Magnetic Graphene Oxide Bearing ZrO2 as a New Composite Catalyst for the Synthesis of 1H-Perimidines

Full text of DOI:10.1080/00304948.2020.1761227

Organic Preparations and Procedures International
The New Journal for Organic Synthesis
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Magnetic Graphene Oxide Bearing ZrO2 as a
New Composite Catalyst for the Synthesis of 1H-
Perimidines
M. A. Amrollahi & F. Ashayeri-Harati
To cite this article: M. A. Amrollahi & F. Ashayeri-Harati (2020): Magnetic Graphene Oxide
Bearing ZrO2 as a New Composite Catalyst for the Synthesis of 1H-Perimidines, Organic
Preparations and Procedures International, DOI: 10.1080/00304948.2020.1761227
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ORGANIC PREPARATIONS AND PROCEDURES INTERNATIONAL
https://doi.org/10.1080/00304948.2020.1761227
EXPERIMENTAL PAPER
Magnetic Graphene Oxide Bearing ZrO2 as a New
Composite Catalyst for the Synthesis of 1H-Perimidines
M. A. Amrollahi and F. Ashayeri-Harati
Department of Chemistry, Yazd University, Yazd, Iran
ARTICLE HISTORY Received 1 January 2019; Accepted 8 December 2019
Development of immobilized catalysts that allow simple work-up procedure, easy separ-
ation and recoverability of the catalyst is a significant challenge.1 In fact, the past decade
has witnessed a growing interest in organic-inorganic hybrid catalysts using several
types of supports and several immobilization strategies.2–9 Synthesis of graphene oxide
(GO) based materials is an important and relatively new research area for organic trans-
formations. The use of magnetic nanoparticles has also grown substantially, due to their
high surface area, excellent accessibility, low toxicity and high biocompatibility.10–15 GO
immobilized iron oxide magnetic nanoparticles represent novel functional materials,
which have been used as heterogeneous catalysts and purifiers of organic pollutants.16–18
Zirconium salts, as homogeneous catalysts, have been cited in the literature in a number
of biologically and pharmaceutically significant organic transformations.19–23 To develop
magnetic heterogeneous catalytic systems for use in organic reactions, we prepared an
inorganic/organic composite (Fe3O4-GO-ZrO2) and investigated its catalytic activity in
organic reactions. 1H-Perimidine is a condensed tricyclic ring system, with unusual
electronic properties, where the lone pair of a pyrrole-like nitrogen participates in the
p-system of the molecule. It shows a transfer of electron density from the heterocycle to
the naphthalene moiety. Perimidines are of special interest as medicinally potent lead
molecules and key intermediates for the synthesis of therapeutic agents.24–26 A variety
of methods have been reported for the synthesis of 1H-perimidine compounds in the
literature.27–37 Although these methods have advantages, some drawbacks include long
reaction times, elevated temperatures, low yields, expensive moisture-sensitive reaction
conditions, tedious workup of the reaction mixture, difficulty in separation of the cata-
lyst, and the use of toxic metals. Thus it is desirable to develop catalytic systems which
are environmentally friendly and more efficient.
In the present study, we report on the preparation and characterization of ZrO2
supported on magnetic graphene oxide complex and its utility for the synthesis of
2-aryl-1H-perimidines by cyclocondensation of 1,8-diaminonaphthalene with aromatic
aldehydes (Scheme 1).
In brief, a magnetic layer of graphene oxide was coated with ZrO2 and characterized
by FT-IR, UV-Vis, SEM, TGA, XRF, XRD and VSM techniques. The synthesized
magnetic complex was employed as a heterogeneous catalyst for the preparation of
CONTACT M. A. Amrollahi
mamrollahi@yazd.ac.ir
Department of Chemistry, Yazd University, P.O. Box 89195-741,
Yazd, Iran
ß 2020 Taylor & Francis Group, LLC

