Design and synthesis of nickel tetra‐2,3‐pyridiniumporphyrazinato trinitromethanide as an influential catalyst and its application in the synthesis of 1,2,4-triazolo based compounds

Article abstract of DOI:10.1016/j.jpcs.2021.110322

The facile and benign syntheses of [1,2,4]triazolo[5,1-b]quinazolines and [1,2,4]triazolo[1,5-b]pyrimidines were studied using novel nickel tetra‐2,3‐pyridiniumporphyrazinato trinitromethanide [Ni(TPPAH)][C(NO₂)₃]₄ as an e

Full text of DOI:10.1016/j.jpcs.2021.110322

Journal of Physics and Chemistry of Solids 160 (2022) 110322
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Journal of Physics and Chemistry of Solids
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Design and synthesis of nickel tetra-2,3-pyridiniumporphyrazinato
trinitromethanide as an influential catalyst and its application in the
synthesis of 1,2,4-triazolo based compounds
,
,
,***
Mohammad Dashteha, Saeed Bagherya *, Mohammad Ali Zolfigola **, Ardeshir Khazaeia
,
,
Sajjad Makhdoomib, Maliheh Safaieec, Jamshid Rakhtshahd ****, Yadollah Bayate,
Asiye Asgarie
a Department of Organic Chemistry, Faculty of Chemistry, Bu-Ali Sina University, Hamedan, 6517838683, Iran
b Department of Pharmacology and Toxicology, School of Pharmacy, Hamedan University of Medicinal Science, Hamedan, Iran
c Department of Medicinal Plants Production, University of Nahavand, Nahavand, 6593139565, Iran
d Department of Inorganic Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
e Faculty of Chemistry and Chemical Engineering, Malek Ashtar University of Technology, Tehran, Iran
A R T I C L E I N F O
A B S T R A C T
Keywords:
The facile and benign syntheses of [1,2,4]triazolo[5,1-b]quinazolines and [1,2,4]triazolo[1,5-b]pyrimidines were
studied using novel nickel tetra-2,3-pyridiniumporphyrazinato trinitromethanide [Ni(TPPAH)][C(NO2)3]4 as an
efficient catalyst. The desired products were synthesized under solvent-free conditions using 10 mg of [Ni
(TPPAH)][C(NO2)3]4 as a catalyst at 80 ◦C. The morphology and structure of [Ni(TPPAH)][C(NO2)3]4 were
studied and characterized using several techniques. The products had good to excellent yields with short reaction
times. The presented catalyst was simply recovered and reused. Some of the obtained products (10 items) are
reported for the first time.
Nickel tetra-2,3-pyridiniumporphyrazinato
trinitromethanide [Ni(TPPAH)][C(NO2)3]4
Solvent-free condition
[1,2,4]Triazolo[1,5-b]pyrimidines
[1,2,4]Triazolo[5,1-b]quinazolines
1. Introduction
chemistry and medicinal chemistry and are used to establish numerous
biologically active compounds [12–14]. These compounds have various
The production of numerous bonds in a one-step process has been
developed as a significant methodology for organic synthesis [1,2].
Multi-component reactions (MCRs) have been considered to synthesize
biologically active compounds and have become a major area of study in
organic chemistry and pharmacology [3,4]. The chief advantages of
MCRs are high bond-forming efficacy, lower cost, easy work-up, energy
saving and hence decreased waste generation by developing green
routes [5,6].
biological properties, for instance therapeutic potentiality [15], anti-
convulsant [16], cytotoxicity [17], antidiabetic [18], anti-tumor [19],
antiviral [20] and cardiovascular activities [21]. Triazolo-quinazolines
and -pyrimidines have been synthesized using numerous methods and
reagents including nano n-propylsulfonated γ-Al2O3 [22], sulfamic acid
[23], Lawesson’s reagent [24] and Nafion-H [25].
Phthalocyanines (Pcs) of transition metals are noteworthy as po-
tential oxidation catalysts due to their low-cost and simple synthesis on a
large scale and their thermal stability [26]. The Pcs are one of the
important groups of macrocycles and are broadly applied for various
purposes such as catalytic systems, Langmuir–Blodgett films, chemical
sensors, molecular metals and liquid crystals [27,28]. Metal Pcs have a
planar structure and are aromatic complexes of porphyrazins [29,30].
Nitrogen-including heterocyclic skeletons have major roles in several
types of chemical compounds. Among these compounds, quinazolines
and pyrimidines are advantageous as building blocks and so have been
investigated widely due to their outstanding pharmacological activities
[7–11]. Additionally, the triazoles are major fundamental motifs in
* Corresponding authors.
** Corresponding author.
*** Corresponding author.
**** Corresponding author.
E-mail addresses: saadybaghery@yahoo.com (S. Baghery), zolfi@basu.ac.ir, mzolfigol@yahoo.com (M.A. Zolfigol), Khazaei_1326@yahoo.com (A. Khazaei), j.
rakhtshah@tabrizu.ac.ir (J. Rakhtshah).
https://doi.org/10.1016/j.jpcs.2021.110322
Received 31 December 2020; Received in revised form 29 July 2021; Accepted 9 August 2021
Available online 13 August 2021
0022-3697/© 2021 Elsevier Ltd. All rights reserved.

