Synthesis and characterization of a novel Fe3O4@SiO2-BenzIm-Fc[Cl]/BiOCl nano-composite and its efficient catalytic activity in the ultrasound-assisted synthesis of diverse chromene analogs

Article abstract of DOI:10.1039/c8nj04938f

In this study, a novel magnetically recoverable Fe₃O₄@SiO₂-BenzIm-Fc[Cl]/BiOCl nano-composite was synthesized using a simple chemical co-precipitation method. This is the first time that a magnetic nano-catalyst bearing ionic liquid, ferrocene and BiOCl is synthesized. The Fe₃O₄@SiO₂-BenzIm-Fc[Cl]/BiOCl nano-composite was characterized by Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX) and field emission scanning electron microscopy (FE-SEM) techniques. The catalytic activities of the novel magnetic nano-composite were evaluated in one-pot three-component synthesis of a wide variety of 2-amino-3-cyano-4H-chromene derivatives under ultrasound irradiation. A simple, facile and highly efficient ultrasound-assisted method was developed to synthesize 4H-chromene derivatives via one-pot, three-component reaction of aldehyde, malononitrile and active phenolic compounds (2-naphthol, 1-naphthol, 3-(dimethylamino)phenol, resorcinol and orcinol) at room temperature. The reaction of aldehyde, malononitrile and orcinol is newly introduced in this paper. The ultrasound-assisted synthesis protocol that was studied in this article exhibits some notable advantages such as short reaction times, operational simplicity, green reaction conditions, high yields and easy work-up and purification steps. In addition, the novel magnetic nano-composite could be easily recovered by an external magnetic field and reused for six-reaction cycles without significant loss of its catalytic activity.

Full text of DOI:10.1039/c8nj04938f

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Synthesis and characterization of a novel
Fe3O4@SiO2–BenzIm-Fc[Cl]/BiOCl nano-
composite and its efficient catalytic activity
in the ultrasound-assisted synthesis of diverse
chromene analogs†
Cite this: New J. Chem., 2019,
43, 135
Reza Mohammadi, * Somayeh Esmati, Mahdi Gholamhosseini-Nazari and
Reza Teimuri-Mofrad
In this study, a novel magnetically recoverable Fe3O4@SiO2–BenzIm-Fc[Cl]/BiOCl nano-composite was
synthesized using a simple chemical co-precipitation method. This is the first time that a magnetic
nano-catalyst bearing ionic liquid, ferrocene and BiOCl is synthesized. The Fe3O4@SiO2–BenzIm-Fc[Cl]/
BiOCl nano-composite was characterized by Fourier-transform infrared spectroscopy (FT-IR), X-ray
diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX) and field emission scanning electron
microscopy (FE-SEM) techniques. The catalytic activities of the novel magnetic nano-composite were
evaluated in one-pot three-component synthesis of a wide variety of 2-amino-3-cyano-4H-chromene
derivatives under ultrasound irradiation. A simple, facile and highly efficient ultrasound-assisted method was
developed to synthesize 4H-chromene derivatives via one-pot, three-component reaction of aldehyde,
malononitrile and active phenolic compounds (2-naphthol, 1-naphthol, 3-(dimethylamino)phenol, resorcinol
and orcinol) at room temperature. The reaction of aldehyde, malononitrile and orcinol is newly introduced
in this paper. The ultrasound-assisted synthesis protocol that was studied in this article exhibits some
notable advantages such as short reaction times, operational simplicity, green reaction conditions, high
yields and easy work-up and purification steps. In addition, the novel magnetic nano-composite could
be easily recovered by an external magnetic field and reused for six-reaction cycles without significant
loss of its catalytic activity.
Received 28th September 2018,
Accepted 12th November 2018
DOI: 10.1039/c8nj04938f
rsc.li/njc
glycine,23 Fe3O4-chitosan nano-particles,24 4-dimethylaminopyridine
(DMAP),25 piperidine26 and Mg/Al hydrotalcite,27 2-ethyl imidazolium
1. Introduction
Heterocyclic compounds containing a 4H-chromene moiety are acetate,28 and tris-hydroxymethylaminomethane (THAM)29 were
present in a wide variety of drugs, many natural products and reported. However, because of the importance of 2-amino-4H-
numerous biologically and pharmaceutically active compounds. chromene derivatives, more efficient and environmentally benign
2-Amino-4H-chromene derivatives are known to exhibit anticancer,1–3 methods are still in demand. In order to introduce a simple,
antioxidant,4,5 anti-inflammatory,6,7 antimicrobial,8,9 anti- green and efficient strategy for the synthesis of these compounds,
tuberculosis,10 antiviral,11 anti-proliferative,12 antibacterial and it is important to use an applied heterogeneous catalyst, an eco-
antifungal,13 anticoagulant and anti-HIV activities.14 Hence, the friendly medium for the reactions, and an appropriate source of
design and synthesis of such compounds is a hot research topic input energy in order to optimize the reaction duration and
for chemists. Synthetic methods using different catalysts such product yield and avoid undesirable side-products.
