0J Nanostruct Chem (2014) 4:110 DOI 10.1007/s40097-014-0110-5
ORIGINAL
BiVO4-NPs as a new and efficient nano-catalyst for the synthesis of 1,8-dioxo-octahydro xanthenes
Amine Shoja • Farhad Shirini • Masoumeh Abedini • Mohammad Ali Zanjanchi
Received: 10 April 2014/Accepted: 27 May 2014
© The Author(s) 2014. This article is published with open access at Springerlink.com
Abstract BiVO4-NPs can be used as a new and efficient nano-catalyst for the promotion of the synthesis of 1,8-dioxo-octahydro xanthenes derivatives. The structures of the products were characterized by their physical properties, comparison with authentic samples and IR, 1H NMR and 13C NMR spectroscopy. Easy preparation of the catalyst, mild reaction conditions, easy work-up procedure, excellent yields and short reaction times are some of the advantages of this work.
Keywords BiVO4-NPs • Nano-particles • 1,8-dioxo-octahydro xanthenes • Aldehyde • Reusable catalyst
Background
Xanthenes and their derivatives have received special attention due to their diverse array of biological activities such as anti-inflammatory, antibacterial and antiviral activities [1-3]. Furthermore, these compounds can be used as leuco dyes [4], in laser technology [5] and pH-sensitive fluorescent materials for the visualization of biomolecular assemblies [6]. Because of their wide range of synthetic, industrial and pharmacological applications, there are
A. Shoja • F. Shirini (&) • M. Abedini • M. A. Zanjanchi Department of Chemistry, College of Science, University of Guilan, P. O. Box 1914, 41335 Rasht, Iran e-mail: shirini@guilan.ac.ir
A. Shoja
e-mail: aminshimi@yahoo.com M. Abedini
e-mail: mabedini@guilan.ac.ir
M. A. Zanjanchi
e-mail: zanjanchi@guilan.ac.ir
Published online: 25 June 2014
several reports in the literature for the synthesis of xan-thene derivatives.
1,8-Dioxo-octahydro xanthene derivatives are among the most important types of xanthenes and for this reason several methods are reported for the synthesis of 1,8-dioxo-octahydro xanthenes using a variety of catalysts and reagents [7-17].
However, these methods suffer from one or more disadvantages such as: long reaction times, low yields, the use of toxic solvents, requirement of excess of reagents/catalysts and harsh reaction conditions. Therefore, it is important to find more efficient catalysts and methods for the synthesis of these types of compounds.
In recent years and because of the unique properties of nano-particles, synthetic chemists focused on the synthesis and characterization of these types of catalysts with lower dimensions named as nano-catalysts [18].
Results and discussion
In recent years, a considerable amount of our research program is focused on the development of new methods and use of new reagents for the synthesis of xanthenes derivatives [19-25]. In continuation of these studies, we have found that BiVO4-NPs as a newly reported reagent [26] is efficiently able to catalyze the synthesis of 1,8-dioxo-octahydro xanthenes. All reactions are performed under mild reaction conditions in good to high yields.
At the first step and to optimize the reaction conditions, the prepared catalyst was used for the promotion of the condensation of benzaldehyde with dimedone, as a model reaction, and compared the effect of different solvents and solvent-free conditions and also the effect of the catalyst load on the reaction yield and time at thermal conditions
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(Table 1). On the basis of these studies, we concluded that the best result can be obtained under the conditions showed in Scheme 1.
Table 1 The effect of different conditions on the model reaction
Entry Conditions
1 EtOH (reflux)
2 H2O (reflux)
3 Solvent-free (60 °C)
4 Solvent-free (100 °C)
5 Solvent-free (120 °C)
6 Solvent-free (120 °C)
BiVO4-NPs Time Conversion (mg) (min) (%)a
20 60 100
20 60 0
20 60 70
20 45 90
20 30 s 100
10 15 80
Reaction conditions: benzaldehyde (1 mmol), dimedone (2 mmol) a GC
O O Ar O
^BiVO4-NPs (20 mg) l'Tï'TÎ'l
+ ArCHO -4—.—^ rJ \] I Lr
r O Solvent-free, 120 oC r^—O^^-^^R
R= Me, H
Scheme 1 Synthesis of 1,8-dioxo-octahydro xanthenes
After optimization of the reaction conditions and to show the general applicability of the method, different types of aromatic aldehydes were subjected to the same reaction under the determined conditions. The obtained results showed that these conversions also were occurred with excellent yields during very short times (Table 2).
It seems that the electronic nature of the functional group on the ring of the aldehyde exerted a slight influence on the reaction time.
A plausible mechanism for the synthesis of 1,8-dioxo-octahydro xanthenes catalyzed by BiVO4-NPs is shown in Scheme 2 [34, 35].
To illustrate the efficiency of the present method, Table 3 compares some of our results obtained from the synthesis of xanthene derivatives with the same results reported by the other groups. This Table clearly shows the applicability and efficiency of the present method. Table 3 also compares the TOF (turnover frequency) of these catalysts in this reaction. As it is clear BiVO4-NPs is superior in terms of TOF to the compared catalysts.
