A highly efficient synthesis of 2,4-diamino-6-arylpyrimidine-5-carbonitrile derivatives using NiCo2O4@Ni(BDC) metal-organic frameworks as a novel and bifunctional catalyst

Article abstract of DOI:10.1016/j.jorganchem.2019.120935

The NiCo₂O₄@Ni(BDC) metal-organic frameworks as a suitable and green catalyst have been developed for the one-pot synthesis of 2,4-diamino-6-arylpyrimidine-5-carbonitrile derivatives. The multi-component reactions of aldehydes, malon

Full text of DOI:10.1016/j.jorganchem.2019.120935

Journal of Organometallic Chemistry 900 (2019) 120935
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
A highly efficient synthesis of 2,4-diamino-6-arylpyrimidine-5-
carbonitrile derivatives using NiCo2O4@Ni(BDC) metal-organic
frameworks as a novel and bifunctional catalyst
Mohammad Ali Ghasemzadeh*, Mina Azimi-Nasrabad, Simin Farhadi,
Boshra Mirhosseini-Eshkevari
Department of Chemistry, Qom Branch, Islamic Azad University, Qom, I. R, Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
The NiCo2O4@Ni(BDC) metal-organic frameworks as a suitable and green catalyst have been developed
for the one-pot synthesis of 2,4-diamino-6-arylpyrimidine-5-carbonitrile derivatives. The multi-
component reactions of aldehydes, malononitrile and guanidine hydrochloride were efficiently cata-
lyzed using a novel metal-organic framework under reflux conditions. Simple procedures, high yields,
short reaction times, and reusability of the catalyst are advantages of this protocol. The catalyst was fully
characterized by FT-IR, SEM, XRD, EDX, TGA, VSM and TEM analysis.
Received 27 May 2019
Received in revised form
1 September 2019
Accepted 11 September 2019
Available online 14 September 2019
© 2019 Published by Elsevier B.V.
Keywords:
Multi-component reactions
Nanoporous
Metal-organic frameworks
Pyrimidine
NiCo2O4@Ni(BDC)
1. Introduction
made them attractive materials for heterogeneous catalysts.
Because of the considerable variety of organic linkers and metal
Recent developments in nanoscience and nanotechnology have
led to new research interest in employingnanometer-sized parti-
cles as an alternative matrix for catalytic reactions. Many reports
show asurprising level of performance of nanoparticles as catalysts
in terms of reactivity, selectivity and improved yields of products
[1].
Nanoporous metal-organic frameworks (MOFs), which are
made of inorganic building units and organic linkers, have been
taken into consideration in the last decade [2]. This new hybrid
material has a crystalline three or two and one-dimensional open
framework [3]. MOF-based structures have unique properties and
features, including structural diversity, high pore volume, high
porosity [4], and high capacity for guest molecular acceptance due
to these specific features. MOFs have been used in a variety of fields
such as storage and separation of gases and as catalyst [5].
Compared to purely inorganic porous materials, MOFs show higher
flexibility for the design of catalytic centers [6]. This flexibility has
ions, MOFs can be modulated in several ways. The size and
appearance of the framework can be changed by using various
linkers, also changing their connectivity via adding different func-
tional groups on the linkers [7,8]. MOFs as green catalysts were
used to increase the speed a number of organic reactions [9]. For
example molybdenum (VI) modified Zr-MOF catalysts for epoxi-
dation of olefins [10], postsynthetic modification of IRMOF-3 with a
copper iminopyridine complex as heterogeneous catalyst for the
synthesis of 2-aminobenzothiazoles [11], basic isoreticular
metaleorganic framework (IRMOF-3) porous nanomaterial as an
appropriate and green catalyst for selective unsymmetrical
Hantzsch coupling reaction [12].
Multi component reactions (MCRs) have become very absorbing
as tools for the fast preparation of compound libraries of small
molecules [13,14]. MCRs are a resource which is time-effective and
therefore an economically desirable process in diversity generation.
Also, MCRs are effective, environmentally friendly, fast, atom eco-
nomic and time-saving. They are a suitable method for the prepa-
ration of compounds with medicinal and biological properties [15].
In recent years, a lot of attention has been paid to the three-
component reaction of aldehydes, malononitrile and guanidine.
* Corresponding author.
