Application of the Fe3O4@1,10-phenanthroline-5,6-diol@Mn nano-catalyst for the green synthesis of tetrazoles and its biological performance

Article abstract of DOI:10.1002/aoc.4005

The Fe₃O₄ magnetic particles were modified with 1,10-phenanthroline-5,6-diol (Phen) and the related Mn complex (Fe₃O₄@Phen@Mn) synthesized as a heterogeneous catalyst to be used for the one-pot three-component synthesis of various tetrazoles. The catalysts were characterized by several methods, such as the elemental analysis, FT-IR, X-ray powder diffraction, dispersive X-ray spectroscopy, scanning electron microscopy, transmission electron microscopy, dynamic light scattering, thermogravimetric-differential thermal analysis, vibrating sample magnetometer and X-ray photoelectron spectroscopy. In addition, the antioxidant and antibacterial activities of the catalyst and its Phen ligand were in vitro screened with 2,2-diphenyl-1-picrylhydrazyl by free radical scavenging methods. Results showed that the synthesized compounds possess strong antioxidant activity (IC50; 0.172 ± 0.005 mg ml^?1) as well as a good antibacterial potential in comparison to standards.

Full text of DOI:10.1002/aoc.4005

Received: 27 May 2017
DOI: 10.1002/aoc.4005
Revised: 30 June 2017
Accepted: 1 July 2017
F U L L P A P E R
Application of the Fe O @1,10‐phenanthroline‐5,6‐diol@Mn
3
4
nano‐catalyst for the green synthesis of tetrazoles and its
biological performance
1
1
2
1
Davood Habibi
| Somayyeh Heydari | Antonio Gil
| Mina Afsharfarnia |
3
4
4
Alireza Faraji | Roya Karamian | Mostafa Asadbegy
1
Department of Organic Chemistry,
Abstract
Faculty of Chemistry, Bu‐Ali Sina
University, Hamedan 6517838683, Iran
The Fe
O magnetic particles were modified with 1,10‐phenanthroline‐5,6‐diol
3 4
2
Department of Applied Chemistry, Public
(Phen) and the related Mn complex (Fe O @Phen@Mn) synthesized as a het-
3
4
University of Navarra, Building Los
Acebos, Campus of Arrosadia, E‐31006
Pamplona, Spain
erogeneous catalyst to be used for the one‐pot three‐component synthesis of
various tetrazoles. The catalysts were characterized by several methods, such
as the elemental analysis, FT‐IR, X‐ray powder diffraction, dispersive X‐ray
spectroscopy, scanning electron microscopy, transmission electron microscopy,
dynamic light scattering, thermogravimetric‐differential thermal analysis,
vibrating sample magnetometer and X‐ray photoelectron spectroscopy. In addi-
tion, the antioxidant and antibacterial activities of the catalyst and its Phen
ligand were in vitro screened with 2,2‐diphenyl‐1‐picrylhydrazyl by free radical
scavenging methods. Results showed that the synthesized compounds possess
3
Young Researchers & Elite Club,
Pharmaceutical Sciences Branch, Islamic
Azad University, Tehran, Iran
4
Department of Biology, Faculty of
Sciences, Bu‐Ali Sina University,
Hamedan 6517838683, Iran
Correspondence
Davood Habibi, Department of Organic
Chemistry, Faculty of Chemistry, Bu‐Ali
Sina University, Hamedan, 6517838683
Iran.
−
1
strong antioxidant activity (IC50; 0.172 ± 0.005 mg ml ) as well as a good
antibacterial potential in comparison to standards.
Email: davood.habibi@gmail.com
KEYWORDS
Antonio Gil, Department of Applied
Chemistry, Public University of Navarra,
Building Los Acebos, Campus of
Arrosadia, E‐31006 Pamplona, Spain.
Email: andoni@unavarra.es
1
3 4
,10‐phenanthroline‐5,6‐diol, biological performance, catalyst, Fe O magnetic particle, tetrazoles
1
| INTRODUCTION
Several catalysts have been reported for the prepara-
[
5]
tion of tetrazoles, including FeCl –SiO , montmorillon-
3
2
[8]
[
6]
[7]
Since the early 1980s, tetrazoles have been of great interest
ite K‐10, TiO2, natrolite zeolite, and recently the
salen complex of Cu(II) supported on super‐paramagnetic
[1]
because of their therapeutic applications. The tetrazole
moiety is present in compounds possessing pharmacologi-
cal properties, such as antihypertensive, anti‐allergic and
antibiotic activity. In addition, they also have widespread
use in coordination chemistry, imaging technology, agri-
culture and manufacturing of explosive materials. There-
fore, extensive efforts have been made to introduce
convenient and efficient routes for the synthesis of
tetrazoles in organic and pharmaceutical communities.
