Manganese oxide nanoparticles supported on graphene oxide as an efficient nanocatalyst for the synthesis of 1,2,4-oxadiazoles from aldehydes

Article abstract of DOI:10.1002/aoc.5838

The easy synthesis of graphene oxide (GO)-supported manganese dioxide (MnO₂) nanoparticles as a stable heterogeneous nanocatalyst (MnO₂@GO) is described. This catalyst was investigated in the synthesis of 1,2,4-oxadiazoles from amido

Full text of DOI:10.1002/aoc.5838

Received: 11 November 2019
DOI: 10.1002/aoc.5838
Revised: 13 April 2020
Accepted: 17 April 2020
C O M M U N I C A T I O N
Manganese oxide nanoparticles supported on graphene
oxide as an efficient nanocatalyst for the synthesis of
1,2,4-oxadiazoles from aldehydes
1
,2
3
1
3
Fariba Saadati
| Babak Kaboudin | Rana Hasanloei
|
1
4
Zeinab Namazifar | Xavier Marset | Gabriela Guillena
1
Department of Chemistry, Faculty of
The easy synthesis of graphene oxide (GO)-supported manganese dioxide
MnO ) nanoparticles as a stable heterogeneous nanocatalyst (MnO @GO) is
Science, University of Zanjan, Zanjan,
45371-38791, Iran
(
2
2
2
Department of Chemistry, University of
British Columbia, 2036 Main Mall,
Vancouver, British Columbia, V6T 1Z1,
Canada
described. This catalyst was investigated in the synthesis of 1,2,4-oxadiazoles
from amidoximes and aldehydes via a cyclization and oxidation process. The
nanocomposite was prepared and characterized using various techniques. The
catalytic application of the nanocomposite was examined in the reaction of a
variety of aldehydes with aliphatic and aromatic amidoximes. The stable and
robust catalyst was recycled for seven consecutive runs without a significant
decrease in the catalytic activity.
3
Department of Chemistry, Institute for
Advanced Studies in Basic Sciences (IASBS),
Gava Zang, Zanjan, 45137-66731, Iran
4
Departamento de Química Orgánica, e
Instituto de Síntesis Orgánica (ISO),
Universidad de Alicante, Alicante, 03080-
Alicante, Spain
K E Y W O R D S
1
,2,4-oxadiazole, graphene oxide, manganese dioxide, nanoparticles, oxidation
Correspondence
Fariba Saadati, Department of Chemistry,
Faculty of Science, University of Zanjan,
Zanjan 45371-38791, Iran; Department of
Chemistry, University of British
Columbia, 2036 Main Mall, Vancouver,
British Columbia V6T 1Z1, Canada.
Email: saadati@znu.ac.ir; fsaadati@chem.
ubc.ca
[
11]
1
| INTRODUCTION
amides in peptide mimetics, ligands for transition metal
[12]
[13]
complexes and liquid crystals.
The synthesis of heteroaromatic ring systems has been
widely researched, owing to their presence in a multitude
of biologically and medicinally active compounds. Among
these heteroaromatic rings, substituted 1,2,4-oxadiazoles
have a myriad of applications in bioactive molecules and
Several methods have been developed for the synthesis
of 1,2,4-oxadiazole derivatives as reported in the literature.
[14]
1,3-Dipolar cycloaddition of nitrile oxides with nitriles
[15]
and azetine
has been reported. The most popular strat-
egy for the synthesis of 1,2,4-oxadiazoles is the O-acylation
[1]
pharmacophore scaffolds like muscarinic receptors, sero-
of amidoximes using activated carboxylic acid derivatives
[
2]
[3]
[16]
[17,18]
[19,20]
toninergic antagonists, growth hormone secretagogues
such as benzoyl cyanides,
acid chlorides
esters,
anhydrides,
[4]
[21,22]
[23]
and inhibitors of human neutrophil elastase and tyrosine
kinase. Furthermore, some 1,2,4-oxadiazole derivatives
are of interest as anti-inflammatory, antirhinoviral,
antibacterial and anticancer agents.
and carboxylic acids,
followed by
[5]
intramolecular cyclodehydration. Another method for the
synthesis of 1,2,4-oxadiazole derivatives is the reaction of
amidoxime with aldehydes for the synthesis of 4,5-dihydro-
1,2,4-oxadiazoles, followed by oxidative dehydrogenation
[6]
[7]
[8]
[9,10]
In addition, they
have also been employed as bioisosteres for esters and
Appl Organomet Chem. 2020;e5838.
wileyonlinelibrary.com/journal/aoc
© 2020 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.5838

