Neat synthesis of octahydroxanthene-1,8-diones, catalyzed by silicotungstic acid as an efficient reusable inorganic catalyst

Article abstract of DOI:10.1134/S107036321605025X

In this article, the first use of silicotungstic acid (H₄SiW₁₂O₄₀) as a catalyst for the synthesis of octahydroxanthene-1,8-diones by the reaction of 5,5-dimethylcyclohexane-1,3-dione (dimedone) with various aldehydes unde

Full text of DOI:10.1134/S107036321605025X

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 5, pp. 1132–1136. © Pleiades Publishing, Ltd., 2016.
Neat Synthesis of Octahydroxanthene-1,8-diones,
Catalyzed by Silicotungstic Acid
as an Efficient Reusable Inorganic Catalyst1
A. Davoodnia, S. Basafa*, and N. Tavakoli-Hoseini
Department of Chemistry, Mashhad Branch, Islamic Azad University, Mashhad, 91735-413 Iran
*e-mail: samira_basafa@yahoo.com
Received November 7, 2015
Abstract—In this article, the first use of silicotungstic acid (H4SiW12O40) as a catalyst for the synthesis of
octahydroxanthene-1,8-diones by the reaction of 5,5-dimethylcyclohexane-1,3-dione (dimedone) with various
aldehydes under thermal solvent-free conditions is described. The obtained results showed that the catalyst has
a high catalytic activity, and the desired products were obtained in high yields. Moreover, the catalyst was
found to be reusable, and a considerable catalytic activity still could be achieved after the fifth run. Easy work-
up and avoidance of using harmful organic solvents are the other advantages of this simple procedure.
Keywords: octahydroxanthene-1,8-diones, silicotungstic acid, 5,5-dimethylcyclohexane-1,3-dione; solvent-
free synthesis
DOI: 10.1134/S107036321605025X
Xanthenes have received great attention because of
their wide range of therapeutic and biological pro-
perties, such as antibacterial [1], antiviral [2], and anti-
inflammatory activities [3]. Also, these compounds
have been used as fluorescent and laser dyes [2, 4, 5].
Heteropoly acids (HPAs) have been pointed out
lately as versatile, environmentally benign, water tolerate,
stable and green heterogeneous and homogenous
catalysts for a variety of organic reactions [17–19].
The use of Keggin-type HPAs as catalysts in organic
synthesis has been developed as a result of their
several advantages, such as environmental compati-
bility, reusability, non-corrosiveness, and relative lack
of disposal problems, which make them economically
and environmentally attractive. Among the various
Keggin-type HPAs, silicotungstic acid H4SiW12O40 is
of interest because of various reported of its
application as catalyst in organic transformations [20–
25]. To the best of our knowledge, there is no report in
the literature on the use of H4SiW12O40 as catalyst for
the synthesis of octahydroxanthene-1,8-diones.
Octahydroxanthene-1,8-diones are important class
of oxygen heterocycle in which a substituted pyran
ring is fused with two cyclohexenone rings [6]. Some
procedures have been reported for the synthesis of
octahydroxanthene-1,8-dione derivatives, employing
dimedone and aldehydes in the presence of a variety of
catalysts such as SbCl3/SiO2 [7], HClO4/SiO2 [8], silica
chloride [9], FeCl3/SiO2 [10], silica sulfuric acid [11],
Dowex-50w [12], Amberlyst-15 [13], [bmim][TFA]
[14], and TMSCl [15]. However, the reported methods
suffer from drawbacks such as long reaction times,
moderate yields, the use of toxic reagents, formation of
by-products, and no agreement with the green
chemistry protocols [16]. All of these disadvantages
make further improvement of the synthesis of such
molecules essential. Therefore, the development of a
new greener and more convenient method using a new
readily available catalyst with high catalytic activity
for the synthesis of octahydroxanthene-1,8-diones is
highly desirable.
As a result of our interest in the synthesis of hetero-
cyclic compounds [26–29], and as a part of our re-
search on the development of environmentally friendly
methods for synthesis of organic compounds using
reusable catalysts [30–37], we report here the first
application of H4SiW12O40 as a catalyst for the efficient
solvent-free synthesis of octahydroxanthene-1,8-diones
(Scheme 1).
To optimize the reaction conditions, a selected
model reaction was carried out with dimedone 1 and 4-
chlorobenzaldehyde 3d, taken in a 2 : 1 molar ratio,
1 The text was submitted by the authors in English.
1132

