Application of basic isoreticular nanoporous metal-organic framework: IRMOF-3 as a suitable and efficient catalyst for the synthesis of chalcone

Article abstract of DOI:10.1039/c4ra16180g

A highly porous isoreticular metal-organic framework (IRMOF-3) was synthesized and employed as a novel efficient heterogeneous catalyst for the synthesis of chalcone via Claisen-Schmidt condensation. The effects of temperature, catalyst amount and solvent

Full text of DOI:10.1039/c4ra16180g

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PAPER
Application of basic isoreticular nanoporous
metal–organic framework: IRMOF-3 as a suitable
and efficient catalyst for the synthesis of chalcone†
Cite this: RSC Adv., 2015, 5, 14221
a
a
a
a
a
b
Songhai Wu, Xin Ma, Jingyu Ran, Yanfei Zhang, Fengxiang Qin and Yong Liu*
A highly porous isoreticular metal–organic framework (IRMOF-3) was synthesized and employed as a novel
efficient heterogeneous catalyst for the synthesis of chalcone via Claisen–Schmidt condensation. The
effects of temperature, catalyst amount and solvent on the yield of chalcone were investigated. The
results showed that IRMOF-3 not only showed high catalytic activities for the Claisen–Schmidt
condensation reaction under environmentally friendly conditions, but remarkably, it could also be facilely
separated from the reaction mixture and reused at least four times. Moreover, it was demonstrated that
the reaction was truly heterogeneous and the contribution from leached active species in the liquid
phase was negligible.
Received 11th December 2014
Accepted 20th January 2015
DOI: 10.1039/c4ra16180g
www.rsc.org/advances
as industrially viable and sustainable alternative to chalcone
synthesis.
Introduction
Chalcones are a family of aromatic ketones with two aromatic
Very recently, the emergency of a new class of crystalline
0
groups bridged by an enone linkage (Ar–COCHCH–Ar ). They porous materials, metal–organic frameworks (MOFs) whose
have attracted increasing attention due to their antibacterial, structure is dened by nodes of metal ions or clusters of metal
anticancer, anti-hyperglycemic, anti-inammatory and antima- ions held in the lattice by multi-topic organic linkers has
1,2
17–20
larial properties. Traditionally, chalcones could be obtained appealed many researchers' attention.
Compared with
via Claisen–Schmidt condensation carried out in acidic or basic traditional porous carbons and inorganic zeolites, these porous
media under homogeneous conditions. Typically, the reaction MOFs possess various advantages such as specic surface areas,
3
4
5
can effectively proceed in the presence of NaOH, KOH, AlCl ,
adjustable pore sizes, adequate framework stability and the
3
6
7
BF3 and dry HCl. However, problems of catalyst recovery and presence of active sites either in the framework or hosted in the
disposal of waste generated should be addressed for these voids.
21,22
In this context, the use of MOFs as solid catalysts or
homogenous catalysts. In the past decade, various heteroge- catalyst supports in organic reactions is a topic under much
neous catalysts have been increasingly used to promote this current investigation trying to take advantage of the potential of
8
23–29
reaction such as silica–sulphuric acid, recyclable SO
3
H- these materials.
Recently, Fe-based MOFs have been repor-
9
10
functionalized ionic liquids, graphene acid, magnesium ted as effective and reusable heterogeneous catalysts for the
11
12
13
30,31
oxide, alkaline-doped carbons and aminopropylated silica.
Claisen–Schmidt reaction.
These studies have shown that
Analogously, many zeolite-based catalysts have been reported as the coordinatively unsaturated metal sites within MOFs are
heterogeneous catalysts for the synthesis of chalcone and its capable of acting as Lewis acid catalysts promoting this reac-
14–16
derivatives.
employing these solid catalysts still suffers from a number of with catalytically-active functional organic sites as basic catalysts
obstacles such as difficulty in the catalyst preparation, use of has not been proposed. IRMOF-3 [Zn O(O C–H NC –CO ], a
Although promising results have been achieved, tion. However, the Claisen–Schmidt reaction employing MOFs
H
)
2 3
4
2
2
6
3
special apparatus and formation of by-products. In this case, an member of the isoreticular MOF family, is a very interesting and
environmentally friendly and efficient catalyst is required to act rare example of a MOF having accessible functional (amino)
32
groups imparting basic character to the material. In addition,
the high surface area and large pore size of IRMOF-3 can make
the active sites completely exposed to the exterior of pore
a
School of Chemical Engineering and Technology, Tianjin University, Tianjin, P.R. facilitating diffusion and the interfacial contact between the
China
33–35
active sites and the reagents.