[
9,10]
Fe O @SiO nano‐particles.
The use of magnetic
3
4
2
nanoparticle catalysts has had significant growth during
[2]
the past decade, as nanoparticles have a large surface‐to‐
[3]
[11–13]
volume ratio compared with bulk materials.
Also,
[4]
the use of nano‐catalysts is in accord with the principles
of green chemistry due to their minimum chemical
wastes, energy efficiency and improved economy. Among
the various magnetic nanoparticles, Fe O is the most
3
4
Appl Organometal Chem. 2017;e4005.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4005

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HABIBI ET AL.
widely used magnetic substance for catalyst support, and
[14]
is less toxic than metallic counterparts.
Reactive oxygen or nitrogen species are formed natu-
rally in living cells, and have important roles in cell sig-
naling. However, high amounts of these compounds are
hazardous to the cells and can damage all major compo-
nents, including nucleic acids, polypeptide chains and
lipids in cell membranes that play an important role in
the development of diseases such as cancer and other dis-
SCHEME 1 Synthesis of tetrazole derivatives
diffraction, dispersive X‐ray spectroscopy, scanning elec-
tron microscopy, transmission electron microscopy,
dynamic light scattering, thermogravimetric‐differential
thermal analysis, vibrating sample magnetometer and X‐
ray photoelectron spectroscopy (Supporting Information).
[15,16]
orders.
Antioxidants may act as free radical scaven-
gers, reducing agents, quenching agents and/or
activators of cellular antioxidant enzymes to prevent free
3.3 | Optimization of the catalyst
[17,18]
radical damage in biological systems.
Also, most of
the bacteria and fungi showed resistance to classical anti-
The next aim of this study was to optimize the conditions
of tetrazole synthesis. Therefore, the catalytic perfor-
mance was investigated in one‐pot three‐component syn-
thesis of 1‐phenyl‐1H‐tetrazole as a model substrate under
several reaction conditions (temperature, amount of the
catalyst and solvent nature).
[19–22]
biotics,
is a matter of urgency.
and the discovery of new active compounds
[23,24]
Herein, we would like to report the application of the
Fe O @Phen@Mn nano‐catalyst in the one‐pot three‐
3
4
component synthesis of various tetrazoles in solvent‐free
conditions at 100 °C (Scheme 1).
3
.4 | The effect of temperature
2
2
| EXPERIMENTAL
The effect of the reaction temperature is summarized in
Table 1 [aniline: 2 mmol; NaN : 2 mmol; HC(OEt) : 2
3
3
.1 | Typical procedure for preparation of
mmol] and is solvent free. The yield is about 27% at room
temperature, despite the fact that the mixture was stirred
for the prolonged reaction time (Entry 1). As the reaction
temperature was increased to 50 °C, the yield also
increased, and when the temperature was raised to
100 °C, an outstanding yield was obtained (Entry 5).
the 1‐substituted‐1H‐tetrazoles (Scheme 1)
A mixture of amine (2 mmol), sodium azide (0.13 g, 2
mmol), triethyl orthoformate (0.296 g, 2 mmol) and the
Fe O @Phen@Mn nano‐catalyst (50 mg) was stirred at
3
4
1
00 °C until the thin‐layer chromatographic monitoring
showed no further progress in the conversion. When the
reaction mixture came to room temperature, the catalyst
was separated by strong magnet, the mixture poured over
ice, and the organic layer extracted with ethyl acetate
3
.5 | The effect of amount of catalyst
To investigate the effect of the catalyst, systematic studies
were carried out in the presence of several different
amounts of catalyst (Table 1). First, a control experiment
was performed in the absence of the Fe O @Phen@Mn
(2 × 20 ml). The resulting solution was then dried over
anhydrous MgSO , the solid filtered, and the solvent con-
4
centrated and recrystallized from the EtOAc/hexane mix-
ture (1:10).
3
4
TABLE 1 Effects of the amount of catalyst and temperatures on
the synthesis of 1‐phenyl‐1H‐tetrazoles
3
| RESULTS AND DISCUSSION
Amount of Mn catalyst
Entry (mg)
T
Time
Yield
(%)
(°C) (min)
3.1 | Synthesis of the Fe O @Phen@Mn
3
4
1
2
3
4
5
6
7
8
9
70
RT
120
120
120
120
40
27
catalyst
70
50
54
The synthesis of the catalyst was carried out via the four
stages that were described in the Experimental section
No catalyst
100
100
100
110
110
100
110
Trace
71
40
50
50
30
60
60
(Scheme SI1).
