Fe3O4@THAM-piperazine: a novel and highly reusable nanocatalyst for one-pot synthesis of 1,8-dioxo-octahydro-xanthenes and benzopyrans

Article abstract of DOI:10.1007/s11164-020-04166-z

Abstract: A novel magnetically heterogeneous nanocatalyst has been successfully synthesized via the immobilization of piperazine on tris (hydroxymethyl) aminomethane-coated Fe₃O₄ magnetic nanoparticles. The described catalyst was ful

Full text of DOI:10.1007/s11164-020-04166-z

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-020-04166-z
Fe O @THAM‑piperazine: a novel and highly
3
4
reusable nanocatalyst for one‑pot synthesis
of 1,8‑dioxo‑octahydro‑xanthenes and benzopyrans
1
1
1
Homayoun Faroughi Niya · Nourallah Hazeri · Maryam Fatahpour ·
Malek Taher Maghsoodlou1
Received: 23 March 2020 / Accepted: 24 April 2020
©
Springer Nature B.V. 2020
Abstract
A novel magnetically heterogeneous nanocatalyst has been successfully synthesized
via the immobilization of piperazine on tris (hydroxymethyl) aminomethane-coated
Fe O magnetic nanoparticles. The described catalyst was fully characterized by
3
4
various techniques such as FT-IR, EDS, DTG/TGA, XRD, TEM, SEM, and VSM
analyses. The catalytic eꢀcacy of Fe O @THAM-piperazine has investigated for
3
4
one-pot synthesis of tetrahydrobenzo[b]pyran and 1,8-dioxo-octahydro-xanthene
derivatives. Notable features of this user-friendly catalytic system include high
yields, high catalytic activity, simple operation, non-toxicity, and easy work-up.
Also, the new nanocatalyst could be easily recovered and reused for six times with-
out signiꢁcant loss of activity.
Graphic abstract
Keywords Heterogeneous nanocatalyst · Fe O @THAM-piperazine · Magnetic
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4
separation
*
Nourallah Hazeri
nhazeri@chem.usb.ac.ir; n_hazeri@yahoo.com
Extended author information available on the last page of the article
Vol.:(012
1
3456789)
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H. Faroughi Niya et al.
Introduction
Nowadays, magnetically heterogeneous nanocatalysts have played an important
role in modern technology and science, especially in organic syntheses [1–3].
These nanoparticles (NPs) are used in various biological ꢁelds and industries
such as drug delivery, bio-separations, hyperthermia, magnetic resonance imag-
ing, and catalytic processes [4–14]. The magnetic nanoparticles have gained
much attention in expanding medical applications. The most popularly used mag-
netic nanoparticles in medical usages such as chromium dioxide (CrO ), iron
2
oxide (Fe O ), maghemite (γ-Fe O ), and cobalt ferrite (Fe CoO ) [15]. Among
3
4
2
3
2
4
various magnetic nanoparticles, Fe O -NPs have diꢂerent attributes, including
3
4
high thermal and mechanical stability, high catalytic activities, high surface area,
easy synthesis, and easy magnetically recovered [7]. Fe O -NPs are applied as
3
4
a Fenton catalytic material [16–19]. Because these nanoparticles contain both
3
+
2+
Fe and Fe ions, they have high catalytic activity, unlike other Fenton reagents
with only one valence state [20–23]. Also, their superior characteristics, such as
easy work-up and reusability, caused that their usages are increased in the one-
pot synthesis [23–27]. In recent years, Fe O MNPs have great valence in the
3
4
modern application within bioengineering and biomedical ꢁelds, such as labeling
and sorting of cells, magnetic resonance imaging (MRI), separation of biomedi-
cal products, as well as cancer chemotherapy [28–30]. Fe O MNPs were synthe-
3
4
sized by several methods that the methods of co-precipitation [31, 32], ionother-
mal [33, 34], and solvothermal [35, 36] are the most important of them. Among
all the present methods, the co-precipitation method was known as a widely used
technique due to its eco-friendly procedure, lower reaction temperature, and easy
operation [37]. By now, several magnetically heterogeneous nanocatalysts have
been reported with high activity and selectivity in multicomponent reactions
(
MCRs) such as Fe O @THAM-SO H [23], MNPs–PhSO H [27], Fe O NPs@
3
3
4
4
3
3
3
4
TiO NTs [38], Fe O @TiO /Cu O [39], and Fe O /PEG@CPTMS-thioami-
2
2
2
3
4
nophenol@Ni [40].
On the other hand, xanthene derivatives, especially 1,8-dioxo-octahydroxan-
thenes, have become very popular due to their pharmacological and therapeutic
characteristics such as antiviral, anti-inꢃammatory, and antibacterial properties.