E-mail address: ghasemzadeh@qom-iau.ac.ir (M.A. Ghasemzadeh).
https://doi.org/10.1016/j.jorganchem.2019.120935
0022-328X/© 2019 Published by Elsevier B.V.

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M.A. Ghasemzadeh et al. / Journal of Organometallic Chemistry 900 (2019) 120935
The synthesis of pyrimidine derivatives has attracted much atten-
tion due to the therapeutic and biological properties. These features
are: antiviral [16e18], antineoplastic [19e21], inflammatory prop-
erties [22] and antibiotic [23]. Pyrimidines also exhibit a limited
area of pharmacological activities such as anticancer [24,25], car-
dioprotective effects [26], antibacterial [27e29] and antifungal ac-
tivities [30,31]. There are many synthetic methods for the synthesis
of pyrimidine derivatives which include the condensation of aro-
matic aldehydes, ethyl cyanoacetate and guanidine nitrate [32], 1,3-
indandione, amino uracils and isatins or acenaphthylene-1,2-dione
[33], condensation of 6- amino-1,3-dimethyl uracil, 1,3-dicarbonyl
compounds and aromatic aldehydes [34]. However, there are only
few reports for the synthesis of 2,4-diamino pyrimidine-5-
carbonitriles via multi component reactions of aromatic alde-
hydes, malononitrile and guanidine hydrochloride, which catalyzed
by some catalysts such as sulfonic acid functionalized LUS-1 [35],
potassium carbonate and tetra butyl ammonium bromide [36] and
sodium hydroxid [37].
Herein, with the aim to improve more efficient synthetic pro-
cedures, reduce the number of separate reaction steps, minimize
by-products and in continuation of our efforts to the preparation of
heterocyclic compounds [38e41], we report here a novel and mild
method for the preparation of 2,4-diamino-6-arylpyrimidine-5-
carbonitriles via multi components reactions of aromatic alde-
hydes, malononitrile and guanidine hydrochloride in the presence
of NiCo2O4@Ni(BDC) metal-organic framework (Scheme 1).
2.2. Preparation of NiCo2O4 nanoparticles
Magnetic NiCo2O4 NPs were prepared by the reported co-
precipitation method [42]. In
a
typical experiment,
Ni(NO3)2$6H2O (0.18 g, 1 mmol) and Co(NO3)2$6H2O (0.36 g,
2 mmol) (Ni and Co, molar ratio 1:2) was dissolved in 30 mL of
deionized water. Subsequently 12 mmol of urea was added into the
mixture and stirred for 30 min. The resulting mixture was trans-
ferred into 50 mL teflon-lined autoclave. The autoclave was sealed
and heated at 120 ꢀC for 6 h. After cooling slowly to room tem-
perature, the resulting precipitate was collected, washed with
deionized water and ethanol for several times, and dried at 60 ꢀC
for 24 h. Finally, the dried black powder was further annealed at
400 ꢀC for 3 h.
2.3. Preparation of NiCo2O4@Ni(BDC) nanocomposite
As shown in Scheme 2, the novel magnetic NiCo2O4@Ni(BDC)
was prepared in a two-step process by using NiCo2O4 as a magnetic
core and terephthalic acid (H2BDC) as a linker. Firstly, the NiCo2O4
(0.1 g) was dispersed into 15 mL ethanol solution under sonication
for 15 min at room temperature. Then, Ni(NO3)2.6H2O (0.42 g) and
terephthalic acid (0.16 g) were added into the mixture and again
stirred under sonication for 30 min at room temperature. Next, the
above mixture was stirred under reflux conditions for 12 h at 80 ꢀC.
When the reaction was completed, the product was separated from
the solvent by magnet and washed several times with water and
ethanol and then dried under vacuum at 60 ꢀC for 12 h. The pre-
pared NiCo2O4@Ni(BDC) MNPs have been structurally character-
ized by FT-IR, XRD, TGA, FE-SEM, EDX, TEM and VSM analysis.
