Green cellulose-based nanocomposite catalyst: Design and facile performance in aqueous synthesis of pyranopyrimidines and pyrazolopyranopyrimidines

Article abstract of DOI:10.1016/j.carbpol.2017.08.019

A cellulose-based nanobiocomposite decorated with Fe₃O₄ nanoparticles was prepared, characterized and applied as an easily recoverable and reusable green nanocatalyst in the synthesis of pyrano[2,3-d]pyrimidine derivatives in water a

Full text of DOI:10.1016/j.carbpol.2017.08.019

Accepted Manuscript
Title: Green cellulose-based nanocomposite catalyst: design
and facile performance in aqueous synthesis of
pyranopyrimidines and pyrazolopyranopyrimidines
Authors: Ali Maleki, Abbas Ali Jafari, Somayeh Yousefi
PII:
S0144-8617(17)30886-X
DOI:
Reference:
http://dx.doi.org/doi:10.1016/j.carbpol.2017.08.019
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1-4-2017
6-7-2017
4-8-2017
Please cite this article as: Maleki, Ali., Jafari, Abbas Ali., & Yousefi, Somayeh.,
Green cellulose-based nanocomposite catalyst: design and facile performance in
aqueous synthesis of pyranopyrimidines and pyrazolopyranopyrimidines.Carbohydrate
Polymers http://dx.doi.org/10.1016/j.carbpol.2017.08.019
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Green cellulose-based nanocomposite catalyst: design and facile performance
in aqueous synthesis of pyranopyrimidines and pyrazolopyranopyrimidines
Ali Maleki,1,* Abbas Ali Jafari2 and Somayeh Yousefi1,2
1 Catalysts and Organic Synthesis Research Laboratory, Department of Chemistry, Iran University of
Science and Technology, Tehran 16846-13114, Iran
2 Department of Chemistry, Faculty of Science, Yazd University, Yazd 89195.741, Iran
*Corresponding author. Tel.: +98 21 77240540; fax: +98 21 73021584. E-mail: maleki@iust.ac.ir (A.
Maleki)
Highlights





A nanobiocomposite was prepared by using a natural carbohydrate polymer, cellulose.
It was characterized by FT-IR, EDX, TEM, FE-SEM, TG/DTA, VSM and ICP-AES analyses.
Average size distribution of Fe3O4 magnetic nanoparticles in cellulose matrix was 25 nm.
Morphology of the biopolymer-based recoverable nanocatalyst was nearly uniform.
Various heterocycles were synthesized by the nanocatalyst in H2O as a green solvent.
Abstract
A cellulose-based nanobiocomposite decorated with Fe3O4 nanoparticles was prepared,
characterized and applied as an easily recoverable and reusable green nanocatalyst in the
synthesis of pyrano[2,3-d]pyrimidine derivatives in water at room temperature. The
characterization was performed by using a variety of conventional analytical instruments such as
Fourier transform infrared spectra (FT-IR), field emission scanning electron microscopy (FE-
SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX), vibrating
sample magnetometer (VSM), thermal analysis (TGA/DTA) and inductively coupled plasma
atomic emission spectroscopy (ICP-AES) analyses. Two series of pyranopyrimidine and
pyrazolopyranopyrimidines derivatives were synthesized by using the present cellulose-based
nanocomposite. This protocol has valuable features like high yield of the products, short reaction
1

times, mild conditions and easy work-up procedure. In addition, the catalyst can be prepared
easily with cheap and green starting materials.
Keywords: Cellulose; Magnetic nanocomposite; Pyran; Pyrimidine; Multicomponent reaction.
2

