An eco-friendly and magnetized biopolymer cellulose-based heterogeneous acid catalyst for facile synthesis of functionalized pyrimido[4,5-b]quinolines and indeno fused pyrido[2,3-d]pyrimidines in water

Article abstract of DOI:10.1007/s11164-016-2752-z

Abstract: A cellulose-based magnetic nano-composite supported SO₃H group was synthesized and characterized using Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, thermogravimetric analysis, X-ray diffraction, and scanning electron microscopy. Thereafter, its capability to promote the one-pot, three-component synthesis of pyrimido [4,5-b] quinolone and pyrido [2,3-d] pyrimidine derivatives was evaluated. The obtained results are indicative of excellent yields and short reaction times. The biopolymer based catalyst is readily recovered and reused several times without a decrease in yield. Graphical Abstract: [Figure not available: see fulltext.]

Full text of DOI:10.1007/s11164-016-2752-z

Res Chem Intermed
DOI 10.1007/s11164-016-2752-z
An eco-friendly and magnetized biopolymer cellulose-
based heterogeneous acid catalyst for facile synthesis
of functionalized pyrimido[4,5-b]quinolines and indeno
fused pyrido[2,3-d]pyrimidines in water
Fatemeh Osanlou1 Firouzeh Nemati1
•
•
Samaneh Sabaqian1
Received: 18 July 2016 / Accepted: 30 September 2016
Ó Springer Science+Business Media Dordrecht 2016
Abstract A cellulose-based magnetic nano-composite supported SO3H group was
synthesized and characterized using Fourier transform infrared spectroscopy, energy-
dispersive X-ray spectroscopy, thermogravimetric analysis, X-ray diffraction, and
scanning electron microscopy. Thereafter, its capability to promote the one-pot, three-
component synthesis of pyrimido [4,5-b] quinolone and pyrido [2,3-d] pyrimidine
derivatives was evaluated. The obtained results are indicative of excellent yields and
short reaction times. The biopolymer based catalyst is readily recovered and reused
several times without a decrease in yield.
&
Firouzeh Nemati
fnemati_1350@yahoo.com; fnemati@semnan.ac.ir
1
Department of Chemistry, Semnan University, Semnan, Iran
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F. Osanlou et al.
Graphical Abstract
Keywords Magnetic cellulose Á Nanocatalyst Á Sulfonic acid Á Green solvent
Introduction
Multi-component reactions are known as versatile synthesis tools for the assembly of
novel and structurally complex molecules from simple starting materials in a
minimum of reaction steps [1]. These reactions have emerged as a valuable method
for the formation and breakage of carbon–carbon and carbon-heteroatom bonds in a
one-pot and simple work-up procedure. The synthesis of highly functionalized
quinolines illustrates the proper application of multi-component reactions because the
quinoline moiety possesses promising biological activities, such as antimalarial,
anticancer, antimicrobial [2], antiallergy, and anti-inflammatory activities, which
essentially associate to the nature and the place of the substituents [3]. In addition to
the abovementioned activities, pyridopyrimidins show a broad spectrum of biological
and pharmacological activity, including antifloate, tyrosine kinase inhibitors, anti-
aggressive [4], antitumor, cardiotonic, heptoprotactive, antifungal, antibronchitic [5],
and calcium antagonist [6].
Recently, effort has been made in order to replace the traditional liquid inorganic
homogeneous acid, with heterogeneous ones, because of their environmental,
economical and industrial aspects. To address the aforementioned issues, the covalently
immobilized –SO3H group onto the surface of a solid support is one of the most
common methods to develop the novel heterogeneous acid catalysts realm [7–11]. To
date, numerous solid supports have been used as anchors for sulfonic acid groups such
as nano-cellulose [12], silica [13], Fe3O4@SiO2 [14], mesoporous silica [15], c-
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An eco-friendly and magnetized biopolymer…
Fe2O3@SiO2 [16], nano-Fe3O4–TiO2 [17], nano-WO3 [18], nano–ZrO2 [19], CuFe2O4
[20], and PEG [21]. Therefore, considering the green chemistry aspects, biopolymers
have attracted much attention as supports for catalytic applications. Among them,
cellulose, as one of the most important biopolymers, has received growing attention as a
non-toxic, renewable, and biocompatible polymer. It has many properties, such as
biocompatible, broad chemical modifying capacity, hydrophilicity, and large surface
area [22–26]. Recently, it has been introduced as a versatile support in many catalysts
[27–31]. Cellulose sulfuric acid as a recyclable solid acid catalyst was prepared by
Shaabani’s group [32] and has been applied in various organic transformations [33].
