An efficient Cu/functionalized graphene oxide catalyst for synthesis of 5-substituted 1H-tetrazoles

Article abstract of DOI:10.1007/s11696-021-01506-0

The copper nanoparticles (Cu NPs) and amide functionalized graphene oxide (Cu-Amd-RGO) catalyst were prepared. This prepared catalyst (Cu-Amd-RGO) used for the synthesis of tetrazole derivatives. The catalyst (Cu-Amd-RGO) was characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction analysis (XRD). The average particle size of Cu was found to be 7.6?nm. The Cu-Amd-RGO catalyst exhibited excellent catalytic activity and recyclability for synthesis of tetrazoles.

Full text of DOI:10.1007/s11696-021-01506-0

Chemical Papers (2021) 75:2891–2899
https://doi.org/10.1007/s11696-021-01506-0
ORIGINAL PAPER
An efcient Cu/ꢀunctionalized graphene oxide catalyst ꢀor synthesis
oꢀ 5‑substituted 1H‑tetrazoles
1
2
3
1
Padmakar A. Kulkarni · Ashis Kumar Satpati · Maiyalagan Thandavarayan · Suresh S. Shendage
Received: 17 May 2020 / Accepted: 7 January 2021 / Published online: 7 February 2021
©
Institute of Chemistry, Slovak Academy of Sciences 2021
Abstract
The copper nanoparticles (Cu NPs) and amide functionalized graphene oxide (Cu-Amd-RGO) catalyst were prepared. This
prepared catalyst (Cu-Amd-RGO) used for the synthesis of tetrazole derivatives. The catalyst (Cu-Amd-RGO) was character-
ized by ꢀeld emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform
infrared spectroscopy (FTIR), and X-ray diꢁraction analysis (XRD). The average particle size of Cu was found to be 7.6 nm.
The Cu-Amd-RGO catalyst exhibited excellent catalytic activity and recyclability for synthesis of tetrazoles.
Keywords Aromatic nitrile · C–N coupling · Tetrazoles · Functionalization of graphene oxide · Heterogeneous catalyst
Introduction
particularly in drugs as isosteric replacement of carboxylic
acid moiety (Holland and Pereira 1967).
Compounds comprising a ꢀve membered ring with four
nitrogen atoms and one carbon atom are known as Tetra-
zoles. Tetrazoles are widely applicable heterocyclic class of
synthetic compounds and not found in nature. Tetrazoles are
commonly used in pharmaceutical since they exhibits prop-
erties such as antifungal, antibacterial (Feinn et al. 2017),
antiallergic (Nohara et al. 1977), anticancer (De Souza et al.
In past, various methods for preparation of tetra-
zole were reported in literature. Sharpless et al. reported
[3+2]-cycloaddition reaction of nitrile group with sodium
azide for synthesis of tetrazoles (Demko and Sharpless
2001). Also the tetrazole synthesis was carried out by using
catalysts such as, Lewis acids (Kumar et al. 1996), zinc (II)
salts, Cu O, ZnO (Kantam et al. 2005), clays, Zn/Al hydro-
2
2
005), antiviral, (Vieira et al. 2005) Moreover, these tetra-
talcite, CuFe O Dendron-functionalized Fe O (Zarchi and
2
4
3
4
zole derivatives have vast applications as a potential ener-
getic material utilized in explosives and rocket propellants
Abadi 2019), nanoparticles (Sreedhar et al. 2011). These
reported procedures have several drawbacks such as toxic
metals, harsh reaction conditions, use of strong Lewis acids,
water sensitivity, extended reaction time, diꢂculty in isola-
tion and recovery of the catalysts.
(
Talawar et al. 2009), in agriculture as plant growth regu-
lator. Presently, researchers are binding aryl thio-tetrazolyl
acetanilides with HIV‐1 reverse transcriptase by making use
of tetrazole derivatives (Gagnon et al. 2009). The above-
mentioned properties of tetrazoles make them a potential
candidate for biochemical and pharmaceutical applications,
Nowadays, inclination toward the heterogeneous cata-
lysts has attracted much interest because of its recyclable
and environmentally benign nature (Shendage et al. 2014).
