Pd(0)-guanidine?MCM-41: a very effective catalyst for rapid production of bis (pyrazolyl)methanes

Article abstract of DOI:10.1002/aoc.5579

In this research, a rapid, green and efficient protocol for synthesis of bis (pyrazolyl)methane derivatives in the presence of Pd(0)-guanidine?MCM-41 catalysts under solvent-free conditions by the following two methods has been reported: (i) via the one-p

Full text of DOI:10.1002/aoc.5579

Received: 7 November 2019
DOI: 10.1002/aoc.5579
Revised: 13 January 2020
Accepted: 15 January 2020
F U L L P A P E R
Pd(0)-guanidine@MCM-41: a very effective catalyst for
rapid production of bis (pyrazolyl)methanes
Hossein Filian1
| Alireza Kohzadian2 | Masoud Mohammadi3
|
Arash Ghorbani-Choghamarani3
| Amirali Karami1
1Department of Chemistry, Khuzestan
In this research, a rapid, green and efficient protocol for synthesis of bis
(pyrazolyl)methane derivatives in the presence of Pd(0)-guanidine@MCM-41
catalysts under solvent-free conditions by the following two methods has been
reported: (i) via the one-pot pseudo five-component reaction among
phenylhydrazine (2 equivalents), ethyl acetoacetate (2 equivalents) and aro-
matic aldehydes (1 equivalent); and (ii) the one-pot pseudo three-component
reaction between 3-methyl-1-phenyl-1H-pyrazol-5(4H)-one (2 equivalents) and
aromatic aldehydes (1 equivalent). Some advantages of this protocol include:
green conditions, extremely short times, high efficiency, proper one-pot opera-
tion, generality of method, easy work-up and recyclability, and reusability of
the catalyst up to five times without significant loss in catalytic activity.
Science and Research Branch, Islamic
Azad University, Ahvaz, Iran
2Young Researchers Club, Ilam Branch,
Islamic Azad University, Ilam, Iran
3Department of Chemistry, Faculty of
Science, Ilam University, P. O. Box
69315516Ilam, Iran
Correspondence
Hossein Filian, Department of Chemistry,
Khuzestan Science and Research Branch,
Islamic Azad University, Ahvaz, Iran.
Email: hosein.filian@gmail.com
K E Y W O R D S
bis (pyrazolyl)methanes, heterogeneous catalyst, multi-component reaction, Pd(0)-
guanidine@MCM-41, reusable catalyst
1 | INTRODUCTION
form a product wherein all or most of the reactants atoms
contribute.[26–29] That is important from the atom eco-
Nanocatalysis is one of the most exciting subfields to
have emerged from nanoscience.[1–7] Its central aim is
the control of chemical reactions by changing the size,
dimensionality, chemical composition and morphology
of the reaction center, and by changing the kinetics
using nanopatterning of the reaction centers.[8–12]
Nanoparticles can substitute conventional materials, and
serve as active and stable heterogeneous catalysts or as
support materials for various catalytic groups.[13–18] Due
to their small sizes, catalytic-active nanoparticles have
higher surface areas and increased exposed active sites,
and thereby improved contact areas with reactants, akin
to those of homogeneous catalytic systems.[19–23]
nomic standpoint.[30] Environmental friendly operation
via reducing the number of synthetic steps and work up,
the energy consumption, reaction time, waste produc-
tion, and eliminating the isolation of unstable intermedi-
ates are among the advantages of MCRs.[20,21,31–34] Over
the last few decades, with increasing environmental con-
cerns, the design of new MCRs with ecofriendly, green
procedures have become increasingly useful tools, espe-
cially in the fields of drug discovery, organic synthesis
and material science.[35–37] Because of the increasing con-
cern of the harmful effects of organic solvents on the
environment and human body, organic reactions that are
operated with green solvents or without conventional
organic solvents have aroused the attention of organic
and medicinal chemists.[38–41] In the past decade, interest
in solvent-free MCRs has expanded and it now encom-
passes wide areas of the chemical enterprise.[20,21,42–44]
For reasons of economy and pollution prevention,
Preparation of chemical, industrial and pharmaceuti-
cal compounds by multi-component reactions (MCRs) is
very significant in consideration of combinatorial
chemistry.[21,24,25] In this technique, more than two
starting materials react together in a one-pot reaction to
Appl Organometal Chem. 2020;e5579.
