A clean, mild, and efficient preparation of aryl 14H-benzo[a,j]xanthene leuco-dye derivatives via nanocatalytic MCM-41-SO3h under ultrasonic irradiation in aqueous media

Article abstract of DOI:10.2174/1386207321666180104111508

Aim and Objective: The present study has developed an efficient and eco-friendly protocol for the synthesis of aryl-14-H-dibenzo[a,j] xanthenes through a one-pot condensation reaction of 2-naphthol and arylaldehydes in aqueous media using the nanocatalyti

Full text of DOI:10.2174/1386207321666180104111508

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5
Combinatorial Chemistry & High Throughput Screening, 2018, 21, 5-13
RESEARCH ARTICLE
eISSN: 1 83 78 56 - 52 40 07 23
A Clean, Mild, and Efficient Preparation of Aryl 14H-benzo[a,j]xanthene
F
I
0
m
a
c
p
tor:
5
a
c
t
.
9
2
leuco-dye Derivatives via Nanocatalytic MCM-41-SO H under Ultrasonic
3
Irradiation in Aqueous Media
SB EC N
I
E
T NH AC ME
*
Mostafa Fathollahi, Shahnaz Rostamizadeh and Ali M. Amani
Department of Chemistry, K. N. Toosi University of Technology, P.O. Box 15875-4416, Tehran, Iran
Abstract: Aim and Objective: The present study has developed an efficient and eco-friendly
protocol for the synthesis of aryl-14-H-dibenzo[a,j] xanthenes through a one-pot condensation
reaction of 2-naphthol and arylaldehydes in aqueous media using the nanocatalytic MCM-41-SO3H
under ultrasonic illumination.
A R T I C L E H I S T O R Y
Material and Methods: Using SEM and XRD analyses, MCM-41-SO3H nanoparticles were
characterized. Therefore, for high magnification, taking the SEM image, the mesoporous surface of
MCM-41-SO3H nanoparticles coated with gold for 2 minutes was characterized. Moreover, at a scan
rate of 0.02° (2θ)/sec, XRD analysis from 1.5° (2θ) to 10.0° (2θ) was performed.
Received: April 21, 2017
Revised: August 24, 2017
Accepted: December 27, 2017
Result: For our considered sample, some well-ordered XRD patterns with one main peak as well as
three minor peaks equal to those of MCM-41 materials were observed.
DOI:
1
0.2174/1386207321666180104111508
Conclusion: The suggested route demonstrates very promising properties like higher yields,
decrease in the time of reaction (5-10 min), mild and straightforward conditions, low level of
toxicity, and inclusion of a cost-efficient and ecofriendly catalyst having considerable reusability.
Keywords: Xanthene, leuco-dye, nanocatalyst, MCM-41-SO
3
H, ultrasonic irradiation, geen chemistry.
1
. INTRODUCTION
montmorillonite K10ꢀ [18], ionic liquids [19], and P-DBSA
[
20] have been reported. Nevertheless, the reported protocols
Much attention has recently been paid to the use of
suffer from various demerits like high levels of solvent
toxicity, severe conditions, insufficient yields, long time of
reaction and excess reagents.
Xanthenes and benzoxanthene derivatives for pharmaceutical
applications, which can be explained by their vast biological
and therapeutic advantages like antibacterial [1], antiviral
Recently, the direction of science and technology has
increasingly been inclined toward the use of green, nature-
based, and reusable catalysts such as the mesoporous and
well-structured MCM-41 nanoparticles, which demonstrate a
narrow distribution of pore sizes of approximately 1.5-10 nm
based on the surfactant cation and a large surface area (up to
[
2], and anti-inflammatory characteristics [3], as well as their
applicability in the photodynamic therapy [4].
Furthermore, Xanthene-based materials have been
investigated in terms of agricultural bactericide activities.
Besides, some benzoxanthene derivatives have found
industrial uses for example, dye in laser technology [5] and
fluorescent radiation for bio-molecular visualization [6].