M. Dashteh et al.
Journal of Physics and Chemistry of Solids 160 (2022) 110322
Scheme 1. Synthesis of nickel tetra-2,3-pyridiniumporphyrazinato trinitromethanide [Ni(TPPAH)][C(NO2)3]4.
Scheme 2. Synthesis of [1,2,4]triazolo[5,1-b]quinazolines and [1,2,4]triazolo[1,5-b]pyrimidines using [Ni(TPPAH)][C(NO2)3]4.
As part of our consideration of the chemistry of Pcs-based catalysts
3-pyridiniumporphyrazinato
trinitromethanide
[Ni(TPPAH)][C
[31,32], herein, we report an investigation on three-component syn-
(NO2)3]4 (Schemes 1 and 2). Some of the obtained products (10 items)
are reported for the first time, and are characterized by several analyses
including melting point, Fourier-transform infrared (FT-IR)
thesis of [1,2,4]triazolo[5,1-b]quinazolines and [1,2,4]triazolo[1,5-b]
pyrimidines
catalyzed
by
novel
nickel
tetra-2,
2

M. Dashteh et al.
Journal of Physics and Chemistry of Solids 160 (2022) 110322
Fig. 1. UV–Vis spectra of (a) [Ni(TPPA)] and (b) [(OH)2Ni(TPPAH)][C(NO2)3]4.
Fig. 2. FT-IR spectra of (a) [Ni(TPPA)] and (b) [Ni(TPPAH)][C(NO2)3]4.
spectroscopy, 1H nuclear magnetic resonance (NMR), 13C NMR and
elemental (CHN) analysis.
ammonium molybdate tetrahydrate [(NH4)6Mo7O24.4H2O] (0.046 g,
0.02 mol), 2,3-pyridine-dicarboxylic acid (1.0 g, 0.006 mol) and nickel
(II) chloride hexahydrate [NiCl2.6H2O] (0.2 g, 0.0008 mol) were ground
together to produce a homogenous mixture. The reaction mixture was
refluxed in 1,2,4-trichlorobenzene (40 mL) at 160 ◦C for 5 h. Then, the
mixture was allowed to cool to room temperature over 5 h. A crude blue
solid was obtained and washed three times with warm water. Then the
solid was washed with warm aqueous NaOH solution (5% w/v), warm
water, warm diluted aqueous hydrochloric acid (2.5% v/v) and warm
2. Experimental
2.1. General procedure for synthesis of [Ni(TPPA)]
The [Ni(TPPA)] was synthesized and purified based on reported
procedures [33]. The general procedure follows: urea (6.5 g, 0.108 mol),
3