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© 2020 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.5579

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FILIAN ET AL.
solvent-free methods are used to modernize classical pro-
cedures by making them cleaner, safer and easier to
perform.[45–47] The demand for both clean and efficient
chemical syntheses is becoming more urgent.[48] Among
the proposed solutions, solvent-free conditions are
becoming more popular, and it is often claimed that the
best solvent is no solvent.[49] The benefits of solvent-free
processes are cost savings, decreased energy consump-
tion, reduced reaction times, a large reduction in reactor
size and capital investment.[20,49]
nanocatalyst in solvent-free conditions and in
a
completely green environment by both methods via the
following protocols: (i) the one-pot pseudo five-
component reaction of phenylhydrazine (2 equivalents),
ethyl acetoacetate (2 equivalents) and arylaldehydes
(1 equivalent); and (ii) the one-pot pseudo three-
component reaction of 3-methyl-1-phenyl-1H-pyrazol-
5(4H)-one
(2
equivalents)
with
arylaldehydes
(1 equivalent).
Pyrazoles or pyrazolones [e.g. bis (pyrazolyl)meth-
anes] are a significant category of bioactive drug goals in
the pharmaceutical industry that show a variety of
biological and medicinal activities, such as anti-HIV,[50]
2 | EXPERIMENTAL
2.1 | Materials and apparatus
antiviral,[51]
gastric
secretion
stimulatory,[52]
antifilarial,[53]
antioxidant,[54]
antihypertensive,[55]
All starting materials, applied solvents and reagents
were purchased from Fluka, Sigma-Aldrich or Merck
Chemical Companies. The structures of the known
compounds were recognized by the comparison of their
NMR data/melting points with those reported in the lit-
erature. Thin-layer chromatography (TLC) was utilized
for the observation of the reaction progress. Bruker
Avance DPX FT-NMR spectrometer was applied for
running the 1H-NMR (500 MHz) and 13C-NMR
(125.7 MHz) spectra. Büchi B-545 apparatus was used
for measuring the melting points in open capillary
tubes. The morphologies and particle sizes of samples
were characterized by field emission-scanning electron
microscopy (FE-SEM), model TESCAN MIRA3 LMH. A
transmission electron microscope (TEM; model Philips
CM200) was used to measure the size and shape of
particles.
anticancer,[56] anti-inflammatory,[57] antimalarial,[58]
antidepressant,[59] antimicrobial,[60] antipyretic[61] and
antibacterial[62] properties. There are two ways to prepare
bis (pyrazolyl)methanes: (i) the one-pot pseudo five-
component reaction among phenylhydrazine, ethyl
acetoacetate and aromatic aldehydes; and (ii) the one-pot
pseudo three-component reaction between 3-methyl-
1-phenyl-1H-pyrazol-5(4H)-one and aromatic aldehydes.
Rare reports of this method (i) compared with the second
method (ii) are provided for preparing bis (pyrazolyl)
methanes.
