Application of silica-bonded imidazolium-sulfonic acid chloride (SBISAC) as a heterogeneous nanocatalyst for the domino condensation of arylaldehydes with 2-naphthol and dimedone

Article abstract of DOI:10.1016/j.molliq.2015.07.049

Abstract In this work, a novel nanostructured silica-bonded ionic liquid namely silica-bonded imidazolium-sulfonic acid chloride (SBISAC) has been prepared, and characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), the

Full text of DOI:10.1016/j.molliq.2015.07.049

Journal of Molecular Liquids 211 (2015) 373–380
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Journal of Molecular Liquids
journal homepage: www.elsevier.com/locate/molliq
Application of silica-bonded imidazolium-sulfonic acid chloride (SBISAC)
as a heterogeneous nanocatalyst for the domino condensation of
arylaldehydes with 2-naphthol and dimedone
b,
b
Ahmad Reza Moosavi-Zare a, , Mohammad Ali Zolfigol , Mahmoud Zarei ,
⁎
⁎
Abdolkarim Zare c, Vahid Khakyzadeh b
a
Department of Chemistry, Sayyed Jamaleddin Asadabadi University, Asadabad 6541835583, Iran
b
Faculty of Chemistry, Bu-Ali Sina University, Hamedan 6517838683, Iran
Department of Chemistry, Payame Noor University, PO Box 19395–3697 Tehran, Iran
c
a r t i c l e i n f o
a b s t r a c t
Article history:
In this work, a novel nanostructured silica-bonded ionic liquid namely silica-bonded imidazolium-sulfonic acid
chloride (SBISAC) has been prepared, and characterized by Fourier transform infrared spectroscopy (FT-IR),
X-ray diffraction (XRD), thermal gravimetric analysis (TGA), differential thermal gravimetric (DTG), trans-
mission electron microscopy (TEM) and energy dispersive X-ray analysis (EDX) spectra. Then, SBISAC was uti-
lized as an efficient and heterogeneous nanocatalyst for the synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a]-
xanthen-11-ones via the one-pot three-component condensation reaction of arylaldehydes with 2-naphthol
and dimedone (5,5-dimethylcyclohexane-1,3-dione) under solvent-free conditions.
Received 11 February 2015
Received in revised form 17 July 2015
Accepted 20 July 2015
Available online xxxx
Keywords:
Silica-bonded imidazolium-sulfonic acid
chloride (SBISAC)
© 2015 Elsevier B.V. All rights reserved.
Nanocatalyst
Multi-component reaction
Solvent-free
12-aryl-8,9,10,12-tetrahydrobenzo[a]-
xanthen-11-one
1. Introduction
promote this reaction, including ceric ammonium nitrate [11], proline
triflate [12], NaHSO4·SiO2 [13], strontium triflate [14], Zr(HSO4)4 [15],
Multi-component reactions (MCRs) play an important role in combi-
natorial chemistry because of the ability to prepare target compounds
with greater efficiency and atomic economy by generating structural
complexity from three or more reactants. Moreover, MCRs offer the
advantages of simplicity and synthetic efficiency over conventional
chemical reactions [1–3].
Xanthenes and benzoxanthenes are of importance as they have vari-
ous biological activities. For example, these compounds have been fre-
quently used as antibacterial [4], anti-inflammatory [5], and antiviral [6]
agents, and as antagonists for inhibiting the action of zoxalamine [7].
Moreover, xanthene derivatives could be applied as dyes [8], and as pH
sensitive fluorescent materials for visualization of biomolecular assem-
blies [9], and in laser technology [10]. The one-pot multi-component
condensation reaction between arylaldehydes, 2-naphthol, and
dimedone (5,5-dimethylcyclohexane-1,3-dione) has been used as the
best procedure for synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a]-
xanthen-11-one derivatives. Several catalysts have been used to
dodecatungstophosphoric acid [16], iodine [17], InCl3/P2O5 [18],
p-toluenesulfonic acid/ionic liquid [19], RuCl4 [20], Brønsted acidic
ionic liquid [21], [Pyridine–SO3H]Cl [22], and tityl chloride [23]. Al-
though several methods and catalysts for the preparation of 12-aryl-
8,9,10,12-tetrahydrobenzo[a]-xanthen-11-ones are known, consider-
ing the different application of these compounds, search for finding
efficient catalysts and methods for their synthesis is still of significance.
