Cellulose sulfonic acid: An efficient heterogeneous catalyst for the synthesis of 1, 8-Dioxo octahydroxanthenes

Article abstract of DOI:10.1155/2010/936107

1,8-Dioxo-octahydroxanthenes have been synthesized good yields via a reaction of aldehydes and dimedone in the presence of cellulose sulfonic acid as a heterogeneous catalyst under solvent-free condition.

Full text of DOI:10.1155/2010/936107

ISSN: 0973-4945; CODEN ECJHAO
E-Journal of Chemistry
2010, 7(3), 717-720
http://www.e-journals.net
Cellulose Sulfonic Acid: An Efficient
Heterogeneous Catalyst for the Synthesis of
, 8-Dioxo-octahydroxanthenes
1
HOSSEIN A. OSKOOIE, LEILI TAHERSHAMSI,
*
MAJID M.HERAVI and BITA BAGHERNEJAD
Department of Chemistry, School of Science,
Azzahra University, Vanak, Tehran, Iran
.
mmh1331@yahoo.com
Received 15 July 2009; Accepted 7 September 2009
Abstract: 1,8-Dioxo-octahydroxanthenes have been synthesized good yields
via a reaction of aldehydes and dimedone in the presence of cellulose sulfonic
acid as a heterogeneous catalyst under solvent-free condition.
Keywords: Xanthene derivatives, Solvent-free condition, Cellulose sulfonic acid, Heterogeneous catalyst.
Introduction
Xanthene derivatives are very important heterocyclic compounds and have been widely used
as dyes fluorescent materials for visualization of bio-molecules and laser technologies due to
1
their useful spectroscopic properties . They have been reported for their agricultural
2
3
4
5
bactericide activity , photodynamic therapy , antiflammatory effect and antiviral activity .
6
These compounds are also utilized as antagonists for paralyzing action of zoxazolamine and
7
in photodynamic therapy (PDT) . The other useful applications of these heterocycles are as
8
9
10
dyes , flouerescent materials for visualization of biomolecules and in laser technologies .
Due to their wide range of applications, these compounds have received a great deal of
attention in connection with their synthesis. A wide variety of methods for the preparation of
the xanthenes have been classified according to starting compounds, e. g. syntheses by
11
cyclization of polycyclic aryltiflate esters , intramolecular trapping of benzynes by
1
2
13
phenols and reaction of aryloxymagnesium halides with triethylorthoformate . However,
many of these methods are associated with several short comings such as long reaction times
(
16 h to 5 days), expensive reagents, harsh conditions, low product yields, use of toxic
organic solvents and difficulty in recovery and reusability of the catalysts. Heterogeneous
catalysts have gained interesting attraction in recent years due to economic and environmental

7
18
MAJID M.HERAVI et al.
considerations. These catalysts are generally inexpensive and easily available. They can
conveniently be handled and removed from the reaction mixture, thus making the experimental
procedure simple and eco-friendly. As part of our continued interest in the development of highly
14
expedient methods for the synthesis of heterocyclic compounds of biological importance , we
would like to report a simple and efficient method to produce 1,8-Dioxo-octahydroxanthenes in
very good yields catalyzed by cellulose sulfonic acid as a heterogeneous and reusable eco-
friendly catalyst under solvent-free conditions (Scheme 1).
X
O
O
O
O
H
2
cellulose sulfonic acid
solvent free/ heat
O
O
X
1
2
3
Scheme 1
Experimental
Chemicals were purchased from the Fluka, Merck and Aldrich chemical companies. Melting
points were measured with a Bamstead Electrothermal 9200 apparatus and are uncorrected.
GC/MS spectra were recorded on an Agilent Technologies 6890 network GC system and an
1
Agilent 5973 network Mass selective detector. HNMR spectra were recorded on a Bruker
DRX Avance spectrometer at 300 MHZ, respectively, with CDCl as solvent. IR spectra
were recorded from KBr disk on the FT-IR Bruker Tensor 27. Thin layer chromatography
3
(TLC) on commercial aluminum-backed plates of silica gel, 60 F254 was used to monitor
the progress of reactions.
Preparation of 1, 8-dioxo-octahydroxanthenes
General procedure
A mixture of an aromatic aldehyde (1 mmol), dimedone (2 mmol) and cellulose sulfonic acid
(
o
0.05 g) was heated at 110 C. The progress of the reaction was monitored by TLC. After
completion of the reaction, hot ethanol or methanol was added to the mixture and the catalyst
was filtered off. The pure product was obtained by recrystallization from the solvent.
Synthesis of 3,4,6-tetrahydro-3,3,6,6-tetramethyl-9-phenyl-2H-xanthane-1,8 (5H,9H)-
dione (4a)
−
1
1
M.p: 206 ºC. IR (KBr) (νmax, cm ): 1670, 1674 (C=O); H NMR (CDC1 , 300 MHz) δ
3
H
(ppm): 1.1 2 (12H, s), 2.01(4H, s), 2.88 (4H, s), 3.46 (1H, s), 7.21-7.30 (m, 5H,
aromatic CH).
Results and Discussion
In a typical general experimental procedure, a mixture of dimedone and aldehyde was heated
in the presence of a catalytic amount of cellulose sulfonic acid, the corresponding
products were obtained in good yields. The results are summarized in Table 1. The
catalyst plays a crucial role in the success of the reaction in terms of time and the yields.