Now, in this report, palladium complex supported
on the surface-modified MCM-41 nanoparticles [Pd(0)-
guanidine@MCM-41] is introduced as a new and effi-
cient reusable catalyst for the synthesize of bis
(pyrazolyl)methanes, as
a
mesoporous recoverable
SCHEME 1 Synthesis of MCM-
41@guanidine@-Pd(0)
SCHEME 2 The pseudo five-component
preparation of bis (pyrazolyl)methanes model reaction

PD(0)-GUANIDINE@MCM-41 CATALYZED MULTICOMPONENT REACTIONS
3 of 10
guanidine nitrate (2 mmol, 0.244 g) and sodium carbon-
ate (2 mmol, 0.212 g) in toluene for 24 hr. The resulting
solid (guanidine@MCM-41) was separated by simple fil-
tration, washed with ethanol and dried at room temper-
ature. Finally, to synthesize Pd(0)-guanidine@MCM-41,
the guanidine@MCM-41 (0.5 g) was dispersed in etha-
nol and was mixed with 0.25 g of palladium acetate
and refluxed for 18 hr. Then, NaBH4 (0.4 mmol) was
added to the reaction mixture and stirred for 2 more
hours. The solid product was obtained by filtration,
washed with ethanol and dried at 60ꢀC in an oven
(Scheme 1).[63]
FIGURE 1 X-ray diffraction (XRD) patterns of (a) MCM-41,
(b) guanidine@MCM-41 and (c) Pd(0)-guanidine@MCM-41
2.3 | General procedure for the synthesis
of bis (pyrazolyl)methanes by the pseudo
five-component reaction using Pd(0)-
guanidine@MCM-41
2.2 | Procedure for the production of
Pd(0)-guanidine@MCM-41
The
Pd(0)-guanidine@MCM-41
was
synthesized
In
a
10-ml round-bottom flask,
a
mixture of
according to the previously reported method.[63] For the
synthesis of pure siliceous MCM-41, NaOH solution
(3.5 ml of 2 M) was added to deionized water (480 ml)
at 80ꢀC. CTAB (1 g) was then added as the template.
The resulting mixture was stirred at 80ꢀC until the
solution became uniform. TEOS (5 ml) was then slowly
added, and the resulting solution was refluxed for 2 hr.
The product was filtered off, washed with deionized
water and dried in an oven at 50ꢀC for 24 hr, followed
by calcination at 550ꢀC for 5 hr with a heating rate of
2ꢀC/min. This procedure gave mesoporous MCM-41.
Then the mesoporous MCM-41 functionalized with
(3-chloropropyl)-trimethoxysilane (CPTMS @MCM-41)
was prepared according to the reported procedure.[28]
The above-mentioned solid (0.5 g) was refluxed with
phenylhydrazine (2 mmol), ethyl acetoacetate (2 mmol)
and aldehyde(1 mmol) was stirred in the presence of
Pd(0)-guanidine@MCM-41 (0.1 mol%) at 80ꢀC under
solvent-free conditions for an appropriate period of time
(Scheme 2). After completion of the reaction
(as monitored by TLC), and cooling the mixture to room
temperature, EtOAc (10 ml) was added, and the reaction
vessel was connected to a condenser, and stirred for
3 min under reflux conditions, followed by centrifugation
and decantation to separate the nanocatalyst; the catalyst
was washed with EtOH (2 × 4 ml), dried and used for the
next run. The solvent obtained from decantation was
evaporated, and the resulting precipitate was
recrystallized from hot EtOH (95%) to give the pure
product.
TABLE 1 The results of optimizing the catalyst quantity, temperature and solvent on the reaction of 4-chlorobenzaldehyde,
phenylhydrazine and ethyl acetoacetate
Entry
Catalyst amount (mol%)
Temp. (ꢀC)
Reflux
Reflux
Reflux
Reflux
25
Solvents
Time (min)
Yielda (%)
1
2
0.050
0.075
0.1
−
14
14
14
18
20
20
20
40
45
45
72
−
87
3
−
98
4
0.1
−
90
5
0.1
−
trace
67
6
0.1
50
−
7
0.1
70
−
82
8
0.1
Reflux
Reflux
Reflux
EtOH
EtOAc
CH3CN
97
9
0.1
94
10
0.1
96
aIsolated yield.

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FILIAN ET AL.