We have recently introduced a new category of Brønsted acidic ionic
liquids (ILs), namely sulfonic acid-functionalized imidazolium salts
(SAFIS) [24–35], and applied them as catalysts or reagent for synthesis of
bis(indolyl)methans [24], N-sulfonyl imines [25], nitro aromatic com-
pounds [26,27], 1-amidoalkyl-2-naphthols [28], benzimidazoles [29], xan-
thenes [30], 1-carbamatoalkyl-2-naphthols [31], 4,4′-(arylmethylene)-
bis(3-methyl-1-phenyl-1H-pyrazol-5-ol)s [32], t-butyl aryl carbamates
[33], 1,2,4,5-tetrasubstituted imidazoles [34], and β-acetamido ketones
[35].
In continuation of our previous projects on the preparation and appli-
cation of SAFIS in organic synthesis, we have prepared a heterogeneous
member of these salts namely silica-bonded imidazolium-sulfonic acid
chloride (SBISAC) (Fig. 1). This novel silica-supported ionic liquid was
characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray
⁎
Corresponding authors.
E-mail addresses: moosavizare@yahoo.com (A.R. Moosavi-Zare),
mzolfigol@yahoo.com (M.A. Zolfigol).
http://dx.doi.org/10.1016/j.molliq.2015.07.049
0167-7322/© 2015 Elsevier B.V. All rights reserved.

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A.R. Moosavi-Zare et al. / Journal of Molecular Liquids 211 (2015) 373–380
TG/DTG analysis was achieved at range of 25 to 600 °C (temperature
increase rate of 10 °C · min−1 under nitrogen atmosphere). Optical ro-
tations were measured in spectral grade solvents using a Perkin–Elmer
341 polarimeter.
3
2.2. General procedure for the preparation of silica-bonded imidazolium-
sulfonic acid chloride (SBISAC)
A mixture of imidazole (0.34 g, 5 mmol), (3-chloropropyl)
triethoxysilane (1.125 g, 5 mmol) and toluene (15 mL) in a 50 mL
round-bottomed flask connected to a reflux condenser, was stirred for
18 h under reflux conditions. In the next step, the obtained white pre-
cipitate was separated by filtration, and reacted with silica (0.30 g,
5 mmol) in refluxed ethyl acetate (15 mL) for 12 h to give a solid after
removing the ethyl acetate. Then, a solution of chlorosulfuric acid
(5 mmol) in chloroform (10 mL) was added dropwise to the resulted
solid at 0 °C (ice-water bath), and stirred for 2 h. The chloroform was re-
moved, and the residue was triturated with chloroform (3 × 10 mL),
and dried under powerful vacuum at 90 °C to give SBISAC as a white
precipitate in 95% yield (Scheme 2).
Fig. 1. The structure of silica-bonded imidazolium-sulfonic acid chloride (SBISAC).
diffraction (XRD), thermal gravimetric analysis (TGA), differential ther-
mal gravimetric (DTG), transmission electron microscopy (TEM) and en-
ergy dispersive X-ray analysis (EDX) spectra, and applied as an efficient
and heterogeneous nanocatalyst for the synthesis of 12-aryl-8,9,10,12-
tetrahydrobenzo[a]-xanthen-11-ones by the one-pot three-component
condensation of aromatic aldehydes with 2-naphthol and dimedone in
the absence of solvent (Scheme 1).
2. Experimental
2.3. General procedure for the synthesis of 12-aryl-8,9,10,12-
2.1. Materials
tetrahydrobenzo[a]-xanthen-11-ones 1a-n
All chemicals were purchased from Merck or Fluka Chemical Com-
panies. The known products were identified by comparison of their
melting points and spectral data with those reported in the literature.
Progress of the reactions was monitored by TLC using silica gel SIL G/
UV 254 plates. The 1H NMR (500 or 300 MHz) and 13C NMR (125 or
75 MHz) were recorded on a Bruker Avance DPX FT-NMR spectrometer
(δ in ppm). Melting points were recorded on a Büchi B-545 apparatus in
open capillary tubes. Thermal gravimetry (TG) and differential thermal
gravimetric (DTG) were analyzed by a Perkin Elmer (Model: Pyris 1).
A mixture of 2-naphthol (0.144 g, 1 mmol), dimedone (0.140 g, 1
mmol), arylaldehyde (1 mmol) and SBISAC (0.005 g) in a 10 mL
round-bottomed flask connected to a reflux condenser, was stirred in
an oil-bath at 100 °C. After completion of the reaction, as monitored
by TLC, the reaction mixture was cooled to room temperature, and ex-
tracted by warm EtOAc (20 mL) to separate the catalyst (the product
is soluble in warm EtOAc; however, SBISAC isn't soluble in this solvent).
EtOAc was removed, and the crude product was recrystallized from
aqueous ethanol (90%) to afford the pure racemic product which
Scheme 1. The reaction of 2-naphthol with aldehydes and dimedone catalyzed by silica-bonded imidazolium-sulfonic acid chloride (SBISAC).