M. Dashteh et al.
Journal of Physics and Chemistry of Solids 160 (2022) 110322
Fig. 3. (a) TGA and (b) DTA of [Ni(TPPAH)][C(NO2)3]4.
under vacuum (Scheme 1).
Table 1
Elemental analysis of (a) [Ni(TPPA)] and (b) [Ni(TPPAH)][C(NO2)3]4.
2.2. General procedure for synthesis of [Ni(TPPAH)][C(NO2)3]4
Element
C
H
N
Wt.% (a)
Experimental
Computational
Experimental
Computational
52.44
55.21
32.10
31.68
2.51
2.32
1.75
1.50
25.62
27.59
27.97
27.71
To a round-bottomed flask (50 mL) including a solution of [Ni
(TPPA)] (3.176 g) in C2H5OH:CH3CN (1:1; 4 mL), trinitromethane (4.0
mmol; 0.604 g; 0.411 mL) was added using a dropper over a period of
Wt.% (b)
◦
60 min while stirring and cooling to keep the temperature at 0–5 C
(caution: trinitromethane should be added with extreme caution due to
its energetic character). Then, the reaction mixture was stirred for a
further 120 min under reflux condition. The violet solid product [Ni
(TPPAH)][C(NO2)3]4 was washed three times with diethyl ether,
dichloromethane and then dried under vacuum (isolated yield 59%,
2.230 g) (Scheme 1).
◦
water consecutively. The obtained crude product was dried at 100 C
under vacuum and purified by dissolving in concentrated sulfuric acid
and pouring the solution into ice-water. The precipitated product was
collected by centrifugation (ca. 200 rpm/10 min) and transferred to a
fine sintered glass funnel where the mass was washed with hot water, a
warm aqueous sodium carbonate solution and warm water consecu-
tively. The [Ni(TPPA)] (isolated yield 41%, 3.176 g) was dried at 100 ◦C
Fig. 4. (a) DRS analysis and (b) Kubelka–Munk function of [Ni(TPPAH)][C(NO2)3]4.
Fig. 5. (a) EDX analysis and (b) SEM coupled EDX (SEM mapping) of [Ni(TPPAH)][C(NO2)3]4.
4

M. Dashteh et al.
Journal of Physics and Chemistry of Solids 160 (2022) 110322
Fig. 6. (a) XRD pattern, (b) TEM and (c and d) SEM of [Ni(TPPAH)][C(NO2)3]4.
Table 2
Optimization reaction conditions for synthesis of 10d.a
Entry
Solvent
Catalyst loading (mg)
Temperature (◦C)
Time (min)
Yieldb (%)
1
–
–
80
120
20
15
60
90
40
120
45
10
10
5
–
2
H2O
10
10
10
10
10
10
10
10
15
20
5
80
70
76
–
3
C2H5OH
Reflux
Reflux
Reflux
80
4
EtOAc
5
CH3CN
–
34
–
65
87
79
80
51
–
6
DMF
7
n-Hexane
Reflux
80
8
PEG
9
–
–
–
–
–
–
–
80
10
11
12
13
14
15
80
80
80
25
120
30
15
10
10
10
r.t.
50
Trace
80
100
a
Reaction conditions: 4-chlorobenzaldehyde (1.0 mmol, 0.140 g), 3-amino-1,2,4-triazole (1.0 mmol, 0.084 g, 0.014 mL), ethyl acetoacetate (1.0 mmol, 0.130 g,
0.008 mL).
b
Isolated yield.
2.3. General procedure for synthesis of products 8–11
mmol, 0.084 g, 0.014 mL), 2-hydroxy-1,4-naphthoquinone (1.0 mmol,
0.174 g, for synthesis of 8) or dimedone (1.0 mmol, 0.140 g, for syn-
thesis of 9) or ethyl acetoacetate (1 mmol, 0.130 g, 0.008 mL, for
A mixture of aldehyde (1.0 mmol), 3-amino-1,2,4-triazole (1.0
5

M. Dashteh et al.
Journal of Physics and Chemistry of Solids 160 (2022) 110322
Table 3
Synthesis of [1,2,4]triazolo[5,1-b]quinazolines (8 and 9) and [1,2,4]triazolo[1,5-b]pyrimidines (10 and 11) using [Ni(TPPAH)][C(NO2)3]4 (10 mg)
under solvent-free conditions at 80 ◦C.a,b
.
a Reaction conditions: synthesis of 8, aldehyde (1.0 mmol), 3-amino-1,2,4-triazole (1.0 mmol, 0.084 g, 0.014 mL), 2-hydroxy-1,4-naphthoquinone
(1.0 mmol; 0.174 g); synthesis of 9, aldehyde (1.0 mmol), 3-amino-1,2,4-triazole (1.0 mmol, 0.084 g, 0.014 mL), dimedone (1.0 mmol, 0.140 g);
synthesis of 10, aldehyde (1.0 mmol), 3-amino-1,2,4-triazole (1.0 mmol, 0.084 g, 0.014 mL), ethyl acetoacetate (1.0 mmol, 0.130 g, 0.008 mL);
synthesis of 11, aldehyde (1.0 mmol), 3-methyl-1H-pyrazol-5-amine (1 mmol, 0.097 g), pyrimidine-2,4,6(1H,3H,5H)-trione (1.0 mmol, 0.128 g, for
synthesis of 11a–c) or 1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione (1.0 mmol, 0.156 g, for synthesis of 11d and e); b Isolated yield.
synthesis of 10) under solvent-free conditions was stirred at 80 ◦C using
[Ni(TPPAH)][C(NO2)3]4 (10 mg) as a catalyst. Also, in other work, a
mixture of aldehyde (1.0 mmol), 3-methyl-1H-pyrazol-5-amine (1
mmol, 0.097 g) and pyrimidine-2,4,6(1H,3H,5H)-trione (1.0 mmol,
0.128 g, for synthesis of 11a–c) or 1,3-dimethylpyrimidine-2,4,6
(1H,3H,5H)-trione (1.0 mmol, 0.156 g, for synthesis of 11d and e) was
stirred under similar conditions. After the end of the reaction, observed
using thin layer chromatography (TLC; n-hexane/ethyl acetate: 1/1), the
6

