Synthesis and Application of Graphene Oxide-supported Aluminium Chloride as a Novel and an Environmentally Friendly Catalyst for the Preparation of Bis(pyrazolyl)methanes

Article abstract of DOI:10.1134/S107042801905018X

The immobilization of AlCl₃, an extremely hygroscopic Lewis acid, on graphene oxide as a support material with a high surface area was studied. The obtained solid material was characterized by FTIR spectroscopy, TGA/DTA analysis, field emission

Full text of DOI:10.1134/S107042801905018X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2019, Vol. 55, No. 5, pp. 694–701. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Zhurnal Organicheskoi Khimii, 2019, Vol. 55, No. 5, pp. 816.
Synthesis and Application of Graphene Oxide–supported
Aluminium Chloride as a Novel and an Environmentally
Friendly Catalyst for the Preparation of Bis(pyrazolyl)methanes
K. Parvanak Boroujenia,*, S. Karimia, and M. M. Eskandarib
a Department of Chemistry, Shahrekord University, Shahrekord, Iran
*e-mail: parvanak-ka@sci.ac.ir
b Nanotechnology Research Center, Research Institute of Petroleum Industry, Tehran, Iran
Received November 24, 2018; revised December 8, 2018; accepted December 16, 2018
Abstract—The immobilization of AlCl3, an extremely hygroscopic Lewis acid, on graphene oxide as a support
material with a high surface area was studied. The obtained solid material was characterized by FTIR
spectroscopy, TGA/DTA analysis, field emission scanning electron microscopy, and energy-dispersive X-ray
spectroscopy and used as an efficient and bench-top environmentally benign catalyst for the preparation of bis
(pyrazolyl)methane derivatives through the condensation of aldehydes and 3-methyl-l-phenylpyrazol-5-one.
The catalyst is reusable for at least nine times with a negligible loss in its catalytic activity.
Keywords: aluminum chloride, graphene oxide, immobilization, catalysis, synthesis, bispyrazolylmethane
derivatives
DOI: 10.1134/S107042801905018X
Graphene is composed of sp2 carbon atoms
arranged in a honeycomb structure with a high specific
surface area. Studying the physics, chemistry, and
biological applications of graphene-type materials
have recently become a fast-growing research field in
materials science [1]. Graphene oxide (GO), a product
of graphene oxidation, bears a number of functional
groups, such as OH, COOH, and epoxide C–O–C, and
offers several advantages over graphene, because its
surface modification permits tailoring the surface
properties for various potential applications in
heterogeneous catalytic processes [2].
immobilization on an inorganic or organic support by
covalent bonding or complexation [3, 4].
5-Pyrazolone derivatives are known to display
diverse pharmacological activities. For example, 2,4-
dihydro-3H-pyrazol-3-one derivatives, including bis
(pyrazolyl)methanes, are used as gastric secretion
stimulatory, anti-inflammatory, antidepressant, anti-
bacterial, antifilarial, antitumor, and antiviral agents [5,
6]. Bis(pyrazolyl)methanes are usually prepared by
one-pot tandem Knoevenagel−Michael reaction of
aldehydes with two equivalents of 3-methyl-l-
phenylpyrazol-5-one. The reaction in the absence of
the catalyst proceeds quite slowly (4–24 h in refluxing
solvents and further 24 h under ambient temperature),
and the products are obtained in moderate yields [7–9].
