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Solvent-Free Preparation of 1,8-Dioxo-Octahydroxanthenes Employing Iron Oxide Nanomaterials

Fatemeh Rajabi
Mohammad Abdollahi
Elham Sadat Diarjani
Mikhail G. Osmolowsky
Olga M. Osmolovskaya
Paulette Gómez-López
Alain R. Puente-Santiago
4 and
Rafael Luque
Department of Science, Payame Noor University, Tehran 19569, Iran
Department of Chemistry, University of Guilan, Rasht 1914, Iran
Institute of Chemistry, Saint-Petersburg State University, Saint-Petersburg 198504, Russia
Department of Organic Chemistry, University of Cordoba, Campus de Rabanales, Edificio Marie Curie (C-3), Ctra Nnal IV-A, Km 396, E14014 Cordoba, Spain
Peoples Friendship University of Russia (RUDN University), 6 Miklukho Maklaya str., 117198 Moscow, Russia
Author to whom correspondence should be addressed.
Materials 2019, 12(15), 2386;
Submission received: 7 June 2019 / Revised: 12 July 2019 / Accepted: 19 July 2019 / Published: 26 July 2019


In this study, 1,8-dioxo-octahydroxanthenes were prepared employing a simple, effective and environmentally sound approach utilizing an iron oxide nanocatalyst under solventless conditions. The proposed iron oxide nanomaterial exhibited high product yields, short reaction times and a facile work-up procedure. The synthesized catalyst was also found to be highly stable and reusable under the investigated conditions (up to twelve consecutive cycles) without any significant loss in its catalytic activity.

1. Introduction

All the natural reactions have at least one catalyst to improve its performance. Nowadays, catalysis is considered as a fundamental pillar in chemistry. Due to the needs of selecting environmentally friendly catalysts to reduce cost issues of the chemical industry [1], the selection of green catalysts has become a key challenge in modern society. Nanocatalysis is an emerging field in catalytic organic transformations. A number of chemical reactions employ nanocatalytic systems due to the larger surface area of nanoparticles compared to their bulk counterparts, giving rise to numerous catalytically active sites which lead the chemical transformations of the adsorbed reactive molecules. For these reasons nanoparticles are considered as suitable heterogeneous catalysts for a wide range of reaction.
Xanthene’s heterocycles and derivatives constitute a relevant type of natural products, featuring relevant biological activities including anti-depressants and antimalarial agents [2], anti-inflammatory [3], antiviral [4], antibacterial [5], and photosensitizers in photodynamic therapy [6]. Xanthene derivatives have also shown interesting properties for fluorescent materials [7], pigments and cosmetics [8] and have been used in biodegradable agrochemicals [9,10] and laser technologies [11].
In recent years, several strategies were disclosed for xanthenes and derivatives syntheses such as intra-molecular phenyl–carbonyl coupling reactions [12], trapping of benzynes by phenols [13], cycloacylation reaction of carbamates [14], cyclodehydrations [15], reaction of aryloxymagnesium halides with triethyl orthoformate [16], reaction of β-naphthol with 2-naphthol-1-methanol [17], carbon monoxide [18] and formamide [19].
Xanthene synthesis is catalyzed by many alternative catalysts, such asp-dodecylbenzenesulfonic acid [20], NaHSO4-SiO2 [21], silica sulfuric acid [22], amberlyst-15 [23], InCl3/ionic liquid [24], triethylbenzyl ammonium chloride [25], phosphomolybdic acid supported on silica gel [26], HClO4-SiO2 [27], ZnO and ZnO-acetyl chloride [28], solventless Dowex-50W ion exchange resin protocols [29], SbCl3/SiO2 [30], silica-supported H14[NaP5W30O110] nanoparticles [31], SiO2–R–SO3H [32], H3PW12O40 supported MCM-41 [33], DABCO–bromine [34], cyanuric chloride [35], TMSCl [36], ZrO(OTf)2 [37] and [Et3N–SO3H]Cl [38]. Other methods have also been documented for such syntheses [39,40,41,42,43], which have disadvantages including the utilization of toxic and/or costly reagents/catalysts/organic solvents, prolonged times of reaction, formation of undesirable or toxic by-products, lack of thermal stability of the reagents and low yields. To overcome the mentioned drawbacks and the growing environmental issues, more effective, practical and benign protocols for xanthenes synthesis and their derivatives represent a promising strategy.
Herein, we report on an evaluation of the catalytic activity of an iron oxide nanomaterial based on SBA-15 (FeNP@SBA-15) as active, stable and recyclable heterogeneous catalysts for the preparation of 1,8-dioxooctahydroxanthene and substituted compounds via solventless reaction between aromatic aldehydes and dimedone (Scheme 1).

