Silica-supported preyssler nanoparticles catalyzed simple and efficient one-pot synthesis of 1,8-dioxodecahydroacridines in aqueous media

Article abstract of DOI:10.1080/15533174.2011.609221

Silica-supported Preyssler nanoparticles (SPNP) was found to be an inexpensive and effective catalyst for the rapid, one-pot three-component synthesis of N-substituted 1,8-dioxodecahydroacridines in high yields, with easy workup procedure. The nanocatalys

Full text of DOI:10.1080/15533174.2011.609221

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Silica-Supported Preyssler Nanoparticles Catalyzed
Simple and Efficient One-Pot Synthesis of 1,8-
Dioxodecahydroacridines in Aqueous Media
a
b
c
b
Ali Javid , Amir Khojastehnezhad , Majid Heravi & Fatemeh F. Bamoharram
a
Department of Chemistry, Ahvaz-Branch, Islamic Azad University, Ahvaz, I. R. Iran
Department of Chemistry, Mashhad-Branch, Islamic Azad University, Mashhad, I. R. Iran
Department of Chemistry, Alzahra University, Vanak, Tehran, I. R. Iran
b
c
Version of record first published: 31 Jan 2012.
To cite this article: Ali Javid , Amir Khojastehnezhad , Majid Heravi & Fatemeh F. Bamoharram (2012): Silica-Supported
Preyssler Nanoparticles Catalyzed Simple and Efficient One-Pot Synthesis of 1,8-Dioxodecahydroacridines in Aqueous Media,
Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:1, 14-17
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:14–17, 2012
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2011.609221
Silica-Supported Preyssler Nanoparticles Catalyzed Simple
and Efficient One-Pot Synthesis of
1
,8-Dioxodecahydroacridines in Aqueous Media
1
2
3
2
Ali Javid, Amir Khojastehnezhad, Majid Heravi, and Fatemeh F. Bamoharram
1
Department of Chemistry, Ahvaz-Branch, Islamic Azad University, Ahvaz, I. R. Iran
Department of Chemistry, Mashhad-Branch, Islamic Azad University, Mashhad, I. R. Iran
Department of Chemistry, Alzahra University, Vanak, Tehran, I. R. Iran
2
3
condensation of an aldehyde, ethyl acetoacetate, and ammo-
Silica-supported Preyssler nanoparticles (SPNP) was found nia. Further, acridinediones synthesized from aldehydes, dime-
to be an inexpensive and effective catalyst for the rapid, done, and different anilines or ammonium acetate via one-pot
one-pot three-component synthesis of N-substituted 1,8-
multicomponent reaction in the presence of different catalysts
dioxodecahydroacridines in high yields, with easy workup pro-
cedure. The nanocatalyst was easily separated from the reaction
mixture and was recycled a couple of times without any appre-
[16–24]
have been reported in the literature.
However, some of
these methods have limitations such as low yields, long reaction
ciable loss in activity. In addition, water as a green solvent was a times, a cumbersome workup procedure, and generation of pol-
solvent of choice.
luting effluents. Furthermore, most of these methodologies do
not meet the requirement of green chemistry, as most of these
Keywords aqueous media, heteropolyacid, nanocatalyst, 1, 8- reactions tend to use expensive reagents that are difficult to re-
dioxodecahydroacridines, one-pot three-component
reaction
cover and recycle in volatile organic solvents that are a threat to
the environment due to their pyrophoric nature, volatility, and
poor recovery.[ So, a new method is needed for the synthe-
25]
sis of acridinedione derivatives with less waste and more facile
isolation of products, with the ability to recover and reuse the
INTRODUCTION
Xanthene and their derivatives are an important family of
catalysts as well.
organic compounds because they have wide range of biological
Among various solid acids, heteropolyacids (HPAs) have
[
1, 2]
and pharmaceutical properties.
In particular, xanthenediones
specific physical and chemical properties. HPAs have very
strong Brønsted acidity and are several times more active than
constitute a structural unit in a number of natural products,[
3, 4]
and have been used as versatile synthons because of the inherent
[26]
mineral acids. Furthermore, they are capable of protonating
[
5]
reactivity of the inbuilt pyran ring. Acridines belong to xan-
thene derivatives that have a 1,4-dihydropyridine (DHP) ring
skeleton. Substituted acridines have been used as antimalari-
and activating the substrate, and in some cases they are more
effective than usual inorganic acid and the traditional acid cat-
alysts and can improve and reduce reaction time. Therefore,
they are widely used as solid acid catalysts either indirectly
as a bulk material or in supported form in homogeneous and
[
6–10]
als and in cancer chemotherapy.
Also, these derivatives are
[
11]
used in the industry, for the production of dyes. Another role
of acridines is to synthesize labeled conjugates with medici-
nals, peptides, proteins, and nucleic acids that exhibit antitumor
[27]
heterogeneous systems for the synthetic reactions. HPAs are
non-toxic, non-corrosive, very stable toward humidity, air sta-
ble, recyclable, eco-friendly, compatible with green chemistry,
easy to handle, and experimentally simple. Also, they are usu-
[
12–14]
and DNA-binding properties.
The synthesis of xanthene-
diones usually condenses appropriate active methylene carbonyl
compounds with aldehydes. Also, the synthesis of polyfunc-
tionalized DHP derivatives has been studied, in particular the
Hantzsch reaction.[ This method involves a three-component
ally solids that are insoluble in non-polar solvents but highly
[28]
soluble in polar ones.
They can be used in low concen-
15]
trations. Of course, the need for character development and
optimization of catalytic efficiency of heteropolyacids to be
felt. Recently, because of the unique properties of nanoparti-
cles along with their novel properties and potential applications
in different fields, synthetic chemists focused on nanocatalysts.
Therefore, synthesis and characterization of new catalysts with
lower dimensions has become the most interesting topic of
Received 13 May 2011; accepted 26 July 2011.
Address correspondence to Ali Javid, Department of Chemistry,
Ahvaz Branch, Islamic Azad University, Ahvaz, I. R. Iran. E-mail:
alijavids@yahoo.com
14

