An efficient regioselective three-component synthesis of tetrazoloquinazolines using g-C3N4 covalently bonded sulfamic acid

Article abstract of DOI:10.1016/j.poly.2019.114217

A green and cost-effective protocol developed using covalently bonded sulfamic acid graphitic carbon nitride (g-C₃N₄/NHSO₃H) for the synthesis of quinazoline derivatives using three-component condensation reaction of benza

Full text of DOI:10.1016/j.poly.2019.114217

Journal Pre-proofs
An efficient regioselective three-component synthesis of tetrazoloquinazolines
using g-C3N4 covalently bonded sulfamic acid
Asadollah Hassankhani, Behnam Gholipour, Sadegh Rostamnia
PII:
S0277-5387(19)30662-X
https://doi.org/10.1016/j.poly.2019.114217
POLY 114217
DOI:
Reference:
Polyhedron
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22 October 2019
25 October 2019
Please cite this article as: A. Hassankhani, B. Gholipour, S. Rostamnia, An efficient regioselective three-component
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doi.org/10.1016/j.poly.2019.114217
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An efficient regioselective three-component synthesis of tetrazoloquinazolines using g-C3N4
covalently bonded sulfamic acid
Asadollah Hassankhani, a,* Behnam Gholipour, b Sadegh Rostamnia b,*
a Department of New Materials, Institute of Science and High Technology and Environmental Sciences,
Graduate University of Advanced Technology, Kerman, Iran. Email: hassankhani_a@yahoo.com
b Organic and Nano Group (ONG), Department of Chemistry, Faculty of Science, University of
Maragheh, PO Box 55181-83111, Maragheh, Iran. Tel:+98(421) 2276066; Fax: +98(421) 2276066;
Email: rostamnia@maragheh.ac.ir; srostamnia@gmail.com
Abstract
A green and cost-effective protocol developed using covalently bonded sulfamic acid graphitic
carbon nitride (g-C3N4/NHSO3H) for the synthesis of quinazoline derivatives using three-
component condensation reaction of benzaldehyde, 2‐ aminotetrazole and dimedone. The XRD,
TEM, SEM, EDX and FT-IR techniques were used to identify the physical and chemical properties
of g-C3N4/NHSO3H. The -NHSO3H solid catalyst, was reused eight times without significant
decrease in activity. This catalyst acts as a benign acid catalyst, a green protocol of a one-pot due
to having significant advantages such as active sites containing SO3H groups, reacting under mild
conditions with high efficiency as well as the ability to recover and reuse without decreasing
activity.
Keywords: Graphitic carbon nitride, sulfamic acid type g-C3N4/NHSO3H, tetrazoloquinazolines,
three-component reaction.
1. Introduction
The use of multi-component (MC) domino strategy has become powerful instrumentation for
quickly synthesizing complex structures, which by obviating the need for separation and
purification of intermediaries leads to reduced waste and reaction time, improves overall
1

performance1. On the other hand, nitrogen-content heterocycles with a tetrazole ring are one of the
common structural units in pharmacological important molecules that span a wide range of targets2,
3. The use of these compounds for the treatment of depression, diabetes, thyroid cancer,
hypertension, hyperlipidemia, glaucoma, coronary heart disease, atherosclerosis, hypothyroidism,
obesity, hypercholesterolemia, cardiac arrhythmias, and congestive heart failure has been
reported4-9.
The synthesis of new heterocyclic compounds because of the extensiveness of its application, a
great interest has attracted. Among these compounds, quinazolines and derivatives represents one
of the most significant classes of heterocyclic compounds in an extensive range of pharmacological
and biological processes10. Aminoazoles are known as excellent building units for multicomponent
reactions (MCRs) because of the presence of nucleophilic centers of reactivity11. Especially the
use of 5-aminopyrazoles and 5-aminotriazoles as a substrate for various MCRs has been widely
studied. However, the interest in nitrogen-rich compounds such as 5-aminetetrazole has been
created in a MCRs only in the past decade, which is expanded due to its unique characteristics. 5-
Aminetetrazole is an important part in certain drugs such as curazole, cefazolin and
cefoperazone12. Cefazolin is an antibiotic to treat a number of bacterial infections13 and
cefoperazone as an effective antibiotic14. Given the importance of multicomponent reactions
(MCRs) in biological and pharmaceutical compounds, various researchers have attempted to
perform MCR reactions using catalysts such as MNPs-SO3H15, MNPs-IL-OAc16, MNPs-
guanidine17, Cu-Adenine@boehmite18, Fe3O4@SiO2@Propyl–ANDSA19 and Iodine20 have been
reported. Over the recent years, green, stable and low-cost catalysts, particularly those based on
graphic carbon nitride, have attracted a lot of attention. Graphic carbon nitride has advantages
such as good chemical stability, low cost, no heavy metal pollution and environmental friendliness
2