These catalysts are usually, eco-friendly, high reactive, eco-
nomical, easy to handle and recoverable. Graphene oxide
and reduced graphene oxide is the widest members of sup-
port materials that have been used as heterogeneous catalyst
and support in numerous organic transformations (Lonkar
et al. 2015). These materials have high surface area, unique
electronic, thermal, easy surface modiꢀcations, high water
dispersibility and mechanical properties. Furthermore, func-
tionalized, graphene could serve as nanoꢀller in composite
materials and prevents agglomeration of metal nanoparticles
*
Suresh S. Shendage
sureshsshendage@gmail.com
1
Department of Chemistry, KET’S Vinayak Ganesh Vaze
College of Arts, Science and Commerce, Mithagar Road,
Mulund (E), Mumbai 400081, India
2
3
Analytical Chemistry Division, Bhabha Atomic
Research Centre, Homi Bhabha National Institute,
Trombay, Mumbai 400 085, India
Department of Chemistry, SRM Research Institute (SRM
University), Kattankulathur, Tamil Nadu 603 203, India
(
Soltani et al. 2012). Graphene oxide shows an exceptional
Vol.:(0
1
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Chemical Papers (2021) 75:2891–2899
hydrophilic nature, due to the enhancement of oxygen trans-
port functional groups on its edges.
paper (Scheme 1). The application of proposed catalyst (Cu-
Amd-RGO) was studied for synthesis of tetrazole derivatives
as a heterogeneous reusable nanocomposite catalyst.
These excellent properties of graphene oxide permit
GO to be functionalized with various functional groups.
Owing to above-mentioned properties functionalized gra-
phene oxide could enhance catalytic activity and reusabil-
ity. Recently, copper supported on diꢁerent solid materials
such as silica gel, alumina, charcoal and montmorillonite
Experimental
All chemicals and reagents were purchased from S D Fine
chem limited and Merck used without puriꢀcation. Reaction
monitored on TLC (Merck silica gel 60). Isolated product
(
Choi et al. 2010) were used as catalyst for diꢁerent organic
zeolites, reactions. Conversely, the important disadvantages
are leaching of copper species from support surface, less
activity, and diꢂculty in recovery are associated with these
reported copper catalysts. These catalysts are merely synthe-
sized by surface assimilation of copper species on surface of
support material (Panahi et al. 2017).
1
conꢀrmed by H NMR spectra was recorded on a Bruker
AC-400 (400 MHz) spectrometer C13 Bruker (100 MHz).
Fourier transform infrared spectra were measured with
−
1
range of 4000–400 cm using Agilent Microlab spectrom-
eter. X-ray powder diꢁraction (XRD) was collected using
Rigaku Miniꢃex model by using CuKα = 1.54 Å. Field-
emission scanning electron microscopy (SEM) on a single
instrument FEI Quanta 200 ESEM FEG and Transmission
electron microscopy (TEM) was measured using JEOL (JEM
2100F, 200 kV) sample dispersed in ethanol and Cu grid
used.
2
Graphite sheet that consists of sp carbon atoms cova-
lently bonded in a honeycomb crystal lattice. The combina-
tion of highest electron mobility, high chemical, mechanical
and thermal stability with low manufacturing cost and metal
immobilization capacity oꢁer many interesting applications
2
in catalysis. The oxidized and exfoliated sheet of sp -hybrid-
ized graphene carries various oxygenated groups, such as
epoxide, hydroxyl, carbonyl, and carboxyl. Among all the
oxygenated groups, the carboxyl group of GO is the most
suitable site for reacting with an aniline group to form an
amide bond. In the reduced graphene oxide (RGO) lattice
which prepared from GO by reduction reaction. In the cop-
per amide functionlized graphene oxide (Cu-Amd-RGO) lat-
tice, amide moiety and copper nanoparticles play vital role
in transition state of cyclization mechanism to form tetra-
zoles. The surface of graphene not only minimizes process-
ing issues like wrinkling, restacking, aggregation but also
causes higher dispersibility in organic solvents than GO
which enhance rate of reaction.