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SAADATI ET AL.
[
24,25]
with chemical oxidants
or electrochemical oxidation
TLC analysis was performed using Merck silica gel
60F254 analytical plates to follow the progress of reac-
tions. Purification was done using column chromatogra-
phy on Merck silica gel 60 (n-hexane–ethyl acetate as
eluent). Deionized water was used for washing and solu-
tion preparation.
[26]
methods.
However, several drawbacks are associated
[27]
with these methods. Toxicity and instability of acid chlo-
rides make them hard to handle and store. Oxidants are
required in stoichiometric amounts relative to the substrate.
Therefore, the development of more efficient, simple, eco-
nomical and environmentally benign methodologies is still
needed for the synthesis of substituted 1,2,4-oxadiazoles.
Recently,
heterogeneous
catalysts
containing
2.2 | Apparatus and instrumentation
nanoparticles have been applied to chemical reactions as
an effective strategy to address the claims of green chemis-
Fourier transform infrared (FT-IR) spectra were recorded
using a Bruker Vector 22 FT-IR spectrophotometer with
[28]
try.
In this context, the chemistry of manganese is
−
1
extremely rich because of its easily accessible Mn(II),
KBr/Nujol mull in the range 400–4000 cm under ambi-
[
29]
1
13
Mn(IV) and Mn(VII) oxidation states
abundance.
and its natural
In comparison with other manganese spe-
cies, manganese oxide nanoparticles have great potential
ent conditions. H NMR and C NMR spectra were
[30]
recorded with a Bruker spectrometer, at frequencies of
250 and 62.5 MHz, respectively, in CDCl . X-ray diffrac-
3
[31,32]
for applications in adsorption of hazardous dyes,
tion (XRD) patterns were collected with Bruker
D8-Advance with Göebel mirror X-ray diffractometer
using Cu-Kα radiation (λ = 1.54 Å). Thermogravimetric
analysis (TGA) and differential scanning calorimetry
(DCS) were performed with a DSC/TG thermal analyzer
(Netzsch STA 409 PC/PG) using Al O pans under air
[
33]
[34,35]
imaging contrast agents,
super capacitors
and a
[36,37]
new generation of catalysts
due to their high surface
area, electrochemical activity, natural abundance, environ-
mentally benign nature and low cost. However, the small
particle size as well as the high surface area of
nanoparticles makes them thermodynamically susceptible
to agglomeration processes, leading to the formation of
larger inactive particles. A valuable approach to overcome
this problem is the development of ecofriendly and biode-
2
3
ꢀ
atmosphere from ambient temperature to 800 C with a
ꢀ
−1
heating rate of 5 C min . The morphology and elemen-
tal composition of synthesized products were studied
using a MIRA3TESCAN-XMU field emission scanning
electron microscopy (FE-SEM) instrument and energy-
dispersive X-ray analysis (EDX). An NT-MDT NTEGRA
PRIMA atomic force microscopy (AFM) instrument was
utilized to investigate the surface topography and height
profile of samples in air by depositing a drop of a dilute
suspension on a clean mica surface. Tapping mode canti-
levers (NT-MDT NSG-01) had force constants of
[
38]
gradable solid materials as supports.
Along this line,
[39]
[40]
various solid supports including cellulose,
biochar,
[41]
[42,43]
graphene
and reduced graphene oxide
have been
reported as supports for MnO nanoparticles. Graphene
2
oxide (GO) is a single sheet of graphite oxide with excel-
lent mechanical properties, high surface area and desirable
compatibility with materials, which make it a promising
[44]
−1
substrate in material chemistry and catalysis.
1.45–15.1 N m , resonant frequencies between 87 and
To the best of our knowledge, there has been no pre-
vious study of the synthesis of 1,2,4-oxadiazoles from
aldehydes in the presence of heterogeneous catalyst. As
part of our continuing investigation of the preparation,
characterization and application of nanocatalysts,
herein we report the preparation and characterization
of MnO2 nanoparticles supported on GO sheets
230 kHz and a tip curvature radius of 6 nm. The chemical
composition of products was investigated using X-ray
photoelectron spectroscopy (XPS) with a fully automated
K-Alpha spectrometer (Thermo-Scientific). Flame atomic
absorption spectrophotometry (AAS; Varian Spectra AA
220 FS) was used for the determination of the level of
metal ions. All pH measurements were done with a Met-
rohm pH meter (model 780) equipped with a combined
[
45,46]
(
MnO @GO). The catalytic performance of the new
2
+
material was studied in the synthesis of 3,5-disubstituted
,2,4-oxadiazole derivatives from the reaction of
amidoximes with aldehydes.
glass electrode. An M–UV–3 Zolalan (Iran) water purifi-
cation system was utilized to produce deionized water.
1
2
2
.3 | Methods
2
2
| EXPERIMENTAL
.1 | Materials
.3.1 | Preparation of MnO @GO
2
nanocatalyst
The chemicals and solvents were purchased from com-
mercial suppliers and used without further purification.
GO was prepared by acid oxidation according to a modi-
[
47]
fied Hummers method.
A mixture of graphite powder