2
M. A. AMROLLAHI AND F. ASHAYERI-HARATI
Scheme 1. ZrO2-incorporated magnetic graphene oxide as a catalyst for the synthesis of 1H-
perimidines.
1H-perimidines by cyclocondensation of 1,8-diaminonaphthalene with aromatic alde-
hydes under mild reaction conditions. Simple workup, high yields, reusability of the
catalyst and dehydrogenation of 2,3 dihydro-1H-perimidine into 1H-perimidine by the
catalyst are among the advantages of this method.
The catalytic activity of Fe3O4-GO-ZrO2 was investigated for the synthesis of 2-phe-
nyl-1H-perimidine via the condensation reaction of 1,8-diaminonaphthalene (1 mmol)
and benzaldehyde (1 mmol) as the model reaction. The model reaction behavior was
studied by nature and amount of the catalyst in EtOH at 70 ꢀC (Table 1).
We explored the catalytic efficiency of GO, ZrOCl2, Fe3O4, Fe3O4-GO and Fe3O4-
GO-ZrO2 (Table 1, entries 1-5). These results establish the fact that among the various
catalysts used, Fe3O4-GO-ZrO2 is the most effective catalyst for the synthesis of 2-phe-
nyl-1H-perimidine. The use of 0.02 g catalyst per mmole of aldehyde at 70 ꢀC in EtOH
has the best activity.
Under the optimized reaction conditions, 1,8-diaminonaphthalene (1 mmol), aromatic
aldehyde (1 mmol) and Fe3O4-GO-ZrO2 (0.02 g) in ethanol (5 mL) gave the correspond-
ing perimidine derivatives in 80–95% yield at 70 ꢀC (Table 2). Electronic effects and the
position of the substituent on the aldehyde have considerable influence on the yield and
speed of the reaction. The structures of these products were characterized by melting
1
point, FT-IR, H- and 13C-NMR spectra (see Experimental section). A possible mechan-
istic interpretation is provided in Scheme 2.
After completion of the reaction, the Fe3O4-GO-ZrO2 composite was recovered using
an external magnetic field and washed with ethanol. The catalyst was dried and acti-
vated at 110 ꢀC in an oven for 2 h. The recycled catalyst was re-applied in the model
reaction under the optimized conditions. The catalyst was found to be reusable for at
least 3 cycles without considerable loss of activity.
In order to verify real heterogeneity of the Fe3O4-GO-ZrO2 catalyst, the Sheldon test
was performed in the model reaction to evaluate the possibility of ZrO2 leaching. Thus
the reaction mixture after 8 min. at 70 ꢀC was filtered and the filtrate further heated at
70 ꢀC for an additional 8 min. The catalytic activity dropped down when the catalyst
was removed from the reaction mixture. The obtained results thus suggested that there
is no appreciable leaching of ZrO2 under the present reaction conditions.
The performance of the Fe3O4-GO-ZrO2 catalyst in the model reaction was compared
with the other reported methods for the synthesis of 2-phenyl-1H-perimidine and the
results are summarized in Table 3. The results show that, with the Fe3O4-GO-ZrO2 as a
catalyst, 2-phenyl-1H-perimidine can be synthesized in a shorter time and with
higher yields.

ORGANIC PREPARATIONS AND PROCEDURES INTERNATIONAL
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Table 1. Different conditions for the synthesis of 1H-perimidine.
Entry
Catalyst (g)
Time (min)
Yield (%)
1
2
3
4
5
6
7
8
GO (0.02)
ZrOCl2 ( 0.02)
Fe3O4 (0.02)
Fe3O4-GO (0.02)
Fe3O4-GO-ZrO2 (0.02)
Fe3O4-GO-ZrO2 (0.01)
Fe3O4-GO-ZrO2 (0.03)
–
25
25
25
25
15
15
15
25
–
60
45
90
95
80
95
50
In summary, we have demonstrated the preparation and characterization of Fe3O4-
GO-ZrO2 as a highly efficient, magnetically recyclable, cheap and novel heterogeneous
catalyst. The catalytic activity was investigated in the synthesis of 1H-perimidine deriva-
tives through the condensation reaction of 1,8-diaminonaphthalene and aromatic alde-
hydes in EtOH under mild reaction conditions. The remarkable advantages of this
method are its simple experimental procedure, short reaction times, re-usabilty, and the
ease of product isolation. Dehydrogenation of 2,3-dihydro-1H-perimidine into 1H-peri-
midine by the catalyst is a principle merit of this method.
Experimental section
All reagents were purchased from Merck and Fluka companies and used without further
purification. Reaction progress was checked by thin layer chromatography (n-hexane/
ethyl acetate, 7:3) using Merck 0.2 mm silica gel 60 F-254 Al plates. The melting points
were obtained on a Bu€chi melting point B-540 apparatus and are uncorrected. The X-
ray diffraction (XRD) data were collected with a Philips Xpert MPD diffractometer
equipped with a Cu Ka anode (k ¼ 1.54 Aꢀ) in the 2h range from 2 to 80. X-ray fluor-
escence (XRF) analysis was carried out with a Bruker S4 Explorer instrument.
€
Thermogravimetric analysis (TGA) was performed on a BAHR-STA 504 analyzer.
Scanning electron microscopy (SEM) images were obtained using a TESCAN, Model:
VEGA 3. FT-IR spectra were recorded as KBr pellets on a Bruker Equinox-55 FT-IR
1
spectrometer. The H- and 13C-NMR spectra were recorded on a Bruker Avance spec-
1
trometer operating at 400- and 100 MHz for H and 13C respectively.
Synthesis of ZrO2- incorporated magnetic graphene oxide (Fe3O4-GO-ZrO2)
The synthesized GO (from purified natural graphite using modified Hummer’s method
(0.30 g) in H2O (25 mL)) was ultrasonicated for 30 min. A solution of ferric chloride
(FeCl3ꢁ6H2O, 0.54 g) and ferrous chloride (FeCl2ꢁ4H2O, 0.20 g) in H2O (30 mL) was
added at room temperature. The temperature was raised to 85 ꢀC and a 30% aqueous