Scheme 2. The synthesis of silica-bonded imidazolium-sulfonic acid chloride (SBISAC).

A.R. Moosavi-Zare et al. / Journal of Molecular Liquids 211 (2015) 373–380
375
Fig. 2. The IR spectrum of SBISAC.
required no further purification. The recovered catalyst was washed
with EtOAc (2 × 20 mL), dried and reused for the next run. The catalyst
was reused for four times without any significant changes in the yield
and the reaction time.
The IR spectrum of the catalyst showed a broad peak at 2500–
3600 cm−1 related to O–H stretching of the SO3H group. Also, the two
peaks observed at 1046 cm−1 and 1106 cm−1 correspond to vibrational
modes of N–SO2 and O–SO2 bonds (Fig. 2).
X-ray diffraction analysis (XRD) pattern of SBISAC was studied in a
domain of 0–90° (Fig. 3). As shown in Fig. 3, the XRD pattern exhibited
diffraction lines of a high crystalline nature at about 2θ ≈ 9.6°, 12.1°,
19.5°, 20.2°, 22.8° and 81.7°.
3. Results and discussion
3.1. The preparation of SBISAC
Thermal gravimetric analysis (TGA) of SBISAC was also investigated.
The corresponding diagrams are depicted in Fig. 4. The thermo-
gravimetry (TG) and differential thermal gravimetric (DTG) of the cata-
lyst showed weight losses in one step (after 325 °C).
Energy-dispersive X-ray spectroscopy (EDX) of the catalyst (Fig. 5)
showed the presence of the expected elements in its structure, i.e. car-
bon, oxygen, nitrogen, sulfur, chlorine and silicon.
In another investigation, the scanning electron microscope (SEM)
micrographs of the catalyst showed that the particles have not
completely agglomerated. Moreover, particles of the catalyst were
observed in nanosize (Fig. 6).
According to the previous works on the synthesis of silica-bonded
imidazolium compounds [36–39], initially, imidazole was reacted with
(3-chloropropyl) trimethoxysilane under reflux conditions to afford I,
which transformed to II as s white precipitate by releasing of one mol-
ecule of HCl. In the next step, II was reacted with silica in refluxed
ethyl acetate to give III. Finally, by the reaction of III with chlorosulfuric,
silica-bonded imidazolium-sulfonic acid chloride (SBISAC) was synthe-
sized (Scheme 2).
3.2. Characterization of SBISAC
The nanostructure of silica-bonded imidazolium-sulfonic acid chlo-
ride was confirmed by TEM (Fig. 7). The TEM micrograph clearly proved
that the particles were in nanosize.
The structure of the silica-bonded imidazolium-sulfonic acid chlo-
ride was characterized by IR, XRD, TG, DTG, EDX, SEM, and TEM analysis.
Fig. 3. The XRD diagram of SBISAC.

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A.R. Moosavi-Zare et al. / Journal of Molecular Liquids 211 (2015) 373–380
Fig. 4. The TG/DTG diagrams of the catalyst.
Fig. 5. The energy-dispersive X-ray spectroscopy (EDX) of SBISAC.

A.R. Moosavi-Zare et al. / Journal of Molecular Liquids 211 (2015) 373–380
377
Table 1
Effect of the catalyst amount and temperature on the reaction between β-naphthol
(1 mmol) with dimedone (1 mmol) and 4-chlorobenzaldehyde (1 mmol).
Entry
Catalyst
Catalyst amount (g)
Temp.(°C)
Time (min)
Yielda (%)
1
2
3
4
5
SBISAC
SBISAC
SBISAC
SBISAC
SBISAC
0.002
0.005
0.01
0.005
0.005
100
100
100
110
70
28
12
12
12
65
81
94
94
94
–
a
Isolated yield.
Table 2
Effect of various solvents on the reaction of β-naphthol (1 mmol) with dimedone
(1 mmol) and 4-chlorobenzaldehyde (1 mmol), in the presence of SBISAC (5 mg).
Entrya
Solvent
Time (min)
Yieldb (%)
1
2
3
4
5
CHCl3
EtOAc
EtOH
CH2Cl2
H2O
30
30
30
30
30
40
33
40
30
45
a
All reactions were carried out under reflux condition.
Isolated yield.
b
Fig. 6. The SEM micrographs of SBISAC.
3.4. Using the optimal conditions for the reaction
3.3. Optimization the reaction condition
To assess the efficiency and the scope of SBISAC in the preparation
of tetrahydrobenzo[a]xanthene-11-ones, various aromatic alde-
hydes (including aldehydes possessing electron-releasing substituents,
electron-withdrawing substituents and halogens on their aromatic
ring) were reacted with β-naphthol and dimedone in the optimal reac-
tion conditions to produce the desired products in high yields and in
short reaction times. The results are displayed in Table 3.