SAADATI ET AL.
3 of 11
(
(
1.5 g) and sodium nitrate (1.5 g) in sulfuric acid
70 ml) was stirred in an ice bath for 20 min. After that,
3 | RESULTS AND DISCUSSION
potassium permanganate (9 g) was introduced into the
mixture and the temperature was kept at 40 C and
stirred for 30 min. To this solution, 100 ml of deionized
water was gradually added. The exothermic reaction
GO as solid support was easily prepared through
ꢀ
oxidation of graphite with acid–KMnO via a modified
4
[
47,48]
Hummers method.
The resulting functionalized GO
was then used to support MnO2 nanoparticles which
were easily prepared in the presence of KMnO4 and
ethanol (Scheme 1). The application of the functionalized
resulted in an increase of the solution temperature to
ꢀ
9
8 C. At this stage deionized water (300 ml) and H O
2
2
7
+
(
10 ml) were slowly added to the reaction mixture.
Afterwards the resulting solid material was washed with
00 ml of diluted hydrochloric acid (0.1 M). The mix-
GO plays a significant role in the reduction of Mn to
4+
Mn by the presence of carbon atoms and anchoring
KMnO and then MnO onto GO sheets due to their
1
4
2
ture was centrifuged and the supernatant was decanted
away. The remaining mixture was then washed succes-
sively with water until the pH value of the solution was
high hydrophilicity.
It is also interesting to note that the strong interac-
tions of GO through its functional groups with MnO2
nanoparticles may prevent the agglomeration and produc
a more durable and robust heterogeneous catalyst.
4
. Finally, the prepared GO was centrifuged and dried
under vacuum.
The resultant GO (0.3 g) was dispersed in ethanol
8 ml) and deionized water (5 ml) by sonicating for
Manganese loading on the MnO @GO was deter-
mined using AAS analysis to be 0.28 mmol g .
2
−
1
(
2
h. An aqueous solution of potassium permanganate
The FT-IR spectra of the GO and MnO @GO
2
(
0.032 g in 2 ml) was added dropwise. The mixed solu-
nanocomposite were investigated in order to get
detailed information about the chemical functional
moieties present in the material (Figure 1). Figure 1a
shows the FT-IR spectrum of the prepared GO. All
characteristic peaks at approximately 3400, 1733, 1600,
ꢀ
tion was then stirred at 35 C for 6 h. Finally, the mix-
ture was centrifuged, washed with water and ethanol
to remove the remaining residual and dried in an oven
ꢀ
at 60 C.
2
3
.3.2 | General procedure for synthesis of
,5-disubstituted 1,2,4-oxadiazoles
MnO @GO (0.14 g,
4
mol%) was dispersed in
2
1
,4-dioxane (1.5 ml) for 10 min. Amidoxime (1 mmol)
and aldehyde (1.5 mmol) were added and the reaction
mixture was refluxed for 24 h. The reaction progress was
monitored by TLC. After the reaction was finished, the
mixture was washed with methanol (4 × 2 ml) and
centrifuged. The combined organic extracts were dried
over MgSO , and concentrated in vacuo, and the
4
corresponding product was afforded by column chroma-
tography on silica gel 60 (n-hexane–ethyl acetate) in high
1
yield. The characterization data resulting from H NMR
13
and C NMR spectroscopy and elemental analyses are
provided in Data S1.
2
FIGURE 1 FT-IR spectra of (a) GO and (b) MnO @GO
2
SCHEME 1 MnO @GO preparation procedure