Several types of catalysts were introduced previously
for this reaction, such as silica-bonded S-sulfonic acid
(SBSSA) [10], sulfuric acid ([3-(3-silicapropyl)
sulfanyl]propyl) ester (SASPSPE) [11], silica sulfuric
acid (SSA) [12], 1-methylimidazolium hydrogen
sulfate under ultrasonic irradiation ([HMIM]HSO4)
[13], silica-bonded ionic liquid ([Sipmim]HSO4) [14],
2-hydroxyethylammonium acetate (2-HEAA) [15],
Aluminum chloride is an excellent Lewis acid
catalyst used in many important organic
transformations. However, it has several drawbacks,
including hygroscopic and corrosive nature, difficulties
in separation and recovery, and generation of waste
during catalytic reactions. Moreover, its use in
catalytic processes usually causes formation of
unwanted side products due to its strong acidity. Thus,
the use of this catalyst does not meet the requirements
of green chemistry protocols and many attempts have
been made to overcome its disadvantages using its
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SYNTHESIS AND APPLICATION OF GRAPHENE OXIDE–SUPPORTED ALUMINIUM
695
Scheme 1.
Cl
Cl
O
O
OH
Al
Cl
OH
HO
Cl
Cl
Cl
Cl
Al
Al
O
Al
Cl
O
O
O
O
O
O
O
O
AlCl3
CO2H
CCl4
O
O
HO
O
HO
Reflux, N2
O
OH
GO
GO_AlCl3
1,3-disulfonic acid imidazolium tetrachloroaluminate
([Dsim]AlCl4) [16], nano n-propylsulphonated γ-Fe2O3
(NPS-γ-Fe2O3) [17], poly(4-vinylpyridine)-supported
ionic liquid ([P4VPy-BuSO3H]HSO4) [18], trityl
chloride (Ph3CCl) [19], boehmite nanoparticles (BNPs)
[20], silica vanadic acid (SVA) [21], and L-proline on
graphene oxide/Fe3O4 nanocomposite [22]. One-pot
three-component condensation of phenylhydrazine,
ethyl acetoacetate, and aldehydes has also been used as
an alternative synthetic approach to bis(pyrazolyl)
methanes [23, 24]. However, many of these methods
have some drawbacks, such as long reaction times,
tedious work-up, low isolated yields, high reaction
temperatures, and use of unrecyclable, hazardous, or
difficult-to handle catalysts. Therefore, to continue the
search for a better, eco-friendly and green, catalyst for
this useful reaction remains an urgent task.
3400, 1733, 1622, and 1227 cm−1 due to OH, C=O,
C=C, and C–O vibrations, respectively. The FTIR
spectrum of GO–AlCl3 (Fig. 1, spectrum 2) contains an
additional band at 604 cm−1 assignable the Al–Cl bond
in AlCl3 [27, 32]. This observation indicates that AlCl3
is attached to the GO surface.
The TGA/DTA curves of GO and GO–AlCl3 are
presented in Figs. 2a and 2b, respectively. The first
weight loss observed in each case around 30–100°C is
due to a loss of moisture. The second weight loss in the
TGA curve of pristine GO (Fig. 2a) is observed at
temperatures higher than 100°C and is likely to be
associated with the structural decomposition of GO.
According to the TGA analysis of GO–AlCl3, the
thermal decomposition of the surface-attached AlCl3
and GO occur in the temperature range 100–360°C
(Fig. 2b). The last weight loss at temperatures higher
than 360°C is due to the continued structural
decomposition of GO. The higher char yield of GO–
AlCl3 at 800°C compared to pristine GO indicates that
the immobilization of AlCl3 on the surface GO surface
imparts a relatively good thermal stability to the
resulting GO–AlCl3.
Taking in consideration the importance of
graphene-type materials for successful immobilization
of catalysts and proceeding with our ongoing research
on the development of new heterogeneous catalytic
systems for organic reactions [25–29], in the present
work we have synthesized GO-supported AlCl3 as an
efficient catalyst for the preparation of bis(pyrazolyl)-
methanes.