as K2CO3,15,16 MW/DUB,17 TFE,18 amino-silane modified Fe3O4
On the other hand, supported heterogeneous catalysts
nanoparticles (MNPs-NH2),19 potassium phthalimide-N-oxyl as reusable and environmentally friendly materials play a key
(POPINO),20 NaBr,21 cetyltrimethylammoniumchloride (CTAC),22 role in modern science and technology, especially in organic
synthesis.30–32 Due to the advantages of the immobilization of
the catalyst on the solid supports, such as easily handling, non-
Department of Organic and Biochemistry, Faculty of Chemistry, University of Tabriz,
toxicity, low solubility and increasing the selectivity of the
Tabriz 5166614766, Iran. E-mail: r.mohammadi@tabrizu.ac.ir;
reactions, these types of heterocatalysts are widely used.33
Fax: +98 413 334 0191; Tel: +98 413 339 3117
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c8nj04938f
Catalysts immobilized on nanostructure supports are more
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Scheme 1 Ultrasound-assisted synthesis of diverse 2-amino-4H-chromenes via Fe3O4@SiO2–BenzIm-Fc[Cl]/BiOCl catalyzed three-component
reactions.
attractive, because they exhibit higher activity and selectivity.34–36 compounds (2-naphthol, 1-naphthol, 3-(dimethylamino)phenol,
Recent studies show that magnetite (Fe3O4) nano-particles have resorcinol and orcinol) catalyzed by the Fe3O4@SiO2–BenzIm-
unique properties such as superparamagnetism, high surface Fc[Cl]/BiOCl nano-composite under ultrasonic conditions were
area, thermal stability, low toxicity, low cost, easy separation from investigated (Scheme 1).
the reaction mixture using an external magnetic field, potential to
immobilize different functional groups and excellent recyclability,
which make them very applicable and useful supports to
2. Experimental
2.1. Materials and apparatus
design and synthesize reusable heterogeneous catalysts.37,38
Furthermore, benzimidazolium based ionic liquids (ILs) have
The chemical reagents used in synthesis were purchased from
received much attention and have been used as environmentally
Merck and Sigma-Aldrich Co. Melting points were determined with
friendly catalysts and solvents, due to their special properties such
a MEL-TEMP model 1202D and are uncorrected. FT-IR spectra were
as negligible volatility, thermal stability, non-inflammability,
recorded on a Bruker Tensor 27 spectrometer as KBr disks. The
high activity and selectivity and easy recyclability. Benzimidazole
1H NMR spectra were recorded using a Bruker Spectrospin Avance
400 spectrometer with DMSO-d6 as solvent and TMS as an internal
based ILs introduced a new possibility to develop new, efficient
and environmentally friendly catalysts for different organic
standard. 13C NMR spectra were determined on the same instru-
reactions.39
ment at 100 MHz. All chemical shifts were reported as d (ppm)
and coupling constants (J) are given in Hz. Elementary analyses
In recent years, the development of ultrasound-assisted
synthesis reactions has been focused in many scientific and
(C, H, N) were performed on a Vario EL III analyzer. X-ray diffraction
industrial investigations. Sonochemical synthesis has many
patterns of samples were taken on a Siemens D500 X-ray powder
benefits such as convenience, improved yields and reaction rates,
diffraction diffractometer (CuK radiation, l = 1.5406 Å). FE-SEM
images of the products were visualized by a TESCAN MIRA3 Field
simplicity and controllability of the reaction compared to tradi-
tional heating methods which generally require longer reaction
Emission Scanning Electron Microscope. A multiwave ultrasonic
times and higher temperatures. Therefore, a large number of
generator (Sonicator 3200; Bandelin, MS 73, Germany), equipped
organic reactions have been carried out under ultrasonic irradia-
with a converter/transducer and titanium oscillator (horn), 12.5 mm
tion in higher yields, shorter reaction times or milder conditions in
accordance with the green chemistry principles.40,41
in diameter, operating at 20 kHz with a maximum power output of
10–60 W, was used for the ultrasonic irradiation. The ultrasonic
generator automatically adjusted the power level.
In the continuation of our interest towards the development
of new efficient synthetic methodologies for various multi-
component reactions using nano-magnetic heterogeneous
catalysts,42–46 herein, we report a simple, facile and highly
2.2. Synthesis of the Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl
nano-composite
efficient ultrasound-assisted method for the synthesis of
2-amino-4H-chromene derivatives. One-pot three-component
2.2.1. Synthesis of 1-(4-ferrocenylbutyl)-1H-benzimidazole (17).
reactions of aldehyde, malononitrile and active phenolic Benzimidazole (2.36 g, 20 mmol) was added to a suspension of
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NaH (60%, 0.80 g, 20 mmol) in dry THF (100 mL), and the (100 MHz, DMSO-d6): d 18.8, 37.7, 57.5, 100.3, 111.9, 113.9,
mixture was stirred at 0 1C for 1 h. Then, 4-chlorobutylferrocene 120.5, 128.2, 128.5, 128.8, 130.9, 137.8, 144.7, 149.9, 156.9,
(1.38 g, 5 mmol) was added and the mixture was heated under 159.8 ppm; anal. calc. for C17H13ClN2O2 (%): C, 65.29; H, 4.19;
reflux for 12 h. After cooling, the excess amount of NaH was N, 8.96; found: C, 65.02; H, 4.21; N, 8.94.