92
60
92
3.2 | Characterization of the
60
35
Fe O @Phen@Mn catalyst
3
4
60
92
The formation of the catalyst was verified by chemical
analysis, inductively coupled plasma, FT‐IR, X‐ray
60
92

HABIBI ET AL.
3 of 8
catalyst to indicate the crucial role of the catalyst (Entry
molecules are competing to occupy the metal active sites
in the Mn catalyst.
3
). Hence, the catalyst was removed from the solution,
and the extra substrate added to the filtrate where no
more tetrazole was produced under the same conditions.
Second, several different amounts of the catalyst were
used, and the best yield was obtained with 50 mg of cata-
lyst. However, a higher amount of catalyst (60 mg) did not
improve the result appreciably (Entries 8, 9).
3
.7 | Characterization of the tetrazole
compounds
All known compounds were characterized by comparing
their physical and spectral data with those reported in
the literature. The structures of the 1H–substituted
tetrazoles were in agreement with their IR and NMR spec-
tra. In the IR spectra of the 1‐H substituted tetrazoles, the
Based on the above observation, it is possible to con-
clude that the catalyst could be an effective catalytic sys-
tem for the synthesis of tetrazoles. To show the
importance of the Phen ligand as a good linker, as well
as to prove whether or not Mn(II) was coordinated to
the Phen ligand or to the OH groups on the surface of
Fe O , some Mn ions from Mn(OAc) were added to the
NH peaks disappeared and one strong absorption band
2
−
1
was detected (C‐N stretching band, ~1640–1690 cm ).
The 1H–substituted tetrazoles are generally acidic sub-
stances and the relevant proton signal will be shifted
downfield, so the peak at δ = 7.80–8.30 ppm can be
attributed to the proton of the tetrazole ring.
3
4
2
blank Fe O and the reaction carried out under the same
3
4
conditions, where the yield of the tetrazole was almost at
trace levels.
3.8 | Synthesis of the tetrazole derivatives
Several tetrazole derivatives were synthesized from the
reaction of various aromatic amines, triethyl
orthoformate and sodium azide by using the
Fe O @Phen@Mn nano‐catalyst [aniline: 2 mmol;
3
.6 | The effect of solvent
In order to study the effect of solvents on the reaction, var-
ious solvents, such as water (H O), benzene (BZ),
2
3 4
dimethyl sulfoxide (DMSO), acetonitrile (ACN), ethanol
NaN : 2 mmol; HC(OEt) : 2 mmol; T = 100 °C; sol-
3 3
(
EtOH) and dimethyl‐formamide (DMF) were examined
vent free]. In order to expand the range of various sub-
strates, the aryl amines with electron‐withdrawing or
electron‐releasing groups were examined as well to
undergo successful one‐pot three‐component reactions
for the synthesis of the 1‐substituted 1H–tetrazoles
under solvent‐free conditions (Table 3).
at 100 °C (Table 2). The reaction in the presence of a coor-
dinating solvent, for example, EtOH had low conversion,
while with H O no reaction was observed even when
the reaction time was prolonged to 5 h. This observation
confirmed that the donor electron solvents had more abil-
ity to occupy the vacant spaces around the existing Mn in
the catalyst, to prevent coordination of sodium azide mol-
ecules. The yield percentage decreased in the following
order using different solvents: 84.0% (DMF) > 65.0%
2
Electron‐releasing groups, such as OCH and CH
3
3
(Entries 3 and 8), will accelerate the reaction rate, so the
reaction will take place in shorter reaction times, while
electron‐withdrawing groups, such as Cl, NO , COCH
2
3
(DMSO) > 45.0% (BZ) > 38.0% (ACN) > 23.0% (EtOH)
and CF (Entries 5–7, 9 and 10), will require longer times
3
>
0.0% (H O). Further investigations showed that cata-
for the reactions to be carried out. The bromine group
(Entry 2) is not a good electron‐withdrawing group, so
its resonance electron releasing will dominate its electron
2
lytic activity is much better in solvent‐free conditions
92.0%) compared with those reactions taking place in sol-
(
vents. These results indicated that the NaN and solvent
withdrawing. The presence of the two CH groups (Entry
3
3
4) will slow the reaction rate due to their steric hin-
TABLE 2 Effect of various solvents on the synthesis of 1‐phenyl‐
drances. Consequently, in comparison with aniline, nei-
ther electron‐releasing nor electron‐withdrawing groups
have positive effects on accelerating reaction rates, appar-
ently due to steric hindrances.
