Effect of Fe(iii)-based MOFs on the catalytic efficiency of the tandem cyclooxidative reaction between 2-aminobenzamide and alcohols

Article abstract of DOI:10.1039/d0nj03136d

The catalytic properties of metal-organic frameworks (MOFs) containing triangular Fe(iii) clusters in the promotion of organic syntheses and photocatalysis applications have been receiving substantial attention for decades. These clusters are appealing due to the strong Lewis acidity afforded by coordinatively unsaturated sites upon the removal of solvent from the framework. In this paper, triangular Fe(iii) cluster-based MOFs were shown to be highly efficient heterogeneous catalysts for the solvent-free one-pot condensation of 2-aminobenzamide and alcohols to form quinazolin-4-ones under microwave irradiation. The Fe-MOF catalysts ranging from microporous to mesoporous structures with a variety of geometrical pore structures were investigated. Because of the open accessible spaces for reactants and high density of active sites, MOF-907, built from trimer Fe clusters and a mixture of two linkers, was more effective than other Fe(iii)-MOFs. The catalyst can be used for a broad substrate scope and recycled several times without a significant drop-off in its activity.

Full text of DOI:10.1039/d0nj03136d

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DOI: 10.1039/D0NJ03136D
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Effect of Fe(III)-based MOFs on catalytic efficiency of Tandem
cyclooxidative reaction between 2-aminobenzamide and alcohols
Minh-Huy Dinh Dang‡ , Trang Thi Minh Nguyen , Linh Ho Thuy Nguyen Trang Thi Thu
,a,b
‡,a,b
a,b,
Received 00th January 20xx,
Accepted 00th January 20xx
a,b
a,b
b,c
a,b*
Nguyen , Thang Bach Phan , Phuong Hoang Tran , Tan Le Hoang Doan
These authors contributed equally to this work
DOI: 10.1039/x0xx00000x
‡
The catalytic properties of metal-organic frameworks (MOFs) containing triangular Fe(III) clusters in the promotion of
organic syntheses and photocatalysis applications have been attracted substantial attention for decades. These clusters are
appealing due to the strong Lewis acidity afforded by coordinatively unsaturated sites upon removal of solvent from the
framework. In this paper, triangular Fe(III) cluster-based MOFs were shown to be highly efficient heterogeneous catalysts
for solvent-free one-pot condensation of 2-aminobenzamide and alcohols to form quinazolin-4-ones under microwave
irradiation. The Fe-MOF catalysts ranging from microporous to mesoporous structures with the variety of geometrical pore
structures were investigated. Owning the opening accessible spaces for reactants and high density of active sites, MOF-907,
built from trimer Fe clusters and a mixture of two linkers, was more effective than other Fe(III)-MOFs. The catalyst can be
used in a broad substrate scope and recycled several times without significant drop-off in its activity.
The use of metal-organic frameworks (MOFs) to catalyze
organic reactions has been explosively increased during the last
Introduction
1
4-19
two decades.
The unique features such as exceptionally
Quinazolin-4-one and its derivatives are a ubiquitous class of
nitrogen-containing heterocycles, which possess wide spectrum
large surface area, structural uniformity, accessibility of active
sites for reactants, and high chemical and thermal stability for
ease of recycling displayed by many MOFs make them attractive
in heterogeneous catalysis.
heterogeneous catalysts indeed show higher activity than the
corresponding homogeneous catalysts.
of well-known MOFs used as heterogeneous catalysts, trigonal
prismatic Fe O(–CO cluster-based MOFs which contain open
Lewis acidic active sites on the cluster have been efficiently
employed in various catalytic transformations, for example
1
-3
of biological activities. Various approaches for the synthesis
of these valuable compounds have been developed such as
carbonylation, hydrogen transfer, and C–H activation.4-6 Among
them, one-pot syntheses have been emerged as effective and
green procedures due to no need for isolation of intermediates
20-24
Accordingly, the MOF-based
2
5-29
Among many kinds
7
and minimization of chemical waste. For example, Lopez et al.