Based on the natural sources, a number of polycyclic
compounds (e.g., xanthene skeleton and polyimides with
xanthenes pendent) have also been obtained [7]. Thus, great
importance has recently been given to the preparation of
benzoxanthene derivatives. In this context, different
preparation routes for these derivatives such as 2-naphthol
and aldehydes reaction using numerous catalytic materials
like CuO nanoparticles [8], Glucose-containing Bronsted
acid [9], Bronsted acid [10], Anion- binding catalysis [11],
N-sulfonic acid poly (4-vinylpyridinium)chloride [12], New
iodine [13], P-dodecylbenzenesulfonic (DBSA) [14], Poly(4-
2
−1
1
3
500 m g ) [21]. MCM-41-SO H has already been prepared
and used as a Brønsted acid, by our research group for some
acid catalyzed reactions [22, 23]. This reagent is
nonhazardous, manageable, and can quite easily be disposed.
Furthermore, as an ecofriendly preparation route, the
ultrasonic-assisted organic synthesis (UAOS) can be
considered as a viable technique for speeding up the organic
reactions [24, 25]. As an advantage, UAOS improves the rate
of the reactions, gives a high yield of pure products, and can
easily be manipulated. Moreover, it has been found that
ultrasound can positively contribute to the conservation of
energy and minimization of waste.
Compared to the previous approaches, the suggested
method is more useful since it involves different concepts of
geen chemistry [26, 27]. As far as we know, there exists no
vinylpyridinium)hydrogen sulfate [15], Mg(BF
4
)
2
doped in
+
3
[
BMlm][BF
4
] [16], p-tert-Butylcalix[8]arene [17],ꢀ Fe -
3
previous study on the application of the MCM-41-SO H as a
*
Address correspondence to this author at the Department of Chemistry, K.
N. Toosi University of Technology, P.O. Box 15875-4416, Tehran, Iran;
Tel: +989354183790; E-mail: shrostamizadeh@yahoo.com
nanocatalyst in the preparation of aryl-14H-dibenzo[a,j]
xanthenes under ultrasonic irradiation and in aqueous media.
1
875-5402/18 $58.00+.00
© 2018 Bentham Science Publishers

6
Combinatorial Chemistry & High Throughput Screening, 2018, Vol. 21, No. 1
Fathollahi et al.
In this regard, the present study has developed an
effective and ecofriendly route for the preparation of aryl-
4H-dibenzo[a,j]xanthenes via our prepared nanocatalyst
min at room temperature was then considered. from the
reaction vessel, HCl gas immediately evolved. After the
completion of the addition, the mixture was shaken for 30
1
under ultrasound irradiation in aqueous media. Our obtained
results are indicative of the favorable products in excellent
yields (Scheme 1).
minutes so that MCM-41-SO
produced (115.9 grams) (Scheme 2).
3
H, as a white solid, was
OH
O
H
OH
+
X
CHO
O
3
Scheme 2. Preparation of MCM-41-SO H.
3
MCM-41-SO H
By employing the scanning electron microscopy (SEM)
and X-ray diffraction (XRD), MCM-41-SO H nanoreactor
has been characterized. For high magnification, taking the
SEM image, the mesoporous surface of MCM-41-SO
nanoparticles coated with gold for minutes was
3
Scheme 1. One-pot synthesis of aryl 14H-dibenzo[a,j]xanthenes
derivatives using MCM-41-SO
irradiation.
3
H as a nanocatalyst under ultrasonic
3
H
2
characterized, the result of which is represented in Fig. (1).
At a scan rate of 0.02°(2θ)/sec, XRD analysis from 1.5°(2θ)
to 10.0°(2θ) was carried out. Fig. (2) shows the XRD
2
2
. MATERIALS AND METHODS
patterns of the prepared MCM-41-SO
3
H sample. Some quite
.1. Experimental
distinct XRD patterns were observed for the MCM-41-SO
3
H
sample, with one major peak as well as three minor ones
relative to those of MCM-41.
