Nickel ferrite (NiFe2O4) nanoparticles as magnetically recyclable nanocatalyst for highly efficient synthesis of 4H-chromene derivatives

Article abstract of DOI:10.1166/jnn.2020.17396

An adapted one-pot route to nanocatalyst-assisted synthesis of 4H-chromenes via three component condensation reaction between dimedone, malononitrile, and a broad range of aryl aldehydes by the use of magnetic nickel ferrite nanoparticles is described. By this achievement, not only a novel route to highly efficient synthesis of these series of heterocycles was introduced but also the scope of these medicinally important IP: 127.0.0.1 productsOn: wasFri, developed 10 Jan 2020 via preparation 23:24:53 of some novel products. Above all, a new application Copyright: of nickel ferrite American nanoparticles Scientific(NiFe Publishers ₂O₄ NPs) as highly efficient, green and magnetically recyclable catalyst _has Delivered _been introduced. by Ingenta Overall, obtaining good to excellent yields of products, environmentally and economic benign procedure, easy handling, availability of starting materials, use of non-toxic solvents, and high recyclability of nano-catalyst could be countered as most important advantages of this methodology.

Full text of DOI:10.1166/jnn.2020.17396

Article
Journal of
Nanoscience and Nanotechnology
Vol. 20, 3206–3216, 2020
Copyright © 2020 American Scientific Publishers
All rights reserved
Printed in the United States of America
www.aspbs.com/jnn
Nickel Ferrite (NiFe O ) Nanoparticles as Magnetically
2
4
Recyclable Nanocatalyst for Highly Efficient
Synthesis of 4H-Chromene Derivatives
Yaghoub Pourshojaei1 , Fatemeh Zolala , Khalil Eskandari , Mahshid Talebi ,
ꢀ2ꢀ∗
1ꢀ†
1ꢀ∗
1ꢀ†
1
1ꢀ3
1
1
Laleh Morsali , Mahnaz Amiri , Arash Khodadadi , Reza Shamsimeymandi ,
1
1
Ehsan Faghih-Mirzaei , and Ali Asadipour
1Department of Medicinal Chemistry, Faculty of Pharmacy and Pharmaceutics Research Center,
Kerman University of Medical Sciences, Kerman, 7616911319, Iran
Neuroscience Research Center, Institute of Neuropharmacology, Kerman University of Medical Sciences, Kerman, 76198-13159, Iran
2
3
Institute of Nano Science and Nano Technology, University of Kashan, Kashan, 8731753153, Iran
An adapted one-pot route to nanocatalyst-assisted synthesis of 4H-chromenes via three component
condensation reaction between dimedone, malononitrile, and a broad range of aryl aldehydes by
the use of magnetic nickel ferrite nanoparticles is described. By this achievement, not only a novel
route to highly efficient synthesis of these series of heterocycles was introduced but also the scope
of these medicinally i mI Pp:o 1r t9a 3n .t 5 p6 r .o6 d5 u. c2 t 0s Ow an s: Td ue ve e, l 3o p1 e Dd ev ci a2 p0 r1e 9p a0 r 6a t: i1o 7n : 4o 4f some novel products.
Above all, a new applicatio Cn oo pf yn ri icg k he tl :f Ae r mr it ee r ni c aan no pS a cr it ei c nl et isf i c( N Pi Fue b lOi sh Ne Pr ss) as highly efficient, green
2
4
and magnetically recyclable catalyst h aDs e bl iev ee nr ei nd tr bo dy uI cn eg de. nO t av erall, obtaining good to excellent yields
of products, environmentally and economic benign procedure, easy handling, availability of starting
materials, use of non-toxic solvents, and high recyclability of nano-catalyst could be countered as
most important advantages of this methodology.
Keywords: Nickel Ferrite Nanoparticles (NiFe O NPs), Green Synthesis, Magnetically
2
4
Recyclable Catalyst, 4H-Chromene.
1
. INTRODUCTION
non-corrosive, highly durable and recyclable catalysts in
chemical reactions [7–9]. On the other hand, the rate of
catalyst-assisted chemical reactions directly depends on
the surface area to volume ratio of catalyst, and also the
number- and how distributing of active sites on catalyst’s
surface [10, 11]. This fact means an excellent catalytic
activity is obtained from smaller particle sizes and higher
surface area of the catalysts which these properties can
be found in nano-scaled catalysts [12]. From above, the
importance of using nano-catalysts in chemical reaction
would be more understood.
In recent decades, the use of heterogeneous and
environmentally-benign catalysts in organic reactions has
attracted much interest of chemists and has widely been
considered in chemical industries [1–3]. In addition, het-
erogeneous catalysts have conventionally been preferred
than homogeneous ones because they have more important
advantages including simplicity in regeneration and reuse
in further cycles, and being commonly environmentally
safe, two important factors from chemical industries and
environmentally point of views [4–6]. Besides above, there
are some other important factors which make a catalyst
more considerable including high durability, high activity,
non-corrosive, non-degradable, and easily separation from
reaction mixture [4, 5]. Among heterogeneous catalysts,
transition metal oxides have known as highly efficient,
Spinel ferrite nano-sized materials such as NiFe O
2
4
are considered as very significant magnetic materials
which exhibited high resistivity, thermal durability and
stability [13]. Up to date, NiFe O nanoparticles have
2
4
been used in numerous ways and applications such
as microwave devices, transformers, transducers, sen-
sors and heterogeneous catalysis [14–16]. Also, mag-
netic nano-sized metal oxides have emerged as attractive
∗
†
Authors to whom correspondence should be addressed.