quenched by the addition of water. After extraction with
2.3.2. 2-Amino-7-hydroxy-5-methyl-4-phenyl-4H-chromene-
dichloromethane, the extract was concentrated and the residue 3-carbonitrile (12b). Cream powder; m.p. 283–285 1C; FT-IR
was subjected to silica column chromatography eluting with (KBr): 3501, 3408, 3333, 3213, 2867, 2074, 1646, 1553 cmÀ1
;
n-hexane/ethyl acetate, 9 : 1, to give 1-(4-ferrocenylbutyl)-1H- 1H NMR (400 MHz, DMSO-d6): d 1.89 (s, 3H, CH3), 4.53 (s, 1H,
benzimidazole as a brown viscous oil; FT-IR: 3102, 2959, methin-H), 6.35 (s, 1H, Ar-H), 6.39 (s, 1H, Ar-H), 6.77 (bs, 2H,
2877, 1693, 1651, 1526 cmÀ1 1H NMR: d 1.46–1.54 (m, 2H, NH2), 7.04 (d, 2H, J = 7.4 Hz, Ar-H), 7.15–7.29 (m, 3H, Ar-H),
;
–CH2–), 1.84–1.91 (m, 2H, –CH2–), 2.34 (t, J = 7.5 Hz, 2H, –CH2–), 9.63 (bs, 1H, OH) ppm; 13C NMR (100 MHz, DMSO-d6): d 18.8,
4.01 (m, 2H, –CH2–), 4.04 (m, 7H, Cp-H), 4.14–4.17 (m, 2H, 38.5, 58.1, 100.3, 112.5, 113.9, 120.7, 126.4, 126.9, 128.5, 137.7,
Cp-H), 7.24–7.30 (m, 2H, benzimid-H), 7.47 (m, 2H, benzimid-H), 145.7, 150.1, 156.8, 159.8 ppm; anal. calc. for C17H14N2O2 (%):
7.73 (m, 1H, benzimid-H), 8.09 (s, 1H, benzimid-H); 13C NMR: C, 73.37; H, 5.07; N, 10.07; found: C, 73.12; H, 5.08; N, 10.04.
d 27.2, 27.9, 28.5, 44.0, 66.0, 66.9, 67.3, 86.9, 108.8, 119.4, 120.7,
121.7, 134.6, 144.8 ppm.
2.3.3. 2-Amino-7-hydroxy-5-methyl-4-(p-tolyl)-4H-chromene-
3-carbonitrile (12c). Light yellow powder; m.p. 236–238 1C; FT-IR
2.2.2. Synthesis of Fe3O4@SiO2@BenzIm-Fc[Cl] (19). Fe3O4@ (KBr): 3492, 3395, 3366, 3219, 3030, 2953, 2876, 2079, 1646, 1564
1
SiO2–propyl chloride was prepared according to reported cmÀ1; H NMR (400 MHz, DMSO-d6): d 1.89 (s, 3H, CH3), 2.23
procedures.43,44 Then, a mixture of Fe3O4@SiO2–(CH2)3Cl (1.0 g) (s, 3H, CH3), 4.47 (s, 1H, methin-H), 6.33 (d, 1H, J = 2.2 Hz, Ar-H),
and 1-(4-ferrocenylbutyl)-1H-benzimidazole (1.0 g) in 10 mL of 6.38 (d, 1H, J = 2.2 Hz, Ar-H), 6.76 (bs, 2H, NH2), 6.92 (d, 2H, J =
toluene was heated at 80 1C in an oil bath. After 72 h, the residue 7.9 Hz, Ar-H), 7.07 (d, 2H, J = 7.9 Hz, Ar-H), 9.64 (bs, 1H, OH)
was filtered, washed with toluene (3 Â 20 mL), MeOH (3 Â 20 mL), ppm; 13C NMR (100 MHz, DMSO-d6): d 18.8, 20.6, 38.1, 58.2,
and CH2Cl2 (3 Â 20 mL) and dried under reduced pressure at 100.2, 112.6, 113.8, 120.7, 126.8, 126.9, 128.7, 129.1, 135.4, 137.7,
50 1C for 48 h to afford Fe3O4@SiO2@BenzIm-Fc[Cl].
142.7, 150.0, 156.7, 159.8 ppm; anal. calc. for C18H16N2O2 (%):
2.2.3. Synthesis of Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl (20). C, 73.95; H, 5.52; N, 9.58; found: C, 73.71; H, 5.55; N, 9.54.
BiCl3 (0.2 g) was dissolved in 10 mL of water and 30 mL of 2.3.4. 2-Amino-7-hydroxy-4-(4-isopropylphenyl)-5-methyl-4H-
acetone. Then, 0.2 g of Fe3O4@SiO2@BenzIm-Fc[Cl] nano- chromene-3-carbonitrile (12d). Light yellow powder; m.p.
particles was added and the mixture was put in an ultrasonic 241–243 1C; FT-IR (KBr): 3451, 3336, 3207, 3117, 2957, 2876,
1
bath for 15 minutes. The suspension was stirred at room 2081, 1642, 1574 cmÀ1; H NMR (400 MHz, DMSO-d6): d 1.15
temperature for 24 hours by a mechanical stirrer. Modified (d, 6H, J = 6.8 Hz, 2 Â CH3), 1.90 (s, 3H, CH3), 2.77–2.84 (m, 1H,
nano-particles were separated from the reaction medium via an CH), 4.47 (s, 1H, methin-H), 6.34 (d, 1H, J = 2.2 Hz, Ar-H), 6.38
external magnetic field and washed with water, EtOH and (d, 1H, J = 2.2 Hz, Ar-H), 6.75 (bs, 2H, NH2), 6.95 (d, 2H, J =
acetone. The desired nano-catalyst was dried under vacuum. 8.1 Hz, Ar-H), 7.13 (d, 2H, J = 8.1 Hz, Ar-H), 9.61 (bs, 1H, OH)
The modified nano-particles were identified using FT-IR, ppm; 13C NMR (100 MHz, DMSO-d6): d 18.8, 23.8, 33.0, 38.1,
FE-SEM, EDX and XRD.
