Piperazine-functionalized nickel ferrite nanoparticles as efficient and reusable catalysts for the solvent-free synthesis of 2-amino-4H-chromenes

Article abstract of DOI:10.1002/jccs.201800291

Piperazine-functionalized nickel ferrite (NiFe₂O₄) nanoparticles were synthesized as recoverable heterogeneous base catalysts using a routine method. The synthesized materials were characterized using various spectroscopic techniques

Full text of DOI:10.1002/jccs.201800291

Received: 25 July 2018
Revised: 8 February 2019
Accepted: 13 February 2019
DOI: 10.1002/jccs.201800291
A R T I C L E
Piperazine-functionalized nickel ferrite nanoparticles as efficient
and reusable catalysts for the solvent-free synthesis of 2-amino-
4H-chromenes
Bahram Pourhasan | Ahmad Mohammadi-Nejad
Department of Chemistry, Dezful Branch, Islamic
Piperazine-functionalized nickel ferrite (NiFe2O4) nanoparticles were synthesized
Azad University, Dezful, Iran
as recoverable heterogeneous base catalysts using a routine method. The synthe-
Correspondence
Bahram Pourhasan, Department of Chemistry,
sized materials were characterized using various spectroscopic techniques such as
infrared, X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray,
thermogravimetry analysis, and vibrating sample magnetometry. Catalytic effi-
Dezful Branch, Islamic Azad University, Dezful,
Iran.
Email: bahramp606@gmail.com
ciency was investigated in the synthesis of 2-amino-4H-chromene derivatives via a
Funding information
Dezful branch, Islamic Azad University
one-pot three component reaction of aldehyde and malononitrile with β or
α-naphthol/5-methyle resorcinol under solvent-free conditions with good to high
yields. This method is operationally simple and has several advantages such as
good to high yield, short reaction times, solvent-free conditions, and easy synthe-
sis. Moreover, the catalyst was recovered easily using an external magnet and
reused three times without distinctive loss in catalytic activity.
KEYWORDS
2-amino-4H-chromenes, magnetic nanocatalyst, nickel ferrite, resorcinol,
solvent free
photomagnetic materials, and heterogeneous catalysts in
chemical synthesis.[7,8] In this work, we use the supported
1
| INTRODUCTION
In recent years, researchers have been interested in nano-
magnetic materials due to their outstanding magnetic proper-
ties, like nanomagnetism in mapping and antenna rod.[1]
Ferrite nanomagnetics were highly investigated these years,
due to their excellent catalytic, electrical, and magnetic prop-
erties, which led to their biocompatibility, low remanence,
and low coercivity. These properties are due to the cationic
arrangement, their size, and scale of particles[2] and make
them one of the best choices for drug transfer, tissue
imaging,[3] biological targets, magnetic resonance imaging
(MRI) instruments, permanent magnets, and sensors.[4,5]
In Ferrite compounds, nickel ferrites have particular
properties such as high saturation magnetization, chemical
stability, and relatively high permeability.[6] Also, these
compounds were applied as magnetic fluids, gas sensors,
nickel ferrite catalyst in green synthesis of a heterocyclic
scaffold. Due to the high surface energy, anisotropic dipolar
attractions, and loss of dispersibility of these magnetic nano-
particles, they usually aggregate to form large clusters.[9]
This problem could be solved with coating or functionaliz-
ing of nanoparticle core, for which, in this work, we prepare
piperazine-functionalized nickel ferrite nanoparticles.
Oxygen-containing heterocyclic compounds have been
synthesized by the chemists for many years, specially
2-amino-4H-chromenes that are one of the best biologically
active compounds, they have wide range of utilities such as
cosmetics, dyes, lasers, and fluorescence markers.[10]
The framework of these compounds exists in fruits and
alkaloids. Also, they are used for synthesis of antimicrobial,
antiviral, and antitumor compounds[11] and used for the
© 2019 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
J Chin Chem Soc. 2019;1–7.
http://www.jccs.wiley-vch.de
1

2
POURHASAN AND MOHAMMADI-NEJAD
production of medicinal scaffolds that show spasmolytic,
diuretic, and antianaphylaxis activities.[12]
5 mmol of NiCl2Á6H2O and 10 mmol of FeCl3.6H2O were
added to the flask, and then 40 mL distilled water and
60 mL of the surfactant were added to it and refluxed. After
1 hr, 15 mL NH3 was poured in the flask, and the reaction
was continued for 1 hr under reflux conditions, and then
cooled and centrifuged. The obtained powder was washed
with water five times and ethanol two times. The precipita-
tion was dried, powdered, and was calcinated at 600ꢀC.