In a proposed mechanism which is supported by the literature [30]
(Scheme 3), at first, aromatic aldehyde is activated by acidic group of
SBISAC to produce a. Then, β-naphthol attacks to the activated carbonyl
group of aldehyde to afford intermediate b. Then, by removing one mole-
cule of H2O from b, orthoquinone methide [(o-QM, c)] is prepared. SBISAC
again activates intermediate c to give d as a Michael acceptor. Afterward,
Michael addition of dimedone to intermediate d affords e. Intermediate e
converts to f after tautomerisation. At last, tetrahydrobenzo[a]xanthene-
11-one produces by removing one molecule of H2O from f.
After full characterization of SBISAC, its catalytic activity was examined
on the reaction of arylaldehydes with β-naphthol and dimedone to pro-
vide 12-aryl-8,9,10,12-tetrahydrobenzo[a]-xanthen-11-ones (Scheme 1).
For this purpose, as a model reaction, the condensation of β-naphthol
(1 mmol) with dimedone (1 mmol) and 4-chlorobenzaldehyde
(1 mmol) was tested using different amounts of SBISAC at range of
70–110 °C in the absence of solvent (Table 1). As it is shown in Table 1,
5 mg of the catalyst was sufficient to promote the reaction efficiently at
100 °C, and give the product in excellent yield and in short reaction time
(Table 1, entry 2).
To compare the efficiency of solution conditions versus the solvent-
free procedure, the reaction between β-naphthol (1 mmol), dimedone
(1 mmol) and 4-chlorobenzaldehyde (1 mmol) using SBISAC (5 mg)
was checked in some solvents (2 mL) under reflux conditions. The
results are summarized in Table 2. As this Table indicates, low yields
of the product were obtained in solution conditions even after elon-
gated reaction times.
In another investigation, recyclability of SBISAC was investigated.
For this purpose, the reaction of β-naphthol (1 mmol) with dimedone
Table 3
The solvent-free synthesis of tetrahydrobenzo[a]xanthene-11-ones using silica-bonded
imidazolium-sulfonic acid chloride (SBISAC).
Entry
R
Time (min)/yielda
(%)
M.p. °C
(Lit.)
1a
1b
1c
1d
1e
1f
1g
1h
1i
1j
1k
1l
1m
1n
C6H5
3-ClC6H4
4-ClC6H4
10/93
10/94
7/94
10/95
11/96
17/85
12/90
11/91
8/93
10/93
15/91
25/85
27/83
25/84
140–152 (151–153) [18]
174–176 (175–178) [23]
177–179 (180–182) [18]
221–224 (223–225) [23]
180–183 (181–182) [16]
169–171 (–) [19]
2,3-Cl2C6H3
2,4-Cl2C6H3
2-BrC6H4
3-BrC6H4
4-BrC6H4
3-NO2C6H4
4-NO2C6H4
3-OHC6H4
2-MeC6H4
3-MeC6H4
4-OMeC6H4
160–162 (–) [19]
186–187 (186–187) [17]
166–169 (168–170) [18]
176–179 (178–180) [18]
238–239 (240–241) [18]
166–168 (161–164) [23]
181–183 (178–180) [23]
202–204 (204–205) [18]
a
Fig. 7. The transmission electron micrographs (TEM) of SBISAC.
Isolated yield.

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A.R. Moosavi-Zare et al. / Journal of Molecular Liquids 211 (2015) 373–380
Cl
O
HN
Cl
S
N
O
S
O
O
R1
HN
O
H
N
H
O
Cl
O
S O
O
O
H
H
O
O
H
HN
N
H
O
O
H
- H2O
R1
H
R1
(a)
(b)
R1
H
R1
Cl
O
O
O
S O
O
HN
N
H
O
O
H
O
O
S
N
0-QM, (c)
(d)
NH
O
Cl
R1
R1
R1
O
H
O
O
O
OH
OH
OH
O
-H2O
tautomerisation
(e)
(f)
Scheme 3. The plausible mechanism for the condensation reaction of β-naphthol with aldehydes and dimedone catalyzed by the SBISAC.
(1 mmol) and 4-chlorobenzaldehyde (1 mmol), was performed in the
presence of SBISAC (5 mg) at 100 °C. After completion of the reaction,
as monitored by TLC, the reaction mixture was cooled to room temper-
ature, extracted with warm EtOAc to separate the catalyst (the product
is soluble in warm EtOAc; however, SBISAC isn't soluble in this solvent).
