Synthesis and characterization of amino glucose-functionalized silica-coated NiFe2O4 nanoparticles: A heterogeneous, new and magnetically separable catalyst for the solvent-free synthesis of pyrano[3,2-: C] chromen-5(4 H)-ones

Article abstract of DOI:10.1039/c8ra02572j

A novel, efficient and one-pot multi-component procedure for the synthesis of simple pyrano[3,2-c]chromen-5(4H)-ones or pyrazolyl pyrano[3,2-c]chromen-5(4H)-ones via reaction of aryl aldehydes, acetophenones and 4-hydroxycoumarin promoted by amino glucose

Full text of DOI:10.1039/c8ra02572j

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Synthesis and characterization of amino
glucose-functionalized silica-coated NiFe2O4
nanoparticles: a heterogeneous, new and
Cite this: RSC Adv., 2018, 8, 22313
magnetically separable catalyst for the solvent-free
synthesis of pyrano[3,2-c]chromen-5(4H)-ones
a
b
Sakineh Pourmirzajania
*
Leila Zare Fekri, Mohammad Nikpassand,
and Behnaz Aghazadehb
A novel, efficient and one-pot multi-component procedure for the synthesis of simple pyrano[3,2-c]
chromen-5(4H)-ones or pyrazolyl pyrano[3,2-c]chromen-5(4H)-ones via reaction of aryl aldehydes,
acetophenones and 4-hydroxycoumarin promoted by amino glucose-functionalized silica-coated
NiFe2O4 nanoparticles under solvent-free conditions without using any other harmful organic reagents
was reported. The structure of this nanoparticle was characterized by transmission electron
microscopies, X-ray diffraction and Fourier transform infrared spectroscopies. The catalyst could easily
be separated from the reaction mixture by using an external magnetic field and it was reusable. The high
purity of the desired products, eco-friendliness, short reaction time and easy workup procedure can be
mentioned as the other advantages of this method.
Received 26th March 2018
Accepted 20th May 2018
DOI: 10.1039/c8ra02572j
rsc.li/rsc-advances
surfaces. They are heterogeneous catalysis that benets from easy
removal of catalyst materials and possible use at high tempera-
Introduction
tures, suffered for a long time from lack of selectivity and
understanding of the mechanistic aspects that are indispensable
in parameter improvements.21 Amino glucose-functionalized
silica-coated NiFe2O4 nanoparticles have attracted a lot of
chemists because of its unique properties such as chemical
inertness, easy synthesis and functionalization, low toxicity and
low cost, high surface area, small crystallite size, superior
controlled selectivity, more active sites and facile removing with
aid of external magnet from the reaction mixture.
Pyranochromenes are a class of important heterocycles with
a wide range of pharmaceutical and biological properties such
as anti-coagulant, spasmolytic, analgesic, myorelaxant, anti-
cancer, cytotoxic, anti-HIV, anti-microbial, anti-tuberculosis,
diuretic and anti-anaphylactic activity.1–9 Moreover, they can
be used as cognitive enhancers for the treatment of neurode-
generative diseases, including Huntington's disease, schizo-
phrenia and myoclonus disease, amyotrophic lateral sclerosis,
Alzheimer's disease, Parkinson's disease, AIDS associated
dementia and Down's syndrome.1 They can act also as additives
in perfumes, food, cosmetics, optical brighteners, dispersed
uorescence and laser dyes.10,11 So far, only a few methods have
been reported for the synthesis of pyrano[3,2-c]chromen-5(4H)-
ones.12–15
Multicomponent reactions (MCRs) are one of the most effi-
cient tools in modern synthetic organic chemistry. They have
advantages such as being fast, simple and easy to implement,
with high atom efficiency. They offer a model for target- and
diversity-oriented synthesis.16–20
Transition-metal nanoparticles are materials: containing
a few tens to several thousand metal atoms, which are stabilized
by ligands, polymers or dendrimers as protecting agents for their
Results and discussion
The multicomponent reaction of benzaldehydes, acetophe-
nones and 4-hydroxycoumarin, simple in nature, is essentially
a condensation reaction. The reaction can be assisted by acti-
vating the carbonyl group of aldehydes with an acidic species or
by improving the nucleophilic property of 4-hydroxycoumarin
in basic media. In continuation of our research for the green
synthesis of heterocyclic compounds,22–29 herein we describe the
synthesis of pyrano[3,2-c]chromen-5(4H)-ones using NiFe2-
O4@SiO2@amino glucose magnetic nanoparticle as a new
catalyst (Scheme 1).