Preparation of graphene oxide (GO)
Graphene oxide prepared as reported in the modiꢀed Hum-
mers’ method (Hummer and Oꢁeman 1958); 2.5 g of graphite
and 1.25 g of NaNO were stirred with 50 mL H SO and 7 mL
3
2
4
H PO in the ice bath for 15 min., and then 8 g of KMnO was
3
4
4
added slowly so at temperature 0 °C to 5 °C. The mixture was
then maintained for 2 h in an ice bath and stirred for 1 h at 40
°C in water bath. Then, heated reaction mass at temperature
98 °C for 2 h, while water was added continuously. Pure water
was added slowly to make the volume 500 ml, followed by
adding 20 mL of H O . Then, reaction mass was centrifuged
2
2
Here, in view of the simple surface modiꢀcations of GO
and good synchronization ability of aniline, the performance
of new approaches toward the grafting of copper amide func-
tionalized graphene oxide (Cu-Amd-RGO) is reported in this
and washed with pure water and 10% HCl solution repeatedly.
Obtained graphene oxide was dried at 80 °C.
Scheme 1 Synthetic route of Cu-Amd- RGO preparation
1
3

Chemical Papers (2021) 75:2891–2899
2893
Preparation of catalyst (Cu‑Amd ‑RGO)
reꢃux for 6 h then cooled reaction mass. Then, it was centri-
fuged and followed by washing of ethanol. Dried at 150 °C
under vacuum for 6 h and obtained material as amide func-
tionalized graphene oxide (Amd-GO).
In a 250-mL round-bottomed ꢃask 2 gm GO and 20 ml DMF-
stirred at 25–30 °C and 20 ml thionyl chloride was added
slowly at 10 °C to 15 °C. Then, temperature of reaction mass
is increased to 25 °C, and heated mixture for 5 h at 80 °C fol-
lowed by cooling for 1 h at room temperature. This chlorin-
ated graphene oxide centrifuged and washed with chloroform.
Dried at 60 °C to 70 °C under vacuum for 8 h, and obtained
material as chlorinated graphene oxide (Cl-GO).
In a 250-mL round-bottomed ꢃask amide functionalized
graphene oxide (Amd-GO) 1.4 gm stirred with solution of
CuCl 0.4 gm in 100 ml water then 5 ml hydrazine hydrate
2
added to above reaction mass at 25–30 °C. Then mixture
was heated for 5 h at 80 °C, cooled and centrifuged catalyst
with washing of ethanol. Dried at 140 °C for 6 to 8 h to get
catalyst as Cu-Amd-RGO.
In a 100-mL round-bottomed ꢃask charged 2.5 gm chlo-
rinated graphene oxide (Cl-GO) and 30 ml aniline heated to
Fig. 1 (a) FEG-SEM image Cu-Amd-RGO (b) TEM image-Amd-RGO (c) TEM image Cu-Amd-RGO (d) particle size distribution curve for Cu
nanoparticles
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Chemical Papers (2021) 75:2891–2899
Table 1 Optimization of reaction conditions for synthesis of 5-substi-
tuted 1H-tetrazole
b
Entry Catalyst
mg)
Solvent NaN3
(mmol))
Time
Yield %
(
(Min.)
