Metal-Organic Framework MIL-101-NH2-Supported Acetate-Based Butylimidazolium Ionic Liquid as a Highly Efficient Heterogeneous Catalyst for the Synthesis of 3-Aryl-2-oxazolidinones

Article abstract of DOI:10.1021/acs.langmuir.8b03153

A novel heterogeneous catalyst, the ionic liquid (IL) of 1-butyl-3-methylimidazolium acetate (BmimOAc) immobilized on MIL-101-NH₂, denoted as IL(OAc^-)-MIL-101-NH₂, was prepared by the "ship-in-a-bottle" strategy. The IL of

Full text of DOI:10.1021/acs.langmuir.8b03153

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Interface-Rich Materials and Assemblies
2
Metal-organic framework MIL-101-NH supported acetate-
based butylimidazolium ionic liquid as a highly efficient
heterogeneous catalyst for the synthesis of 3-aryl-2-oxazolidinones
Siying Chong, Tongtong Wang, Lichun Cheng, Huiyi Lv, and Min Ji
Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.8b03153 • Publication Date (Web): 22 Dec 2018
Downloaded from http://pubs.acs.org on December 24, 2018
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Metal-organic framework MIL-101-NH2 supported
acetate-based butylimidazolium ionic liquid as a
highly efficient heterogeneous catalyst for the
synthesis of 3-aryl-2-oxazolidinones
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S. Y. Chong, a T. T. Wang, a L.C. Cheng, b H. Y. Lv,*b and M. Ji*a
a School of Chemistry, Faculty of Chemical, Environmental and Biological Science and
Technology, Dalian University of Technology, Dalian 116023, China. E-mail: jimin@dlut.edu.cn.
b Department of Pharmacy, The Second Affiliation Hospital of Dalian Medical University,
Dalian 116027, China. E-mail: lvhuiyi@gmail.com.
KEYWORDS: Ionic liquid; Immobilization; Metal-organic frameworks; Heterogeneous catalyst;
3-Aryl-2-oxazolidinones
ABSTRACT: A novel heterogeneous catalyst, the ionic liquid (IL) of 1-butyl-3-
methylimidazolium acetate (BmimOAc) immobilized on MIL-101-NH2, denoted IL(OAc-)-MIL-
101-NH2, was prepared by ‘ship-in-a-bottle’ strategy. The IL of BmimOAc was prepared in the
MIL-101-NH2 nanocages primordially, in which the condensation product of MIL-101-NH2’s
amine group with 1,1'-carbonyldiimidazole (CDI) reacted with 1-bromo butane， and then the
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intermediate exchanged with potassium acetate. The structure and physico-chemical properties
of IL(OAc-)-MIL-101-NH2 were characterized by PXRD, SEM, FT-IR, DRS UV–Vis, nitrogen
adsorption-desorption, and elemental analysis. The results indicated that BmimOAc was
anchored in the MIL-101-NH2 skeleton via acylamino group and confined in the nanocages in
the form of a single molecule. The composite material of IL(OAc-)-MIL-101-NH2 exhibited
excellent catalytic activity and catalytically synthesized 3-aryl-2-oxazolone in an excellent yield
of 92 %. It can be reused up to six times without noteworthy loss of its activity and demonstrated
distinct size-selective property for substrates. It was conjectured that the diffusion kinetics of
reactants could be controlled by the aperture size of the metal-organic framework (MOF) support.
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Introduction
3-Aryl-2-oxazolidinones, key heterocyclic compounds, are recently attracting much research
interests in the fields of fine chemicals and organic syntheses. As a result of their prominent
activity, 3-aryl-2-oxazolidinones have been regarded as a novel class of neuroleptic agents,
antibiotics, blood thinners, antimicrobial agents, fungicides, HIV-1 protease inhibitors, and vital
structural components in agrochemicals as well as pharmaceuticals.1-5
During the past decade, many catalysts and synthetic methods have been applied to obtain 3-
aryl-2-oxazolidinones. Traditional synthetic methods use isocyanates or phosgenes as starting
materials.6-10 Although satisfactory both conversion and selectivity are observed, these processes
are considered non-green since toxic starting substrates are used. Alternative synthetic methods
via the cross-coupling reactions of tosylated pyridines and aryl halides catalyzed by palladium
have been reported.11-12 However, the toxic and unstable phosphine ligands existing in the
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palladium catalyst are also disgusted. Other catalysts like Cu2O and CuI are utilized to synthesize
3-aryl-2-oxazolidinones by the reaction of aryl halides with oxazolidin-2-ones13-15 and amino
alcohol carbamates with aryl iodides.16 But most of them show multiple disadvantages such as
higher costs, metal pollutant in the reaction system and the generation of toxic waste in the
product.