2. Materials and Methods

2.1. Synthesis of Iron Oxide Nanocatalyst

A suspension of aminopropyl-functionalized SBA-15 materials (2.35 g, NH2 loading 0.85 mmol g−1) in an excess of absolute MeOH was combined with Salicylaldehyde (2 mmol, 0.244 g). The mixture color became yellow by imine formation in 6 h, after which Fe(NO)3·9H2O, (1 mmol) was added. The resulting mixture was slightly heated for 24 h, followed by formation of metal oxide nanoparticles indicated by the formation of a dark red color in the solution. The final material was filtered off, rinsed with methanol and water until colorless washings and subsequently oven-dried overnight at 80 °C. FeNP@SBA-15 exhibited 620 m2·g−1 of surface area and a pore size of 4.8 nm (5–7 nm iron oxide nanoparticle sizes). Typical Fe3+ bands at BE 714 eV (Fe2p3/2) and 725 eV (Fe2p1/2) were observed by XPS for the synthesized catalyst, with only traces (<1%) of zerovalent Fe.

2.2. Preparation of 1,8-Dioxo-Octahydroxanthenes

The model reaction comprised the multicomponent reaction between an aldehyde (5 mmol), dimedone (10 mmol) and FeNP@SBA-15 (0.165 g, 0.5 mol%). In a typical reaction run, the mixture of the three components was heated at 80 °C under continuous stirring for a certain time. Reaction completion was monitored by TLC, after which the mixture was left to cool down at room temperature, followed by dissolution in dichloromethane (50 mL) and rotary evaporation to yield the final xanthene product (upon recrystallization in ethanol). The catalyst was recovered from the mixture via filtration, washed with hot ethyl acetate, oven-dried and reused in subsequent reaction runs. All products are well known and were fully characterized by IR and NMR.