Usually, 2-amino-4H-chromenes are prepared by one pot,
three-component reactions of activated methylene compounds
malononitrile, aromatic or aliphatic aldehydes, and activated
phenols (α and β naphthol, and resorcinol) with a solvent and a
catalyst. Recently, catalysts that have been used in this
reaction were nano-ZnO,[13] Fe3O4-chitosan,[14] piperazine,[15]
K2CO3,[16]
Pd-graphene
oxide,[17]
ZnAl2O4–Bi2O3
nanopowder,[18] Ceric Ammonium Nitrate (CAN),[19]
polystyrene/para toluenesulfonic acid (PTSA),[20] sodium
acetate,[21] and sulfamic acid.[22] While some of the reported
methods suffer from disadvantages, like toxicity and harmful
catalysts, organic solvents, long reaction time, low yield, and
tedious synthesis procedures. In this research, we have reported
the one-pot three-component synthesis of 2-amino-4H-
chromenes from the reaction of aldehydes and malononitrile
and naphthols in the presence of piperazine-functionalized
nickel ferrite nanoparticles as novel heterogeneous catalysts.
2.2.2
| Synthesis of 3-chloroaminopropyl-functionalized
NiFe2O4 nanoparticles
An amount of 0.6 g of the NiFe2O4 nanoparticle was poured
into a 250 mL flask containing 50 mL of toluene and was
sonicated for 3*15 min. After the addition of
3-chloropropyletrimethoxysilane (CPTS) (1.5 g), the mixture
was refluxed for 48 hr at 60ꢀC. The resulting mixture was
centrifuged and washed three times with toluene, ethanol
and was dried in a vacuum oven.
2.2.3
| Piperazine-functionalized nickel ferrite nanoparticles
An amount of 0.5 g NiFe2O4@propyl-Cl was dispersed in
30 mL dried toluene with sonication for about 0.5 hr. After
the addition of 5 mmol piperazine (0.43 g) and 5 mmol tri-
methylamine (7 mL), the mixture was refluxed for 48 hr.
The precipitates were separated using a magnet and washed
with toluene and ethanol, and then dried in a vacuum oven
for 4 hr.
2
| EXPERIMENTAL
2.1 | Material characterization
All Chemicals were purchased from Merck and fluka chemi-
cal company. X-ray diffraction of the sample was recorded
via a GE Inspection Technologies/Seifert-FPM, X-ray dif-
fraction (XRD) diffractometer (Cu-Kα, λ = 0.154 nm). The
scanning electron microscope measurement was carried out
on a Hitachi S-4700 field emission-scanning electron micro-
scope. Thermogravimetry analysis (TGA) of the functiona-
lized catalyst was conducted using a Perkin Elmer TG/DTA
instrument in the range of 30–800ꢀC under a N2 atmosphere.
The magnetic properties analyzed and hysteresis diagrams
were obtained using a 7300 vibrating sample magnetometry
(VSM) system (Lake Shore Cryotronic Inc, Westerville,
OH) at room temperature. Melting points were measured
with a capillary tube on a thermo fisher IA 9100 apparatus.
Infrared (IR) spectra were obtained with a Galaxy series
Fourier-transform infrared 5000 between 400–4,000 cm−1
2.3 | General procedure for synthesis of 2-amino-4H-
chromenes
A mixture of aldehydes (0.5 mmol), activated phenols
(β-naphthol, α-naphthol, and 5-methylresorcinol) (0.5 mmol),
malononitrile (0.6 mmol), and 0.04 g of the nanocatalyst
was added to the tube and stirred at 110ꢀC for appropriate
time as shown in Table 1 (monitored by Thin-layer chroma-
tography (TLC) [ethyl acetate/n-hexane, 1:3]). After comple-
tion of the reaction, it was cooled to room temperature, the
product was dissolved in hot ethanol and the catalyst was
separated with an external magnet. The remaining solution
was concentrated and cooled to room temperature. The
obtained crystals were filtrated and air dried.
with a KBr-pressed disk technique. HNMR and 13CNMR
spectra were obtained with Bruker 300 MHz and 400 MHz
1
in DMSO-d6 and tetramethylsilan (TMS) as a standard.