58.2, 100.3, 112.8, 113.9, 120.9, 126.1, 126.5, 126.9, 137.7, 143.2,
150.1, 156.8, 159.9 ppm; anal. calc. for C20H20N2O2 (%):
C, 74.98; H, 6.29; N, 8.74; found: C, 74.73; H, 6.31; N, 8.70.
2.3.5. 2-Amino-4-(2-chlorophenyl)-7-hydroxy-5-methyl-4H-
2.3. General procedure for the synthesis of 2-amino-4H-
chromenes derivatives under ultrasound irradiation
A mixture of an aldehyde (1 mmol), malononitrile (1.1 mmol), chromene-3-carbonitrile (12e). Cream powder; m.p. 270–272 1C;
an appropriate C–H acid 3, 5, 7, 9 or 11 (1 mmol), and FT-IR (KBr): 3500, 3394, 3332, 3219, 2972, 2188, 1650, 1464 cmÀ1
;
Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl (10 mg) in ethanol : water 1H NMR (400 MHz, DMSO-d6): d 1.85 (s, 3H, CH3), 5.04 (s, 1H,
(3 : 2, 5 mL) was sonicated at ambient temperature. When the methin-H), 6.32–6.39 (m, 2H, Ar-H), 6.84 (bs, 2H, NH2), 6.92
reaction was completed [monitored by thin layer chromatogra- (d, 1H, J = 6.2 Hz, Ar-H), 7.17–7.26 (m, 2H, Ar-H), 7.40 (dd, 1H,
phy (TLC), using n-hexane/ethyl acetate (3 : 1) as the eluent], the J = 7.5 Hz, J = 1.4 Hz, Ar-H), 9.68 (bs, 1H, OH) ppm; 13C NMR
catalyst was separated using an external magnet and the reac- (100 MHz, DMSO-d6): d 18.6, 20.9, 56.3, 100.3, 111.8, 113.9,
tion mixture was cooled and the precipitate was filtered, 120.1, 127.9, 128.2, 129.3, 130.2, 131.5, 137.7, 142.7, 150.3,
washed and dried. The crude product was crystallized from 157.0, 160.2 ppm; anal. calc. for C17H13ClN2O2 (%): C, 65.29;
ethanol. The structures of the new compounds 12a–f were H, 4.19; N, 8.96; found: C, 65.03; H, 4.22; N, 8.92.
1
characterized by IR, H NMR, 13C NMR and CHN analysis.
2.3.6. 2-Amino-7-hydroxy-5-methyl-4-(naphthalen-2-yl)-4H-
2.3.1. 2-Amino-4-(4-chlorophenyl)-7-hydroxy-5-methyl-4H- chromene-3-carbonitrile (12f). Light yellow powder; m.p.
chromene-3-carbonitrile (12a). Cream powder; m.p. 256–258 1C; 272–274 1C; FT-IR (KBr): 3490, 3399, 3319, 3206, 2923, 2074,
1
FT-IR (KBr): 3443, 3351, 3319, 3190, 3028, 2941, 2871, 2073, 1648, 1642, 1497 cmÀ1; H NMR (400 MHz, DMSO-d6): d 1.92 (s, 3H,
1
1551 cmÀ1; H NMR (400 MHz, DMSO-d6): d 1.88 (s, 3H, CH3), CH3), 4.71 (s, 1H, methin-H), 6.35–6.38 (m, 2H, Ar-H), 6.84 (bs,
4.57 (s, 1H, methin-H), 6.33 (d, 1H, J = 2.2 Hz, Ar-H), 6.39 (d, 1H, 2H, NH2), 7.14 (dd, 1H, J = 8.5 Hz, J = 1.6 Hz, Ar-H), 7.44–7.51
J = 2.2 Hz, Ar-H), 6.83 (bs, 2H, NH2), 7.05 (d, 2H, J = 8.4 Hz, Ar-H), (m, 2H, Ar-H), 7.62 (s, 1H, Ar-H), 7.78–7.86 (m, 3H, Ar-H), 9.66
7.34 (d, 2H, J = 8.4 Hz, Ar-H), 9.68 (bs, 1H, OH) ppm; 13C NMR (bs, 1H, OH) ppm; 13C NMR (100 MHz, DMSO-d6): d 18.8, 38.7,
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57.8, 100.4, 112.2, 113.9, 120.7, 125.0, 125.6, 125.7, 126.3, 127.5, Fe3O4@SiO2 nano-particles were allowed to react with
127.6, 128.5, 131.8, 132.8, 137.9, 142.9, 150.0, 156.9, 159.9 ppm; (3-chloropropyl)trimethoxysilane to obtain chloropropyl containing
anal. calc. for C21H16N2O2 (%): C, 76.81; H, 4.91; N, 8.53; found: nano-particles.50–52 On the other hand, 1-(4-ferrocenylbutyl)-1H-
C, 76.58; H, 4.94; N, 8.50.