Chemicals were purchased from Merck and Sigma-
Aldrich while no additional purification was taken into
account. A Büchi B-540 device was used to record the
melting points, which were also uncorrected. Using an ABB
Bomem Model FTLA 200-100 instrument, the record of the
IR spectra was taken into account. Using a Bruker DRX-300
1
13
Avance spectrometer, H and C NMR spectra were
calculated at 300 and 75 MHz while TMS was used as an
internal standard. Chemical shifts are assumed to be (δ) with
respect to TMS. Furthermore, coupling constants (J) are
given in Hertz (Hz). Concerning mass spectra, a Shimadzu
QP 1100 EX mass spectrometer with 70eV ionization
potential was taken into account.
2
.2. Synthesis and Functionalization of MCM-41
In this study, MCM-41 modification was taken into
3
Fig. (1). XRD patterns for MCM-41 and MCM-41-SO H materials.
account so that the sulfonic groups can covalently be
anchored on the channels’ internal surface and the silica-
supported substance can be supported through Bronsted acid
characteristics. Besides, in order to synthesize MCM-41, the
cetyltrimethylammonium bromide (CTMABr) was employed
as the templating agent [28]. The template of the surfactant
was then discarded from the prepared material through
calcinations at 540 °C for 6 h.
MCM-41 was modified by means of a 100 mL suction
flask with a fixed pressure dropping funnel having
chlorosulfonic acid (81.13g, 0.7mol) and a gas inlet tube
used to conduct HCl gas over an adsorbing solution. 60.0
grams of MCM-41 was charged into the said tube and a
drop-wise addition of chlorosulfonic acid in a period of 30
3
Fig. (2). SEM images for MCM-41-SO H materials.

A Clean, Mild, and Efficient Preparationꢀ
Combinatorial Chemistry & High Throughput Screening, 2018, Vol. 21, No. 1
7
2
.3. Reusability of the Catalyst
(d, J=8.62 HZ, 2H), 7.54 (d, J=8.84 HZ, 2H), 7.8 (d, J=5.17
13
HZ, 2H), 7.9(d, J=4.18 HZ, 2H), 8.6 (d,J=8.52 HZ, 2H). C
3
Next, we investigated the reusability of MCM-41-SO H.
NMR(75 MHz, DMSO): δ=156.6, 147.8, 137.9, 136.9,
With this end in view, a mixture of aldehyde (1 mmol), 2-
naphthol (2 mmol) and MCM-41-SO H (0.1g) and water:
3
1
1
30.8,130.6, 128.9, 128.8, 128.6,123.3, 127.7, 127.5, 126.9,
24.5, 123.4, 117.6, 114.4,69, 35.67 MS(EI):m/e (%)=464
EtOH (50:50) (10ml) was taken into account. The
temperature rose to 30°C while the mixture was kept under
ultrasonic irradiation for a proper duration of time. After the
reaction was completed (managed by TLC, 2/1 petroleum
ether/ethyl acetate), the evaporation and dilution of the water
(
49.6), 465 (19.7).
Compound 3c: IR (KBr): 3168, 1637, 1596, 1570, 1509,
1
1
386, 1237, 1124, 738. H NMR (300 MHz, DMSO): δ= 3.54
(
s, J=3.54 Hz, 1H), 7.05 (s, J=6.98 Hz, 1H) 7.09 (d, J=6 Hz,
H), 7.24 (t, J= 9 Hz, 2H), 7.35 (t, J=9 Hz, 2H), 7.65 (d,
J=9 Hz,2H), 7.73 (d, J=8.1 Hz, 2H), 9.72 (s, J= 9.72 Hz,
2
3 3
with CHCl /CH OH was performed, and consequently the
catalyst was filtrated off. Furthermore, using simple
filtration, the catalyst was separated. Besides, in the
1
3
1
1
1
1
H). C NMR(75 MHz, DMSO):δ=155.3,138.52, 137,
34.6, 129.31, 127.72, 127.54, 126.12, 125.99, 124.13,
23.48, 122.64, 122.15, 120.85, 118.62, 118.18, 112.45,
08.64, 35.6. MS (EI): m/e (%) =397(40.6), 398 (15.7), 399
3
succeeding reactions, the recovered MCM-41-SO H was
used again with no considerable reduction in activity even
after three runs.