EtOAc was removed, and the recovered catalyst was washed with
EtOAc, dried and reused for the synthesis of 12-aryl-8,9,10,12-
tetrahydrobenzo[a]-xanthen-11-ones according to the mentioned pro-
cedure. The catalyst was reused for four times without any significant
changes in the yields and the reaction times (Fig. 8).
ones, we have tabulated the results of these catalysts to perform the re-
action of β-naphthol with dimedone and 4-chlorobenzaldehyde, in
Table 4. As Table 4 indicates, SBISAC has remarkably improved the syn-
thesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a]-xanthen-11-ones; the
reaction times were shorter, and the yields were higher when our cata-
lyst was utilized.
To recognize the scalability of our method, we examined some reac-
tions in larger scale (15 mmol of each reactants). The respective results
are summarized in Table 5. As shown in Table 5, the reactions were
To compare the efficiency of our catalyst with the reported catalysts
for the synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a]-xanthen-11-
Table 4
Comparison of the results of the synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a]-
xanthen-11-ones catalyzed by our new catalyst with those obtained by the recently
reported catalysts.a.
Reaction condition
Catalyst
loading
Time
(min)
Yieldb
(%)
Ref.
TrCl, solvent-free, 110 °C
7 mol%
10 mol%
10 mol%
25 mol%
0.1 g
10 mol%
2 mol%
5 mol%
30 mol%
20 mol%
0.005 g
45
10
30
40
30
120
35
60
30
40
7
90
88
87
89
90
85
86
92
80
76
94
[23]
[30]
[40]
[41]
[42]
[19]
[19]
[16]
[18]
[18]
[Dsim]Cl, solvent-free, 110 °C
Py(HSO4)2, solvent-free, 110 °C
[Et3N–SO3H]Cl, solvent-free, 120 °C
CA–SiO2, solvent-free, 60 °C
pTSA, [bmim]BF4, 80 °C
pTSA, solvent-free, 120 °C
PWA, solvent-free, 60 °C
InCl3, solvent-free, 120 °C
P2O5, solvent-free, 120 °C
SBISAC, solvent-free, 100 °C
c
–
a
The reactions were carried out by the condensation of β-naphthol with dimedone and
4-chlorobenzaldehyde.
b
Fig. 8. The condensation of β-naphthol (1 mmol) with dimedone (1 mmol) and 4-
chlorobenzaldehyde (1 mmol) in the presence of the recycled SBISAC.
Isolated yield.
Our work.
c

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379
[11] A. Kumar, S. Sharma, R.A. Maurya, J. Sarkar, Diversity oriented synthesis of
benzoxanthene and benzochromene libraries via one-pot, three-component reac-
tions and their anti-proliferative activity, J. Comb. Chem. 12 (2010) 20–24.
[12] J. Li, L. Lu, W. Su, A new strategy for the synthesis of benzoxanthenes catalyzed by
proline triflate in water, Tetrahedron Lett. 51 (2010) 2434–2437.
[13] B. Das, K. Laxminarayana, M. Krishnaiah, Y. Srinivas, An efficient and convenient protocol
for the synthesis of novel 12-aryl- or 12-alkyl-8,9,10,12-tetrahydrobenzo[a]xanthen-11-
one derivatives, Synlett (2007) 3107–3112.
Table 5
The scalability of the synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a]-xanthen-11-ones
by the reaction of 2-naphthol (15 mmol) with arylaldehydes (15 mmol) and dimedone
(15 mmol) using SBISAC (0.075 g) at 100 °C.
Entry
R
Time (min)/yielda (%)
1a
1c
1i
C6H5
25/89
7/92
15/90
35/82
4-ClC6H4
3-NO2C6H4
3-MeC6H4
[14] J. Li, W. Tang, L. Lu, W. Su, Strontium triflate catalyzed one-pot condensation of
β-naphthol, aldehydes and cyclic 1,3-dicarbonyl compounds, Tetrahedron Lett. 49
(2008) 7117–7120.
1m
[15] N. Foroughifar, A. Mobinikhaledi, H. Moghanian, A catalytic and green procedure for
synthesis of 12-Aryl- or 12-alkyl-8,9,10,12-tetrahydrobenzo[α]xanthen-11-one
derivatives under solvent-free conditions, Int. J. Green Nanotechnol. Phys. Chem. 1
(2009) 57–63.
[16] H.-J. Wang, X.-Q. Ren, Y.-Y. Zhang, Z.-H. Zhang, Synthesis 12-aryl or 12-alkyl-8,9,10,12-
tetrahydrobenzo[a]xanthen-11-one derivatives catalyzed by dodecatungstophosphoric
acid, J. Braz. Chem. Soc. 20 (2009) 1939–1943.