As shown in Scheme 2, the NiFe2O4@SiO2@amino glucose
magnetic nanoparticle was synthesized in three steps from
commercially available materials. MNPs were coated by silica
using a sol–gel process. The NiFe2O4@SiO2 core–shell structures
aDepartment of Chemistry, Payame Noor University, PO Box 19395-3697, Tehran, Iran.
E-mail: chem_zare@pnu.ac.ir; chem_zare@yahoo.com
bDepartment of Chemistry, Rasht Branch, Islamic Azad University, Rasht, Iran
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Scheme 1 Multicomponent synthesis of pyrano[3,2-c]chromen-5(4H)-ones using NiFe2O4@SiO2@amino glucose.
were then sequentially treated with 3-chloropropyltrime- region 2930, 3120 and 3415 cmꢀ 1 refer to the stretching band of
thoxysilane. Next, it was treated with aminoglucose to obtain the C–H aliphatic, OH stretching and NH stretching, in order.
amino
nanoparticles.
glucose-functionalized
silica-coated
NiFe2O4
The structure of NiFe2O4@SiO2@glucose amine was also
analyzed by XRD analysis. In Fig. 2 the XRD patterns of NiFe2-
In the FT-IR spectrum of the NiFe2O4@SiO2@amino glucose O4@SiO2@glucose amine and pure NiFe2O4 are illustrated. The
magnetic nanoparticle (Fig. 1), the absorption band of Fe–O was comparison of the XRD patterns indicated that both patterns
appeared in 590 cmꢀ1, the absorption band of Si–O–Si in SiO2 exhibits peaks at 30ꢁ, 36ꢁ, 45ꢁ, 50ꢁ, 54ꢁ, 58ꢁ and 62ꢁ which are
shell were appeared in 1088, 912 and 512 cmꢀ1. The peaks in
Scheme 2 Stepwise synthesis pathway of NiFe2O4@SiO2@amino glucose.
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Fig. 1 FT-IR spectra of (a) NiFe2O4, (b) NiFe2O4@SiO2, (c) NiFe2O4@SiO2@glucose amine.
The most common method to determine concentration of
acidic sites is temperature programmed desorption (TPD) of
a basic probe molecule, mostly ammonia. For this test, the
sample were pretreated at 573 K for 2 h. Aerwards, ammonia
was adsorbed onto the surface of the samples at 393 K. The total
amount of desorbed ammonia was determined by reaction with
a diluted solution of sulphuric acid and titration with sodium
hydroxide. The results are shown in Table 1. It can be seen that
the numbers of acidic sites increase from NiFe2O4 and NiFe2-
O4@SiO2 to NiFe2O4@SiO2@glucose amine.
In order to evaluate the catalytic capability of the synthesized
heterogeneous catalyst (NiFe2O4@SiO2@glucose amine) in
organic reactions, we chose to examine its activity in a one-pot
reaction for the synthesis of pyrano[3,2-c]chromen-5(4H)-ones.
Initially, we observed that the reaction of 4-nitro-
benzaldehyde with 4-hydroxycoumarin and acetophenone in
NiFe2O4@SiO2@glucose amine could be a suitable choice for
the synthesis of pyrano – chromene 4b. This protocol proceeds
smoothly at room temperature to afford product 4b in fairly
high yield. We have also carried out the sample reaction in the
NiFe2O4, NiFe2O4@SiO2, SiO2 or in the absence of catalyst. On
the other hand, variables affecting on the reaction yields such as
the type of solvent, the amount of catalyst, different tempera-
tures, and solvent-free conditions were studied (Table 2). As
Fig. 2 The XRD of (a) NiFe2O4@SiO2@glucose amine and (b) NiFe2O4.
representative of HNTs structure (JCPDS no. 54-0964) and broad
peak in 10–30ꢁ is related to NiFe2O4 covered by SiO2.
Next, the morphology and nanoparticle size of the synthe-
sized magnetic catalyst was characterized by Transmission
Electron Microscope (TEM) (Fig. 3). As shown in Fig. 2, the
catalyst particles possess near spherical morphology with
average diameter of about 20–40 nm. Furthermore, TEM images
show some aggregation, which was illustrated the successful
graing of the polymer on to magnetic nanoparticles.