Exploring facile economical methods for separation of catalysts, magnetite nano-
particles (Fe3O4) has attracted much interest in recent years because they can be easily
recovered from the reaction mixture using an external magnet. Concerning their
specific features, such as low-toxicity, high degree of chemical stability, they have
found diverse application in chemical, biomedical, and material science [34–40]. In
addition, they are adaptable to large-scale production. Considering all of these
advantages and in continuation of our efforts to develop environmental benign
synthetic methodology [14, 20, 41–48], we report the preparation and characterization
of Fe3O4@Cellulose sulfuric acid as a superior heterogeneous acid catalyst (Scheme 1)
in the synthesis of structurally diverse functionalized pyrimido[4,5-b]quinolines and
indeno fused pyrido[2,3-d]pyrimidines via one-pot condensation of 6-amino-1,3-
dimethyl uracil, 1,3-dicarbonyl compounds with aromatic aldehydes in water at 80 °C.
Experimental
All chemicals were purchased from Sigma-Aldrich and Merck company and used
without further purification. The progress of the reaction was monitored by TLC on
commercial aluminum-backed plates of silica gel 60 F254, visualized using
Scheme 1 Schematic representation of Fe3O4@Cellulose-SO3H
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F. Osanlou et al.
ultraviolet light. Melting points were determined in open capillaries using an
1
Electrothermal 9100 without further corrections. H NMR and 13C NMR spectra
were recorded using a Bruker DRX-400 spectrometer at 400 and 100, respectively.
Elemental analyses were performed on a Perkin-Elmer CHN analyzer, 2400 series
II. Nano-Fe3O4@Celloluse-SO3H was characterized by FT-IR spectra, which were
obtained from potassium bromide pellets in the range of 400–4000 cm-1 using a
Shimadzu 8400 s spectrometer. X-ray diffraction (XRD) was detected by Philips
˚
using Cu-Ka radiation of wavelength 1.54 A; Scanning electron Microscopy, FE-
SEM-EDX, analysis was performed using Tescanvega II XMU Digital Scanning
Microscope. Samples were coated with gold at 10 mA for 2 min prior to analysis.
The magnetic property of the catalyst was confirmed by using a vibrating sample
magnetometer (VSM, Lakeshore7407) at room temperature. Thermogravimetric
analyses (TGA) was obtained using a LINSEIS model STS PT 16,000 thermal
analyzer under air atmosphere at a heating rate of 5 °C min-1
.
Preparation of Fe3O4 nanoparticles
MNPs were synthesized by co-precipitation method according to our earlier report
[14].
Preparation of Fe3O4@Cellulose
The nano-Fe3O4@Cellulose composite was prepared by adding a suspension of
cellulose (2 wt%) to a suspension of the MNPs in water (10 mg/mL). The obtained
mixture was heated at 70 °C for 2 h. The nano-Fe3O4@Cellulose were isolated with
external magnetic field and washed with deionized water two to three times, and
then dried in an oven [49].
Preparation of Fe3O4@Cellulose-SO3H
A flask equipped with a constant-pressure dropping funnel and a gas inlet tube for
conducting HCl gas over an adsorbing solution was charged with Fe3O4@Cellulose
(1 g). Then, neat chlorosulfonic acid (0.022 mL, 3 mmol) was added drop-wise
over a period of 15 min in an ice bath (0–5 °C). HCl gas immediately evolved from
the reaction vessel. After that, the mixture was shaken for 1 h at room temperature
and Fe3O4@Cellulose-SO3H was collected as a dark brown solid. The catalyst was
washed with EtOH three times and dried at room temperature [13].
Loading of H1
The optimum concentration of H? of Fe3O4@Cellulose-SO3H was determined by
acid–base potentiometric titration of the aqueous suspension of catalyst with
standard NaOH solution [19]. At first, 0.1 g catalyst was dispersed in 20 mL H2O by
ultrasonic bath for 60 min at room temperature. The amount of the acid was
neutralized by addition of standard NaOH solution (0.093 N) to the equivalence
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An eco-friendly and magnetized biopolymer…
point of titration. The required volume of NaOH to this point was 4.3 mL. This is
equal to a loading of 3.9 mmol H?/g.