The SEM micrographs of GO and GO–AlCl3 are
presented in Fig. 3. As seen from a comparison of the
SEM images of GO (Fig. 3a) and GO–AlCl3 (Fig. 3b),
The GO–AlCl3 catalyst was synthesized by the
reaction of GO prepared by oxidizing natural graphite
powder with anhydrous AlCl3 (Scheme 1). The Al
content of GO–AlCl3 was measured by atomic
absorption spectroscopy to obtain 1.2 mmol Al/g
catalyst. The chloride content of GO–AlCl3 as
determined by the Mohr titration method [30] was 2.9
mmol Cl/g catalyst. The high Cl/Al molar ratio (< 2)
in GO–AlCl3 suggests that AlCl3 is present as dimer (–
Al2Cl5) [31], which is a predominant aluminium
species among the other possible ones (e.g. –AlCl2 and
–AlCl) (Scheme 1).
The FTIR spectrum of GO depicted in Fig. 1
(spectrum 1) shows characteristic IR bands at about
Fig. 1. FTIR spectra of (1) GO and (2) GO-AlCl3.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 5 2019

PARVANAK BOROUJENI et al.
696
(a)
(a)
(b)
Fig. 2. TGA/DTA analysis of (a) GO and (b) GO–AlCl3.
the flat and smooth morphology of graphene sheets is
disturbed after functionalization, and the surface of
GO–AlCl3 is composed of wrinkled thin films closely
associated with each other. However, the SEM
micrographs show that functionalization does not
destroy the morphology of graphene oxide sheets.
(b)
Figure 4 shows the energy dispersive X-ray (EDS)
spectrum of GO–AlCl3, which confirms the presence
of Al and Cl in GO–AlCl3 and absence of any
impurities, thereby providing evidence for successful
immobilization of AlCl3 on GO.
Fig. 3. SEM images of (a) GO and (b) GO–AlCl3.
optimization of the reaction conditions, we reacted
different types of aromatic aldehydes having electron-
donor and electron-acceptor substituents (Table 1,
entries 1–6, 9–11). These condensation reactions
proceeded smoothly and were complete within 10–25
min in 93–96% yields. Interestingly, even with acid-
sensitive aldehydes, such as furan-2-carboxaldehyde
and thiophene-2-carboxaldehyde, no side reactions
were observed, and the corresponding products were
obtained in 93 and 94% yields, respectively, in 20 min
(entries 7, 8). Pentanal, too, gave the expected bis
(pyrazolyl)methane product within 30 min in 91%
Having synthesized and characterized GO–AlCl3,
we investigated its catalytic application in the
synthesis of bis(pyrazolyl)methanes (Scheme 2). To
this end, we studied the reaction of 1 equiv of 4-
bromobenzaldehyde with 2 equiv of 3-methyl-l-
phenylpyrazol-5-one in the presence of different molar
ratios of GO–AlCl3 in various solvents, as well as
under solvent-free conditions at different temperatures.
The best yield of the product was obtained in refluxing
ethanol with 0.04 mmol of GO–AlCl3. After
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SYNTHESIS AND APPLICATION OF GRAPHENE OXIDE–SUPPORTED ALUMINIUM
yield (entry 12). As seen from Table 1, the nature of
697
the substituents in the aromatic ring of the aldehyde
only slightly affected the reaction time. The aldehydes
with electron-acceptor substituents (entries 1, 2)
reacted faster than the aldehydes with electron-donor
substituents (entries 9–11). This finding can be exp-
lained by the mechanism of the reaction (Table 1). The
first step involves formation of a benzylidene
intermediate I via condensation of 3-methyl-l-phenyl-
pyrazol-5-one with activated aldehyde followed by a
loss of H2O. The subsequent 1,4-nucleophilic Michael-
type addition of another 3-methyl-l-phenylpyrazol-5-
one molecule to activated intermediate I leads to a bis-
(pyrazolyl)methane product. It is clear that inter-
mediate I is more susceptible to 1,4-nucleophilic
Fig. 4. EDS spectrum of GO–AlCl3.