4
M. A. AMROLLAHI AND F. ASHAYERI-HARATI
Table 2. Synthesis of perimidine derivatives using Fe3O4-GO-ZrO2 as a catalyst.a
Time
Entry
1
Aldehyde
Product
(min) Yieldb) (%) M.p. ðꢀCÞ Lit. ðꢀCÞ Ref.
15
95
185-187 183-184 33
2
3
15
80
138-140 141-142 36
20
20
25
85
80
85
210-213
211 27
4
5
188-189 189-191 37
208-210 210-211 36
6
7
15
15
95
85
182-183
183-185
180 34
185 34
8
9
15
15
85
80
174-176 176-178 27
113-115 116-118 37
10
20
85
181-183
–
–
aReaction conditions: 1,8-diaminonaphthalene (1 mmol), aromatic aldehyde (1 mmol), EtOH, 70 ꢀC.
bIsolated yields.

ORGANIC PREPARATIONS AND PROCEDURES INTERNATIONAL
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Scheme 2. The proposed mechanism of synthesizing perimidines catalyzed by Fe3O4-GO-ZrO2.
ammonia solution was gradually added to increase the pH up to 10. After being rapidly
stirred for 45 min, the solution was cooled to room temperature. Subsequently, the
resulting black precipitate was centrifuged and washed three times with deionized (DI)

6
M. A. AMROLLAHI AND F. ASHAYERI-HARATI
Table 3. Comparison of Fe3O4-GO-ZrO2 catalysis with reported syntheses of 1H-perimidine.
Catalyst
Solvent
Time
Yield (%)
Ref.
Catalyst-free
Catalyst-free
Pa/C
EtOH
Solvent-free
Xylene
4 h
1.5 h
3 h
90
71
50
95
27
28
33
Fe3O4-GO-ZrO2
EtOH
15 min
This work
water and lastly dried at 60 ꢀC. For preparation of the Fe3O4-GO-ZrO2 complex, the
prepared Fe3O4-GO (0.2 g) in H2O (30 mL) and ZrOCl2ꢁ8H2O (0.03 g) was ultrasoni-
cated for 60 min. Then NaBH4 (1 wt %, 10 mL) was added and the solution heated in an
oil bath at 100 ꢀC under a water-cooled condenser for 24 h. After that, the solution was
cooled at room temperature and subsequently the resulting precipitates were centrifuged
and washed three times with DI water and lastly dried at 60 ꢀC. The catalyst was fully
characterized using FT-IR, UV-Vis, SEM, TGA, XRF and XRD techniques, and the data
from each of these techniques were submitted for review. A full data set is available
from the corresponding author upon request.
General procedure for the synthesis of perimidines by using Fe3O4-GO-ZrO2 as
a catalyst
In the typical procedure, a mixture containing 1,8-diaminonaphthalene (1 mmol,
0.158 g), the appropriate aromatic aldehyde (1 mmol) and Fe3O4-GO-ZrO2 (0.02 g) in
EtOH (10 mL) was stirred at 70 ꢀC until the reaction was completed. The completion of
the reactions was checked by TLC. Then, a magnet was used for separating the Fe3O4-
GO-ZrO2. The solvent was evaporated under reduced pressure, and the residue was
recrystallized from ethanol. Melting points may be seen in Table 2. Other data for the
1
synthesized perimidines have been provided below, and original spectra (IR, H- and
13C-NMR) for all compounds were submitted for review.
2-Phenyl-1H-perimidine (Table 2, Entry 1)
1
Yield 95%, orange crystals, mp 185-187 ꢀC. IR: (cmꢂ1) 3364, 3047, 1650, 1598, 1483. H
NMR (CDCl3): d 5.4 (s, 1H), 6.5 (d, 1H), 7.1-7.2 (m, 1H), 7.3-7.4 (m, 4H), 7.5 (br, 3H),
7.6 (s, 2H). 13C NMR (CDCl3): d 106, 118, 127, 128, 129, 130, 140, 142, 153.
2-(p-Tolyl)-1H-perimidine (Table 2, Entry 2)
Yield 80%, orange crystals, mp 138-140 ꢀC. IR: (cmꢂ1) 3365, 3042, 1612, 1601, 1486.
3-(1H-Perimidine-2-yl)-phenol (Table 2, Entry 3)
1
Yield 85%, yellow crystals, mp 210-213 ꢀC. IR: (cmꢂ1) 3399, 3285, 1670, 1601, 1487. H
NMR (DMSO-d6): d 5.7 (s, 1H), 6.5 (d, 2H), 6.8 (br, 2H), 7.1-7.2 (m, 4H), 7.5-7.6 (m,
1H), 7.7-7.8 (m, 1H). 13C NMR (DMSO-d6): d 104, 116, 127, 128, 131, 133, 134,
138, 142.

