Methionine-Coated Fe3O4 Nanoparticles: An Efficient and Reusable Nanomagnetic Catalyst for the Synthesis of 5-Substituted 1H-Tetrazoles

Article abstract of DOI:10.1134/S1070428020090237

Abstract: Methionine-coated Fe₃O₄ nanoparticles, a magnetically reusable and environmentally friendly heterogeneous catalyst, was synthesized. The new catalyst was characterized by FT-IR spectra, XRD, SEM, and EDX analysis and was us

Full text of DOI:10.1134/S1070428020090237

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2020, Vol. 56, No. 9, pp. 1646–1653. © Pleiades Publishing, Ltd., 2020.
Methionine-Coated Fe O Nanoparticles:
3
4
An Efficient and Reusable Nanomagnetic Catalyst
for the Synthesis of 5-Substituted 1H-Tetrazoles
a,
a
a
A. Karimian *, M. Namvar-Mhaboub , and R. Abbasi
a
Department of Chemistry, Faculty of Sciences, University of Gonabad, Gonabad, 9691957678 Iran
e-mail: a_karimian87@yahoo.com
*
Received March 26, 2020; revised April 4, 2020; accepted April 16, 2020
Abstract—Methionine-coated Fe O nanoparticles, a magnetically reusable and environmentally friendly
3
4
heterogeneous catalyst, was synthesized. The new catalyst was characterized by FT-IR spectra, XRD, SEM, and
EDX analysis and was used to catalyze the cycloaddition of nitriles and sodium azide in DMSO at 120°C to
give the corresponding 5-substituted 1H-tetrazoles. Methionine-coated Fe O nanoparticles proved to be highly
3
4
efficient for this organic reaction. The catalyst can be easily separated and reused several times without loss of
activity. The proposed procedure also offers several benefits such as quick reaction, high yields, clean process,
low-cost heterogeneous catalyst, low loading of catalyst, and simple operation.
Keywords: tetrazoles, methionine, heterogeneous catalyst, magnetically recoverable catalyst
DOI: 10.1134/S1070428020090237
INTRODUCTION
[27], Ln(OTf) /SiO [28], Zn–Cu alloy [29],
3 2
I /NaHSO /SiO [30], mesoporous ZnS nanospheres
2
4
2
Tetrazoles constitute an essential class of hetero-
cyclic compounds that have gained much interest due
to wide range of their use in medicine [1–4]. For ex-
ample, tetrazole ring is present in various biologically
active compounds such as antibiotics, antiviral (i.e.,
HIV) [5], antiplatelet [6], cardiazol [7], and “sartan”
family drugs. Heterocyclic compounds containing
a tetrazole moiety are also used in materials science
[31], COY zeolite [32], cuttlebone [33], and P O [34].
2 5
Recently, a few research teams have also used micro-
wave irradiation to shorten the reaction time [35–39].
Based on the facts mentioned above and in con-
tinuation of our research program on the synthesis of
heterogeneous catalysts and heterocyclic compounds
[
40–44], we now report the synthesis of methionine-
coated Fe O nanoparticles as a novel, efficient, and
3
4
[
8], coordination chemistry [9], and as plant growth
recyclable heterogeneous catalyst with high catalytic
activity. Furthermore, recent developments of hetero-
geneous catalysts, especially magnetic nanoparticle-
supported catalysts, have become an important line of
research in organic synthesis [40]. These magnetic
nanoparticles can be easily separated from the reaction
medium by an external magnet and repeatedly used.
regulators in agriculture [10].
Accordingly, it is important to search for efficient
methods of synthesis of 5-substituted 1H-tetrazoles.
The commonly employed method involves the [3+2]-
cycloaddition reaction between nitriles and azides.