[17] R.-Z. Wang, L.-F. Zhang, Z.-S. Cui, Iodine-catalyzed synthesis of 12-aryl-8,9,10,12-
tetrahydro-benzo[a]xanthen-11-one derivatives via multicomponent reaction,
Synth. Commun. 39 (2009) 2101–2107.
[18] G.C. Nandi, S. Samai, R. Kumar, M.S. Singh, An efficient one-pot synthesis of
tetrahydrobenzo[a]xanthene-11-one and diazabenzo[a]anthracene-9,11-dione
derivatives under solvent free condition, Tetrahedron 65 (2009) 7129–7134.
[19] J.M. Khurana, D. Magoo, pTSA-catalyzed one-pot synthesis of 12-aryl-8,9,10,12-
tetrahydrobenzo[a] xanthen-11-ones in ionic liquid and neat conditions, Tetrahe-
dron Lett. 50 (2009) 4777–4780.
a
Isolated yield.
successfully performed at the larger scale without significant loss of the
yields.
The mentioned xanthene derivatives which produce in achiral
media were racemic. To confirm this subject, optical activity of the com-
pounds were measured by polarimeter. This study clearly confirmed the
racemization of the xanthene derivatives in our protocol.
4. Conclusions
In conclusion, we have synthesized a novel nanostructured silica-
supported ionic liquid namely silica-bonded imidazolium-sulfonic acid
chloride (SBISAC), and successfully used as catalyst for the one-pot
three-component condensation of arylaldehydes with 2-naphthol
and dimedone. The novel catalyst was fully characterized by several
techniques including Fourier transform infrared spectroscopy (FT-IR),
X-ray diffraction (XRD), thermal gravimetric analysis (TGA), differential
thermal gravimetric (DTG), transmission electron microscopy (TEM)
and energy dispersive X-ray analysis (EDX).
[20] K. Tabatabaeian, A. Khorshidi, M. Mamaghani, A. Dadashi, M.K. Jalali, One-pot syn-
thesis of tetrahydrobenzo[a]xanthen-11-one derivatives catalyzed by ruthenium
chloride hydrate as a homogeneous catalyst, Can. J. Chem. 89 (2011) 623–627.
[21] M. Zakeri, M.M. Heravi, M. Saeedi, N. Karimi, H.A. Oskooie, N. Tavakoli-Hoseini, One-
pot green procedure for synthesis of tetrahydrobenzo[a]xanthene-11-one catalyzed
by Brønsted ionic liquids under solvent-free conditions, Chin. J. Chem. 29 (2011)
1441–1445.
[22] A.R. Moosavi-Zare, M.A. Zolfigol, M. Zarei, A. Zare, V. Khakyzadeh, Preparation, char-
acterization and application of ionic liquid sulfonic acid functionalized pyridinium
chloride as an efficient catalyst for the solvent free synthesis of 12-aryl-8,9,10,12-
tetrahydrobenzo[a]-xanthen-11-ones, J. Mol. Liq. 186 (2013) 63–69.
[23] A. Khazaei, M.A. Zolfigol, A.R. Moosavi-Zare, A. Zare, M. Khojasteh, Z. Asgari, V.
Khakyzadeh, A. Khalafi-Nezhad, Organocatalyst trityl chloride efficiently promoted
the solvent-free synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a]-xanthen-11-
ones by in situ formation of carbocationic system in neutral media, Catal. Commun.
20 (2012) 54–57.
[24] M.A. Zolfigol, A. Khazaei, A.R. Moosavi-Zare, A. Zare, Ionic liquid 3-methyl-1-sulfonic
acid imidazolium chloride as a novel and highly efficient catalyst for the very rapid
synthesis of bis(indolyl)methanes under solvent-free conditions, Org. Prep. Proced.
Int. 42 (2010) 95–102.
[25] M.A. Zolfigol, A. Khazaei, A.R. Moosavi-Zare, A. Zare, 3-methyl-1-sulfonic acid
imidazolium chloride as a new, efficient and recyclable catalyst and solvent for
the preparation of n-sulfonyl imines at room temperature, J. Iran. Chem. Soc. 7
(2010) 646–651.
[26] A. Khazaei, M.A. Zolfigol, A.R. Moosavi-Zare, A. Zare, An efficient method for the ni-
tration of phenols with NaNO2 in the presence of 3-methyl-1-sulfonic acid
imidazolium chloride, Sci. Iran. Trans. C Chem. Chem. Eng. 17 (2010) 31–36.
[27] M.A. Zolfigol, A. Khazaei, A.R. Moosavi-Zare, A. Zare, H.G. Kruger, Z. Asgari, V.
Khakyzadeh, M. Kazem-Rostami, Design of ionic liquid 3-methyl-1-sulfonic acid
imidazolium nitrate as reagent for the nitration of aromatic compounds by in situ
generation of NO2 in acidic media, J. Org. Chem. 77 (2012) 3640–3645.