2. Experimental
2.1. Materials
2.4. General procedure for the synthesis of 2,4-diamino-6-
arylpyrimidine-5-carbonitriles catalyzed by NiCo2O4@Ni(BDC)
under reflux conditions
Chemicals were purchased from the Sigma-Aldrich and Merck in
high purity. All of the materials were of commercial reagent grade
and were used without further purification. All melting points are
uncorrected and were determined in capillary tube on Boetius
melting point microscope. 1H NMR and 13C NMR spectra were ob-
tained on Bruker 400 MHz spectrometer with DMSO‑d6 as solvent
using TMS as an internal standard. FT-IR spectra were recorded on
Magna-IR, spectrometer 550. The elemental analyses (C, H, N) were
obtained from a Carlo ERBA Model EA 1108 analyzer. Powder X-ray
diffraction (XRD) was carried out on a Philips diffractometer of
A
mixture of aromatic aldehyde (1 mmol), malononitrile
(1.2 mmol), guanidine hydrochlorid (1 mmol), NiCo2O4@Ni(BDC)
MNPs (0.008 g) in ethanol (5 mL) was heated in the oil bath under
reflux conditions at 80 ꢀC for 2e2.5 h. After completion of the re-
action as indicated by TLC, the reaction mixture was cooled to room
temperature and solid obtained was dissolved in dichloromethane,
the catalyst was insoluble in CH2Cl2 and separated by a simple
filtration. The solvent was evaporated and the residue was recrys-
tallized from ethanol to give pure compounds in high yields. All of
the products were characterized and identified with m.p., 1H NMR,
13C NMR and FT-IR spectroscopy techniques.
X'pert Company with mono chromatized Cu
Ka radiation
(l
¼ 1.5406 Å). Microscopic morphology of products was visualized
by SEM (LEO 1455VP). The mass spectra were recorded on a Joel D-
30 instrument at an ionization potential of 70 eV. The composi-
tional analysis was done by energy dispersive analysis of X-ray
(EDX, Kevex, Delta Class I). Thermogravimetric analysis (TGA) was
performed on a Mettler Toledo TGA under argon and heated from
room temperature to 825 ꢀC. The approximate sample weight was
10 mg in TG experiment with 10 ꢀC/min heating rate.Magnetic
property of the sample was measured with a vibrating sample
magnetometer (VSM) instrument MDKFT.Transmission electron
microscopy (TEM) was performed with a Jeol JEM-2100UHR,
operated at 200 kV.
2.5. Spectral data of the new products
2.5.1. 2,4- diamino-6-(4-isopropylphenyl)pyrimidine-5-
carbonitrile) 4j)
Gray solid; m.p 125e128 ꢀC; 1H NMR (DMSO‑d6, 400 MHz)
d
.:
1.19 (d, 6H,2CH3), 2.9 (m, 1H, CH), 7.4 (s, 2H, NH2), 3.4 (s, 2H, NH2),
7.1e7.3 (m, 4H, H- Ar); 13C NMR (DMSO‑d6, 100 MHz)
: 23.1, 33.0,
d
79.2, 115.3, 124.3, 127.9, 131.9,148.1, 163.7, 165.5, 169; IR (KBr) v:
Scheme 1. Synthesis of 2,4- diamino-6-arylpyrimidine-5-carbonitriles using
NiCo2O4@Ni(BDC)
Scheme 2. Preparation of NiCo2O4@Ni(BDC) MOF.

M.A. Ghasemzadeh et al. / Journal of Organometallic Chemistry 900 (2019) 120935
3
3350 (NH2), 2197 (C^N),1485 (C]C),1383 (CH3), cmꢁ1; MS (EI) (m/
z): 253.31; Anal.calcd. for C14H15N5: C 66.38, H 5.97, N 27.65. Found
C 65.7, H 5.89, N 27.5.
NiCo2O4@Ni(BDC) occurred below 350 ꢀC, indicating the removal of
the occluded DMF and water from of the coordinating polymer
frameworks. Below 350 ꢀC, NiCo2O4@Ni(BDC) MOF exhibited
weight loss of 23%e25% (wt) %. After the first weight loss, the TGA
curve for the NiCo2O4@Ni(BDC) reached a plateau at temperatures
of 380e430 ꢀC. This illustrates the stability of the framework of the
NiCo2O4@Ni(BDC) structure at the temperature of guest desorption
and framework decomposition. The onset temperature of the sec-
ond weight loss corresponded to the decomposition of organic
species in the framework. The onset decomposition temperature at
450 ꢀC was for NiCo2O4@Ni(BDC) in the second stage.
An EDX analysis was used to confirm the chemical purity of the
NiCo2O4@Ni(BDC) sample as well as its stoichiometry. The results of
Fig. 4 show that typical characteristic peaks of Ni, O, C and Co el-
ements in the survey spectrum, verifying the existence of them in
the NiCo2O4@Ni(BDC).