Fig. 3 The TEM image of synthesized NiFe2O4@SiO2@glucose amine.
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Table 1 Concentration of acidic sites determined by the method
NH3-TPD
Nucleophilic addition of the enolic form of the ketone and
subsequent dehydration can lead to chalcone 6. Then, Michael
addition of 3 to 6 to produce intermediate 8, followed by simple
condensation of the hydroxyl group with the carbonyl and
dehydration, forms product 4.
NiFe2O4@SiO2@glucose
Catalyst
NiFe2O4 NiFe2O4@SiO2 amine
Acid surface
180 315 1450
We compared the efficiency of this method with recently
reported methods (Table 4).
sites (mmol gꢀ1
)
The recyclability and reusability of catalyst was studied in the
model
one-pot
three-component
reaction
between
shown in Table 2, the reaction under solvent-free conditions is
more efficient.
To check the generality of this method, different derivatives
of benzaldehydes and acetophenones were subjected to the
reaction with 4-hydroxycoumarin. The results are summarized
in Table 3.
All of the synthesized compounds were characterized by IR,
NMR, HR-Ms, elemental analysis and by comparison with
authentic samples for known compounds.
4-nitrobenzaldehyde, acetophenone and 4-hydroxycoumarin. At
the end of the reaction, the separated catalyst can be reused
aer being washed with warm EtOH and drying at 80 ꢁC.
NiFe2O4@SiO2@glucose amine was used again for subsequent
experiments under similar reaction conditions. The catalyst
could be reused for the next cycle without any notable loss of its
activity. Yields of the product decreased only slightly aer
reusing the catalyst ve times.
In continuation of our study, we triggered to synthesize
a new category of pyrazolylpyrano chromenes 4k–m and bis
pyranochromene 4n as shown in Scheme 3.
Experimental section
Materials and methods
A
plausible mechanism for the formation of pyr-
Chemicals were purchased from Merck and Fluka. All solvents
used were dried and distilled according to standard procedures.
Melting points were measured on an Electrothermal 9100
apparatus. IR spectra were determined on a Shimadzu FT-IR
anochromene 4 is shown in Scheme 4. Initially, NiFe2O4@-
SiO2@glucose amine can increase the electrophilic character of
the carbonyl species by virtue of its inherent Brønsted acidity.
Table 2 Optimization of reaction condition
Entry
Catalyst
Catalyst amount
Reaction condition
Time (min)
Yield (%)
1
2
3
4
5
6
7
8
—
SiO2
NiFe2O4
NiFe2O4@SiO2
NiFe2O4@SiO2@glucose amine
NiFe2O4@SiO2@glucose amine
NiFe2O4@SiO2@glucose amine
NiFe2O4@SiO2@glucose amine
NiFe2O4@SiO2@glucose amine
NiFe2O4@SiO2@glucose amine
NiFe2O4@SiO2@glucose amine
—
Reux in EtOH
Stir, rt, EtOH
Stir, rt, EtOH
Stir, rt, EtOH
Stir, rt, EtOH
Stir, rt, EtOH
Stir, rt, EtOH
Stir, rt, CH3CN
Stir, rt, H2O
720
750
720
300
40
40
60
60
45
Trace
15
24
53
90
87
85
76
84
0.05 g
0.05 g
0.05 g
0.05 g
0.07 g
0.03 g
0.05 g
0.05 g
0.05 g
0.05 g
9
10
11
Solvent free, rt
25
25
96
94
Solvent free, 80 ꢁC
Table 3 Synthesis of pyrano[3,2-c]chromen-5(4H)-ones using NiFe2O4@SiO2@glucose amine
Entry
Benzaldehyde
Acetophenones
Product
Time (min)
Yield (%)
Mp (ꢁC) (Lit mp)
Ref.