Other routes for the synthesis of tetrazoles include the
use of thioamides, imidoyl chlorides, oximes, hetero-
cumulenes, ketones, amines, alkenes, or isocyanides as
starting materials in the presence of azide ion source
RESULTS AND DISCUSSION
[
5]. These procedures utilize numerous catalysts such
Magnetite nanoparticles were coated by methionine
residues in a one-pot aqueous reaction. The FT-IR
spectra of Fe O nanoparticles and methionine-coated
as Pd catalysts [11], CuI [12], Cu O [13], ZnO [14],
CuFe O [15], CuSO ·5H O [16], Fe(OAc) [17],
2
2
4
4
2
2
3
4
Fe O @chitin [18], Cu-MCM-41 [19], InCl [20],
magnetite Fe O nanoparticles are shown in Fig. 1. For
3
4
3
3 4
AgNO [21], FeCl /SiO [22], ZnCl [23], ZrOCl ·
Fe O nanoparticles, the characteristic Fe–O band is
3 4
observed at 580 cm . The broad band at 3358 cm
3
3
2
2
2
–
1
–1
8
H O [24], B(C H ) [25], DPPA/DBU [26], BaWO
2
6
5 3
4
1
646

METHIONINE-COATED Fe O NANOPARTICLES
1647
3
4
was attributed to OH groups [45, 46]. In the methio-
nine-coated magnetite Fe O nanoparticles, the original
3
4
bands of Fe O nanoparticles are observed. In addition,
3
4
–
1
new bands are present at around 1600 and 1390 cm ,
which correspond to C=O and C–O stretching vibra-
tions, respectively, of the amino acid residues. The
band at 2870 cm was assigned to C–H stretching
vibrations of methionine on Fe O nanoparticles [47].
2
1
–
1
3
4
–
1
It can also be seen that the band around 3400 cm
becomes more intense after functionalization due to
overlap of N–H and O–H stretching bands.
3900
3400
2900
2400
ν, cm–1
1900
1400
900
The XRD pattern of methionine-coated Fe O nano-
3
4
particles is shown in Fig. 2. The XRD data prove the
crystalline phase of Fe O , and the pattern is consistent
Fig. 1. FT-IR spectra of (1) Fe O nanoparticles and
3
4
3
4
(2) methionine-coated Fe O NPs.
3
4
with the standard magnetite pattern (JCPDS no. 89-
319) [48]. Accordingly, one can conclude that the
modification process does not affect the crystalline
structure of Fe O . Figure 3 illustrates the morphology
(311)
4
300
3
4
(440)
2
00
of functionalized Fe O nanoparticles. As can be seen,
3
4
the particle size is distributed from ~40 to 500 nm.
(
220)
(
400)
(511)
(422)
The EDS analysis was performed to probe the
elemental composition of both Fe O NPs and methio-
100
0
3
4
(622)
(
111)
(620)
70
nine-coated magnetite nanoparticles (Fig. 4). For pure
magnetite, peaks related to Fe and O can be observed
in the EDX spectra. In the case of functionalized Fe O
2
0
30
40
2
50
θ, deg
60
3
4
NPs, new peaks of C and S appeared due to methionine
residues. However, the Fe and O peaks are the main
constituents of functionalized nanoparticles. These
results confirmed the existence of methionine and
Fe O in these nanoparticles. Methionine-coated mag-
Fig. 2. XRD pattern of Met-Fe O NPs.
3
4
3
4
netite nanoparticles were very stable, and nanoparticles
did not precipitate over a long time.
Detailed bonding structure of the amino acid
residues on the Fe O surface was elucidated by
3
4
attenuated total reflectance Fourier transform infrared
spectroscopy (ATR-FTIR) and by in situ IR absorption
spectroscopy [49]. On the basis of the obtained results,
possible binding mode of the amino acid to magnetite
nanoparticles is shown in Fig. 5. The amino acid
residues are linked to the Fe O surface through the
3
4
carboxy groups.
Following our interest in the preparation of catalysts
for the synthesis of heterocycles [50], methionine-
coated Fe O nanoparticles were used as a novel
heterogeneous catalyst to produce 5-substituted 1H-tet-
razoles by reaction of aromatic nitriles with sodium
azide (Scheme 1). To optimize the conditions, the cy-
cloaddition of benzonitrile (1a) and sodium azide was
chosen as a model reaction. Table 1 shows the effect of
different factors, viz., the amount of the catalyst, sol-
vent nature, and temperature, on the yield of 5-phenyl-
Fig. 3. SEM image of distributed Met-Fe O nanoparticles.