General procedure for the synthesis of pyrimido[4,5-b]quinolones
and pyrido[2,3-d]pyrimidines
Fe3O4@Cellulose-SO3H (0.025 g, 0.097 mmol H?) was added to a mixture of
benzaldehyde (1.0 mmol), 6-amino-1,3-dimethyluracil (1.0 mmol), and 1,3-dike-
tone (1.0 mmol) in distilled water (1 mL). The reaction mixture was heated in an oil
bath at 80 °C with stirring for the appropriate time upon completion of the reaction,
monitored by TLC, and then the reaction mixture was allowed to cool to room
temperature. The obtained solid was dissolved in hot EtOH and the catalyst was
separated using an external magnet. The pure products were afforded in 80–95 %
yields after recrystallization in EtOH, and characterized by mp, IR, and NMR
analysis.
Spectral data of new products
5-(4-bromophenyl)-1,3-dimethyl-5,8,9,10-tetrahydropyrimido[4,5-b]quinoline-
2,4,6(1H,3H,7H)-trione (5b)
mp [ 300 °C; IR (KBr): (vmax/cm-1): 3365, 1703, 1595; 1H NMR(400 MHz,
DMSO-d6): d 1.94 (m, 2H), 2.24 (m, 2H), 2.51 (m, 2H), 3.1 (s, 1H), 3.4 (s, 3H), 3.45
(s, 3H), 7–7.4 (m, 4H), 9.1 (s, 1H); 13C NMR (100 MHz, DMSO-d6): d 21.15,
26.94, 28.11, 30.73, 33.96, 37.06, 90.10, 112.78, 119.38, 130.45, 131.04, 144.27,
146.37, 150.98, 152.22, 161.20, 195.31 ppm. Anal. Calced for C17H18BrN3O3: C
52.05, H 4.59, N 10.71; found: C 51.92, H 4.45, N 10.57.
5-(4-methoxyphenyl)-1,3-dimethyl-5,8,9,10-tetrahydropyrimido[4,5-b]quinoline-
2,4,6(1H,3H,7H)-trione (5c)
1
mp 294–297 °C; IR (KBr, cm-1): 3346, 2956, 1701, 1664; H NMR(400 MHz,
DMSO-d6): d 1.95 (m, 2H), 2.24 (m,2H), 2.55 (m,2H), 3.1 (s,1H), 3.46 (s,1H), 3.49
(s,1H), 3.67 (s,3H),6.7–7.1 (m,4H), 9.07 (S,1H); 13C NMR (100 MHz, DMSO-d6):
d 21.20, 26.93, 28.09, 30.63, 33.13, 37.14, 55.34, 90.89, 113.52, 113.58, 129.01,
139.34, 143.99, 151.00, 151.73, 157.92, 161.26, 195.39 ppm. Anal. Calced for
C18H21N3O4: C 62.97, H 6.12, N 12.24; found: C 62.85, H 5.96, N 12.09.
Result and discussion
The route leading to nano-Fe3O4@Cellulose-SO3H is illustrated in Scheme 2.
The magnetized catalyst was prepared from low cost commercially available
materials. Initially, the nano-Fe3O4 magnetic particles have been prepared by a
chemical co-precipitation in basic solution [14]. Then, the nano-Fe3O4@Cellulose
composite was prepared simply by dispersing of the nano-Fe3O4 particles in
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F. Osanlou et al.