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Functionalized (“task-specific”) ionic liquids (TSILs) as green catalysts or reaction media have
aroused extensive interest because of their unique characteristics like low volatility, adjustable
acidity, and good fluidity.17-20 The synergistic effects of their anions and cations can stimulate
the substrates by the hydrogen bonds between catalysts and starting materials, which is beneficial
to improve the catalytic activity, reaction rates, and objective product selectivity.21-22
Furthermore, some TSILs exhibit excellent catalytic performance in the synthesis of 3-aryl-2-
oxazolidinones. Over the last few years,23-26 Gao and co-workers have dedicated to the synthesis
of 3-aryl-2-oxazolidinones including the condensation reaction of diethyl carbonate with 2-
(arylamino) alcohols,27 the reaction of carbonic ester with arylamine28-29 and the coupling
reaction of epoxides with aryl carbamates by using different TSILs as catalyst.30 Among them,
by means of the catalysis of 10 mol % BmimOAc, the good yield of 3-aryl-2-oxazolidinones
with 98% was obtained at the reaction temperature of 140 °C after 9 h. However, the complex
process of product purification and catalyst reclamation hamper their commercialization. The
most simple and effective solution to these conundrums is the immobilization of ionic liquid onto
the solid material with the certain mechanical strength and the high surface area, such as
crosslinked polystyrene-divinylbenzene,31 KIT-632, and Fe3O4 nanoparticles.33 TSILs
immobilized on robust backings not only separated efficiently reactants and recycles after the
reaction, but also boosted effective sites on the catalyst surface and reduced the used amount of
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TSILs, which displayed a large number of advantages rather than the direct use of TSILs.34 Very
recently, the study of using Fe3O4 @SiO2 as carriers to support imidazolium-based ionic liquids
have been reported.35 This catalyst was utilized in the reaction of carbonic ester with
phenylamine to 3-aryl-2-oxazolidinones, which showed excellent activity and recyclability. It is
a great inspiration for the development of the environmental friendly synthesis of 3-aryl-2-
oxazolidinones.
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Metal-organic frameworks (MOFs) have attracted tremendous interests in many fields, such as
drug delivery,36 separation science,37-38 magnetism,39 sensing,40 gas storage41, and heterogeneous
catalysis.42 Besides the catalytic activity of pure MOFs, their advantageous and unique
characteristics including the regular and tunable pore structures,43 high surface area,44 diversity
in the functionality and chemical compositions of metal nodes and organic linkers, MOFs are
also considered for supporting ‘heterogenizing’ carrier materials to improve recovery of
catalysts.45-48 Some beginning researches of the immobilization of ionic liquids on MOFs have
been reported by our team in the past few years. We have studied amino-functionalized basic
ionic liquid was immobilized on HKUST-1 as a heterogeneous catalyst for the Knoevenagel
condensation reaction of malononitrile with benzaldehyde,49 the Brønsted acidic ionic liquid was
immobilized on MIL-101 as a heterogeneous catalyst for the acetalization of glycol with
benzaldehyde,50 the Pd-containing chloride ionic liquid was immobilized on CuBTC as a
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heterogeneous catalyst for the selective oxidation of cyclohexene, and carboxyl ionic liquid -
functionalized MIL-101-NH2 as a bifunctional heterogeneous catalyst for the cycloaddition
reaction of propylene oxide with carbon dioxide.52 It noted that onic liquids immobilized on
MOFs showed a higher dispersion owe to the anchoring sites in the MOFs are regularly
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distributed, which can let them carry the homogeneous sites with beneficial microenvironment
for mass diffusion and transfer.
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In this contribution, we aim to develop a simple and effective catalyst system without any toxic
reagents and transition metal catalyst in order to obtain the bioactive 3-aryl-2-oxazolidinones.