Also, they have been applied in visualization of biomolecules, laser technology,
and photodynamic therapy [41]. The tetrahydrobenzo[b]pyrans are well known as
an important class of organic compounds owing to their application in the treat-
ment of several neurodegenerative disorders such as Parkinson’s disease, Alzhei-
mer’s disease, Huntington’s disease, and amyotrophic lateral sclerosis [42]. Due
to the importance of 1,8-dioxo-octahydro-xanthene and tetrahydrobenzo[b]pyran
derivatives, there is an extensive interest in the synthesis of such compounds.
Tris (hydroxymethyl) aminomethane (THAM) was introduced as an inexpen-
sive and non-toxic buꢂer solution that widely used molecular biology and bio-
chemistry [43–45]. The buꢂer range and pKa of THAM were measured around
the pH of 8.6 and 7-9, respectively [46]. Tris (hydroxymethyl) aminomethane is
rich in donor–acceptor groups due to three CH OH groups and a NH functional
2
2
1
3

Fe O @THAM-piperazine: a novel and highly reusable…
3
4
group [47], which makes it useful for coating on the surface of Fe O NPs to
3
4
2
+
improve the stability of Fe O NPs through interacting THAM with Fe and pre-
3
4
venting from its oxidation by the air [48].
In this research, we report a heterogeneous basic nanocatalyst using piperazine
as a basic functional group on tris (hydroxymethyl) aminomethane immobilized on
Fe O nanoparticles. Then, the activity of this novel and recyclable nanocatalyst
3
4
is investigated for the pseudo-three-component synthesis of 1,8-dioxo-octahydro-
xanthene derivatives from the reaction between benzaldehyde (1) and dimedone
(
2), and also the three-component synthesis of tetrahydrobenzo[b]pyran derivatives
using benzaldehyde (1), dimedone (2), and malononitrile (3) (Scheme 1).
Experimental
General
Melting points of all compounds were determined with an Electrothermal 9100
1
apparatus. IR and H NMR spectra of known compounds were recorded on FT-IR-
JASCO-460 plus spectrometer and BRUKER DRX 300 MHz in DMSO at 300 Hz,
respectively. All the chemicals were purchased from Aldrich and Merck and were
used without further puriꢁcation.
Synthesis of Fe O MNPs
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Fe O MNPs have been synthesized using the chemical co-precipitation technique
3
4
according to previously reported route [23]. Initially, the mixture FeCl ·6H O
3
2
(
10.0 mmol) and FeCl ·4H O (5.0 mmol) were stirred in 100 mL deionized water
2 2
until the solids were completely dissolved under a ꢃow of nitrogen. In the next
Scheme 1 Fe O @THAM-piperazine catalyzed one-pot synthesis of 1,8-dioxo-octahydro-xanthene and
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4
tetrahydrobenzo[b]pyran derivatives
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H. Faroughi Niya et al.
step, to the solution, ammonium hydroxide solution (25%) was added dropwise
and stirred vigorously at a rate of 1000 rpm. After reaching the pH value to 11–12,
the resulting mixture was allowed to stir vigorously at room temperature, for 1 h.
Finally, the obtained magnetic nanoparticles were ꢁltered and washed with EtOH
and Et O and dried at 60 °C in an oven, for 2 h.
2
Synthesis of Fe O @THAM MNPs
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4
THAM-capped Fe O NPs were constructed according to previously reported route
3
4
[
49]. Fifty mL of ethanol was added to the synthesized Fe O (1 g) and was dis-
3 4
persed using an ultrasonic bath for 30 min. Then, THAM (2 g) was added to this
suspended mixture and was reꢃuxed at 100°C under N atmosphere for 24 h. After
2
cooling to room temperature, prepared Fe O @THAM were separated by an exter-
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4
nal magnet and washed several times with H O in order to completely remove the
2
unreacted compound and dried at 60 °C.
Synthesis of Fe O @THAM––CH CH –Cl MNPs
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4
2
2
Fe O @THAM–CH CH –Cl NPs were prepared according to previous reports [27].
3
4
2
2
First, 50 mL of CH CN was added to the as-synthesized MNPs (1 g) and was ultra-
3
sonically dispersed for 15 min. Next, dichloroethane (1 mL, 12.6 mmol) was added
dropwise to the mixture of Fe O @THAM–CH CH –Cl in acetonitrile, and trieth-
3
4
2
2
ylamine (0.1 mL) was used as a proton scavenger. After that, the resulting mixture
was reꢃuxed under N atmosphere for 24 h. Finally, after cooling ꢁnal product to
2
room temperature, the desired product was washed with water/ethanol, ꢁltered using
a magnet, and dried at 60 °C.