compared to metal based catalysts. g-C3N4 is the most stable allotrope of covalent carbon nitride,
that has been widely used as a novel metal-free visible light photocatalyst for water reduction and
oxidation21, degradation of organic pollutants22, CO2 capture23 and organic synthesis24. Recently,
several reports have been reported on the use of graphitic carbon nitride as acid catalyst for organic
reactions in the literature, including GN/SO3H nanocomposite for the synthesis of spirooxindole
derivative25 and sulfonated graphitic carbon nitride for esterification of fatty acids26.Given the
importance of these compounds here, we report the use of -SO3H bonded graphite carbon nitride
(g-C3N4/NHSO3H) as a green and cost-effective heterogeneous acid catalyst for the regioselective
three-component (3-CRs) synthesis of tetrazoloquinazolines derivatives (Scheme 1).
Scheme 1. The regioselectivity of the 3-CRs synthesis of tetrazoloquinazolines.
2. Experimental
2.1. Materials and apparatus
Melamine was obtained from Merck. The other materials were also purchased from Sigma‐
Aldrich, Merck (Germany) and Fluka (Switzerland), and were used without further purification.
Infrared Raman (IR) spectra were obtained by a Shimadzu IR-460 spectrometer. Scanning Electron
Microscopy (SEM) images were recorded by a Zeiss-DSM 960A microscope. Transition Electron
Microscopy (TEM) images were recorded on a Zeiss EM 900 TEM. The crystalline structure of
3

the nanoparticles was examined by X-Ray Diffraction (XRD) instrument (Philips-PW1800
diffractometer).
2.2. Synthesis of g-C3N4 nanosheets
g-C3N4 nanosheets were synthesized using of melamine based on previously reported27. Initially,
10 grams of melamine was placed in the alumina crucible with a cover and heated for 4 h at 550
◦C (heating rate: 3 °C min-1) in an electric tube furnace. After cooling naturally, the yellow product
was collected.
2.3. Synthesis of g-C3N4/NHSO3H
Synthesis of g-C3N4/NHSO3H was achieved according to previously reported method by Varma
et.al., with using melamine instead urea26. Accordingly, 0.5 g of as-synthesized g-C3N4 sheets was
dispersed in 40 mL dry dichloromethane (DCM) and stirred for 30 min and 30 min again in tip
sonicated condition. Next, a solution of 6 mL of chlorosulfonic acid (ClSO3H) in 10 mL dry DCM
was added dropwise to the solution and stirred for a 10 h. After that, the g-C3N4/NHSO3H (1.2
mmol.g-1 S) were collected and washed with deionized water and ethanol and then dried at 50 oC
for 6h.
2.4. Synthesis of tetrazoloquinazolines
Benzaldehyde (1 mmol), 2‐ aminotetrazole (1 mmol), dimedone (1 mmol), the catalyst (0.01 g,
o
1.2 mol%) were added to a 3 mL ethanol and stirred for 4 h at 80 C. After completion of the
reaction, after separation of the solid catalysis, the reaction temperature was cooled downed to 0
4

°C to precipitate. Then, the precipitate was washed with water and dried. The crude product was
recrystallized by ethanol to afford the final product.
For investigating the reusability of the catalyst after completion the reaction, the mixture was
filtered (in 80 oC) and the g-C3N4/NHSO3H catalyst was rinsed twice with ethyl acetate; the filtrate
was dried and the solvent was vaporized under vacuum and was reused for the next run.
2.5. Spectral data of synthesized compounds
All compounds are known and are previously reported in the literatures28,29. For see the NMR
data, please see supporting information.
3. Results and discussion
As a part of our continuing effort toward the synthesis of solid catalysis and organic molecules30,
herein, we describe the regioselective 3-CRs synthesis of tetrazoloquinazolines through the
condensation reaction of aldehydes, 5‐ aminotetrazole, and dimedone or 1.3-Cyclohexanedione
in the presence of covalently bonded sulfamic acid onto the g-C3N4 surfaces (Scheme 1).
Initially, g-C3N4 was synthesized through a Varma method22 and, it was then reacted with
chlorosulfonic acid based on Zolfigol’s method31 to obtain g-C3N4/NHSO3H (Fig. 1). Then, the
effect of g-C3N4/NHSO3H as Bronsted acid catalyst was investigated in the synthesis of
tetrazoloquinazolines.
5

