Ultrasound promoted rapid and green synthesis of 1,8-dioxo-octahydroxanthenes derivatives using nanosized MCM-41-SO3H as a nanoreactor, nanocatalyst in aqueous media

Article abstract of DOI:10.1016/j.ultsonch.2009.10.004

An efficient and green procedure has been developed for the synthesis of 1,8-dioxo-octahydroxanthenes derivatives. The reaction was carried out in water under ultrasound irradiation, using nanosized MCM-41-SO₃H. In this method, several types of

Full text of DOI:10.1016/j.ultsonch.2009.10.004

Ultrasonics Sonochemistry 17 (2010) 306–309
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Short Communication
Ultrasound promoted rapid and green synthesis of 1,8-dioxo-octahydroxanthenes
derivatives using nanosized MCM-41-SO3H as a nanoreactor, nanocatalyst
in aqueous media
a
b
Shahnaz Rostamizadeh a, , Ali Mohammad Amani , Gholam Hossein Mahdavinia ,
*
Gelareh Amiri a, Hamid Sepehrian c
a Department of Chemistry, KN Toosi University of Technology, P.O. Box 15875-4416, Tehran, Iran
b Department of Chemistry, Islamic Azad University–Marvdasht Branch, Marvdasht, Iran
c Jaber Ibn Hayan Research Laboratories, Nuclear Science and Technology Research Institute, AEOI, P.O. Box 11365/8486, Tehran, Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
An efficient and green procedure has been developed for the synthesis of 1,8-dioxo-octahydroxanthenes
derivatives. The reaction was carried out in water under ultrasound irradiation, using nanosized MCM-
41-SO3H. In this method, several types of aromatic aldehyde, containing electron-withdrawing groups
as well as electron-donating groups, were rapidly converted to the corresponding 1,8-dioxo-octahydrox-
anthenes in good to excellent yields. This novel synthetic method is especially favored because it provides
a synergy of the nanosized MCM-41-SO3H and ultrasound irradiation which offers the advantages of high
yields, short reaction times, simplicity and easy workup compared to the conventional methods reported
in the literature.
Received 20 February 2009
Received in revised form 4 October 2009
Accepted 6 October 2009
Available online 13 October 2009
Keywords:
Ultrasonic irradiation
Green chemistry
Nanocatalyst
Ó 2009 Elsevier B.V. All rights reserved.
MCM-41-SO3H
1,8-Dioxo-octahydroxanthenes
1. Introduction
In recent years more attractive possibilities have been arisen by
the development of various new silica materials with ordered
Ultrasound process technology is a unique method for the acti-
vation and acceleration of processes in chemistry and has been
increasingly used in organic synthesis in the last three decades
[1–3]. It promotes most types of catalytic processes in chemical
syntheses and has a generally accelerating impact on heteroge-
neous reactions as well as intercalation of guest molecules into
host inorganic layered solids. Furthermore, the impetus for ultra-
sound developments in organic synthesis is the increasing require-
ment for environmentally clean technology by improving product
yields and selectivities, enhancing product recovery and quality
through application to crystallization and other product recovery
and purification processes [4]. Sonication allows the use of non-
activated and crude reagents as well as an aqueous solvent system;
therefore, it is eco-friendly and non-toxic. Ultrasound is widely
used for improving the traditional reactions that use expensive re-
agents, strongly acidic conditions, long reaction times, high tem-
peratures, unsatisfactory yields and incompatibility with other
functional groups [5].
structure [6]. one of the best-known examples is MCM-41, which
is a structurally well-ordered mesoporous material with a narrow
pore size distribution between 1.5 and 10 nm, depending on the
surfactant cation and a very high surface area up to 1500 m2 gÀ1
[7]. It has been proven that Si-MCM-41 lacks Brönsted acid sites
and exhibits only weak hydrogen-bonded type sites [8,9]. An addi-
tional possibility to develop acidic solids is the modification of the
surface of suitable support materials, as the chemical functional-
ities of these materials can be uniformly modified by covalent
anchoring of different organic moieties [10]. While several types
of solid sulfonic acids have been created in recent years, there have
been only a few reports about their applications as catalyst in
chemical transformations. Furthermore, to the best of our
knowledge there is no report on the use of these materials as
nanocatalysts in the synthesis of 1,8-dioxo-octahydroxanthenes.
The obtained nanocatalysts were tested for the synthesis of
1,8-dioxo-octahydroxanthenes under ultrasonic irradiation in
aqueous media.
There has been considerable interest in the synthesis of 1,8-di-
oxo-octahydroxanthens, due to their significant biological activity
[11,12]. Some other benzoxanthenes are also utilized in industries
as dyes in laser technology [13]. They have also been used in
* Corresponding author. Tel.: +98 21 22853308; fax: +98 21 22853650.
E-mail address: shrostamizadeh@yahoo.com (S. Rostamizadeh).
1350-4177/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.ultsonch.2009.10.004