3
2 6
)
developed a one-pot synthesis of quinazolin-4-ones from 2-
8
nitrobenzamides and aldehydes. The compounds were also
obtained via one-pot condensation of 2-aminobenzamide and
alcohols in the catalysis of metal salts or metal complexes.9-13
Although good yields could be achieved utilizing homogeneous
and heterogeneous catalysts, these methods suffer from some
certain disadvantages including long reaction times, use of
ligands or additives, harsh reaction conditions, large excess
amounts of non-recycled catalysts, and volatile organic
Therefore, the search and exploration of more
environmentally benign and efficient catalysts for the synthesis
of quinazolin-4-ones are highly in demand.
3
0,31
32-35
36
oxidation,
photochemical reactions,
polymerization,
hydrogenation, rearrangement, and condensation.38-40
37
14
Herein, we demonstrate one-pot synthesis of quinazolin-4-one
derivatives from solvent-free condensation of 2-
aminobenzamide and alcohols in the catalysis of series of
triangular Fe(III) cluster-based MOFs. The reaction was
conducted under microwave irradiation to reduce reaction time
as well as increase yield based on spectacular accelerations of
8
-13
solvents.
4
1-43
the heating rate.
In this research, we wish to understand the
correlation between the framework structure of the MOFs and
their catalytic activity by analyzing effect of their structural
characteristics and density of the active sites per a certain
volumetric unit on the reaction. As a result of the catalytic
study, the Fe(III)-MOFs were efficiently heterogeneous catalysts
in the solvent-free microwave-assisted synthesis of quinazolin-
a. Center for Innovative Materials and Architectures (INOMAR), Ho Chi Minh City,
Viet Nam.
Vietnam National University-Ho Chi Minh City, Ho Chi Minh City, Viet Nam.
b.
c.
Department of Organic Chemistry, Faculty of Chemistry, University of Science, Ho
4
-ones.MOFs' topological structures play an essential role in
Chi Minh City, Viet Nam.
†
Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
enhancing catalytic performance. Importantly, MOFs'
topological factor shows higher effect on the reaction
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performance than active site concentration. Additionally, MOF- Synthesis of catalytic materials
07, composed of trimer Fe(III) clusters and mixture of two All Fe-MOFs were synthesized with iron (IIDI)OnI:it1r0a.1t0e39n/oDn0aNhJy0d31r3a6tDe
View Article Online
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linkers, 4,4’,4’’-benzene-1,3,5-triyl-tris(benzoic acid) (H
3
BTB), (Fe(NO
3
)
3
•
4
9H
2
0-48
O) and different organic ligands according to the
The synthetic procedure and activation process
2
,6-naphthalenedicarboxylic acid (H NDC), exhibited the literature.
2
highest catalytic efficiency among of the MOFs and catalysts were described in detail in the Supporting Information (SI,
due to its structural properties including large surface area, high Section 2). In general, powder products were obtained through
density of open active sites, and accessible open space (Figure reaction between iron (III) nitrate nonahydrate and organic
1
).
linkers added slowly into a mixture of DMF and monocarboxylic
acid. The mixture was stirred for 1ꢀmin at room temperature,
and then transferred into a vial or a Teflon-lined stainless-steel
autoclave and heated at temperature conditions: 100ꢀ°C, 120 °C
in an isothermal oven for a day. The solid products were washed
with DMF for 3 days to remove guest molecules and exchanged
solvent by suitable solvents: methanol, acetone for 3 days.
Finally, the samples were activated by heating under low
pressure for 24 h.