M. Dashteh et al.
Journal of Physics and Chemistry of Solids 160 (2022) 110322
Fig. 7. (a) Recyclability study of [Ni(TPPAH)][C(NO2)3]4 in synthesis of 10d after 10 min and (b) XRD pattern of [Ni(TPPAH)][C(NO2)3]4 after four consecu-
tive runs.
from the monocyclic ring in the [Ni(TPPAH)][C(NO2)3]4, compared
Table 4
with [Ni(TPPA)] which shows B or Soret band at 368 nm [35,36]. The
Elemental analysis of recycled [Ni(TPPAH)][C(NO2)3]4.
optical band-gap energy (Ebg = 1240/λmax) for [Ni(TPPAH)][C(NO2)3]4
Element
C
H
N
is 1.98 eV.
FT-IR analysis: The FT-IR analysis of [Ni(TPPAH)][C(NO2)3]4 is
Wt.%
Experimental
32.10
31.68
1.73
1.50
27.95
27.71
achieved in the range of 400–4000 cmꢀ 1 (Fig. 2). The FT-IR spectrum
shows the functional groups that exist in this compound. The broad
peaks around 3209 and 3070 cmꢀ 1 are assigned to the stretching vi-
brations of N–H and aromatic C–H bands, respectively (the broad peaks
at 3387 and 3064 cmꢀ 1 are related to stretching vibrations of O–H in
surface and aromatic C–H bands in [Ni(TPPA)], respectively). The sharp
peaks at 1531 and 1345 cmꢀ 1 can be attributed to the stretching
vibrational modes of –NO2. Remarkably, the peak at 761 cmꢀ 1 is con-
nected to Ni–ligand coordination bonds (the peak at 738 cmꢀ 1 is linked
to formation of Ni–ligand coordination bonds).
Computational
solid mass precipitate was filtered off and washed with ethanol to
separate the catalyst from other materials (the catalyst was insoluble in
ethanol and the reaction mixture was soluble). The solvent of the filtrate
was evaporated and the crude product was recrystallized from ethanol
to give the corresponding products 8–11. The analytical data and
spectral images for compounds are presented in the Supporting
Information.
TGA and DTA: The TGA is applied for determination of thermal
stability of [Ni(TPPAH)][C(NO2)3]4 up to 600 ◦C (Fig. 3). These analyses
show about 2% weight loss around 25–100 ◦C that can be ascribed to
elimination of the adsorbed water and other physically adsorbed sol-
vents remaining from the extraction procedure. The second weight loss
(about 14%) at 240–325 ◦C is because of removal of the trini-
tromethanide group after the extraction procedure. Lastly, the chief
weight loss (about 17%) in the range of 325–430 ◦C is ascribed to
decomposition of the nickel tetra-2,3-pyridiniumporphyrazinato group.
The TGA and DTA curves show that this compound is stable up to
430 ◦C. At temperatures above 430 ◦C, the structure of the catalyst is not
stable and is destroyed.
3. Results and discussion
3.1. Characterization of [Ni(TPPAH)][C(NO2)3]4
The [Ni(TPPA)] was produced via the process of Yokote et al. [33], in
the
reaction
of
urea,
2,3-pyridine-dicarboxylic
acid,
(NH4)6Mo7O24⋅4H2O and NiCl2⋅6H2O. In the next step, [Ni(TPPAH)][C
(NO2)3]4 was formed using reaction between [Ni(TPPA)] and trinitro-
methane in ethanol-acetonitrile (1:1) under reflux conditions. Finally,
the morphology and structure of novel [Ni(TPPAH)][C(NO2)3]4 were
studied using several techniques: UV–Vis, FT-IR, thermal gravimetric