benzimidazole was prepared by the reaction of benzimidazole
with 4-chlorobutylferrocene. Subsequently 1-(4-ferrocenylbutyl)-
1H-benzimidazole reacted with Fe3O4@SiO2–(CH2)3Cl to afford
Fe3O4@SiO2@BenzIm-Fc[Cl] nanoparticles. Finally, the Fe3O4@
SiO2@BenzIm-Fc[Cl]-coupled BiOCl nano-composite was pre-
3. Results and discussion
The new magnetic nano-catalyst Fe3O4@SiO2@BenzIm-Fc[Cl]/ pared by using a simple chemical co-precipitation method using
BiOCl was prepared following the multistep protocol shown in BiCl3 at room-temperature. Chemical analysis of the prepared
Scheme 2. A literature survey showed that Fe3O4/BiOCl nano- magnetic nano-particles and Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl
composites were previously synthesized and their photo- nano-composite was studied by Fourier transform infrared
catalytic efficiency was studied,47–49 but the catalytic activity of spectroscopy (FT-IR), field emission scanning electron micro-
these nano-composites has not been investigated. Following our scopy (FE-SEM), energy dispersive X-ray (EDX) and X-ray diffrac-
recent studies on the design and synthesis of novel ferrocene tion (XRD) analysis.
containing ionic liquids supported on Fe3O4 nano-particles, here
The FT-IR spectra of (a) Fe3O4, (b) Fe3O4@SiO2, (c) Fe3O4@
we report novel generation of this nano-catalyst as a Fe3O4@ SiO2@(CH2)3Cl, (d) Fe3O4@SiO2@BenzIm-Fc[Cl] and (e) Fe3O4@
SiO2@BenzIm-Fc[Cl]/BiOCl nano-composite. Initially, the chemical SiO2@BenzIm-Fc[Cl]/BiOCl are shown in Fig. 1. In the FT-IR
co-precipitation of Fe2+ and Fe3+ ions in NH4OH solution was spectroscopy of the nano-particles, the absorption peaks at about
performed in order to prepare magnetic Fe3O4 nano-particles. 580 cmÀ1 are related to Fe–O bond vibrations. The absorption
Subsequently, silica-coated magnetic nano-particles (Fe3O4@SiO2) peaks at about 1080 cmÀ1 in all Fe3O4@SiO2 core–shell MNPs are
were easily achieved using the known Stober method. Then, the linked to the asymmetric stretching vibrations of Si–O–Si. In the
Scheme 2 Synthesis of the Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl nanocomposite.
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Fig. 1 The FT-IR spectra of (a) Fe3O4, (b) Fe3O4@SiO2, (c) Fe3O4@SiO2@(CH2)3Cl, (d) Fe3O4@SiO2@BenzIm-Fc[Cl] and (e) Fe3O4@SiO2@BenzIm-
Fc[Cl]/BiOCl.
FT-IR spectroscopy of Fe3O4@SiO2–(CH3)3Cl MNPs more than synthesized one are presented in Fig. 2. The EDX spectrum
Fe–O and Si–O–Si bond vibrations, an absorption peak at and data of Fe3O4@SiO2@BenzIm-Fc[Cl] nano-particles intro-
2918 cmÀ1 appeared which is related to the asymmetric stretch- duced the presence of the expected elements (C, N, O, Si, Cl and
ing vibration of aliphatic C–H. The FT-IR spectroscopy of Fe) in their regions. The EDX spectrum of the novel synthesized
Fe3O4@SiO2@BenzIm-Fc[Cl] MNPs shows an absorption peak at Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl nano-composite indicated
above 3000 cmÀ1 related to the stretching vibration of aromatic the presence of the expected elements (C, N, O, Si, Cl, Fe and
C–H on benzimidazole and ferrocene groups. The absorption peaks Bi) and confirmed the structure of the nano-catalyst. The
at 1643 and 1549 cmÀ1 are also linked to the stretching vibration of presence of Bi in the EDX spectrum of the final nano-catalyst
CQN and CQC bonds on aromatic rings. Finally, in the FT-IR confirmed the synthesis of a nano-composite.
spectroscopy of the Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl nano-
The X-ray diffraction (XRD) pattern of the modified Fe3O4
composite, the absorption peak at about 530 cmÀ1 is assigned to nano-particles was measured at 0 to 80 degrees. As shown in
Bi–O stretching vibration and the absorption peak at 1460 cmÀ1 is Fig. 3, the diffusion pattern of Fe3O4@SiO2@BenzIm-Fc[Cl] nano-
assigned to the stretching vibration peak of the Bi–Cl band in the particles shows the crystalline dispersions of Fe3O4 magnetic
BiOCl structure. These results revealed the successful synthesis of nano-particles. The XRD pattern of Fe3O4@SiO2@BenzIm-Fc[Cl]
the Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl nano-catalyst.
nano-particles exhibited diffraction peaks at 2y = 31.61, 35.41,
Energy-dispersive X-ray spectroscopy (EDX) analysis of 43.11, 531, 57.31 and 63.91 which are in good agreement with the
Fe3O4@SiO2@BenzIm-Fc[Cl] nano-particles and the newly standard XRD pattern of Fe3O4 MNPs (JCPDS card no. 85-1436).
