the superparamagnetic nanocatalyst was separated
and the reaction mixture turned clear. Complete and
accurate matching of the melting point range with what

POURHASAN‐KISOMI ET AL.
11 of 18
TABLE 4 Preparation of tetrahydro‐4H‐chromene and pyrano[2,3‐d]pyrimidinone derivatives by using Fe3O4@MCM‐41@Zr‐piperazine‐
MNPs as the catalyst
M. p. (°C)
Time
(min)
Yield
(%)a
Entry
Aldehyde
Product
Found
Reported
[Ref.]
[13]
1
C6H5CHO
4ab
10
81
227‐229
225‐228
[13]
2
3
4‐ClC6H4CHO
4bb
10
90
207‐209
229‐232
208‐210
230‐233
[13]
3‐ClC6H4CHO
4cb
20
87
[13]
4
5
2‐ClC6H4CHO
4‐BrC6H4CHO
4db
5
89
88
216‐218
201‐203
213‐215
199‐201
[13]
4eb
15
[14]
6
7
3‐BrC6H4CHO
4fb
20
89
85
225‐227
178‐179
227‐229
176‐179
[13]
4‐NO2C6H4CHO
4gb
6
[13]
8
9
3‐NO2C6H4CHO
2‐NO2C6H4CHO
4hb
10
4
84
92
202‐204
218‐219
202‐205
213‐217
[13]
4ib
(Continues)

12 of 18
POURHASAN‐KISOMI ET AL.
TABLE 4 (Continued)
M. p. (°C)
Found
Time
(min)
Yield
(%)a
Entry
Aldehyde
Product
Reported
[Ref.]
[13]
10
4‐MeOC6H4CHO
4jb
20
88
196‐198
200‐204
[13]
11
12
2‐MeOC6H4CHO
4‐OHC6H4CHO
4kb
20
35
82
86
203‐265
208‐210
198‐203
210‐214
[13]
4lb
[13]
13
14
4‐MeC6H4CHO
4mb
8
85
90
215‐217
266‐268
211‐214
262‐265
[13]
2‐Naphthaldehyde
4mnb
45
[13]
15
16
4‐NMe2C6H4CHO
4nb
10
20
63
84
202‐204
264‐267
199‐203
266‐268
[15]
Terephthalaldehyde
4ob
[15]
17
Isophthalaldehyde
4pb
40
81
240‐242
243‐244
(Continues)

POURHASAN‐KISOMI ET AL.
13 of 18
TABLE 4 (Continued)
M. p. (°C)
Found
Time
(min)
Yield
(%)a
Entry
Aldehyde
Product
Reported
[Ref.]
[13]
18
C6H5CHO
6ac
20
90
220‐222
219‐222
[13]
19
20
4‐ClC6H4CHO
6bc
10
90
237‐239
238‐240
238‐240
240‐241
[16]
3‐ClC6H4CHO
6cc
30
91
[13]
21
22
2‐ClC6H4CHO
4‐BrC6H4CHO
6dc
35
10
85
88
210‐213
225‐227
209‐214
227‐230
[13]
6ec
[13]
23
24
25
4‐FC6H4CHO
6fc
30
84
92
88
263‐246
238‐240
260‐263
264‐266
237‐239
261‐264
[13]
4‐NO2C6H4CHO
6gc
6
[13]
3‐NO2C6H4CHO
6hc
15
(Continues)