4
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SAADATI ET AL.
240 and 1025 cm− can be assigned to OH, C=O,
1
desorption of chemisorbed and physisorbed water and
1
C=C, carbonyl C=O and epoxy C=O, respectively. The
peaks at 2920 and 2850 cm are due to the vibrations
organic solvents.
115–310 C (27.13%) corresponded to the release of CO,
A
large weight loss at around
−
1
ꢀ
of =CH3 and =CH , respectively. Comparison of the
CO and steam due to the decomposition of the oxygen
2
2
FT-IR spectra shows that all the bands of GO
functional groups of the GO layers. The next mass loss
occurred at around 310–570 C with a weight loss of
18.94%, presumably due to the combustion of the carbon
ꢀ
remained in the MnO @GO spectrum (Figure 1b). The
2
−
1
absorption band at about 560 cm is attributed to the
Mn=O stretching vibration while that at 1220 cm is
attributed to the stretching of hydrated MnO2.
−
1
skeleton of the nanocomposite. The last weight loss,
[49]
ꢀ
occurring at about 570 C, is due to the release of lattice
[36]
Raman spectra of GO and MnO @GO were recorded
oxygen from the decomposition of MnO into Mn O .
2 2 3
2
(
Figure 2). As can be seen, there are no significant differ-
The gradual weight loss during the analysis confirms the
thermal stability of the prepared nanocatalyst.
ences between them. Both spectra present D and G peaks
centered at ca 1343 and ca 1590 cm , respectively, a
broad 2D peak at around 2670 cm and a second-order
band centered at ca 2850 cm .
TGA and differential thermoanalysis (DTA) were
applied for investigation of the thermal behavior of the
−
1
The DSC technique was applied for the investigation
of the thermal behavior of the prepared nanocomposite.
The DSC profile reveals two exothermic events at around
−1
−
1 [50]
ꢀ
209 and 401 C with caloric value of −608 and
−114.2 J g− for MnO @GO (Figure 4).
1
2
prepared MnO @GO nanocomposite. The TGA curve of
Figure 5 shows the XRD patterns of GO and
2
ꢀ
sample can be mainly divided into four consecutive
MnO @GO. The diffraction peak at 2θ of around 12.25
2
ꢀ
weight losses between 25 and 800 C (Figure 3). The first
can be ascribed to the (001) plane of GO nanosheets. On
the basis of this peak, the interlayer spacing is larger than
ꢀ
weight loss, about 10.49% below 115 C, is attributed to
2
FIGURE 2 Raman spectra of (a) GO and (b) MnO @GO
2
FIGURE 4 DSC analysis of MnO @GO
FIGURE 3 Thermogravimetric diagram of MnO
2
@GO
2
FIGURE 5 XRD patterns of (a) GO and (b) MnO @GO