ORGANIC PREPARATIONS AND PROCEDURES INTERNATIONAL
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2-(1H-Perimidin-2-yl)-phenol (Table 2, Entry 4)
Yield 80%, yellow crystals, mp 188-189 ꢀC. IR: (cmꢂ1) 3390, 3305, 3050, 1668,
1605, 1487.
2-(4-Methoxyphenyl)-1H-perimidine (Table 2, Entry 5)
Yield 85%, golden crystals, mp 208-210 ꢀC. IR: (cmꢂ1) 3366, 3037, 1623, 1557
1483, 1139.
2-(4-Nitrophenyl)-1H-perimidine (Table 2, Entry 6)
Yield 95%, yellow crystals, mp 182-183 ꢀC. IR: (cmꢂ1) 3105, 3045, 1604, 1538, 1417,
1
1347. H NMR (DMSO-d6): d 5.5 (s, 1H), 6.0 (d, 2H), 7.0-7.2 (m, 4H), 7.2-7.4 (m, 2H),
7.8 (d, 2H). 13C NMR (DMSO-d6): d 105, 115, 123, 127, 129, 134, 142, 147, 150.
2-(3-Nitrophenyl)-1H-perimidine (Table 2, Entry 7)
Yield 85%, light orange crystals, mp 183-185 ꢀC. IR: (cmꢂ1) 3348, 3041, 1602, 1525,
1416 1370.
2-(4-Chlorophenyl)-1H-perimidine (Table 2, Entry 8)
Yield 85%, light orange crystals, mp 174-176 ꢀC. IR: (cmꢂ1) 3388, 3034, 1632, 1599,
1
1483, 745. H NMR (DMSO-d6): d 5.4 (s, 1H), 6.6 (br, 2H), 7.0-7.4 (m, 6H), 7.6 (br,
2H). 13C NMR (DMSO-d6): d 104, 115, 121, 127, 130, 131, 134, 141, 143.
2-(2-Chlorophenyl)-1H-perimidine (Table 2, Entry 9)
Yield 80%, light orange crystals, mp 113-115 ꢀC. IR: (cmꢂ1) 3381, 3335, 1643, 1598,
1480, 750.
2-(4-Bromophenyl)-1H-perimidine (Table 2, Entry 10)
Yield 85%, light orange crystals, mp 181-183 ꢀC. IR: (cmꢂ1) 3381, 3037, 1643, 1598,
1
1480. H NMR (DMSO-d6): d 5.2 (s, 1H), 6.5 (d, 2H), 6.8 (s, 2H), 6.9-7.1 (m, 4H) 7.2
(d, 2H). 13C NMR (DMSO-d6): d 104, 115, 118, 127, 129, 134, 143, 143.1, 157.
Acknowledgment
The authors thank the Research Council of Yazd University for financial support.
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