14
1
2
3
4
5
6
7
8
9
10
3-Nitro
4-Nitro
4-Hydroxy
Benzaldehyde
4-Methoxy
4-Chloro
4-Chloro
4-Methyl
4-Chloro
Benzaldehyde
Acetophenone
Acetophenone
Acetophenone
Acetophenone
Acetophenone
4-Chloro
3-Nitro
3-Nitro
Acetophenone
4-Chloro
4a
4b
4c
4d
4e
4f
4g
4h
4i
10
10
15
12
15
10
10
15
10
10
95
98
93
95
90
94
95
93
97
96
123–125 (122–123)
228–230 (230–231)
167–169
166–168 (170–171)
143–144 (143–144)
238–240 (239–241)
189–190
152–154
176–178 (176–177)
145–147 (149–151)
13 and 15
This work
12–15 and 30
12a,b and 30
12 and 15
This work
This work
13 and 14
12 and 14
4j
a
All the isolated products were characterized on the basis of their elemental analyses, physical properties and IR, 1H, 13C NMR spectral analysis,
HR-Ms or by direct comparison with authentic materials. b Isolated yields.
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Scheme 3 Synthesis of pyrazolyl and bis pyrano[3,2-c]chromenes.
Scheme 4 Proposed mechanism for the synthesis of pyranochromene 4.
1
8600 spectrophotometer. H and 13C NMR spectra were deter- 12 h at room temperature under N2 atmosphere, the products
mined on a Bruker 400 DRX Avance instrument at 500 and 125 was collected from the solution using a magnet, and then
MHz. Elemental analyses were recorded on a Carlo-Erba washed several times with water and ethanol and dried at 25 ꢁC
EA1110CNNO-S analyser.
under vacuum.
Thin layer chromatography (TLC) was carried out with ethyl
Synthesis of NiFe2O4@SiO2–Cl MNPs. 500 mg NiFe2O4@SiO2
nanoparticles were dispersed into 50 ml toluene and sonicated
acetate : n-hexane 1 : 4 on TLC Silica gel 60 F254
.
Synthesis of silica-coated NiFe2O4 (NiFe2O4@SiO2 MNPs). for 20 min, followed by the addition of 0.5 ml (3-chloropropyl)
Typically, 500 mg of the NiFe2O4 nanoparticle were dispersed by trimethoxysilane (CPTES). Then, the mixture was reuxed at
ultrasonic vibration in a mixture of ethanol (20 ml), deionized 110 ꢁC with continuous stirring for 12 h under a nitrogen ow.
water (3 ml) and 1 ml of 25 wt% concentrated aqueous The resulting NiFe2O4@SiO2–Cl MNPs was collected by
ammonia solution for 20 min. Subsequently, 0.7 ml of tetrae- magnetic separation followed by washing with toluene and
ꢁ
thylorthosilicate (TEOS) was added dropwise. Aer stirring for ethanol several times and drying at 60 C for 6 h.
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Table 4 Comparison of present method for the synthesis of 4d with
some previous methods
HRMs (m/z 397.1). Anal calc. for C24H15NO5: C, 72.54; H, 3.80; N,
3.52. Found: C, 72.53; H, 3.81; N, 3.54.
4-(4-Hydroxyphenyl)-2-phenylpyrano[3,2-c]chromen-5(4H)-one
(4c). White solid, mp: 167–169 ꢁC, 1H NMR (DMSO-d6, 400
MHz): d ¼ 5.4 (s, 1H), 6.88–7.92 (m, 14H), 9.8 (s, 1H, phenolic O–
H) ppm. 13C NMR (DMSO-d6, 100 MHz): d ¼ 37.63, 103.56,
105.78, 109.72, 111.04, 111.37, 115.84, 116.50, 119.24, 121.97,
130.21, 133.83, 137.72, 139.05, 142.756, 143.64, 149.62, 151.58,
154.48, 160.48 ppm. FT-IR (KBr): 3239, 3069, 2930, 1707 (C]O),
1572, 1486, 1237 (C–O) cmꢀ1. HRMs (m/z 368.1). Anal alc. for
Entry Condition
Time (min) Yield (%) Ref.
1
2
3
4
MWI, 60 ꢁ
I2, AcOH, 100 ꢁ
C
15
50
92
98
78
92
30
C
14a
15a
13a
AuCl3, AgOTf (3 mol%), reux 360
Ca(OTf)2, BuNPF6, 120 ꢁ
C
240
a
This pyranochromene was synthesized in
a two step protocol,
synthesis of chalcone followed by reaction with 4-hydroxycoumarin.
C
24H16O4: C, 78.25; H, 4.38. Found: C, 78.21; H, 4.40.