3
4
1
5
(
H-tetrazole (2a). In the absence of a catalyst,
-phenyl-1H-tetrazole was obtained in 32% yield
Table 1, entry no. 1). Among the variety of the sol-
vents tested (Table 1, entry nos. 2–6), the best result
was obtained in DMSO. Other solvents, such as H2O,
DMF, MeCN, and CHCl3 gave the required product in
a low yield despite prolonged reaction time. At a lower
temperature (100°C, Table 1, entry no. 7), the reaction
3
4
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 9 2020

1648
KARIMIAN et al.
Fig. 4. EDX spectra of (a) Fe O and (b) Met-Fe O NPs.
3
4
3
4
progressed slowly. To examine the effect of catalyst
loading, the reaction was carried out in DMSO at
taken alone as catalyst gave the product in medium
yield (70%, entry no. 10), whereas only 55% of 2a was
obtained using Fe3O4 nanoparticles alone (entry
1
20°C in the presence of 0.05, 0.07, and 0.03 g of
no. 11). Therefore, methionine-coated Fe O nano-
Met-Fe O NPs. The largest yield of 2a was achieved
3
4
3
4
particles can be proposed as an efficient solid acid
catalyst for the synthesis of 5-substituted 1H-tetrazoles.
using 0.05 g of the catalyst in DMSO (Table 1, entry
no. 2). Further increase of the amount of the catalyst
did not accelerate the reaction (Table 1, entry no. 8). In
contrast, lower catalyst loading decreased the yield
even after longer reaction time (Table 1, entry no. 9).
Various substituted benzonitriles 1a–1k were re-
acted with sodium azide in the presence of 0.05 g of
methionine-coated Fe3O4 nanoparticles in DMSO at
1
20°C (Table 2). The rate of the reaction and product
To demonstrate the catalytic effect of methionine-
yields depended on the substituent in the aromatic ring
of the initial nitrile. Aromatic nitriles 1b–1d containing
electron-withdrawing substituents such as Br, Cl, and
coated Fe O nanoparticles, the synthesis of 2a was
3
4
also performed using Fe O NPs and methionine sepa-
3
4
rately. As shown in Table 1, 100% conversion was
achieved after 10 min in the presence of methionine-
coated Fe O nanoparticles (entry no. 2). Methionine
NO gave the corresponding tetrazoles 2b–2d with
2
excellent yields in short reaction time (Table 2).
Aromatic nitriles 1e–1k with electron-donating groups
3
4
(
Me, OMe, OEt, OH, NMe ) were also successfully
2
MeS
converted into tetrazoles 2e–2k but with longer reac-
tion time. Moreover, aliphatic nitrile such as 4-methyl-
pentanenitrile (1m) smoothly reacted under the opti-
mized conditions to afford tetrazole 2m in 85% yield.
NH3
O
SMe
HO
OH
OH
All tetrazoles 2a–2m were reported previously; they
were characterized by spectral and analytical data and
also by comparison of their melting points with the
reported values. For example, The IR spectra of all
compounds 2a–2m showed absorption bands at 3100–
O
O
H N
Fe O core
3
4
NH3
3
O
HO
Scheme 1.
MeS
O
Methionine–Fe O NPs
DMSO, 120°C
3
4
N
N
N
R
CN
+
NaN3
H N
3
N
H
R
SMe
1a–1m
2a–2m
Fig. 5. Possible bonding structure of Met-Fe O nanoparticles.
For R, see Table 2.
3
4
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 9 2020

METHIONINE-COATED Fe O NANOPARTICLES
1649
3
4
Table 1. Synthesis of 5-phenyl-1H-tetrazole (2a) under different conditions
Entry no.