Cellulose
OH
OH
OH
HO
OH
HO
HO
OH
N
NH H O
,
3
2
HO
,
2
HO
HO
.4H O
FeCl2
OH
OH
HOFe3O4
nano-
Fe3O4
.6H O
FeCl3
2
OH
2
OH
OH
HO
HO
OH
HO
OH
OH
HO
H
SO 3
Cl
OH
OSO3
H
HO
OH
HO3SO
HO
HO
HO
HO
HO
Fe3O4
OH
OHOSO3
OH
OH
H
OH
HO3SO
HO
OSO3
H
OH
nano-Fe O
H
4@Cellulose-SO3
3
Scheme 2 Preparation of nano-Fe3O4@Cellulose-SO3H
aqueous cellulose solution. The resulting magnetic composite was functionalized
using chlorosulfonic acid and fully characterized by FT-IR, FE-SEM, EDX, XRD,
TGA, and VSM techniques. The FT-IR spectrum of the synthesized nano-
Fe3O4@Cellulose-SO3H in comparison to that of nano-Fe3O4 and nano-Fe3O4@-
Cellulose is shown in Fig. 1. The presence of major bands around 550 cm-1 is
attributed to the vibration of Fe–O [50]. Typical wave numbers of the hydroxyl
groups of cellulose, such as –CH–OH and –CH2–OH stretching are in the range of
3400–3300 cm-1. The methylene groups stretching, from the incorporated
molecule, are located at 2900 cm-1 and the band in the 3000–2800 cm-1 range
is attributed to the –C–H groups. The OH bending vibration of the cellulose surface
is located at 1639 cm-1, the primary and secondary hydroxyl bending appeared in
Fig. 1 FTIR spectra of Fe3O4 (a), Fe3O4@Cellulose (b), and Fe3O4@Cellulose-SO3H (c)
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An eco-friendly and magnetized biopolymer…
Fig. 2 The XRD pattern of Fe3O4, @Cellulose, Fe3O4@Cellulose and Fe3O4@Cellulose-SO3H
the range of 1500–1200 cm-1, and C–O stretching vibration is observed at
1100 cm-1 [51, 52].
After functionalization of nano-Fe3O4@cellulose composite with SO3H group,
The characteristic peaks of the OSO3H group of chlorosulfonic acid were observed
at 3300, 1581, 1288, and 1064 cm-1, that corresponds to O–H, S=O, and S–O
groups, respectively, indicating the presence of –OSO3H group bonded to magnetic
composite [53].
The presence of magnetite crystal phase in cellulose sulfuric acid was identified
with the X-ray diffraction powder (Fig. 2). The characteristic XRD peaks of Fe3O4
appeared at 2h = 31.1°, 39°, 45.2°, 50.43°, 56.6°, and 65.84° corresponding to the
(220), (311), (400), (422), (511), and (440) planes of Fe3O4 crystal, that match well
with standard spectra [54]. According to Debye–Scherrer formula, the average
crystal size of magnetite particles was calculated to be 8.91 nm. As can be seen in
the XRD pattern of Fe3O4@Cellulose, the position and the relative intensities of
observed peaks are similar to those of nano-Fe3O4 and cellulose. This result
confirms the presence of the Fe3O4 crystalline structure in the final product.
Notably, the same peaks are also observed in Fe3O4@cellulose-SO3H XRD spectra,
which indicate the structural ability of Fe3O4@cellulose with –SO3H modification
[51].
The morphology and structure of synthesized composites were determined with
scanning electron microscopy (SEM) (Fig. 3). The SEM image of Fe3O4@Cellulose
composite showed that the Fe3O4 nanoparticles have been dispersed in a cellulose
matrix (Fig. 3a). In addition the SEM image of Fe3O4@Cellulose-SO3H has
definitely been altered upon functionalization as shown in Fig. 3b.
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F. Osanlou et al.
Fig. 3 FE-SEM analysis of Fe3O4@Cellulose (a), Fe3O4@Cellulose-SO3H (b)
C Kα
O Kα
4000
3500
3000
2500
2000
1500
1000
500
3500
3000
2500
2000
1500
1000
500
(b)
(a)
O Kα
N Kα
FeLα
N Kα
AuMβ
S Kβ
S Kα
C Kα
AuMα
FeKα
FeLα
α
FeK
AuM
β
AuMα
FeKβ
FeKβ
AuLl
AuL
α
AuLα
10
AuLl
keV
keV
0
0
0
5
10
0
5
(c)
Fig. 4 EDX analysis of Fe3O4@Cellulose (a) and Fe3O4@Cellulose-SO3H (b) and elemental mapping
data of Fe3O4@Cellulose-SO3H (c)
The EDX spectrum of Fe3O4@Cellulose and Fe3O4@Cellulose-SO3H as an exact
elemental analysis is depicted in Fig. 4 and shows the presence of C, O, and Fe of
Fe3O4@Cellulose composite (Fig. 4a) and C, O, Fe, and S of Fe3O4@Cellulose-
SO3H acid catalyst, that clearly indicate the efficient preparation of Fe3O4@Cel-
lulose composite. The appearance of Au elements in EDX analysis is the result of
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An eco-friendly and magnetized biopolymer…
Fig. 5 TGA spectra of
Fe3O4@Cellulose (a),
Fe3O4@Cellulose-SO3H (b)
the coating of materials by the layer of Au element. In addition, an elemental map of
the catalyst showed the presence of S, O, C, and Fe, too.