[28] M.A. Zolfigol, A. Khazaei, A.R. Moosavi-Zare, A. Zare, V. Khakyzadeh, Rapid synthesis
of 1-amidoalkyl-2-naphthols over sulfonic acid functionalized imidazolium salts,
Appl. Catal. A Gen. 400 (2011) 70–81.
[29] A. Khazaei, M.A. Zolfigol, A.R. Moosavi-Zare, A. Zare, E. Ghaemi, V. Khakyzadeh,
Z. Asgari, A. Hasaninejad, Sulfonic acid functionalized imidazolium salts/FeCl3
as novel and highly efficient catalytic systems for the synthesis of benzimid-
azoles at room temperature, Sci. Iran. Trans. C Chem. Chem. Eng. 18 (2011)
1365–1371.
Acknowledgments
The authors gratefully acknowledge the Bu-Ali Sina University
Research Council and Center of Excellence in Development of Environ-
mentally Friendly Methods for Chemical Synthesis (CEDEFMCS) and
the University of Sayyed Jamaleddin Asadabadi for providing support
to this work.
References
[1] J. Zhu, H. Bienayme (Eds.), Multicomponent Reactions, Wiley, Weinheim, 2005.
[2] E. Ruijter, R. Scheffelaar, R.V.A. Orru, Multicomponent reaction design in the quest
for molecular complexity and diversity, Angew. Chem. Int. Ed. 50 (2011)
6234–6246.
[3] (a) A. Khazaei, M.A. Zolfigol, A.R. Moosavi-Zare, F. Abi, A. Zare, H. Kaveh, V.
Khakyzadeh, M. Kazem-Rostami, A. Parhami, H. Torabi-Monfared, Discovery
of an in situ carbocationic system using trityl chloride as a homogeneous
organocatalyst for the solvent-free condensation of β-naphthol with aldehydes
and amides/thioamides/alkyl carbamates in neutral media, Tetrahedron 69
(2013) 212–218;
(b) A.R. Moosavi-Zare, M.A. Zolfigol, S. Farahmand, A. Zare, A.R. Pourali, R. Ayazi-
Nasrabadi, Synthesis of 2,4,6-triarylpyridines using ZrOCl2 under solvent-free
conditions, Synlett 25 (2014) 193–196.
[4] Hideo, T.; Teruomi, J., (Sankyo Co.) Jpn. Patent 56005480, 1981.
[5] J.P. Poupelin, G. Saint-Ruf, O. Foussard-Blanpin, G. Marcisse, G. Uchida-Ernouf, R. Lacroix,
Synthese et proprietes anti inflammatoires de derives du bis (hydroxy 2 naphtyl 1)
methane. I. Derives monosubstitues|[synthesis and antiinflammatory properties of bis
(2 hydroxy 1 naphthyl) methane derivatives], Eur. J. Med. Chem. 13 (1978) 67–71.
[6] R.W. Lambert, J.A. Martin, J.H. Merrett, K.E.B. Parkes, G.J. Thomas, PCT Int. Appl.
(1997) WO9706178.
[7] G.B.D. Rao, M.P. Kaushik, A.K. Halve, An efficient synthesis of naphtha[1,2-
e]oxazinone and 14-substituted-14H-dibenzo[a, j]xanthene derivatives promoted
by zinc oxide nanoparticle under thermal and solvent-free conditions, Tetrahedron
Lett. 53 (2012) 2741–2744.
[8] F. Shirini, N.G. Khaligh, Succinimide-N-sulfonic acid: an efficient catalyst for the syn-
thesis of xanthene derivatives under solvent-free conditions, Dyes Pigments 95
(2012) 789–794.
[9] C.G. Knight, T. Stephens, Xanthene-dye-labelled phosphatidylethanolamines as
probes of interfacial pH. Studies in phospholipid vesicles, Biochem. J. 258 (1989)
683–687.
[30] M.A. Zolfigol, V. Khakyzadeh, A.R. Moosavi-Zare, A. Zare, S.B. Azimi, Z. Asgari, A.
Hasaninejad, Preparation of various xanthene derivatives over sulfonic acid func-
tionalized imidazolium salts (SAFIS) as novel, highly efficient and reusable catalysts,
C. R. Chim. 15 (2012) 719–736.
[31] A. Zare, T. Yousofi, A.R. Moosavi-Zare, Ionic liquid 1,3-disulfonic acid imidazolium
hydrogen sulfate: a novel and highly efficient catalyst for the preparation of
1-carbamatoalkyl-2-naphthols and 1-amidoalkyl-2-naphthols, RSC Adv. 2 (2012)
7988–7991.