Table 1. Synthesis of bis(pyrazolyl)methanes by the GO–AlCl3-catalyzed reaction of aldehydes with 3-methyl-l-
phenylpyrazol-5-one
Ph
HO
R
N
Cat
R
H
R
H
N
CH3
CH3
H
CH3
N
H
H3C
N
HO
O
CH3
CH3
O
H
N
+
N
_H2O
HO
R
N
H
N
O
N
N
Cat
O
N
N
OH
Ph
Ph
Ph
Ph
Ph
I
R
H
CH3
H3C
_
Cat
Cat : GO AlCl3
N
N
N
N
HO
OH
Ph
Ph
Entry
R
Time, min
Yield, %a,b
mp, °C
1
2
4
5
3
6
7
8
4-NO2C6H4
3-NO2C6H4
4-ClC6H4
4-BrC6H4
4-CN C6H4
C6H5
10
10
15
15
20
20
20
20
96
94
94
95
94
96
93
94
169–171 (170–172 [10])
149–152 (151–153 [11])
213–216 (215–217 [14])
180–184 (181–183 [19])
211–213 (210–212 [12])
169–171 (168–170 [16])
186–189 (188–189 [20])
181–184 (181–183 [20])
Furan-2-
Thiophene-2-
9
4-MeC6H4
4-OHC6H4
4-MeC6H4
C4H9
20
25
24
30
93
94
93
91
200–204 (201–203 [21])
151–154 (153–155 [22])
176–178 (177–179 [18])
122–124 (125–127 [15])
10
11
12
a
All reactions were carried out in refluxing EtOH in the presence of GO–AlCl3 (0.04 mmol).
Isolated yield. All products are known compounds and were identified by a comparison of their physical and spectral data with those of
the authentic samples.
b
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PARVANAK BOROUJENI et al.
aluminum by atomic absorption spectroscopy revealed
698
a negligible release of AlCl3.
The reusability of the catalyst was also examined.
After each reaction the catalyst was filtered off,
washed with ethanol, dried, and reused in consecutive
cycles for the preparation of bis(pyrazolyl)methanes.
As seen from Fig. 5, GO–AlCl3 can be reused at least
nine times without loss of its efficiency.
We also explored the possibility to synthesize bis
(pyrazolyl)methanes by one-pot three-component
condensation of aromatic aldehydes with phenyl-
hydrazine and ethyl acetoacetate in the presence of
GO–AlCl3. It was pleasing to observe that these reac-
tions proceeded smoothly in refluxing ethanol and re-
sulted in highs yield of the desired product (Scheme 2).
Fig. 5. Recyclability of GO–AlCl3 (0.04 mmol) after 15-min
reaction of 1 mmol of 4-bromobenzaldehyde with 2 mmol
of 3-methyl-l-phenylpyrazol-5-one in refluxing EtOH.
addition, when the aromatic aldehyde contains
electron-donor substituents [33].
The good catalytic performance of GO–AlCl3
encouraged us to test its catalytic efficiency for the
synthesis of 1,8-dioxo-octahydroxanthenes by the reaction
of 5,5-dimethylcyclohexane-1,3-dione (dimedone) with
aldehydes. As seen from Scheme 3, the corresponding
1,8-dioxo-octahydroxanthenes formed in high yields in
aqueous ethanol at room temperature. These results are
important from two points of view. First, to the best of
our knowledge, the precedents of successful reactions
of dimedone with aldehydes at room temperature are
rare, and these reactions require high temperatures or
additional energy (ultrasonic or microwave radiation)
to occur [34–36]. Second, the fact that the GO–AlCl3
works well in aqueous media makes this catalyst an
interesting option for eco-friendly synthesis. The
moisture resistance of GO–AlCl3 can be attributed to
the hydrophobic nature of GO which protects the
water-sensitive Lewis acid from hydrolysis.
Further on we compared the catalytic activities of
GO–AlCl3 and anhydrous AlCl3. The reaction of
1 equiv of 4-bromobenzaldehyde with 2 equiv of 3-
methyl-l-phenylpyrazol-5-one in the presence of a
stoichiometric amount or an excess AlCl3 in refluxing
ethanol gave as little as 60% of the corresponding
product along with unwanted by-products. The by-
product formation can be explained by the reactivity
(stronger Lewis acidity) of AlCl3, and, therefore, its
lower selectivity. The reaction at room temperature in
the presence of AlCl3 gave no products within 2 h.