The material is nding
b
School of Chemistry and Chemical Engineering, Tianjin University of Technology,
Tianjin, P.R. China. E-mail: yongliutju2013@163.com; Fax: +86-022-87401961; Tel:
increasing application as solid catalysts and exhibits good to
excellent catalytic performance for several organic trans-
+
†
1
86-022-87401961
35–40
formations.
In particular, it has been shown that the basicity
Electronic supplementary information (ESI) available. See DOI:
0.1039/c4ra16180g
of aniline-like amino moieties is enhanced, along with the
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35
catalytic activity, when inside the pores of MOF channels. The yielding pale yellow cube-shaped crystals (yield ꢃ60% based on
better performance of IRMOF-3 over other amminic catalysts 2-aminoterephthalic acid).
41
has been further rationalized by DFT calculations, suggesting
that increased IRMOF-3 activity, as a basic catalyst, should be
mostly related to its water adsorption. Zn-centres within its
framework interact more strongly with the produced water
molecules in the reaction process, intercepting and blocking
the formed water molecules and thus preserving the properties
of the catalytically active amino moieties.
These ndings suggest that IRMOF-3 and similar structures
are interesting and promising heterogeneous catalyst candi-
dates for liquid phase reactions. In this study, we herein report
our results for the application and direct using of unfunction-
alized IRMOF-3 as a suitable and efficient heterogeneous cata-
lyst for the Claisen–Schmidt reaction with high yield of
biological and medicinal interest chalcone. In addition, the
MOF catalyst can be easily separated and recovered efficiently
without signicant degradation in activity.
Claisen–Schmidt condensation reaction
The Claisen–Schmidt reaction of benzaldehyde with aceto-
phenone using IRMOF-3 as catalyst was carried out in a 25 mL
three-necked ask equipped with a magnetic stirring and a
reux condenser. The IRMOF-3 catalyst was activated under
ꢀ
vacuum at 160 C for 6 h prior to use. In a typical reaction, a
solution of acetophenone (0.58 mL, 5 mmol) in 5 mL DMSO was
placed into the ask containing the IRMOF-3 catalyst (100 mg,
10 mol%). The catalyst concentration was calculated with
respect to the zinc/benzaldehyde molar ratio. The mixture was
heated and benzaldehyde (0.51 mL, 5 mmol) was dropped into
the three-necked ask when the temperature rose to 140 C.
ꢀ
Reaction conversion was monitored by withdrawing aliquots
from the reaction mixture at different time intervals. Aer
separating the catalyst by ltration, the ltrate was extracted
with dichloromethane and analyzed by gas chromatography
(Agilent 6890N GC-FID system). The product composition was
further conrmed by GC-MS (HP 6890/5973). The analysis was
carried out directly aer sampling to avoid any additional
conversion in the reaction mixture. To investigate the reus-
ability of catalyst, IRMOF-3 was separated from reaction system
at the end of the reaction, washed with copious amounts of
anhydrous DCM and dried under vacuum at ambient temper-
ature for 1 h, then reused for a second run.
Experimental
Materials and instrumentation
3 2 2
Zinc nitrate hexahydrate (Zn(NO ) $6H O) and 2-amino-
terephthalic acid (H ATA) were purchased from Sigma-Aldrich.