The post-synthetic modification (PSM) strategy was adopted to construct BmimOAc confined
inside MIL-101-NH2 nanocages as a heterogeneous catalyst for the reaction of propylene
carbonate with phenylamine to 3-aryl-2-oxazolidinones. The new heterogeneous catalyst
exhibited superior catalytic activity and wide substrate scope. It mainly owes to the combination
of the ideal microenvironment of the MIL-101-NH2 nanocages with the beneficial virtue of the
ionic liquid catalyst.
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Experimental
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Materials
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All chemicals were commercially available and used without further purification.
Chromic nitrate hydrate (99%, Cr (NO3)3 9 H2O), 2-aminoterephthalic acid, sodium
hydroxide (NaOH), sodium sulfate anhyfrous (Na2SO4), N, N-dimethyl-formamide
(DMF), N, N-carbonyldiimidazole (CDI), 1, 8-Diazabicyclo [5.4.0] undec-7-ene (DBU),
1-bromo butane, potassium acetate(KOAc), phenylamine and propylene carbonate were
analytical reagent grade and purchased from Aladdin Industrial Corporation. Anhydrous
ethanol, toluene, trichloromethane (CHCl3), petroleum ether and ethyl acetate were
bought from Tianjin Kemiou Chemical Reagent Co., Ltd. TLC silica plate (60F-254) and
silica gel (230-400 mesh) were bought from Qingdao Haiyang Chemical Co., Ltd.
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Preparation of catalysts
The synthesis procedure of the IL(OAc-)-MIL-101-NH2 was shown in Scheme 1. MIL-
101-NH2 was hydrothermally synthesized. It was further purified using hot ethanol,
deionized water, and DMF. Then, it was modified by using DBU and CDI to form IM-
MIL 101-NH2.53 After that, IM-MIL-101-NH2 was further treated with 1-bromo butane
and exchanged with potassium acetate.54
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Scheme 1. The synthesis of the IL(OAc-)-MIL-101-NH2
Preparation of MIL-101-NH2
MIL-101-NH2 was prepared by a mild hydrothermally process.55 Typically, a mixture of 2-
aminoterephthalic acid (0.72 g, 4 mmol), Cr(NO3)3 9H2O (1.6 g, 4 mmol), NaOH (0.4 g, 1 mmol)
and 30 mL deionized water were added in an autoclave with a teflon container. The autoclave
was heated at 150 °C in an oven for 8 h. Then the slurry was collected by centrifugation at 7000
rpm for 2 min. The green solids were washed three times with deionized water, DMF and ethanol
respectively, and dried in an oven under the vacuum at 100 °C for 12 h. Then, MIL-101-NH2
was obtained.
Preparation of IM-MIL-101-NH2
IM-MIL-101-NH2 was prepared by the reaction of CDI with amino groups of MIL-101-NH2.53
Typically, MIL-101-NH2 (1 g) and DBU (3 mg,0.02 mmol) were added in toluene (20 mL) and
stirred at room temperature (r.t.) for 1 h, then CDI (357 mg, 2.2 mmol) was added and stirred at
r.t. for 12 h. The slurry was filtered, the solids were washed three times with 100 mL toluene and
dried in an oven under the vacuum at 100 °C for 12 h to give IM-MIL-101-NH2.
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Preparation of IL(Br-)-MIL-101-NH2
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IL(Br-)-MIL-101-NH2 was prepared by the alkylation of 1-bromo butane with the imidazolyl
of MI-MIL-101-NH2.54 Typically, IM-MIL-101-NH2 (1.2 g) was added in toluene (20 mL) at
0 °C. The mixture was slowly added 1-bromo butane (360 mg, 2.6 mmol) and stirred at 0 °C for
1 h. Then the slurry was transferred into a flask with a reflux device and carried out at 70 °C for
24 h. The slurry was filtered, and the solids were washed several times with 100 mL toluene and
dried in an oven under the vacuum at 100 °C for 12 h to give IL(Br-)-MIL-101-NH2.
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Preparation of IL(OAc-)-MIL-101-NH2
IL(OAc-)-MIL-101-NH2 was prepared by the ion exchange method of Br- on IL(Br-)-MIL-101-
NH2 with OAc- of potassium acetate.54 Typically, IL(Br-)-MIL-101-NH2 (1.5 g), potassium
acetate (294 mg, 3 mmol) and ethanol (25 mL) were added into a flask with a reflux device and
reacted with stirring at 40 °C for 12h. The slurry was filtered, and the solids were washed several
times with 100 mL of deionized water and dried in an oven under the vacuum at 100 °C for 12 h
to give IL(OAc-)-MIL-101-NH2.