S. Rostamizadeh et al. / Ultrasonics Sonochemistry 17 (2010) 306–309
307
photodynamic therapy [14] and are fluorescent materials for visu-
alization of biomolecules [15–18].
Numerous methods have been reported in the literature for the
synthesis of 1,8-dioxo-octahydroxanthenes. The classical method
involves the condensation of two molecules of dimedone (5,5-di-
methyl-1,3-cyclohexanedione) with aromatic aldehydes [19–21],
using different catalysts such as p-dodecylbenzenesulfonic acid
[22], triethylbenzylammonium chloride [23], diammonium hydro-
gen phosphate under various conditions [24], sulfonic acid under
ultrasonic irradiation [25] In this paper, we had the opportunity
to further explore the catalytic activity of MCM-41-SO3H in the
synthesis of 1,8-dioxo-octahydroxanthenes.
Herein, we would like to report an efficient route for the synthe-
sis of these compounds from the reaction of readily available and
non expensive starting materials of dimedone and an aromatic
aldehyde, inside the channels of MCM-41-SO3H as nanocatalysts
under ultrasonic irradiation.
2. Results and discussion
In continuation of our work to develop new and eco-friendly
synthetic methodologies [26,27], herein we report a novel, green,
facile and efficient one-pot method for the synthesis of 1,8-di-
oxo-octahydroxanthene derivatives catalyzed by MCM-41-SO3H
as a nanoctalyst under ultrasonic irradiation (Scheme 1).
During our investigation, at first, we chose 4-nitrobenzaldehyde
and dimedone (mole rate 1:2) under ultrasonic irradiation as mod-
el reactants and examined the effect of the amount of MCM-41-
SO3H (Scheme 2, Table 1). According to this data, the optimum
amount of catalyst was 0.05 g as shown in Table 1. Further increas-
ing the amount of catalyst did not improve the yield and the reac-
tion time. In order to evaluate the effect of solvent, we examined
different solvents under room temperature for the above model
reaction (Table 1). The outstanding feature of data that can be elic-
ited from Table 1 is the role of the antihydrophobic property of
water in this reaction.
To show the high catalytic activity of MCM-41-SO3H, the effect
of other Lewis acids such as ZrOCl2, ZrOCl2/K10, NaHSO4, NaHSO4/
SiO2 were also investigated in the above model reaction. As shown
in Table 1 when the above mixture was reacted under ultrasonic
irradiation for 3 h in the presence of these Lewis acids, only the
intermediate was detected, which further proves the superior cat-
alytic activity of MCM-41-SO3H in this transformation. Thus, it is
noticeable that the synergy of the nanosized MCM-41-SO3H and
ultrasound irradiation has facilitated this efficient protocol. The
combined use of MCM-41-SO3H and ultrasound is best explained
in terms of the intercalation of guest molecules (reactant) into host
nanoreactors.
Scheme 2.
ward nanocatalyst channels, and also they accompanied by inherent
Brönsted acidity of -SO3H groups, which are capable of bonding with
carbonyl oxygen of the aldehydes, assist in generation of ionic inter-
mediates through activation of reactants, Scheme 2. In other words,
ionic intermediates are generated inside the nanoreactor by suffi-
cient energy released during the collapse and strong polarity of
the –SO3H groups. By using this nanocatalyst, the reaction rates
and yields under the reaction condition are enhanced, whereas in
the presence of mentioned Lewis acids no product is obtained.
In order to show the effect of ultrasonic irradiation in these
reactions, the synthesis of 3i was investigated as a typical example
in the presence of 0, 0.1, 0.2 and 0.05 g of MCM-41-SO3H with and
without ultrasonic irradiation at 60 and 90 °C (Table 2). The reac-
tion rates and yields were dramatically enhanced by ultrasound.
The rate enhancement under ultrasound may be attributed to the
cavitation, activation of the catalyst and the intercalation of guest
molecules into host nanoreactor by sonic waves. In the absence of
sonic waves, at 90 °C the products were formed in moderate yields
(40–50%) and at 60 °C reaction didn’t progress. The role of ultra-
sound in promoting the rapid and green synthesis of 1,8-dioxo-
octahydroxanthenes derivatives is evident from the fact that the
corresponding reactions under stirred conditions without ultra-
sound (silent reactions) needed much longer time for promotion,
in all cases with lowered yields (Table 2). Based on the results of
this study, it seems that the ultrasound irradiation improves the
reaction times and yields.
For a deeper insight in the influence of ultrasound on this work
and in order to evaluate the scope and limitations of this work, we
focused our attempts on the synthesis of the 1,8-dioxo-octahy-
droxanthenes using dimedone and benzaldehyde derivatives, the
results of which are shown in Table 3. All of the reactions were car-
ried out within 15–90 min and no by-product was observed by TLC
analysis. The reaction worked well with electron-withdrawing
(NO2, Cl, CN) as well as electron-donating (Me, MeO) groups, giving
various xanthene derivatives in 80–99% yields. As shown in Table
3, the method is general and includes a variety of functional
groups.
As a matter of fact, localised intense pressure and temperature
regions generated by ultrasound help in insertion of reactants to-
3. Experimental
Chemicals were obtained from Merck and Sigma–Aldrich and
used without further purification. Melting points were recorded
Scheme 1.