2
Other analytical grade reagents were purchased from Guangfu
Chemicals Reagent Co. Ltd (Tianjin, China) and used without
further purication. Nitrogen physisorption measurements
were conducted using a NOVA 2000 series volumetric adsorp-
tion system (Quantachrome Corporation, USA), with samples
ꢀ
pretreated under vacuum at 150 C for 3 h. Thermalgravimetric Results and discussion
analysis was conducted on TGA/DSC1/1100 (METTLER
Catalyst synthesis and characterization
TOLEDO). Prior to the TGA measurement, samples were fully
ꢀ
When synthesizing porous MOF-based materials, it is crucial to
carry out the solvent exchange since this step will facilitate the
evacuation of the material frameworks.
evacuated at 100 C under vacuum overnight. During the
ꢀ
ꢀ
ꢁ1
measurement, each sample was heated from 30 C to 650 C
43,44
ꢀ
During this solvent
under nitrogen atmosphere with a heating rate of 10 C min
.
exchange step, strongly interacting DMF molecules were
replaced by more weakly interacting DCM molecules that would
be facilely removed under vacuum in the subsequent activation
step. It was observed that the IRMOF-3 was achieved as pale
X-ray diffraction (XRD) was carried out at ambient temperature
using Cu-Ka radiation on Rigaku D/max 2200/PC diffractometer
(Rigaku Corporation, Japan). Scanning electron microscopy
studies were conducted on a S-4800 scanning electron micro-
scope (SEM). Fourier transform infrared (FT-IR) spectra were
obtained on a Nicolet Nexus 670 instrument, with samples
being dispersed on potassium bromide pallets.
2
yellow crystals in a yield of 60% (based on H ATA).
XRD, SEM and FT-IR measurements were performed to
conrm the formation of the IRMOF-3 structure. A very sharp
ꢀ
peak at around 2q of 6.8 was observed on the XRD diffracto-
gram, indicating that a highly crystalline material was produced
Catalysts preparation
(
Fig. 1). The overall XRD patterns of the IRMOF-3 were in good
45
IRMOF-3 was prepared and activated according to a modied agreement with those previously reported in the literature.
4
2
literature procedure. A solid mixture of Zn(NO ) $6H O (6.81 The SEM (Fig. S1†) and the optical microscopic photograph
3
2
2
g, 22.9 mmol) and H
2
ATA (1.50 g, 8.30 mmol) were dissolved in (Fig. S2†) showed that well-shaped cubic crystals were obtained.
0
200 mL of N,N -dimethylformamide (DMF) and stirred for 30 The FT-IR spectrum of IRMOF-3 exhibited a signicant differ-
min at room temperature. The solution was then divided into 10 ence compared to that of the 2-aminoterephthalic acid. In the
mL portions and transferred to 20 scintillation vials. The tightly spectra of 2-aminoterephthalic acid, there was a strong peak at
ꢀ
ꢁ1
capped vials were heated at 100 C in an isothermal oven for 18 1690 cm , which represented the C]O stretching vibration in
ꢁ
1
22
h. Aer slowly cooling of the vials to room temperature, the free carboxylic acids (1760–1690 cm ). The intensity of this
solid product was removed and washed with dry DMF (3 ꢂ 12 peak in the spectra of the IRMOF-3 was found to be signicantly
mL) for 3 days. Subsequently, anhydrous dichloromethane lower than the case of the free acid linker. Moreover, the spectra
ꢁ1
(
DCM) (3 ꢂ 12 mL) was used to replace the DMF for 3 days. The of the IRMOF-3 exhibited a strong peak at 1580 cm , indicating
ꢀ
residual solvents were removed under vacuum at 160 C for 6 h, the deprotonation of –COOH groups in 2-aminoterephthalic
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Scheme 1 The Claisen–Schmidt condensation of benzaldehyde with
acetophenone using the IRMOF-3 catalyst.
were withdrawn from the reaction mixture at different time
intervals and analyzed by GC during the course of the reaction.
No by-products were detected by GC, indicating that Cannizaro
reaction or other undesired side reactions did not take place
under these experimental conditions. As seen in Fig. 3, the
reaction occurred readily to give 31% yield of chalcones aer 24
Fig. 1 X-ray diffraction patterns of the IRMOF-3.
ꢀ
h at 100 C, while yields of 40%, 66% and 78% were observed at
ꢀ ꢀ ꢀ
1
10 C, 120 C and 140 C, respectively. As expected, the yield of
chalcone increased as the temperature rose. It should be noted
that DMSO might decompose at higher temperature. For this
reason, 140 C was employed as the ideal temperature to
4
6
acid upon the reaction with metal ions. Moreover, The peaks
ꢁ
1
centered at 3470 and 3359 cm were indicative of the presence
of amino groups of the 2-aminoterephthalic ligand.