(
5.2).
3
. RESULTS AND DISCUSSION
3
For the first time, in the present study, MCM41-SO H
has been employed as an effective nanocatalyst for the
preparation of the xanthene derivatives and transformations.
It is shown that the suggested catalyst is highly advantageous
owing to its low level of toxicity, inexpensiveness,
manageability, and considerable catalytic activity as a
promising and ecofriendly material. Therefore, following our
research group’s previous works on the development of
green synthetic routes [29-32], the present study has
introduced an innovative, ecofriendly, straightforward, and
viable one-pot strategy for the preparation of aryl-14-H-
dibenzo[a,j]xanthenes derivatives using the catalytic
Fig. (3). Reusability of MCM-41-SO3H.
amounts of MCM-41-SO
Scheme 1).
3
H under ultrasonic irradiation
(
2
.4. Preparation of Aryl-14H-dibenzo [a,j]xanthenes
The reactions were conducted through a highly facile
route, in which the need for the use of the toxic organic
solvents or inert atmospheres was removed. The reactions
were performed at 30°C for 5-10 min using a 1:2 molar ratio
mixture of aldehyde and 2-naphtol in the presence of 100 mg
Procedure: aldehyde (1 mmol), 2-naphthol (2 mmol) and
3
MCM-41-SO H (0.1g) and water: EtOH (50:50) (10 ml)
were mixed. The temperature rose to 30°C while the mixture
was kept under ultrasonic irradiation for a proper duration of
time (Table 1). After the reaction was completed (controlled
by TLC, 2/1 petroleum ether/ethyl acetate), the evaporation
3 2
of MCM-41-SO H using H O-EtOH as a solvent at 25 kHz
under ultrasonic irradiation. As far as we know, no previous
studies have been conducted using ultrasonic-assisted
strategies for this transformation.
3 3
and dilution of the water with CHCl /CH OH occurred, and
subsequently the catalyst was filtrated off. Under vacuum,
the solvent evaporation was taken into account. Finally,
recrystallization of the resultant solid materials from ethanol
was observed.
In what follows, the procedures involved are discussed in
detail.
Ar
The spectral data of some representative products;
OH
MCM-41-SO
3
H
ArCHO +
2
Compound 3a: IR (KBr): 3281, 3121, 3044, 1668, 1586,
H
2
O:EtOH, U.S.
30°C
1
O
3
1
534, 1509, 1401, 1242. H NMR (300 MHz DMSO) δ= 1.8
1
2
ꢀ
(
s, J=1.88 HZ, 3 H), 6.63 (s, J=6.63 HZ, 1H), 7.29 (d,
J=6.30 HZ, 2H), 7.45 (d, J=8.08 Hz, 2H), 7.52 (t, J=6.57
HZ, 4H), 7.59 (d,J=6.43 HZ, 2H), 7.91 (d, J=6.57, 4H), 8.63
Scheme 3. Synthesis of aryl 14H-dibenzo[a,j]xanthenes derivatives
using MCM-41-SO3H as a nanocatalyst under ultrasonic irradiation
1
3
(
d, J=7.46HZ , 2H), 9.7 (s, J=9.72 Hz,1H). C NMR (75
MHz, DMSO) δ=168, 147.85, 140.17, 137.38, 130.84,
Initially, we selected the reaction of 4-chloroben-
zaldehyde and 2-naphtholes (compound 3g) as a model
reaction for investigation of different reaction parameters
under ultrasonic irradiation (Scheme 3). In order to evaluate
the catalytic amount in this condensation reaction, in an
initial study, 4-chlorobenzaldehyde and β naphtol were
reacted in water-etanol (10ml) for 8 min under ultrasonic
irradiation in the presence of 0, 0. 5, 0.1, and 0.15 g of
1
3
(
30.62,128.91, 128.57, 128.15, 123.4, 119, 117.66, 117.36,
5.94, 23.75. MS (EI): m/e (%)=415 (44.8), 416 (30.4), 417
3.4).