2,4-Diphenylpyrano[3,2-c]chromen-5(4H)-one (4d). White solid,
mp: 166–168 ꢁC, 1H NMR (DMSO-d6, 400 MHz): d ¼ 5.41 (s, 1H),
6.78–7.64 (m, 15H) ppm. 13C NMR (DMSO-d6, 100 MHz): d ¼
36.71, 103.12, 105.21, 109.11, 111.13, 111.38, 114.78, 115.03,
121.45, 126.76, 128.14, 135.87, 142.09, 143.91, 145.12, 145.67,
147.16, 151.09, 153.98, 165.41 ppm. FT-IR (KBr): 3099, 2987,
1665 (C]O), 1609, 1487, 1234 (C–O) cmꢀ1. HRMs (m/z 352.1).
Anal calc. for C24H16O3: C, 81.80; H, 4.58. Found: C, 81.81; H,
4.56.
Synthesis of NiFe2O4@SiO2@amino glucose. 500 mg NiFe2-
O4@SiO2–Cl MNPs were dispersed into 50 ml toluene and
sonicated for 30 min, followed by the addition oꢁf 0.5 ml glucose
amine. Then, the mixture was reuxed at 110 C with contin-
uous stirring for 12 h under a nitrogen ow. The resulting
functionalized NiFe2O4@SiO2@aminoglucose was collected by
magnetic separation followed by washing with toluene and
ꢁ
ethanol several times and drying at 80 C for 8 h.
4-(4-Methoxyphenyl)-2-phenylpyrano[3,2-c]chromen-5(4H)-one
(4e). White solid, mp: 143–144 ꢁC, 1H NMR (DMSO-d6, 400
General procedure for preparation of pyrano[3,2-c]chromen-
5(4H)-ones 4a–n. A mixture of aldehyde 1 (1.0 mmol), aceto-
phenone derivative 2 (1.0 mmol), 4-hydroxycoumarin 3 (1.0
mmol) and 0.05 g NiFe2O4@SiO2@aminoglucose were stirred at
room temperature under solvent free condition for the required
reaction time according to Tables 2 and 3 Aer completion of
the reaction, as indicated by TLC (TLC Silica gel 60 F254, ethyl
acetate : n-hexane 1 : 4), the resulting mixture was diluted with
hot ethanol (10 ml) and the catalyst separated by an external
magnet and washed with hot distilled water (5 ml) and ethanol
(3 ml) two times. The ltrate was cooled down to room
temperature and the crude products which precipitated were
collected and recrystallized from ethanol if necessary. All of the
synthesized compounds were characterized by their physical
constants, IR, 1H NMR, 13C NMR spectroscopy, HR-Ms and
elemental analysis. Some derivatives of the pyranochromenes
are known and were compared with authentic samples match-
ing melting points and spectras.
MHz): d ¼ 3.50 (s, 3H), 5.59 (s, 1H), 7.19–8.17 (m, 14H) ppm. 13
C
NMR (DMSO-d6, 100 MHz): d ¼ 36.65, 54.58, 103.27, 105.82,
109.09, 111.27, 111.83, 114.62, 115.24, 123.74, 125.87, 129.87,
135.87, 142.38, 143.84, 145.63, 145.43, 151.87, 152.41, 153.49,
163.09 ppm. FT-IR (KBr): 2938, 1666 (C]O), 1495, 1388, 1261
(C–O), 1102 cmꢀ1. HRMs (m/z 382.12). Anal calc. for C25H18O4:
C, 78.52; H, 4.74. Found: C, 78.51; H, 4.71.
2,4-Bis(4-chlorophenyl)pyrano[3,2-c]chromen-5(4H)-one
(4f).
White solid, mp: 238–240 ꢁC, 1H NMR (DMSO-d6, 400 MHz): d ¼
6.10 (s, 1H), 7.07–8.09 (m, 13H) ppm. 13C NMR (DMSO-d6, 100
MHz): d ¼ 36.80, 103.72, 105.47, 109.71, 111.38, 111.06, 113.49,
115.05, 123.29, 123.93, 129.04, 135.62, 142.40, 143.21, 143.63,
145.63, 148.38, 151.09, 152.32, 161.32 ppm. FT-IR (KBr): 2934,
1675 (C]O), 1605, 1495, 1221 (C–O), 1098, 1016 cmꢀ1. HRMs
(m/z 420.03). Anal calc. for C24H14Cl2O3: C, 68.43; H, 3.35.
Found: C, 68.41; H, 3.37.