NEAT SYNTHESIS OF OCTAHYDROXANTHENE-1,8-DIONES
1133
Scheme 1.
O
R
O
O
O
H4SiW12O40
+
R
H
Solvent-free
100°C
O
O
1
2a−2n
3a−3n
R = C6H5 (a), 4-BrC6H4 (b), 2-ClC6H4 (c), 4-ClC6H4 (d), 3-HOC6H4 (e), 4-HOC6H4 (f), 4-MeOC6H4 (g), 4-MeC6H4 (h),
3-O2NC6H4 (i), 4-O2NC6H4 (j), 2-thienyl (k), 2-pyridyl (l), Et (m), n-Pr (n).
under different sets of reaction conditions. The results
are summarized in Table 1. As seen in this table, no
product was observed, when the reaction was carried
out under solvent- free conditions without any catalyst,
even after a long reaction time (entry 1). Varying the
percentage of the catalyst showed that 5 mol % of
H4SiW12O40 was sufficient to push the reaction to
completion within 20 min (entry 15). The H4SiW12O40-
catalyzed reaction was evaluated in various solvents
and under solvent-free conditions. The product yield in
refluxing H2O, MeOH or CHCl3 was low, even after
prolonged reaction time (entries 19–21), whereas
relatively good yields were obtained in refluxing EtOH
or CH2Cl2 (entries 22 and 23). However, the best
results in terms of yield, as well as, reaction time, were
obtained under solvent-free conditions (entry 15). The
optimum reaction temperature was found to be 100°C
(entry 15).
To show the generality of this model reaction, a
range of octahydroxanthene-1,8-diones were prepared
by the reaction of dimedone and different aromatic and
aliphatic aldehydes under optimized reaction condi-
tions. The results which are presented in Table 2, show
that the reactions with different aromatic aldehydes
with both electrona-acceptor and electron-donor sub-
stituents all provide high product yields. At the same
time, the yields with aliphatic aldehydes are moderate.
To demonstrate the merits of the developed
methodology, we compared our results with those
obtained with the other catalysts reported for the
synthesis of octahydroxanthene-1,8-diones. As shown
a
Table 1. Optimization of reaction conditions for synthesis of compound 3d, catalyzed by H4SiW12O40
Entry Catalyst,
Time,
min
Entry Catalyst,
Time,
min
Solvent
T, °C
Yieldb, %
Solvent
T, °C
Yieldb, %
no.
mol %
no.
13
14
15
16
17
18
19
20
21
22
23
mol %
1
–
1
1
1
1
2
2
2
2
4
4
4
–
–
–
–
–
–
–
–
–
–
–
–
120
90
120
30
30
20
20
30
25
20
20
30
25
20
–
4
5
5
5
5
7
5
5
5
5
5
–
120
90
25
30
94
92
99
98
97
98
25
27
15
80
73
2
75
85
86
88
79
86
88
90
87
91
93
–
–
3
100
110
120
90
100
20
4
–
110
20
5
–
120
20
6
–
100
20
7
100
110
120
90
H2O
MeOH
CHCl3
EtOH
Reflux
Reflux
Reflux
Reflux
180
120
240
120
240
8
9
10
11
12
100
CH2Cl2 Reflux
110
a Reaction conditions: dimedone (2 mmol), and 4-chlorobenzaldehyde (1 mmol). b Isolated yields.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 5 2016

1134
DAVOODNIA et al.
Table 2. Synthesis of octahydroxanthene-1,8-diones 3a–3n,
catalyzed by H4SiW12O40
We also used our optimized reaction conditions to
evaluate the reusability of the catalyst H4SiW12O40. To
this end, we used as a model, the synthesis of
compound 3d. After completion of the reaction, the
catalyst was recovered from the reaction mixture
according to the procedure outlined in the
experimental section. It was found that the catalyst
could be used at least five times with only a slight
reduction in its activity. In the first experiment, the
yield of the product 3d was found to be 99%, and the
yields in the next experiments were 98, 98, 97, and
96%, respectively. Furthermore, the evidence showing
that the catalyst retains its structure was obtained from
a comparison of the FTIR spectra of the recovered
catalyst after the 5th run (see figure, curve 2) with that
of the fresh catalyst (see figure, curve 1) for the model
reaction. As seen, the spectra are almost identical.
a
Comp. Time, Yieldb,
mp, ºC
no
min
%
found
reported
3a
3b
3c
3d
3e
3f
25
30
20
20
30
25
20
25
30
25
40
35
40
40
95
97
91
99
88
91
96
91
89
90
88
90
55
65
205–207
244–246
233–234
234–236
225–227
250–251
245–247
212–214
168–170
227–229
158–160
199–201
143–145
128–130
203–205 [38]
240–242 [39]
230–232 [38]
230–232 [39]
223–225 [40]
249–251 [41]
244–246 [41]
214–215 [38]
165–166 [40]
224–226 [42]
163–164 [43]
204–205 [43]
[44]
3g
3h
3i
3j
In conclusion, we describe an efficient procedure
for the preparation of octahydroxanthene-1,8-diones by
the reaction of dimedone and different aldehydes in the
presence of a catalytic amount of H4SiW12O40 under
solvent-free conditions. This procedure offers several
advantages, including clean reactions, high yields, low
cost of the catalyst, and environmentally friendly
medium, as well as, the ease of accomplishment which
makes it a useful and attractive protocol for the
synthesis of octahydroxanthene-1,8-diones. The
catalyst can be recycled after simple handling and it
could be used at least five times without any
substantial reduction in its catalytic activity.
3k
3l
3m
3n
[44]
a
Reaction conditions: dimedone 1 (2 mmol), an aldehyde 2 (1 mmol),
H4SiW12O40 (0.05 mmol, 5 mol % based on aldehyde), 100ºC,
solvent-free. b Isolated yields.
in Table 3, the present method offers more suitable
conditions and gives higher yields of the target products.
EXPERIMENTAL
2
1
All of the chemicals were purchased from Merck
and Aldrich and used without purification. The IR
spectra were obtained using a Tensor 27 Bruker
1
spectrophotometer in KBr disks. The H NMR spectra
were recorded at 400 and 500 MHz on Bruker 400 and
Bruker 500 spectrometers. The melting points were
measured on a Stuart SMP3 melting point apparatus.
General procedure for the synthesis of
octahydroxanthene-1,8-diones 3a–3n. To a mixture
of dimedone 1 (2 mmol), and an aldehyde 2 (1 mmol)
in a round-bottom flask, H4SiW12O40 (0.05 mmol,
5 mol % based on aldehyde) was added. The mixture
was heated on an oil bath at 100°C for 20–40 min. The
reaction progress was monitored by TLC. Upon
completion, the reaction mixture was cooled down to
room temperature, and cold ethanol was added. The
precipitated product was filtered off and recrystallized
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber, cm–1
FTIR spectra of (1) the fresh H4SiW12O40 catalyst and
(2) the catalyst recovered after the 5 run for the model
synthesis of compound 3d.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 5 2016