2.5.2. 2,4- diamino-6-(4-cyanophenyl)pyrimidine-5-carbonitrile
(4k)
Yellow solid, m.p. 167e170 ꢀC, 1H NMR (DMSO‑d6, 400 MHz)
d:
1.19 (d, 6H,2CH3), 2.9 (m, 1H, CH), 7.4 (s, 2H, NH2), 6.2 (s, 2H, NH2),
7.2e7.4 (m, 4H, H- Ar); 13C NMR (DMSO‑d6,100 MHz)
d: 79.6, 112.2,
115.3, 118.4, 126.0, 132.5, 139.1,163.5, 166.3, 169.3; IR (KBr) v:
3350(NH2), 2198(C^N), 1698 (C]N), 1400 (C]C), cmꢁ1; MS (EI)
(m/z): 236.08; Anal. calcd. for C12H8N6: C 61.01, H 3.41, N 35.58.
Found C 61.0, H 3.43, N 35.0.
3. Results and discussion
The XRD pattern of the NiCo2O4@Ni(BDC) nanocatalyst is shown
in Fig. 5. The positions and relative diffraction peaks at around
Initially, the metal-organic framework NiCo2O4@Ni(BDC) was
synthesized and characterized by different spectroscopic tech-
niques including FE-SEM, EDX, XRD, TGA, TEM, VSM and FT-IR
analysis.
2q
¼ 18.89ꢀ, 31.20ꢀ, 36.88ꢀ, 38.4ꢀ, 44.47ꢀ, 55.4ꢀ, 59.16ꢀ, 65.12ꢀ, and
76.9ꢀ for NiCo2O4@Ni(BDC) nanocrystallites confirm well with its
structure [43].
Scanning electron microscopy (SEM) is an effective tool for
determining the size distribution, particle shape, and porosity. The
basis of the operation of a scanning electron microscope is the
interaction of electron beam with matter, which carries out the
emission of electrons and photons from the material. Fig. 1 shows
FE-SEM images of the as-synthesized NiCo2O4@Ni(BDC) sample.
Scanning electron microscopy of NiCo2O4@Ni(BDC) is obtained to
investigate the morphology and the particle size of this
organiceinorganic hybrid material. The results revealed that the
presence of well-formed crystals.
The magnetic properties of NiCo2O4 and NiCo2O4@Ni(BDC) were
studied by using vibration sample magnetometry (VSM) at room
temperature. As shown in Fig. 6, the magnetic saturation (MS)
values of the NiCo2O4 NPs is
5 , and for the NiC-
emugꢁ1
o2O4@Ni(BDC) composite is 2 emugꢁ1. The slightly lower MS value
of NiCo2O4@Ni(BDC) mainly results from the introduction of
Ni(BDC). The presence of suitable magnetic properties allows
NiCo2O4@Ni(BDC) to be completely, efficiently and quickly sepa-
rated from the reaction mixture by an external magnet.
The structure of NiCo2O4@Ni(BDC) was studied by using the
transmission electron microscopy (TEM) (Fig. 7). These images are
an appropriate tool for determining the size and structure of par-
ticles. The TEM images show that small particles of 30e50 nm
which confirmed by the FE-SEM images.
To optimize the reaction conditions, the condensation reaction
of 4-chlorobenzaldehyde, malononitrile and guanidine hydrochlo-
ride was selected as a model study to examine the effect of the
catalyst, solvent and reactants for the synthesis of 2,4-diamino
pyrimidine-5-carbonitrile derivatives (Scheme 3).
To explore the effect of the solvent in the preparation of 2,4-
diamino-6-(4-chlorophenyl)pyrimidine-5-carbonitrile, we pre-
formed the model reaction using NiCo2O4@Ni(BDC) metal-organic
framework under various solvents and also solvent-free condi-
tions in different temperatures. The best results were obtained
under reflux conditions. Fig. 8 shows that, the solvent has a great
The composition of NiCo2O4@Ni(BDC) was further studied by
Fourier transform infrared (FT-IR) (Fig. 2). Compared to NiCo2O4,
the NiCo2O4@Ni(BDC) spectrum shows higher adsorption bands,
which are related to the Ni(BDC) structure. As shown in Fig. 2a, the
absorption bands at 526 and 440 cmꢁ1 are related to NieO and
CoeO in NiCo2O4 nanoparticles. For the NiCo2O4@Ni(BDC) metal
organic frameworks (Fig. 2b), characteristics peaks at 1678 and
733 cmꢁ1 are assigned to the COOꢁ groups and absorption bands at
1508, 1423 and 1282 cmꢁ1 are assigned to the CeH in the BDC ring,
which clearly indicates the presence of Ni(BDC). Moreover, the
stretching vibrations of NieO and CoeO are appeared at 548 and
428 cmꢁ1 NiCo2O4@Ni(BDC) which these absorption bands repre-
sent the maintenance of the catalyst structure.