The participations are identical.
3206
J. Nanosci. Nanotechnol. 2020, Vol. 20, No. 5
1533-4880/2020/20/3206/011
doi:10.1166/jnn.2020.17396

Pourshojaei et al.
NiFe O NPs as Magnetically Recyclable Nanocatalyst for Highly Efficient Synthesis
2 4
Figure 1. Some selected pharmacological active compounds having chromene moiety and amine functionalized alkoxy groups.
heterogeneous catalysts in organic reactions [17, 18]. Their
widespread applications as catalyst in organic reactions
scaffolds. Furthermore there are some other heterocycles
containing chromene scaffold which have exhibited very
IP: 193.56.65.20 On: Tue, 31 Dec 2019 06:17:44
are related to their good dispersing in reaction mixtures,
significant pharmacological activities (Fig. 1). Besides
providing a large surface area to interact with s uDb es tl ri va tee rse, d bya bI no gv ee ns tt ar uctures, some important drugs and pharmacolog-
Copyright: American Scientific Publishers
easily separation from reaction mixture by only a magnet
without need to filtration or centrifugation, and capability
to reuse in further cycles [19–21].
In recent decades, a wide number of chromene deriva-
tives with important biological and pharmacological activ-
ities have been recognized that can be used as medicine to
treat human diseases. For example, Troglitazone (an anti-
diabetic and anti-inflammatory drug) [22], Calanolide A
ical active agents have also been recognized that in their
chemical structures amine functionalized alkoxy groups
have been seen (Fig. 1). It is believed that these functional
groups are responsible to their biological and pharmaco-
logical activities [27–29].
Considering the importance of biological and pharma-
ceutical active compounds and their role in treatment of
human disease as drug to make human life safer, synthe-
sis of these kinds of compounds and extend their domain
is inevitable and is attracted the interest of chemists and
pharmacologists [30–33].
[
(
a new non-nucleoside reverse transcriptase inhibitor
NNRTI)] [23], Vitamine E [24], Uvafzelin (an anti-
microbial agent) [25], and Phaseollidin (a naturally occur-
ring chromene in role of an enzyme) [26] can be countered
as medicinally important compounds bearing chromene
From above, and in continuous of our attempts on
catalytic green synthesis of novel medicinally important
Scheme 1. An efficient and green synthesis of 4H-chromene derivatives using nickel ferrite nanoparticles.
J. Nanosci. Nanotechnol. 20, 3206–3216, 2020
3207

NiFe O NPs as Magnetically Recyclable Nanocatalyst for Highly Efficient Synthesis
Pourshojaei et al.
2
4
heterocycles [34–37], herein we wish to report our recent
work on efficient synthesis of 4H-chromene derivatives by
the use of a broad range of aryl-aldehydes 1, malononi-
trile (2), and dimedone (3) in the presence of nickel ferrite
nanoparticles (NiFe O NPs) as magnetically recyclable
radiation. FT-IR spectra were recorded on Bruker, FT-IR
alpha model. The morphologies of the fabricated MNPs
were investigated using a scanning electron microscopy
(FE-SEM, ZEISS, SIGMA VP-500, Germany). The mag-
netic properties of the samples were detected at room tem-
perature using a vibrating sample magnetometer (VSM,
Meghnatis Kavir Kashan Co., Kashan).
2
4
catalyst via a green protocol (Scheme 1).
Over this three component reaction, NiFe O NPs
2
4
showed that can effectively catalyze this two steps reac-
tion (condensation reaction and intramolecular cyclization
respectively, see reaction’s mechanism). Furthermore, the
use of NiFe O NPs as green and magnetically recyclable
2
.4. Typical Procedure to the Synthesis of 4a
To a stirring mixture of 4-(2-morpholinoethoxy)benzalde-
hyde (0.235 g, 1 mmol) and malononitrile (0.132 g,
2
NiFe O NPs (0.012 g, 5 mol%), dimedone (0.140 g,
1
conditions for the time indicated in Table II. After com-
pletion of reaction which was found out by monitoring on
TLC, the mixture was poured into boiling THF (10 mL)
and then the catalyst was separated by a magnet, washed
2
4
catalyst has some other significant advantages such as con-
venient work-up, high safety, easy recyclability, high dura-
bility, and easy handling. In this work, besides successfully
synthesis and characterization of novel heterocyclic com-
pounds, a modified preparation, high activation, and regen-
eration of NiFe O NPs as an eco-friendly, magnetically
3
mmol) dissolved in 10 cm EtOH, in the presence of
2
4
mmol) was added. The mixture was heated under reflux
2
4
reusable and highly efficient catalyst have been explained.