To evaluate the catalyst leaching level, GO–AlCl3
was stirred in refluxing ethanol for 2 h, after which it
was filtered off and washed. The filtrate was found to
be inactive in the reaction of aldehydes with 3-methyl-
1-phenylpyrazol-5-one. Analysis of the filtrate for
Scheme 2.
Me
OH
Me
GO-AlCl3
(0.04 mmol)
EtOH
O
O
Ar
H
N
N
N
N
ArCHO + 2 PhNHNH2
+
2
Me
OEt
Ph
Ph
Reflux
HO
Ar = 4-BrC6H4, 17 min, 94%;
Ar = 3-NO2C6H4, 13 min, 96%.
Scheme 3.
O
Ar
O
O
GO-AlCl3
(0.05 mmol)
2
+
ArCHO
EtOH-H2O (1 : 1)
rt
O
O
Ar = 3-NO2C6H4, 17 min, 95%;
Ar = 4-NO2C6H4, 15 min, 96%.
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SYNTHESIS AND APPLICATION OF GRAPHENE OXIDE–SUPPORTED ALUMINIUM
699
Table 2. Comparison of the efficiency of different catalysts in the reaction of benzaldehyde with 3-methyl-l-phenylpyrazol-5-one
Entry
Catalyst, solvent, temperature
SBSSA, EtOH, reflux
Time, min
120
120
60
Yield, %a
80 [10]
89 [11]
93 [12]
92 [13]
89 [14]
90 [15]
91 [16]
93 [17]
95 [18]
95 [19]
90 [20]
95 [21]
98 [22]
96
1
2
SASPSPE, EtOH, reflux
3
SSA, H2O-EtOH, 70°C
4
[HMIM]HSO4, EtOH, ultrasonic irradiation, rt
[Sipmim]HSO4, EtOH, reflux
2-HEAA, EtOH, rt
45
5
120
15
6
7
[Dsim]AlCl4, solvent-free, 50°C
NPS-γ-Fe2O3, H2O, rt
40
8
180
42
9
[P4VPy-BuSO3H]HSO4, EtOH, reflux
Ph3CCl, solvent-free, 60°C
BNPs, solvent-free, 80°C
10
12
11
10
12
SVA, EtOH, 40°C
30
13
GO/Fe3O4/L-proline, EtOH, reflux
GO–AlCl3, EtOH, reflux
10
14
20
a
Isolated yield.
We also compared the efficiency of GO–AlCl3
Graphene oxide was prepared at the Nanotechnology
Research Laboratory, Research Institute of Petroleum
Industry, Tehran, Iran. Reaction monitoring and
control of product purity were performed by GLC on a
Shimadzu GC 14A gas chromatograph or by TLC on
silica gel PolyGram SILG/UV254 plates. The IR
spectra were obtained on a Shimadzu 8300 FTIR
spectrophotometer. The 1H NMR spectra were
recorded on a 400-MHz spectrometer. The melting
points were determined on a Fisher–Jones melting-
point apparatus. The TGA/DTA curves were obtained
a Stanton Redcraft STA–780 instrument at a 10°C/min
heating rate in N2. The field emission scanning
electron microscopy (FESEM) images were taken on a
Tescan MIRA3 FEG-SEM, and the EDS spectra were
measured on a LEO 1455 VP microscope.
catalyst and other known catalysts in a typical reaction
for the synthesis of bis(pyrazolyl)methanes. The
resulting data are collected in Table 2. As seen, GO–
AlCl3 is comparable to other catalysts in terms of
reaction times and yields.