Characterization techniques
The powder X-ray diffraction (PXRD) data were recorded on a Rigaku diffractometer
(D/MAX 2400, 12 kW) using Cu Kα radiation (40 kV, 100 mA, λ= 0.1541 nm), the scanning
angle from 0.5 to 20 degree with a scanning rate of 4 degree/min. The BET surface area
measurements were performed with Nitrogen adsorption-desorption isotherms at -196 °C using a
Quantachrome AUTOSORB 1 C apparatus. Before the analysis, samples were evacuated at
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100 °C for 12 h. Fourier transform infrared spectroscopy (FT-IR) was performed on Bruker-
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Tenson 27 infrared spectrometer in the range 400-4000 cm
using KBr pellets. Diffuse
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reflectance UV-Vis spectra were performed on Agilent Cary 5000 spectrophotometer. Scanning
electron microscopy (SEM) images were obtained on the JSM-6360 LV instrument. Elemental
analysis (EA) was performed on Vario EL III. 1H NMR and 13C NMR datas were obtained on the
Varian INOVA-500MHz NMR spectroscopy (USA).
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Catalytic test
Scheme 2. The reaction of propylene carbonate with phenylamine to 3-aryl-2-oxazolidinones by
IL(OAc-)-MIL-101-NH2 catalyst.
The catalytic test of ionic liquids(ILs) immobilized MIL-101-NH2 catalysts was evaluated by
using the reaction of propylene carbonate with phenylamine to 3-aryl-2-oxazolidinones (Scheme
2). A typical experiment, phenylamine (186 mg, 2 mmol), propylene carbonate (2 mL, 20 mmol)
and the catalyst of IL(OAc-)-MIL-101-NH2 (100 mg) were added into a round bottom flask. The
slurry was stirred for 9 h in a constant temperature oil bath at 140 °C. After the starting material
was no longer detected, the slurry was cooled slowly to r.t. Then the obtained mixture was
collected by centrifugation. The liquid phase was poured to deionized water and extracted with
CHCl3. After drying, filtering and concentrating the combined organic phases, the residue was
purified by flash column chromatography to afford 3-aryl-2-oxazolidinones. The structure was
determined by NMR. 1H NMR (500 MHz, CDCl3) δ 7.53 (d, J = 8.6, 0.8 Hz, 2H), 7.36 (t, J = 8.5,
7.6 Hz, 2H), 7.13 (t, J = 7.4 Hz, 1H), 4.83 - 4.71 (m, 1H), 4.10 (t, J = 8.5 Hz, 1H), 3.61 (dd, J =
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8.6, 7.1 Hz, 1H), 1.52 (d, J = 6.3 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 154.84 (s), 138.36 (s),
128.97 (s), 123.88 (s), 118.14 (s), 69.48 (s), 51.83 (s), 20.63 (s). The IL(OAc-)-MIL-101-NH2
catalyst was washed three times with ethanol and dried for 12 h in an oven at 100 °C under the
vacuum for the next reaction.
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Results and discussions
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Physico-chemical properties of IL(OAc-)-MIL-101-NH2
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The PXRD patterns of as-synthesized samples were shown in Figure 1. The diffraction peaks
of all samples were in good agreement with that of MIL-101-NH2 reported previously,55 while
some slight weakening in the intensity of Bragg were monitored in IM-MIL-101-NH2, IL(Br-)-
MIL-101-NH2 and IL(OAc-)-MIL-101-NH2. It indicated that the textural of the MIL-101-NH2
kept intact during the immobilization procedure, and the MIL-101-NH2 can act as a stable and
tunable matrix for the incorporation of versatile functionalities. In addition, the octahedral crystal
morphology of as-synthesized samples can also be observed from the scanning electron
microscopy (SEM) images (Figure 2), which was proved that the shape characteristic of the
MOFs was maintained during the post-synthetic modification process.
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-
IL(OAc )-MIL-101-NH2
-
IL(Br )-MIL-101-NH2
IM-MIL-101-NH2
MIL-101-NH2
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2 Theta/Degree
Figure 1. PXRD patterns of MIL-101-NH2(black), IM-MIL-101-NH2 (red), IL(Br-)-MIL-101-
NH2 (blue) and IL(OAc-)-MIL-101-NH2(green).