2.3.1
| 2-Amino-3-cyano-5-hydroxy-7-methyle-4-(phenyl)-
4H-chromene (4j)
IR (KBr, cm−1): νmax = 3,505, 3,412, 3,333, 3,210, 2,195,
1,650, 1,628, 1,595, 1,410, 1,070, 850, and 705; HNMR
2.2 | Synthesis of piperazine-functionalized nickel
ferrite nanoparticles (NiFe2O4@propyl-Pip)
1
2.2.1
| Synthesis of NiFe2O4 nanoparticles
(400 MHz, DMSO-d6): δ = 2.08 (s, 3H, CH3),4.42 (s,1H,
CH), 6.25 (s, 2H, Ar-H), 6.73 (br, 2H, NH2), 6.98 (d,
J = 6.4 Hz, 2H, ArH), 7.05 (t, J = 6.5 Hz, 1H, ArH), 7.14
(d, J = 6.4 Hz, 2H, ArH), and 9.55 (s, 1H, OH); 13CNMR
(100 MHz, DMSO-d6): δ = 20.8, 36.4, 57, 106.8, 108.4,
111.6, 120.8, 126.2, 127.0, 128.2, 138, 145.9, 149.8, 154.4,
and 160.4 (Table 1 entry 10).
At first, we prepared extraction of berry leaves as a surfac-
tant. For this purpose, after washing and drying of leaves in
a oven, they were milled and poured into a 500 mL flask
and refluxed with 110 mL ethanol and 290 mL water. After
24 hr, they were filtered via a vacuum pump and a brownish
viscous liquid was obtained. For preparation of NiFe2O4,

POURHASAN AND MOHAMMADI-NEJAD
3
TABLE 1 Synthesis of 2-amino-4H-chromene via NiFe2O4 under solvent free conditions
M.P. (ꢀC)
Found
Entry
Phenol
Aldehyde
Time (min)
Yield (%)a
Reported (ref)
255–256[23]
257–259[24]
189–190[25]
295–296[26]
252–253[27]
203–205[28]
198–200[29]
229–230[30]
209–210[31]
—
Product
4a
1
β-Naphthol
4-Methyle benzaldehyde
2-Chloro benzaldehyde
3-Nitro benzaldehyde
Benzaldehyde
40
50
40
40
60
60
50
45
50
30
40
30
90
88
83
95
81
85
78
87
83
80
88
85
253–256
255–257
193–195
280–281
247–250
200–201
195–199
209–212
207–210
270–275
280–283
265–267
2
β-Naphthol
4b
3
β-Naphthol
4c
4
β-Naphthol
4d
5
β-Naphthol
4-Hydroxy-3-methoxy benzaldehyde
4-Dimethylamino benzaldehyde
4-Methyle benzaldehyde
3-Choloro benzaldehyde
Benzaldehyde
4e
6
α-Naphthol
4f
7
α-Naphthol
4g
8
α-Naphthol
4h
9
α-Naphthol
4i
10
11
12
3,5-Dihydroxy toluene
3,5-Dihydroxy toluene
3,5-Dihydroxy toluene
Benzaldehyde
4j
2,6-Dichloro benzaldehyde
2-Bromo benzaldehyde
—
4k
—
4l
aIsolated yield.
2.3.2
| 2-Amino-3-cyano-5-hydroxy-7-methyle-
nanoparticles
(NiFe2O4@propyl-Cl).
Finally,
the
4-(2, 6-dichlorophenyl)-4H-chromene (4k)
NiFe2O4@propyl-Pip catalyst was synthesized by the nucle-
ophilic chloro displacement of CPTS with piperazine.