1H‐tetrazoles
Entry
Solvent
Yield %
1
H
2
O
0.0
2
3
4
5
6
7
EtOH
CH CN
23
38
45
65
84
92
3
.9 | Comparison of the catalytic
3
performances of various catalysts
Benzene
DMSO
A number of synthetic methods have been reported in
recent years for the preparation of 1H–substituted
tetrazoles (Scheme 2 and Table 4, equations 1–5). The
applied method (equation 6) compared with those methods
DMF
Solvent‐free

4
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HABIBI ET AL.
TABLE 3 Preparation of the 1‐substituted 1H–tetrazoles by using the Mn catalyst
[8]
Entry
Substrate
Product
Time (min)
Yield (%)
Mp, found (Lit.) (°C)
1
40
92
63–66 (64–65)
2
3
4
55
60
85
90
93
82
176–180 (183–185)
113–115 (114–115)
132–134 (133–135)
5
6
75
80
86
84
156–158 (157–158)
127–131 (127–131)
7
8
9
70
50
80
85
92
94
88
85
199–203 (201–202)
93–95 (94–95)
174–177 (177)
1
0
124–128 (125–127)
reported in the literature to show its advantages. The disad-
vantages of methods 1–5 are summarized in Table 4.
3.10 | The plausible mechanism
The plausible mechanism for the synthesis of different 1‐
substituted 1H–tetrazoles from the reaction of aromatic
amine, sodium azide and triethyl orthoformate in the
presence of Mn nano‐catalyst under solvent‐free condi-
tions is shown in Scheme 3. The proposed mechanism is
probably due to the Lewis acidity of the Mn catalyst,
which can catalyze the transformation by dissociation of
triethyl orthoformate and easy formation of the interme-
diate to do the cyclization reaction to produce the final
product.
3.11 | The catalyst reusability
Recovery and reusability of the catalyst are important
because of the environmental and economical aspects,
so the reusability of the Fe O @Phen@Mn catalyst was
3
4
SCHEME 2 Different methods for the syntheses of tetrazoles
also investigated [reaction conditions: aniline: 2 mmol;

HABIBI ET AL.
5 of 8
TABLE 4 Comparison of the catalytic performances of various catalysts
Equation Disadvantages
Ref.
[
25]
1
Application of a large excess of hydrazoic acid (highly toxic, explosive and volatile), low yield, long reaction times (24 h),
harsh reaction conditions and the use of sulfuric acid, which is toxic, extremely corrosive, and cannot be easily
recovered and recycled.
[
26]
2
In situ formation of hydrazoic acid (highly toxic, explosive and volatile), use of hydrochloric acid (toxic, corrosive and
homogeneous reagent that cannot be easily recovered and reused) and application of organic solvents. Trimethylsilyl
azide is a highly flammable substance and incompatible with the presence of moisture, strong oxidizing agents and
strong acids. It is toxic by inhalation, in contact with eye, skin and if swallowed or when it is exposed to water. Also,
isocyanides are toxic and very reactive with any materials containing active hydrogens, such as water, alcohol, amines,
bases and acids. Therefore, working with these materials is very hard. In addition, a byproduct of this reaction is
3
trimethylsilane (Me SiH), which is a toxic and flammable substance and may cause flash fire and target organ damage.
[
27]
3
In situ formation of hydrazoic acid (highly toxic, explosive and volatile) and application of a large excess of glacial acetic
acid, which is corrosive, and cannot be easily recovered and reused.
[
[
28]
27]
4
5
Application of a volatile organic solvent (CH
3 2 4
OC H OH).
Application of a high boiling point organic solvent (DMSO), which needs a complicated isolation procedure.