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Procedure for Fe-MOFs-catalyzed oxidative cyclization
between 2-aminobenzamide with benzyl alcohol
A mixture of benzyl alcohol (1.5 mmol), 2-aminobenzamide (0.5
mmol), Fe-MOF (4.2 mol%) and tert-butyl hydroperoxide (TBHP)
(
70% in water) (2 mmol) was heated by microwave irradiation
system at 120 °C for 1.5 minutes. After reaction completion, the
mixture was dissolved with ethyl acetate and centrifuged to
remove the catalyst. The product was purified by column
chromatography (9:1 ratio of n-hexane/ethyl acetate). The
structure of 2-phenylquinazolin-4(3H)-one compound was
confirmed via melting point, FT-IR, H and C NMR, GC-MS. For
the reusable survey, the catalyst was washed with ethyl acetate
(3 x 2 mL) and dried at 80 °C for next cycle.
3 2 6
Figure 1.Structure of MOF-907. Trigonal prismatic Fe O(–CO ) are joined with linear
2,6-naphthalenedicarboxylate (NDC2−) and triangular 4,4′,4”-benzene-1,3,5-
triyltris(benzoate) (BTB3−) to form MOF-907 framework. Atom colors: Fe: blue
polyhedral. C: black, and O: red. All H atoms are omitted for clarity. The yellow and
orange spheres indicate the free space in the cages.
1
13
Experimental
General Methods
Powder X-ray diffraction data were collected on a Bruker D8
Advance employing Ni filtered Cu Kα (λ = 1.54059 Å) radiation
Result and discussions
Structural characterization
A series of trigonal prismatic Fe(III) cluster-based MOFs,
including MOF-907, MOF-908, MOF-909, PCN-280, PCN-285,
MIL-88B, MIL-100, MIL-101 and MIL-126 were synthesized
(
2
Section 3). Ultrahigh-purity-grade N and He (99.999% purity)
were used throughout adsorption experiments. Thermo-
gravimetric analysis (TGA) curves were recorded on a TA Q500
thermal analysis system under airflow (Section 4). The air used
has a purity of 99.99%. The chemicals were measured by using
Sartorius balance. Low-pressure N
were carried out on Micromeritics 3Flex surface
characterization analyzer (Section 5). A liquid N bath was used
for measurements at 77 K. Microwave irradiation were
conducted on a CEM Discover SP apparatus. Column
chromatography was performed on silica gel 60, 0.04−0.06 mm
4
4-52
based on the reported literature
powder X-ray diffraction (XRD), thermogravimetric analysis
TGA), and N adsorption isotherm measurement. The full
and characterized by
(
2
2
sorption measurements
results have been presented in the Supporting Information (SI,
Sections 3-5). Indeed, the XRD patterns of the initial Fe-MOF
materials were similar to the previously reported works proven
by the highly agreement of XRD patterns between as-
synthesized, activated samples, and simulated patterns. The
observed residual mass of MOFs analyzed by TGA was
a
2
(
5
230–400 mesh). Melting points were recorded with a Buchi B-
45 melting point Apparatus. Fourier transform infrared (FT-IR)
spectra were measured on a Bruker E400 FT-IR spectrometer.
2 3
consistent with the expected mass of Fe O after framework
decomposition (calculated based on the structural formula)
further demonstrating that the resulting MOFs are highly pure
and single phase. Finally, the permanent porosity of Fe-MOFs
1
13
Nuclear magnetic resonance ( H and C NMR) spectra were
acquired on a Bruker advance II 500 MHz NMR spectrometer.
Chemical shifts were quoted in parts per million (ppm) and
referenced to the appropriate solvent peak. Gas
chromatography-mass spectrometry (GC-MS) measurements
were carried out on an Agilent GC System 7890 equipped with
a mass selective detector (Agilent 5973N) and a capillary DB-
was proven by N
2
adsorption isotherms at 77ꢀK. The
specific surface area was determined by the Brunauer–
Emmett–Teller (BET) method, which is slightly approximate the
theoretical geometrical surface area determined from the
crystal structure.
5
MS column (30 m × 250 µm × 0.25 µm).