analysis (TGA), differential thermal analysis (DTA), inductively coupled
plasma (ICP) spectroscopy, CHN analysis, diffuse reflectance spectros-
copy (DRS), energy-dispersive X-ray spectroscopy (EDX), scanning
electron microscopy (SEM)-coupled EDX (SEM mapping), X-ray
diffraction (XRD), field emission (FE)-SEM and transmission electron
microscopy (TEM). The lone-pair electrons of the non-coordinated ni-
trogens of the catalyst precursor are orthogonal to ring p-orbitals which
participate in aromaticity and are coordinated to the central metal (Ni).
Therefore, these non-coordinated lone pairs are completely concen-
trated and localized at their corresponding nitrogens. Thus, these ni-
trogens have more basic ability than others. The acidic protons of
trinitromethane connect to two near non-coordinated nitrogen lone
pairs of the catalyst structure via hydrogen bonding (driving force of
hydrogen bonding via formation of 5-membered ring).
ICP and CHN analysis: The exact percentage of Ni in [Ni(TPPAH)][C
(NO2)3]4 is 3.45 wt% according to the ICP result. The CHN analysis of
[Ni(TPPAH)][C(NO2)3]4 is summarized in Table 1. The CHN data of [Ni
(TPPA)] and [Ni(TPPAH)][C(NO2)3]4 are shown in Figs. S43 and S44.
DRS analysis: The DRS and Kubelka–Munk function (derived from
DRS) of [Ni(TPPAH)][C(NO2)3]4 are investigated (Fig. 4). The main
peaks in the range 300–400 nm show the transition between valence
band and conduction band. The weak absorption in the UV–Vis region is
probably due to transitions including outer states; for example surface
traps, deficiency states, or impurity. The Kubelka–Munk theory is
applied to describe the energy band gap of the [Ni(TPPAH)][C(NO2)3]4
produced from DRS. The measured band gap energy for [Ni(TPPAH)][C
(NO2)3]4 is 1.98 eV (based on UV–Vis spectrum). The broad band at
around 569 nm is due to the electronic ligand–field transition of Ni2+ in
tetrahedral coordination [37–39].
UV–Vis analysis: The UV–Vis spectrum of the [Ni(TPPAH)][C
(NO2)3]4 in DMSO displays a strong Q-band at 631 nm (Fig. 1b),
compared with [Ni(TPPA)] which shows a strong Q-band at 627 nm
(Fig. 1a). Also the visible absorption spectra display a vibration satellite
at 572 nm – compared with [Ni(TPPA)] which displays a vibration
satellite at 569 nm – and this band is characteristic for Pc derivatives and
the blue shift of the Q-band corresponding to Pcs is typical of pyr-
idinoporphyrazine complexes [34]. Additionally, the characteristic
EDX analysis and SEM mapping: The homogeneous and corre-
sponding signals of the elements C, N, Ni and O are clearly shown in the
EDX elemental mapping (Fig. 5), additionally confirming that the tri-
nitromethanide molecules are attached on the [Ni(TPPA)] surface by
close interface exchange. As predictable, C is the chief element for all
materials, with average contents about 61.7 wt%. This analysis shows
average contents of 14.9 wt% N, 12.5 wt% Ni and 10.9 wt% O.
band at the 374 nm region (B or Soret band) relates to π→π* transition
7