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Figure 2. SEM images of MIL-101-NH2, IM-MIL-101-NH2, IL(Br-)-MIL-101-NH2 and IL(OAc-
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)-MIL-101-NH2
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The FT-IR spectra of as-synthesized samples were recorded in the spectral range 500-3600 cm-
1, as shown in Figure 3a. MIL-101-NH2 exhibited obvious bands in the region of 1750-1300 cm-1
(Figure 3a-I), correspond to COO- symmetric, asymmetric stretching vibration, and C-C
stretching vibration, which demonstrated that the presence of the carboxylate linker of MIL-101-
NH2. The weak peak at 960 cm-1 and the sharp peak at 761 cm-1 attributed to C-H in-plane and
out-plane bending vibration of aromatic rings.56 Additionally, the obvious peak at 1662 cm-1 and
the very weak double peaks at 3382 cm-1 and 3307 cm-1 can be attributed to N-H bending
vibration, N-H asymmetric and symmetric stretching vibration of the amino groups,57
respectively. All those peaks of MIL-101-NH2 can be correspondingly found in the spectrum of
IM-MIL-101-NH2, IL(Br-)-MIL-101-NH2 and IL(OAc-)-MIL-101-NH2. The evidence above
proved that the MOF framework remained intact upon the attachment of the catalyst, which was
consistent with the results of PXRD and SEM. Different from MIL-101-NH2, immobilized MIL-
101-NH2 catalysts (Figure 3a-II, 3a-III, and 3a-IV), showed the characteristics of the imidazole
groups peak at 3459 cm-1, 1180 cm-1 and 843 cm-1, assigned to C-H stretching vibration, C-N
stretching vibration and in-plane C-H bending vibration, respectively.58 In addition, the decrease
of the peak at 1662 cm-1 was accompanied by the appearance of an obvious peak at 3100 cm-1,
which was attributed to the N-H stretching vibration of the acylamino groups. It demonstrated
that imidazole was grafted onto the amino groups of MIL-101-NH2 via acylamino groups
successfully. Furthermore, as shown in Figure 3c and 3d, the characteristic peaks at 2953 and
2865 cm-1 can be assigned to saturated C-H asymmetric and symmetric stretching vibration due
to the alkylation of imidazole with 1-bromo butane. The corresponding DRS UV–Vis spectra of
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as-synthesized samples were illustrated in Figure 3b. Compared with the first three sets of
samples, IL(OAc-)-MIL-101-NH2 exhibited obvious peak in the region of 206-210 nm (Figure
3b-IV), correspond to OAc- absorption peak. All the evidence above indicated that the ILs were
synthesized successfully and existed in MIL-101-NH2.
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(a)
(b)
IL(OAc-)-MIL-101-NH2
3459
1662
IL(Br-)-MIL-101-NH2
IM-MIL-101-NH2
MIL-101-NH2
(IV)
3382
3307
1180
2
0
8
834
2953
2865
3100
(III)
(II)
(I)
960
761
3500
3000
2500
2000
1500
1000
500
200
300
400
500
600
700
800
Wavenumbers cm-1
Wavenumber (nm)
Figure 3. (a) FT-IR spectra. (b) DRS UV-Vis spectra of MIL-101-NH2(black), IM-MIL-101-
NH2 (red), IL(Br-)-MIL-101-NH2 (blue) and IL(OAc-)-MIL-101-NH2(green).
The nitrogen adsorption/desorption isotherms of as-synthesized samples were used to
investigate the textural properties (Figure 4a) The nitrogen adsorption-desorption isotherms of
the four groups of as-synthesized samples were shown as the type I isotherm. By comparison
with the MIL-101-NH2, IM-MIL-101-NH2, IL(Br-)-MIL-101-NH2 and IL(OAc-)-MIL-101-NH2
exhibited a considerable reduction in the adsorbed amount of nitrogen. IM-MIL-101-NH2, IL(Br-
)-MIL-101-NH2 and IL(OAc-)-MIL-101-NH2 showed relatively lower total pore volume and
BET surface area than MIL-101-NH2 (Table 1) synchronously. Furthermore, the porous size of
MIL-101-NH2 is 1.99 nm, that of IL(OAc-)-MIL-101-NH2 is 1.86 nm (Figure 4b). The
decreasing total pore volume, porous size, and BET surface area can be attributed to the
incorporation of ILs inside the MIL-101-NH2 nanocages. The above data suggested the
encapsulation of ILs guest inside MIL-101-NH2 rather than the surface. Even so, the catalyst of
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IL(OAc-)-MIL-101-NH2 still remained high surface area and open cavities with 0.98 m3·g -1 and
502.7 m2·g -1 respectively, which was benefited the propagation and diffusion of the product and
reactant in the catalytic process.