Figure 1. Synthesis of sulfonated graphitic carbon nitride.
The FT-IR spectrum of g-C3N4 and g-C3N4/NHSO3H are illustrated in (Fig. 2). In the IR spectrum
of g-C3N4 the peaks at 1235,1325, 1434, and 1567 cm-1 are related to aromatic C-N stretching
vibrations and at the 1541 cm−1 and 1644 cm−1 are related to C=N stretching vibrations32. The peak
at 806 cm-1 assigned to the vibration of triazine units33. The peaks around 2900-3500 cm−1 is
indicative of the N-H stretching vibrations and O-H groups related to water molecules on the
catalyst surface34. In the IR spectrum of g-C3N4, after sulfonation, in addition to the g-C3N4 peaks,
the vibration bands at 1068 cm-1 (S=O symmetric stretching), 1136 cm-1 (S=O asymmetric
stretching) and 1413 cm-1 (asymmetric SO2 stretching) were related to the SO3H groups35 (Fig. 2).
6

Figure 2. FT-IR spectrum of g-C3N4 (red) and g-C3N4/NHSO3H (blue).
Figure 3 shows the SEM (a, b) images of the layered structure of pure g-C3N4 and SO3H
functionalized g-C3N4. As shown the synthesized graphitic carbon nitrides are as a planar sheet-
like form for both g-C3N4 and g-C3N4/NHSO3H. The SEM image also indicates the 2-D
morphology of the synthesized g-C3N4 and g-C3N4/NHSO3H structure. It also exhibition that the
g-C3N4/NHSO3H morphology has not changed after acid-functionalization. Surface profiles of the
planar area from the upside surface of g-C3N4/NHSO3H is shown in Figure 3d, presenting the
correspondence topography quantitatively.
7

Figure 3. (a) SEM image of g-C3N4 and its zoomed image (c); (b) SEM image of g-
C3N4/NHSO3H and its surface profile (d).
A nanosheet-like morphology of g-C3N4 and g-C3N4/NHSO3H were depicted in the TEM image.
Characterization showed that the morphologies of the g-C3N4 and g-C3N4/NHSO3H are distinctly
similar and both of them have 2D nanosheet morphology (Figure 4a, b). The energy dispersive X-
ray spectroscopy (EDX) of the g-C3N4/NHSO3H nanosheet is shown in (Fig. 4c). In the EDX
spectrum of g-C3N4/NHSO3H certain peaks for the O, C, N and S elements. The presence of sulfur
can clearly be seen, which confirmed the presence of SO3H components in the synthesized g-
C3N4/NHSO3H. The crystallinity and phase structure of the 2D g-C3N4/NHSO3H nanosheet was
determined by X-ray diffraction. The XRD patterns of g-C3N4 and g-C3N4/NHSO3H illustrate in
Fig. 4d. The characteristic peaks located at 2θ values of 27.5° and 13.1°, matching with the (002)
and (100) peaks of g-C3N4 surface which accordance with the results reported in the literatures36,37
.
8

Figure 4. (a and b) TEM image of g-C3N4 and g-C3N4/NHSO3H. (c) EDX spectra of g-
C3N4/NHSO3H. (d) XRD pattern of g-C3N4 and g-C3N4/NHSO3H.
After demonstrated main structure for g-C3N4/NHSO3H as a Bronsted sulfonic acid functionalized
2D nanosheet N-rich solid acid, the application of that was explored for the synthesis of
tetrazoloquinazolines using benzaldehyde (2 mmol), 2‐ aminotetrazole (2 mmol), and dimedone
(2 mmol). To obtain optimum conditions, different parameters such as solvent, reaction time and
temperature were investigated. At first, the reaction progress was investigated in the absence of
the catalyst, and after 24 hours no product was observed (Table 1, entries 1). Subsequently, various
amounts of catalysts were selected for the reaction and 0.01 g was selected as the desired amount.
In this reaction, various temperatures were investigated and it was found that 80 ° C is the optimum
9