M. Dashteh et al.
Journal of Physics and Chemistry of Solids 160 (2022) 110322
Scheme 3. The predicted structures of reaction adduct.
XRD, FE-SEM and TEM analyses: The high dispersion of [Ni
[5,1-b]quinazolines 8 and 9) and ethyl acetoacetate 5 (for synthesis of
[1,2,4]triazolo[1,5-b]pyrimidines 10) under solvent-free conditions at
(TPPAH)][C(NO2)3]4 is shown by the XRD pattern of the combined
materials with special peaks for Ni (Fig. 6a). The XRD pattern of this
compound presents a broad maximum with the amorphous peak at 2θ =
27.4. The morphology of this compound is investigated using TEM
(Fig. 6b) and SEM (Fig. 6c and d) analyses. The TEM image of this
compound is in appropriate agreement with XRD analysis and confirms
organized rod-like channels with high uniformity for the material.
Furthermore, the surface morphology of the [Ni(TPPAH)][C(NO2)3]4 is
investigated by SEM imaging. This clearly shows particles with spherical
morphology for the material. The particle size distribution has an
average diameter of above 100 nm (XRD data of [Ni(TPPAH)][C
(NO2)3]4 seen in Fig. S40).
◦
80 C. Also, in other work, the reactions between aldehyde 1, pyrimi-
dine-2,4,6(1H,3H,5H)-trione 6a or 1,3-dimethylpyrimidine-2,4,6
(1H,3H,5H)-trione 6b and 3-methyl-1H-pyrazol-5-amine 7 for the syn-
thesis of [1,2,4]triazolo[1,5-b]pyrimidines 11 by using [Ni(TPPAH)][C
(NO2)3]4 as a catalyst are investigated under similar conditions.
With the aim of determining the appropriate reaction conditions for
synthesis of 10d, the substrates 4-chlorobenzaldehyde, 3-amino-1,2,4-
triazole and ethyl acetoacetate are stirred together under solvent-free
conditions (Table 2, entry 1) individually under catalyst-free condi-
tions at 80 ◦C. There is no 10d formation even after 120 min. This
demonstrates the requirement of [Ni(TPPAH)][C(NO2)3]4 as a catalyst
in synthesis of 10d. At that point a similar reaction is carried out with 10
mg of catalyst in several solvents and solvent-free conditions (Table 2,
entries 2–9). The 10d is synthesized under the related conditions and
yield of the reaction is considered. From the above optimization, it is
obvious a solvent-free conditions is appropriate for synthesis of 10d. The
similar reaction is also checked with other amounts of catalyst under
solvent-free conditions at 80 ◦C (Table 2, entries 10–12). The appro-
priate amount of catalyst for synthesis of 10d is 10 mg (this may be due
3.2. Catalytic application of [Ni(TPPAH)][C(NO2)3]4 in synthesis of
[1,2,4]triazolo[5,1-b]quinazolines and [1,2,4]triazolo[1,5-b]pyrimidines
The [Ni(TPPAH)][C(NO2)3]4 (10 mg) catalyzes synthesis of [1,2,4]
triazolo[5,1-b]quinazolines and [1,2,4]triazolo[1,5-b]pyrimidines from
the reaction between aldehydes 1,3-amino-1,2,4-triazole, 2,2-hydroxy-
1,4-naphthoquinone 3 or dimedone 4 (for synthesis of [1,2,4]triazolo
8