To determine the thermal stability of the catalyst, thermogravimetric analysis
(TGA) was used. TG curves of Fe3O4@Cellulose and Fe3O4@Cellulose-SO3H are
shown in Fig. 5. The weight loss of Fe3O4@Cellulose is about 60 % at 315–400 °C,
corresponding to the thermal decomposition of cellulose chains. The pattern of mass
loss was changed in TGA analysis of Fe3O4@Cellulose-SO3H (Fig. 5b), which
confirms the functionalization of magnetic cellulose with –SO3H [17]. Moreover,
the catalyst was stable up to 200 °C, indicating its safe use at temperature range
80–150 °C in related organic reactions.
One of the most important advantages of the magnetic catalysts is their super-
paramagnetic behavior, making their separation feasible by an external magnet. For
this reason the magnetic property of as-synthesized acid catalyst was evaluated by
VSM analysis (Fig. 6). In VSM analysis, good magnetization saturation
(21.2 emu g-1) and no hysteresis were ascribed to super-paramagnetic behavior
of the Fe3O4@Cellulose-SO3H. So it can be simply recovered using an external
magnet.
To check if it is able to catalyze the reactions under study, we have considered
the one-pot, three-component synthesis of functionalized pyrimido[4,5-b]quinolines
and indeno fused pyrido[2,3-d]pyrimidines derivatives. In order to optimize the
reaction condition, the reaction of benzaldehyde (1 mmol), uracil (1 mmol), and
dimedone (1 mmol) for the synthesis of corresponding product 1,3,8,8-tetra methyl-
5-phenyl-5,8.9,10-tetrahydropyrimido[4,5-b]quinolone-2,4,6(1H,3H,7H)-trione (4a)
was selected as the model reaction (Scheme 3). In this regard, various reaction
parameters such as solvent, temperature and the amount of catalyst were
investigated. In addition, with particular reference to the importance of green
chemistry, the model reaction was tried in water and solvent-free state as green
conditions (Table 1). As Table 1 shows, in the absence of the catalyst, a low yield
of the products were obtained (Table 1, entry 1).
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F. Osanlou et al.
Fig. 6 VSM analysis of Fe3O4@Cellulose-SO3H
Scheme 3 The model reaction
To clarify the dependency of the catalytic activity to the presence of –SO3H
group, the model reaction was conducted with Fe3O4 and Fe3O4@Cellulose. As the
desired product is formed slightly in these cases, it seems to be reasonable to
conclude that the catalytic effect is risen from the –SO3H group (Table 1, entries 12
and 13). Finally, the best results are obtained with the following reaction condition,
0.025 g catalyst (0.097 mmol/g H?) at 80 °C in water (Table 1, entry 3). The keto-
enol tatumerization equilibrium of the 1,3-dicarbonyl compound has been
recognized as an important factor for the success of this reaction and water is a
very favorable option for a solvent if a cyclic dicarbonyl reactant is employed
[55, 56].
To establish the efficiency of the novel acid catalyst in previously mentioned
kinds or reactions, we dealt with the reaction of the substituted aryl aldehydes and
the other diketones such as 1,3-cyclohexandione and indanedione in optimized
reaction condition (Scheme 4), and the results depicted in Table 2. All the
123

An eco-friendly and magnetized biopolymer…
Table 1 Optimization of the three-component reaction of benzaldehyde (1), 6-amino-1,3-dimethyluracil
(2), and dimedone (3) under various conditions
Entry Catalyst
Catalyst (g) Solvent
Temp (°C) Time (min) Yielda (%)
1
–
–
H2O
80
360
60
30
30
65
55
50
50
180
60
85
30
30
Trace
62
2
Fe3O4@Cellulose-SO3H 0.01
Fe3O4@Cellulose-SO3H 0.025
Fe3O4@Cellulose-SO3H 0.05
Fe3O4@Cellulose-SO3H 0.025
Fe3O4@Cellulose-SO3H 0.025
Fe3O4@Cellulose-SO3H 0.025
Fe3O4@Cellulose-SO3H 0.025
Fe3O4@Cellulose-SO3H 0.025
Fe3O4@Cellulose-SO3H 0.025
Fe3O4@Cellulose-SO3H 0.025
H2O
80
3
H2O
80
95
4
H2O
80
90
5
Free
100
Reflux
Reflux
16
6
Ethanol
Acetonitrile
50
7
45
8
Etheylacetate Reflux
50
9
H2O
H2O
H2O
H2O
H2O
25
50
10
11
12
13
70
100
80
67
90
Fe3O4@Cellulose
Fe3O4
0.025
0.025
Trace
Trace
80
Reaction conditions: Benzaldehyde (1.0 mmol), 6-amino-1,3-dimethyluracil (1.0 mmol), dimedone
(1.0 mmol), solvent (1 mL)
a
Isolated yields
Scheme 4 Synthesis of various functionalized pyrimido[4,5-b]quinolines and indeno fused pyrido[2,3-
d]pyrimidines derivatives
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F. Osanlou et al.