Compound 3b: IR(KBr): 3049, 3029 , 1591 , 1509,
1
1
4
457, 1406, 1242, 1175, H NMR (300 MHz, DMSO): δ=
.8 ( s, J =4.84 Hz, 2 H), 6.65 (s, J=6.65 HZ,1H),6.7 (d,
J=8.64 HZ, 2H), 7.25 (m, 5H), 7.44 (t, J=7.62 HZ, 2H), 7.52

8
Combinatorial Chemistry & High Throughput Screening, 2018, Vol. 21, No. 1
Fathollahi et al.
MCM41-SO
3
H separately. Using 0.1 g of MCM-41-SO
3
H,
preparation of aryl-14-H-dibenzo[a,j] xanthene derivatives is
completely removed. Using NMR, IR, and melting point, the
products were all characterized. Besides, our obtained results
were compared with the results of the recorded literature. A
large number of aromatic aldehydes were used and
benzoxanthene derivatives were all produced in high-to-
excellent yields (Table 4).
the best result was obtained (yield=95%). When lower
catalytic amounts were applied, the yield decreased.
However, by further increases (over 0.1 g) in the amount of
the catalyst, -the reaction times and yields did not change.
Besides, when no catalytic amount was applied, the yield
was observed to be very low (Table 1).
For investigation of the impact of the ultrasonic
irradiation on the reactions, 14-(4-chlorophenyl)14-H-
dibenzo[a,j]xanthenes were synthesized using 0, 0.5, 0.1, and
The proposed route can be considered as an overall
approach that allows for electron-withdrawing and electron-
donating constituents. Furthermore, since the reaction was
carried out under mild conditions, it did not affect such
moieties as methoxy that is mostly cleaved in the strictly
acidic reaction environments.
0
3
.15 g of MCM-41-SO H in the presence and in the absence
of ultrasonic irradiation (Table 2).
According to the results, under sonication, shorter
reaction times and higher product yields are generally
observed. As the results show, using ultrasound, both the
reaction times and the product yields are thus improved.
Cl
CHO
The generality of the suggested protocol can be
understood by the numerous substituted aryl aldehydes used
for the preparation of the related products in high to
excellent yields (Table 3).
OH
MCM-41-SO H
3
+
2
H O:EtOH, U.S.
2
O
3g
3
0°C
Cl
1
2
These high yields were accordingly transformed, while
the amount of unfavorable byproducts was not significant.
As opposed to some previous studies, in the present study,
the need for the use of the toxic or toxic organic solvents for
Scheme 4. Three-component one-step synthesis of 4-chloro-phenyl-
14H-dibenzo[a,j]xanthenes.
Table 1. The time and yield of reaction for 3g as a function of solvent and catalytic amount.
a
Entry
Conditions
Solvent
OH
Catalyst(g)
Time
Yield (%)
1
2
3
4
5
6
7
8
9
MCM-41-SO
3
3
3
3
3
3
3
H, U.S., 30 ºC
C
2
H
5
0.1
0.1
0.1
0.05
0.15
0.1
0.1
0.1
0.1
0.1
0
10 min
10 min
8min
10 min
8 min
35 min
20 min
6h
0
MCM-41-SO
MCM-41-SO
MCM-41-SO
MCM-41-SO
MCM-41-SO
MCM-41-SO
H, U.S., 30 ºC
H, U.S., 30 ºC
H, U.S., 30 ºC
H, U.S., 30 ºC
H, U.S., 30 ºC
H, U.S., 30 ºC
H
2
O
0
H
H
H
2
2
2
O: C
O: C
O: C
2
H
H
H
5
5
5
OH
OH
OH
95
70
95
38
45
77
30
35
0
2
2
THF
DMSO
O: C
THF
DMSO
O: C
MCM-41-SO
MCM-41-SO
MCM-41-SO
3
3
3
H, Reflux
H, Reflux
H, Reflux
H
H
2
2
2
H
5
OH
OH
6 h
1
1
0
1
6 h
Without catalyst, U.S., 30 ºC
2
H
5
90min
Table 2. Comparison of product yields and the catalytic amount with or with no sonication for preparation of 14-(4-chlorophenyl)-
4-H-dibenzo[a,j]xanthene.