3 | RESULTS AND DISCUSSION
3.1 | Catalyst preparation
SCHEME 3 Pd(0)-guanidine@MCM-41catalyzed the
synthesis of bis (pyrazolyl)methanes
The presented work tries to describe a Pd-complex
immobilized onto the MCM-41 as
a
reusable
MCM-41
nanocatalyst.
nanoparticles
Initially,
with
the
modified
3-choloropropyltriethoxysilane
(CPTMS@MCM-41 NPs) have been prepared according
to the reported procedure.[63] In order to prepare
guanidine@MCM-41 NPs, guanidine has been grafted on
CPTMS @MCM-41 NPs via substitution reaction of NH2
with terminal Cl groups. Finally, the catalyst was synthe-
sized by the reaction of guanidine@MCM-41with Pd
(OAc)2 (Scheme 1).
2.4 | General procedure for the synthesis
of bis (pyrazolyl)methanes by the pseudo
three-component reaction using Pd(0)-
guanidine@MCM-41
A mixture of 3-methyl-1-phenyl-1H-pyrazol-5(4H)-one
(2 mmol), aldehyde (1 mmol) and Pd(0)-
guanidine@MCM-41 (0.1 mol%) was stirred at 80ꢀC.
After completion of the reaction (as monitored by TLC)
and cooling the mixture to room temperature, EtOH
(10 ml) was added, refluxed for 1 min, and the insoluble
catalyst was separated by centrifugation and decanting
[the catalyst was washed by EtOH (2 × 4 ml), dried and
used for the next run]. The EtOH resulted from the
decanting was evaporated, and the solid residue was
recrystallized from EtOH (95%) to afford the pure
product.
3.2 | Catalyst characterizations
The as-prepared Pd(0)-guanidine@MCM-41 was previ-
ously characterized as a novel mesoporous nanocatalyst
in our laboratory using Fourier transform-infrared (FT-
IR), scanning electron microscopy (SEM), energy-
dispersive spectroscopy, Wavelength Dispersive X-ray
(WDX), Brunauer−Emmett−Teller, TEM, thermal gravi-
metric analysis and inductively coupled plasma (ICP)
TABLE 2 The one-pot pseudo five-component production of bis (pyrazolyl)methanes using MCM-41@guanidine-Pd(0)
Mp (ꢀC)
Comp. no
Ar
Time (min)
Yielda (%)
TOF (min−1
63.333
53.529
50.000
54.705
45.500
42.857
31.851
70.000
54.705
63.333
48.421
45.500
42.857
40.454
28.000
)
Found
Reported
166–168[66]
229–231[66]
148–150[66]
221–223[67]
198–200[66]
174–176[66]
191–193[66]
208–210[66]
151–153[66]
240–242[66]
224–226[66]
175–177[67]
172–174[67]
251–253[66]
213–216[68]
1
C6H5
15
17
18
17
20
21
27
14
17
15
19
20
21
22
30
95
91
90
93
91
90
86
98
93
95
92
91
90
89
84
165–167
230–228
149–151
220–222
197–199
173–175
191–193
209–211
150–152
241–243
225–227
175–177
173–175
252–254
212–214
2
4-O2NC6H4
3-O2NC6H4
2-O2NC6H4
4-MeC6H4
4-MeOC6H4
3,4-(MeO)2C6H3
4-ClC6H4
3-ClC6H4
2-ClC6H4
2,4-(Cl)2C6H3
4-FC6H4
3
4
5
6
7
8
9
10
11
12
13
14
15b
3-BrC6H4
2-BrC6H4
4-OHCC6H4
aIsolated yield.
bReaction conditions: terephthalaldehyde (1 mmol), ethyl acetoacetate (4 mmol), phenylhydrazine (4 mmol), Pd(0)-guanidine@MCM-41 (0.1 mol%).