ꢀ
38
continue with the analysis of other reaction variables. Also,
In order to further conrm the structural features, Nitrogen
adsorption–desorption isotherms of the solvothermal synthe-
sized IRMOF-3 were displayed in Fig. S3.† Thermal degradation
investigations of solid materials are quite necessary as many
applications depend on their thermal stability. As shown in
Fig. S4,† there was a little weight loss while the temperature was
several Claisen–Schmidt processes have been effectively oper-
ꢀ
9,10,16,47
ated at around 140 C.
In addition, IRMOF-3 has exhibi-
ted several advantages in terms of yields over other catalysts. In
comparison with the performance of IRMOF-3, only about 60%
of the chalcone yield was obtained using graphene acid as
10
catalyst at the same temperature and 58% yield of chalcone
ꢀ
lower than 350 C, indicating that IRMOF-3 was stable up to 350
C. It was also veried by the DTA result (Fig. 2).
11
was achieved with MgO at higher temperature.
ꢀ
The optimal reaction conditions (DMSO, a temperature of
ꢀ
1
40 C and 24 h) were used for the next experiment. As catalyst
Catalytic studies
dosages were depended on the nature of the catalysts as well as
the substrates, the effect of catalyst concentration on the reac-
tion was then investigated in the presence of 6 mol%, 8 mol%
and 10 mol% IRMOF-3 catalyst, respectively. It was observed
that 78% yield of chalcone was achieved aer 24 h using 10
mol% IRMOF-3 catalyst (Fig. 4). As expected, decreasing the
catalyst concentration to 6 mol% led to a signicant drop in the
reaction rate, with 62% yield being observed aer 24 h. It was
found that the reaction could afford a yield of 73% at 8 mol%
The IRMOF-3 was chose as a solid basic catalyst for the Claisen–
Schmidt condensation reaction of benzaldehyde with aceto-
phenone to yield chalcone as the principal product (Scheme 1).
ꢀ
ꢀ
Initial experiments were conducted in DMSO at 100 C, 110 C,
ꢀ
ꢀ
1
20 C and 140 C to investigate the effect of temperature on the
yield of chalcone in the presence of 10 mol% IRMOF-3. Aliquots
Fig.
2 FT-IR spectra of 2-aminoterephthalic acid (a) and the
IRMOF-3 (b).
Fig. 3 Effect of temperature on the chalcone yield.
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Fig. 5 Effect of different catalysts on chalcone yield.
Fig. 4 Effect of catalyst concentration on chalcone yield.
When a solid catalyst is used, the possibility that some of
active sites could migrate from the solid support to the liquid
phase should be taken into account as these leached species
catalyst in 24 h. It was noteworthy that only 8% yield was
observed in the absence of catalyst. Obviously, the reaction
could not proceed without catalysts, which is accord with the
37
would lead to a homogeneous catalysis. To clarify if active
species leached from the solid IRMOF-3 catalyst affected the
catalytic activity of the Claisen–Schmidt condensation reaction,
an experiment was performed through a simple centrifugation
during the course of the reaction. Aer removing the solid
catalyst from the reaction mixture, if further conversion was still
observed in the solution phase, this would indicate that the
active species were from the solution rather than from the solid
catalyst. In our study, the organic phase was separated from the
solid catalyst aer reacting for 3 h with 10 mol% of fresh
IRMOF-3 catalyst. The reaction solution was then transferred to
a new reactor vessel, stirred for additional 21 h at the same
temperature. Experimental result showed that the nal yield of
chalcone was 30% but still far from the 78% observed when
IRMOF-3 was always present in the reaction mixture (Fig. 6).
Although a low degree of homogeneous catalysis still existed, it
30
result by literature. Meanwhile, high yield also implied the
efficiency of IRMOF-3 in this reaction. Conventionally, the
Claisen–Schmidt reaction required a large amount of aqueous
or alcoholic KOH as the catalyst which could not be reused. In
toluene/aqueous biphasic system with 10% aqueous KOH, a
4
conversion percentage of only 15% was observed aer 24 h.