SAADATI ET AL.
5 of 11
in graphite due to the introduction of oxygen-containing
functional groups on the graphite sheets. The XRD pat-
multilayer structure of the support. The results also
reveal that MnO nanospheres are densely dispersed on
2
tern of the MnO @GO is similar to that observed for
pure GO.
the surface of GO sheets owing to chemical interac-
tions (Figure 7b).
2
Furthermore, from the EDX data (Figure 6), C, O and
The detailed elemental composition of the as-
Mn are the main elements of MnO @GO. Apparently, C
prepared MnO @GO nanocomposite was probed using
2
2
was the most abundant constituent in the composite
which comes from the support backbone. The EDX
XPS and the corresponding results are presented in
Figure 8. According to the Mn 2p spectrum, two strong
peaks of Mn 2p3/2 and Mn 2p1/2 were centered at 642.38
results indicated that MnO had been successfully incor-
2
[
51]
porated in the nanocomposite.
FE-SEM analysis was employed to visualize the
morphology of the nanocatalyst (Figure 7). The FE-
and 653.58 eV, respectively (Figure 8a).
This result
7+
4+
implies that Mn was successfully reduced to Mn on
the surface of the GO. XPS analysis further confirmed the
presence of carbon and functional groups in GO by show-
ing the peaks related to C 1s at 284.68, 285.68, 287.58 and
SEM images of GO and MnO @GO with wrinkles and
2
folds clearly indicated a two-dimensional planar and
2
FIGURE 6 EDX analysis of MnO @GO
2
FIGURE 7 FE-SEM images (a) GO and (b) MnO @GO

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SAADATI ET AL.
2
89.28 eV corresponding to C=C/C=C, C=O, C=O and
A histogram of particle size distribution obtained
[52]
O=C=O, respectively (Figure 8b).
from AFM measurements for MnO particles is shown
2
Surface topography was observed for nanoparticles on
the GO surface using AFM. Figure 9 shows the two- and
three-dimensional AFM images of nanocomposite disper-
sion in water after deposition on a freshly cleaved mica
in Figure 10. Statistical analysis confirmed an average
diameter of 24 nm.
To further understand the catalytic performance of
the MnO @GO nanocatalyst, a comprehensive study of
2
surface. The AFM image reveals that the MnO particles
are spherical as deposited on the GO sheets.
the synthesis of 1,2,4-oxadiazoles from aldehydes was
carried out. In order to determine the optimal reaction
2
2
FIGURE 8 XPS spectra of MnO @GO: (a) full range and (b) Mn 2p and (c) C 1s regions
2
FIGURE 9 Two- and three-dimensional AFM images of MnO @GO composite

SAADATI ET AL.
7 of 11
conditions, the coupling of benzaldehyde with
benzamidoxime was investigated as a model reaction in
the presence of the nanocatalyst (Table 1). In this reac-
tion, various amounts of catalyst were surveyed and it
other than 1,4-dioxane, such as CHCl , CH CN, water,
ethanol and toluene. Moderate yields were obtained
when the reaction was performed in ethanol and acetoni-
3
3
trile, and no product was generated in CHCl , water and
3
was found that lower amounts of MnO decreased the
toluene under the same reaction conditions (Table 1,
2
reaction yield (Table 1, entries 1–3). To further determine
the solvent effect, the reaction was carried out in solvents
entries 3–8). Also, it was found that increasing the reac-
tion temperature to 95 C improved the reaction efficiency
ꢀ
FIGURE 10 Particle size distribution
histogram for MnO @GO
2
a
TABLE 1 Screening of various parameters for reaction of benzamidoxime and benzaldehyde
ꢀ
b
Entry
Catalyst (mol %)
Solvent
Temp. ( C)
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
9
2
3
4
4
4
4
4
4
4
4
4
4
4
-
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
95
95
95
60
100
100
78
80
80
50
30
95
95
95
24
24
24
24
24
24
24
24
24
24
24
12
6
28
75
80
—
—
—
25
55
45
15
5
CHCl
3
2
H O
Toluene
EtOH
3
CH CN
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1
1
1
1
1
0
1
2
3
4
40
24
20
24
a
Reaction conditions: benzamidoxime (1 mmol), benzaldehyde (1.5 mmol), catalyst (X mol%) and solvent (1.5 ml).
Isolated yield.
b

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SAADATI ET AL.
a
2
TABLE 2 Synthesis of 1,2,4-oxadiazoles by reaction of aldehydes with amidoximes in the presence of MnO @GO nanocatalyst
3
3
a (80%)
3b (83%)
3c (60%)
d (50%)
3e (45%)
3f (60%)
3
g (50%)
3h (52%)
3i (45%)
3
j (40%)
3k (85%)
3l (80%)
3
3
m (85%)
3n (45%)
3o (80%)
p (70%)
3q (60%)
a
Reaction conditions: amidoxime (1.0 mmol), aldehyde (1.5 mmol), catalyst (4 mol%) and solvent (1.5 ml).