Catalytic properties
2
| J. Name., 2012, 00, 1-3
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Table 1.Study of the effect of various catalysts in the synthesis of 2-phenylquinazolin-4(3H)-onea
View Article Online
DOI: 10.1039/D0NJ03136D
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Weightb
mg)
Volume
(cm3)
Density
(g cm-3)
Pore size distribution
(Å)
Active site density
GC Yield
(%)
Entry
Catalysts
(
(1023 cluster Å-3)
1
2
3
4
5
6
7
8
9
PCN-285
MOF-909
MOF-908
MOF-907
MIL-101
PCN-280
MIL-126
MIL-88B
MIL-100
16.31
16.78
16.59
20.21
21.90
34.36
35.34
36.61
35.02
0.047
0.047
0.047
0.047
0.047
0.047
0.047
0.047
0.047
0.347
0.357
0.353
0.430
0.466
0.731
0.752
0.779
0.745
22
24
23
19
29; 34
12
-
0.909
0.963
0.979
1.269
1.821
1.965
2.235
3.018
3.241
95
13
40
95
95
45
18
40
95
19
25; 29
58
10
11
12
HKUST-1
ZIF-8
MOF-177
53.72
48.74
19.88
0.047
0.047
0.047
1.143
1.037
0.423
18-22
-
-
-
30
20
8
59
11
60
12.7
a
Reaction condition: benzyl alcohol (1.5 mmol, 162 mg), 2-aminobenzamide (0.5 mmol, 68 mg), TBHP (2 mmol, 277 µL), were heated by
b
microwave irradiation system at 120 °C in 1.5 minutes. Weight calculated based on volume density from crystallographic data.
In this study, we performed an oxidative cyclization reaction in para position each other while MOF-909 and 908 are meta
between 2-aminobenzamide and benzyl alcohol in effect of the position. Therefore, the basic property of nitrogen on MOF-909
Fe(III)-based MOF catalysts. The features of the MOF materials and 908 is higher than PCN-285 which decreases Lewis acidity
were investigated for the reaction since catalytic activity of Fe-cluster. This caused a reduction in catalytic efficiency of
depended on factors such as active site density of the MOF-909 and 908. MIL-88 material has high density of active
5
3,54
2
-1
materials,
the adsorption and diffusion of the substrates site but its surface area is too small of about 164 m g (shown
55,56
onto the internal surface of the material,
structures with in table S1). As a result, substances those are difficult to move
5
7
pore size and surface area. Accordingly, we performed an into the pores to react leading the low yield. These results
oxidation reaction on the substrate of benzyl alcohol with the demonstrated that the structural features of the catalysts may
catalysts as shown in Table 1. The catalysts were constructed play an important role rather than the number of active sites.
3 2 6
from Fe O(CO ) clusters with the organic linkers (Section S2, Indeed, PCN-285, MOF-907, MIL-100, and MIL-101 displayed
Supporting Information). The Fe-MOFs were employed as the excellent catalytic efficiency with 95% yield encouraging us
heterogeneous catalysts for the microwave-assisted radical to further study how the structural features of those MOFs
oxidative cyclization that displayed not only highly porous (type of pore, pore size and shape, and pore environment)
property but strong Lewis acidity from generation of affected the catalytic reaction. Moreover, some MOFs of the
3
coordinatively unsaturated metal sites in the Fe O SBUs. The other metals such as HKUST-1 (Cu), ZIF-8 (Zn), and MOF-177
effect of the MOFs structure on the reaction was investigated (Zn). The reactions catalyzed by these MOF gave low yields
based on comparison of their catalytic ability in the same (Table 1, entries 10-12).This exhibits that the Lewis acidity of Fe-
volume space in structure. As we expected, the highest Fe- MOFs show higher efficient than the other MOFs in the
cluster active sites found in MIL-100 exhibited the best reaction.
performance in promotion of the reaction between benzyl
alcohol and 2-aminobenzamide for the synthesis of 2-
phenylquinazolin-4(3H)-one as shown in Table 1, entry 9.
