Synthesis of substituted pyrimidine using ZnFe2O4 nanocatalyst via one pot multi-component reaction ultrasonic irradiation

Article abstract of DOI:10.1002/jhet.4048

A highly efficient, eco-friendly, recyclable heterogeneous ZnFe₂O₄ nanocatalyzed synthesis of 2-amino-4-substituted 1,4-dihydrobenzo[4,5]imidazo[1,2-a]pyrimidine-3-carbonitrile (4a-j) derivatives via one pot multicomponent reaction o

Full text of DOI:10.1002/jhet.4048

Received: 14 February 2020
DOI: 10.1002/jhet.4048
Revised: 24 May 2020
Accepted: 30 May 2020
A R T I C L E
Synthesis of substituted pyrimidine using ZnFe2O4
nanocatalyst via one pot multi-component reaction
ultrasonic irradiation
Pravin Chavan1
Rohini Shelke4
Megha Rai8
| Sachin Bangale2 | Dattatraya Pansare3
| Shivaji Jadhav5 | Shrikrushna Tupare6 | Dhanraj Kamble7
|
|
1Department of Chemistry, Doshi Vakil
College, Raigad, India
Abstract
2Department of Chemistry, G. M. Vedak
College of Science Tala, Raigad, India
3Department of Chemistry, Deogiri
College, Aurangabad, India
4Department of Chemistry, Sadguru
Gadage Maharaj College Karad, Satara,
India
5Department of Chemistry, Tarai College
of Arts and Science, Aurangabad, India
A highly efficient, eco-friendly, recyclable heterogeneous ZnFe2O4 nano-
catalyzed synthesis of 2-amino-4-substituted 1,4-dihydrobenzo[4,5]imidazo
[1,2-a]pyrimidine-3-carbonitrile (4a-j) derivatives via one pot multicomponent
reaction of benzimidazole (1), substituted aromatic aldehyde (2a-j) and
malononitrile (3) under ultrasonic irradiations. Significance of this synthetic
approach is short reaction time, easy handling, simplicity, efficiency, high
yield, and recoverable catalyst.
6Department of Chemistry, K.E.S.
Anandibhai Pradhan Science College,
Raigad, India
7Department of Chemistry, S. B. College
of Science, Aurangabad, India
8Department of Chemistry, Dr. Rafiq
Zakaria College for Women, Aurangabad,
India
Correspondence
Pravin Chavan, Department of Chemistry,
Doshi Vakil College, Goregaon, Raigad,
Maharashtra, India.
Email: chemistryp141286@gmail.com
Dattatraya Pansare, Department of
Chemistry, Deogiri College, Aurangabad-
431005, Maharashtra, India.
Email: dnpansare74@gmail.com
1 | INTRODUCTION
purification of various intermediates.1 Benzo[4,5]imidazo
[1,2-a]pyrimidines have recently attracted attention as
Multi-component reactions (MCRs) are efficient and pow-
erful protocols for the rapid synthesis of highly selective
products and organic components, as well as multiple and
diverse new bonds have been created in highly efficient
and atom-economical manner through one pot synthesis.
Thus it saved time, energy and evaded multistep
important fused nitrogen heterocyclic scaffords in the field
of drugs and pharmaceuticals. These heterocycles have
been widely used as Antifungal,2 hepatoprotective,3
antihypertensive,4 antitumour,5 and cardiotonic agent.6
Pyrimidine ring is one of the most important class of
heterocyclic compounds found in many natural products.
J Heterocyclic Chem. 2020;1–8.
wileyonlinelibrary.com/journal/jhet
© 2020 Wiley Periodicals LLC.
1

2
CHAVAN ET AL.