NEAT SYNTHESIS OF OCTAHYDROXANTHENE-1,8-DIONES
1135
Table 3. Comparison of the efficiency of various catalysts in the synthesis of octahydroxanthene-1,8-diones
Conditions
Yield,
%
Catalyst
Time, min
References
solvent
T, ºC
Reflux
Reflux
80
Trimethylsilyl chloride
Fe3+-Montmorillonite
Hydrotrope
CH3CN
480–600
360
72–84
84–96
80–92
82–96
[39]
[41]
[45]
[46]
[42]
[47]
[48]
[49]
[43]
[40]
[44]
[38]
EtOH
H2O
60–90
180
Silica-supported preyssler nanoparticles
p-Dodecylbenzenesulfonic acid
Dowex-50W
H2O
Reflux
H2O or EtOH
25–30 60–180 (ultrasound irradiation) 63–94
–
100
Reflux
110
150–300
360
78–91
73–84
94–95
87–95
85–95
65–90
20–98
Polyaniline-p-toluenesulfonate salt
Cellulose sulfonic acid
Cyanuric
H2O
–
300–360
40–70
40–80
360
–
120
SbCl3/SiO2
–
120
L-Proline
ClCH2CH2Cl
60
SmCl3
–
–
120
480–1440
20–40
H4SiW12O40
100
88–99 This work
from ethanol to give compounds 3a–3n in high yields.
The filtrate was evaporated to dryness under reduced
pressure. The solid catalyst was collected, dried at 80°
C under vacuum and reused for the same experiment.
All the products were characterized according to
comparison of their melting points with those of authe-
ntic samples. The structures of some products were
also confirmed by their IR and 1H NMR spectral data.
(400 MHz, CDCl3), δ, ppm: 0.99 s (6H, 2CH3), 1.12 s
(6H, 2CH3), 2.17 d (J = 16.0 Hz, 2H, CH2), 2.26 d (J =
16.0 Hz, 2H, CH2), 2.50 s (4H, 2CH2), 4.83 s (1H,
CH), 7.48 d (J = 8.0 Hz, 2H, Harom), 8.10 d (J = 8.0 Hz,
2H, Harom). IR spectrum (KBr disc), νmax, cm–1: 2959,
2870, 1663, 1515, 1361, 1201, 1166, 1139, 868.
ACKNOWLEDGMENTS
9-(4-Bromophenyl)-3,3,3,3-tetramethyloctahyd-
roxanthene-1,8-dione (3b). 1H NMR spectrum
(400 MHz, CDCl3), δ, ppm: 0.99 s (6H, 2CH3), 1.11 s
(6H, 2CH3), 2.17 d (J = 16.0 Hz, 2H, CH2), 2.24 d (J =
16.0 Hz, 2H, CH2), 2.46 s (4H, 2CH2), 4.70 s (1H,
CH), 7.18 d (J = 8.0 Hz, 2H, Harom), 7.34 d (J = 8.0 Hz,
2H, Harom). IR spectrum (KBr disc), νmax, cm–1: 2964,
2875, 1661, 1469, 1361, 1198, 1166, 1089, 844.
The authors express their gratitude to the Islamic
Azad University, Mashhad Branch for its financial
support.
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