308
S. Rostamizadeh et al. / Ultrasonics Sonochemistry 17 (2010) 306–309
Table 1
The effect of amount of MCM-41-SO3H, solvent and different catalysts for synthesis of 3b and 3i.
Entry
Catalysta,b
Amount of catalyst (g)
Solvent
Time (min)
Yield (%)c
a
1
2
3
4
5
6
7
8
ZrOCl2
0.1
0.3
0.4
0.4
0.1
0.5
0
0.05
0.05
0.05
0.05
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
Neat
EtOH
180
180
180
180
60
60
180
60
Intermediate
Intermediate
Intermediate
Intermediate
95
ZrOCl2/K10a
NaHSO4
NaHSO4/SiO2
a
a
MCM-41-SO3Hb
MCM-41-SO3Hb
MCM-41-SO3Ha
MCM-41-SO3Ha
MCM-41-SO3Hb
MCM-41-SO3Hb
MCM-41-SO3Hb
95
Intermediate
95
94
Intermediate
Intermediate
9
10
11
60
180
180
a
b
c
Reaction was performed with 4-nitrobenzaldehyde and dimedone (mole rate 1:2) under ultrasonic irradiation.
Reaction was performed with 4-cyanobenzaldehyde and dimedone (mole rate 1:2) under ultrasonic irradiation.
Isolated yield.
Table 2
Comparison of the amount of catalyst and yields with or without sonication for the synthesis of 3i.
Entry
MCM-41-SO3H (g)
With sonication
Yield (%)
Without sonication
Yield (%)a
Time (min)
Time (min)
Yield (%)b
Time (min)
1
2
3
4
0
0
96
95
95
80
60
60
60
0
50
45
40
180
60
60
0
180
180
180
180
0.2
0.1
0.05
Trace
Trace
0
60
a
Reaction was performed at 90 °C.
Reaction was performed at 60 °C.
b
Table 3
Preparation of 1,8-dioxo-octahydroxanthenes catalyzed by MCM-41-SO3H under ultrasonic irradiation.a,b
Product
Ar
Time (min)
Yield (%)
Mp (°C)
Found
Reported (Lit.)
3a
3b
3c
3d
3e
3f
3g
3h
3i
4-PhCH2O-C6H4
4-CN-C6H4
4-Cl-C6H4
2,4-Cl2-C6H4
2-MeO-C6H4
4-MeO-C6H4
4-MeCONH-C6H4
4-Me-C6H4
15
60
60
60
60
60
15
90
60
95
94
86
90
88
95
96
99
95
145–147
230
–
215–217(24)
232–233(24)
250–252(21)
190–191(19)
241–243(21)
305–306(24)
218–219(21)
226–228(22)
236–237
248–249
199–200
250–251
305–306
220–222
229–230
4-NO2-C6H4
a
The yields refer to the isolated pure products.
The products were characterized from their spectral data (IR, 1H NMR, 13C NMR and mp) and comparison with literature.
b
on a Büchi B-540 apparatus and are uncorrected. IR spectra were
recorded on an ABB Bomem ModelFTLA200-100 instrument. 1H
and 13C NMR spectra were measured with a Bruker DRX-300
Avance spectrometer at 300 and 75 MHz using TMS as an internal
standard. Chemical shifts are reported (d) relative to TMS, and cou-
pling constants (J) are reported in Hertz (Hz). Mass spectra were
recorded on a Shimadzu QP 1100 EX mass spectrometer with
70 eV ionization potential.
MCM-41 was modified using a 100 mL suction flask equipped
with a constant pressure dropping funnel containing chlorosul-
fonic acid (81.13 g, 0.7 mol) and a gas inlet tube for conducting
HCl gas over an adsorbing solution. Into it was charged 60.0 g of
MCM-41 and chlorosulfonic acid was then added dropwise over a
period of 30 min at room temperature. HCl gas evolved from the
reaction vessel immediately. After completion of addition the mix-
ture was shaken for 30 min. and the white solid (MCM-41-SO3H)
was obtained (115.9 g).
3.1. Synthesis and functionalization of MCM-41
3.1.1. Characterization
In the present work MCM-41 was modified to covalently anchor
sulfonic groups on the inside surface of channels and provide the
silica supported material with Brönsted acid properties. The
MCM-41 was synthesized according to the previously described
method using cetyltrimethylammonium bromide (CTMABr), as
the templating agent [28]. The surfactant template was then re-
moved from the synthesized material by calcination at 540 °C for
6 h.
XRD analysis was performed from 1.5° (2h) to 10.0° (2h) at a
scan rate of 0.02° (2h)/sec. The XRD patterns after the calcinations
of synthesized cerium (IV) silicate samples are presented in Fig. 1.
The sample of MCM-41-SO3H produced relatively well-defined
XRD patterns, with one major peak along with three small peaks
identical to those of MCM-41 materials [29]. The SEM image of
mesoporous MCM-41-SO3H was taken using 2 min gold coat for
high magnification and is shown in Fig. 2.