It is found in vitamins such as thiamine (a), folic acid
(b) and in medicinal scaffold such as antifungal flu cyto-
sine (c), antibacterial brodimoprim (d), and antipsychotic
drug risperidone (e) (Figure 1).7–10
reaction of benzimidazole (1) and malononitrile (3) with
substituted aromatic aldehyde (2a-j) in methanol under
ultrasonic irradiations. Author has selected normal spinel
catalyst ZnFe2O4 for present synthesis because ammonia
molecule preferred to adsorbed on the surface of Zn atom
of spinal zinc ferrite and it is used to removal of ammo-
nia.37 Zinc Ferrite (ZnFe2O4) proves its vital role as
nanocatalyst in present organic synthesis.
Based on the importance of these compounds, various
catalyst have been reported for synthesis of benzo[4,5]
imidazo[1,2-a]pyrimidines including MgO, C5H5N,
11–21
Me2NH, Et3N, N2H4,p-TSA, NH4OAc, and InCl3.
However, some of the reported synthetic methods have
several disadvantages such as low yields, hazardous sol-
vent, long reaction time, high temperature reactions,
expensive, and large amount of catalyst. Due to these
facts, it is important to find an efficient, milder, faster,
and more eco-friendly protocols with excellent yields for
the synthesis of benzo[4,5]imidazo[1,2-a]pyrimidines.
Recently, nanoparticles of mixed metal oxide
(ZnFe2O4) have been broadly used in modern organic
synthesis. Some examples of synthesized compounds by
using (ZnFe2O4) nanocatalyst are 2,3-dihydroquinazolin-
4(1H)ones22 and pyrano[2,3-d]pyrimidines23 derivatives.
ZnFe2O4 is one of the economically efficient, insoluble in
organic solvents, easily recover, easy to separate, having
low surface area, heterogeneous, and economically cheap
nanocatalyst.24–29 Use of ZnFe2O4 nanocatalyst in organic
synthesis resulted in several benefits such as yield
improvement, time reduction, commercially efficient,
suitable experimental procedure to work up and recovery
of catalyst etc.
2 | RESULT AND DISCUSSION
2.1 | Catalyst characterization
2.1.1 | XRD analysis-
The crystalline size (d) was determined by Scherrer's
formula-
0:9λ
d =
βcosθ
The XRD pattern of the ZnFe2O4 particles (Figure 2)
calcined at 180, 300, 500, 800, and 1000ꢀC temperature.
Series of diffraction peaks at 20ꢀ were assigned different
to planes (111), (311), (400), (422), and (511). According
to the (311) diffraction pattern of ZnFe2O4 crystal, the
particle size of ZnFe2O4 can be calculated from the full
width at half-maximum using the Scherrer's equation.
Obviously, the particle size of ZnFe2O4 changes as the Tc
controlled fewer than 180, 300, 500, 800, and 1000ꢀC, the
order is 22, 22, 25, 32, and 32 nm, respectively. These
indicate that the crystallinity of ZnFe2O4 accelerated as
the Tc above 500ꢀC.
With reference to above literature survey, in continu-
ation to our previous research work of pharmaceutical
moieties,30–36 we have focused on synthesis of imidazo
[1,2-a]pyrimidine-3-carbonitrile derivatives (4a-j) using
efficient and heterogeneous Zinc Ferrite (ZnFe2O4) as
nanocatalyzed one-pot three-component condensation
FIGURE 2 XRD pattern of calcinied mixed precursor at
FIGURE 1 Fused pyrimido heterocyclic drugs
various temp

CHAVAN ET AL.
3
FIGURE 3 SEM images of
ZnFe2O4 (1) low resolution and
(2) high resolution
-5
2.1.2 | SEM analysis-
7.2
7.0
6.8
6.6
6.4
6.2
6.0
5.8
5.6
-10
-15
-20
-25
Morphological study of ZnFe2O4 nanocatalyst was carried
out with the help of SEM technique represented in
Figure 3.
SEM analysis clearly indicates that the particle sizes
are irregular with nano size range. Some nanoparticles
agglomerations containing very fine particle, the shape of
particles are not defined porous nature, small, and large
core approximately (5 μm). Porous size of particles is a
favorable to a gas sensing application.