Fig. 2 EDX analysis of (a) Fe3O4@SiO2@BenzIm-Fc[Cl] and (b) Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl.
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Fig. 3 XRD patterns of (a) Fe3O4@SiO2@BenzIm-Fc[Cl] and (b) Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl.
But the XRD patterns of the Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl
nano-composite displayed distinctive peaks at 2y = 12.21, 24.61,
26.21, 32.91, 33.71, 36.91, 41.31, 47.11, 50.01, 54.41, 55.41, 58.91,
and 77.81 which are well matched with the tetragonal phase
JCPDS-ICDD File No. 01-085-0861. These distinctive peaks were
very obvious, suggesting the formation and good crystallinity of
the novel synthesized Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl nano-
composite.
The surface morphology and size of the Fe3O4@SiO2@
BenzIm-Fc[Cl] nano-particles and Fe3O4@SiO2@BenzIm-Fc[Cl]/
BiOCl nano-composite were evaluated using Field Emission
Scanning Electron Microscopy (FE-SEM) analysis (Fig. 4). The
FE-SEM images of the Fe3O4@SiO2@BenzIm-Fc[Cl] nano-
particles showed that the shapes of these particles are mostly
spherical with non-smooth surfaces which increase the surface
areas and activity of these particles. The FE-SEM images of
Fe3O4@SiO2@BenzIm-Fc[Cl] nano-particles also displayed that
the particles are uniformly distributed and the sizes of the
magnetic nano-particles are about 40 nm. The FE-SEM images
of the Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl nano-composite showed
that BiOCl was synthesized on the Fe3O4@SiO2@BenzIm-Fc[Cl]
nano-particles as irregular plates which are around 150 nm in
width and about 50 nm in thickness.
In continuation, we decided to investigate the catalytic activity
of the Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl nano-composite in
the synthesis of 2-amino-4H-chromene derivatives. At first, the
reaction of 4-chlorobenzaldehyde (1a) (1 mmol), malononitrile (2)
(1.1 mmol) and 2-naphthol (3) (1 mmol) under ultrasound
irradiation was chosen as a test reaction. The reaction was studied
Fig. 4 FE-SEM images of (a and b) Fe3O4@SiO2@BenzIm-Fc[Cl] and
(c and d) Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl.
under different conditions and the progress of the reactions was of the catalyst to 15 mg didn’t show improvement in the
monitored by TLC. In this context, the effects of catalyst loading reaction. Then, the subsequent optimization of the reaction
on the reaction were examined initially. In the absence of catalyst, conditions affirmed the selection of ethanol–water (3 : 2, v/v) as
3-amino-1-(4-chlorophenyl)-1H-benzo[ f ]chromene-2-carbonitrile the best solvent for the synthesis of the desired product (4a), in
(4a) was obtained after 60 minutes only in 10% yield. With an excellent yield. Finally, we tried to test the effect of ultra-
increase in the amount of catalyst to 10 mg, the yield of the sound irradiation power on the reaction of 4-chlorobenzaldehyde,
desired product (4a) was gradually increased. But more addition malononitrile and 2-naphthol. Various ranges of irradiation
140 | New J. Chem., 2019, 43, 135--145
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Table 1 Synthesis of 3-amino-1H-benzo[f]chromene derivatives using 10 mg of the Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl nanocatalyst
Entry
Aldehyde
Product
Time (min)
Yield (%)
Obs. m.p. (1C)
Lit. m.p. (1C)
1
2
3
4
5
6
7
8
4-Chlorobenzaldehyde
Benzaldehyde
(4a)
(4b)
(4c)
(4d)
(4e)
(4f)
(4g)
(4h)
(4i)
15
18
18
18
18
20
20
15
18
20
20
20
96
93
95
93
92
90
87
96
92
88
84
82
208–210
280–281
212–214
233–235
272–274
220–222
192–194
186–188
217–219
270–272
224–226
227–229
207–20943
279–28143
212–21543
232–23443
270–27343
218–22043
192–19443
186–18743
215–21843
269–27243
224–22643
225–22743
4-Bromobenzaldehyde
4-Fluorobenzaldehyde
4-Methylbenzaldehyde
4-Isopropylbenzaldehyde
4-Methoxybenzaldehyde
4-Nitrobenzaldehyde
3-Nitrobenzaldehyde
2-Chlorobenzaldehyde
Thiophene-2-carbaldehyde
4-Pyridinecarboxaldehyde
9
10
11
12
(4j)
(4k)
(4l)
powers (30–60 W) were studied and the best results were (Table 2). A literature survey revealed that 4H-benzo[h]chromene
obtained when the irradiation power was 50 W. derivatives possess many biological and pharmacological
Subsequently, the method was developed towards various activities such as cytotoxicity and anticancer activity53 and a
aldehydes to obtain the related 3-amino-1H-benzo[f]chromene number of methods have been reported for the synthesis of
derivatives 4a–l. Accordingly, a number of aromatic aldehydes these compounds. Here, our new method for the synthesis of
with electron-withdrawing groups as well as electron-donating these compounds was examined. For this reason three-
groups and a few heteroaromatic aldehydes were subjected component reactions between 1-naphthol, malononitrile and
to reaction with malononitrile and 2-naphthol in the presence a series of aldehydes were performed in the presence of 10 mg
of a catalytic amount of Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl of Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl nano-composite in
nanocomposite under ultrasonic irradiation. In all cases, the ethanol–water (3 : 2, v/v) under ultrasonic irradiation. A group
corresponding products 4a–l were obtained within 15–20 min of 2-amino-4H-benzo[h]chromene derivatives (6a–l) were
in excellent yields (Table 1).