14 of 18
POURHASAN‐KISOMI ET AL.
TABLE 4 (Continued)
M. p. (°C)
Found
>300
Time
(min)
Yield
(%)a
Entry
Aldehyde
Product
Reported
[Ref.]
[13]
26
4‐OHC6H4CHO
6ic
35
59
>300
[13]
27
4‐Terephthalaldehyde
6jc
25
87
>300
>300
aPercentage yield = [actual yield (e.g. in grams)/ predicted theoretical yield (same mass units as above)] x 100.
bThe reaction was done via condensation of aldehyde (1 mmol), malononitrile (1.2 mmol), dimedone (1 mmol), and Fe3O4@MCM‐41@Zr nanocatalyst (0.03 g)
in 3 ml aqueous ethanol (3:7) at 75 °C.
cThe reaction was done via condensation of aldehyde (1 mmol), malononitrile (1.2 mmol), barbituric acid (1 mmol), and Fe3O4@MCM‐41@Zr nanocatalyst
(0.03 g) in 3 ml aqueous ethanol (1.5:1.5) at 80 °C.
FIGURE 9 Photographs of an aqueous
suspension of Fe3O4@MCM‐41@Zr‐
piperazine‐MNPs before (a) and after (b)
magnetic capture
is given in the reference articles is another proof to this
matter, however, the presence of nanocatalyst, as impu-
rity in the obtained product, leads to lower the overall
melting point of the compound and also increase the
range of the melting point value. Additionally, checking
the results of 1HNMR and 13CNMR analysis of the
obtained product ensure us not remaining the
nanocatalyst which has an organic functional group like
piperazine.
In order to reveal the competence of the catalyst, it
was essential to compare the catalytic efficiency of
Fe3O4@MCM‐41@Zr‐piperazine‐MNPs with previous
methods. Thus the synthesis of 2‐amino‐4‐(4‐
chlorophenyl)‐7,7‐dimethyl‐5‐oxo‐5,6,7,8‐tetrahydro‐4H‐
chromene‐3‐carbonitrile 4b (entry 2, Table 4) and
7‐amino‐5‐(4‐bromophenyl)‐2,4‐dioxo‐1,3,4,5‐tetrahydro‐
2H‐pyrano[2,3‐d]pyrimidine‐6‐carbonitrile 6j (entry 22,
Table 4) was mentioned as model reactions with the

POURHASAN‐KISOMI ET AL.
15 of 18
selected catalysts and the results were presented in
Table 5. With an overall look at Table 5, we can perceive
that not only our method is the best choice comparing to
other mentioned catalytic systems in terms of yield and
reaction time, but also high activity, low consumption
of organic solvents, compatibility with environment and
TABLE 5 Comparison of the efficiency of Fe3O4@MCM‐41@Zr‐piperazine‐MNPs with other reported catalysts in the studied reactions
Time Yield
Entry Product
Catalyst
Amount
Condition
(min) (%)
[Ref.]
[16]
[8]
1
2
3
4
5
6
N‐Methylimidazole
TMAH
(S)‐proline
Na2SeO4
(0.2 mol)
(0.1 mol)
(0.5 mol)
(0.1 g)
C2H5OH / r.t.
H2O / r.t
H2O / r.t
H2O: C2H5OH (1:1) / reflux 180
H2O / 80‐90 °C
60 95
30–120 83
[65]
[66]
[67]
[29]
120
97
90
90
95
HDMBAB
(0.12 mol)
7.5
30
Tetrabutylammonium bromide (0.1 mol)
(TBAB)
H2O / reflux
[13]
[19]
[25]
[35]
[28]
7
Fe3O4@SiO2 /DABCO
(0.05 g)
H2O / 80 °C
25
240
90
69
89
95
93
90
p‐Dodecylbenzenesulfonic acid (4 × 10−4 mol) H2O / reflux
8
9
10
11
(Diacetoxyiodo)benzene
[H2‐DABCO][H2PO4]2
KAl(SO4)2.12H2O (alum)
(0.05 mol)
(0.05 g)
(0.1 mol)
H2O: C2H5OH (1:1) / reflux 30
H2O: C2H5OH (1:2) / reflux 15
H2O / 80 °C
40
Fe3O4@MCM‐41@Zr‐Piperazine (0.03 g)
H2O: C2H5OH (7:3) / reflux 10
[This work]
[26]
12
Diammonium hydrogen
phosphate
L‐Proline
KAl(SO4)2.12H2O (alum)
Tetrabutylammonium bromide (0.1 mol)
(TBAB)
(0.1 mol)
H2O: C2H5OH (1:1) / r.t.
120
81
[27]
[28]
[29]
13
14
15
(0.05 mol)
(0.1 mol)
H2O: C2H5OH (1:1) / r.t.
H2O/ 80 °C
H2O / reflux
90
30
25
75
85
85
[16]
16
17
[DABCO](SO3H)2(HSO4)2
Fe3O4@MCM‐41@Zr‐piperazine (0.03 g)
(2 × 10−5 mol) H2O / reflux
5
87
90
H2O: C2H5OH (1:1) / 80 °C 10
[This work]
SCHEME 3 A plausible mechanism for
the preparation of tetrahydro‐4H‐
chromene 4 and pyrano[2,3‐d]
pyrimidinone 6 derivatives