PD(0)-GUANIDINE@MCM-41 CATALYZED MULTICOMPONENT REACTIONS
5 of 10
SCHEME 4 The suggested mechanism for
the pseudo five-component preparation of bis
(pyrazolyl)methanes
3.3 | Catalytic studies
3.3.1 | Checking catalytic activity of
Pd(0)-guanidine@MCM-41 for the
synthesis of bis (pyrazolyl)methanes via
the pseudo five-component reaction
SCHEME 5 The pseudo three-component preparation of bis
(pyrazolyl)methanes model reaction
In early research to obtain optimal reaction conditions,
the effect of temperature, solvent type and catalyst quan-
tity was investigated on the condensation of
phenylhydrazine (2 mmol), ethyl acetoacetate (2 mmol)
and 4-chlorobenzaldehyde (1 mmol; Scheme 2). The reac-
tion was examined at 70, 80 and 90ꢀC, as well as under
reflux conditions in ethanol, ethyl acetate and acetoni-
trile using 0.05, 0.075 and 0.1 mol% of Pd(0)-
guanidine@MCM-41 on the basis of Pd. The best results
were obtained in solvent-free conditions using 0.01 g
Pd(0)-guanidine@MCM-41 at 80ꢀC (Table 1, entry 3).
To appraise the performance and scope of the
nanocatalyst, bis (pyrazolyl)methanes were synthesized
by the condensation of phenylhydrazine, ethyl
acetoacetate and aromatic aldehydes under the optimized
reaction conditions (Scheme 3). As can be observed in
this table, all aldehydes (containing benzaldehyde and
arylaldehydes bearing halogens, electron-withdrawing
techniques.[63] Our first goal in this report was to charac-
terize more completely the Pd(0)-guanidine@MCM-41,
so the catalyst characterizations were absolutely com-
pleted using the X-ray diffraction (XRD) technique.
XRD patterns of (a) MCM-41, (b) guanidine@MCM-
41 and (c) Pd(0)-guanidine@MCM-41 are shown in
Figure 1. As reported in previous works,[64,65] MCM-41
phase was identified from the XRD patterns by the
three characteristic peaks related to the strong (100),
smaller (110) and (200) reflections, which confirm the
hexagonal pore arrangement of MCM-41. According to
Figure 1, in the XRD patterns of the Pd(0)-
guanidine@MCM-41, there were no well-resolved peaks
corresponding to d100, d200 and also the decrease in
intensity of the peak at d100, which are strong evidences
revealing that the well-grafting of Pd complex into
MCM-41 channels occurred.

6 of 10
FILIAN ET AL.
TABLE 3 The results of optimizing the catalyst quantity, temperature and solvent on the reaction of 4-chlorobenzaldehyde,
3-methyl-1-phenyl-1H-pyrazol-5(4H)-one
Entry
Catalyst amount (mol%)
Temp. (ꢀC)
60
Solvents
Time (min)
Yielda (%)
1
2
3
4
5
5
6
0.05
0.075
0.1
−
5
5
98
98
97
79
94
92
96
50
−
50
−
5
0.1
40
−
18
40
45
45
0.1
Reflux
Reflux
Reflux
EtOH
EtOAc
CH3CN
0.1
0.1
aYield of isolated product.
by the pseudo five-component reaction, our research
team decided to evaluate its catalytic capability to
accomplish the synthesis via pseudo three-component
condensation. To this end, the reaction of
4-chlorobenzaldehyde (1 mmol) and 3-methyl-1-phenyl-
1H-pyrazol-5(4H)-one (2 mmol) was considered as a
model reaction (Scheme 5) and, like the previous method,
the effects of temperature, solvent type and different
values of the catalyst were tested by examining the reac-
tion in the presence of 0.05, 0.075, 0.1 mol% of Pd(0)-
guanidine@MCM-41 at 40, 50 and 60ꢀC in solvent-free
conditions, and also in some solvents (acetonitrile, ethyl
acetate and ethanol). The best results were received in the
absence of solvent at 50ꢀC using 0.1 mol% Pd(0)-
guanidine@MCM-41 (Table 3, entry 3).
SCHEME 6 The production of bis (pyrazolyl)methanes using
Pd(0)-guanidine@MCM-41
groups and electron-donating groups) produced the
desired derivative in a short time with high yields
(Table 2). However, it is worth mentioning that the time
process of the reaction of aldehydes with electron-
donating groups was longer than aldehydes with
electron-withdrawing groups.