SILICA-SUPPORTED PREYSSLER NANOPARTICLES
15
O
Ar
O
O
O
SPNP
ArCHO
+
2
+
NH4OAc
H O , reflux
2
N
H
(1a-h)
(2)
(3)
(4a-h)
SCH. 1.
research. We know that as the particle size decreases, the rel- RESULTS AND DISCUSSION
ative number of surface atoms increases and thus the activity
In our continued interest in the development of a highly ex-
increases.[ Moreover, due to quantum size effects, nanometer- pedient methodology for the synthesis of fine chemicals and
29]
sized particles may exhibit unique properties for a wide range of heterocyclic compounds of biological importance by usage of
applications.[
30]
[36–47]
heteropoly and nanoheteropolyacids as catalyst,
we report
Recently, these considerations raised the interest for synthe- here the synthesis of 1,8-dioxodecahydroacridines in the pres-
[
31–33]
sis of Keggin nanocatalysts,
activity of Preyssler nanocatalysts has been largely overlooked. at reflux condition (Scheme 1).
For this reason, we have reported the synthesis and characteri-
We propose the possible following mechanism to account
for the reaction (Scheme 2). As can be seen, reaction proceeds
but the synthesis and catalytic ence of SPNP as an acidic catalyst, in water as a green solvent
zation of silica-supported Preyssler nanoparticles (SPNP).[
34]
A
Preyssler acid is a highly acidic catalyst from heteropolyacid via one-pot Knoevenagel condensation, Michael addition, and
family with excellent catalytic activity in a variety of acid- cyclodehydration. We think that acid catalysts such as HPAs
[
35]
catalyzed reactions.
Therefore, we hope that to get better might promote the reaction by accelerating the formation of
the behaviors of this catalyst with nanoparticle size in organic enol from the 1,3-dicarbonyls, such as dimedone, in the rate-
reactions and synthesizes. So, in continuation of our work with determining step.
[
36–47]
application of HPA in organic reactions,
in this article we
We first examined the reaction of benzaldehyde (1a), dime-
wish to describe the synthesis of 1,8-dioxodecahydroacridines done (2), and ammonium acetate (3) in the presence of catalytic
by use of SPNP as heterogeneous catalyst under mild reaction amount of several acids. The results are summarized in Table 1.
conditions. The novelty of this work lies in the shorter time
As it is observable, the reaction was carried out when het-
[16–25]
period than in earlier works,
greenness of the used catalyst.
reusable new derivatives, and eropolyacids used as catalyst. Apparently, SPNP acid catalyst
was more effective regarding time consumption and in light of
SCH. 2.