Replacement of environmentally unacceptable anhydrous KOH
with solid catalysts has been shown to effectively reduce the
amount of catalyst for Claisen–Schmidt reactions. Moreover,
the catalyst concentrations used in this study were comparable
to those of other solid catalysts in the condensation reaction of
11–13,30
acetophenone to aromatic aldehydes.
Due to the fact that the nature of the amine-decorated MOFs
IRMOF-3) or its synthetic components may play an important
(
role in the synthesis of chalcones, in comparison with homo-
geneous aniline catalyst having similar aromatic amino groups
with IRMOF-3, the reaction was carried out in DMSO using 10
mol% H
2
ATA, Zn(NO
3
)
2
$6H
2
O, aniline and IRMOF-3 catalysts at
ꢀ
140 C. Zn(NO ) $6H O, one component of the IRMOF-3
3
2
2
exhibited signicantly lower activity for the reaction than the
solid catalyst, with a yield of 11% being obtained aer 6 h. It
should be noted that the reaction using the organic linker of the
IRMOF-3 (i.e. H
resembling most the aromatic amino functionality in the MOFs
based on H ATA, was also included as homogeneous basic
2
ATA) gave approximately 15% yield. Aniline,
2
catalyst for comparison. It was observed that a yield of 25% was
obtained aer 24 h under the same reaction conditions (Fig. 5).
Compared to aniline, which, in principle, should yield a similar
behavior under the same conditions, the reactivity and basicity
of the amino groups was enhanced when incorporated inside
the MOF structure. These results indicated that the amino
groups on the linkers in the MOF structure would be one of
reasons for high catalytic activity in the Claisen–Schmidt reac-
tion. However, the role of the amine moiety in the catalyst
structure still needs further investigation.
Fig. 6 Leaching test indicated no contribution from homogeneous
catalysis of active species leaching into reaction solution.
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could be ascribed to non-catalytic thermal condensation in reaction generates water and its inherent moisture sensitivity
30
44
accordance with previous literature. In conclusion, these reported for Zn O based metal–organic frameworks, the
4
results clearly indicated that the Claisen–Schmidt reaction IRMOF-3 samples could be stable and performed high catalytic
could only occur in the presence of the solid IRMOF-3 catalyst, activity under the studied reaction conditions. As previous
and there was no contribution from leached active species in studies reported, with the presence of high boiling point
49
the liquid phase.
4
solvents, Zn O cluster salvation occurred, resulting in a
Varieties of solvents were previously employed for the hydrophobic barrier that protected the clusters from decom-
35
Claisen–Schmidt condensation, signicantly depending on the plexation by water. Furthermore, the catalytically active amino
nature of the catalyst material. For the reaction employing groups embedded in IRMOF-3 could be instead protected
NaNO /HAP as catalyst, ethanol, DMF, dioxane and DCM were because its framework Zn-centres interact more strongly with
3
reported to be relatively ineffective, while high yields were the produced water molecules, thus intercept and block the
48
41
observed for the case of methanol. Dhakshinamoorthy et al. water molecules. In order to investigate the recoverability and
also investigated the effect of solvent on the condensation reusability of IRMOF-3, the reaction was carried out in DMSO at
ꢀ
reaction using a MOF-based catalyst Fe(BTC), and demon- 140 C using 10 mol% of IRMOF-3 catalyst. Aer reaction, the
strated that toluene was the best choice for the reaction among solid was ltered off, washed with copious amounts of anhy-
other common solvents such as chlorobenzene, decane and drous DCM, dried under vacuum at ambient temperature for 1
30
acetonitrile. Moreover, it was also reported that the higher the h and reused for another consecutive run without further
hydrophobicity of the porous material, the less the effect of the treatment. As shown in Fig. 8, no signicant degradation in
42
solvent and the faster the diffusion of the products. Since catalytic activity was observed when considering the small
IRMOF-3 is a hydrophilic solid (not all Zn atoms in IRMOF-3 are
fully coordinated), it is certain that the polarity of the solvent
35
has a large impact on the performance of the catalyst. There-
fore the solvent effect in the Claisen–Schmidt reaction was
explored here. In this work, it was found that a combination of
DMSO and the IRMOF-3 catalyst afforded excellent yields for the
reaction (Fig. 7). This could be explained by the hydrogen bond
acceptor power of DMSO, which stabilized the –NH group in
2
the protonated form, and thus increased the rate of proton
35
transfer from the substrate to the amine catalyst. Experi-
mental results also showed that nitrobenzene was relatively
ineffective for the process, as less than 30% yield was obtained
aer 24 h. The DMF exhibited better performance with 45%
yield achieved aer 24 h (Fig. 7). However, the effect of different
solvents on the rate of the reaction using the IRMOF-3 catalyst
was complex and further investigations would be needed.
