Magnetic MIL-101-SO3H: A highly efficient bifunctional nanocatalyst for the synthesis of 1,3,5-triarylbenzenes and 2,4,6-triaryl pyridines

Article abstract of DOI:10.1039/c6ra24574a

A magnetic MIL-101-SO₃H was synthesized and successfully used as a highly active nanocatalyst for the synthesis of 1,3,5-triarylbenzenes and 2,4,6-triaryl pyridines. The prepared nanocatalyst was characterized by Fourier transform infrared spec

Full text of DOI:10.1039/c6ra24574a

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Magnetic MIL-101-SO3H: A highly efficient bifunctional nanocatalyst for the
synthesis of 1,3,5-triarylbenzenes and 2,4,6-triaryl pyridines
Mahmoud Borjian Boroujeni, Alireza Hashemzade, MohammadꢀTayeb Faroughi, Ahmad
Shaabani,* Mostafa Mohammadpour Amini*
Faculty of Chemistry, Shahid Beheshti University, G. C., P. O. Box 19396-4716, Tehran, Iran
*
Email addresses: a-shaabani@sbu.ac.ir, m-pouramini@sbu.ac.ir
Abstract
A magnetic MILꢀ101ꢀSO3H was synthesized and successfully used as a highly active nanoctalyst
for the synthesis of 1,3,5ꢀtriarylbenzenes and 2,4,6ꢀtriaryl pyridines. The prepared nanocatalyst
was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy,
energyꢀdispersive Xꢀray and Xꢀray powder diffraction. It is found that the catalyst can be easily
separated from the reaction mixture by an external magnetic field and recycled for several times
without a significant loss of activity.
Keywords
:
MILꢀ101, nanocatalyst, magnetic separation, 1,3,5ꢀtriarylbenzenes, 2,4,6ꢀtriaryl pyridines, metalꢀ
organic framework
1. Introduction
Metalꢀorganic frameworks (MOFs) are an important new class of porous materials that widely
used in separation, sensors, gas storage and catalysis due to their unique combination properties,
such as adjustable pore size, crystalline open structures, high density of active sites and
functionality.1ꢀ3 MOFs with their high surface area can be used as a heterogeneous catalyst or
support for organic transformations such as CꢀH bond activation, C–C bond formation, aerobic
oxidation, and multiꢀcomponent reactions (MCRs).4ꢀ9

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Among the various metal organic frameworks that have been investigated, MILꢀ101 has been
widely used due to its excellent stability under catalytic conditions, high metal content, and high
surface area.10,11 MILꢀ101 by its 3D pore structure is used as a reusable solid catalyst for
autoxidation of benzylic hydrocarbons and aerobic oxidative desulfurization of
dibenzothiophene.12, 13 As well as, MILꢀ101 is widely used as a support for metal phthalocyanine
complexes,14 polyoxometalates15 and nanoparticles.16ꢀ18 It is important to note that the most
important strategy to improve properties of MOFs for catalytic applications is functionalizing of
MOFs in monofunctional and multifunctional active sites.19, 20 For instance, sulfonation of MILꢀ
101 has been developed and has been used for oneꢀpot deacetalizationꢀnitroaldol reaction and the
ring opening of epoxides with alcohols.21ꢀ23 Bifunctional Au@MILꢀ53(NH2) and MILꢀ101ꢀCrꢀ
SO3HꢀAl(III) are used for aerobic oxidation/Knoevenagel condensation and benzylation reaction
of aromatic hydrocarbons, respectively.24,25 Recently, the synthesis of magnetic framework
composites (MFCs) has attracted a considerable attention in catalyst because of their low
toxicity, high catalytic activity, and easy separation of the catalyst after the end of reactions.
Immobilization of magnetic nanoparticles on MOFs such as ZIfꢀ8 and MILꢀ101 has produced
highly efficient adsorbent for anionic dyes, removing textile dyes, and efficient catalyst for
oxidation of alcohols.26ꢀ29 To the best of our knowledge, there is no report on utilization of
magnetic MILꢀ101ꢀSO3H for an organic transformation.
1,3,5ꢀTriarylbenzenes are an important polycyclic aromatic compounds with potential
applications in fields of conducting polymers, organic light emitting diodes, synthetic
dendrimers, special ligands and resistance materials.30 Consequently, numerous methods for
synthesis of these compounds have been developed in recent years. Paraꢀtoluene sulfonic acid,30
Bi(OTf)3,31 TiCl4,32 and H6P2W18O62/nanoclinoptilolite33 are used as catalysts for synthesis of