0
200
400
600
800
1000
Temperature (0C)
2.1.3 | TG-DTA analysis
FIGURE 4 TG-DTA curve of mixed precursor
Differential thermal analysis (DTA) was performed at
heating rate of 10 K/min to investigate the thermal prop-
erties of ZnFe2O4. Figure 4 indicates dehydration, decom-
position, and denitration of given materials. The
following reactions clearly matched with Figure 4.
product transformation was not observed which despite
of long reaction time and amount of product (Table 1,
entry 1) formed was meager. Therefore, we focused on
the search for suitable catalyst. With the help of Selected
Lewis acid catalysts- FeCl3, AlCl3, CuSO4.5H2O, and
ZnFe2O4, nanoparticles carried out present reaction
which resulted moderate (74%, 68%, 66%, and 94%)
yields. Among these (Table 1, entries 2-5), ZnFe2O4 nano-
particle was selected as catalyst in present work giving
good yield and easy recovery, within shorter reaction
time (Table 1, entry 5). Similar, examination of different
solvents such as MeOH, DCE, ACN, and EtOH (Table 1,
entries 5-8) were done by using model reaction under
ultrasonic irradiations. We found MeOH as a suitable sol-
vent for our particular organic synthesis of substituted
pyrimidine due to its uniform solubility, excellent yield
and short reaction time (Table 1, entry 5).
2C2NH5O2 + ð9=2ÞO2 ! N2 " + 4CO2 " + 5H2O "
ZnðNO3Þ3 + FeðNO3Þ3 + 4C2H5NO2 ! ZnFe2O4 + 8CO2
" + 10H2O " + 5N2 "
ZnFe2O4 powder stable at about 800ꢀC temperature.38,39
The synthesized ZnFe2O4 have efficiency to play the
role of Nanocatalyst so it was used in the synthesis of
2-Amino-4-substituted
1,4-dihydrobenzo[4,5]imidazo
[1,2-a]pyrimidine-3-carbonitrile (4a-j) derivatives. Ini-
tially, reaction model of (2-aminobenzimidazole (1),
4-chlorobenzaldehyde (2a) and malononitrile (3) was
chosen to optimize the reaction conditions at 70ꢀC. Opti-
mization results of reaction scheme such as different sol-
vents, various catalysts, yield and reaction time are
shown in Table 1.
Conversion of reaction was studied with reference to
amount of catalyst, Scheme 1 reaction was carried out
with or without catalyst. In the absence of catalyst,
Also differential percentage of molar concentrations
(5, 10, 15, and 20 mol%) of catalyst (ZnFe2O4
nanoparticles) were studied at 70ꢀC temperature, under
ultrasonic irradiations. Amongst these various amount of
catalyst (Table 1, entries 9-11), 10 mol% (Table 1, entry 5)
ZnFe2O4 nanoparticles catalyst was observed suitable, as

4
CHAVAN ET AL.
TABLE 1 Optimizations of solvents and catalysts in the synthesis (2-amino-4-substituted 1,4-dihydrobenzo[4,5]imidazo[1,2-a]
pyrimidine-3-carbonitrile)
Entry
Solvent
Neat
Catalyst (mol%)
None
Time (min)
Yields %
1
180
120
180
180
90
25
74
68
66
96
76
80
85
76
95
95
2
MeOH
MeOH
MeOH
MeOH
DCE
FeCl3 (10)
3
AlCl3 (10)
4
CuSO4.5H2O(10)
ZnFe2O4(10)
ZnFe2O4(10)
ZnFe2O4(10)
ZnFe2O4 (10)
ZnFe2O4 (5)
ZnFe2O4 (15)
ZnFe2O4 (20)
5
6
120
120
90
7
CAN
8
EtOH
MeOH
MeOH
MeOH
9
96
10
11
90
90
Note: Reaction conditions: benzimidazole (1) (1 mmol), 4-chloro benzaldehyde (2a) (1 mmol), malononitrile (3) (1 mmol), 8 mL solvent and
70ꢀC temperature under ultrasonic irradiations. The bold value shows best result.