Synthesis of Fe O @THAM‑piperazine
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4
First, 50 mL methanol was added to 1 g of the prepared magnetite Fe O @
3
4
THAM–CH CH –Cl nanoparticles and was dispersed using an ultrasonic bath for
2
2
2
0 min. Next, piperazine (2.0 g) was added dropwise to the reaction mixture and was
stirred at 90 °C under N atmosphere for 24 h. The resulting nanoparticles (Fe O @
2
3
4
THAM-piperazine) were separated by an external magnet and washed several times
with ethanol in order to completely remove the unreacted compound and dried at
6
0 °C.
General procedure for pseudo‑three‑component synthesis
of 1,8‑dioxo‑octahydro‑xanthene derivatives
A mixture of dimedone (2.0 mmol), aldehydes (1.0 mmol), and Fe O @THAM-
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4
piperazine (10 mg) as catalyst in 5 mL of H O:EtOH (1:1) as solvent was reꢃuxed
2
at 100 °C for the appropriate time. After the completion of the reaction, which was
monitored by thin layer chromatography (TLC), the catalyst was extracted from
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3

Fe O @THAM-piperazine: a novel and highly reusable…
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4
the reaction mixture using an external magnet, and the product was collected by
ltration.
ꢁ
General procedure for three‑component synthesis of tetrahydrobenzo[b]pyran
derivatives
A mixture of dimedone (1.0 mmol), malononitrile (1.0 mmol) aldehydes (1.0 mmol),
and Fe O @THAM-piperazine (10 mg) as catalyst in 5 mL of H O:EtOH (1:1) as
3
4
2
solvent was stirred at 100 °C for the appropriate time. After the completion of the
reaction, which was monitored by thin layer chromatography (TLC), the catalyst was
ꢁ
ltered from the reaction mixture using an external magnet, and the desired products
were aꢂorded by ꢁltration.
Selected spectra for three known products are given below
9
‑(3,4‑dimethoxyphenyl)‑3,3,6,6‑tetramethyl‑3,4,5,6,7,9‑hexahydro‑1Hxan-
−1
thene‑1,8(2H)‑dione (4d) IR (KBr, cm ): 3007 (C–H
), 2957 (C–H
),
aromatic
aliphatic
3
1
1
666 (CO), 1627 (CO), H NMR (400 MHz, CDCl ): δ 1.03 (s, 6H, 2CH ), 1.13
3
(
s, 6H, 2CH ), 2.20 (d, J=16.2 Hz, 2H, 2CH ), 2.27 (d, J=16.5 Hz, 2H, 2CH ),
3
2
2
2
.48 (s, 4H, 2CH ), 3.81 (s, 3H, OCH ), 3.87 (s, 3H, OCH ), 4.27 (s, 1H, CH), 6.73
2 3 3
(
d, J=8.1 Hz, 2H, Ar-H), 6.78 (dd, J=8.2 Hz, J=1.8 Hz, 2H, Ar-H), 6.92 (d, 1H,
J=0.18 Hz, Ar-H).
2
‑amino‑5,6,7,8‑tetrahydro‑4‑(4‑chlorophenyl)‑7,7‑dimethyl‑5‑oxo‑4H‑
−1
chromene‑3‑carbonitrile (5b) IR (KBr, cm ): 3380 (NH ), 3285 (NH ), 2958 (C–
2
2
1
H
), 2188 (CN), 1248 (CO), H NMR (300 MHz, DMSO-d ): δ 0.96 (s, 3H, CH ),
aliphatic
6 3
1
.05 (s, 3H, CH ), 2.13 (d, 1H, J=15.9 Hz), 2.27 (d, 1H, J=16.2 Hz), 2.52 (s, 2H,
3
CH ), 4.22 (s, 1H, CH), 7.08 (s, 2H, NH ), 7.19 (d, 2H, Ar, J=8.1 Hz), 7.36 (d, 2H, Ar,
2
2
J=8.1 Hz).
2
‑amino‑5,6,7,8‑tetrahydro‑4‑(4‑nitrophenyl)‑7,7‑dimethyl‑5‑oxo‑4H‑chromene‑3‑car-
−1
bonitrile (5e) IR (KBr, cm ): 3395 (NH ), 3324 (NH ), 2963 (C–H
), 2192
2
2
aliphatic
3
1
(
CN), 1250 (CO), H NMR (300 MHz, DMSO-d ): δ 0.97 (s, 3H, CH ), 1.06 (s,
6
3
H, CH ), 2.13 (d, 1H, J=15.6 Hz), 2.28 (d, 1H, J=16.2 Hz), 2.52 (d, 2H, CH ,
3
2
J=8.7 Hz), 4.38 (s, 1H,CH), 7.20 (s, 2H, NH ), 7.46 (d, 2H, Ar, J=8.1 Hz), 8.19 (d,
2
2
H, Ar, J=8.7 Hz).