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triarylbenzenes. Despite the efficiency of these methods, there are some limitations such as
tedious workup, noneꢀrecyclability of the catalyst and long reaction times.
2,4,6ꢀTrisubstituted pyridines are an important materials in supramolecular chemistry due
to their pꢀstacking ability and excellent thermal stability that were used in highꢀperformance
Flrpic based organic lightꢀemitting device (OLED).34 Consequently, the synthesis of these
materials remains interesting topic in modern synthetic chemistry.35 In recent years, various
methods have been developed for their synthesis, including classical heating condition,
microwave irradiation, and sonication in the presence of bismuth triflate, copper triflate, and
mesoporous nanocrystalline MgAl2O4 catalysts.36ꢀ39 Nevertheless, the development of new
heterogeneous catalyst for the synthesis of 2,4,6ꢀtrisubstituted pyridines is in high demand.
In continuation of our ongoing research in the sustainable benign pathway for organic
transformations and nanocatalysis,40ꢀ43 we have introduced a novel bifunctional nanocatalyst and
investigated its catalytic activity for the synthesis of 1,3,5ꢀtriarylbenzenes and 2,4,6ꢀtrisubstituted
pyridines.
2. Experimental
2.1. Materials and Methods
The FTꢀIR spectra were recorded on a Bomem MBꢀSeries FTꢀIR spectrometer. The Xꢀray
powder diffraction (XRD) pattern was recorded on a STOE diffractometer with CuꢀKα radiation
(λ=1.5418 Å). The scanning electron microscopy (SEM) and the energy dispersive Xꢀray
spectroscopy (EDS) analyses were performed using a Philips XLꢀ30 instrument. All samples for
1
morphological studies were sputtered with gold before observation. The H NMR spectra were
recorded on a BRUKER DRXꢀ300 AVANCE spectrometer using CDCl3 and DMSOꢀd6 as
solvents and tetramethylsilane (TMS) as internal standard. The melting points of the products

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were measured by an electrothermal 9100 apparatus. The concentrations of iron were estimated
using an inductively coupled plasma optical emission spectrometer (ICPꢀOES) Varian Vista
PRO Radial. The CHN analysis was performed using a PerkinꢀElmer 2400 CHN analyzer.
2.2. General procedure for the synthesis of the MIL-101
The MILꢀ101 was prepared by hydrothermal reaction according to the previous report.44 Briefly,
Cr(NO3)3.9H2O (2.00 g, 5.00 mmol), terephthalic acid (0.82 g, 5.00 mmol) and deionized water
(24 mL) were loaded in a hydrothermal chamber and heated at 220 °C for 18 h. The resulted pale
green solid was collected and washed several times with deionized water, DMF and hot ethanol
and then soaked in ethanol 95% for 24 h. Finally, the powder was dried overnight at 150 °C.
2.3. General procedure for the synthesis of magnetic MIL-101
The synthesis of magnetic MILꢀ101 was carried out according to the literature procedure.28
Briefly, 2.00 mmol FeCl3.6H2O and 1.00 mmol FeCl2.4H2O were added to 100 mL an aqueous
suspension containing 0.50 g of MILꢀ101. The suspension was sonicated for 10 min and then
vigorously was stirred and was degassed with nitrogen for 2 h, and this followed by addition of
15 mL NH4OH solution to form black suspension. The suspension was separated by the magnet
decantation, washed with distilled water, ethanol and, finally was dried under vacuum at the
room temperature. ICPꢀAES analysis showed 17 wt.% Fe is loaded in magnetic MILꢀ101.
2.4.General procedure for the synthesis of magnetic MIL-101-SO3H
The activated MILꢀ101 (2.00 g) was stirred in 30 mL CHCl3 at 25 °C for 15 min, ClSO3H (0.60
g, 5.10 mmol) in 15 mL CHCl3 was added dropwise, and then the mixture was stirred for 2 h at