temperature for the reaction (Table 1, entries 5-10). In the next step, the effect of variant solvents
was investigated and the isopropyl alcohol solvent was selected as the appropriate solvent.
Table 1. Reaction optimization for the synthesis of tetrazoloquinazolines. a
Entry Catalyst (amount of Cat.)
solvent
i-PrOH
i-PrOH
i-PrOH
i-PrOH
i-PrOH
i-PrOH
i-PrOH
i-PrOH
i-PrOH
i-PrOH
EtOH
T (oC)
100
80
80
80
80
80
80
100
80
60
80
80
80
80
80
Time (h)
Yield (%)
-
1
2
-
24
4
4
4
4
2
4
4
4
4
4
4
4
4
4
AlCl3 (10 mol %)
trace
30
35
65
75
95
95
95
70
75
60
70
55
3
FeCl3 (10 mol %)
4
CuO (10 mol %)
5
6
7
8
g-C3N4/NHSO3H (0.005gr)
g-C3N4/NHSO3H(0.01gr)
g-C3N4/NHSO3H(0.01gr)
g-C3N4/NHSO3H(0.01gr)
g-C3N4/NHSO3H(0.02gr)
g-C3N4/NHSO3H(0.01gr)
g-C3N4/NHSO3H(0.01gr)
g-C3N4/NHSO3H(0.01gr)
g-C3N4/NHSO3H(0.01gr)
g-C3N4/NHSO3H(0.01gr)
g-C3N4/NHSO3H(0.01gr)
9
10
11
12
13
14
15
CH3CN
DMF
DMSO
Toluene
20
a Reaction conditions: benzaldehyde (1 mmol), 2‐ aminotetrazole (1 mmol), and dimedone (1
mmol) in 3 mL of solvent.
Subsequently, optimal conditions for a wide range of aromatic aldehyde and dimedone were
applied to investigate the scope of the current protocol. As shown in Table 2, the use aromatic
aldehydes including electron‐ deficient groups such as 4-NO2, 4-Cl, 4-Br and 2,6-Cl2 and an
electron‐ rich such as 4-Me and 2,5-(OMe) in the same period of 4-6 hours leads to
tetrazoloquinazolines in high yields. These results clearly show how the g-C3N4/NHSO3H catalyst
plays an important role in synthesis tetrazoloquinazolines.
10

Table 2. Three-component coupling synthesis of tetrazoloquinazolines. a
Entry
Ar
β-diketone Time Yield Melting point
Reported melting
pointref (oC)
(h)
4
(%)
95
(oC)
> 270
1
2
Ph
dimedone
dimedone
dimedone
dimedone
dimedone
dimedone
dimedone
dimedone
> 270 [38]
2,4-Cl2-C6H4
4-Cl-C6H4
2-Cl-C6H4
4-Br-C6H3
3-O2N-C6H4
2-O2N-C6H4
4-O2N-C6H4
4
4
94
94
89
87
93
90
95
91
92
> 270
> 270 [38]
254-256 [38]
> 270 [38]
3
255-257
> 270
4
5
5
6
250-253
279-282
262-264
248-250
268-270
302-306
246-249 [38]
281-283 [39]
261-263 [38]
248-249 [38]
270-272 [39]
304-305 [39]
6
4
7
5
8
4
9
4-OCH3-C6H4 dimedone
4-CH3-C6H4 dimedone
4.5
4.5
10
a Reaction condition: aldehyde (1 mmol), 2‐ aminotetrazole (1 mmol), and dimedone (1 mmol)
in 3 mL i-PrOH at 80 oC in presence of 1.2 mol% of catalyst.
In continuing on the basis of results obtained the use of 1.3-cyclohexanedione to extend the
synthesis of tetrazoloquinazolines was studied. Similar results according to Table 2 for both groups
of electron‐ deficient and electron‐ rich on the aromatic ring were observed (Table 3). These
results clearly show how the g-C3N4/NHSO3H catalyst plays an important role in synthesis
tetrazoloquinazolines.
11