The proposed mechanism for synthesis of bis
(pyrazolyl)methanes using Pd(0)-guanidine@MCM-41
nanocatalyst[43] has been shown in Scheme 4. At the
beginning of the reaction, palladium nanocatalyst acti-
vates carbonyl groups in the ethyl acetoacetate, and then
phenyl hydrazine attacks the carbonyl groups to afford
pyrazolone (I), and was further rearranged into tautomer
(II). In the next step, a Knoevenagel-type of reaction
takes place between activated aldehydes and tautomer
(II) followed by the liberation of a water molecule to form
intermediate (III). In the following, a Michael addition
reaction between intermediate (III) and tautomer (II) is
facilitated to form intermediate (IV). Finally, the
corresponding products are formed by tautomerization
and aromatization of intermediate (IV).
In order to assess the generality and efficacy of
Pd(0)-guanidine@MCM-41 for the production of bis
(pyrazolyl)methanes,
3-methyl-1-phenyl-1H-pyrazol-
5(4H)-one was reacted with arylaldehydes (with various
substituents) under the optimal reaction conditions
(Scheme 6). The results are summarized in Table 4. As
the data in this table show, the nanocatalyst was gen-
eral and highly efficient for the reaction; all aromatic
aldehydes (containing electron-withdrawing substitu-
ents, electron-donating substituents and halogens)
afforded the corresponding products in high yields
within short reaction times.
The mechanism supported by the literature[44] for the
synthesis of bis (pyrazolyl) methanes via the pseudo
three-component reaction is illustrated in Scheme 7.
3.3.2 | Examining catalytic activity of
Pd(0)-guanidine@MCM-41 for the
synthesis of bis (pyrazolyl)methanes via
the pseudo three-component reaction
3.4 | Recyclability of the catalyst
The recovery capability of Pd(0)-guanidine@MCM-41
was considered for the synthesis of compound 8 in
pseudo three-component condensation methods. The
results showed that our catalysts were reusable in the
pseudo three-component condensation (Figure 2) for six
After super performance of Pd(0)-guanidine@MCM-41
as catalyst in the synthesis of bis (pyrazolyl)methanes

PD(0)-GUANIDINE@MCM-41 CATALYZED MULTICOMPONENT REACTIONS
7 of 10
TABLE 4 The one-pot pseudo three-component production of bis (pyrazolyl)methanes using Pd(0)-guanidine@MCM-41
Mp (ꢀC)
Comp. no
Ar
Time (min)
Yielda (%)
TOF (min)
192
Found
Reported
1
C6H5
5
5
5
5
6
7
9
5
5
5
7
6
9
8
15
96
95
96
96
93
92
90
97
95
95
93
94
91
93
87
165–167
222–220
149–151
228–230
198–200
175–177
190–192
222–224
239–241
242–244
207–209
176–178
250–252
249–251
214–216
166–168[66]
229–231[66]
148–150[66]
221–223[67]
198–200[66]
174–176[66]
191–193[66]
208–210[66]
151–153[67]
240–242[66]
224–226[66]
175–177[67]
172–174[67]
251–253[66]
213–216[68]
2
4-O2NC6H4
3-O2NC6H4
2-O2NC6H4
4-MeC6H4
4-MeOC6H4
3,4-(MeO)2C6H3
4-ClC6H4
3-ClC6H4
2-ClC6H4
2,4-(Cl)2C6H3
4-FC6H4
190
3
192
4
192
5
155
6
131
7
100
8
194
9
190
10
11
12
13
14
15b
190
186
156
3-BrC6H4
2-BrC6H4
4-OHCC6H4
101
116
58
aIsolated yield.
bReaction conditions: terephthalaldehyde (1 mmol), 3-methyl-1-phenyl-1H-pyrazol-5(4H)-one (4 mmol), Pd(0)-guanidine@MCM-41 (0.1 mol%).