Furthermore, the catalyst efficiency with other same ones
has been evaluated.
3
ꢀ
with boiling acetone (5 cm ꢀ, and dried at 100 C for
h to use in further cycles. The mixture was evaporated
1
to obtain crude product. In final step, crud product was
recrystallized in boiling EtOH to afford crystalline pure
product 4a.
2
. EXPERIMENTAL DETAILS
2
.1. Materials and Methods
Chemicals were purchased from Fluka and Merck chem-
ical companies. Fourier transform infrared (FT-IR) spec-
tra were recorded on Bruker, FT-IR alpha model.
Electrothermal KSB1N apparatus was handled for melt-
2
.5. Representative Spectral Data
2-Amino-7,7-dimethyl-4-(4-(2-morpholinoethoxy)phenyl)-
5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile 4a:
IP: 193.56.65.20 On: Tue, 31 Dec 2019 06:17:44
ꢀ
Lemon chiffon crystals; M.p.: 247–248 C; FT-IR (KBr):
ing points measurements. FT-NMR Bruker Avance Ultra
Copyright: American Scientific Publishers
1
Shield Spectrometer (at 300 for H NMR and at D7 e5 li Mv e Hr ez d byv¯In=g e3 n5 t6a 3, 3366, 3080, 2960, 2882, 2750, 2703, 2193,
1
3
for C NMR in DMSO as solvent) was used for recording
H and C NMR. Elemental analyses (C, H, N, S) were
1649, 1606, 1508, 1459, 1372, 1245, 1211, 1133, 1042,
848, 606 cm ; H NMR (DMSO-d , 300 MHz): 7.11
1
13
−1
1
6
performed on a Heraeus Rapid analyzer and the results
were found in good agreement (± 0.3%) with the calcu-
lated values. TLC-Grade silica gel-G/UV (254 nm) plates
were handled for monitoring of reaction progress.
(2H, d, J = 9 Hz, CH ꢀ, 6.99 (2H, s, NH ꢀ, 6,94 (2H, d,
Ar
2
J = 9 Hz, CH ꢀ, 4.38 (2H, brs, OCH ꢀ, 4.16 (1H, s,
Ar
2
CH), 3,95 (2H, brs, CH O), 3.79 (2H, brs, CH O), 3.50
2
2
(4H, brs, CH NCH ꢀ, 3.23 (2H, brs, NCH ꢀ, 2.52 (2H, m,
2
2
2
CH ꢀ, 2.27 (1H, d, J = 15 Hz, CH), 2.10 (1H, d, J =
2
2
.2. NiFe O NPs Catalyst Preparation
15 Hz, CH), 1.06 (3H, s, CH ꢀ, 0.97 (3H, s, CH ꢀ ppm;
2
4
3
3
1
3
Spinel ferrites were synthesized by the typical co precipi-
C NMR (DMSO-d , 75 MHz): ꢁ = 196.1, 162.7, 158.8,
6
tation method. Fe(NO ꢀ ·9H O (0.01 mol) and Ni(NO ꢀ ·
156.6, 138,2, 128,8, 120.2, 114.9, 113.3, 63.7, 62.5, 58.9,
55.4, 52.1, 50.4, 35.2, 32.2, 28.9, 27.2 ppm; Anal. calcd
for C H N O : C, 68.06; H, 6.90; N, 9.92. Found:
3
3
2
3 2
6
H O (0.005 mol) were dissolved in distilled water and
2
ꢀ
stirred vigorously for 30 minutes at 80 C under contin-
ued stirring. In this procedure, aniline was used as a base
to alkalinize media and added to the mixture of the two
salts gradually until the system is solidified. The formed
precipitate was washed with distilled water and ethanol
several times by employing an external magnetic field and
2
4
29
3
4
C, 68.12; H, 6.87; N, 9.98.
2-amino-7,7-dimethyl-5-oxo-4-(4-(2-(piperidin-1-yl)eth-
oxy)phenyl)-5,6,7,8-tetrahydro-4H-chromene-3-carbo-
ꢀ
nitrile 4b: White crystals; M.p.: 165–167 C; FT-IR (KBr):
v¯ = 3371, 3276, 3080, 2959, 2637, 2189, 1682, 1607,
ꢀ
−1
1
then dried at 80 C for 6 hours. Finally, the samples were
1510, 1363, 1254, 1142, 1041, 840, 560 cm ; H NMR
placed in an open-air atmosphere that was preheated at
(DMSO-d , 300 MHz): ꢁ = 7.08 (2H, d, J = 9 Hz,
6
ꢀ
3
00 C for thermal treatment. The temperature with steps
CH ꢀ, 7.01 (2H, s, NH ꢀ, 6.91 (2H, d, J = 9 Hz, CH ꢀ,
Ar
2
Ar
ꢀ
ꢀ
of 100 C rose to 500 C, and the samples were kept at
each temperature for 1 h.