In summary, we have reported
a
novel
heterogeneous form of the Lewis acid catalyst AlCl3
and showed that it can be used as a convenient catalyst
for the preparation of bis(pyrazolyl)methane and 1,8-
dioxo-octahydroxanthene derivatives under mild
conditions and in aqueous medium. The catalyst is
stable (as a bench-top catalyst) and can be reused at
least nine times with no loss of catalytic activity. Short
reaction times, high yields, easy work-up, and green
conditions are further advantages of the proposed
protocol. The possibility of other uses of the GO–
AlCl3 catalyst in aqueous media for several organic
transformations is under investigation.
Synthesis of GO. Concentrated H2SO4, 90 mL, was
added to 10 mL of a cooled (5°C) and magnetically
stirred 85% H3PO4 placed in a double-jacket reactor.
Graphite, 1 g (particle size < 50 µm) and 5 g of
potassium permanganate were mixed together in a
porcelain mortar to form a homogeneous solid mixture.
This solid mixture was gradually added into the
H2SO4–H3PO4 mixture over a period of 2 h. The
temperature of the mixture was kept at 5°C and stirring
EXPERIMENTAL
All chemicals were either prepared at the
Department of Chemistry, Shahrekord University,
Shahrekord, Iran or purchased from Merck and Fluka.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 5 2019

PARVANAK BOROUJENI et al.
700
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of the mixture was continued for 3 h and then, without
stopping stirring, the temperature of the mixture was
stepwise raised to 25°C for 3 h and then to 55°C for
further 2 h, and stirring at this temperature was
continued 12 h. The mixture was then cooled to 5°C,
poured into crushed ice, and stirred. Hydrogen
peroxide (30%) was then slowly added to the resulting
mixture until an ochre color was achieved. The
precipitate that formed was separated by filtration and
successively washed with deionized water (2 × 50 mL),
conc. HCl (2 × 10 mL), and deionized water until the
washings no longer contained sulfate and manganese
ions (by barium and sodium bismuthate tests). Finally,
the solid material was washed with ethanol and
acetone and dried at 70°C.
Synthesis of GO–AlCl3. A solution of 0.5 g of
anhydrous AlCl3 and 1g of GO in 30 mL of CCl4 was
refluxed for 12 h under an N2 atmosphere, after which
a further 0.25-g portion of AlCl3 was added, and the
mixture was stirred for 6 h, filtered, washed in a
Soxhlet apparatus with ethanol (95%) to remove
excess AlCl3, and dried at 80°C.
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Typical procedure for the synthesis of bis-
(pyrazolyl)methanes from the reaction of aromatic
aldehydes with 3-methyl-l-phenylpyrazol-5-one. A
mixture of 1 mmol of 4-bromobenzaldehyde, 2 mmol
of 3-methyl-l-phenylpyrazol-5-one, 0.04 mmol of GO–
AlCl3, and 3 mL of ethanol was stirred under reflux.
After completion of the reaction (by TLC), the catalyst
was filtered off and washed with 5 mL of ethanol, and
the filtrate was concentrated on a rotary evaporator
under reduced pressure to obtain 4,4'-[(4-
bromophenyl)methylene]bis(3-methyl-1-phenyl-pyra-
zol-5-ol). Whenever required, the products were
purified by recrystallization from ethanol.
11. Tayebi, S., Baghernejad, M., Saberi, D., and Niknam, K.,
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ACKNOWLEDGMENTS
18. Parvanak Boroujeni, K. and Shojaei, P., Turk. J. Chem.,
2013, vol. 37, p. 756.
19. Zare, A., Merajoddine, M., MoosaviZare, A.R., and
The authors gratefully acknowledge the partial
support of this study by Shahrekord University and
Research Institute of Petroleum Industry.
Zarei, M., Chin. J. Catal., 2014, vol. 35, p. 85.
20. Bakherad, M., Keivanloo, A., Amin, A.H., Doosti, R.,
CONFLICT OF INTEREST
No conflict of interest was declared by the authors.
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