9
10
11
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53
54
55
56
57
58
59
60
1000
800
600
400
200
0
(b)
(a)
IL(OAc-)-MIL-101-NH2
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0.6
0.5
0.4
0.3
0.2
0.1
0.0
1.99 nm
-
IL(Br-)-MIL-101-NH2
IM-MIL-101-NH2
MIL-101-NH2
IL(OAc )-MIL-101-NH2
-
IL(Br )-MIL-101-NH2
IM-MIL-101-NH2
MIL-101-NH2
1.90nm
1.87nm
1.86nm
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
Pore width (nm)
0.0
0.2
0.4
0.6
0.8
1.0
2
4
6
8
10
12
14
16
18
20
Relative Pressure P/P0
Pore width (nm)
Figure 4. (a) The N2 adsorption-desorption isotherms (b) pore size distribution curve from BJH
method of MIL-101-NH2 (black), IM-MIL-101-NH2 (red), IL(Br-)-MIL-101-NH2 (blue) and
IL(OAc-)-MIL-101-NH2(green).
Table 1. Specific surface area and pore volume of the sample.
Specific surface area
SBET/m2. g-1
1471.6
Pore volume
V/m3. g-1
2.38
Sample
MIL-101-NH2
IM-MIL-101-NH2
IL(Br-)-MIL-101-NH2
IL(OAc-)-MIL-101-NH2
714.3
1.21
575.3
1.15
502.7
0.98
The loading amounts of BmimOAc active ingredient in MIL-101-NH2 nanocages were
measured by an element analysis (Table 2). The nitrogen content of IL(OAc-)-MIL-101-NH2 was
8.26 mmol g-1, which was much higher than that of MIL-101-NH2 with 4.43 mmol g-1. The
significant increase of the nitrogen content implied ILs immobilization on MIL-101-NH2, which
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was accorded with the preceding characteristics of nitrogen physical adsorption-desorption.
Because of the formula weight of IL(Br-)-MIL-101-NH2 and IL(OAc-)-MIL-101-NH2 increased
after the alkylation reaction and ion exchange progress, the nitrogen content of IL(Br-)-MIL-101-
NH2 and IL(OAc-)-MIL-101-NH2 were lower than that of IM-MIL-101-NH2. According to the
results of elemental analysis of the nitrogen element, the loading amount of ionic liquid in
IL(OAc-)-MIL-101-NH2 was calculated to be 1.94 mmol g-1.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
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35
36
37
38
39
40
41
42
43
44
45
46
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48
49
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57
58
59
60
Table 2. Elemental analysis of as-synthesized samples.