4-(4-Chlorophenyl)-2-(3-nitrophenyl)pyrano[3,2-c]chromen-5(4H)-
Analytical data for the selected compounds
1
ꢁ
one (4g). White solid, mp: 189–190 C, H NMR (DMSO-d6, 400
MHz): d ¼ 5.64 (s, 1H), 7.37–8.09 (m, 10H), 8.32 (s, 1H), 8.58 (s, 1H),
8.83 (s, 1H) ppm. 13C NMR (DMSO-d6, 100 MHz): d ¼ 36.29, 103.72,
105.48, 109.76, 111.39, 111.38, 115.41, 116.03, 119.61, 121.92,
130.04, 131.32, 133.72, 137.43, 139.85, 142.28, 144.93, 145.38,
147.72, 151.48, 154.05, 162.51 ppm. FT-IR (KBr): 3065, 2934, 1667
(C]O), 1609, 1572, 1392, 1245 (C–O), 1171 (C–Cl) cmꢀ1. HRMs (m/
z 431.06). Anal calc. for C24H14ClNO5: C, 66.75; H, 3.27; N, 3.24.
Found: C, 66.71; H, 3.29; N, 3.27.
4-(3-Nitrophenyl)-2-phenylpyrano[3,2-c]chromen-5(4H)-one (4a).
White solid, mp: 123–125 ꢁC, 1H NMR (DMSO-d6, 400 MHz): d ¼
5.41 (s, 1H), 7.05–7.92 (m, 14H) ppm. 13C NMR (DMSO-d6, 100
MHz): d ¼ 34.34, 103.34, 105.65, 109.28, 111.62, 111.74, 114.72,
115.82, 119.03, 119.38, 121.92, 127.72, 130.29, 135.87, 137.63,
139.72, 142.49, 145.83, 147.87, 151.54, 154.75, 162.09 ppm. FT-IR
(KBr): 3077, 2938, 1707 (C]O), 1613, 1495, 1510 and 1388 (NO2),
1237 (C–O) cmꢀ1. HRMs (m/z 397.1). Anal calc. for C24H15NO5: C,
72.54; H, 3.80; N, 3.52. Found: C, 72.51; H, 3.83; N, 3.55.
4-(4-Nitrophenyl)-2-phenylpyrano[3,2-c]chromen-5(4H)-one (4b).
White solid, mp: 228–230 ꢁC, 1H NMR (DMSO-d6, 400 MHz): d ¼
5.42 (s, 1H), 7.23–7.97 (m, 14H) ppm. 13C NMR (DMSO-d6, 100
MHz): d ¼ 37.82, 103.60, 105.92, 109.54, 111.98, 111.19, 115.04,
116.04, 119.82, 121.62, 130.59, 133.72, 137.82, 139.48, 142.80,
145.27, 147.48, 151.38, 154.73, 162.24 ppm. FT-IR (KBr): 2918,
2-(3-Nitrophenyl)-4-p-tolylpyrano[3,2-c]chromen-5(4H)-one (4h).
White solid, mp: 152–154 ꢁC, 1H NMR (DMSO-d6, 400 MHz): d ¼
2.31 (s, 3H), 5.61 (s, 1H), 7.11–8.11 (m, 8H), 8.25 (d, J ¼ 8.2 Hz,
1H), 8.53–8.59 (m, 1H), 8.79 (s, 1H) ppm. 13C NMR (DMSO-d6,
100 MHz): d ¼ 31.29, 37.58, 103.40, 105.78, 109.72, 111.49,
111.48, 113.87, 116.28, 119.98, 121.76, 130.28, 131.73, 133.28,
133.69, 137.68, 139.29, 142.72, 145.63, 147.59, 151.73, 154.21,
161.82 ppm. FT-IR (KBr): 3089, 2922, 1675 (C]O), 1604, 1527,
1495, 1347, 1216 (C–O) cmꢀ1. HRMs (m/z 411.11). Anal calc. for
1663 (C]O), 1523 and 1356 (NO2), 1600, 1400, 1233 (C–O) cmꢀ1
.
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C25H17NO5: C, 72.99; H, 4.16; N, 3.40. Found: C, 72.98; H, 1151 cmꢀ1. HR-Ms (m/z 657.23). Anal calc. for C44H33O6: C,
4.19; N, 3.41.