1. Introduction
Pyranopyrimidine and pyrazolopyranopyrimidine are the fused heterocyclic compounds that
exhibit diverse biological properties. Compounds with such annulated uracils have antitumor,
antidepressants, antibacterial, antihypertensive, vasodilator, hepatoprotective, bronchiodilators,
cardiotonic and antiallergic activities. Furthermore, some of them exhibit antimalarial,
antifungal, analgesics and herbicidal properties (Bararjanian, Balalaie, Movassagh, & Amani,
2009; Brahmachari & Banerjee, 2014; Dinakaran, Bomma, & Srinivasan, 2012; Heravi,
Mousavizadeh, Ghobadi, & Tajbakhsh, 2014; McCoy et al., 2010; Deb, & Bhuyan, 2010; Yu &
Wang, 2005; Yu, Yu, & Liu, 2014). They have received considerable attention as potential
pharmaceutical compounds. Preparation of these molecules containing a uracil ring possesses
significant synthetic challenges. A few published reports usually require harsh reaction
conditions, long reaction times, operational complexity and involved organic solvents and wastes
(Brahmachari et al., 2014; Deb, & Bhuyan, 2010; Yu et al., 2014; Ziarani et al., 2013).
Therefore, design and development of new routes for the synthesis of these kinds of heterocyclic
molecules have attracted much attention in the research to introduce rapid protocols for these
compounds.
Recently, one-pot multicomponent reactions of aromatic aldehyde, malononitrile and
barbituric acid have produced pyrano[2,3-d]pyrimidines in the presence of a few catalysts
(Abedini, Shirini, Mohammad-Alinejad Omran, Seddighi, & Goli-Jolodar, 2015; Ramesh &
Lalitha, 2015). But, design of cheap, efficient, easily recoverable and reusable green catalysts for
both economic and environmental points of view is of prime importance.
Nowadays, functionalized magnetic metal nanoparticles and supported superparamagnetic
materials are deeply under consideration in both academic and industrial research centers
3

because of their wide potential applications in chemistry, medicine, catalysis and materials
science. They can be classified as powerful alternatives to classic materials of supported
heterogeneous catalysts because of their diversity, availability and high specific surface area.
Magnetically separable nanocatalysts provide an easy and efficient means for the isolation of the
catalysts from the reaction mixture by simply using of an external magnet without any
requirement for the other complex work-up procedures. Further important aspects of these kind
of the nanocatalysts are their activity, stability, reusability and environmentally-benign which are
of great importance in the field of green chemistry (Gawande, Branco, & Varma, 2013).
Polymer-matrix nanocomposites cause the nanoparticles have better physicochemical
properties and therefore exhibit better catalytic activities. Cellulose as a renewable carbohydrate
polymer with molecular formula of (C6H10O5)n; n = 10,000 to 15,000, where n is depended on
the cellulose source material, is one of the most common organic natural polymers that includes
1,4-anhydro-D-glucopyranose units. Cellulose deserves some important properties such as
biocompatibility, biodegradability, environmentally-friendly and a broad range of chemical
variability makes it a fantastic option as a green support of the catalysts (Klemm, Heublein,
Fink, & Bohn, 2005; Vaddula, Saha, Varma, & Leazer, 2012; Chen, Huang, & Li, 2014; Corobea
et al., 2016; Trache, Hussin, Mohamad Haafiz, & Thakur, 2017).
Keeping these important facts in mind, design and performance of the green and sustainable
nanocatalysts in chemical reactions have attracted our interests (Maleki & Kamalzare, 2014b;
Maleki, Ghamari, & Kamalzare, 2014a, Maleki, Alirezvani, & Maleki, 2015a; Maleki, Jafari,
Yousefi, & Eskandarpour, 2015b; Maleki, Movahed, & Paydar, 2016a; Maleki, A., Rahimi, R.,
& Maleki, 2016b). In connection with our previous research on the green reaction protocols,
herein, we have developed a one-pot synthetic route for the three-component synthesis of fused
4

pyrano[2,3-d]pyrimidines 4 from condensation reaction of various aromatic aldehydes 1, active
methylene compounds 2 and barbituric or thiobarbituric acid 3 in the presence of a catalytic
amount of cellulose-based magnetic nanocomposite in water at room temperature. In addition, to
investigate the effectiveness of the prepared nanocatalyst in similar multicomponent reactions, it
was applied in another four-component reaction for the synthesis of pyrazolopyranopyrimidine
derivatives. They were synthesized from the condensation reaction of various aromatic aldehydes
1, barbituric acid 3, hydrazine hydrate 5 and ethyl acetoacetate 6 in the presence of a catalytic
amount of the present cellulose-based magnetic nanocomposite in water as a green reaction
medium at room temperature.
2. Experimental
2.1. Materials and methods
All solvents, chemicals and reagents were purchased from Merck, Fluka and Aldrich
chemical companies. Melting points were measured on an Electrothermal 9100 apparatus and are
uncorrected. IR spectra were recorded on a Shimadzu IR-470 spectrometer. 1H and 13C NMR
spectra were recorded on a Bruker NMR spectrometer at 500 and 125 MHz, respectively. FE-
SEM images were obtained on a ZEISS SIGMA VP instrument. TEM images were obtained on a
Zeiss-EM10C-100KV instrument. EDX analysis was recorded on ZEISS SIGMA VP with
Oxford EDS attachment. ICP-AES analysis was provided on a Shimadzu ICPS-7000. The
magnetic property was measured on VSM-AGFM vibrating sample magnetometer. TGA and
DTA were measured by an STA504.
2.2. Preparation of Fe3O4@cellulose nanocomposite
First, cellulose was directly dissolved in NaOH/urea/H2O solution which was precooked to -
8 °C to yield 4 wt% of cellulose solution. Then, it was centrifuged at 2000 rpm for 30 min for
5