1
Entry
Miligram of MCM-41-SO
3
H
With Sonication
Without Sonication
Time
Yield
Time
Yield
1
2
3
4
0
90 min
60 min
8 min
nill
45
95
95
360 min
360 min
360 min
360 min
nill
5
50
100
150
77
77
8 min

A Clean, Mild, and Efficient Preparationꢀ
Combinatorial Chemistry & High Throughput Screening, 2018, Vol. 21, No. 1
9
Table 3. MCM-41-SO3H-mediated preparation of Aryl-14-H-dibenzo[a,j]xanthenes under ultrasonic irradiation.
M.P.(lit.m.p)/[◦C] Found
Ref
Yield
Time
(min)
Product
Ar
Aldehyde
(
%)
4
-Acet-C
6
H
4
CHO
1
82-183
80
5
5
3a
3b
1
2
O
HNOCCH3
CHO
Ph-O-CH
2
-C
6
H
4
1
1
66-167
38-139
90
86
2
OCH Ph
O
3-indol
H
N
6
3c
3d
3
4
O
O
4
-MeO-C
6
H
4
CHO
OMe
2
03-205(203-205)
29]
9
8
8
6
5
1
10
[
O
2
-Meo-C
6
H
4
CHO
2
2
58-259(260-262)
29]
33-234(227-229)
OMe
10
10
3e
3f
5
6
[
O
4
-Me-C
6
H
4
CHO
O
[
29]
Me
4
-Cl-C
6
H
4
CHO
2
95(289-290)
29]
9
8
9
5
0
7
8
8
6
3g
3h
3i
7
8
9
[
Cl
O
2
-Cl-C
6
H
4
CHO
2
2
13-215(214-216)
29]
Cl
Cl
[
O
CHO
Cl
2
4
2 6 4
,4-Cl -C H
54-255(254-255)
29]
[
O
-NO
2
-C
6
H
4
CHO
3
09-310(311-312)
29]
8
9
7
6
8
8
3j
10
11
[
O
NO2
3
-NO
2
-C
6
H
4
CHO
2
15(210-211)
29]
3k
[
O N
2
O
(
Table 3) Contd….

1
0
Combinatorial Chemistry & High Throughput Screening, 2018, Vol. 21, No. 1
Fathollahi et al.
M.P.(lit.m.p)/[◦C] Found
Ref
Yield
%)
Time
(min)
Product
Ar
Aldehyde
(
CHO
4
6 4
-F-C H
2
37-238(239-240)
29]
8
1
6
3l
12
[
O
F
CHO
6 4
3-Br-C H
1
94-195(194-195)
29]
8
9
9
0
2
7
10
7
3m
3n
3o
13
14
15
Br
[
O
CHO
C
6 5
H
1
89(184-185)
29]
[
O
CHO
4
-BrC6H4
1
2
93-195(194-195)
29]
10
[
O
Br
3
-Cl-C
6
H
4
CHO
12-214(210-213)
29]
8
8
5
0
10
10
3p
3q
16
17
Cl
[
O
C
6
H
5
OHC
1
79-181(178-180)
29]
[
O
Table 4. Efficiency comparison of MCM-41-SO3H and other catalysts for the synthesis.