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An eco-friendly and magnetized biopolymer…
Scheme 5 The proposed mechanism
Table 3 Comparison of the efficiency of Fe3O4@Cellulose-SO3H with the other reported catalysts for
the synthesis of 4f
Entry
Catalyst
Catalyst loading
Condition
Time (min)
Yield (%)
1
2
3
4
q-TSA
20 mol %
20 mg
2 ml
H2O/90 °C
H2O/70 °C
H2O/95 °C
H2O/80 °C
150
30
89 [60]
Fe3O4@SiO2–SO3H
[bmim]Br
92 [57]
210
20
90 [59]
Fe3O4@Cellulose-SO3H
20 mg
90 (This work)
investigated arylaldehydes with either electron-donating or electron-withdrawing
substituent afforded corresponding products in high yields and short reaction time.
The proposed mechanism presented sequences, including condensation, addition,
cyclization, and dehydration, was reported in the literature (Scheme 5) [57, 59–61].
On the basis of the mechanism, the adduct (I) is created through the Fe3O4@Cel-
lulose-SO3H-catalyzed Knoevenagel condensation between the aldehyde and cyclic
1,3-diketone. Then, the 6-amino-1,3-dimethyluracil attacks to the adduct (I) via a
Michael addition to produce an open chain intermediate (II). Subsequently,
intermediate (II) undergoes intra molecular cyclization by the reaction of
nucleophilic amino function to carbonyl group followed by dehydration to generate
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F. Osanlou et al.
Fig. 7 FTIR of a fresh catalyst
and b recycled catalyst after five
runs
product (III). The aromatization take place in synthesis of indeno fused pyrido[2,3-
d]pyrimidines (6a–f).
In order to show the advantages of the new catalyst, a comparison of the use of
nano-Fe3O4@Cellulose-SO3H with the other reported catalysts for the synthesis of
the target products has been shown in Table 3. These results demonstrate that the
new catalyst promotes the reaction more effective in terms of short reaction times
and simple conditions. Furthermore, the yield of products in the presence of nano-
Fe3O4@Cellulose-SO3H is comparable to the reported catalysts.
The reusability and recovery of the catalyst are important issues for the catalytic
reactions which make the method economically valuable, industrially profitable and
environmentally sustainable. So the model reaction under optimal condition was
selected to investigate the turns that the catalyst may keep holds its catalytic activity.
After completion the reaction, the mixture decanted and hot ethanol added to it. The
catalyst was easily separated using an external magnet, washed with ethanol, dried at
70 °C, and used for the next cycle. The recovered catalyst was added to fresh
substrates of the mentioned reaction for at least five times without any noticeable
reduction in catalytic activity. The yields of the five runs were found to be 95, 93, 90,
88, and 85 %, respectively. The slight decrease in the yield could probably be due to
the gradual loss of the catalyst during the work-up procedure. The acidity of the
understudy catalyst after five runs was measured using potentiometric titration and
was obtained 3.9 mmol H?/g that was equal to the fresh catalyst. In addition the FT-
IR of this recovered sample was recorded which was identical with that of taken for
the characterization of the novel prepared catalyst (Fig. 7).
Conclusion
In summary, an eco-friendly, efficient and heterogeneous acid catalyst, Fe3O4@-
Cellulose-SO3H was prepared, characterized and applied for one-pot, three-
component synthesis of pyrimido[4,5-b]quinolones and pyrido[2,3-d]pyrimidines
123

An eco-friendly and magnetized biopolymer…
derivatives. Application of cellulose as a green and recoverable biopolymer, use of
water as solvent, easy recovery of catalyst, and low catalyst loading are some merits
of this methodology.
Acknowledgment The authors gratefully acknowledge Semnan University Research Council for
financial support of this work.