Table 3. g-C3N4/NHSO3H catalyzed the MC-synthesis of tricyclic tetrazoloquinazolines.
Entry
Ar
Ketone
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
9
Ph
1,3-Cyclohexanedione
1,3-Cyclohexanedione
1,3-Cyclohexanedione
1,3-Cyclohexanedione
1,3-Cyclohexanedione
1,3-Cyclohexanedione
1,3-Cyclohexanedione
1,3-Cyclohexanedione
1,3-Cyclohexanedione
1,3-Cyclohexanedione
4
4
4
6
6
4
4
4
4
5
94
92
91
88
90
95
91
95
88
90
4-Br-C6H4
4-Cl-C6H4
2-Cl-C6H4
2,4-Cl2-C6H3
3-O2N-C6H4
2-O2N-C6H4
4-O2N-C6H4
4-OCH3-C6H4
4-CH3-C6H4
10
Reaction condition: aldehyde (1 mmol), 2‐ aminotetrazole (1 mmol), and 1, 3-cyclohexanedione
(1 mmol) in 3 mL i-PrOH at 80 oC.
The proposed mechanism for g-C3N4/NHSO3H is illustrate in Scheme 2. This catalyst with having
ionic liquid type (IL-type) acid groups (H+) which can act as electrophoretic species. In pathway
a, the aldehyde have to protonated in the presence of g-C3N4/NHSO3H, and in the next step,
Knoevenagel condensation with dimedone resulted in the formation of a conjugated α,β-
unsaturated diketone compound which the results of NMR studies don’t show progress of this
pathway. study it goes to After the reaction of Michael addition with 5-aminotetrazole as
nucleophile, cyclization leads to the formation of the desired product. A possible mechanism is
shown in Scheme 2. In pathway b, it is conceivable that the initially, tetrazole-enaminone as an
intermediate formed from reaction between 2‐ aminotetrazole and dimedone. The latter then with
formation of β- aminotetrazole conjugated α,β-unsaturated compound, 6,6-dimethyl-9-phenyl-
12

5,6,7,9-tetrahydrotetrazolo[5,1-b]quinazolin-8(4H)-one as target molecule (TM) of
tetrazoloquinazoline produces by ring annulation (Scheme 2).
Scheme 2. The possible mechanism for the synthesis of tetrazoloquinazolines over catalysis of g-
C3N4/NHSO3H.
The recovery and reuse of the catalyst using the model reaction (benzaldehyde (1 mmol), 2‐
o
aminotetrazole (1 mmol), and dimedone (1 mmol) in 3 mL i-PrOH at 80 C in presence of 1.2
mol% of g-C3N4/NHSO3H catalyst.) were also investigated. During successive cycles, the model
reacts under optimized conditions there was no significant decrease in activity. After completion
of the reaction, the catalyst was separated by a centrifuge and washed using ethyl acetate and
water. The g-C3N4/SO3H catalyst was able to work up to 8 times without loss of catalytic power,
indicating that the catalyst g-C3N4/NHSO3H is stable under the reaction conditions. The TEM
image after 8 times reuse shows that the g-C3N4/SO3H morphology is preserved.
13

Fig. 6 (a) Reusability of g-C3N4/NHSO3H in the synthesis of tetrazoloquinazoline and its (b)
TEM image.
The results of our work are summarized in Table 4 in comparison with the catalysts previously
reported in the literature. As can be seen, this metal-free catalyst exhibited good catalytic activity
with excellent yields (95%) in shorter time than most of the reported works.
Table 4. Comparison of different methods in the synthesis of tetrazoloquinazolines using
different reagents and reaction conditions.
Entry
Catalyst
Conditions
HOAc, 100oC
solvent-free, 30oC
CH3CN, Reflux
i-PrOH, refluxing
i-PrOH, 80oC
Time (h) Yield (%)Ref
1
2
3
4
5
NaN3 (2 mmol), Hg(OAc)2
TsOH (10 mol%)
6
67 [40]
84 [41]
8
AlCl3 (20 mol%)
4
20 min
4
92 [42]
Iodine (10 mol%)
83 [38]
g-C3N4/NHSO3H (0.01gr)
This work
Conclusion
In conclusion, g-C3N4/NHSO3H was studied as a green and stable catalyst with the ability to
recovery and reuse for the synthesis of tetrazoloquinazolines under mild conditions. Physical and
chemical properties of g-C3N4/NHSO3H have been proven using various analytical techniques. All
derivatives of tetrazoloquinazolines using various aromatic aldehydes and dimedone and 1, 3-
14

cyclohexanedione ketones in the presence of 2-aminotetrazole with high yield were synthesized.
The results showed that g-C3N4 is an excellent substrate for the support of organic groups as
catalyst. The g-C3N4/NHSO3H catalyst can be recovered after the reaction so that it can be reused
at least 8 times without a slight decrease in the reaction efficiency.
Competing interests
The author(s) declare no competing interests.
Acknowledgement
The authors are thankful for financial supports from Iran National foundation of Science (INSF).
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