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room temperature. The catalyst was separated by an external magnet, was washed three times
with CHCl3, and was dried to give magnetic MILꢀ101ꢀSO3H.
2.5.General procedure for the synthesis of 1,3,5-triarylbenzenes
The magnetic MILꢀ101ꢀSO3H (30 mg), acetophenone (0.36 g, 3.00 mmol), and toluene (5 mL)
were added to a 25 mL round bottom flask and the reaction mixture was stirred for 3 h at 100 °C.
Upon completion of the reaction, the reaction mixture was cooled to the room temperature and
the catalyst was separated by an external magnet and crude product was obtained by evaporation
of solvent. The solid product was purified through recrystallization in mixture of EtOH and H2O
(3:1, v/v).
2.6.General procedure for the synthesis of 2,4,6-triaryl pyridines
A mixture of acetophenones (2.00 mmol), aromatic aldehydes (1.00 mmol), ammonium acetate
(2.00 mmol) and the magnetic MILꢀ101ꢀSO3H (30 mg) were added to a 25 mL round bottom
flask and the reaction mixture was stirred for 2 h at 110 °C. Upon completion the reaction, the
reaction mixture was cooled to the room temperature, eluted with hot ethanol and the catalyst
was separated by an external magnet. The product was obtained by recrystallization of ethanol
solution.
Results and discussion
The magnetic MILꢀ101ꢀSO3H nanocatalyst was prepared according to the following twoꢀstep
procedure: i) Magnetic MILꢀ101 was synthesized according to the reference procedure28 and ii)
The magnetic MILꢀ101 was sulfonated by simple treatment with chlorosulfonic acid to give the
bifunctional catalyst. Powder XRD patterns of the MILꢀ101, magnetic MILꢀ101 and magnetic

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MILꢀ101ꢀSO3H are shown in Figure 1. The diffraction peaks of the MILꢀ101 and Fe3O4
nanoparticles are observed in the XRD pattern of the magnetic MILꢀ101 which confirms the
formation of Fe3O4 nanoparticles in the nanocomposite. The relative intensities of the diffraction
peaks are decreased in the magnetic MILꢀ101 that confirms encapsulation of the Fe3O4
nanoparticles within the pores of MILꢀ101 was occurred.28 The intensity of the Fe3O4
nanoparticles in the XRD pattern of the magnetic MILꢀ101 was relatively low due to the low
content of the Fe3O4 nanoparticles in the nanocomposite.
Figure 1. The XRD patterns of the MILꢀ101 (A), magnetic MILꢀ101 (B) and the magnetic MILꢀ101ꢀSO3H
nanocatalyst (C).
The FTꢀIR spectra of MILꢀ101, magnetic MILꢀ101, and magnetic MILꢀ101ꢀSO3H nanocatalyst
are shown in Figure 2. Characteristic vibration bands are observed around 1390 and 1510 cmꢀ1
for the (OꢀCꢀO) groups which confirmed the presence of the dicarboxylate. The broad band
around 3340 cmꢀ1 is attributed to the water molecules within the pores of the MILꢀ101. The FTꢀ
IR spectrum of the magnetic MILꢀ101 shows an absorption band at 570 cmꢀ1 ascribes the FeꢀO

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group vibration. The FTꢀIR spectrum of the magnetic MILꢀ101ꢀSO3H nanocatalyst exhibits
broad bands around 1000ꢀ1250 cmꢀ1 which can be attributed to the O=S=O symmetric and
asymmetric starching vibration modes that confirmed the MILꢀ101 was functionalized.
According to the elemental analysis data, sulfur content of catalyst was 1.3 mmol/g. The
number of H+ site of the catalyst determined by acidꢀbase titration was 1.2 meq/g.
Figure 2. FTꢀIR spectra of the MILꢀ101(A), the magnetic MILꢀ101 (B), and the magnetic MILꢀ101ꢀSO3H (C)
The SEM analysis was used to study the morphology and the structure of the magnetic MILꢀ101ꢀ
SO3H nanocatalyst. The SEM images show an excellent dispersity of the Fe3O4 nanoparticles
that incorporated into the MILꢀ101 pores (Figure 3). Moreover, the energy dispersive
spectroscopy (EDS) analysis confirmed the existence of C, O, Cr, S, and Fe in the magnetic
MILꢀ101ꢀSO3H nanocatalyst (Figure 4).