References
1. J. Safari, S. Gandomi-Ravandi, Z. Akbari, J. Adv. Res. 4, 6 (2013)
2. I.R. Siddiqui, P. Rai, R. Rahila, H. Sagir, P. Singh, RSC Adv. 5, 35 (2015)
3. R.M. Singh, N. Sharma, R. Kumar, M. Asthana, S. Upadhyay, Tetrahedron Lett. 68, 50 (2012)
4. J.M. Khurana, A. Chaudhary, B. Nand, A. Lumb, Tetrahedron Lett. 53, 24 (2012)
5. I. Devi, B.S.D. Kumar, P.J. Bhuyan, Tetrahedron Lett. 44, 45 (2003)
6. N.A. Hassan, M.I. Hegab, F.M. Abdel-Motti, S.H.A. Hebah, F.M.E. Abdel-Megeid, A.I. Hashem, J.
Heterocycl. Chem. 44, 4 (2007)
7. A. Shaabani, Z. Hezarkhani, M.T. Faroghi, Monatsh. Chem. (2016). doi:10.1007/s00706-016-1717-7
8. M. Shamsi-Sani, F. Shirini, M. Abedini, M. Seddighi, Res. Chem. Intermed. 42, 2 (2016)
9. E. Kolvari, N. Koukabi, M.M. Hosseini, J. Mol. Catal. A: Chem. 397, 68 (2015)
10. A.R. Kiasat, L. Hemat-Alian, Res. Chem. Intermed. 41, 2 (2015)
11. M. Wu, Y. Wang, D. Wang, M. Tan, P. Li, W. Wu, N. Tsubaki, J. Porous Mater. 23, 1 (2016)
12. B. Sadeghi, M.H. Sowlat Tafti, J. Iran. Chem. Soc. 13, 8 (2016)
13. M.A. Zolfigol, Tetrahedron 57, 46 (2001)
14. F. Nemati, M.M. Heravi, R. Saeedi Rad, Chin. J. Catal. 33, 11–12 (2012)
15. E. Mehrasbi, Y. Sarrafi, A. Vahid, H. Alinezhad, Res. Chem. Intermed. 41, 7 (2015)
16. S. Mahdudi, D. Saberi, A. Heydari, J. Iran. Chem. Soc. 12, 5 (2015)
17. A. Amoozadeh, S. Golian, S. Rahmani, RSC Adv. 5, 57 (2015)
18. A. Amoozadeh, S. Rahmani, J. Mol. Catal. A: Chem. 396, 96–107 (2015)
19. E. Kolvari, N. Koukabi, M.M. Hosseini, M. Vahidian, E. Ghobadi, RSC Adv. 6, 9 (2016)
20. F. Nemati, A. Elhampour, M.B. Natanzi, S. Sabaqian, J. Iran. Chem. Soc. 13, 6 (2016)
21. R.H. Vekariya, H.D. Patel, RSC Adv. 5, 61 (2015)
22. A.M. Salgueiro, A.L. Daniel-da-Silva, A.V. Gira˜o, P.C. Pinheiro, T. Trindade, Chem. Eng. J. 229,
276–284 (2013)