Entry
Catalyst
Temperature (◦C)
Time
h)
Yield
(%)
(
1
2
3
5
6
7
8
9
Iodine
p-TSA
90
2.5 -5
15–24
6-12
4-8
82-95
81–93
90-95
78-95
87–93
74–93
72–90
80–94
64–78
80–84
78–91
125
125
125
110
125
125
125
125
130
100
Sulfamic acid
H
2
SO
PTC
Selecfluor
Fe(HSO
Amberlyst-15
4
/SiO
2
2-3
6-11
23 min
0.5-2
3
4 3
)
1
1
1
0
1
2
5 2
K CoW12O40.3H O
LiBr
1-2
Dowex-50W
1-2
(
Table 4) Contd….

A Clean, Mild, and Efficient Preparationꢀ
Entry Catalyst
Combinatorial Chemistry & High Throughput Screening, 2018, Vol. 21, No. 1 11
Temperature (◦C)
Time
h)
Yield
(%)
(
1
1
1
1
1
1
1
3
4
5
6
7
8
9
NaHSO
CoPy Cl
Yb(OTf) , ILs
or InCl
/Al
BO
MCM-41-SO
4
90
0.5-1
2-8
74–91
65–94
78–95
87–97
60-95
85-98
95
2
2
85
3
110
3-7
P
2
O
5
3
80
MW, 900 W
120
0.5-1
P
2
O
5
2
O
3
10-15 min
1.5-3
H
3
3
3
H, U.S.
30
5 min
The mixture of reagents was sonicated for 5-10 minutes.
In our studies, we found that water and ethanol was the most
appropriate solvent for this transformation giving the best
results (Table 3).
results for the synthesis of dibenzoxanthenes with the results
from the recent literature (Table 4).
Reduction in the time of reaction (5-10 min), mild
reaction condition, and use of cost-effective and easy to
prepare catalyst are among the merits of the proposed
approach, as compared to the recorded approaches in the
literature. Our suggested procedure for this transformation is
shown in Scheme 4.
We have also observed that only (0.1 g) of MCM-41-
SO H had a significant effect on the yield of compound 3h
3
and was sufficient to push the reaction forward. It is worth
mentioning that greater volumes of catalyst (0.15 g) did not
increase the yield. On the other hand, reduction in the
catalytic amount resulted in the reduction in the yield of the
reaction.
3
After that, the MCM-41-SO H sample’s reusability and
recycling was verified. To this end, we first put p-
Cholorobenzaldehyde (1 mmol), 2-naphthol (2 mmol) and
It is important to mention that in order that the impact of
ultrasonic irradiation can be verified, this work has done the
above model reaction with no sonication and under reflux
condition in which the reaction goes to completion in 6h and
the yield of compound 3h was 77%. However, under
ultrasound the yield for 3h was 95% (Table 1, Entry 8).
3
0.1 g MCM-41-SO H in ethanol/water (50:50) (5 ml) as
solvent at 30°C under ultrasonic irradiation. By the
completion of the reaction as monitored by TLC analysis, the
mixture of the reaction was stirred for 10 minutes at a
temperature of 80°C. The produced solid (catalyst) was
separated by simple filtration and recovered. Moreover,
3
MCM-41-SO H was reused in the next reactions while no
significant reduction was observed the in the catalytic
activity even after three runs of the reaction.
The process scope and generality are shown in more
detail in Table 2 (Scheme 1) through the preparation of the
1
4H-dibenzo[a,j]xanthenes series.
The reactions were all performed within 5-10 min
CONCLUSION
without any byproduct seen under TLC analysis. These
reactions fit appropriately with both of electron-withdrawing
The present study has introduced a very efficient
preparation route for the preparation of aryl-14-H-dibenzo
[a,j]xanthenes based on the reaction between aldehydes and
(
NO2, Cl) and electron-donating (Me, MeO) groups, offering
numerous xanthenes’ derivatives in 80-97% yields. As
observed in Table 2, the proposed method seems to be
comprehensive and can work with different functional
groups.