80.35; H, 5.06. Found: C, 80.34; H, 5.11.
4-(4-Chlorophenyl)-2-phenylpyrano[3,2-c]chromen-5(4H)-one (4i).
White solid, mp: 176–178 ꢁC, 1H NMR (DMSO-d6, 400 MHz): d ¼
5.63 (s, 1H), 7.14–7.83 (m, 9H), 7.89–8.02 (m, 2H), 8.14 (d, J ¼
8.0 Hz, 2H), 8.72 (s, 1H) ppm. 13C NMR (DMSO-d6, 100 MHz): d ¼
36.46, 103.21, 105.51, 109.12, 110.93, 111.21, 113.63, 118.09,
119.27, 123.27, 130.05, 131.18, 133.72, 136.20, 138.51, 142.72,
145.63, 151.06, 154.18, 160.93 ppm. FT-IR (KBr): 3087, 2987, 1673
(C]O), 1613, 1565, 1475, 1323, 1256 (C–O) cmꢀ1. HRMs (m/z
386.07). Anal calc. for C24H15ClO3: C, 74.52; H, 3.91. Found: C,
74.58; H, 3.99.
Conclusion
In conclusion, we have developed NiFe2O4@SiO2@glucose
amine as a new, mild and efficient avenue for the synthesis of
pyrano[3,2-c]chromen-5(4H)-ones. This nano particles were
synthesized for the rst time and can act as a promoter to
activate the substrate molecule for the synthesis of pyrano[3,2-c]
chromen-5(4H)-ones. The operational simplicity, the excellent
yields of products, ease of separation and recyclability of the
magnetic catalyst, waste reduction and high selectivity are the
main advantages of this method. Furthermore, this new avenue
is cheap and environmentally benign. This novel concept is
expected to use to development of more benign reactions.
2-(4-Chlorophenyl)-4-phenylpyrano[3,2-c]chromen-5(4H)-one (4j).
White solid, mp: 145–147 ꢁC, 1H NMR (DMSO-d6, 400 MHz): d ¼
5.58 (s, 1H), 7.27–7.85 (m, 8H), 8.01 (d, J ¼ 7.8 Hz, 2H), 8.09 (d, J ¼
7.8 Hz, 2H), 8.23–8.32 (m, 1H), 8.74 (s, 1H) ppm. 13C NMR (100
MHz, DMSO-d6) d (ppm): 36.51, 103.18, 105.93, 109.62, 111.04,
111.32, 113.61, 118.17, 119.40, 123.36, 130.12, 131.14, 133.63,
136.72, 138.90, 142.24, 145.05, 151.20, 156.82, 161.14 ppm. FT-IR
(KBr): 3011, 2965, 1679 (C]O), 1600, 1545, 1432, 1278 (C–
Conflicts of interest
O) cmꢀ1. HRMs (m/z 386.05). Anal calc. for C24H15ClO3: C, 74.52; There are no conicts to declare.
H, 3.91. Found: C, 74.54; H, 3.95.
(4k). Off white solid, mp: >300 C, H NMR (DMSO-d6, 400
1
ꢁ
Acknowledgements
MHz): d ¼ 5.63 (s, 1H), 7.07 (d, J ¼ 7.6 Hz, 2H), 7.11–8.03 (m,
18H), 8.12 (s, 1H) ppm. 13C NMR (DMSO-d6, 100 MHz): d ¼ 56.9,
101.9, 105.6, 111.0, 111.7, 112.9, 117.7, 119.4, 119.8, 121.1,
123.3, 129.5, 129.7, 131.0, 131.6, 133.4, 133.7, 135.0, 135.4,
138.0, 138.2, 139.5, 140.4, 145.8, 151.7, 153.7, 163.0 ppm. FT-IR
(KBr): 2973, 1721 (C]O), 1672, 1632, 1481, 1209 (C–O),
1108 cmꢀ1. HRMs (m/z 494.16). Anal calc. for C33H22N2O3: C,
80.15; H, 4.48; N, 5.66; found: C, 80.10; H, 4.41, N, 5.67.
Financial support from the Research Council of Payame Noor
University of Rasht and Roodsar branch is sincerely
acknowledged.
References
(4l). Off white solid, mp: 287–289 ꢁC, 1H NMR (DMSO-d6, 400
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(4m). Off white solid, mp: 265–267 ꢁC, H NMR (DMSO-d6,
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