SCHEME 1 Model
reaction- synthesis of 2-amino-
4-substituted 1,4-dihydrobenzo4,5
imidazolo[1,2-a]pyrimidine-
3-carbonitrile (4a) catalyzed by
ZnFe2O4 under ultrasonic
irradiations
it recurred higher yield, short reaction time, and catalyst
recovery at 70ꢀC under ultrasonic irradiations. We also
studied the reaction scheme for various temperatures but
we observed that given reaction scheme produced several
biproduct formation at higher temperature and found
various spot on TLC. ZnFe2O4 is also plays vital role in
rate of reaction so we finalized 70ꢀC as reaction tempera-
ture. After increasing the amount of catalyst, no improve-
ment was observed in reaction results.
After fixing protocol for synthesis of series of reaction,
benzimidazole (1 mmol), malononitrile (1 mmol) were
treated with substituted aromatic aldehydes (1 mmol) in
presence of ZnFe2O4 (10 mol%) as a catalyst.
percentage of yields and electron releasing groups
increased the reaction times with no outstanding effect
on the percentage of yields due to ultrasonic effect. Con-
sequently, this protocol gives the desired products in
good yields and in relatively short reaction times
(Table 2).
Step I- in reaction, intermediate (5) occurred via
Knoevenagel condensation between malononitrile (3) and
aromatic aldehyde (2a-j) in the presence of heterogeneous
ZnFe2O4 nanocatalyst. In step II- immediate Michael addi-
tion adduct (6) occurred from 2-aminobenzimidazole (1)
intermediate (5) and finally, 2-amino-4-substituted-1,-
4-dihydrobenzo[4,5]imidazo[1,2-a]pyrimidine-3-carbonitrile
(4a-j) was formed from intramolecular cyclisation of
Michael adduct (6) (Scheme 3). After completion of individ-
ual reaction, reaction mixture was cooled at room tempera-
ture following addition of 7 mL of ethyl acetate to this
mixture. The reaction mixture as filtered using G1 sinter
funnel and ZnFe2O4 nanocatalyst was covered washing
with double distilled water, dried and used for other suit-
able purposes. The products were purified by column
In continuation to our present research work, we
have also studied the effect of electron withdrawing, elec-
tron releasing and halogen groups at different positions
in aromatic ring of various aldehydes in the synthesis of
2-amino-4-substituted
1,4-dihydrobenzo[4,5]imidazo
[1,2-a]pyrimidine-3-carbonitrile illustrated in Table 2.
Aldehyde bearing electron withdrawing groups
decreased the reaction time with slightly increased the

CHAVAN ET AL.
5
TABLE 2 ZnFe2O4 nanocatalyzed multi-component synthesis of 2-amino-4-substituted-1,4-dihydrobenzo[4,5]imidazo[1,2-a]pyrimidine-
3-carbonitrile (4a-j)
Yield (%)
M.P. (ꢀC)
Entry
R1
Product
Time (min)
Found
96
Reported (ref.)
Found
Reported (ref.)
1
4-Cl-C6H4
4a
4b
4c
4d
4e
4f
75
82
89
81
79
84
74
79
88
77
9327
8927
9127
8629
8029
8829
9229
-
232-235
240-243
265-267
205–208
210–213
222-225
218–220
236–239
216–218
224–227
23827
24027
27027
2
3-Br-C6H4
4-F-C6H4
93
3
94
4
4-MeO-C6H4
4-HO-C6H4
4-Me-C6H4
4-CN-C6H4
2,4- (Cl)2C6H3
2-OH-4-MeOC6H3
4-NO2-C6H4
92
-
5
89
21529
6
92
-
7
4g
4h
4i
96
21529
8
95
-
-
-
9
93
-
10
4j
95
-
Note: Reaction conditions- benzimidazole (1) (1 mmol), aromatic aldehyde (2a-j) (1 mmol), malononitrile (3) (1 mmol), ZnFe2O4 (10 mol%)
catalyst and methanol (8 mL) at 70ꢀC under ultrasonic irradiations.