Fig. 3 shows the thermogravimetric analysis (TGA) curve of
NiCo2O4@Ni(BDC) MOF. This nanocomposite exhibited two-stage
weight loss in the TGA curve. The first weight loss of the
Fig. 1. FE-SEM images of NiCo2O4@Ni(BDC)

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M.A. Ghasemzadeh et al. / Journal of Organometallic Chemistry 900 (2019) 120935
Fig. 2. FT-IR spectra of the NiCo2O4 (a) and NiCo2O4@Ni(BDC) (b).
In continuation of our research, we ran the study model using
different amounts of NiCo2O4@Ni(BDC) nanocatalyst under reflux
conditions. As shown in Fig. 10, the optimum concentration of
NiCo2O4@Ni(BDC) MNPs was obtained at 0.008 g. A value greater
than 0.008 g does not change the time and yield of the reaction.
The scope and limitation of this research were examined when
we obtained the optimized reaction conditions. A diversity of al-
dehydes were used in this study in presence of NiCo2O4@Ni(BDC)
MNPs under reflux conditions. We observed that various aryl al-
dehydes could be introduced in high efficiency and produced high
yields of products in high purity. The summarized results of Table 1
show that sterically hindered aromatic aldehydes need to longer
reaction times in comparison with p-substituted aryl aldehydes. In
addition, aromatic aldehydes bearing electron-withdrawing groups
such as Br, and Cl in the p-position reacted very smoothly, in short
reaction times and high yields while reactants with electron-
releasing groups such as methoxy decreased both the rate of the
reaction and the yield of the corresponding product.
Fig. 3. TGA profile of the NiCo2O4@Ni(BDC)
A plausible mechanism for the preparation of 2,4-diamino-6-
arylpyrimidine-5-carbonitriles in the presence of NiC-
o2O4@Ni(BDC) nanostructure as catalyst is depicted in Scheme 4
based on the obtained results together with previous published
paper [35]. It is supposed that catalytically active site of NiC-
o2O4@Ni(BDC) NPs is Ni2þ that behaves as a Lewis acid and co-
ordinates to the carbonyl groups of the aldehyde and double and
triple bonds of the reactants and intermediates. Firstly, interme-
diate І is formed through the Knoevenagel reaction between
malononitrile and aldehyde, and subsequently olefin ІІ is produced
by dehydration. Subsequent condensation of the guanidine 3 and
olefin ІІ followed by intramolecular cyclization and the oxidation
which affords the corresponding products 4 (a-k).
3.1. Catalyst recovery
Fig. 4. The EDX spectrum of NiCo2O4@Ni(BDC)
After completion of the reaction, the reaction mixture was dis-
solved in dichloromethane and then the catalyst was separated
magnetically. The NiCo2O4@Ni(BDC) MNPs were washed three to
four times with water and ethanol and dried at 60 ꢀC for 12 h. The
separated catalyst was used for six cycles with a slightly decreased
in its activity (Fig. 11). In conclusion, we were able to express that a
series of 2,4-diamino-6-arylpyrimidine-5-carbonitrile derivatives
could be obtained by the catalytic application of the NiC-
o2O4@Ni(BDC) metal-organic frameworks under reflux conditions.
In addition, to prove the stability and performance of the recovered
effect on the accelerating of the reaction. The best results (93%
Yield) were obtained in ethanol for this multi component reaction.
Then, to demonstrate the importance of the present research in
compared to other catalysts, the model reaction was performed in
the presence of various catalysts such as KOH, MgO, ZnO, CuI,
NaOH, Ni(BDC) and NiCo2O4@Ni(BDC) using ethanol as solvent
under reflux conditions. As shown in Fig. 9, the nanoporous metal-
organic framework was the best catalysts with respect to reaction
time and yield of the obtained product.