4.36 (2H, t, J = 6 Hz, OCH ꢀ, 4.14 (1H, s, CH), 3.32
2
(
2
2H, t, J = 6 Hz, NCH ꢀ, 3.12 (4H, brs, CH NCH ꢀ,
2
2
2
.52 (2H, m, CH ꢀ, 2.26 (1H, d, J = 15 Hz, CH), 2.10
2
2
.3. Catalysts Characterization
(1H, d, J = 15 Hz, CH), 1.78–1.75 (4H, m, 2 × CH ꢀ,
2
X-ray diffraction (XRD) pattern was recorded by a Philips-
X’pertpro, X-ray diffractometer using Ni-filtered Cu Ka
1.51 (2H, brs, CH ꢀ, 1.04 (3H, s, CH ꢀ, 0.96 (3H, s,
2
3
1
3
CH ꢀ ppm; C NMR (DMSO-d , 75 MHz): ꢁ = 196.1,
3
6
3208
J. Nanosci. Nanotechnol. 20, 3206–3216, 2020

Pourshojaei et al.
NiFe O NPs as Magnetically Recyclable Nanocatalyst for Highly Efficient Synthesis
2 4
ꢀ
1
6
2
62.6, 158.8, 156.7, 138.0, 128.8, 120.2, 114.8, 113.3,
crystals, M.p.: 206–208 C; FT-IR (KBr): v¯ = 3651,
3.1, 56.4, 55.4, 53.1, 50.4, 35.2, 32.2, 28.8, 27.2, 23.1,
2.0 ppm; Anal. calcd for C H N O : C, 71.23; H, 7.41;
3466, 3240, 2915, 2870, 1695, 1668, 1614, 1570, 1491,
1105, 755, 697 cm ; H NMR (DMSO-d , 300 MHz):
−1
1
2
5
31
3
3
6
N, 9.97. Found: C, 71.21; H, 4.37; N, 10.05.
-Amino-7,7-dimethyl-4-(3-(2-morpholinoethoxy)phenyl)-
ꢁ = 7.62–7.59 (2H, d, J = 9 Hz, CH ꢀ, 7.43–7.41 (2H, d,
Ar
2
J = 9 Hz, CH ꢀ, 7.10–7.07 (2H, d, J = 9 Hz, CH ꢀ,
Ar
Ar
5
-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile 4c:
7.00 (2H, s, NH ꢀ, 6.96–6.92 (2H, d, J = 9 Hz, CH ꢀ,
2
Ar
ꢀ
Light yellow crystals, M.p.: 248–249 C; FT-IR (KBr):
5.06 (2H, s, OCH ꢀ, 4.16 (1H, s, CH), 2.52 (2H, m, CH ꢀ,
2 2
v¯ = 3381, 3286, 3036, 2961, 2396, 2184, 1651, 1450,
2.27 (1H, d, J = 15 Hz, CH), 2.12 (1H, d, J = 15 Hz,
−1
1
13
1
368, 1267, 1213, 1130, 1049, 906, 557 cm ; H NMR
CH), 1.05 (3H, s, CH ꢀ, 0.97 (3H, s, CH ꢀ ppm; C NMR
3
3
(
7
DMSO-d , 300 MHz): ꢁ = 7.24 (1H, t, J = 9 Hz, CH ꢀ,
(DMSO-d , 75 MHz): ꢁ = 196.1, 162.6, 158.9, 157.3,
6
Ar
6
3
4
,06 (2H, s, NH ꢀ, 6.83 (1H, dd, J = 9 Hz, J = 3 Hz,
137.7, 137.1, 131.8, 132.2, 128.7, 121.3, 120.3, 114.9,
113.4, 68.8, 58.9, 50.4, 35.2, 32.2, 28.8, 27.2 ppm; Anal.
calcd for C H BrN O : C, 62.64; H, 4.84; N, 5.84.
2
CH ꢀ, 6.75 (1H, d, J = 9 Hz, CH ꢀ, 6.73 (1H, s, CH ꢀ,
Ar
Ar
Ar
4
(
.31 (2H, t, J = 6 Hz, OCH ꢀ, 4.16 (1H, s, CH), 3.82
2
25 23
2
3
4H, t, J = 6 Hz, CH , OCH ꢀ, 3.29 (2H, t, J = 6 Hz,
Found: C, 62.70; H, 4.75; N, 5.96.
2-Amino-4-(3-((4-bromobenzyl)oxy)phenyl)-7,7-dimethyl-
2
2
NCH ꢀ, 3.08 (4H, brs, CH NCH ꢀ, 2.52 (2H, m, CH ꢀ,
2
2
2
2
2
.27 (1H, d, J = 15 Hz, CH), 2.13 (1H, d, J = 15 Hz,
5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile 4g
Papaya whip crystals, M.p.: 195–197 C; FT-IR (KBr):
:
1
3
ꢀ
CH), 1.05 (3H, s, CH ꢀ, 0.97 (3H, s, CH ꢀ ppm; C NMR
3
3
(
1
6
DMSO-d , 75 MHz): ꢁ = 196.1, 163.0, 158.9, 158.2,
v¯ = 3446, 3331, 3100, 2960, 2188, 1675, 1600, 1490,
6
−1
46.9, 130.0, 1120.3, 120.2, 114.5, 113.0, 112.5, 64.4,
3.4, 58.5, 55.9, 52.6, 50.4, 35.9, 32.3, 28.8, 27.2 ppm;
1364, 1269, 1204, 1140, 1035, 857, 805, 767, 698 cm ;
1
H NMR (DMSO-d , 300 MHz): ꢁ = 7.61 (2H, d,
6
Anal. calcd for C H N O : C, 68.06; H, 6.90; N, 9.92.