degasification. The solution was immersed in a 250 mL of H2SO4 (5 wt%) for 12 h to regenerate
the cellulosic film. The resulting film was washed with distilled water. The obtained wet film was
put in a 250 mL mixture of aqueous FeCl3.6H2O and FeCl2.4H2O for 24 h. Then, it was washed
with distilled water in order to remove the excess ions adsorbed on the surface of the film. After
that, it was immersed in 250 mL of NaOH (4 M) for 30 min. Finally, it rinsed with distilled water
several times to obtain the nanocomposite.
2.3 Synthesis of pyrano[2,3-d]pyrimidine derivatives (4a-o)
A solution of an aldehyde 1 (1.0 mmol), malononitrile or ethyl cyanoacetate 2 (1.0 mmol),
barbituric or thiobarbituric acid 3 (1.0 mmol) in 3 mL of tap water and in the presence of the
nanocomposite (2 mg) was stirred at room temperature for appropriate time according to Table
1. After completion of the reaction, the catalyst was removed easily by an external magnet and
the residual product was collected by filtration and washed with ethanol and recrystallized to
yield pure products.
2.4 Synthesis of pyrazolopyranopyrimidine derivatives (7a-i)
Ethyl acetoacetate (0.13 ml, 1 mmol) was added to a solution of hydrazine hydrate (96%,
0.05 ml, 1 mmol) in H2O (2 ml) over 15 min. Then, aromatic aldehyde (1 mmol), barbituric acid
(0.128 g, 1 mmol), and Fe3O4@cellulose nanocomposite (5 mg) were added and the mixture was
stirred at room temperature for the time indicated in Table 2. After completion of the reaction (as
monitored by TLC), the mixture was cooled and filtered. The precipitate was recrystallized from
EtOH to give pure compound.
2.5 Spectral data of the selected product 7-amino-6-cyano-5-(2-nitrophenyl)-4-oxo-2-thioxo-5H-
pyrano[2,3-d]pyrimidine 4m
6

White solid: FT-IR (KBr, cm-1): 3425, 3371, 3193, 2898, 2198, 1674, 1573, 1396; 1H NMR
(500 MHz, DMSO-d6) δ: 4.99 (1H, s, CH), 7.23 (2H, s, NH2), 7.42-7.77 (4H, m, ArH); 12.33
(1H, br s, NH), 13.52 (1H, br s, NH); 13C NMR (125 MHz, DMSO-d6) δ: 56.0, 123.3, 123.7,
125.3, 127.1, 130.5, 133.4, 135.1, 149.1, 161.4, 163.2, 173.0.
3 Results and discussion
3.1. Preparation of Fe3O4/cellulose
There were a few methods in literatures for the preparation of Fe3O4/cellulose
nanocomposite. As a known route, the nanocomposite of Fe3O4/cellulose was prepared via in-
situ synthesis of Fe3O4 in the presence of cellulosic film. In the next report, the nanocomposite
was obtained by the addition of ammonium hydroxide to a mixture of cellulose, FeSO4 and
Fe2(SO4)3 at 60 ºC (Edjlali, Hosseinzadeh, & Abolhasani, 2014). The nanocomposite was also
synthesized by adding cellulose microspheres in a mixture of FeCl2.4H2O and FeCl3.6H2O
solution followed by adding ammonia solution at 60 ºC (Luo, Liu, Zhou, & Zhang, 2009). In this
work, the Fe3O4 nanoparticles were incorporated into the cellulose matrix/pores that had not
enough catalytic activity. But, in our previously reported method, the nanocomposite was
obtained via in-situ synthesis of Fe3O4 nanoparticles in a solution of FeCl3.6H2O and
microcrystalline cellulose film at room temperature (Maleki et al., 2014b; Maleki et al., 2015b).
The preparation of cellulosic film allows the nanoparticles to be diffused better in the cellulose
texture. In this procedure, the Fe3O4/cellulose nanocomposite was prepared with high content of
Fe3O4 nanoparticles. As a result, the nanocomposite had excellent catalytic activity in chemical
reactions.
3.2. FT-IR spectra
7