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Figure 3. The SEM images of magnetic MILꢀ101 (A) and magnetic MILꢀ101ꢀSO3H nanocatalyst (B, C)
Figure 4. The EDS analysis of magnetic MILꢀ101ꢀSO3H nanocatalyst

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The N2 adsorptionꢀdesorption isotherms for MILꢀ101 and magnetic MILꢀ101 are shown
in the ESI, and Table 1 lists the specific surface area and total pore volume of MILꢀ101,
magnetic MILꢀ101 and magnetic MILꢀ101ꢀSO3H. As expected, specific surface area and total
pore volume were decreased after functionalization, using magnetic nanoparticles and
incorporation of SO3H groups into the structure of MILꢀ101. The decrease of specific surface
area and total pore volume indicates that magnetic nanoparticles were unambiguously
encapsulated within the pores of MILꢀ101.
Table 1. Specific surface area and total pore volume of MILꢀ101, magnetic MILꢀ101 and magnetic MILꢀ101ꢀSO3H
Catalyst
Surface area (m2gꢀ1) Total pore volume (mL gꢀ1)
MILꢀ101
1835
0.87
0.33
0.21
Magnetic MILꢀ101
647
Magnetic MILꢀ101ꢀSO3H 453
The presence of Lewis acid CrΙΙΙ sites and also SO3H groups as Brønsted acid sites,
encourage us to evaluate the catalytic properties of magnetic MILꢀ101ꢀSO3H nanocatalyst for the
synthesis of 1,3,5ꢀtriphenyllbenzene from acetophenone in toluene (Table 2). The reaction in the
absence of the magnetic MILꢀ101ꢀSO3H nanocatalyst did not result in the desired product (Table
2, Entry 1). When the reaction was carried out in the presence of pristine MILꢀ101 (5%), the
product was obtained in 30% within 3 h (Table 2, Entry 2). The yield of product was increased to
35% in the presence of the magnetic MILꢀ101 (Table 2, Entry 3). These observations indicate
that CrΙΙΙ sites in MILꢀ101 and the active sites of magnetic nanoparticle as a Lewis acid have a
synergic effect for catalyzing the reaction. As the amount of the magnetic MILꢀ101ꢀSO3H was
increased, the reaction went to completion at 100 °C (Table 2, Entries 4ꢀ8). This indicates the
Brønsted acid sites increase the catalytic activity of magnetic MILꢀ101 in the reaction. In order
to determine the best solvent, various solvents such as H2O, DMF, CH3CN, toluene, and

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dichloromethane were tested. The results showed that the yield of the reaction in toluene was
higher than either other solvents or solventꢀfree conditions (Table 2, Entries 9ꢀ13). After
screening different temperatures, 100 °C was obtained as the best temperature for the reaction.
The optimized conditions for the synthesis of the 1,3,5ꢀtriphenyllbenzene were 30 mg of the
magnetic MILꢀ101ꢀSO3H in toluene as a solvent at 100 °C.
a
Table 2. Screening the reaction conditions for the synthesis of 1,3,5ꢀtriphenyllbenzene
Entry
1
Catalyst (mg)
None
Solvent
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
neat
Temperature (°C)
100
Yield b ( %)
0
2
3
MILꢀ101 (30)
100
100
100
100
100
100
100
100
100
100
82
30
35
45
60
70
80
90
80
0
Magnetic MILꢀ101 (30)
4
Magnetic MILꢀ101ꢀSO3H (6)
Magnetic MILꢀ101ꢀSO3H (12)
Magnetic MILꢀ101ꢀSO3H (18)
Magnetic MILꢀ101ꢀSO3H (24)
Magnetic MIL-101-SO3H (30)
Magnetic MILꢀ101ꢀSO3H (30)
Magnetic MILꢀ101ꢀSO3H (30)
Magnetic MILꢀ101ꢀSO3H (30)
Magnetic MILꢀ101ꢀSO3H (30)
Magnetic MILꢀ101ꢀSO3H (30)
Magnetic MILꢀ101ꢀSO3H (30)
Magnetic MILꢀ101ꢀSO3H (30)
5
6
7
8
9
10
11
12
13
14
15
H2O
DMF
25
15
40
90
70
CH3CN
39
dichloromethane
toluene
110
90
toluene
a Reaction conditions: acetophenone (3.00 mmol), catalyst, solvent (5 mL), 3h
b Isolated yield