ILs loading
Sample
N/mmol. g-1
amount/mmol. g-1
MIL-101-NH2
4.43
11.12
7.93
8.26
——
——
2.08
1.94
IM-MIL-101-NH2
IL(Br-)-MIL-101-NH2
IL(OAc-)-MIL-101-NH2
Catalytic performance
The catalytic performance of the IL(OAc-)-MIL-101-NH2 catalyst was evaluated by using the
reaction of phenylamine with propylene carbonate to 3-aryl-2-oxazolidinones (Table 3). Without
any catalyst, the reaction hardly took place (entry 1). The pure MIL-101-NH2 had a lower 3-aryl-
2-oxazolidinones yield at the temperature of 140 °C (entry 2), which was probably due to the
Lewis alkalinity of the amino site in the metal-organic framework. Fortunately, the reaction
proceeded successfully in the presence of IL(OAc-)-MIL-101-NH2. The yield of 3-aryl-2-
oxazolanones increased rapidly with the increase of the amount of catalyst, and the steady yield
was obtained in the case of 10 mol% of the catalyst (entries 3-5). Both the reaction time and
temperature influenced the reaction performance of propylene carbonate with phenylamine
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obviously. When the temperature was lower than 140 °C, the 3-aryl-2 oxazolidinones yield
increased with increasing temperature, and when the temperature raised to 150 °C, the yield was
significantly decreased (entries 6-8). A similar phenomenon was found in the homogeneous
catalytic process also.31 It demonstrated that the reaction of propylene carbonate and
phenylamine was highly sensitive to the temperature. From the date in Table 3, it can be seen
that with the reaction time increased from 7 to 9 h, the yield of 3-aryl-2-oxazolidinones raised at
a constant speed (entries 9-11) and the highest yield of 92% was obtained when the reaction was
carried out for 9 h. Compared with pure ionic liquid catalysis, the same good catalytic results
were obtained (entries 12). It is well known that the coordinatively unsaturated metal sites (CUSs)
of MIL-101-NH2 possesses an intrinsic coordination capacity with electron-rich functional
groups, that allows phenylamine to attach to the catalyst surface through the N-Cr bond, which
might influence the maximum yield of 3-aryl-2-oxazolidinones. From the above, the optimum
reaction conditions were established as follows: 0.2 mmol IL(OAc-)-MIL-101-NH2, 2 mmol
phenylamine, 10 mmol propylene carbonate, 140 °C, and 9 h.
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Table 3. Optimization of the reaction conditions [a].
Time
T
AN/PC/Cat.
molar ratio
1/10/X
Yield[b]
[%]
0
Entry
Catalyst
[h]
9
[℃]
140
140
130
130
130
120
1
2
3
4
5
6
none
MIL-101-NH2
9
1/10/0.05
1/10/0.05
1/10/0.1
18
IL(OAc-)-MIL-101-NH2
IL(OAc-)-MIL-101-NH2
IL(OAc-)-MIL-101-NH2
IL(OAc-)-MIL-101-NH2
9
49
9
71
9
1/10/0.15
1/10/0.1
72
9
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IL(OAc-)-MIL-101-NH2
IL(OAc-)-MIL-101-NH2
IL(OAc-)-MIL-101-NH2
IL(OAc-)-MIL-101-NH2
IL(OAc-)-MIL-101-NH2
IL(OAc-)
9
140
150
140
140
140
140
1/10/0.1
1/10/0.1
1/10/0.1
1/10/0.1
1/10/0.1
1/10/0.1
92
84
70
82
92
92
8
9
9
7
10
11
12
8
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10
9
[a] Reaction conditions: phenylamine (2 mmol), propylene carbonate (20 mmol).
[b] Isolated yield of 3-aryl-2-oxazolidinones.
Under the identical reaction conditions, the reusability of the IL(OAc-)-MIL-101-NH2 catalyst
was tested. After each reaction, the IL(OAc-)-MIL-101-NH2 catalyst was recovered by
sedimentation and centrifugation, washed three times with hot ethanol and dried for 12 h in an
oven at 100 °C under the vacuum for the next reaction. It was observed in Figure 5 (a) that the
catalyst was cycled six times with the little loss of catalytic activity. The hot filtration test was
performed to clarify the IL(OAc-)-MIL-101-NH2 catalyst was really heterogeneous and/or some
leached ILs consist in the liquid phase as shown in Figure 5 (b). After reacting for 1 h, the
reaction was stopped and the catalyst was separated from the reaction mixture. Then the liquid
was moved to another round bottom flask and allowed to react again. No further noteworthy
increase in yield of 3-aryl-2-oxazolidinones was observed. These results revealed that the ILs
immobilized on MIL-101-NH2 was stable and difficult to let out under reaction conditions. The
slight decrease of the yield in the recycling process might be speculated on the slower diffusion
rate of aniline from the inside to the outside of MIL-101-NH2 nanocages or the adsorption effect
on aniline of MIL-101-NH2.
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100
80
60
40
20
0
(b)
(a)
100
80
60
40
20
0
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Catalyst was filtered after 1h
With IL(OAc-)-MIL-101-NH2 catalyst
0
2
4
6
8
10
1
2
3
4
5
6
Reaction time (h)
Recycle time
Figure 5. For the catalytic test: (a)Recycling of the IL(OAc-)-MIL-101-NH2 (b)The hot filtration
test: with IL(OAc-)-MIL-101-NH2 (black); catalyst was filtered after 1 h (red).