M.A. Ghasemzadeh et al. / Journal of Organometallic Chemistry 900 (2019) 120935
5
Fig. 5. XRD pattern of NiCo2O4@Ni(BDC)
Scheme 3. The model reaction for the synthesis of 2,4-diamino-6-(4-chlorophenyl)
pyrimidine-5-carbonitrile.
nanocatalyst, the FT-IR spectrum and the XRD pattern of the
recovered NiCo2O4@Ni(BDC) is given after six runs uses (Fig. 12). As
seen, there is no significant difference between the XRD and FT-IR
of fresh and recovered nanocomposite. These facts prove that the
appearance and structure of NiCo2O4@Ni(BDC) catalyst remained
intact in recycles and there was no considerable deformation or
leaching after 6 runs.
In this research to confirm that we used a heterogeneous cata-
lyst, hot filtration experiment was conducted using 4-
chlorobenzaldehyde, malononitrile and guanidine hydrochloride
Fig. 6. Magnetization curves of the NiCo2O4(a) and NiCo2O4@Ni(BDC) (b).
Fig. 7. TEM images of NiCo2O4@Ni(BDC)

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M.A. Ghasemzadeh et al. / Journal of Organometallic Chemistry 900 (2019) 120935
Fig. 8. Preparation of corresponding pyrimidine in different solvents.
Scheme 4. Proposed reaction mechanism for preparation of 2,4-diamino-6-
arylpyrimidine-5-carbonitriles using NiCo2O4@Ni(BDC) MNPs.
Fig. 9. The model reaction was carried out by various catalysts.
Fig. 11. Reusability of the NiCo2O4@Ni(BDC) nanocomposite.
Fig. 10. The effect of different amounts of NiCo2O4@Ni(BDC) on the model reaction.
Table 1
NiCo2O4@Ni(BDC)NPs catalyzed one-pot synthesis of 2,4-diamino-6-arylpyrimidine-5-carbonitrile derivativesa.
Number
Ar
Product
T (min)
Yielda (%)
mp, oC
Mp.[Ref]b
1
2
3
4
5
6
7
8
4-Cl-C6H4
4a
4b
4c
4d
4e
4f
4g
4h
4i
120
150
180
150
120
120
150
150
150
160
150
93
88
82
90
90
90
91
93
87
85
91
265e267
235e237
170e172
236e239
237e239
258e260
258e260
262e264
256e258
125e128
127e130
265e26637
236e23837
17236
4-MeO-C6H4
2-OH-C6H4
C6H5
237e23937
235e23737
260e26237
26036
4-F-C6H4
4- BreC6H
4-OH-C6H4
3-MeO-C6H4
4-Me-C6H4
4-CH(CH3)2eC6H4
4-CN-C6H4
261e26335
255e25735
9
10
11
c
4j
4k
….
….
c
a
Reaction conditions: aldehyde (1 mmol), malononitrile (1.2 mmol), guanidine hydrochlorid(1 mmol) and NiCo2O4@Ni(BDC) NPs (0.008 g).
Isolated yield.
New compounds.
b
c

M.A. Ghasemzadeh et al. / Journal of Organometallic Chemistry 900 (2019) 120935
7
Fig. 12. The XRD pattern and FT-IR spectrum of the recovered NiCo2O4@Ni(BDC)
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about 20 min in the presence of NiCo2O4@Ni(BDC) MNPs in ethanol
under reflux conditions. Then, the filtered reaction media was
continued under stirring without a catalyst for 8 h; no product
formation was observed, indicating that no homogeneous catalyst
was involved. Furthermore, energy-dispersive X-ray spectroscopy
(EDX) analysis of the filtrate (hot) discloses the absence of Ni and Co
species in the filtrate.
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4. Conclusion
We have developed a green and straightforward protocol for the
synthesis of 2,4-diamino-6-arylpyrimidine-5-carbonitrile de-
rivatives via a multi component condensation reactions in the
presence of NiCo2O4@Ni(BDC) as a novel nanocatalyst under reflux
conditions. The attractive features of this protocol are the simple
procedure, cleaner reaction conditions, and the use of recyclable
nanocatalyst. Satisfactory yields of products and easy workup make
this a useful protocol for green synthesis of this class of compounds.
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