Solvent
DMSO
DMSO
DMF
Catalyst
Catalyst loading, g
Time, h
Temperature, °C Yield, %
1
2
3
4
5
6
7
8
9
–
–
5
120
120
32
Met-Fe O NPs
0.05
0.05
0.05
0.05
0.05
0.05
0.07
0.03
0.05
0.05
10 min
100
70
3
4
Met-Fe O NPs
2
120
3
4
H O
2
Mete-Fe O NPs
2
2
Reflux
Reflux
Reflux
100
30
3
4
CH CN
Met-Fe O NPs
15
3
3
4
CHCl3
DMSO
DMSO
DMSO
DMSO
DMSO
Met-Fe O NPs
2
Traces
85
3
4
Met-Fe O NPs
10 min
10 min
30 min
30 min
1
3
4
Met-Fe O NPs
120
100
65
3
4
Met-Fe O NPs
120
3
4
1
0
Methionine
Fe O NPs
120
70
11
120
55
3
4
Table 2. Synthesis of 5-substituted 1H-tetrazoles 2a–2m in the presence of 0.05 g of Met-Fe O NPs (DMSO, 120°C)
3
4
Reaction time,
min
Melting point, °C
Compound no.
R
Yield, %
found
215
reported
2
2
2
2
2
2
2
2
2
2
2
2
2
a
b
c
d
e
f
Ph
10
18
100
98
214 [26]
4-BrC H
265–266
262
268–270 [51]
261–262 [33]
218–219 [33]
251–252 [19]
151–152 [52]
229–230 [53]
204–205 [33]
234–235 [33]
234–235 [33]
282–284 [54]
212–214 [53]
95–96 [33]
6
4
4-ClC H
10
100
100
95
6
4
4-O NC H
4
10
217–218
254
2
6
4-MeC H
30
6
4
4
3-MeC H
30
90
149–150
230–231
206
6
g
h
i
4-MeOC H
55
90
6
4
3,5-(MeO) C H
3
1 h
1 h
1 h
1 h
1 h
1 h
85
2
6
4-EtOC H
90
234–235
233–234
278–280
214–215
95
6
4
j
4-HOC H
85
6
4
k
l
4-Me NC H
4
80
2
6
Naphthalen-1-yl
3-Methylbutyl
90
m
85
Table 3. Comparison of various catalysts for the synthesis of 5-phenyl-1H-tetrazole
Entry no.
Catalyst
COY zeolite [32]
Conditions (solvent, temperature, time)
DMF, 120°C, 14 h
Yield, %
90
1
2
3
4
5
6
7
8
9
Cuttlebone [33]
DMSO, 110°C, 20 min
Solvent-free, 110°C, 20 min
DMSO, 130°C, 1 h
98
Fe O @chitin [18]
95
3
4
CAES [55]
95
Zn/Al hydrocalcite [56]
CuFe O [15]
DMF, 120–130°C, 12 h
DMF, 120°C, 12 h
84
92
2
4
DPPA/DBU [26]
Toluene, reflux, 16 h
93
TEA·HCl [57]
Toluene, 100°C, 24 h
DMSO, 120°C, 1 h
90
Cu(II)/Fe O @APTMS-DFX [58]
98
3
4
–
1
0
[t-Bu Sn(OH)(H O)] +2OTf [59]
H O, 85°C, 1 h
2
96
2
2
22
11
ChCl–ZnCl [54]
140°C, 30 min
90
2
1
2
Methionine-Fe O NPs [this work]
DMSO, 120°C, 10 min
100
3
4
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 9 2020

1650
KARIMIAN et al.
1
00
diate B. Removal of the catalyst by simple filtration
and acidic work-up gives tetrazole tautomers C and D.
The more stable 1H-tautomer D is the major product.
1
00
9
5
9
0
8
5
8
0
8
6
4
2
0
0
0
0
The reusability of the catalyst was also investigated.
After completion of the cycloaddition reaction, Met-
Fe O NPs were separated from the reaction mixture
by an external magnet, washed with distilled water and
hot ethyl acetate several times to remove organic
products, dried at 70°C for 1 h, and used in the next
cycle. As shown in Fig. 6, the nanocatalyst could be
reused at least four times without considerable loss of
activity.
3
4
0
EXPERIMENTAL
1
2
3
4
5
Cycle number
All materials and reagents were purchased from
Merck and used without further purification. Methio-
nine (98%) was purchased from Sigma–Aldrich. The
melting points were determined with an Electrothermal
Type 9200 melting point apparatus. The FT-IR spectra
were recorded on a Thermo Nicolet Avatar 370 FT-IR
Fig. 6. Recyclability of Met-Fe O NPs for the reaction of
3
4
benzonitrile with sodium azide.