Results and discussion
Herein, we reported the synthesis of Fe O @THAM-piperazine nanocatalyst for the
3
4
ꢁ
rst time. The synthesis of new nanocatalyst was performed in four stages, accord-
ing to Scheme 2. Initially, magnetite (Fe O ) nanoparticles were synthesized by
3
4
the chemical co-precipitation method and coated with Tris (hydroxymethyl) ami-
nomethane and subsequently modiꢁed by dichloroethane and piperazine. Then, the
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H. Faroughi Niya et al.
Scheme 2 Preparation of Fe O @THAM-piperazine
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4
Fe O @THAM-piperazine nanoparticles were identiꢁed by Fourier X-ray spectros-
3
4
copy (EDS), ꢁeld emission scanning electron microscopy (FE-SEM), transform
infrared (FT-IR), thermogravimetric (TGA), X-ray diꢂraction (XRD), diꢂerential
thermal analysis (DTA), transmission electron microscopy (TEM), and vibrating
sample magnetometer (VSM) analyses.
Morphology and size of samples
The SEM images of Fe O @THAM-piperazine and Fe O nanoparticles are shown
3
4
3
4
in Fig. 1. It is clear that the particles of uncoated Fe O (Fig. 1a) and Fe O @
3
4
3
4
THAM-piperazine (Fig. 1b) are the same in both size and shape. Spherical morphol-
ogy with an average particle size of about 16 nm for nanoparticles was observed.
Also, EDS analyses of Fe O @THAM-CH CH -Cl and Fe O @THAM-piperazine
3
4
2
2
3
4
nanoparticles are presented in Fig. 1. As can be seen, the Fe O @THAM-CH CH -
3
4
2
2
Cl nanoparticles have Fe, O, C, N, and Cl elements (Fig. 1c). Also, the elemental
compositions of Fe O @THAM-piperazine nanoparticles are 53.4%, 24.4%, 19.3%,
3
4
and 3% for Fe, O, C, N, respectively (Fig. 1d). The absence of Cl element in the
EDS spectrum of Fe O @THAM-piperazine demonstrates that piperazine was
3
4
immobilized on the surface of Fe O @THAM-CH CH -Cl MNPs. The particle size
3
4
2
2
distribution of Fe O (a) and Fe O @THAM-piperazine (b) is shown in Fig. 2.
3
4
3
4
The shape and morphology of Fe O @THAM-piperazine nanoparticles were
3
4
studied by TEM (Fig. 3), which exhibits a spherical morphology. This result was
also conꢁrmed by the achieved SEM date.
FT‑IR analysis
The FT-IR analysis of Fe O @THAM-piperazine and Fe O nanoparticles is
3
4
3
4
shown in Fig. 4. The FT-IR spectra of the Fe O NPs were conꢁrmed by stretching
3
4
1
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Fe O @THAM-piperazine: a novel and highly reusable…
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Fig. 1 SEM images and EDS spectrums of Fe O and Fe O @THAM-piperazine
3
4
3
4
Fig. 2 Particle size distribution diagram of Fe O (a) and Fe O @THAM-piperazine (b)
3
4
3
4
−1
vibrations at 550–650 cm , which are assigned to Fe-O bond. Also, the absorption
−
1
−1
peaks at about 3374 cm and 1618 cm are due to stretching vibration and bending
vibration of O-H bond on the surface of Fe O , respectively (Fig. 4a). The spec-
3
4
trum of Fe O @THAM-piperazine (Fig. 4b) shows the broad bond which appears
3
4
−
1
at 3200 cm is probably attributed to the N–H bond of piperazine, which is over-
lapped by the OH stretching vibration. Furthermore, the absorption peak at about
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H. Faroughi Niya et al.
Fig. 3 TEM images of Fe O @THAM-piperazine
3
4
Fig. 4 FT-IR spectra of Fe O (a) and Fe O @THAM-piperazine (b)
3
4
3
4
1
3

Fe O @THAM-piperazine: a novel and highly reusable…
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374 cm− is due to bending vibration of the CH group of the organic layer on the
1
3
2
surface of Fe O (Fig. 4b).