Interestingly, there was no tendency of catalytic performance
observed when the active site density increased from PCN-285
to MIL-100 (Table 1, entries 1-9). From Table 1, the MOFs with
pore size distribution from 19 Å have high catalytic capacity
except MOF-909, MOF-908 and MIL-88B. Materials PCN-285,
MOF-909 and MOF-908 were all made of azo linker and had
similar pore size distribution as well as active site density (entry
1-3), however, azo and acid group of linker inside PCN-285 are
This journal is © The Royal Society of Chemistry 20xx
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Table 2.Study of the effect of active site and structure of Fe- catalyst (95%). Temperatures caused different yields for the
MOF in the synthesis of 2-methyl-2-phenyl-2,3-dihydro- same period of 15 minutes (Table S5, entries 6-11). The
quinazolin-4(1H)-onea
View Article Online
DOI: 10.1039/D0NJ03136D
optimized temperature for experiments was found to be 120 °C
with the yield up to 95%. Reaction time was also concerned
Table S5, entries 12-17). Interestingly, the reaction achieved
(
the highest yield at an extremely short time – only 1.5 minutes.
The reaction also involved by the concentration of TBHP. The
yield would be decreased when gradually reducing the amount
of TBHP (Table S5, entries 18-20). Furthermore, we considered
the oxidizing agents on the reaction (Table S5, entries 21-23).
TBHP demonstrated the highest oxidation with the best
performance.
In order to ensure the reaction depended only on the catalytic
ability of the material, the leaching test was necessary. MOF-
907 would be removed from the mixture after finishing the
reaction at 30 seconds by centrifugation, equivalent to 55%
yield. Then, we continued the reaction in 1 minute and obtained
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Entry Catalysts
Pore type
GC Yield (%)
1
2
3
4
PCN-285
MOF-907
MIL-101
MIL-100
Mesoporous
1-D channel
Cage
8
15
0
Cage
0
aReaction condition: 1-phenylethanol (1.5 mmol, 183 mg), 2-
aminobenzamide (0.5 mmol, 68 mg), TBHP (2 mmol, 277 µL), 0.047
3
cm catalysts were heated by microwave irradiation system at 120
6
0% of the product. Compared with the reaction in 1.5 minutes
°C in 1.5 minutes.
at the same condition (Table S5, entry 15), it was clear that the
efficiency of the leaching process is much lower after removing
the catalyst from the reaction mixture. An aliquot of the first 30
seconds was taken from the reaction mixture filtrate for
analysis by inductively coupled plasma – optical emission
spectrometry (ICP–OES). The concentration of cation Fe3+ was
determined to be 39.4 ppm causing reaction efficiency to
increase by 5%. Following leaching test, survey of catalytic
reusability was performed. The product formed with 85% yield
in the 5th run utilizing the recovered catalyst, which had not
change of its crystallinity and morphology (Figure S30). The
reaction mechanism was proposed. Initially, alcohol was
oxidized into aldehyde A by TBHP and Fe-MOF. Next, amine
group in 2-aminobenzamide attacked the carbonyl group in
aldehyde to form intermediate B. Then, the amide group
conducted cyclization and oxidation to create the product. The
catalyst was returned to its original form (Scheme 1).
With the initial results in hand, a similar reaction was mentioned
to evaluate the influence of structural features on catalytic
activity. Four Fe-MOFs with the highest performance in Table 1
were chosen as catalysts for the reaction between 1-
phenylethanol and 2-aminobenzamide (Table 2). As a result,
MOF-907 catalyst presented a highest catalytic activity of the
other MOFs. Even though both MIL-100 and MIL-101 have high
surface area, large pore size and almost the highest active site
density, the synthesis did not proceed in the presence of these
MOFs. This result confirmed that besides the surface area and
the pore size, the size and type of the porous window also
greatly influence the catalytic performance. MOF-907 possesses
1
-D interconnected channels (19ꢀÅ) with an accessible pore
36
window of 13ꢀÅ, hence the reactants could be well-distributed
throughout the pores in order to access and interact with the
open active sites of Fe O clusters. Furthermore, the small 3-D
3
pore windows of cage-type mesopores found in MIL-100 (5.0ꢀÅ)
and MIL-101 (11.7ꢀÅ) could not be suitable for the movement of
the reactants into the pores.