S. Rostamizadeh et al. / Ultrasonics Sonochemistry 17 (2010) 306–309
309
J1 = 16.3 Hz, J2 = 6.7 Hz, 2CH2, H-4, H-5), 2.47 (4H, s, 2CH2, H-2,
H-7), 4.73 (1H, s, H-9), 4.99 (2H, s, CH2-Bn), 6.85 (2H, d,
J = 8.6 Hz, ArH), 7.23 (2H, d, J = 8.6 Hz, ArH), 7.27–7.42 (5H, m,
ArH); 13C NMR (75 MHz, CDCl3): dC: 27.37, 29.28, 30.99, 32.20,
40.84, 50.78, 69.93, 114.34, 115.75, 127.56, 127.85, 128.51,
129.36,136.81,137.23, 157.33, 162.13, 196.49; MS (EI): m/e = 456
(M+), 365, 321, 273, 217, 91, 77, 41.
3,3,6,6-Tetramethyl-9-(4-nitrophenyl)-1,8-dioxooctahydroxanth-
ene (Table 3, 3i): IR (KBr, cmÀ1) Vmax: 3040, 2964, 1662, 1619, 1516,
1470, 1363, 1346, 1203, 1168, 1141, 1114, 1004, 870, 836, 694;1H
NMR (300 MHz; CDCl3; Me4Si): dH: 0.99 (6H, s, 2CH3), 1.12 (6H, s,
2CH3), 2.21 (4H, dd, J1 = 16.4 Hz, J2 = 6.7 Hz, 2CH2, H-4, H-5), 2.49
(4H, s, 2CH2, H-2, H-7), 4.82 (1H, s, H-9), 7.46–7.49 (2H, m, ArH),
8.08–8.11 (2H, m, ArH).
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3.2. Synthesis of 1,8-dioxo-octahydroxanthenes: general procedure
A mixture of aldehyde (1 mmol), dimedone (2 mmol), MCM-41-
SO3H (0.05gr; ꢀ5 mol%, –SO3H group) and water (5 mL) were
mixed and the temperature was then raised to 60 °C and main-
tained under ultrasonic irradiation (25 kHz) for the appropriate
time (Table 3). After completion of the reaction, the water was
evaporated and CHCl3 (10 mL) was added and the mixture stirred
for at least 10 min. The mixture was filtered and evaporated in va-
cuo, the residues were purified by recrystallization from EtOH.
3.2.1. The spectral data of some representative products
3,3,6,6-Tetramethyl-9-(4-benzyloxyphenyl)-1,8-dioxooctahy-
droxanthene (Table 3, 3a): IR (KBr, cmÀ1) Vmax 3033, 2963, 2871,
1665, 1625, 1604, 1506, 1451, 1359, 1264, 1216, 1196, 1139,
1024, 1001, 840, 738, 696, 606, 535; 1H NMR (300 MHz; CDCl3;
Me4Si): dH: 1.00 (6H, s, 2CH3), 1.10 (6H, s, 2CH3), 2.21 (4H, dd,
[29] J.S. Beck, J.C. Vartulli, W.J. Roth, M.E. Leonowicz, C.T. Kresge, K.D. Schmitt, C.T.-
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