SCHEME 2 Synthesis of
2-amino-4-substituted
1,4-dihydrobenzo[4,5]imidazo
[1,2-a]pyrimidine-3-carbonitrile
(4a-j) catalyzed by ZnFe2O4
under ultrasonic irradiations
SCHEME 3 Mechanism
for the synthesis of 2-amino-
4-substituted-1,4-dihydrobenzo
[4,5]imidazo[1,2-a]pyrimidine-
3-carbonitrile (4a-j) is outlined
in Scheme 2. These products
formed by multistep reaction in
one pot

6
CHAVAN ET AL.
chromatography. The synthesized series of compounds
appropriate size beaker using stoichiometric amount
(1:1:4) and dissolved until clear solution was obtained.
This clear solution was evaporated (80ꢀC) using hot plate
and thick gel was obtained, again on increasing tempera-
ture (180ꢀC) of hot plate thick gel, nanocrystalline pow-
der was formed. Finally, the synthesized powder was
sintered at 300, 500, 800, and 1000ꢀC temperature for
4 hours. ZnFe2O4 nanoparticle was characterized by the
X-ray diffraction (XRD) patterns were recorded on
(Bruker AXS D8 Advance X-ray diffractometer) using
1
were characterized by FTIR, H NMR, 13C NMR, analysis.
Advantages of present method were efficiency, high per-
centage of yields, shorter reaction time, simplicity and easy
work-up.
3 | CONCLUSION
Present research work concludes, an highly efficient, syn-
thesis of 2-amino-4-substituted 1,4-dihydrobenzo[4,5]
imidazo[1,2-a]pyrimidine-3-carbonitrile (4a-j) via one pot
three component condensation reaction of benzimidazole
(1), malononitrile (3) and aromatic aldehyde (2a-j) using
heterogeneous ZnFe2O4 nanoparticles catalyst at 70ꢀC
under ultrasonic irradiation. Some nanoparticles agglom-
erations containing very fine particle, the shape of parti-
cles are not defined porous nature and small and large
core approximately (5 μm). Outcome of this synthetic
protocol are reduced reaction time, one time chemical
addition, easy handling, simplicity, efficiency, high yield,
and recoverable catalyst.
monochromatic
Cu-Kα
radiation38
(wavelength
λ = 1.5406 Å), SEM and TG-DTA methods.
4.3 | General procedure for synthesis of
2-amino-4-(R)-1,2-dihydroxybenzo[4,5]
imidazo[1,2-a]pyrimidine-3-carbonitrile
derivatives (4a-j)
A round bottom flask was charged with benzimidazole
(1) (1 mmol), aromatic aldehyde (2a-j) (1 mmol),
malononitrile (3) (1 mmol), and ZnFe2O4 (10 mol%) cata-
lyst in methanol (8 mL). The mixture was irradiated in
ultrasonic bath at (70ꢀC). The reaction condition was
assessed by TLC plate using ethyl acetate and cyclohex-
ane (7:3) as solvent. After the completion of reaction, add
4 mL of methanol in reaction mixture, dissolved total cat-
alyst in methanol and evaporated the solvent using high
pressure vacuum pump. Finally, the product was purified
by recrystallization techniques using ethanol to afford
the pure products.
4 | EXPERIMENTAL
4.1 | General experimental information
All A.R. Grade chemicals were used. They were pur-
chased from Sigma-Aldrich and Avra Chemicals.