synthesized successfully according to this simple and efficient
After this initial success, the generality of the method for the method in high yields.
synthesis of 2-amino-4H-benzo[h]chromene derivatives was exam-
After establishing a general method for the synthesis of
ined. In this context, replacement of the 2-naphthol with 1-naphthol 3-amino-1H-benzo[ f ]chromenes 4, as well as 2-amino-4H-
could be expected to furnish 2-amino-4H-benzo[h]chromenes 6a–l benzo[h]chromene derivatives 6, we tried to synthesize another
Table 2 Synthesis of 2-amino-4H-benzo[h]chromene derivatives using 10 mg of the Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl nanocatalyst
Entry
Aldehyde
Product
Time (min)
Yield (%)
Obs. m.p. (1C)
Lit. m.p. (1C)
1
2
3
4
5
6
7
8
4-Chlorobenzaldehyde
Benzaldehyde
(6a)
(6b)
(6c)
(6d)
(6e)
(6f)
(6g)
(6h)
(6i)
15
15
18
15
15
18
20
15
18
20
25
25
96
93
94
92
90
89
87
97
90
86
88
86
245–247
217–219
240–242
233–234
207–209
204–206
192–194
238–240
217–219
251–253
187–189
170–172
246–24754
216–21754
240–24155
232–23454
205–20755
204–20555
193–19455
238–23955
218–22054
253–25455
188–19055
168–17054
4-Bromobenzaldehyde
4-Fluorobenzaldehyde
4-Methylbenzaldehyde
4-Isopropylbenzaldehyde
4-Methoxybenzaldehyde
4-Nitrobenzaldehyde
3-Nitrobenzaldehyde
2-Chlorobenzaldehyde
Thiophene-2-carbaldehyde
2-Furancarboxaldehyde
9
10
11
12
(6j)
(6k)
(6l)
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Table 3 Synthesis of 2-amino-7-(dimethylamino)-4H-chromene derivatives using 10 mg of the Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl nanocatalyst
NJC
Entry
Aldehyde
Product
Time (min)
Yield (%)
Obs. m.p. (1C)
Lit. m.p. (1C)
1
2
3
4
5
6
7
8
4-Chlorobenzaldehyde
Benzaldehyde
(8a)
(8b)
(8c)
(8d)
(8e)
(8f)
(8g)
(8h)
(8i)
20
22
22
22
25
25
28
20
22
25
28
28
94
90
89
90
91
87
86
95
90
86
84
85
200–202
205–205
214–216
180–182
242–243
225–227
175–177
225–227
206–208
193–195
215–217
238–240
202–20556
206–20756
212–21457
174–17857
240–24256
226–22856
176–17856
224–22657
207–20957
195–19757
217–22056
240–24256
4-Bromobenzaldehyde
4-Fluorobenzaldehyde
4-Methylbenzaldehyde
4-Isopropylbenzaldehyde
4-Methoxybenzaldehyde
4-Nitrobenzaldehyde
3-Nitrobenzaldehyde
2-Chlorobenzaldehyde
Thiophene-2-carbaldehyde
Pyridine-3-carbaldehyde
9
10
11
12
(8j)
(8k)
(8l)
Table 4 Synthesis of 2-amino-4H-chromene derivatives using 10 mg of the Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl nanocatalyst
Entry
Aldehyde
Product
Time (min)
Yield (%)
Obs. m.p. (1C)
Lit. m.p. (1C)
1
2
3
4
5
6
7
8
4-Chlorobenzaldehyde
Benzaldehyde
(10a)
(10b)
(10c)
(10d)
(10e)
(10f)
(10g)
(10h)
(10i)
(10j)
(10k)
(10l)
8
10
10
10
12
12
15
8
12
15
15
15
98
95
92
93
90
87
88
97
86
84
85
83
235–237
230–232
234–236
288–290
186–188
195–197
190–192
214–216
175–177
185–187
202–204
190–192
239–24158
231–23359
233–23559
292–29459
185–18759
196–19860
192–19460
212–21460
170–17259
188–18961
204–20659
189–19162
4-Bromobenzaldehyde
4-Fluorobenzaldehyde
4-Methylbenzaldehyde
4-Isopropylbenzaldehyde
4-Methoxybenzaldehyde
4-Nitrobenzaldehyde
3-Nitrobenzaldehyde
2-Chlorobenzaldehyde
Thiophene-2-carbaldehyde
2-Furancarboxaldehyde
9
10
11
12
Table 5 Synthesis of 2-amino-5-methyl-4H-chromene derivatives using
10 mg of the Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl nanocatalyst
Time Yield M.p.