NaN : 2 mmol; HC(OEt) : 2 mmol; solvent free]. There-
according to the following formula: DPPH free radical
3
3
fore, the catalyst was separated by filtration after the first
run, washed with ethanol and dried at 120 °C under vac-
uum, and then used for the next successive runs under the
same conditions (Figure 1). No significant loss of activity
was observed, indicating that the applied catalyst is capa-
ble and has high stability during the one‐pot synthesis of
scavenging (%) = [1 – (A – A )/A ] × 100, where, A
is absorbance of the reaction mixture containing 2.5 ml
s
b
c
s
of samples + 1 ml of DPPH, A is absorbance of the reac-
b
tion mixture containing 2.5 ml of samples + 1 ml of
methanol, and A is absorbance of the control sample con-
c
taining 1 ml of DPPH + 2.5 ml of methanol. Also, the
IC50 value, which represents the concentration of the
sample causing 50% inhibition, was determined. Tests
were carried out in triplicate, and ascorbic acid was used
as a positive control.
1‐substituted 1H–tetrazoles.
4
4
| BIOLOGICAL PERFORMANCE
.1 | Antioxidant performance
4
.2 | Antibacterial performance
Free radical scavenging activity of the compounds was
[29]
evaluated according to Mensor et al.
In order to obtain
The potential antibacterial effects of the complexes were
evaluated against a panel of microorganisms, including
two Gram‐positive [namely Bacillus cereus (PTCC
1247) and Staphylococcus aureus (ATCC 25923)] and
two Gram‐negative bacteria [namely Escherichia coli
(ATCC 35218) and Pseudomonas aeruginosa (ATCC
dilutions, different concentrations of samples were pre-
−
1
pared in methanol (0.2–1.0 mg ml ), and 2.5 ml of each
concentration was added to 1.0 ml of alcohol solution of
2
,2‐diphenyl‐1‐picrylhydrazyl (DPPH; 0.3 mmol). The
samples were first kept in darkness at room temperature
for 30 min, and then bleaching of DPPH was read at
[
30]
27853)].
Stock cultures were maintained on nutrient
5
17 nm against a blank (methanol). The inhibition as a
agar media at 40 °C, then subcultured in nutrient Broth
media at 37 °C prior to each antibacterial test. The
percentage for each concentration was calculated
SCHEME 3 Proposed mechanism for
preparation of tetrazoles by the Mn nano‐
catalyst

6
of 8
HABIBI ET AL.
4.4 | Antibacterial activity
It is well known that S. aureus (+), E. coli (−) and Bacillus
[
31,32]
species are food poisoning agents,
and results from
the antibacterial assessments of the samples, and positive
and negative controls are presented (Tables 6 and 7). The
studied compounds were dissolved in DMSO at concen-
−
1
trations of 0.01, 0.1 and 1.0 mg ml . Because DMSO
was used as a solvent, it was also screened as a negative
control against all bacteria in this study and no activity
was found. In this research, assessment of the compound
antibacterial properties showed the acceptable concentra-
tion‐dependent inhibition effect in comparison with some
of the positive controls. Old studies generally showed that
the biological activity of compound is mainly attributed to
its major components, and also the synergistic or antago-
nistic effect of components in a minor percentage of the
3 4
FIGURE 1 Reusability of the Fe O @Phen@Mn catalyst in the
synthesis of tetrazoles
[
33]
reaction mixture.
Among the bacterial species taken
in this study, E. coli (−) showed more resistance against
all the compounds. When comparing the antibacterial
activity of the studied samples, especially the Mn complex
to those of the reference antibiotics, the inhibitory ability
of some of the compounds was found to be good. For
example, while all the tested bacteria are resistant to
complexes were dissolved in DMSO to a final concentra-
tion of 1 mg ml , and then sterilized by filtration using
−
1
0
.45‐μm Millipore. Negative controls were prepared by
using DMSO and salts, and penicillin and gentamicin
used as positive reference standards. The diameters of
the generated inhibition zones by the complexes were
measured as well.
4.3 | Antioxidant capacity
Our results showed that the synthesized compounds
−
1
showed excellent dose‐dependent (0.2–1 mg ml ) anti-
radical properties (43.22–77.31%; Table 5).
In all antioxidant assays, more activity is reflected in a
lower IC50 value. Vitamin C (ascorbic acid) as a synthetic
antioxidant represented the IC50 value that was lower
than all the compounds studied here. The effectiveness
of the compounds as DPPH radical scavengers ranged in
the following descending order: ascorbic acid (0.124 ±
FIGURE 2 Comparison of the DPPH radical scavenging ability
(
IC50 value) of the studied compounds [the Mn complex (C1) and
−
1
−1
0
.004 mg ml ) > C1 (0.172 ± 0.005 mg ml ) > C2
the 1,10‐phenanthroline‐5,6‐diol (Phen) ligand (C2)] and ascorbic
acid (as a positive control)
−
1
(0.570 ± 0.010 mg ml ; Figure 2).