IR (KBr, cm−1): νmax = 3,495, 3,393, 3,251, 2,198, 1,648,
1,580, 1,401, 1,328, 1,138, 830, and 782; 1HNMR
(300 MHz, DMSO-d6): δ 2.17 (s, 3H, CH3), 5.56 (s, 1H,
CH), 6.26 (s, 1H, ArH), 6.28 (s, 1H, ArH), 6.88 (br, 2H,
NH2), 7.23 (t, J = 8.0 Hz, 1H, ArH), 7.29 (d, J = 8.0 Hz,
1H, ArH), 7.45 (d, J = 8.0 Hz, 1H, ArH), and 9.55 (s, 1H,
OH); 13CNMR (75 MHz, DMSO-d6): δ = 20.8, 33.1, 52.2,
104.7, 106.3, 111.3, 120.0, 128.1, 128.7, 130.1, 134.4,
135.7, 137.8, 138.4, 150.5, 154.7, and 160.1 (Table 1
entry 11).
3.1 | Characterization of NiFe2O4@propyl-Cl
The catalyst was characterized using IR spectroscopy, TGA,
powder XRD, VSM, scanning electron microscopy (SEM),
and energy-dispersive X-ray (EDX) spectroscopy.
IR spectroscopy was usually used to determine the kind
of chemical bonds. Specially, the 100–1,000 cm−1 range
shows vibrational signals for metal ions in the crystal lat-
tice.[32] Figure 1 shows the FT IR spectra of pure NiFe2O4
(a) and NiFe2O4@propyl-Pip (b) in the wavenumber range
400–4,000 cm−1. There are two bands in spinel structures
(MFe2O4), the first band is seen at 576 cm−1 that shows Fe-
O stretching vibration in the tetrahedral configuration and
other observed at 480 cm−1 for Fe-O stretching in the
2.3.3
| 2-Amino-3-cyano-5-hydroxy-7-methyle-
4-(2-bromophenyl)-4H-chromene (4l)
IR (KBr, cm−1): νmax = 3,490, 3,388, 3,234, 2,205, 1,650,
1
1,580, 1,399, 1,141, and 755; HNMR (300 MHz, DMSO-
d6): δ 2.18 (s, 3H, CH3), 5.08 (s, 1H, CH), 6.30 (s, 1H,
ArH), 6.36 (s, 1H, ArH), 6.83 (br, 2H, NH2), 6.91 (d,
J = 8.0 Hz, 1H, ArH), 7.07 (t, J = 7.8 Hz, 1H, ArH), 7.24
(t, J = 7.5 Hz,1H, ArH), 7.52 (d, J = 7.5 Hz, 1H, ArH), and
9.62 (s, 1H, OH); 13CNMR (75 MHz, DMSO-d6): δ = 20.8,
35.6, 56.0, 106.6, 107.6, 111.5, 120.1, 122.6, 128.0, 128.1,
130.0, 132.2, 138.4, 145.0, 149.8, 154.6, and 160.2 (Table 1
entry 12).
SCHEME 1 Preparation of piperazine-functionalized nickel ferrite
nanoparticles
3
| RESULTS AND DISCUSSION
The piperazine-functionalized nickel ferrite magnetic nano-
particle (NiFe2O4@propyl-Pip) was prepared following the
procedure shown in Scheme 1. First, nickel ferrite nanoparti-
cles were prepared via coprecipitation of nickel (II) and iron
(III) ions in the presence of berry leave extracts (as a surfac-
tant). Then, the NiFe2O4 nanoparticle was treated with CPTS
to obtain 3-chloroaminopropyl-functionalized NiFe2O4
FIGURE 1 IR spectrum of (a) NiFe2O4 and (b) NiFe2O4@propyl-Pip

4
POURHASAN AND MOHAMMADI-NEJAD
C-H bending vibrations at 1,450 cm−1. These results show
that the functional groups were successfully attached onto
the surface of the magnetic particles.