Ultrasonication irradiator was performed (230 V AC,
50 Hz, liquid holding capacity of bath, 5.5 L) at tempera-
ture 70ꢀC. Water condenser fixed with round bottom
flasks having reaction ingredients were suspended at cen-
ter of the ultrasonication bath up to the completion of
4.3.1 | 2-Amino-4-(4-chlorophenyl)-
1,4-dihydrobenzo[4,5]imidazolo[1,2-a]
pyrimidine-3-carbonitrile(4a)
1
reaction. H NMR spectra were recorded on a Bruker-
400 MHz NMR and 13C NMR spectra were recorded on
100 MHz 13C NMR. The IR spectra were reported on a
Perkin-Elmer FT-IR Spectrometer Melting points were
measured manually by open capillary. TLC was carried
out on aluminum sheets (precoated with 0.2 mm layer of
silica gel). All reagents were commercially available. TG-
DTA analysis, XRD spectra was recorded by Bruker AXS
D8 Advance X-ray diffractometer. SEM images were
obtained on S-4800 Type-II, HITACHI Japan.
Yield 94%; yellow solid; M.P. 232-235ꢀC. FT IR (KBr cm−1):
3254, 2933, 2187, 1675, H NMR (400 MHz, DMSO-d6) δ
8.62 (s, 1H, NH), 7.63 (d,1H, Ar), 7.43-7.40 (m, 2H, Ar), 7.32
(d, 2H, Ar), 7.24 (d, 1H, Ar), 7.18 (d, 2H, Ar), 6.89 (s, 2H,
NH2), 5.27 (s, 1H, CH). 13C NMR (100 MHz, DMSO-d6) δ
151.60, 149.39, 144.1, 135.3, 131.3, 131.0, 129.1, 128.1, 123.1,
121.9, 120.0, 119.0, 116.1, 113.1, 62.0, 55.4.
1
4.3.2 | 2-Amino-4-(3-bromophenyl)-
1,4-dihydrobenzo[4,5]imidazolo[1,2-a]
pyrimidine-3-carbonitrile(4b)
4.2 | Preparation of ZnFe2O4
nanoparticles
ZnFe2O4 nanoparticle was prepared by combustion
method. In this preparation, urea was used as fuel. Ini-
tially, zinc nitrates, iron nitrates and urea are taken in
Yield 90%; yellow solids; M.P. 240-243ꢀC. 3278, 2939,
2189, 1683, H NMR (400 MHz, DMSO-d6) δ 8.61 (s, 1H,
NH), 7.58 (d, 1H, Ar), 7.51 (d, 2H, Ar), 7.29(t, 3H, Ar),
1

CHAVAN ET AL.
7
7.15 (t, 1H, Ar), 6.89 (t, 1H, Ar), 6.88 (s, 2H, NH2), 5.27
(s, 1H, CH). 13C NMR (100 MHz, DMSO-d6) δ 152.0,
149.1, 144.0, 141.1, 131.6, 130.5, 130.1, 129.0, 123.2, 122.0,
120.0, 119.1, 116.1, 112.3, 61.6, 53.0.
1H, Ar), 7.26-7.14 (m, 3H, Ar), 7.10 (t, 1H, Ar), 6.92 (s, 2H,
NH2), 5.27 (s, 1H, CH). 13C NMR (100 MHz, DMSO-d6) δ
151.6, 149.4, 144.1, 135.3, 131.4, 131.2, 129.1, 128.3, 123.2,
121.8, 120.2, 119.1, 116.0, 113.1, 62.0, 55.5, 17.6.
4.3.3 | 2-Amino-4-(4-fluorophenyl)-
1,4-dihydrobenzo[4,5]imidazolo[1,2-a]
pyrimidine-3-carbonitrile(4c)
4.3.7 | 2-amino-4-(4-cynophenyl)-
1,4-dihydroxybenzo[4,5]imidazo[1,2-a]
pyrimidine-3-carbonitrile(4g)
Yield 92%; yellow solid; M. P. 265-267ꢀC, 3279, 2940,
2182, 1691, H NMR (400 MHz, DMSO-d6) δ 8.26 (s, 1H,
white solid, Yield 96%; M. P. 218-220ꢀC, FTIR (KBr
1
1
cm−1): 3310, 3266, 2973,2191, 1685, H NMR 400 MHz,
NH), 7.59 (d, 1H, Ar), 7.21-7.18 (m, 5H, Ar), 7.10 (t, 1H,
Ar), 7.00 (t, 1H, Ar), 6.78 (s, 2H, NH2), 5.33 (s, 1H, CH).