SCHEME 7 The suggested mechanism for
the pseudo three-component preparation of bis
(pyrazolyl)methanes

8 of 10
FILIAN ET AL.
FIGURE 2 The recycling experiment of
Pd(0)-guanidine@MCM-41 in the production of
bis (pyrazolyl)methanes in the pseudo three-
component condensation
The FT-IR spectrums of the recycled catalyst are
shown in Figure 3. The results show that good agreement
was observed for FT-IR of fresh Pd(0)-guanidine@MCM-
41 (Figure 3a) and recycled catalyst (Figure 3b).
Therefore, Figure 3 shows good stability of Pd(0)-
guanidine@MCM-41 after recycling.
3.5 | Leaching study
In order to consider the leaching of Pd into the reaction
media, ICP-atomic emission spectroscopy analysis was
performed. In this sense, the palladium content in the
reaction media and in the synthesis of product 7 was
found to be 0.87%. The results show that the leaching of
Pd during the reaction process is negligible.
FIGURE 3 Fourier transform-infrared (FT-IR) spectrums of
Pd(0)-guanidine@MCM-41 and recovered catalyst
3.6 | Comparison
times, with insignificant loss of activity. The nanocatalyst
was recycled in both ways as described in the
Experimental section.
Also, in order to examine the stability of the catalyst
after recycling, the recycled catalyst has been
characterized using the FT-IR technique.
In order to demonstrate the superiority of our catalyst
to other reported catalysts for the synthesis of bis
(pyrazolyl)methanes, the results of the reaction of
4-chlorobenzaldehyde with phenylhydrazine and ethyl
acetoacetate for the pseudo five-component reaction
TABLE 5 Comparison results of Pd(0)-guanidine@MCM-41 with other catalysts reported in the literature
Catalyst
Conditions
Type of reaction
Time (min)
Yield (%)
TON
75.3
74.6
6.1
TOF (min−1
5.38
)
Ref.
MCM-41@ guanidine-Pd(0)
MCM-41@ guanidine-Pd(0)
Aspirin
Solvent-free, 80ꢀC
Solvent-free, 50ꢀC
EtOH/H2O, 60ꢀC
CH3CN, rt
i
14
5
98
97
92
97
80
96
94
85
90
−
ii
i
14.92
0.20
−
[69]
30
5
[70]
[71]
[72]
[73]
[74]
[34]
AP-SiO2
ii
i
3.2
0.64
DCDBTSD
Solvent-free, 80 ꢀC
Solvent-free, 80ꢀC
Solvent-free, 50ꢀC
EtOH, Reflux
40
8
8.0
0.20
CuFe2O4
i
24.0
94
3.00
[Pyridine–SO3H]Cl
SASPSPE
ii
ii
ii
8
11.75
0.18
132
20
25
Ni-guanidine@MCM-41 NPs
Acetonitrile, 80ꢀC
11.2
0.56

PD(0)-GUANIDINE@MCM-41 CATALYZED MULTICOMPONENT REACTIONS
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(i) as well as the outcomes of the reaction of
4-chlorobenzaldehyde
with
3-methyl-1-phenyl-1H-
pyrazol-5(4H)-one for the pseudo three-component
reaction (ii) are presented in Table 5. As it can be seen
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heterogeneous and recyclable catalyst for the synthesis of
bis (pyrazolyl)methane derivatives by the two following
methods: (i) the one-pot pseudo five-component reaction
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ethyl
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Hossein Filian https://orcid.org/0000-0003-1847-5285
Masoud Mohammadi https://orcid.org/0000-0002-
1043-3470
Arash Ghorbani-Choghamarani https://orcid.org/0000-
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How to cite this article: Filian H, Kohzadian A,
Mohammadi M, Ghorbani-Choghamarani A,
Karami A. Pd(0)-guanidine@MCM-41: a very
effective catalyst for rapid production of bis
(pyrazolyl)methanes. Appl Organometal Chem.
2020;e5579. https://doi.org/10.1002/aoc.5579
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