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With the optimized conditions established, the synthesis of different 1,3,5ꢀtriarylbenzene
derivatives was examined in the presence of magnetic MILꢀ101ꢀSO3H in toluene. As shown in
Table 3, acetophenone with a wide array of functional groups on the benzene ring such as bromo,
chloro, fluoro, and methyl were employed to synthesis of 1,3,5ꢀtriarylbenzenes.
Table 3. Synthesis of 1,3,5ꢀtriarylbenzenes using magnetic MILꢀ101ꢀSO3H nanocatalysta
Entry
Ar
Time (h)
Yield (%)
Product
2a
Mp (°C)/ Reference
170ꢀ172 [30]
179ꢀ181 [30]
262ꢀ264 [30]
248ꢀ250 [30]
238ꢀ240 [30]
140ꢀ142 [30]
1
2
3
4
5
6
phenyl
3
3.5
4
90
85
80
80
80
75
pꢀCH3C6H4
pꢀBrC6H4
pꢀClC6H4
pꢀFC6H4
pꢀMeOC6H4
2b
2c
4
2d
4
2e
4
2f
a Reaction conditions: Phenyl methyl ketone (3.00 mmol), catalyst (30 mg), toluene (5 mL) at 100 °C
b Isolated yield
Based on the previous report,33 a plausible mechanism was proposed in Scheme 1. At
first, acetophenone was protonated in the presence of magnetic MILꢀ101ꢀSO3H nanocatalyst and
enol form of acetophenone was generated. A reaction between protonated acetophenone (A) and
(B) was followed by dehydration of α,βꢀunsaturated carbonyl compound (C), and then (C)
activated in the presence of catalyst and subsequently was reacted with another protonated

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acetophenone molecule to produce compound (D). After dehydrogenation of D and prototropic
shift, compound (E) generated the electrocyclization and dehydrogenation of it produced 1,3,5ꢀ
triphenylbenzene.
Scheme 1. Plausible reaction mechanism for synthesis of 1,3,5ꢀtriphenylbenzene.

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Encouraged by the above discovery, we further investigated the possibility of using magnetic
MILꢀ101ꢀSO3H nanocatalyst for the synthesis of 2,4,6ꢀtriaryl pyridines via the reaction of
acetophenone, benzaldehyde and ammonium acetate under solventꢀfree conditions. After
screening different conditions, the best reaction conditions were 30 mg nanocatalyst under
solventꢀfree conditions at 110 °C (Table 4).
a
Table 4. Screening the reaction conditions for the synthesis of 2,4,6ꢀtriaryl pyridine
Entry
Catalyst (mg)
ꢀ
Temperature Yield b %
1
2
3
4
5
6
7
8
120
110
110
110
110
110
110
110
15
25
30
55
65
75
85
95
MILꢀ101 (30)
Magnetic MILꢀ101 (30)
Magnetic MILꢀ101 SO3H nanocatalyst (6)
Magnetic MILꢀ101 SO3H nanocatalyst (12)
Magnetic MILꢀ101 SO3H nanocatalyst (18)
Magnetic MILꢀ101 SO3H nanocatalyst (24)
Magnetic MIL-101 SO3H nanocatalyst (30)
a Reaction conditions: acetophenone (2.1 mmol), benzahdehyde (1.00 mmol), ammonium acetate (2.00 mmol), catalyst, 110 °C
b Isolated yield