3
4
XRD analysis
The XRD patterns of Fe O @THAM-piperazine and Fe O nanoparticles (Fig. 5)
3
4
3
4
identically display peaks positions at about 2θ=74.43, 62.79°, 57.35°, 53.85°,
3.36°, 35.68°, and 30.03°, which are indexed as (6 6 0), (4 4 0), (5 1 1), (4 2 2),
4
(
4 0 0), (3 1 1), and (2 0 2), respectively. Also, the XRD pattern of Fe O @THAM-
3 4
piperazine (Fig. 5b) presents an additional broad peak at 2θ=0°–20°, which corre-
sponds to the amorphous organic immobilized onto the Fe O nanoparticles.
3
4
TG/DTG analysis
TG/DTG analysis was used for studying the thermal resistance of Fe O @THAM-
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4
piperazine nanoparticles in a nitrogen atmosphere with a test speed of 10 °C per
minute between 25–600 °C (Fig. 6). The ꢁrst weight loss below 180 °C, accom-
panied by endothermic peaks in the DTG diagrams, is related to the desorption of
physically adsorbed solvent and moisture (5.26%). The combustion of the organic
moiety grafted on the Fe O NPs (THAM-piperazine) occurred in the temperature
3
4
range of 180–600 °C (10.87%). The results are indicative of the amount of loaded
organic materials (THAM-piperazine) on 1 g of Fe O NPs equal to 108.7 mg. Fur-
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4
thermore, the DTG curve shows an exothermic step in 275 °C due to the decom-
position of organic material in the nanocatalyst. This is proof of the stabling of the
Fe O @THAM-piperazine nanoparticles below this temperature.
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4
Fig. 5 XRD pattern of Fe O (a) and Fe O @THAM-piperazine (b)
3
4
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4
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H. Faroughi Niya et al.
Fig. 6 TGA and DTG curves of Fe O @THAM-piperazine
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4
Fig. 7 VSM spectra of Fe O (a) and Fe O @THAM-piperazine (b)
3
4
3
4
Magnetic properties
The room temperature magnetization behaviors of Fe O and Fe O @THAM-
3
4
3
4
piperazine nanoparticles were analyzed by the VSM analytical method (Fig. 7).
As can be seen, both Fe O MNPs and Fe O @THAM-piperazine MNPs show
3
4
3
4
typical superparamagnetic behavior. The severity of the saturation magnetiza-
tion (Ms) of Fe O MNPs and Fe O @THAM-piperazine MNPs were 116.6 and
3
4
3
4
−
1
3
3.43 emu g , respectively. This decrease in MS value can be attributed to the
successful loading of organic materials (THAM-piperazine) on the surface of
Fe O MNPs.
3
4
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Fe O @THAM-piperazine: a novel and highly reusable…
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Table 1 Eꢂect of solvent on
Entry
1
2
3
Solvent
EtOH
Time (min)
Yield (%)
model reaction at 60 °C
55
35
35
35
87
80
a
H O:EtOH (1:1)
2
H O
2
aBold indicates rate of solvent for high amount of product
Catalytic application of Fe O @THAM‑piperazine
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4
After identifying the new nanocatalyst, it was decided to study its catalytic activity
for the synthesis of 1,8-dioxo-octahydro-xanthenes and tetrahydrobenzo[b]pyrans
(
Scheme 1). The pseudo-three-component reaction of benzaldehyde (1) and dime-
done (2) was selected as a model reaction. Initially, the eꢂect of solvent was deter-
mined and the results were registered in Table 1. It was found that the reaction accel-
erated in H O:EtOH (1:1) in the presence of 0.01 g of Fe O @THAM-piperazine as
2
3
4
catalyst at 60 °C (Table 1, entry 2).
In the next step, to achieve the optimal conditions, the amount of Fe O @
3
4
THAM-piperazine was investigated and the results clearly showed that the
amount of 10 mg of Fe O @THAM-piperazine MNPs is the best choice for the
3
4
Table 2 Optimization of reaction conditions for the synthesis of 1,8-dioxo-octahydro-xanthenes
Entry
Catalyst (gr)
Temperature (°C)
Time (min)
Yield (%)
1
2
3
4
5
7
8
9
No catalyst
0.005
0.01
0.015
0.01
0.01
0.01
0.01
50
50
50
50
r.t
60
70
90
100
110
40
35
35
35
95
35
30
20
15
15
56
54
84
53
60
87
86
88
88
80
1
1
0a
0.01
0.01
1
aBold indicates appropriate reaction condition to produce high amount of product
1
3

H. Faroughi Niya et al.
catalyst (Table 2, entry 3). Finally, the eꢂect of temperature was investigated, and
the best conversion has resulted at 100 °C for 15 min. In the optimal conditions,
the corresponding product was synthesized with a good yield of 88%. (Table 2,
entry 10).