Found: C, 68.17; H, 6.82; N, 9.99.
-Amino-7,7-dimethyl-5-oxo-4-(4-(piperidin-1-yl)phenyl)-
J = 9 Hz, CH ꢀ, 7.43 (2H, d, J = 9 Hz, CH ꢀ, 7.23
2
4
29
3
4
Ar
Ar
(1H, t, J = 9 Hz, CH ꢀ, 7.04 (2H, s, NH ꢀ, 6.68 (1H, d,
Ar
2
2
J = 9 Hz, CH ꢀ, 6.77 (1H, s, CH ꢀ, 6.75 (1H, d,
Ar
Ar
1
2
5
,6,7,8-tetrahydro-4H-chromene-3-carbonitrile 4d: Yellow
J = 9 Hz, CH ꢀ, 5.06 (2H, dd, J = 15 Hz, J = 12 Hz,
Ar
ꢀ
crystals, M.p.: 224–225 C; FT-IR (KBr): v¯ = 3395, 3325,
OCH ꢀ, 4.17 (1H, s, CH), 2.52 (2H, m, CH ꢀ, 2.26
2
2
3
1
3
(
(
(
060, 2936, 2193, 1657, 1607, 1513, 1365, 1237, 1211,
(1H, d, J = 15 Hz, CH), 2.11 (1H, d, J = 15 Hz, CH),
−
1
1
13
138, 1035, 920, 830, 560 cm ; H NMR (DMSO-d ,
1.05 (3H, s, CH ꢀ, 0.97 (3H, s, CH ꢀ ppm; C NMR
6
3
3
IP: 193.56.65.20 On: Tue, 31 Dec 2019 06:17:44
00 MHz): ꢁ = 6.97 (2H, d, J = 9 Hz, CH ꢀ, 6.94
(DMSO-d , 75 MHz): ꢁ = 196.1, 163.0, 159.0, 158.6,
Ar
6
Copyright: American Scientific Publishers
2H, s, NH ꢀ, 6.84 (2H, d, J = 9 Hz, CH ꢀ, 4.07
146.8, 137.0, 131.8, 130.3, 129.9, 121.4, 120.2, 120.1,
2
A
Delivered by Ingenta
r
1H, s, CH), 3.08 (4H, t, J = 6 Hz, CH NCH ꢀ, 2.52
114.5, 113.0, 112.8, 68.8, 58.5, 50.4, 35.9, 32.2, 28.7,
27.3 ppm; Anal. calcd for C H BrN O : C, 62.64;
2
2
2H, m, CH ꢀ, 2.25 (1H, d, J = 15 Hz, CH), 2.10 (1H, d,
2
25 23
2
3
J = 15 Hz, CH), 1.61 (4H, brs, 2 × CH ꢀ, 1.54–1.51
H, 4.84; N, 5.84. Found: C, 62.69; H, 4.81; N, 5.86.
2-Amino-4-(4-((4-chlorobenzyl)oxy)phenyl)-7,7-dimethyl-
5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile 4h:
2
(
2H, m, CH ꢀ, 1,04 (3H, s, CH ꢀ, 0.96 (3H, s, CH ꢀ ppm;
2 3 3
1
3
C NMR (DMSO-d , 75 MHz): ꢁ = 196.1, 162.4, 158.8,
6
ꢀ
1
5
50.8, 135.2, 128.1, 120.4, 116.1, 113.1, 59.1, 50.5,
0.0, 35.1, 32.2, 28.9, 27.2, 25.8, 24.3 ppm; Anal. calcd
White crystals, M.p.: 199–201 C; FT-IR (KBr): v¯ =
3453, 3328, 3160, 2965, 2194, 1671, 1599, 1508, 1366,
−1
1
for C H N O : C, 73.18; H, 7.21; N, 11.13. Found:
1247, 1139, 1013, 841, 591 cm ; H NMR (DMSO-d ,
2
3
27
3
2
6
C, 73.23; H, 7.17; N, 11.24.