SAADATI ET AL.
9 of 11
SCHEME 2 Proposed mechanism
for formation of 1,2,4-oxadiazoles using
2
MnO @GO nanocatalyst
(Table 1, entries 9–11). Also, it was found that only
2
6
4 and 40% of the desired product was obtained after
and 12 h (Table 1, entries 12 and 13).
Having established the optimal reaction conditions,
the scope and limitations of the reaction were next exam-
ined in the presence of 4 mol% nanocatalyst in
1
,4-dioxane for various types of amidoximes and alde-
ꢀ
hydes at 95 C (Table 2).
In this survey, aromatic aldehydes with electron-
donating groups reacted very quickly, while in the case of
using aldehydes with electron-withdrawing groups, the
reactivity decreased and longer reaction times were
required (Table 2). It is important to mention that steri-
cally congested ortho-substituted benzaldehyde gave the
corresponding product in moderate yield (Table 2, 3e).
To broaden the utility of the nanocatalyst the reaction
was investigated with heteroaromatic aldehydes and ami-
doxime and the results showed that they reacted success-
fully to furnish the corresponding oxadiazoles (Table 2,
2
FIGURE 11 Recycling experiment of MnO @GO
recycled catalyst was determined from AAS analysis of
the supernatant. In this regard, no significant leaching of
manganese occurred during the reaction, indicating that
the catalyst worked in a heterogeneous manner.
3
n–p). Furthermore, to extend the scope of the reaction,
various aliphatic and aromatic amidoximes were used,
Therefore the recoverability and reusability of
showing a good tolerance (Table 2, 3i–m and 3q). The
MnO @GO was investigated in the reaction of
2
results strongly confirm the capability of the MnO @GO
benzamidoxime and benzaldehyde. After each reaction,
the catalyst was separated from the reaction mixture by
centrifugation and then was washed with methanol to
remove organic materials and subsequently dried at
2
nanocatalyst in cyclization of a broad range of aldehydes
with both aromatic and aliphatic amidoxime substrates.
The probable reaction mechanism for the synthesis
of 1,2,4-oxadiazoles catalyzed by GO-supported MnO2
nanoparticles under heterogeneous conditions is shown
in Scheme 2. The reaction presumably occurs through
nucleophilic addition of =OH functional group of ami-
doxime on the carbonyl function of aldehyde to form
hemiacetal I, which is protonated under the reaction
ꢀ
60 C. The recovered catalyst could be reused directly in
further reactions. It was shown that the recovery can be
effectively achieved for more than seven reaction runs
without significant loss in product yields (Figure 11).
[53]
conditions (II).
Then, intramolecular nucleophilic
4 | CONCLUSIONS
attack of the amino group to the protonated hemiace-
tal moiety provides 4,5-dihydro-1,2,4-oxadiazole (III).
A new manganese-based nanocomposite catalyst of
MnO2 nanoparticles on GO sheets was prepared and
completely characterized. The developed material
appears to be an efficient heterogeneous catalyst in the
synthesis of 1,2,4-oxadiazoles from the reaction of
3
,5-Disubstituted 1,2,4-oxadiazole is obtained by oxida-
tion of cyclic intermediate III.
Further, the leaching of manganese oxide from the
catalyst was analyzed. The amount of manganese in the

10 of 11
SAADATI ET AL.
amidoximes with aldehydes via cyclization and oxidation
process with broad scope of the substrates. Most impor-
tantly, the catalyst could be easily recycled and reused
without significant loss of catalytic activity. The easy
recovery, excellent performance and negligible leaching
of metal species (none detected using AAS) mean that
this protocol fulfills the criteria established for green
catalysis. Such a suitable catalytic efficiency could be
attributed to the high surface area, uniform distribution
and favorable accessibility of the active sites in the pre-
pared nanocatalyst.
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ACKNOWLEDGEMENTS
The authors are grateful to the Research Council of Uni-
versity of Zanjan, Institute for Advanced Studies in Basic
Sciences (IASBS), the University of British Columbia, the
University of Alicante (VIGROB-173) and the Spanish
Ministerio de Economía, Industria y Competitividad
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