The XRD patterns of synthesized magnetic nanoparticles
are shown in Figure 2. Similarity of peaks in the NiFe2O4
and NiFe2O4@propyl-Pip patterns shows the retentions of
the type of spinel structure in core during the functionaliza-
tion. Synthesized samples have seven assignable diffraction
peaks at 2θ = 30.4, 35.8, 37.3, 43.4, 54.0, 57.5, and 63.1
that correspond to (220), (311), (222), (400), (422), (511),
and (440) planes of NiFe2O4, respectively. These results
indicate that the NiFe2O4 cores are pure and have a good
match with the standard sample (JCPDS-862267).[34]
The average crystal size was calculated using the
Debye–Scherrer equation, D = 0.9λ/βcosθ, where λ is the
wavelength of the X-ray source, β is the width of the half
maximum peak, θ is the Bragg angle. From the width of the
peak 2θ = 35.8 (311), the size of the magnetic NiFe2O4 was
obtained to be about 35 nm with the Debye–Scherrer equa-
tion, which is smaller than that obtained using SEM
analysis.
FIGURE 2 The XRD patterns of NiFe2O4 and NiFe2O4@propyl-Pip
SEM images of NiFe2O4@propyl-Pip with different
magnitudes are shown in Figure 3. As can be seen from
Figure 3, magnetic NiFe2O4@propyl-Pip particles have a
mean diameter of about 39–51 nm.
The EDX spectroscopy results are shown in Figure 4.
This diagram shows that only O, N, Si, Fe, and Ni elements
exist in the functionalized catalyst. The existence of N sig-
nals shows that the piperazine was successfully grafted on
the surface of the NiFe2O4 nanoparticles.
FIGURE 3 SEM images of NiFe2O4@propyl-Pip
The TGA diagram was used to study the thermal stability
of compounds at high temperatures. Figure 5 shows the
TGA and derivative thermogravimetry (DTG) curve of the
nanocatalyst. The TGA curve has three loss steps over the
temperature range of TG analysis. The first stage has 3%
mass losses until 230ꢀC that was related to the elimination
of surface OH groups on the NiFe2O4 core and vaporization
of the trapped solvents. The next weight loss occurs in
octahedron.[33]
Absorption
bands
appearing
at
3,200–3,500 cm−1 can be attributed to N-H and O-H stretch-
ing vibration bands. Also, NiFe2O4@propyl-Pip shows the
absorption band at 1,085 cm−1, which corresponds to the Si-
O stretching vibrations. The existence of alkyl groups on the
surface of the nanocatalyst is confirmed by the weak ali-
phatic C-H stretching vibrations at 2,850–2,960 cm−1 and
FIGURE 4 The EDX of NiFe2O4@propyl-Pip

POURHASAN AND MOHAMMADI-NEJAD
5
TABLE 2 Optimization of reaction conditions
Amount of
catalyst (g)
Yield
(%)a
Entry
Condition
Time
12 hr
1
2
3
4
5
6
7
Chloroform/reflux
Ethanol/reflux
Acetonitrile/reflux
DMF/reflux
0.04
65
55
60
52
65
75
80
0.04
12 hr
12 hr
0.04
0.04
12 hr
Water/reflux
Solvent free/80ꢀC
0.04
12 hr
0.04
120 min
80 min
Solvent
0.04
free/100ꢀC
8
Solvent
0.04
0.04
0.04
—
40 min
40 min
40 min
40 min
40 min
40 min
40 min
95
90
78
20
70
85
95
free/110ꢀC
9
Solvent
free/120ꢀC
FIGURE 5 TGA curve of functionalized NiFe2O4
10
11
12
13
14
Solvent
free/140ꢀC
Solvent
free/110ꢀC
Solvent
0.02
0.03
0.10
free/110ꢀC
Solvent
free/110ꢀC
Solvent
free/110ꢀC
aIsolated yield.
can determine the remanent magnetization (Mr) and coerciv-
ity (Hc). The hysteresis loops show the superparamagnetic
behavior of NiFe2O4 and functionalized NiFe2O4 particles in
which Mr and the Hc are close to zero (Mr = 4.1 and
1.9 emu per g, and Hc = 103 and 155 Oe, respectively).[35]
FIGURE 6 Magnetic hysteresis loop of (a) NiFe2O4 and (b) functionalized
NiFe2O4
230–400ꢀC that is about 20% of mass, this mass loss was
attributed to the decomposition of the organic surface. The
third stage mass loss continues to 750ꢀC, related to the
release of structure water molecules and the remaining
organic groups.