After the optimization of the various reaction parameters, the catalytic system
was applied for the synthesis of 1,8-dioxo-octahydro-xanthene derivatives using
various aldehydes with para-, meta-, ortho-substituted groups. The corresponding
products were synthesized with short reaction times and excellent to good yield
of 80%-95% (Table 3).
In another study, in order to deꢁne the catalytic activity of the Fe O @
3
4
THAM-piperazine MNPs, the synthesis of tetrahydrobenzo[b]pyrans was per-
formed as same conditions and the products were prepared in good yields,
so we have accomplished two reactions at the similar conditions. As shown in
Table 4, various aldehydes with para-, meta-, ortho-substituted were reacted
with dimedone (2) and malononitrile (3) under optimized conditions to produce
tetrahydrobenzo[b]pyrans. The high yields of the respective products conꢁrmed
the catalytic role of Fe O @THAM-piperazine MNPs.
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4
A proposed mechanism for the synthesis of tetrahydrobenzo[b]pyrans has been
outlined in Scheme 3 according to the literature [54]. Fe O @THAM-piperazine is
3
4
an eꢀcient catalyst for synthesis of cyano oleꢁn C from Knoevenagel condensation
of arylealdehyde (1) and malononitrile (3) via formation iminium ion A and ammo-
nium ion B. Also, Fe O @THAM-piperazine produced enamine D from dimedone
3
4
(
2), which upon addition to cyano oleꢁn C and then subsequent intramolecular
cyclization hydrolysis of iminium ion F provided the desirable products (5a–g).
Table 3 Synthesis of 1,8-dioxo-octahydro-xanthene derivatives in the optimal conditions
Entry
R1
Product
Time
Yield (%)
M.p (°C)
M.p (°C) [Refs.]
1
2
3
4
5
6
7
H
4-Cl
4-Br
3,4-di OCH3
4-NO2
3-NO2
2,4-di Cl
4a
4b
4c
4d
4e
4f
15
25
30
15
5
15
15
88
80
85
95
90
93
87
199–201
224–227
234–237
171–173
170–172
172–173
242–244
202–205 [50]
227–229 [50]
238–240 [51]
172–174 [51]
169–171 [50]
170–172 [51]
245–247 [52]
4g
1
3

Fe O @THAM-piperazine: a novel and highly reusable…
3
4
Table 4 Synthesis of tetrahydrobenzo[b]pyran derivatives in the optimal conditions
Entry
R1
Product
Time
Yield (%)
M.p (°C)
M.p (°C) [Refs.]
1
2
3
4
5
6
7
H
4-Cl
4-Br
2-NO2
4-NO2
3-NO2
2,4-di Cl
5a
5b
5c
5d
5e
5f
10
15
10
15
5
5
25
82
74
90
85
92
88
77
226–228
209–211
196–198
228–230
177–178
200–203
197–199
225–227 [42]
209–211 [42]
195–197 [53]
230–232 [53]
176–177 [42]
199–201 [43]
200–202 [43]
5g
Stability and recyclability of the catalyst
For checking the revocability and reusability of Fe O @THAM-piperazine nano-
3
4
catalyst, the pseudo-three-component reaction between benzaldehyde 1 and dime-
done 2 under optimized conditions was selected. After completion of the reaction,
hot ethanol was added to the reaction mixture and the corresponding product was
dissolved. Then, the nanocatalyst was magnetically separated and washed with
EtOH. Then, the recovered catalyst was reused in the subsequent run under the
same conditions as the ꢁrst one. As shown in Fig. 8, the catalyst could be recy-
cled at least six without any signiꢁcant reduction in its activities.
Conclusions
In summary, Fe O MNPs-supported amorphous organic layer (THAM-pipera-
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4
zine) was successfully prepared and characterized by various techniques includ-
ing FT-IR, EDS, DTG/TGA, XRD, TEM, SEM, and VSM. Then, the catalytic
activity of newly synthesized nanocatalyst was evaluated in the synthesis of
1
,8-dioxo-octahydro-xanthene and tetrahydrobenzo[b]pyran derivatives. Note-
worthy advantages of this study are easy product separation and puriꢁcation, high
yield of products, recyclability, and reusability of the Fe O @THAM-piperazine
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MNPs for six reaction cycles without any signiꢁcant decrease in catalytic activity.
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H. Faroughi Niya et al.