M. Dashteh et al.
Journal of Physics and Chemistry of Solids 160 (2022) 110322
Scheme 4. Plausible mechanism for synthesis of [1,2,4]triazolo[5,1-b]quinazolines 8 using [Ni(TPPAH)][C(NO2)3]4 as a catalyst.
to the presence of various active acidic sites in the structure of the
catalyst, the functional groups of the reactants including 4-chlorobenzal-
dehyde, 3-amino-1,2,4-triazole and ethyl acetoacetate are protonated
and inactivated. As a result, the reaction progresses to the formation of a
by-product and the isolated yield of the major product decreases). Later
with the optimization of solvent and catalytic amounts, the reaction
temperature is also optimized. To determine the optimum temperature,
reactions are carried out at various temperatures and yields of 10d are
obtained (Table 2, entries 13–15). From these descriptions, the optimum
temperature for this process is established to be 80 ◦C.
of [Ni(TPPAH)][C(NO2)3]4 under solvent-free conditions at 80 ◦C. The
isolated yield of the reaction is 87% after 10 min, and 70% after the fifth
run.
These compounds could be puzzle pieces in our research on devel-
oping our newly established “anomeric based oxidation” mechanism
[40–42]. In contrast to our expected products, the spectral data show
that the reaction proceeds toward the synthesis of 8 (Scheme 3).
According to the results, a possible mechanism is suggested (Scheme
4) [22–25], in which [Ni(TPPAH)][C(NO2)3]4 acts as a bifunctional
catalyst. In the first step, [Ni(TPPAH)][C(NO2)3]4 activates the carbonyl
group of aldehyde 1 to attack the enolate form of 2-hydroxy-1,4-naph-
thoquinone 3. Then, the Knoevenagel condensation between activated
aldehyde 1 and enolate 3 leads to synthesis of heterodiene 12 via
elimination of one molecule of water. In the next step, synthesis of in-
termediate 13 happens via nucleophilic attack of 3-amino-1,2,4-triazole
2 to heterodiene 12. Intramolecular cyclization via the condensation of
the amino group of 2 with 2-hydroxy-1,4-naphthoquinone 3 in the in-
termediate 13 via elimination of one molecule of water yields the
desired product 8. In this entire method, [Ni(TPPAH)][C(NO2)3]4 is
regenerated and reused for consequent reaction. The reported studies
and X-ray crystallography investigations show that this mechanism
proceeds via path A [22–25] and the amino group inside the ring in
3-amino-1,2,4-triazole 2 reacts with intermediate 12 and the desired
product 8 is formed.
To determine the substrate scope of this catalytic process, numerous
aldehydes possessing electron-withdrawing and electron-donating
groups are applied (Table 3). All of them provide suitable yields,
which show the substrate scope in addition to the functional group
tolerance of this process. Aldehydes possessing electron-withdrawing
groups produce reasonably higher yields than those of electron-
donating ones.
In this part of our investigation, the catalyst can be recovered and
reused in up to four successive runs. To assess the recyclability of [Ni
(TPPAH)][C(NO2)3]4, the reaction of 4-chlorobenzaldehyde, 3-amino-
1,2,4-triazole and ethyl acetoacetate under solvent-free conditions at
80 ◦C is also studied. After the end of reaction determined using TLC, the
catalyst is recovered by filtration and thoroughly washed with ethanol.
Then it is dried in the oven and applied for the next runs. Fig. 7a links the
difference of related product yield with the number of runs. The reus-
ability illustration shows that the catalyst can be reused in up to four
consecutive runs without decrease in yield of the related product. The
exact percentage of Ni in recycled [Ni(TPPAH)][C(NO2)3]4 is known to
be 3.01 wt% based on the ICP result. Elemental analysis from the ob-
tained [Ni(TPPAH)][C(NO2)3]4 after its reuse is also investigated. The
CHN analysis results are summarized in Table 4. The XRD pattern of [Ni
(TPPAH)][C(NO2)3]4 after four successive runs confirms the stability of
its structure in the course of the recycling process (Fig. 7b). Moreover,
the XRD patterns of [Ni(TPPAH)][C(NO2)3]4 (before and after recycling)
show the stability of described catalyst structure (XRD data of recycled
[Ni(TPPAH)][C(NO2)3]4 is presented in Fig. S41). Elemental analysis
data of [Ni(TPPAH)][C(NO2)3]4 are shown in Fig. S45. The reaction is
scaled up to 10 mmol of 4-chlorobenzaldehyde, 3-amino-1,2,4-triazole
and ethyl acetoacetate for the synthesis of 10d in the presence of 100 mg
4. Conclusions
The [Ni(TPPAH)][C(NO2)3]4 is efficaciously employed as a novel
heterogeneous catalyst for synthesis of [1,2,4]triazolo[5,1-b]quinazo-
lines and [1,2,4]triazolo[1,5-b]pyrimidines from reactants aldehyde, 3-
amino-1,2,4-triazole, 2-hydroxy-1,4-naphthoquinone or dimedone or
ethyl acetoacetate under benign reaction conditions. Also, in other
study, the reaction between aldehydes, 3-methyl-1H-pyrazol-5-amine
and pyrimidine-2,4,6(1H,3H,5H)-trione or 1,3-dimethylpyrimidine-
2,4,6(1H,3H,5H)-trione for synthesis of [1,2,4]triazolo[1,5-b]pyrimi-
dines is investigated under similar conditions in the presence of [Ni
(TPPAH)][C(NO2)3]4 as a catalyst. These compounds are synthesized
with good yields and appropriate functional group tolerance. The [Ni
(TPPAH)][C(NO2)3]4 is significant in view of its simple preparation,
9

M. Dashteh et al.
Journal of Physics and Chemistry of Solids 160 (2022) 110322
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functional group transformations and should also find wide catalytic
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Mr. Mohammad Dashteh, Ph.D. Student of Organic Chemistry, Dr.
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of Organic Chemistry, Mr. Sajjad Makhdomi, Master of Toxicology, Dr.
Maliheh Safaiee, Ph.D. of Organic Chemistry, Dr. Jamshid Rakhtshah,
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Declaration of competing interest
The authors declare no conflict of interest.
Acknowledgments
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We thank Bu-Ali Sina University and the Iran National Science
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