TABLE 5 Free radical scavenging activity (%) of the C1 and C2 compounds at several concentrations and standards
−1
Concentration (mg ml
)
Compound
C1
0.2
0.4
0.6
0.8
1
Average
70.14
a
b
a
a
c
b
a
c
b
a
c
c
a
58.05 ± 1.5
69.13 ± 1.0
47.18 ± 2.9
82.16 ± 1.0
75.10 ± 2.1
52.63 ± 2.1
81.85 ± 1.4
71.12 ± 1.1
51.13 ± 0.9
80.31 ± 1.1
77.31 ± 2.2
66.28 ± 2.3
79.14 ± 1.6
a
C2
43.22 ± 0.5
52.10
a
Ascorbic acid
80.74 ± 2.7
80.84
The experiment was performed in triplicate and values expressed as mean ± SD.
Values within columns with various superscripts (a–c) are significantly different (P < 0.05).

HABIBI ET AL.
7 of 8
TABLE 6 Antibacterial activities of the C1 and C2 compunds
Inhibition zone (mm)
P. aeruginosa (−)
Compound
C1
Concentration
E. coli (−)
B. cereus (+)
S. aureus (+)
−
−
−
1
1
1
a
b
c
a
a
a
1.0 (mg ml
.1 (mg ml
)
)
)
14 ± 0.15
13 ± 0.36
9 ± 0.11
8 ± 0.43
7 ± 0.23
10 ± 0.15
8 ± 0.36
9 ± 0.22
7 ± 0.64
a
b
b
0
c
0.01 (mg ml
NA
7 ± 0.11
NA
−
−
−
1
1
1
C2
1.0 (mg ml
)
)
)
7 ± 0.14
NA
NA
NA
NA
NA
7 ± 0.26
NA
NA
8 ± 0.13
NA
NA
0.1 (mg ml
0.01 (mg ml
The experiment was performed in triplicate and values expressed as mean ± SD. Values with various superscripts within each column (a–c) (for any bacteria in
various concentrations) are significantly different (P < 0.05); NA, not active.
TABLE 7 Antibacterial activity of positive and negative controls
Inhibition zone (mm)
Microorganism
Positive controls
Negative controls
Gentamicin
Penicillin
NA
Fe(OAc)
NA
2
Mn(OAc)
2
DMSO
NA
S. aureus (+)
E. coli (−)
32 ± 0.13
NA
NA
NA
NA
NA
NA
B. cereus (+)
P. aeruginosa (−)
25 ± 0.18
33 ± 0.34
NA
NA
NA
NA
NA
NA
NA
NA
The experiment was performed in triplicate and values expressed as mean ± SD. NA, not active.
penicillin, the antibacterial effect of C1 (the Mn complex)
was higher than that of penicillin on these bacteria. The
results indicate that the C1 and roughly the C2 (the
Furthermore, this catalytic system has some advan-
tages, such as simplicity of the procedure, inexpensive
raw material, commercially available and non‐toxic
reagents, and simple magnetic work‐up.
1
,10‐phenanthroline‐5,6‐diol ligand) compounds can be
used in the treatment of diseases caused by the tested
bacteria.
ACKNOWLEDGEMENT
The authors are thankful to the Bu‐Ali Sina University,
Hamedan 6517838683 Iran, for the financial support of
this work.
5
| CONCLUSIONS
In conclusion, several tetrazole derivatives were synthe-
sized by using the Fe O @Phen@Mn nano‐catalyst in dif-
ORCID
3
4
ferent stages. This catalyst was found to be efficient and
effective for the rapid synthesis of various tetrazoles in
solvent‐free conditions at 100 °C. The further research
showed high catalytic performance with efficient
recycling.
Davood Habibi http://orcid.org/0000-0002-2386-8502
Antonio Gil http://orcid.org/0000-0001-9323-5981
REFERENCES
Also, a suitable reaction condition was optimized by
considering the effect of various parameters, such as the
reaction time, the amount of catalyst and several solvents
in order to obtain the maximum conversion of substrates.
In addition, the antioxidant and antibacterial activities
of the Mn catalyst and its Phen ligand were screened with
DPPH, and the results showed that they possess strong
antioxidant activity as well as good antibacterial potential
in comparison to standards.
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How to cite this article: Habibi D, Heydari S, Gil
A, et al. Application of the Fe O @1,10‐
3
4
phenanthroline‐5,6‐diol@Mn nano‐catalyst for the
green synthesis of tetrazoles and its biological
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