16
A. JAVID ET AL.
TABLE 1
This nanocatalyst also showed excellent reusability in these
Effect of various acid catalysts amount on
reactions. We recycled the catalyst four times without any ap-
preciable loss in activity.
1,8-dioxodecahydroacridines synthesis
Isolated
Time yield (%)
EXPERIMENTAL
Entry
Catalyst
Conditions
(h)
[Ref.]
All chemicals were obtained from Merck Company and used
as received. SPNP were synthesized according to a previous re-
20]
1
2
3
4
5
6
7
8
B(C6F5)3
L-Proline
Zn(OAc)2
H3[PW12O40]
H4[SiW12O40]
H4[PW11VO40]
solvent free
H2O, reflux
H2O, reflux
H2O, reflux
H2O, reflux
H2O, reflux
3.5
3
3
6
8
10
3
2
80[
82[
84[
[34]
port. For synthesis of this catalyst to a solution of surfactant
23]
in cyclohexane (0.2 M), a solution of Preyssler acid in a spec-
ified amount of water was added. The molar ratio of water to
surfactant selected was 3, 5, and 7. Then, tetraethoxysilane was
added into the micro emulsion phase. After mixing for various
times (8, 12, 18, 25, and 30 h) at room temperature, dispersed
Preyssler acid/SiO2 nanostructures were centrifuged (1500 rpm)
and the particles were rinsed with acetone (4 times) and dried
in a vacuum oven. The optimum ratio of water to surfactant was
23]
a
75
67
36
76
a
a
a
H14[NaP5W30O110] H2O, reflux
H2O, reflux
a
SPNP
91
Reaction of benzaldehyde (1 mmol), dimedone (2 mmol), and am-
monium acetate (1 mmol) in presence of different amount of acid
catalysts. Finding reported in the present article.
3:1 and the optimum time was 30 h.
a
Preparation of 1,8-Dioxodecahydroacridines
SPNP catalyst (0.03 mmol) was added to a solution of aro-
yields of reactions in comparison with neat Preyssler, Keggin matic aldehyde (1 mmol), dimedone (2 mmol), and ammonium
heteropolyacids, and other reported catalysts.
acetate (1 mmol) in water (15 mL). The mixture was refluxed
The best ratio of aromatic aldehyde, dimedone, ammonium for 2 h. After completion of the reaction (the progress of the re-
acetate, and SPNP catalyst at mole is 1:2:1:0.03. It is noteworthy action was monitored by TLC), the mixture was cooled and the
that the reactions were completed after about 2 h, and more time solid residue was separated and dissolved in dichloromethane.
did not affect on the reaction process.
The solution was filtered and solid SPNP catalyst was isolated
Also, the effect of various solvents on the rate of the reaction and could be reused (the solvent was evaporated and the crude
◦
was studied (Table 2). As can be seen, ethanol and water were catalyst was washed with diethyl ether and dried at 100 C for
favorable solvents under reflux conditions for this synthesis. 1 h). The organic phase was evaporated and the reaction mix-
But water was chosen because it is acceptable solvent for green ture was recrystallized in ethanol to give pure product. All the
chemistry and environment.
products are known compounds and the spectral properties and
After optimizing the conditions, we next examined the gen- melting points of them matched well with those reported previ-
erality of these conditions to other substrates (aldehydes). The ously.[
16–24]
results are summarized in Table 3. It could be seen that by using
Spectroscopic and physical data of some representative com-
this nanocatalyst, the aromatic aldehydes containing electron- pounds are given subsequently.
donating and electron withdrawing groups afforded the products
3
,3,6,6-tetramethyl-9-(4-bromophenyl)-3,4,6,7,9,10-
with excellent yields.
hexahydroacridine-1,8(2H,5H)-dione (4c)
H NMR (300 MHz, CDCl3) δ: 0.95(s, 6H, 2CH3), 1.06(s,
1
6
7
2
2
H, 2CH3), 2.18–2.37(m, 8H, 4CH2), 5.11(s, 1H, CH),
.13(s, 1H, NH), 7.20(d, J = 8.3 Hz, 2H, Ar), 7.36(d,
H, J = 8.3 Hz, Ar) ppm; IR (KBr) ν: 3394, 3073,
TABLE 2
Effect of various solvents and conditions on
,8-dioxodecahydroacridines synthesis
1
−1
+
949, 1740, 1612 cm ; MS (20 eV) m/z: 429(M +2),
+
Entry
Solvent/Conditions
Time (h)
Isolated yield (%)
427(M ); Anal. Calcd. for C23H26NO2Br: C, 64.49; H,
6
.12; N, 3.27. Found: C, 64.42; H, 6.09; N, 3.35.
1
2
3
4
5
6
Acetonitrile/reflux
Ethyl acetate/reflux
Ethanol/reflux
10
20
3
20
10
2
32
0
92
0
27
91
3
,3,6,6-tetramethyl-9-(3-nitrophenyl)-3,4,6,7,9,10-
hexahydroacridine-1,8(2H,5H)-dione (4f)
H NMR (300 MHz, CDCl3) δ: 0.97(s, 6H, 2CH3), 1.09(s,
1
◦
H2O/25 C
6H, 2CH3), 2.15–2.40(m, 8H, 4CH2), 5.15(s, 1H, CH),
◦
H2O/50 C
7.04(s, 1H, NH), 7.33–8.07(m, 4H, Ar) ppm; IR (KBr)
H2O/reflux
−1
ν: 3356, 3042, 2966, 1742, 1640, 1553, 1358 cm ; MS
+
(20 eV) m/z: 394(M ); Anal. Calcd. for C23H26N2O4:
Reaction of benzaldehyde (1 mmol), dimedone (2 mmol), and am-
monium acetate (1 mmol) in presence of SPNP catalyst (0.03 mmol),
in various solvents (15 mL) and different conditions.
C, 70.03; H, 6.64; N, 7.10. Found: C, 69.63; H, 6.67;
N, 7.24.