The DTG curve shows that the decomposition of the
organic layer occurred at 270ꢀC. These data show that the
synthesized catalyst is stable at around or below 200ꢀC.
Figure 6 shows the plots of room temperature magnetic
hysteresis curves of functionalized NiFe2O4 and NiFe2O4. It
is obvious that the magnetization increases with growing
magnetic field and saturated near 9,000 Oe for both sam-
ples. Also, the amount of saturation magnetization (Ms) for
NiFe2O4 is 25 emu/g and for NiFe2O4@propyl-Pip is
8 emu/g. This decline is due to the coverage of the organic
layer on the nickel ferrite core. In the hysteresis curve, we
3.2 | 2-Amino-4H-choromene synthesis via
functionalized NiFe2O4
Efficiency of the synthesized catalyst was investigated via
the 2-amino-4H-chromene reactions (Scheme 2). At the first
step to study the solvent effect and optimizing the reaction
conditions, we used benzaldehyde, malononitrile, and
β-naphthol as a model. Reaction was refluxed with water,
ethanol, acetonitrile, chloroform, and Dimethylformamide
(DMF) but the yield of all reactions was medium even with
a long reaction time (Table 2). Then, the reaction was carried
out with 0.04 g of the catalyst at different temperatures with-
out any solvent. Results showed that raising the temperature
till 110ꢀC causes an increase in the reaction yield, and at
higher temperature, yield decreases. For investigating the
effect of the catalyst amount, reaction was carried out with-
out catalysts and with 0.02, 0.03, 0.04, and 0.10 g of the
nanocatalyst.
As can be seen from Table 2, the best conditions for this
reaction were solvent free at 110ꢀC and 0.04 g of
NiFe2O4@propyl-Pip, because the reaction could be carried
out in high yield (Table 2, entry 8). Furthermore, the effi-
ciency of NiFe2O4 and NiFe2O4@prop-Cl was investigated
SCHEME 2 Synthesis of 2-amino-4H-chromenes

6
POURHASAN AND MOHAMMADI-NEJAD
95
such as 2, 6-dichloro benzaldehyde, 2-chloro benzaldehyde,
and 2-bromo benzaldehyde were studied and the results are
summarized in Table 1. On the other hand, aliphatic alde-
hydes such as propionaldehyde and butyraldehyde were also
examined under the same conditions, but the corresponding
products were isolated only in a trace amount.
An important specificity of each catalyst is recovery and
reusability, which gives rise to low cost of the product and
protection of the environment. To study catalyst reusability,
an optimized model reaction was used. After completion of
the reaction, it was cooled to room temperature, the product
was dissolved in hot ethanol and the catalyst was separated
with an external magnet. It was washed two times with etha-
nol, dried at 70ꢀC for 1 hr, and reused for the next reaction.
As shown in Figure 7, the catalyst can be used four times in
this reaction without noticeable loss of its activity.
To determine the ability of this catalyst, we compare the
result of NiFe2O4@ propyl-Pip in the synthesis of 2-amino
4-H-chromene with α and β-naphthol, benzaldehyde, and
malononitrile in Table 3. As seen, NiFe2O4@ propyl-Pip is
an efficient catalyst due to the suitable reaction time and
good yield, also easy separation and reusability are advan-
tages of our prepared catalyst.
93
92
3
91
4
1
2
RUN
FIGURE 7 Reusability of NiFe2O4@propyl-Pip with model reaction under
optimized conditions
TABLE 3 Comparison of NiFe2O4@ propyl-pip with some catalysts in
2-amino-4H-chromene synthesis
Time
(min)
4d/4i
Yield
(%)
4d/4i
Catalyst
14[NaP5W30O110
Condition
Ref
[36]
[37]
H
]
180/165
180/180
91/93
90/90
H2O/reflux
CH3CN/reflux
Methanesulfonic
acid
CTAB
150/150
60/60
92/92
95/95
95/92
H2O/r.t
[38]
CuSO4.5H2O
H2O/reflux
Solvent free
[39]
3.2.1
| Proposal mechanism
NiFe2O4@
propyl-pip
40/50
This work
The mechanistic rationale portraying of the reaction is given
in Scheme 3. Firstly, the Knoevenagel condensation of mal-
ononitrile with the aromatic aldehyde was carried out
(according to the literature),[40,41] the resulting product is
subsequently attacked by the β-naphthol anion to produce
the intermediate II in the presence of piperazine as a catalyst.