-Amino-7,7-dimethyl-4-(4-morpholinophenyl)-5-oxo-
300 MHz): ꢁ = 7.51–7.45 (4H, m, CH ꢀ, 7.10 (2H, d,
Ar
2
J = 9 Hz, 2CH ꢀ, 7.00 (2H, s, NH ꢀ, 6.94 (2H, d,
Ar
2
5
,6,7,8-tetrahydro-4H-chromene-3-carbonitrile 4e: Light
J = 9 Hz, CH ꢀ, 5.07 (2H, s, OCH ꢀ, 4.16 (1H, s, CH),
Ar
2
ꢀ
yellow crystals, M.p.: 225–227 C; FT-IR (KBr): v¯ = 3453,
2.52 (2H, m, CH ꢀ, 2.27 (1H, d, J = 15 Hz, CH), 2.12
2
3
1
3
325, 3068, 2967, 2198, 1665, 1602, 1513, 1365, 1249,
(1H, d, J = 15 Hz, CH), 1.05 (3H, s, CH ꢀ, 0.97 (3H, s,
3
−1
1
13
119, 1033, 923, 838, 559 cm ; H NMR (DMSO-d ,
CH ꢀ ppm; C NMR (DMSO-d , 75 MHz): ꢁ = 196.1,
6
3
6
00 MHz): ꢁ = 7.01 (2H, d, J = 9 Hz, CH ꢀ, 6.96 (2H, s,
162.6, 158.9, 157.3, 137.7, 136.7, 132.8, 129.9, 128.9,
128.7, 120.3, 114.9, 113.4, 68.8, 58.9, 50.4, 35.2, 32.2,
28.8, 27.2 ppm; Anal. calcd for C H ClN O : C, 69.04;
Ar
NH ꢀ, 6.86 (2H, d, J = 9 Hz, CH ꢀ, 4.09 (1H, s, CH),
2
Ar
3
2
.72 (4H, brs, CH OCH ꢀ, 3.07 (4H, brs, CH NCH ꢀ,
2 2 2 2
25 23
2
3
.52 (2H, m, CH ꢀ, 2.25 (1H, d, J = 15 Hz, CH), 2.10
H, 5.33; N, 6.44. Found: C, 69.10; H, 5.28; N, 6.47.
2-Amino-4-(3-((4-chlorobenzyl)oxy)phenyl)-7,7-dimethyl-
5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile 4i:
2
(
1H, d, J = 15 Hz, CH), 1.04 (3H, s, CH ꢀ, 0.96 (3H, s,
3
1
3
CH ꢀ ppm; C NMR (DMSO-d , 75 MHz): ꢁ = 196.1,
3
6
ꢀ
1
6
62.5, 158.8, 151.1, 135.9, 128.2, 120.3, 115.3, 113.5,
6.6, 59.1, 50.4, 48.9, 35.1, 32.2, 28.9, 27.2 ppm; Anal.
White crystals, M.p.: 195–196 C; FT-IR (KBr): v¯ = 3469,
3370, 3061, 2959, 2195, 1661, 1596, 1493, 1368, 1247,
−1
1
calcd for C H N O : C, 69.64; H, 6.64; N, 11.07. Found:
1214, 1160, 1026, 814, 558 cm ; H NMR (DMSO-d ,
2
2
25
3
3
6
C, 69.71; H, 6.60; N, 10.98.
-Amino-4-(4-((4-bromobenzyl)oxy)phenyl)-7,7-dimethyl-
-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile 4f: White
300 MHz): ꢁ = 7.52–7.45 (4H, m, CH ꢀ, 7.23 (1H, t,
Ar
2
J = 6 Hz, CH ꢀ, 7.04 (2H, s, NH ꢀ, 6.88–6.84 (1H, m,
Ar
2
5
CH ꢀ, 6.77–6.75 (1H, d, J = 6 Hz, CH ꢀ, 6.76 (1H, s, CH ꢀ,
Ar
Ar
Ar
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NiFe O NPs as Magnetically Recyclable Nanocatalyst for Highly Efficient Synthesis
Pourshojaei et al.
2
4
1
2
5
(
.07 (2H, dd, J = 18 Hz, J = 12 Hz, OCH ꢀ, 4.17
2
1H, s, CH), 2.52 (2H, m, CH ꢀ, 2.27 (1H, d, J = 15 Hz,
2
CH), 2.12 (1H, d, J = 15 Hz, CH), 1.05 (3H, s, CH ꢀ,
3
1
3
0
.97 (3H, s, CH ꢀ ppm; C NMR (DMSO-d , 75 MHz):
3 6
ꢁ
= 196.1, 163.0, 159.0, 158.6, 146.8, 136.5, 132.8,
1
6
30.0, 129.9, 128.9, 120.2, 120.1, 114.5, 113.0, 112.8,
8.8, 58.5, 50.4, 35.9, 32.2, 28.7, 27.3 ppm; Anal. calcd
for C H ClN O : C, 69.04; H, 5.33; N, 6.44. Found:
2
5
23
2
3
C, 69.09; H, 5.35; N, 6.42.
Figure 3. XRD pattern of NiFe O NPs.
2
4
3
. RESULTS AND DISCUSSION
Nickel ferrite nanoparticles were synthesized by a slight
modification of the precipitation reported method [13].
The FT-IR spectrum of the prepared NiFe O nanopar-
2
4
ticles (Fig. 2) reveals a characteristic vibration band at
−
1
−
1
3
411 cm and a deformation band at 1624 cm corre-
sponded to the adsorbed H O molecules at the surface of
2
the NiFe O nanoparticles. The bands centered at 662 and
2
1
4
−
5
76 cm are characteristic for metal oxide vibration bands
for nickel ferrite and these confirm the spinel structure of
the prepared NiFe O nanoparticles.