61,62
Additionally, due to
3-
2-
construction of highlyhydrophobic linkers, BTC and NDC ,
MOF-907 is the most hydrophobic than other MOFs leading to
easy diffusion of the reactants. The formation of acetophenone
from 1-phenylethanol oxidation caused a decrease in
polarization of the molecule. The acetophenone molecule
interacts well with the material by non-polar interaction
therefore 2-aminobenzamide can easily attack into its carbonyl
group.Indeed, the effect of structure hydrophobicity on
catalyticactivity was demonstrated by Yejun Guan and co-
63
worker.
Scheme 1. Proposed mechanism of the synthesis quinazolin-4(3H)-one derivatives.
Effect of other conditions on the synthesis of quinazolin-4(3H)-
one compounds
After the investigation about Fe-MOFs, we screened a range of
reactions with MOF-907 as a catalyst to find out the optimal
conditions (Table S5). The yield of the product was affected by
the ratio between catalyst and 2-aminobenzamide (Table S5,
entries 1-6). The performance is optimized using 4.2 mol%
4
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Synthesis of quinazolin-4(3H)-one derivatives was investigated aminobenzamide and secondary alcohol ViweweArreticle O2n,li3ne-
by using some primary alcohols. The reactions of aromatic dihydroquinazolin-4(1H)-one compounDdOsI.: 10.H10o3w9/eDv0eNrJ,0313th6De
alcohols achieved excellent yield (Table 3, a-d). For 1-butyl reaction occurred more difficult with longer times and lower
alcohol, the yield is lower (e) since its radical was not stable. This yields. For cycloalkanols, the yield would be reduced when the
led to the formation of many by-products (shown in Scheme size of the ring increased from 1 – 2 carbon elements (f-h). The
S1). Besides, secondary alcohols were mentioned (Table 3, performance was only 50% for 2-propanol (i) and extremely low
entries 6-10). The products of the reaction between 2-
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Table 3.Effect of alcohols on synthesis of quinazolin-4(3H)-one and 2,3-dihydroquinazolin-4-(1H)-one derivatives.
a
-1
Entry
Alcohols
Products
Yield (%)
TOF (h )
1
95b
902.5
a
2
3
95b
88b
902.5
835.9
b
c
4
5
85b
70b
807.4
664.9
d
e
6
7
95c
70c
67.7
49.9
f
g
8
9
40c
22.8
h
50c
25c
35.6
10.7
i
10
k
a
b
c
TOF (Turnover frequency): moles of product formed per mole of catalyst per hour; 1.5 min; 20 min.
This journal is © The Royal Society of Chemistry 20xx
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when using 1-phenylethanol as a substrate (k).
assistance from the Central Laboratory for Analysis, Science of
View Article Online
DOI: 10.1039/D0NJ03136D
University.
In general, the significant reduction in performance compared
to primary alcohols is due to the stereoscopic interaction
between the NH
Notes and references
2
group and the alkyl group in intermediate B
group attacks
(
shown in Scheme 2). As a result, this NH
2
1
2
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products. Moreover, planar structure of acetophenone from
oxidation of 1-phenylethanol interacts with the catalytic surface
causing the free space around it to narrower than other
secondary alcohols. This makes 2-aminobenzamide only attack
from above acetophenone. The result shows an extremely low
efficiency of reaction with 1-phenylethanol.
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DOI: 10.1039/D0NJ03136D
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Fe-MOFs used as efficient heterogeneous catalysts in tandem cyclooxidative reaction under
microwave irradiation
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