In addition, we decided to study the catalytic activity of the recycled catalyst for the synthesis of xanthenes derivatives. After the separation of the product, the catalyst was
Table 2 Preparation of 1,8-dioxo-octahydro xanthenes in the presence of BiVO4-NPs
Isolated yields
Entry Aldehydes R Time (min) Yield (%)a M.p. (°C) Found Reported
1 C6H5CHO Me 30 s 99 197-198 199-201 [15]
2 4-ClC6H4CHO Me 30 s 99 227-229 229-231 [15]
3 3-ClC6H4CHO Me 30 s 98 186-187 186-187 [15]
4 2-ClC6H4CHO Me 30 s 98 224-225 225-227 [27]
5 4-BrC6H4CHO Me 30 s 97 239-240 240-242 [28]
6 3-BrC6H4CHO Me 30 s 95 281-282 281-283 [21]
7 4-FC6H4CHO Me 30 s 98 259-260 259-262 [21]
8 4-NO2C6H4CHO Me 4 94 223-224 224-226 [15]
9 3-NO2C6H4CHO Me 30 s 96 164-165 164-166 [15]
10 2-NO2C6H4CHO Me 4 93 251-252 251-252 [27]
11 3-MeOC6H4CHO Me 4 95 190-191 192-194 [21]
12 3-MeC6H4CHO Me 5 98 205-206 206-208 [9]
13 Cinnamaldehyde Me 3 90 170-172 172-174 [15]
14 4-Me2NC6H4CHO Me 3 96 220-221 221-223 [29]
15 C6H5CHO H 30 s 99 203-204 203-205 [27]
16 4-ClC6H4CHO H 30 s 99 228-229 229-232 [27]
17 4-BrC6H4CHO H 30 s 97 227-228 229-231 [27]
18 3-BrC6H4CHO H 30 s 95 280-281 281-283 [21]
19 4-NO2C6H4CHO H 30 s 94 263-264 263-265 [23]
20 3-NO2C6H4CHO H 30 s 96 280-281 281-282 [19]
21 2-NO2C6H4CHO H 30 s 96 238-240 238-240 [19]
22 4-OHC6H4CHO H 30 s 98 245-246 245-247 [30]
23 4-MeOC6H4CHO H 6 95 200-201 200-201 [19]
Scheme 2 Proposed mechanism for the synthesis of 1,8-dioxo-octahydro xanthenes catalyzed by BiVO4-NPs
Table 3 Comparison of the results of the reaction of dimedone with 4-ClC6H4CHO using BiVO4-NPs with some of those reported in the literature
Entry Catalyst (mol%) Conditions Time (h) Yield (%) TOF (h-1) Refs.
1 ZrOCl28H2O (10) Solvent-free, 120 °C 0.66 95 14.4 [9]
2 MCM-41-SO3H (5) H2O, 60 °C 1 86 17.2 [12]
3 N-Sulfonic acid poly(4-vinyl pyridinium) chloride (4) Solvent-free, 100 °C 0.05 98 490 [23]
4 1-Butyl-3-methylimidazolium hydrogen sulfate (72) Solvent-free, 80 °C 3.5 95 0.38 [28]
5 Silica sulfuric acid (7.8) Solvent-free, 80 °C 0.5 92 23.6 [31]
6 ZrO(OTf)2 (1) Solvent-free, 90 °C 0.066 94 1,424 [32]
7 Silicabonded N-propyl sulfamic acid (1.02) EtOH, reflux 3 91 29.7 [33]
8 Fe3O4 NPs (10) Solvent-free, 100 °C 0.33 88 26.7 [34]
9 ZnO NPs (10) Solvent-free, 80 °C 0.25 96 38.4 [35]
10 BiVO4-NPs (6.2) Solvent-free, 120 °C 30 s 99 956 This work
washed with acetone and derived at 70 °C. As shown in Fig. 1, BiVO4-NPs can be recycled at least six times without significant decrease in its catalytic activity (Table 2, entry 2).
Conclusion
In conclusion, we have introduced an efficient and convenient approach for the synthesis of 1,8-dioxo-octahydro xanthenes using BiVO4-NPs as a novel nano-catalyst.
This method has several advantages such as: ease of preparation and handling of the catalyst, simplicity and
easy work-up, high reaction rates, excellent yields and effective reusability of the catalyst for several times without considerable decrease in yields.
Methods
General
All chemicals were purchased from Merck or Fluka Chemical Companies. All yields refer to the isolated products. Products were characterized by their physical constants and comparison with authentic samples. The purity
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1 2 3 4 5
Time(min) ■ Isolated yield (%)
Fig. 1 Reusability of BiVO4-NPs in the reaction of 4-chlorobenzal-dehyde with dimedone
determination of the substrates and reaction monitoring were accompanied by TLC using silica gel SIL G/UV 254 plates. The FT-IR spectra were run on a VERTEX 70 Brucker company (Germany). The 1H NMR (300, 400 and 500 MHz) and 13C NMR (100 MHz) were run on a Bruker Avance DPX-400 FT-NMR spectrometer (8 in ppm).
General procedure
Synthesis of 1,8-dioxo-octahydro xanthene derivatives
A mixture of dimedone or cyclohexadione (2 mmol), aldehyde (1 mmol) and BiVO4-NPs (20 mg) was stirred at 120 °C under solvent-free conditions for the appropriate time. After completion of the reaction [monitored by TLC: EtOAc: n-hexane (2:8)], the reaction was cooled to room temperature, ethanol (5 mL) was added and the mixture was filtered. Evaporation of the solvent, followed by recrystallization of the residue from EtOH:H2O (95:5) afforded the pure products in good to high yields. The physical and spectral data of the known compounds were in agreement with those reported in the literature.
Acknowledgments The authors are thankful to the Guilan University Research Council for the partial support of this work.
Open Access This article is distributed under the terms of the Creative Commons Attribution License which permits any use, distribution, and reproduction in any medium, provided the original author(s) and the source are credited.
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