1
2
3
4
5
6
7
8
9
1
1
2
3
4
5
5
5
5
5
5
5
5
DMF
DMF
DMF
DMF
Water
EtOH
DMSO 1.4
Toluene 1.4
DMF
DMF
DMF
1.4
120
110
60
81
88
94
96
1.4
1.4
1.4
1.4
1.4
30
500
400
60
480
30
30
30
No reaction
2
86
21
97
93
91
1.5
1.3
1.2
0
1
Fig. 2 XRD pattern of copper amide functionalized graphene oxide
a
Reaction conditions: benzonitrile (0.1 g), NaN (1.4 mmol), (Cu-
3
b
Amd-RGO) (5 mg), DMF (5 ml), temperature at 130 °C, isolated
yields
General procedure for the synthesis of 5‐substituted
1H‐tetrazoles
Cu nanoparticles (Cu NPs). The synthesized catalyst
(Cu-Amd-RGO) was characterized by Fourier transform
infrared spectroscopy (FTIR) analysis. FTIR analysis
(Supplementary Information ꢀgure S1) shows that aro-
matic C=O stretching vibrations in the GO materials was
Benzonitrile 0.1 g, and sodium azide 0.092 g, DMF (5 ml),
and 5 mg catalyst were transferred in a 25-ml round-bottomed
ꢃask. The ꢃask was mounted on mechanical stirrer and the
reaction mass was stirred at 120 ˚C for 30 min. Then, mixture
was cooled to room temperature. After the reaction is over the
catalyst was regenerated by ꢀltration and ꢀnally washed with
−
1
marked at 1746.16 cm . The O–H deformation vibration
−
1
−1
at 3345.06 cm and the C–O stretching at 1046.87 cm
1
0 ml of ethyl acetate in order to remove the contamination
(Gupta et al. 2018). Functionalization of graphene oxide
was carried by chlorination and condensation of Aniline
to form amide moiety. The FTIR spectra of Cu-Amd-
from reaction. To the ꢀltrate dilute HCl (15 ml) was added
and stirred for 15 min. The organic phase was removed and
the aqueous phase was further extracted with10ml of ethyl
acetate. Final organic phase was obtained by combination of
−
1
RGO the O–H deformation vibration at 3345.06 cm
1
disappeared. The new peak at 2980.52 cm- represents
(C–H) stretching vibrations of phenylic group (Joseph
organic phases was washed with 10 ml H O, then it was dried
2
−
1
over anhydrous sodium sulfate and concentrated to obtain the
crude 5-phenyltetrazole. Finally, impurities from the products
were removed by column chromatography. Final products were
et al. 2015). Two peaks 1733.02 cm corresponding to
the amide carbonyl (C=O) stretch and the peak at about
−
1
1539.03 cm (C–N) which may be due to copper oxide
1
13
−1
characterized by H NMR and C NMR spectroscopy (Sup-
plementary Information).
nanocomposite (Rani et al. 2014). The peak at 535.57 cm
corresponds to Cu–O stretching vibration characteristic of
CuO nanoparticles (Gulati et al. 2018).
FTIR data show successful reduction in copper ions to
copper nanoparticles on graphene oxide. Modiꢀcation of
graphene oxide sheet using aniline to form amide, which
show change in stretching vibrations carbonyl moiety to
amide carbonyl having less frequency value.
Results and discussion
Fourier transform infrared spectroscopy (FT‑IR)
The new (Cu-Amd-RGO) catalyst was prepared by amide
functionalization of graphene oxide using aniline and
Scheme 2 Synthesis of tetra-
N
N
C
zole using Cu-Amd-RGO as
Cu-Amd-RGO
N
N
heterogeneous catalyst
C
Solvent , Temprature
N
H
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Chemical Papers (2021) 75:2891–2899
2895
Table 2 Cu-Amd-RGO
catalyzed synthesis of
a
5
-substituted 1H-tetrazole
a
derivatives
Yieldb
%
Entry
Reactant
Product
Time (min)
a
Reaction conditions:
1
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Chemical Papers (2021) 75:2891–2899
O
C
NH
C
N
CuO
O
NH
C
NaN3
Na
N
CuO
N
N
N
N
N
N
C
C
NH
1
+
Nacl
O
NH
C
HCl
CuO
N
N
C
O
N
NH
C
N
CuO
Na
N
N
2
N
C
N
Na
3
Scheme 3 A plausible mechanism for the formation of Tetrazoles using Cu-Amd-RGO
SEM and TEM analysis
sheets, which demonstrates a good blending between
Amd-GO sheet and Cu NPs (Fig. 1a).
The morphology of prepared catalyst is characterized by
SEM, TEM and XRD. In Figure 1a FEG-SEM image evi-
dently shows that the Cu grain infuses between Amd-GO
The TEM images represent the surface morphology
of the amide functionalized graphene oxide (Amd-G).