13C NMR (100 MHz, DMSO-d6) δ 172.2, 160.1 (C-F),
152.0, 148.9, 144.1, 135.5, 131.0, 130.2, 123.3, 122.1, 119.8,
119.1, 116.8, 115.1, 112.7, 60.2, 54.6.
DMSO-d6) δ 8.82 (s, 1H, NH), 7.81 (d, 1H, Ar), 7.71-7.48
(m, 4H, Ar), 7.32 (t, 1H, Ar), 7.22 (t, 1H, Ar), 7.05 (t, 1H,
Ar), 6.85 (s, 2H, NH2), 5.10(s, 1H, CH), 13C NMR
(100 MHz, DMSO-d6): δ 162.1, 155.5, 150.8, 147.1, 140.1,
136.9, 131.1, 125.1, 123.1, 120.4, 118.1, 117.9, 116.1, 113.5,
112.6, 60.3, 54.6.
4.3.4 | 2-amino-4-(4-methoxyphenyl)-
1,4-dihydrobenzo[4,5]imidazolo[1,2-a]
pyrimidine-3-carbonitrile(4d)
4.3.8 | 2-amino-4-(2,4-dichlorophenyl)-
1,4-dihydroxybenzo[4,5]imidazo[1,2-a]
pyrimidine-3-carbonitrile(4h)
yellow solid; Yield 90%; M. P. 205-208ꢀC, 3268, 2936,
1
2186, 1684, 1196, H NMR (400 MHz, DMSO-d6) δ 8.51
white solid, Yield 95%; M. P. 236-239ꢀC, FTIR (KBr
1
(s, 1H, NH), 7.94 (d, 2H, Ar), 7.65 (t, 1H, Ar), 7.20-7.15
(m, 1H Ar), 7.10 (t, 1H, Ar), 7.00 (t, 1H, Ar), 6.91(d, 2H,
Ar), 6.79 (s, 2H, NH2), 5.16 (s, 1H,CH), 3.40 (s, 3H CH3).
13C NMR (100 MHz, DMSO-d6) δ 161.0, 151.3, 149.2,
144.1, 133.5, 133.4, 129.4, 127.3, 124.1, 123.2, 120.1, 115.6,
115.0, 113.9, 64.1, 63.0, 52.7, 14.3.
cm−1): 3297, 3250, 2953,2151, 1646, H NMR 400 MHz,
DMSO-d6) δ 8.61 (s, 1H, NH), 7.50 (s, 1H, Ar), 7.36-7.41
(m, 2H, Ar), 7.15 (m, 2H, Ar), 6.95 (m, 2H, Ar), 6.72 (s,
2H, NH2), 5.07(s, 1H, CH), 13C NMR (100 MHz, DMSO-
d6): δ 161.2, 152.4, 148.1, 147.1, 139.1, 136.8, 130.1, 122.3,
123.2, 121.4, 117.9, 117.8, 117.1, 112.8, 111.9, 59.8, 54.7.
4.3.5 | 2-amino-4-(4-hydroxyphenyl)-
1,4-dihydroxybenzo[4,5]imidazo[1,2-a]
pyrimidine-3-carbonitrile(4e)
4.3.9 | 2-amino-4-(2-hydroxy,4-
methoxyphenyl)-1,4-dihydroxybenzo[4,5]
imidazo[1,2-a]pyrimidine-3-carbonitrile(4i)
white solid, Yield 88%; M. P. 210-213ꢀC, FTIR (KBr cm−1):
3298, 3246, 2931,2185, 1674, 1H NMR 400 MHz, DMSO-d6)
δ 8.22 (s, 1H, NH), 7.59 (d, 1H, Ar), 7.21-7.18 (m, 5H, Ar),
7.10 (t, 1H, Ar), 7.00 (t, 1H, Ar), 6.78 (s, 2H, NH2), 5.33 (s,
1H, OH), 5.10(s, 1H, CH), 13C NMR (100 MHz, DMSO-d6):
δ 160.1, 152.1, 148.8, 143.0, 135.1, 130.9, 130.1, 123.3, 123.5,
120.2, 119.1, 116.9, 116.1, 113.1, 112.6, 60.3, 55.7.