Substrate scope
IL(OAc-)-MIL-101-NH2 was proved as the effective catalyst for the reaction of propylene
carbonate and phenylamine to 3-aryl-2-oxazolidinones. Then various types of aromatic amines
were utilized as starting materials in this reaction (Table 4). In general, amines bearing electron-
withdrawing (Cl, Br) were obtained higher yields than those bearing electron-donating (Me,
OMe) (entries 2-5). According to previous studies,26, 28, 35 the reaction mechanism of propylene
carbonate with phenylamine to 3-aryl-2-oxazolidinones by IL(OAc-)-MIL-101-NH2 catalyst as
shown in Scheme 3. The C-2 hydrogen of the imidazolium cation of IL(OAc-)-MIL-101-NH2
catalyst acts as a donor of hydrogen bond and thus set up effective electrophilic sites with the
carbonyl oxygen of propylene carbonate by making hydrogen bond interaction. At the same time,
the acetate anion of IL(OAc-)-MIL-101-NH2 interacts with phenylamine to form intermediates.
Then a nucleophilic reaction The liquid phase was poured with deionized water curs between the
activated phenylamine and propylene carbonate and the final product is obtained by losing a
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molecule of H2O and intramolecular cyclization. The amines with electron-withdrawing are more
easily activated and transformed into intermediate. So the higher yields can be obtained form as
listed in Table 4. Steric hindrance was to have a great influence in the cases of para-
bromophenylamine, meta-bromophenylamine, and ortho-bromophenylamine (entries 5-7).
Ortho-bromophenylamine is more hardly activated and more difficult to participate in the next
reaction process. Therefore, the yield was highly dependent on the steric effects of the aromatic
amines. In addition, propylene carbonate can also react with aromatic diamines or naphthylamine
to form the expected products (entries 8-9). The reason for the lower yield might be due to the
steric factor and the difficult rotation in the confined microenvironment. Notably, N-heterocyclic
aromatic amines, such as the pyridin-2-ylamine were also applicable in this system (entries 10).
10
11
12
13
14
15
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60
Table 4. The reaction of propylene carbonate and aromatic amines catalyzed by IL(OAc-)-MIL-
[a]
101-NH2
.
Aromatic
amine
Yield[b]
[%]
Entry
Product
1
2
3
4
92
85
80
91
94
5
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8
9
10
[a] Reaction conditions: aromatic amines (2 mmol), propylene carbonate (20 mmol),
IL(OAc-)-MIL-101-NH2 (0.2 mmol),140 °C,9 h.
[b] Isolated yield of 3-aryl-2-oxazolidinones.
Scheme 3. Proposed reaction mechanism of phenylamine with propylene carbonate to 3-aryl-2-
oxazolidinones catalyzed by IL(OAc-)-MIL-101-NH2
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Conclusions
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8
In this study, we developed a new shape-selective catalyst based on the PSM strategy to
immobilize ionic liquid into metal-organic framework MIL-101-NH2. The catalytically active
groups BmimOAc are grafted onto the amino groups of MIL-101-NH2 via acylamino groups and
confined inside MIL-101-NH2 nanocavities. The resulting IL(OAc-)-MIL-101-NH2 catalyst
showed superior catalytic performance as a catalyst in the formation of 3-aryl-2-oxazolidinones
with excellent yield. It should be pointed out that the confined microenvironment of IL(OAc-)-
MIL-101-NH2 catalyst provides shape-selective catalytic properties for the differentiation of
substrates. Additionally, extensive substrate range, easy recovery, and recyclability of the
catalyst for at least 6 times without a significant decrease in activity offer an easy, high-
efficiency， continuable catalytic system to synthesize 3-aryl-2-oxazolidinones. This design
9
10
11
12
13
14
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concept would bridge the gap between homogeneous and heterogeneous catalysis by an
amalgamation of ILs organocatalyst and MOFs.
Corresponding Author
M. Ji*a
a
School of Chemistry, Faculty of Chemical, Environmental and Biological Science and
Technology, Dalian University of Technology, Dalian 116023, China. E-mail:
jimin@dlut.edu.cn.
Funding Sources
Support of this work by the National Natural Science Foundation of China (21573016) is
gratefully acknowledged.
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