FT-IR spectrum indicates the formation of Fe3O4/cellulose. As can be seen in Fig. 1a, the
adsorptions marked with arrows at near 3346, 2889, 1610 and 1336 are ascribed to the stretching
and bending vibrations of OH and CH2 groups of cellulose, respectively. The absorptions of Fe-
O bond can be seen around 630 and 582 cm-1. Furthermore, Fig. 1b shows the catalyst stability
after 5 times reusing in the organic reactions. As can be seen from the FT-IR spectrum of the
nanocatalyst, it had good chemical stability and almost nothing was happened for its
carbohydrate matrix, cellulose Fe3O4 or composite functionalities during the chemical reactions.
3.3. Elemental analysis
An EDX analysis was provided to approve the presence of C, O and Fe elements in the
nanocomposite structure (Fig. 2). In addition, ICP-AES analysis of the Fe3O4/cellulose
nanocomposite showed that the Fe content in the nanocomposite was about 35.7%. This data
about nanoparticle loading in carbohydrate matrix was also confirmed by the results obtained
from thermal analysis.
3.4. Structure and morphology of the nanocomposite
The structure, morphology and particle size were characterized by conventional
nanomaterials analysis instruments. Fig. 3a shows the FE-SEM image of pristine cellulose film.
By comparing this image with the FE-SEM of Fe3O4/cellulose nanocomposite in Fig. 3 (b,c), it
confirmed that iron oxide has been successfully embedded in the cellulosic matrix.
Furthermore, the prepared nanocomposite was studied by TEM technique (Fig. 4a, b). TEM
images were used to understand the morphology of the nanocomposite, precisely. It can be
concluded that Fe3O4 nanoparticles were effectively diffused in texture and also adsorbed into the
cellulose film by electrostatic forces or chemical interactions. In other words, significant
8

core/shell preparation of the nanomaterials in the carbohydrate cellulose matrices can also be
concluded. Finally, to determine the average size distribution of the nanoparticles, 90 particles
were used randomly. According to the histogram, the sizes of most of the nanoparticles were
about 20-25 nm (Fig. 4c).
b3.5. Magnetic properties
The magnetic property of the nanocomposite was investigated at room temperature under 8
kOe applied field by using VSM technique. The obtained saturation magnetization from the
hysteresis loop was about 8.15 emu g-1. As can be seen in Fig. 5a, the magnetization increased
with an increase of the magnetic field. It exhibited a small hysteresis loop and low coercivity.
This is characteristic of superparamagnetic particles. Therefore, the nanocomposite can be
known as an excellent magnetically-recoverable and renewable nanocatalyst.
3.6. Thermal behavior of the Fe3O4/cellulose nanocomposite
The thermal behavior of the prepared nanocomposite was investigated by TG/DTA
analyses over the temperature range of 20-800 °C at air atmosphere (Fig. 5b,c). Thermal
analysis identified three separate weight loss regions on the TG curve. The first weight loss up
to 160 ºC is due to the removal of water from the nanocomposite. The second weight loss
observed in the temperature domain 220–336 ºC is due to decomposition and elimination of
some organic groups from the nanocomposite. Over 336 ºC the mass loss is great and can be
associated with the elimination of the organic groups associated/linked to nanoparticles.
9

3.7. Application of Fe3O4/cellulose nanocomposite for the synthesis of pyranopyrimidine
derivatives
A model experiment was carried out by using 1.0 mmol of each of 3-nitrobenzaldehyde
(0.151 g), malononitrile (0.066 g) and 2-thiobarbituric acid (0.144 g) for optimizing the reaction
conditions. Higher yields of the products were obtained in H2O rather than other solvents such as
EtOH, EtOH/H2O, CH3CN and CHCl3. Also, the best result was obtained with 2 mg of the
nanocatalyst.
There is a comparison between nano-Fe3O4/cellulose and two other catalysts DABCO (Bhat,
Shalla, & Dongre, 2014) for obtaining 4e (83%) and choline chloride/ZnCl2 (Yadav & Quraishi,
2014) for obtaining 4j (67%) and 4o (42%). Based on the results, by using Fe3O4/cellulose
nanocatalyst, the products were gathered in high yields [4e (90%), 4j (90%) and 4o (76%)]. This
difference can be explained by the fact that nanocatalysts have considerable catalytic activity
because of their nanometer dimensions which increase their specific surface area. Furthermore,
the most important superiorities of the present catalyst are ease of separation, reusability and the
green nature of the nanocatalyst. The ease of separation of the catalyst is another factor for
obtaining products in high yields. For clarifying the need of the nano-Fe3O4/cellulose catalyst, a
few tests were carried out in the presence of each of the nanocomposite components (Fe3O4 and
cellulose) and also absence of the Fe3O4/cellulose. In these conditions, yields of the reactions
were trace or very low after 3 h. As a result, the nanocatalyst had an important role in the
reaction. The mechanism of the reaction can be explained by Lewis acid properties of the Fe3O4
and also synergistic effect of cellulose in conjunction with Fe3O4 nanoparticles.
As is evident from Table 1, different kinds of aldehydes have employed in the reaction and
pyranopyrimidines 4a-o were obtained as sole products in high yields. This confirms wide scope
and applicability of the method for the synthesis of heterocyclic compounds. The products were
10