When solid catalysts are employed for organic trans-
formations, issues that should be seriously considered are the Fig. 8 Catalyst recycling studies.
stability as well as the deactivation and reusability of the cata-
lysts. Despite the fact that Claisen–Schmidt condensation
Fig. 9 XRD patterns of the (a) fresh and (b) reused IRMOF-3 after the
4th run.
Fig. 7 Effect of different solvents on chalcone yield.
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Scheme 2 Proposal mechanism of chalcone synthesis catalyzed by IRMOF-3 via imine intermediate.
amount of catalyst lost during the recycling process. Moreover, FT-IR, SEM, TGA, and nitrogen physisorption measurements. In
more than 65% yield was still achieved in the forth run. Two addition, we have shown that IRMOF-3 can catalyse efficiently
peaks corresponding to the amino groups were also observed on the Claisen–Schmidt reaction of benzaldehyde with aceto-
the FT-IR of the reused IRMOF-3. Indeed, there was almost no phenone to synthesize chalcone as the major product. To the
difference in terms of IR spectrum between the fresh and best of our knowledge, the condensation reaction in the pres-
recovered IRMOF-3 (Fig. S5†). XRD result of the reused catalyst ence of the unfunctionalized IRMOF-3 has not been reported in
aer the 4th run showed that the overall structure of the the literature. Under optimal reaction conditions, a high yield of
IRMOF-3 catalyst could be maintained during the course of the 78% was obtained. Moreover, the IRMOF-3 catalyst was truly
reaction. However, compared with the result of the fresh heterogeneous and could be successively recycled at least three
IRMOF-3, the low signal in the XRD result of the recycled times without signicant degradation in catalytic activity. Due
catalyst indicated that the crystallinity of the reused catalyst to the excellent catalytic property, cheap raw materials and
decreased signicantly, which may have a negative effect on the simple preparation, it is apparent that the IRMOF-3 catalyst can
catalytic activity. Further investigations would be needed to be an industrially viable and sustainable alternative to other
clarify the reason of the catalyst deactivation in the synthesis of solid catalysts for the synthesis of chalcones. This achievement
chalcone using the IRMOF-3 catalyst (Fig. 9).
would contribute to the development of metal–organic frame-
The Claisen–Schmidt condensation of benzaldehydes and works as efficient heterogeneous catalysts, which would be
acetophenones has been promoted by multiple solid base interested to the chemical industry.
2–4,11–15
catalysts.
Reaction mechanisms that depend essentially
on the nature of the catalytic material may be different. Besides
the classic basic catalyst procedure, Romanelli et al. proposed
Acknowledgements
13
an alternative mechanism on the basis of imine formation.
A
We greatly acknowledge the nancial support from the National
Natural Science Foundation of China (no. 41003040, no.
similar reaction pathway was suggested here for the Claisen–
Schmidt condensation over porous IRMOF-3 (Scheme 2). When
weaker bases, such as organic amines were involved in the
catalytic process, the benzaldehyde molecules and the amino
groups formed the C]N imine species, which was proposed to
be one of the intermediates. The rst step of imine formation
was the attack by the nucleophilic amine on the carbonyl. Rapid
proton transference resulted in a carbinolamine, which then
4
1373114 and no. 41201487). We are also grateful for the
Program of Introducing Talents of Discipline to Universities
no. B06006).
(
References
50
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was attacked by the acetophenone anion and one proton was
incorporated to form the intermediate 1. Finally the interme-
diate 1 formed chalcone and the catalysts were regenerated.
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