2-naphtol by the catalytic activity of MCM-41-SO H under
3
sonication. Furthermore, this method has made use of a
straightforward, quick, easily implementable, and inexpen-
sive mechanism for preparing these products. Besides, the
considered catalyst is straightforwardly produced and
In order that the proposed approach can be further
corroborated, a comparison was made between our obtained
X
H
+
O
O
OH
X
H
H
3
MCM-41-SO H
H
OH
OH+
OH MCM-41-SO H
3
H
X
H
X
OH
OH+
HO
OHHO
OH
X
H
+
OH
OH
2
-H O
2
Product
H
X
X
Scheme 5. A provisional mechanism for the synthesis of aryl 14H-dibenzo[a,j]xanthenes.

1
2
Combinatorial Chemistry & High Throughput Screening, 2018, Vol. 21, No. 1
Fathollahi et al.
removed using a convenient filtration. Due to such a
convenient catalytic production and elimination, this
protocol can be considered as an attractive option for
different chemical applications.
[10]
Xu, J.H.; Yuan, T.; Yue, K.L.; Xin, Y.W.; Feng, S. Direct
construction of xanthenes and benzophenone derivatives via
Bronsted acid controlled Diels-Alder reaction of 3-vinylchromones
and arynes. Tetrahedron, 2016, 72(52), 8565-8577.
[11]
Alison, E.M.; Kailasham, R.; Marisa, C. K. Xanthene-4,5-diamine
derivatives: a study of anion-binding catalysis. Tetrahedron Lett.,
2
015, 56(37), 5180-5184.
CONSENT FOR PUBLICATION
[
12]
Shirini, F.; Abedini, M.; Pourhasan, R. N-sulfonic acid poly (4-
Vinylpyridinium) chloride:
A novel polymeric and reusable
Not applicable.
catalyst for the preparation catalyst for the preparation of xanthenes
derivatives. Dyes and Pigments, 2013, 99(1), 250-255.
[
[
13]
14]
Koneni, V.S.; Abdhesh, K.; Ranga, P.D.; Bikash, K. A new iodine
catalyzed regioselective synthesis of xanthenes Synthons.
Tetrahedron Lett., 2012, 53(26), 3281-3283.
CONFLICT OF INTEREST
The authors declare no conflict of interest, financial or
otherwise.
Davinder, P.; Amreeta, P.; Mahendra N. Microwave-assisted green
synthesis of dibenzo[a,j]xanthenes using P-dodecylbenzensulfonic
acid as an efficient Bronsted acid catalyst under solvent-free
conditions. Comptes Rendus Chimie., 2012, 15(8), 675-678.
Ghaffari, K.N. Poly(4-vinylpyridinium)hydrogen Sulfate: A novel
and efficient Catalyst for the synthesis of 14-aryl-14H-
dibenzo[a,j]xanthenes under conventional heating and ultrasound
irradiation. Ultrasonics Sonochem., 2012, 19(4), 736-739.
ACKNOWLEDGEMENTS
[
15]
Authors gratefully acknowledge the partial financial
support by Research Council of K.N. Toosi University of
Technology. The authors also would like to express their
gratitude to Mr. Mojtaba Kharrasi, MA in English Language
and Literature, for highly improving, proofreading, and
editing of the text making it so much more comprehensible
and professional.
[16]
4 2 4
Rad, M.K.; Azimi, C. Mg(BF ) doped in [BMlm][BF ]:A
homogenous ionic liquid-Catalyst for efficient Synthesis of 1,8-
dioxo-octahydroxanthenes, decahydroacridines and 14-aryl-14H-
dibenzo[a,j]xanthenes. J. Mol. Catalysis A: Chemical, 2012,
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Piyali, S.; Chhanda, M. p-tert-butylcalix[8]arene: An effective
nano-ranged organocatalyst for the syntheses of xanthenes and
acridines. Curr. Organocatalysis. 2016, 3(2), 205-215.
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