23. C. Esmaeili, M. Ghasemi, L.Y. Heng, S.H.A. Hassan, M.M. Abdi, W.R.W. Daud, H. Ilbeygi, A.F.
Ismail, Carbohydr. Polym. 114, 253–259 (2014)
24. S. Rostamnia, B. Zeynizadeh, E. Doustkhah, A. Baghban, K.O. Aghbash, Catal. Commun. 68, 77–83
(2015)
25. Y. Habibi, L.A. Lucia, O.J. Rojas, Chem. Rev. 110, 6 (2010)
26. C. Johansson, J. Bras, I. Mondragon, P. Nechita, D. Plackett, P. Simon, D.G. Svetec, S. Virtanen,
M.G. Baschetti, C. Breen, Bioresources. 7, 2 (2012)
27. Z. Ghasemi, S. Shojaei, A. Shahrisa, RSC Adv. 6, 61 (2016)
28. A. Shaabani, H. Nosrati, M. Seyyedhamzeh, Res. Chem. Intermed. 41, 6 (2015)
29. L. Edjlali, R.H. Khanamiri, J. Abolhasani Monatsh. Chem. 146, 8 (2015)
30. B. Liu, Z. Zhang, K. Huang, Cellulose 20, 4 (2013)
31. H.R. Shaterian, F. Rigi, Res. Chem. Intermed. 40, 5 (2014)
32. A. Shaabani, A. Rahmati, Z. Badri, Catal. Commun. 9, 1 (2008)
33. R.H. Vekariya, H.D. Patel, ARKIVOC 1, 136–159 (2015)
34. R.K. Sharma, S. Dutta, S. Sharma, R. Zboril, R.S. Varma, M.B. Gawande, Green Chem. 18, 11
(2016)
35. B. Liu, Z. Zhang, ACS Catal. 6, 326 (2016)
36. B. Liu, Y. Ren, Z. Zhang, Green Chem. 17, 1610 (2015)
37. Z. Zhang, J. Zhen, B. Liu, K. Lv, K. Deng, Green Chem. 17, 1308 (2015)
38. Sh Yin, J. Sun, B. Liu, Z. Zhang, J. Mater. Chem. A 3, 4992 (2015)
39. Z. Zhang, Z. Yuan, D. Tang, Y. Ren, K. Lv, B. Liu, Chem. Sus. Chem. 7, 3496 (2014)
40. N. Mei, B. Liu, J. Zheng, K. Lv, D. Tang, Z. Zhang, Catal. Sci. Technol. 5, 3194 (2015)
123

F. Osanlou et al.
41. F. Nemati, A. Elhampour, H. Farrokhi, M. Bagheri, Natanzi. Catal. Commun. 66, 15 (2015)
42. F. Nemati, M.M. Heravi, A. Elhampour, RSC Adv. 5, 57 (2015)
43. F. Nemati, S.H. Nikkhah, A. Elhampour, Chin. Chem. Lett. 26, 11 (2015)
44. F. Nemati, A.G.G. Ghiyaei, B. Notash, M.H. Shayegan, V. Amani, Tetrahedron Lett. 55, 25 (2014)
45. F. Nemati, A. Elhampour, S. Zulfaghari, Phosphorus, Sulfur Silicon Relat. Elem. 190, 10 (2015)
46. F. Nemati, A. Elhampour, Res. Chem. Intermed. 42, 7611 (2016)
47. A. Elhampour, F. Nemati, M. Kaveh, Chem. Lett. 45, 223 (2016)
48. A. Elhampour, F. Nemati, J. Chin. Chem. Soc. 63, 653 (2016)
49. L.C. Fidale, M. Nikolajski, T. Rudolph, S. Dutz, F.H. Schacher, T. Heinze, J. Colloid Interface Sci.
390, 1 (2013)
50. M.H. Beyki, M. Bayat, S. Miri, F. Shemirani, H. Alijani, Ind. Eng. Chem. Res. 53, 39 (2014)
51. X. Sun, L. Yang, Q. Li, J. Zhao, X. Li, X. Wang, H. Liu, Chem. Eng. J. 241, 174–183 (2014)
52. P.V. Chavan, K.S. Pandit, U.V. Desai, M.A. Kulkarni, P.P. Wadgaonkar, RSC Adv. 4, 79 (2014)
53. H.R. Shaterian, M. Ghashang, M. Feyzi, Appl. Catal. A 345, 2 (2008)
54. S. Peng, H. Meng, Y. Ouyang, J. Chang, Ind. Eng. Chem. Res. 53, 6 (2014)
55. H.M. Savanur, R.G. Kalkhambkar, G. Aridoss, K.K. Laali, Tetrahedron Lett. 57, 3029 (2016)
56. J.H. Clark, D.J. Macquarrie, J. Sherwood, Chem. Eur. J. 19, 5174 (2013)
57. F. Nemati, R. Saeedirad, Chin. Chem. Lett. 24, 5 (2013)
58. K. Tabatabaeian, A.F. Shojaei, F. Shirini, S.Z. Hejazi, M. Rassa, Chin. Chem. Lett. 25, 2 (2014)
59. S.-J. Ji, S.-N. Ni, F. Yang, J.-W. Shi, G.-L. Dou, X.-Y. Li, X.-S. Wang, D.-Q. Shi, J. Heterocycl.
Chem. 45, 3 (2008)
60. G.K. Verma, K. Raghuvanshi, R. Kumar, M.S. Singh, Tetrahedron Lett. 53, 4 (2012)
61. K. Mohammadi, F. Shirini, A. Yahyazadeh, RSC Adv. 5, 23586 (2015)
123