16 of 18
POURHASAN‐KISOMI ET AL.
easy separation via an external magnetic field are
some superiorities of our new proposed catalyst. As
shown in this table, Fe3O4@MCM‐41@Zr‐piperazine‐
MNPs can be proposed as a useful catalyst in terms of
compatibility with the environment, yields of the
products and reaction times compared to the other
reported systems.
intramolecular cyclization and tautomerization to give
the iminium ion (g); upon hydrolysis of this ion the
product 4 can be formed.
3.3 | Reusability of the catalyst
A conceivable mechanism of the catalyst working in
the reaction is outlined in Scheme 3. Accordingly, we sug-
gest that Fe3O4@MCM‐41@Zr‐piperazine‐MNPs is an
effective catalyst for the generation of iminium ion (a)
which its higher reactivity compared to the carbonyl
group species is utilized to facilitate the Knoevenagel con-
densation between aryl aldehyde 1 and anionic form of
malononitrile 2 (through H adsorption by piperazine),
which proceeds via intermediate (c) and, after dehydra-
tion, olefin (d) is produced. Fe3O4@MCM‐41@Zr‐pipera-
zine‐MNPs also catalyzes the formation of a proposed
enamine intermediate (e) from β‐ diketone 3, which
reacts with the cyano olefin (d) via a nucleophilic
addition to produce intermediate (f) followed by an
To investigate the activity constancy of the catalyst, the
catalyst was reused five times in the synthesis of 2‐amino‐
4‐(4‐chlorophenyl)‐7,7‐dimethyl‐5‐oxo‐5,6,7,8‐tetrahydro‐
4H‐chromene‐3‐carbonitrile 4b (entry 2, Table 4) and
7‐amino‐5‐(4‐chlorophenyl)‐2,4‐dioxo‐1,3,4,5‐tetrahydro‐
2H‐pyrano[2,3‐d]pyrimidine‐6‐carbonitrile 6b (entry 19,
Table 4) under both the best reactions conditions. The cat-
alyst was magnetically recovered after each run, washed
with ethanol, dried in air prior to use and tested for its
activity in the subsequent run. This procedure was
repeated 5 times for both reactions and each time the
mentioned product was obtained by the recovered catalyst
with the slight change in the reaction time and yield as
shown in Figures 10 and 11.
FIGURE 10 Reusability of
Fe3O4@MCM‐41@Zr‐piperazine‐MNPs in
the synthesis of 2‐amino‐4‐(4‐
chlorophenyl)‐7,7‐dimethyl‐5‐oxo‐5,6,7,8‐
tetrahydro‐4H‐chromene‐3‐carbonitrile 4b
FIGURE 11 Reusability of
Fe3O4@MCM‐41@Zr‐piperazine‐MNPs in
the synthesis of 7‐amino‐5‐(4‐
chlorophenyl)‐2,4‐dioxo‐1,3,4,5‐
tetrahydro‐2H‐pyrano[2,3‐d]pyrimidine‐6‐
carbonitrile 6b

POURHASAN‐KISOMI ET AL.
17 of 18
[13] S. R. Kamat, A. H. Mane, S. M. Arde, R. S. Salunkhe, IJPCBS.
2014, 4, 1012.
4 | CONCLUSION
[14] J. Albadi, A. Mansournezhad, T. Sadeghi, Res. Chem. Intermed.
2015, 41, 8317.
In conclusion, based on different represented analyses,
Fe3O4@MCM‐41@Zr modified with piperazine, as a
new stable and highly active catalyst, has been synthe-
sized successfully and surveyed its capability in preparing
a variety of tetrahydro‐4H‐chromene and pyrano[2,3‐d]
pyrimidinone derivatives under mild conditions. The
green conditions, excellent yields, practicability, opera-
tional simplicity, product purity, cost efficiency and
environmentally profits are the considerable advantages
of this protocol. According to these observations, it could
be deduced that this green, recyclable and cost‐effective
catalyst, with simple experimental and work‐up
procedure, makes it a useful alternative to the previous
methodologies for the scale‐up of these one‐pot three‐
component reactions.
[15] H. Kefayati, M. Valizadeh, A. Islamnezhad, Electrochemistry
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We are thankful to the Research Council of the Univer-
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