identified by spectral data IR and comparing with those reported literature authentic samples.
Also, 4m was characterized by IR, 1H and 13C NMR spectral data analyses. The workup
procedure of the products was easy as the nanocatalyst can be separated simply by an external
magnet. Therefore, this process offers attractive advantages like operational simplicity and
environmentally benign nature. Furthermore, one of the most important features of the present
green protocol was its chemoselectivity and also chemospecificity. This reaction gave a single
product and there was no need for controlling of the by-product(s) formation. This advantageous
beside recoverability of the biodegradable and eco-friendly catalyst and using of water as a green
reaction medium make this research highly favorable for large-scale synthesis.
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A proposed mechanism for the formation of the product 4a-o was shown in Scheme 1. Initially,
an intermediate (A) was produced from a Knoevenagel condensation between an aromatic
aldehyde (1) and malononitrile (2) and another intermediate (B) was formed from a Michael
addition with barbituric or thiobarbituric acid (3) in the presence of Fe3O4/cellulose nanocatalyst.
After that, an intermolecular cyclization of C from the enol form of B produces compound D.
Finally, a tautomerization affords the target products 4a-o.
3.8. Application of Fe3O4/cellulose nanocomposite for the synthesis of pyrazolopyranopyrimidine
derivatives
Due to success of the Fe3O4/cellulose nanocomposite in green synthesis of pyranopyrimidine
derivatives, we decided to develop its catalytic activity investigation for the synthesis of
pyrazolopyranopyrimidine derivatives, too. In this regard, a model experiment was performed by
using 1.0 mmol of each of 4-methylbenzaldehyde, ethyl acetoacetate, hydrazine hydrate and
barbituric acid for optimizing the reaction conditions. The best yields of the products were
obtained in H2O rather than other solvents such as EtOH, EtOH/H2O, CH3CN and CHCl3. Also,
the best result was obtained bu using 5 mg of the nanocatalyst. Subsequently, a series of
differently pyrazolopyranopyrimidine derivatives were prepared successfully under optimal
conditions. The results are listed in Table 2.
a Reaction conditions: aldehyde (1.0 mmol), ethyl cyanoacetate (1.0 mmol), barbituric acid (1.0
mmol), hydrazine hydrate (1 mmol), cellulose-based nanocomposite (5 mg), water (2 mL), room
temperature.
b Isolated yields.
Conclusions
In summary, we have introduced an attractive cellulose-based nanobiocomposite catalyst for the
one-pot three-component synthesis of pyrano[2,3-d]pyrimidine and pyrazolopyranopyrimidine
derivatives. This efficient protocol let the synthesis biologically and pharmaceutically
pyranopyrimidine derivatives in water with easier isolation and recovery of the catalyst in
12

comparison with literature reports. Easy workup procedure, reusability of the catalyst as well as
high atom economy, excellent yields, mild and green reaction conditions and chemoselectivity
are some important aspect of the present protocol. This reaction gave a single product and there
was no need for controlling of the by-product(s) formation. This advantageous beside
recoverability of the biodegradable and eco-friendly catalyst and using of water as a green
reaction medium make this research highly favorable for chemical and biological large-scale
synthesis.
Acknowledgements
The authors gratefully acknowledge the partial support from the Research Council of the
Iran University of Science and Technology. We also would like to thank the anonymous
reviewers for their time spent critically reviewing the manuscript and providing the valuable
comments and constructive criticisms that have really improved our manuscript.
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Wave number (cm-1)
Fig. 1. FT-IR spectra of: (a) fresh Fe3O4/cellulose nanocomposite and (b) recovered
Fe3O4/cellulose nanocomposite after 5 times reusing in the reactions.
17