SILICA-SUPPORTED PREYSSLER NANOPARTICLES
17
TABLE 3
One-pot synthesis of 1,8-dioxodecahydroacridines in the presence of SPNP as catalyst
Yield (%)a
Mp ( C)
◦
Lit. ( C)
◦
Entry
Aldehyde
Product
1
2
3
4
5
6
7
8
C6H5CHO
4-CH3OC6H4CHO
4-BrC6H4CHO
4a
4b
4c
4d
4e
4f
91
93
88
87
90
85
88
92
191–193
274–276
241–243
>300
279–281
286–288
>300
192 (9)
270 (9)
241 (9)
299 (9)
286 (9)
288 (9)
>300 (9)
269 (9)
4-ClC6H4CHO
4-NO2C6H4CHO
3-NO2C6H4CHO
4-CNC6H4CHO
4-CH3C6H4CHO
4g
4h
274–276
aIsolated yield after 2 h.
CONCLUSION
21. Shen, W.; Wang, L.M.; Tian, H.; Tang, J.; Yu, J.J. J. Fluorine Chem. 2009,
30, 522–527.
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28–241.
3. Balalaie, S.; Chadegani, F.; Darviche, F.; Bijanzadeh, H.R. Chin. J. Chem.
2009, 27, 1953–1956.
1
In conclusion, we have used SPNP as an efficient,
reusable, and green solid acid catalyst for synthesis of 1,8-
dioxodecahydroacridines that were prepared via one-pot three-
component reaction of aryl aldehydes, dimedone, and ammo-
2
2
2
nium acetate in water as green solvent and reflux conditions. Ex- 24. Niknam, K.; Panahi, F.; Saberi, D.; Mohagheghnejad, M. J. Heterocyclic
Chem. 2010, 47, 292–300.
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simplicity of operation, and easy workup are some advantages
of this protocol.
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