3
400 (N–H) and 1000–1300 cm–1 (tetrazole ring),
whereas no absorption band at 2240 cm (C≡N) was
–
1
observed.
1
spectrometer (Madison, WI). The H NMR spectra
In continue, we compared the reported methods
with the other catalysts recently reported for synthesis
tetrazole derivatives in the literature. As it is found
were recorded on a Bruker Avance 400 MHz instru-
ment at room temperature using CDCl or DMSO-d as
3
6
solvent and tetramethylsilane as reference. The mass
spectra (electron impact, 70 eV) were recorded with
a Varian MAT CH7 instrument (Bremen). Elemental
analysis was performed on a Thermo Finnigan Flash
EA micro analyzer (Milan, Italy).
(
Table 3), the Met-Fe O NPs are the more efficient
3 4
catalysts than many of the methods reported in the
literature for this reaction.
A plausible reaction mechanism is shown in
Scheme 2. It has been proposed that the cycloaddition
of nitriles and sodium azide is accelerated through the
positive charge of the catalyst surface, which activates
the nitrile for azide addition via hydrogen bonding of
nanoparticles with the nitrile nitrogen atom. Initially,
coordination of the nitrile nitrogen atom to Met-Fe O
Synthesis of methionine-coated Fe O nano-
3
4
particles. Methionine (1.3 g) was dissolved in 50 mL
of deionized water, 1.3 g of Fe O was added to the
3
4
amino acid solution, and the mixture was stirred at
0°C for 3 h. The catalyst was separated from the
7
solution using a magnet, washed with deionized water
several times, and dried in an oven at 60°C overnight.
3
4
NPs gives complex A, which accelerates the cyclization
step by increasing the electrophilicity of the nitrile
group. The [3+2]-cycloaddition involving the C≡N
bond and azide ion occurs instantly to form interme-
Typical procedure for the preparation of
5
-phenyl-1H-tetrazole in the presence of methio-
nine-coated Fe O nanoparticles. A mixture of benzo-
3
4
nitrile (1a, 1 mmol), sodium azide (1 mmol), and Met-
Scheme 2.
Fe O nanoparticles (0.05 g) in DMSO (5 mL) was
3
4
stirred at 120°C. The progress of the reaction was
monitored by TLC. After completion of the reaction,
the mixture was cooled, the catalyst was separated
from the mixture with an external magnet, and the
solution was treated with 4 N aqueous HCl (10 mL)
and ethyl acetate (2×10 mL). The combined extracts
were washed with distilled water, dried over anhydrous
sodium sulfate, and concentrated to give crystalline
D
C
5
-phenyl-1H-tetrazole (2a). The product was recrys-
tallized from n-hexane–ethyl acetate (1:1) to give white
crystals.
B
A
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 9 2020

METHIONINE-COATED Fe O NANOPARTICLES
1651
3
4
The spectral data of some representative 5-sub-
stituted-1H-tetrazoles are given below.
4-(1H-Tetrazol-5-yl)phenol (2j). White solid. IR
–
1
spectrum, ν, cm : 3252 (N–H), 3100, 3066, 3019,
000–2220 (OH), 1615, 1599, 1511, 1466, 1413, 1285
3
5
-Phenyl-1H-tetrazole (2a). White solid. IR spec-
1
–1
(N–N=N), 835, 752, 514. H NMR spectrum, δ, ppm:
trum, ν, cm : 3125 (N–H), 3045, 2982, 2833, 2766,
692, 2607, 2557, 1614, 1564, 1486, 1466, 1409, 1254
N–N=N), 1164 (C–N), 1056, 988, 784. H NMR spec-
6
.95 d (2H, Harom, J = 8.4 Hz), 7.87 d (2H, Harom, J =
2
(
1
8.8 Hz), 10.00 br.s (1H, OH). Mass spectrum: m/z 162
+
[
M] . Found, %: C 51.86; H 3.77; N 34.55. C H N O.
trum, δ, ppm: 3.50 br.s (1H, NH), 7.62 s (3H, Harom),
7 6 4
+
Calculated, %: C 51.85; H 3.73; N 34.55.