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With the optimized reaction conditions in hand, we tested the scope of the reaction for the
synthesis of different 2,4,6ꢀtriaryl pyridine derivatives using acetophenones and benzaldehyds
with a wide array of functional groups on the aromatic ring. All products were obtained in good
to excellent yields (Table 5).
Table 5. Synthesis of 2,4,6ꢀtriaryl pyridines using magnetic MILꢀ101ꢀSO3H nanocatalysta
Entry
R1
H
R2
H
Time (h)
Yield (%)
Product
4a
Mp (°C)/ Reference
135ꢀ137 [37]
119ꢀ121[37]
125ꢀ127[37]
154ꢀ156 [42]
175ꢀ177 [42]
186ꢀ188 [42]
190ꢀ192[42]
1
2
3
4
5
6
7
2
2.5
2.5
3
90
85
85
80
80
85
80
H
4ꢀCH3
4ꢀCl
H
4b
H
ac
4ꢀCH3
4ꢀCH3
4ꢀCl
4ꢀCl
4d
4ꢀCH3
H
3
4e
3
4f
4ꢀOCH3
5
4g
a Reaction conditions: Phenyl methyl ketone (3.00 mmol), catalyst (30 mg,), toluene (5 mL) 110 °C
b Isolated yield
Based on the previous reports,45,46 a proposed reaction pathway for the synthesis of 2,4,6ꢀ
triaryl pyridine is shown in Scheme 2. Initially, acetophenone (A) in the presence of catalyst is

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converted to its enol form and consequently, gives nucleophilic addition to the benzaldehyde (B)
to generate Aldol condensation product (C). After that, enamine (D) forms from the reaction of
acetophenone and ammonia source, which attack to the α,β unsaturated carbonyl compound (C)
in a Micheal addition to produce intermediate (E). Then cyclization lead to dihydropyridine (F)
and finally aerobic oxidation generated 2,4,6ꢀtriphenylpyridine. As illustrated in Scheme 2,
magnetic MILꢀ101ꢀSO3H nanocatalyst plays an important role to accelerate this transformation.
Scheme 2. Plausible reaction mechanism for synthesis of 2,4,6ꢀtriphenylpyridine.

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The recyclability of the magnetic MILꢀ101ꢀSO3H nanocatalyst was surveyed for the
synthesis of the 1,3,5ꢀtriarylbenzenes and 2,4,6ꢀtriaryl pyridines under the optimized conditions.
After the reaction time, the nanocatalyst was separated by an external magnet, washed, dried and
reused in the next run. It was observed that in the next three consecutive uses of the magnetic
MILꢀ101ꢀSO3H nanocatalyst, the catalytic activity did not significantly decrease (Figure 5).
100
80
60
40
20
0
1
2
3
Run
Figure 5. Recycle of the magnetic MILꢀ101ꢀSO3H nanocatalyst for the synthesis of the 1,3,5ꢀtriarylbenzenes
3. Conclusion
The magnetic MILꢀ101ꢀSO3H nanocatalyst was prepared by a uniform distribution of Fe3O4
nanoparticles within the pores of MILꢀ101. The structure of the catalyst was confirmed by the
XRD, FTꢀIR, EDS and the SEM. The new nanocatalyst successfully was used for the synthesis
of the 1,3,5ꢀtriarylbenzenes and 2,4,6ꢀtriaryl pyridines with fairly good yields. The magnetic
MILꢀ101ꢀSO3H nanocatalyst showed advantages such as recyclability, magnetic separablitiy,
good chemical stability, low solubility in organic solvents, and high surface area. Further work to
prepare new catalysts based on MOFs for organic transformation is currently investigation in our
laboratory.

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Acknowledgement
We gratefully acknowledge financial support from the Catalyst Center of Excellence (CCE) of
Shahid Beheshti University and the Iran National Elites Foundation (INEF).
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Page 19 of 19
RSC Advances
View Article Online
DOI: 10.1039/C6RA24574A
Magnetic MIL-101-SO3H: A highly efficient bifunctional nanocatalyst for the
synthesis of 1,3,5-triarylbenzenes and 2,4,6-triaryl pyridines
Mahmoud Borjian Boroujeni, Alireza Hashemzade, Mohammad-Tayeb Faroughi, Ahmad
Shaabani,* Mostafa Mohammadpour Amini*
O
Magnetic MIL-101-SO3H
O
O
H
N
NH4OAc