Scheme 3 Possible mechanism for the synthesis of tetrahydrobenzo[b]pyran in the presence of Fe O @
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THAM-piperazine MNPs as a catalyst
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Fe O @THAM-piperazine: a novel and highly reusable…
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Fig. 8 Reusability of Fe O @THAM-piperazine MNPs as a catalyst in the synthesis of 9-(phenyl)-
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3
,3,6,6-tetramethyl-3,4,5,6,7,9-hexahydro-1Hxanthene-1,8(2H)-dione
Acknowledgements The authors are grateful to the research aꢂairs of the University of Sistan and
Baluchestan.
References
1
2
3
4
5
6
7
8
9
.
.
.
.
.
.
.
.
.
J.E. Mondloch, E. Bayram, R.G. Finke, J. Mol. Catal. A 355, 1 (2012)
P. Munnik, P.E. de Jongh, K.P. de Jong, Chem. Rev. 115, 6687 (2015)
J.A. Widegren, R.G. Finke, J. Mol. Catal. A 198, 317 (2003)
S. Shylesh, V. Schünemann, W.R. Thiel, Angew. Chem. Int. Ed. 49, 3428 (2010)
V. Polshettiwar, R. Luque, A. Fihri, H. Zhu, M. Bouhrara, J.M. Basset, Chem. Rev. 111, 3036 (2011)
D. Wang, D. Astruc, Chem. Rev. 114, 6949 (2014)
B. Karimi, F. Mansouri, H.M. Mirzaei, Chem. Cat. Chem. 7, 1736 (2015)
R.N. Baig, R.S. Varma, Chem. Commun. 49, 752 (2013)
M.A. Zolꢁgol, R. Ayazi-Nasrabadi, S. Baghery, Appl. Organomet. Chem. 30, 500 (2016)
1
1
1
1
1
1
1
1
0. M.A. Zolꢁgol, R. Ayazi-Nasrabadi, S. Baghery, Appl. Organomet. Chem. 30, 273 (2016)
1. R. Dalpozzo, Green Chem. 17, 3671 (2015)
2. M. Zhang, J. Zheng, J. Wang, J. Xu, T. Hayat, N.S. Alharbi, Sens. Actuator B-Chem 282, 85 (2019)
3. Q. Fang, J. Zhang, L. Bai, J. Duan, H. Xu, K.C.F. Leung, S. Xuan, J. Hazard. Mater. 367, 15 (2019)
4. W. He, X. Guo, J. Zheng, J. Xu, T. Hayat, N.S. Alharbi, M. Zhang, Inorg. Chem. 58, 7255 (2019)
5. W. Fu, H. Yang, S. Liu, M. Li, G. Zou, Mater. Let. 60, 1728 (2006)
6. D. Du, W. Shi, L. Wang, J. Zhang, Appl. Catal. B-Environ. 200, 484 (2017)
7. A. Mani, T. Kulandaivellu, S. Govindaswamy, A.M. Mohan, Environ. Sci. Pollut. Res. 25, 20419
(
2018)
1
1
2
2
2
8. M. Ma, Y. Yang, W. Li, R. Feng, Z. Li, P. Lyu, Y. Ma, J. Mater. Sci. 54, 323 (2019)
9. B. Zhang, J. Chen, J. Wang, Y. Huyan, H. Zhang, Q. Zhang, J. Chem. Eng. Data 63, 3913 (2018)
0. X. Jiang, L. Li, Y. Cui, F. Cui, Ceram. Int. 43, 14361 (2017)
1. H. Ren, Y. Su, Z. Han, R. Zhou, J. Chem. Technol. Biotechnol. 92, 1421 (2017)
2. B. Zhang, P. Li, H. Zhang, H. Wang, X. Li, L. Tian, N. Ali, Z. Ali, Q. Zhang, Chem. Eng. J. 291,
2
87 (2016)
2
2
2
2
3. H. Faroughi Niya, N. Hazeri, M.T. Maghsoodlou, Appl. Organomet. Chem. 34, e5472 (2020)
4. A.R. Moosavi-Zare, M.A. Zolꢁgol, M. Zarei, A. Zare, V. Khakyzadeh, J. Mol. Liq. 211, 373 (2015)
5. H.R. Shaterian, F. Mordi, Res. Chem. Intermed. 41, 291 (2015)
6. F. Khorami, H.R. Shaterian, Res. Chem. Intermed. 41, 3171 (2015)
1
3