Cellulose Sulfonic Acid: An Efficient Heterogeneous Catalyst
719
In the absence of the catalyst, the reaction of benzaldehyde with dimedone as an example,
could be carried out but the product was obtained in very low yield after prolonged time.
The catalyst is very active, stable to air and moisture, nontoxic and inexpensive. In addition,
it can be quantitatively recovered by filtration and reused. We were able to separate
cellulose sulfuric acid from the reaction medium easily by washing with CH Cl . After
2
2
drying it was reused for subsequent reactions.
Table 1. Solvent-free synthesis of 1,8-dioxo-octahydroxanthene derivatives catalyzed by
cellulose sulfonic acid.
o
m.p, C
a
Entry
X
Product Time, h Yield, %
Found
Reported
1
5
6
6
6
6
6
5
5
1
H
3a
3b
3c
3d
3e
3f
5
6
5
5
5
5
6
6
94
95
94
95
95
94
95
94
206
231
225
167
227
229
243
219
204-205
228-230
222-224
168-170
226-228
228-230
241-243
217-218
1
1
1
1
1
1
1
2
3
4
5
6
7
8
4-OH
4-Br
3-NO2
4-NO2
4-Cl
4-OCH3
4-CH3
3g
3h
Yields refer to isolated products.
Thus, this process could be also interesting for large-scale synthesis. In order to
show the general applicability of the method, the reaction of structurally diverse
aldehydes with dimedone (Scheme 1) under similar conditions was investigated. By this
method, the reactions were carried out easily and very cleanly in the presence of
o
cellulose sulfonic acid (0.05 g) at 110 C under solvent-free conditions to produce
xanthene derivatives in good yields and no undesirable by-products are observed. This
protocol offers advantages in terms of its simple procedure and work-up and excellent
yields. The experimental procedure is very simple, convenient and has the ability to
tolerate a variety of other functional groups such as methyl, methoxy, nitro, hydroxyl,
halide under the reaction conditions. It was indicated that both electron rich and electron
deficient aldehydes worked well, mostly leading to high yields of products. It is
noteworthy to mention that similar results were obtained in H O, but in longer reaction
2
o
times. All reactions were carried out under solvent-free condition at 110 C and the
1
desired products were characterized by melting points, HNMR and IR spectroscopic
analyses. The optimum temperature was also examined using the reaction of
benzaldehyde and dimedone in the presence of cellulose sulfonic acid under solvent-free
o
condition and the best result was obtained at 110 C. Among the tested solvents such as
methanol, ethanol, DMF, CH CN, chloroform, 1,2-dichloroethane and solvent-free
3
system, the reaction was more facile and proceeded to gave highest yield, under solvent
free conditions.
In summary, we have found a simple, convenient, straightforward and practical
procedure for the synthesis of xanthene derivatives under solvent-free condition. All starting
materials are readily available from commercial sources. Moreover, there is no need for dry
solvents or protecting gas atmospheres. Some advantages of this procedure are: 1) the
experimental simplicity and the easy work-up procedure, 2) the compatibility with various
functional groups, 3) use of the inexpensive, green, easy to handle and reusable catalyst and 4)
high yields of the products. The procedure is very simple and can be used as an alternative to
the existing procedures.

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MAJID M.HERAVI et al.
Acknowledgments
Prof. Hossein A. Oskooie gratefully acknowledges partial financial support from the
research council of Azzahra University.
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