Fig. 2. EDX pattern of Fe3O4/cellulose nanocomposite.
a
18

b
c
Fig. 3. FE-SEM images of: a) the pristine cellulose film and b,c) Fe3O4/cellulose nanocomposite
in different magnifications.
Frequency, 20-
25, 38
Frequency, 25-
30, 23
Frequency, 15-
Frequency, F3r0e-quency, 35-
20, 11
35, 9
40, 9
FrequFerenqcuy,e,n0cy, , 0
Frequency, , 0
Particle diameter (nm)
19

Fig. 4. a,b) TEM images of Fe3O4/cellulose nanocomposite in different magnifications and c)
particle size distribution diagram of the magnetic Fe3O4/cellulose nanocomposite.
b
Fig. 5. a) Magnetization curve of Fe3O4/cellulose nanocomposite at room temperature (Insert: a
magnified view of the -200 to 200 Oe regions); b) TGA and c) DTA curves of the
Fe3O4/cellulose nanocomposite.
20

Scheme 1. Proposed mechanism for the formation of 4a-o.
21

Table 1. Synthesis of pyrano[2,3-d]pyrimidine derivatives in the presence of the nanocatalyst.a
Entry Produc
t
R
H
X
Y Time Yieldb
(min) (%)
Mp (°C)
Reported
Observed
208-210
1
2
3
4
5
CO2E O 40
t
92
95
96
98
90
206-210 (Bhat et al., 2014)
296-298 (Bhat et al., 2014)
290-293 (Bhat et al., 2014)
295-300 (Bhat et al., 2014)
289-293 (Bhat et al., 2014)
4a
4b
4c
4d
4e
4-Me CO2E O 20
t
297-300
296-298
297-300
292-294
4-
OMe
CO2E O 20
t
4-Cl CO2E O 40
t
4-NO2 CO2E O 40
t
6
7
H
CN
CN
O
O
35
20
90
96
206-207 205-207 (Yadav et al., 2014)
4f
4-Br
228-230
230-231 (Bararjanian et al.,
2009)
4g
8
9
2-NO2
3-NO2
CN
CN
O
O
30
30
90
98
254-255 253-256 (Abedini et al., 2015)
4h
4i
266-268
268-270 (Bararjanian et al.,
2009)
10
11
4-NO2
CN
CN
O
S
30
20
90
93
244-245
239-240 (Bararjanian et al.,
2009)
4j
4-
115-118 116-118 (Yadav et al., 2014)
4k
MeO
12
13
14
4-Br
CN
CN
CN
S
S
S
40
30
30
95
96
96
234
248
236 (Bararjanian et al., 2009)
This work
4l
4m
4n
2-NO2
3-NO2
237-
238c
230-233 (Yadav et al., 2014)
22

15
4-NO2
CN
S
30
76
235
235-236 (Bararjanian et al.,
2009)
4o
a Reaction conditions: aldehyde (1.0 mmol), malononitrile or ethyl cyanoacetate (1.0 mmol),
barbituric or thiobarbituric acid (1.0 mmol), cellulose-based nanocomposite (2 mg), water (3
mL), room temperature.
b Isolated yields.
c Yields of the five subsequent runs by using the same recovered catalyst were 96, 95, 94, 92 and
91%, respectively.
Table 2. Synthesis of pyrazolopyranopyrimidines in the presence of the nanocatalyst.a
Entry Product
R
Time Yieldb
Mp (°C)
Reported
217-219 218-219 (Li, Zhao, Mo, & Zhang, 2014)
(min)
(%)
Observed
1
2
3
4
5
6
7
8
9
H
4-Me
2-Cl
20
15
35
30
40
35
30
30
25
90
95
86
89
87
92
95
82
85
7a
7b
7c
7d
7e
7f
200-201
223
200-201 (Li et al., 2014)
223-225 (Li et al., 2014)
222-223 (Li et al., 2014)
208-209 (Li et al., 2014)
266-267 (Li et al., 2014)
233-234 (Li et al., 2014)
211-212 (Li et al., 2014)
176-177 (Li et al., 2014)
4-Cl
222-224
208-209
267
2-NO2
3-NO2
4-NO2
4-Br
235
7g
7h
7i
210-212
176-177
2-thienyl
23