H. Faroughi Niya et al.
2
7. H. Faroughi Niya, N. Hazeri, M.R. Kahkhaie, M.T. Maghsoodlou, Res. Chem. Intermed. 46, 1685
(
2020)
2
2
8. A. Abo Markeb, A. Alonso, A.D. Dorado, A. Sànchez, X. Font, Environ. Technol. 37, 2099 (2016)
9. M. Seifan, A. Ebrahiminezhad, Y. Ghasemi, A.K. Samani, A. Berenjian, Appl. Microbiol. Biotech-
nol. 102, 175 (2018)
3
3
0. P. Biehl, M. Von der Lühe, S. Dutz, F.H. Schacher, Polymer 10, 91 (2018)
1. I.S. Smolkova, N.E. Kazantseva, H. Parmar, V. Babayan, P. Smolka, P. Saha, Mater. Chem. Phys.
1
55, 178 (2015)
3
3
3
3
3
3
2. R. Mehdaoui, L. Chaabane, E. Beyou, M.H.V. Baouab, J. Iran. Chem. Soc. 16, 645 (2019)
3. X. Huang, C. Xu, J. Ma, F. Chen, Adv. Powder Technol. 29, 796 (2018)
4. F. Chen, S. Xie, X. Huang, X. Qiu, J. Hazard. Mater. 322, 152 (2017)
5. W. Chen, L. Xiong, F. Chen, Micro. Nano Lett. 12, 711 (2017)
6. L. Xiong, R. Chen, F. Chen, RSC Adv. 6, 101048 (2016)
7. A.M. Atta, G.A. El-Mahdy, H.A. Al-Lohedan, S.A. Al-Hussain, Int. J. Electrochem. Sci. 10, 2621
(
2015)
3
3
8. D. Beketova, M. Motola, H. Sopha, J. Michalicka, V. Cicmancova, F. Dvorak, L. Hromadko, B. Fru-
marova, M. Stoica, J.M. Macak, A.C.S. Appl, Nano Mater. 3, 1553 (2020)
9. N. Orooji, A. Takdastan, R.J. Yengejeh, S. Jorꢁ, A.H. Davami, Res. Chem. Intermed. 46, 2833
(
2020)
4
4
4
4
4
4
0. N.N. Pesyan, S. Bibak, M. Aalinejad, J. Iran. Chem. Soc. 17, 411 (2020)
1. B. Das, P. Thirupathi, K.R. Reddy, B. Ravikanth, L. Nagarapu, Catal. Commun. 3, 535 (2007)
2. A. Saha, S. Payra, A. Asatkar, A.R. Patel, S. Banerjee, Curr. Organocatal. 6, 177 (2019)
3. I.N. Bastos, G.M. Platt, M.C. Andrade, G.D. Soares, J. Mol. Liq. 139, 121 (2008)
4. P. Pannuru, A. Rani, P. Venkatesu, M.-J. Lee, Int. J. Biol. Macromol. 112, 720 (2018)
5. A. Ibrahim-Hashim, D. Abrahams, P.M. Enriquez-Navas, K. Luddy, R.A. Gatenby, R.J. Gillies,
Cancer Med. 6, 1720 (2017)
4
6. Y.A. Kondratenko, A.A. Nikonorova, A.A. Zolotarev, V.L. Ugolkov, T.A. Kochina, J. Mol. Struct.
1
207, 127813 (2020)
4
4
4
5
5
7. T. Zeng, Y. Lu, S. Jin, L. Sun, B. Zhong, D. Wang, J. Wang, H. Liu, J. Mol. Struct. 1180, 764 (2019)
8. M. Hajibabaei, M.A. Senejani, F. Shaꢁei, App. Organomet. Chem. 34, e5641 (2020)
9. S.M. El-Sigeny, M.F. Abou Taleb, Life Sci. J. 12, 161 (2015)
0. Z. Abdi Piralghar, M.M. Hashemi, A. Ezabadi, Polycycl. Aromat. Comp. (2019)
1. F. NooriSadeh, M. Fatahpour, N. Hazeri, M.T. Maghsoodlou, M. Lashkari, Acta Chem. Iasi 25, 24
(
2017)
5
5
2. L. Moradi, M. Mirzaei, RSC Adv. 9, 19940 (2019)
3. M. Bakherad, F. Moosavi, A. Keivanloo, R. Doosti, E. Moradian, M. Armaghan, Res. Chem.
Intermed. 45, 2981 (2019)
5
4. R. Pourhasan-Kisomi, F. Shirini, M. Golshekan, Appl. Organomet. Chem. 32, e4371 (2018)
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maps and institutional aꢀliations.
Aꢀliations
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Homayoun Faroughi Niya · Nourallah Hazeri · Maryam Fatahpour ·
Malek Taher Maghsoodlou1
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Department of Chemistry, Faculty of Science, University of Sistan and Baluchestan,
P.O. Box 98135-674, Zahedan, Iran
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