Then, cyclization occurred by nucleophilic attack of an OH
group on the cyano (CN) moiety to give intermediate (III).
The intermediate (III) was converted into the 2-amino-4H-
chromene derivatives via tautomerization.
SCHEME 3 Possible mechanism for the synthesis of 2-amino-4H-
chromene derivatives
4
| CONCLUSIONS
In conclusion, we prepared an effective nickel ferrite mag-
netic nanocatalyst via the coprecipitation method for the syn-
thesis of some new and known 2-amino-4H-chromenes. The
special features of the catalyst are facial preparation, low
cost compound, easy recovery, and reusability, which make
it a useful catalyst.
in the reaction and isolated yields were consequently 55 and
67%, respectively.
To evaluate the efficiency of the prepared catalyst, we
used different types of aromatic aldehydes with electron-
releasing (such as methyl, dimethyl amino, and hydroxyl) or
electron-withdrawing (such as nitro, chloro, and bromo)
groups and α-naphthol or β-naphthol under the optimized
reaction conditions and afforded the corresponding 2-amino-
4H-chromene derivatives in good to high yields (Table 1).
We studied the reaction of aldehydes and malononitrile with
3, 5-dihydroxy toluene under similar conditions. It was
found that the corresponding 2-amino-4H-chromenes could
also be obtained in good to high yields without any diffi-
culty. To demonstrate the scope and limitation of the proce-
dure, the reactions of ortho-substituted aromatic aldehydes
ACKNOWLEDGMENT
We are thankful for financial and equipmental support from
Dezful branch, Islamic Azad University.
ORCID
Bahram Pourhasan https://orcid.org/0000-0003-0801-
1479

POURHASAN AND MOHAMMADI-NEJAD
7
[23] Q. Zhuang, L. Rong, J. Wang, S. Tu, X. Wang, D. Shi, Chin. J. Org. Chem.
2003, 23, 671.
[24] S. M. Baghbanian, N. Rezaei, H. Tashakkorian, Green Chem. 2013, 15, 3446.
[25] H. Mehrabi, N. Kamali, J. Iran. Chem. Soc. 2012, 9, 599.
[26] S. Karamthulla, S. Pal, M. N. Khan, L. H. Choudhury, RSC Adv. 2014, 4,
37889.
[27] A. R. Moosavi-Zare, M. A. Zolfigol, O. Khaledian, V. Khakyzadeh,
M. H. Beyzavi, H. G. Kruger, Chem. Eng. J. 2014, 248, 122.
[28] T.-S. Jin, J.-C. Xiao, S.-J. Wang, T.-S. Li, X.-R. Song, Synlett 2003, 2003,
2001.
[29] T.-s. Jin, H. Xie, Y.-p. Xue, T.-s. Li, Asian J. Chem. 2008, 20, 5145.
[30] T.-S. Jin, J.-C. Xiao, S.-J. Wang, T.-S. Li, Ultrason. Sonochem. 2004,
11, 396.
REFERENCES
[1] P. Sivakumar, R. Ramesh, A. Ramanand, S. Ponnusamy,
C. Muthamizhchelvan, Mater. Res. Bull. 2011, 46, 2204.
[2] M. A. Iqubal, S. S. Islam, K. Ghosh, R. A. Molla, S. M. Islam, J. Inorg.
Organomet. Polym. 2017, 27, 1730.
[3] F. M. Golkhatmi, B. Bahramian, M. Mamarabadi, Mater. Sci. Eng. C 2017,
78, 1.
[4] Z. Peng, K. Hidajat, M. Uddin, J. Colloid Interface Sci. 2004, 271, 277.
[5] S.V. Bhosale, P. Mhaske, N. Kanhe, A. Navale, S. Bhoraskar, V. Mathe,
S. Bhatt, in: AIP Conf. Proc., AIP, 2014, pp. 1694–1695.
[6] A. Khojastehnezhad, M. Rahimizadeh, F. Moeinpour, H. Eshghi,
M. Bakavoli, C. R. Chim. 2014, 17, 459.
[7] C. Xiangfeng, J. Dongli, Z. Chenmou, Sens. Actuators B Chem. 2007,
123, 793.