Morphology of Amd-GO was observed to have flaky
texture, and folded features of GO indicating its layered
1
3

Chemical Papers (2021) 75:2891–2899
2897
synthesis of 5-substituted 1H-tetrazole was evaluated. To
optimize the reaction conditions, initially, the reaction of
benzonitrile and sodium azide was selected as model reac-
tion. Due to the harsh reaction conditions for the synthesis
of tetrazole, the reaction parameters and media have large
impact on the yield and time of reaction. The reaction was
screened for various parameters such as temperature, sol-
vent, amount of sodium azide and catalyst loading. To opti-
mize the catalyst quantity, the model reaction was carried
out in the presence of variable amounts of the catalyst.
The results showed that (Table 1, entries 1–4) 5 mg of the
catalyst was the ideal amount of catalyst. The various sol-
vents were examined by the model reaction (Table 1, entries
4
–9). Among them, DMF was found to be the best solvent
Fig. 3 Reusability of Cu-Amd-RGO catalysta
(
Table 1, entry 3) in terms of the time and yield of desired
product. Then, amount of sodium azide was also investi-
gated in order to get maximum yield of the product. Results
showed that 1.4 mmol of sodium azide gave maximum yield
of the reaction product (Table 1, entry 4 and entries 9–11).
Subsequently, the optimized reaction parameters were
explored for the synthesis of 5-substituted 1H-tetrazole
derivatives (Scheme 2, Table 2 entries 1–10). As shown in
Table 2, this protocol is general for various electron-rich
as well as electron poor substituted benzonitrile (Table 2
entries 2–9). Thiophene-2 carbonitrile aꢁorded 89% yield of
the product in 79 min (Table 2 entry10). A plausible mecha-
nism for the formation of Tetrazoles using Cu-Amd-RGO
catalyst is shown in Scheme 3.
microstructure (Fig. 1b). This clearly shows the surface
modiꢀcation of GO after functionalization.
TEM images revealed spherical shape of Cu NPs with
diameters 7.6 nm (Fig. 1d). The particle size distribution is in
the range of 2–12 nm (Fig. 1d). TEM image of Cu-Amd-RGO
nanocomposite showed that the Cu NPs were homogeneously
distributed on the graphene oxide sheets without aggregation.
XRD diꢀraction analysis
XRD patterns for Cu-Amd-RGO are shown in Fig. 2. RGO
shows a diꢁraction peak at 2θ=26.6°, which is the charac-
teristic peak of the RGO (JCPDS File no. 03-0401).
The three other peaks at 44.7°, 50.1°, and 73.8° cor-
responding to (111), (200), and (220) planes (fcc) are the
characteristic peaks of copper, matches with JCPDS ꢀle
No. 04–0836 (Gupta et al. 2018). The peaks at 20.8°, 24.6°
and 36.07° correspond to aniline (Rani et al. 2014). Dop-
ing of Cu nanoparticles and amide functionalization results
change in interplanar spaces of RGO surface, which may
be shifted slight higher than 2θ value as reported (Fig. 2).
In general, it is of great importance to investigate the use
of a new material in the practical application. Therefore,
the catalytic activity of the Cu-Amd-RGO composite for
Reusability of the catalysta
The recyclability of the Cu-Amd-RGO catalyst was studied
for the model reaction. The catalyst from the reaction mix-
ture was recovered by centrifugation. Then, it was washed
with ethyl acetate. Then, the reaction pot was charged with
fresh reactants and used for next run. The Cu-Amd-RGO
catalyst could be recycled over 6 runs without any major loss
of its activity. This clearly speciꢀes the practical importance
of this catalyst (Fig. 3).
Table 3 Comparison of the
b
Entry
Catalyst
Time
Yield (%)
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1
2
3
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Cu-Amd-RGO
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3
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1
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Chemical Papers (2021) 75:2891–2899
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Acknowledgements This work was financially supported by our
institute (KET’S V. G. Vaze College). The catalysts and ꢀnal reaction
product analyses were carried out at SAIF, IIT Mumbai, and instru-
mentation department Solapur University. We (Authors) thank all our
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