8
.05 s (2H, Harom). Mass spectrum: m/z 146 [M] .
Found, %: C 57.53; H 4.15; N 38.32. C H N . Cal-
culated, %: C 57.53; H 4.14; N 38.34.
5-(Naphthalen-1-yl)-1H-tetrazole (2l). White
7
6
4
–
1
solid. IR spectrum, ν, cm : 3412 (N–H), 3051, 2721,
625, 1525, 1389, 1257 (N–N=N), 1131 (C–N), 965,
1
5
-(4-Bromophenyl)-1H-tetrazole (2b). Yellow
1
–
1
864. H NMR spectrum, δ, ppm: 7.64–7.74 m (3H,
Harom), 7.97–8.0 m (1H, Harom), 8.03–8.08 m (1H,
Harom), 8.12–8.19 m (1H, Harom), 8.57–8.61 m (1H,
solid. IR spectrum, ν, cm : 3335 (N–H), 3089, 2996,
845, 2725, 1652, 1605, 1483, 1275 (N–N=N), 1157
C–N), 1054, 830. H NMR spectrum, δ, ppm: 7.76–
2
(
7
1
+
+
Harom). Mass spectrum: m/z 196 [M] . Found, %:
.99 m (4H, Harom). Mass spectrum: m/z 226/224 [M] .
C 67.34; H 4.10; N 28.56. C H N . Calculated, %:
Found, %: C 37.70; H 2.85; N 24.60. C H BrN .
11
8
4
7
5
4
C 67.34; H 4.11; N 28.55.
Calculated, %: C 37.36; H 2.24; N 24.90.
5
-(4-Nitrophenyl)-1H-tetrazole (2d). Yellow solid.
ACKNOWLEDGMENTS
–
1
IR spectrum, ν, cm : 3440 (N–H), 3334, 3115, 2975,
2
9
8
819, 1633, 1488, 1341, 1242 (N–N=N), 1140 (C–N),
95. H NMR spectrum, δ, ppm: 3.21 br.s (1H, NH),
The authors gratefully acknowledge the partial support of
this study by the University of Gonabad Research Council.
This research did not receive any specific funding.
1
.30–8.33 m (2H, Harom), 8.45–8.48 m (2H, Harom).
+
Mass spectrum: m/z 191 [M] . Found, %: C 43.70;
H 2.80; N 36.66. C H N O . Calculated, %: C 43.98;
H 2.64; N 36.64.
CONFLICT OF INTEREST
The authors declare no conflict of interest.
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7
5
5
2
5
-(3-Methylphenyl)-1H-tetrazole (2f). White
–
1
solid. IR spectrum, ν, cm : 3303 (N–H), 3121, 2980,
2
8
7
870, 2612, 1605, 1486, 1250 (N–N=N), 1150 (C–N),
1
90. H NMR spectrum, δ, ppm: 2.50 s (3H, CH ),
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+
2
3
4
m/z 160 [M] . Found, %: C 59.90; H 5.05; N 35.02.
C H N . Calculated, %: C 59.99; H 5.03; N 34.98.
8
8
4
5
-(4-Methoxyphenyl)-1H-tetrazole (2g). White
–
1
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(
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+
Mass spectrum: m/z 175 [M] . Found, %: C 54.55,
H 4.58, N 31.78. C H N O. Calculated, %: C 54.54;
8
8
4
H 4.58; N 31.80.
5
6
5
-(3,5-Dimethoxyphenyl)-1H-tetrazole (2h).
–
1
White solid. IR spectrum, ν, cm : 3130 (N–H), 3105,
942, 2758, 1605, 1559, 1431, 1290 (N–N=N), 1166
C–N), 1054, 846. H NMR spectrum, δ, ppm: 3.85 s
6H, OMe), 6.72 t (1H, Harom, J = 2.2 Hz), 7.22 d (2H,
2
(
(
1
https://doi.org/10.1016/S0149-7634(02)00010-6
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trum: m/z 206 [M] . Found, %: C 52.44; H 4.85;
N 27.17. C H N O . Calculated, %: C 52.42; H 4.89;
9
10
4
2
N 27.17.
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