Yellow solid, Yield 93%; M. P. 216-218ꢀC, FTIR (KBr
1
cm−1): 3267, 3226, 2948, 2161, 1639, H NMR 400 MHz,
DMSO-d6) δ 8.58 (s, 1H, NH), 7.60 (s, 1H, Ar), 7.31-7.39
(m, 2H, Ar), 7.14 (m, 2H, Ar), 6.78 (m, 2H, Ar), 6.69 (s,
2H, NH2), 5.06(s, 1H, CH), 13C NMR (100 MHz, DMSO-
d6): δ 160.2, 151.4, 149.1, 146.1, 138.1, 134.8, 134.1, 121.3,
123.1, 120.4, 118.0, 117.6, 117.0, 112.1, 111.1, 59.6, 55.4.
4.3.6 | 2-Amino-4-(4-methylphenyl)-
1,4-dihydrobenzo[4,5]imidazolo[1,2-a]
pyrimidine-3-carbonitrile(4f)
4.3.10 | 2-amino-4-(4-nitrophenyl)-
1,4-dihydroxybenzo[4,5]imidazo[1,2-a]
pyrimidine-3-carbonitrile(4j)
yellow solid; Yield 85%; M.P. 230-233ꢀC. FTIR (KBr cm−1):
3284, 2954, 2183, 1677, H NMR (400 MHz, DMSO-d6) δ
yellow solid, Yield 95%; M. P. 224-227ꢀC, FTIR (KBr
1
1
cm−1): 3305, 3259, 2987, 2189, 1675, H NMR 400 MHz,
8.56 (s, 1H, NH), 7.62 (d,1H, Ar), 7.43 (d, 1H, Ar), 7.31 (d,
DMSO-d6) δ 8.76 (s, 1H, NH), 7.71-7.48 (m, 4H, Ar),

8
CHAVAN ET AL.
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7.34-7.22 (t, 4H, Ar), 6.81 (s, 2H, NH2), 5.09 (s, 1H, CH),
13C NMR (100 MHz, DMSO-d6): δ 161.1, 156.5, 161.8,
149.1, 141.1, 137.9, 133.1, 126.1, 124.1, 120.4, 119.1, 118.9,
116.1, 113.6, 119.6, 61.3, 54.7.
ACKNOWLEDGMENTS
We are grateful to Department of Chemistry, Doshi Vakil
Arts, G.C.U.B. Science and Commerce College,
Goregaon, Raigad for providing the necessary laboratory
facility during our research.
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CONFLICT OF INTEREST
The authors confirm that, this article content has no con-
flict of interest.
[27] R. M. Borade, S. B. Somvanshi, S. B. Kale, R. P. Pawar, K. M.
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ORCID
Pravin Chavan https://orcid.org/0000-0002-1232-9343
Dattatraya Pansare https://orcid.org/0000-0002-0419-
3538
Rohini Shelke https://orcid.org/0000-0002-2053-4785
[30] D. N. Pansare, R. N. Shelke, C. D. Pawar, Lett. Org. Chem.
2017, 14(7), 517.
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How to cite this article: Chavan P, Bangale S,
Pansare D, et al. Synthesis of substituted
pyrimidine using ZnFe2O4 nanocatalyst via one pot
multi-component reaction ultrasonic irradiation.
J Heterocyclic Chem. 2020;1–8. https://doi.org/10.
1002/jhet.4048