2
4
Figure 3 shows the X-ray diffraction pattern (XRD) of
the NiFe O NPs. In the XRD pattern, the distinguished
2
4
ꢀ
ꢀ
ꢀ
ꢀ
diffraction peak centered at 2ꢂ∼36 , 43.7 , 57.8 and 63.5
Figure 4. SEM image of NiFe O NPs.
2
4
related respectively to the (311), (440), (511) and (400)
plane of the NiFe O with an cubic inverse spinel-type
2
4
IP: 193.56.65.20 On: Tue, 31 Dec 2019 06:17:44
After preparation and characterization of NiFe O nano
catalyst, this magnetically recyclable nano-scaled material
which is in agreement with the standard data for the
NiFe O NPs structure (JCPDS 742081) [13]. In addi-
tion, scanning electron microscopy (SEM) was applied to
observe the morphology of NiFe O NPs (Fig. 4). SEM
2
4
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2
4
Delivered by Ingenta
as amphoteric Lewis catalyst was applied to the efficient
synthesis of 4H-chromene derivatives via a three com-
ponent one-pot reaction (Scheme 1). Before starting of
expanding reaction scope, compound 4h was selected as
model and we tried to find optimum conditions for reaction
progress (Table I). From loading model reaction in various
solvents including water, DMF, THF, toluene, acetonitrile,
dichloromethane, chloroform and ethanol, it is found that
reaction would go forward more effective and faster in
ethanol than others. After selecting reaction solvent, we
2
4
image of as-prepared NiFe O NPs shows the nickel ferrite
2
4
nanoparticles have a diameter of nearby 30 nm without any
amorphous or other kinds of crystallized phase particles.
Figure 5 shows the hysteresis loop of nickel ferrite
ꢀ
nanoparticles calcinated at 500 C. Magnetic characteriza-
tion of the nanoparticles was done using vibrating sample
magnetometry at ambient temperature (300 K) with max-
imum applied field up to 8 kOe. This graph shows the
MꢃHꢀ loops of 30 nm sample. The saturation magnetiza-
tion obtained at room temperature is found to be around
−1
0
.8 emu ·g .
Figure 2. FT-IR spectrum of NiFe O nanoparticles.
Figure 5. Magnetization curve for magnetic NiFe O nanoparticles.
2
4
2
4
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Pourshojaei et al.
NiFe O NPs as Magnetically Recyclable Nanocatalyst for Highly Efficient Synthesis
2 4
a
Table I. Effect of different conditions to the synthesis of 4h.
tried to find best temperature to reaction performance via
run reaction in numerous temperatures from room tem-
perature to boiling point of the solvent (78 C). From
b
Temperature Yield
ꢀ
ꢀ
Entry
Catalyst (mol%)
Solvent
( C)
(%)
investigations on finding best temperature for the reaction,
it was found that reaction progress in refluxing ethanol
would be faster and cause to obtain product with higher
yield. In addition, it should be noticed that no remarkable
product without using catalyst would be obtained. Among
different catalysts which were used to investigate reaction
progress, NiFe O NPs act significantly better than other
1
2
3
4
5
6
7
8
9
Catalyst-free
CHCl3
CHCl3
50
50
50
Reflux
50
50
50
50
50
50
50
50
70
60
50
70
60
r.t.
40
60
70
Reflux
Reflux
Reflux
Reflux
Reflux
–
NiFe O NPs (5 mol%)
60
53
45
51
55
40
72
43
47
70
88
58
55
52
57
49
50
67
86
92
97
95
92
96
96
2
4
NiFe O NPs (5 mol%)
CH CN
2
4
3
NiFe O NPs (5 mol%)
CH Cl2
2
4
2
NiFe O NPs (5 mol%)
PhCH3
THF
DMF
2
4
NiFe O NPs (5 mol%)
2
4
NiFe O NPs (5 mol%)
2
4
2
4
NiFe O NPs (5 mol%)
Ethanol
2
4
applied catalysts. The results of this experiment were sum-
marized in Table I. Furthermore, in solvent-free conditions
no considerable yield was obtained even using catalyst.
After finding optimum conditions to reaction perfor-
mance, to derivatization of the products, the reaction was
loaded in the presence of NiFe O NPs (5 mol%) at reflux-
NiFe O NPs (5 mol%)
H O
2
4
2
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
NiFe O NPs (5 mol%)
Solvent-free
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
2
4
Ni(NO ꢀ ·6H O (5 mol%)
3
2
2
Fe(NO ꢀ ·9H O (5 mol%)
3
3
2
In(OTf) (5 mol%)
3
Na WO ·2H O (5 mol%)
2
4
2
2
4
Na MoO ·2H O (5 mol%)
2
4
2
ing ethanol by the use of dimedone, malononitrile and a
broad range of arylaldehydes. The results of this work led
to obtain product 4a–n with good to excellent yields which
they could be seen with more details in Table II.