[32] A. Khazaei, M.A. Zolfigol, A.R. Moosavi-Zare, Z. Asgari, M. Shekouhy, A. Zare, A.
Hasaninejad, Preparation of 4,49-(arylmethylene)-bis(3-methyl-1-phenyl-1H-
pyrazol-5-ol)s over 1,3-disulfonic acid imidazolium tetrachloroaluminate as a
novel catalyst, RSC Adv. 2 (2012) 8010–8013.
[33] M.A. Zolfigol, V. Khakyzadeh, A.R. Moosavi-Zare, G. Chehardoli, F. Derakhshan-
Panah, A. Zare, O. Khaledian, Novel ionic liquid 1,3-disulfonic acid imidazolium hy-
drogen sulfate {[Dsim]HSO4} efficiently catalyzed N-boc protection of amines, Sci.
Iran. Trans. C Chem. Chem. Eng. 19 (2012) 1584–1590.
[34] M.A. Zolfigol, A. Khazaei, A.R. Moosavi-Zare, A. Zare, Z. Asgari, V. Khakyzadeh, A.
Hasaninejad, Design of ionic liquid 1,3-disulfonic acid imidazolium hydrogen sulfate
[10] P.V. Shinde, A.H. Kategaonkar, B.B. Shingate, M.S. Shingare, Surfactant catalyzed con-
venient and greener synthesis of tetrahydrobenzo[a]xanthene-11-ones at ambient
temperature, Beilstein J. Org. Chem. 7 (2011) 53–58.
as
a dual-catalyst for the one-pot multi-component synthesis of 1,2,4,5-
tetrasubstituted imidazoles, J. Ind. Eng. Chem. 19 (2013) 721–726.

380
A.R. Moosavi-Zare et al. / Journal of Molecular Liquids 211 (2015) 373–380
[35] A. Zare, T. Hekmat-Zadeh, S. Mirzaei-Monfared, M. Merajoddin, H. Torabi-Monfared,
M.A. Zolfigol, A.R. Moosavi-Zare, E. Rostami, M. Mokhlesi, F. Derakhshan-Panah, S.
Porbahi, S. Balandeh, Ionic liquid 3-methyl-1-sulphonic acid imidazolium chloride
{[Msim]Cl}: a highly efficient, mild and green catalyst for the synthesis of
β-acetamido ketones, S. Afr. J. Chem. 65 (2012) 63–68.
[36] M. Nouri-sefat, D. Saberi, K. Niknam, Preparation of silica-based ionic liquid an effi-
cient and recyclable catalyst for one-pot synthesis of α-aminonitriles, Catal. Lett.
141 (2011) 1713–1720.
[37] M. Baghernejad, K. Niknam, Synthesis of 4,4′-(arylmethylene)bis(1H-pyrazol-5-ols)
using silica-bonded ionic liquid as recyclable catalyst, Int. J. Chem. 4 (2012) 52–60.
[38] K. Niknam, A. Piran, Silica-grafted ionic liquids as recyclable catalysts for the synthe-
sis of 3,4-dihydropyrano[c]chromenes and pyra-no[2,3-c]pyrazoles, Green Sustain.
Chem. 3 (2013) 1–8.
[40] A. Zare, R. Khanivar, M. Hatami, M. Mokhlesi, M.A. Zolfigol, A.R. Moosavi-Zare, A.
Hasaninejad, A. Khazaei, V. Khakyzadeh, Efficient synthesis of 12-aryl-8,9,10,12-
tetrahydrobenzo[a]-xanthen-11-ones using ionic liquid pyrazinium di(hydrogen
sulfate) {Py(HSO4)2} as a novel, green and homogeneous catalyst, J. Mex. Chem.
Soc. 56 (2012) 389–394.
[41] A. Zare, R. Khanivar, M. Merajoddin, M. Kazem Rostami, M.M. Ahmad Zadeh, A.R.
Moosavi-Zare, A. Hasaninejad, Triethylamine bonded sulfonic acid {[Et3N–
SO3H]Cl} as an efficient and homogeneous catalyst for the synthesis of 12-aryl-
8,9,10,12-tetrahydrobenzo[a]xanthen-11-ones, Iran. J. Catal. 2 (2012) 107–114.
[42] N. Karimi, H.A. Oskooie, M.M. Heravi, L. Tahershamsi, Caro's acid–silica gel-catalyzed
one-pot synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a] xanthen-11-ones, Synth.
Commun. 41 (2011) 307–312.
[39] A. Chrobok, S. Baj, W. Pudlo, A. Jarzebski, Supported hydrogensulfate ionic liquid
catalysis in Baeyer–Villiger reaction, Appl. Catal. A Gen. 366 (2009) 22–28.