Entry Aldehyde
Product (min) (%)
(1C)
1
2
3
4
5
6
4-Chlorobenzaldehyde
Benzaldehyde
4-Methylbenzaldehyde
4-Isopropylbenzaldehyde (12d)
2-Chlorobenzaldehyde
2-Naphthaldehyde
(12a)
(12b)
(12c)
6
8
8
10
10
10
98
96
95
93
90
88
256–258
283–285
236–238
241–243
270–272
Fig. 5 Comparison of the ultrasonic-assisted method with solvent-free
and reflux conditions for the synthesis of 2-amino-4H-chromene deriva-
(12e)
(12f)
272–274 tives catalyzed with Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl.
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groups were investigated under the optimized reaction condi-
tions. The results given in Table 3 showed that this one-pot
three-component condensation completed within 20–28 min
with good isolated yields.
Encouraged by the above mentioned success of a new
Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl catalyzed method, we decided
to use resorcinol as another enolizable C–H acid derivative. The
literature survey showed that due to the versatile biological proper-
ties of these 2-amino-4H-chromene derivatives, the syntheses of
these compounds are well studied and numerous methods for
their synthesis are reported. In continuation, three component
reactions of various aldehydes, malononitrile and resorcinol
catalyzed by Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl nano-composite
under ultrasonic irradiation are investigated in order to develop
and explore the scope and generality of this catalytic method.
The results are summarized in Table 4. Aromatic aldehydes
Fig. 6 Recyclability of the Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl nanocata-
lyst on the synthesis of 4a.
important class of chromene-annulated heterocycles, namely containing electron-releasing and electron-withdrawing sub-
2-amino-7-(dimethylamino)-4H-chromenes 8 (Table 3). To achieve stituents on their aromatic rings react to give products in high
this aim, 3-dimethylaminophenol was chosen as the C–H acid in to excellent yields in short reaction times. The reaction times of
the three-component reaction. We were interested in the synthesis aromatic aldehydes having electron-withdrawing groups are
of 2-amino-4-aryl-7-(dimethylamino)-4H-chromene-3-carbonitrile rather faster than those having electron-donating groups.
derivatives because of their numerous medicinal properties
Based on the optimized reaction conditions, the reaction
especially anticancer activities. Therefore, various aldehydes was further extended using various aromatic aldehydes with
containing either electron-withdrawing or electron-donating malononitrile and orcinol to synthesize the corresponding
Table 6 Comparison of the present method with the reported methods
Entry
Compound
Catalyst, solvent, condition
Time
Yield (%)
Ref.
Triazine-based porous polymer, H2O, 80 1C
Silica-supported piperazine, CHCl3, reflux
[cmmim]Br, solvent-free, 110 1C
(SiO2@Im-Fc[OAc]), solvent-free, 90 1C
Nanocatalyst, EtOH/H2O, sonication
6 h
24 h
15 min
20 min
15 min
88
71
90
92
96
63
64
65
42
1
This work
Nanostructured diphosphate Na2CaP2O7, H2O, reflux
Nanozeolite clinoptilolite, H2O, reflux
Sodium-modified hydroxyapatite, H2O, reflux
Silica-supported piperazine, CHCl3, reflux
[TEA–PEG800–DIL][Cl], H2O, reflux
4 h
20 min
3 h
7 h
15 min
15 min
90
95
96
74
95
96
66
67
68
64
2
3
4
54
Nanocatalyst, EtOH/H2O, sonication
This work
Piperidine, EtOH, 35 1C
Tris-hydroxymethylamino methane, EtOH/H2O, R.t.
Nanocatalyst, EtOH/H2O, sonication
12 h
2.5 h
20 min
47
85
94
69
29
This work
Triazine-based porous polymer, solvent-free, 80 1C
Potassium phthalimide-N-oxyl, H2O, reflux
Amino-appended b-cyclodextrins, H2O, R.t.
Hydrotalcite, H2O, 60 1C
2-Ethylimidazolium acetate, solvent-free, 67.5 1C
Nanocatalyst, EtOH/H2O, sonication
6 h
15 min
5 h
5 h
29 min
8 min
85
92
90
90
94
98
63
20
70
27
28
This work
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2-amino-5-methyl-4H-chromene derivatives (12a–f) in excellent References
yields as shown in Table 5. The new synthesized compounds
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Finally, we decided to combine the sonication method with
solvent-free and traditional reflux conditions. For this reason,
the synthesis of compounds 4a, 6a, 8a, 10a and 12a catalyzed
with Fe3O4@SiO2@BenzIm-Fc[Cl]/BiOCl were studied under
different conditions. As summarized in Fig. 5, all 2-amino-4H-
chromene derivatives were synthesized more efficiently under
ultrasonic irradiation with respect to yields and reaction times.
Furthermore, the reusability of the catalyst was investigated
with the model reaction under modified conditions and the
results are shown in Fig. 6. After completion of the reaction, the
catalyst was separated using an external magnet. The collected
nano-catalyst was washed several times with EtOH prior to
reuse. The recovered nano-catalyst could be reused for six runs
without significant decrease in activity.
To highlight the efficiency and applicability of the new
method, we compared the results of Fe3O4@SiO2@
BenzIm-Fc[Cl]/BiOCl catalyzed reactions with other reported
methodologies. As shown in Table 6, the Fe3O4@SiO2@
BenzIm-Fc[Cl]/BiOCl nanocatalyst and new ultrasonic assisted
method has a significant impact on the performance of the
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In summary, a new approach for the synthesis of modified
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for the synthesis of a wide variety of 2-amino-4H-chromene
derivatives. The reactions were performed under ultrasonic
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