[8] C. H. Cunningham, T. Arai, P. C. Yang, M. V. McConnell, J. M. Pauly,
S. M. Conolly, Magn. Reson. Med. 2005, 53, 999.
[9] D. K. Yi, S. S. Lee, J. Y. Ying, Chem. Mater. 2006, 18, 614.
[10] M. P. Surpur, S. Kshirsagar, S. D. Samant, Tetrahedron Lett. 2009,
50, 719.
[11] J. K. Rajput, P. Arora, G. Kaur, M. Kaur, Ultrason. Sonochem. 2015,
26, 229.
[12] R. Magar, P. Thorat, V. Jadhav, S. Tekale, S. Dake, B. Patil, R. Pawar,
J. Mol. Catal. A Chem. 2013, 374, 118.
[13] S. Zavar, Arab. J. Chem. 2017, 10, S67.
[14] J. Safari, L. Javadian, Ultrason. Sonochem. 2015, 22, 341.
[15] A. Mobinikhaledi, N. Foroughifar, M. A. Bodaghi Fard, Synth. React.
Inorg. Metal Org. Nano Metal Chem. 2010, 40, 179.
[16] M. Pourmohammad, M. Mokhtary, C. R. Chim. 2015, 18, 554.
[17] S. Akocak, B. S¸en, N. Lolak, A. S¸avk, M. Koca, S. Kuzu, F. S¸en, Nano-
Struct. Nano-Objects 2017, 11, 25.
[31] B. Maleki, S. Babaee, R. Tayebee, Appl. Organomet. Chem. 2015, 29, 408.
ꢀ
ꢀ
[32] A. Baykal, N. Kasapoglu, Y. Köseoglu, M. S. Toprak, H. Bayrakdar,
J. Alloys Compd. 2008, 464, 514.
[33] R. Waldron, Phys. Rev. 1955, 99, 1727.
[34] H. Panda, R. Srivastava, D. Bahadur, J. Phys. Chem. C 2009, 113, 9560.
[35] K. Petcharoen, A. Sirivat, Mater. Sci. Eng. B 2012, 177, 421.
[36] M. M. Heravi, K. Bakhtiari, V. Zadsirjan, F. F. Bamoharram,
O. M. Heravi, Bioorg. Med. Chem. Lett. 2007, 17, 4262.
[37] M. M. Heravi, B. Baghernejad, H. A. Oskooie, J. Chin. Chem. Soc.-Taip.
2008, 55, 659.
[38] T.-S. Jin, J.-C. Xiao, S.-J. Wang, T.-S. Li, Ultrason. Sonochem. 2004, 11, 393.
[39] F. K. Behbahani, S. Maryam, J. Korean Chem. Soc. 2013, 57, 357.
[40] B. Datta, M. Pasha, Ultrason. Sonochem. 2012, 19, 725.
[41] S. R. Kolla, Y. R. Lee, Tetrahedron 2011, 67, 8271.
[18] M. Ghashang, Res. Chem. Intermed. 2016, 42, 4191.
[19] Y. Li, X. Meng, G. Cai, B. Du, B. Zhao, Res. Chem. Intermed. 2014,
40, 699.
[20] M. V. Reddy, G. C. S. Reddy, Y. T. Jeong, Tetrahedron Lett. 2016, 57,
1289.
[21] M. T. Maghsoodlou, M. Safarzaei, M. R. Mousavi, N. Hazeri,
J. Aboonajmi, M. Shirzaei, Iran. J. Org. Chem 2014, 6, 1197.
[22] M. Ghashang, S. S. Mansoor, K. Aswin, Res. Chem. Intermed. 2015, 41,
3117.
How to cite this article: Pourhasan B, Mohammadi-
Nejad A. Piperazine-functionalized nickel ferrite
nanoparticles as efficient and reusable catalysts for the
solvent-free synthesis of 2-amino-4H-chromenes.
J Chin Chem Soc. 2019;1–7. https://doi.org/10.1002/
jccs.201800291