Y(NO ꢀ·6H O (5 mol%)
3
2
CuSO ·5H O (5 mol%)
4
2
NiFe O NPs (5 mol%)
2
4
NiFe O NPs (5 mol%)
2
4
In respect of the obtained yield of products, it is gener-
ally comprehend that the process of the reaction tolerates
both electron-withdrawing and electron-donating groups
on aromatic rings of aldehydes because the yields of
products with electron withdrawing groups on arylalde-
hydes rings would be higher than ones having electron
donating groups. The structure of 4 was clearly deduced
NiFe O NPs (5 mol%)
2
4
NiFe O NPs (5 mol%)
2
4
NiFe O NPs (5 mol%)
2
4
NiFe O NPs (4 mol%)
2
4
NiFe O NPs (3 mol%)
2
4
NiFe O NPs (6 mol%)
2
4
NiFe O NPs (8 mol%)
2
4
Notes: aReaction time: 40 min. bIsolated yield.
IP: 193.56.65.20 On: Tue, 31 Dec 201
from FT-IR, H NMR, C NMR spectroscopies, and also
1
9 06:17:4413
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a
Table II. Nano NiFe O -catalyzed synthesis of 2-amino-7,7-dimethyl-4-aryl-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile derivatives.
2
4
b
Entry
1
Product
Time (min)
45
Yield (%)
M.P. (lit.)
c
H C
H C
3
93
91
90
247–248
3
O
O
O
N
O
N
NH2
4a
c
2
50
165–167
c
3
45
248–249
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NiFe O NPs as Magnetically Recyclable Nanocatalyst for Highly Efficient Synthesis
Pourshojaei et al.
2
4
Table II. Continued.
b
Entry
4
Product
Time (min)
60
Yield (%)
M.P. (lit.)
c
90
224–225
c
5
40
90
225–227
4e
c
6
30
95
206–208
c
7
35
93
195–197
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c
8
40
97
199–201
c
9
35
95
195–196
10
30
90
230–231 (228–230) [38]
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Pourshojaei et al.
NiFe O NPs as Magnetically Recyclable Nanocatalyst for Highly Efficient Synthesis
2 4
Table II. Continued.
b
Entry
Product
Time (min)
25
Yield (%)
M.P. (lit.)
11
95
184–185 (183–185) [38]
12
30
89
211–213 (210–212) [39]
13
35
93
219–221 (217–219) [38]
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14
25
96
210–212 (209–211) [38]
15
30
94
225–227 (224–226) [38]
16
25
95
247–249 (210–213) [38]
J. Nanosci. Nanotechnol. 20, 3206–3216, 2020
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NiFe O NPs as Magnetically Recyclable Nanocatalyst for Highly Efficient Synthesis
Pourshojaei et al.
2
4
Table II. Continued.
b
Entry
Product
Time (min)
30
Yield (%)
M.P. (lit.)
17
94
152–153 (150–152) [41]
18
30
93
288–289 (287–289) [40]
19
25
93
222–223 (221–223) [39]
Notes: aReaction conditions: Arylaldehyde 1 (1 mmol), malononitrile 2 (1.5 mmol), dimedone 3 (1 mmol), NiFe O NPs (5 mol%), EtOH (10 mL), under reflux conditions.
2
4
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b
Isolated yield. cNovel compound.
elemental analyses and was confirmed. For example, the
1
H NMR spectrum of 4a indicates two doublet peaks
at 7.11 and 6.94 ppm correlated to four protons of aro-
matic ring, a distinguishable singlet at 6.99 ppm for NH2
group, a singlet at 4.38 ppm for two protons of OCH2
group, one sharp singlet at 4.16 ppm corresponded to the
central methine proton (CH), two broad singlets at 3,95
and 3.79 ppm related to four protons of morpholin ring
(
CH OCH ꢀ, a broad singlet at 3.50 ppm refers to other
2 2
four protons of morpholin ring (CH NCH ꢀ, a broad sin-
2
2
glet at 3.23 ppm corresponded to two protons of NCH2
side chain. Also, four protons of primary dimedone ring
were appeared at 2.52, 2.27, 2.10 ppm as one multiplate
and two doublet respectively. In addition, six protons of
two methyls groups (2 ×CH ꢀ were appeared as two sin-
3
1
3
glets at 1.06 and 0.97 ppm. CNMR spectrum of 4a also
shows 19 distinct resonances in agreement with the pro-
posed structure. Furthermore, FT-IR spectrum of 4a obvi-
ously exhibited the NH , CN and carbonyl groups at 3563,
2
−1
3
366, 2193 and 1649 cm respectively compatible with
proposed structures.
An admissible mechanism to the nano NiFe O -
2
4
catalyzed synthesis of 4H-chromenes is described in
Scheme 2. In this proposed cascade pathway, in the
first step, alylaldehyde in the presence of NiFe O NPs
2
4
Scheme 2. A proposed mechanism to NiFe O NPs-catalyzed synthesis
2 4
is reacted with malononitrile to give int. 5. Afterwards
of product 4.
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Pourshojaei et al.
NiFe O NPs as Magnetically Recyclable Nanocatalyst for Highly Efficient Synthesis
2 4
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. CONCLUSION
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