3. Results and Discussion

The catalytic performance of nanocatalysts is well known to depend on morphology, particle size and structure of nanoparticles [44]. A number of conventional techniques such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and inductively coupled plasma/mass spectrometry (ICP/MS) have been used to study textural and morphological properties of FeNP@SBA-15 catalysts [44].
We have previously reported in our earlier papers about the catalytic performance of FeNP@SBA-15 in various types of organic transformations including oxidation of sulfides to sulfoxides [44], esterification of carboxylic acids [45], oxidation of styrene derivatives [46] and oxidative esterification of alcohols and aldehydes (Table S1) [47]. The results of the mentioned reports confirmed the high catalytic activities of supported FeNP in different conditions.
To ascertain the optimum amount of FeNP@SBA-15 to use and select optimum synthetic conditions, a model reaction was selected based on the use of benzaldehyde and dimedone as reagents. As seen in Table 1, entry 1, 3,3,6,6-tetramethyl-9-phenyl-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione was only obtained in poor yields in the absence of FeNP@SBA-15 at 100 °C or higher temperatures.
According to the experimental results above, the efficiency of the FeNP@SBA-15 was initially found to be influenced by both the amount of the catalyst and the solvent nature. Results under solventless conditions provided improved catalytic performance of FeNP@SBA-15 (Table 1, entries 1, 6–17). By adding a small amount of FeNP@SBA-15 to the model reaction mixture, the rate of reaction was dramatically accelerated under solventless conditions, leading to completion within 30 min (Table 1, entry 16). Under such optimized results, the scope of the reaction was further investigated for the preparation xanthene derivatives using a variety of substituted benzaldehydes.
Table 2 shows that this system can be easily applied to various structurally different benzaldehyde containing electron-releasing or withdrawing group. The results of the optimized reaction in Table 2 shows that rates of reaction can be affected by different substituents in the aromatic rings. It is obvious that electron-withdrawing groups improved both yield and the rate of reaction through the activation of aromatic rings (Table 2, entries 2–4). On the other hand, the presence of electron-donating groups led to slower reaction rates (and reduced yields) as compared to electron-withdrawing groups (Table 2, entries 8 and 9).
The efficiency of FeNP@SBA-15 as catalyst in the proposed synthesis was further compared with a range of literature reported data for the same chemistries (Table 3) [48,49,50,51,52,53,54,55]. Results demonstrated that our method can provide excellent yields at moderate times of reaction with respect to reported procedures.
Furthermore, the stability of the Fe-containing catalyst under the investigated reaction conditions was subsequently explored under optimized conditions. As Table 4 indicates, iron nanoparticles supported on SBA-15 could be recycled and reused twelve times without any appreciable reduction in catalytic activity. No iron leaching was detected in solution (<0.01 ppm, ICP-AES analysis), strongly supporting the stability of the proposed system under the optimized reaction conditions.
Figure 1 also depicts a uniform distribution of particle sizes, which can also be observed in the used catalysts, and the high activity of catalysts is preserved well for up to ten runs.
The reaction mechanism is shown in Scheme 2 in which the acidity of the Fe-containing material plays a key role in activating the carbonyl group in the first step as well as in the generated intermediate to close the catalytic circle (Scheme 2), generating the xanthene derivatives via final dehydration at 80 °C. A similar reaction mechanism based on similar acid–base carbonyl activation reactions has been recently described for Cirujano et al. using acidic H-USY or Al-MCM supports of metal oxide nanoparticles [56].

4. Conclusions

The solventless preparation of 1,8-dioxo-octahydroxanthenes from aromatic aldehydes and dimedone was successfully accomplished employing supported iron oxide nanocatalyst. The proposed catalytic system was found to be highly stable and reusable (up to 12 times), recovered by using simple filtration, without any activity loss. Effectiveness, generality, less reaction time, high yields, low catalyst loading, simplicity and easy work-up procedure as well as the benefits of neat reaction conditions are promising points for the presented methodology.

Supplementary Materials

The following are available online at, Table S1: Selected spectroscopic data.

Author Contributions

M.A. and E.S.D. conducted all experimental work. F.R., M.G.O. and R.L. supervised, discussed, edited and revised the manuscript, O.M.O., P.G.-L. and A.R.P.-S. wrote original manuscript.


F.R. is grateful to Payame Noor University and Iran National Science Foundation (INSF) for the support of this work. The publication has been prepared with support from RUDN University Program 5-100.

Conflicts of Interest

The authors declare no conflict of interest.


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Scheme 1. Schematic illustration of the solventless multicomponent synthesis of xantheses catalyzed by FeNP@SBA-15.
Scheme 1. Schematic illustration of the solventless multicomponent synthesis of xantheses catalyzed by FeNP@SBA-15.
Materials 12 02386 sch001
Figure 1. Transmission electron microscopy image of spent FeNP@SBA-15 (after 10 runs).
Figure 1. Transmission electron microscopy image of spent FeNP@SBA-15 (after 10 runs).
Materials 12 02386 g001
Scheme 2. Reaction mechanism for the proposed xanthene syntheses.
Scheme 2. Reaction mechanism for the proposed xanthene syntheses.
Materials 12 02386 sch002
Table 1. Optimization of synthetic conditions for the synthesis of xanthenes a.
Table 1. Optimization of synthetic conditions for the synthesis of xanthenes a.
EntryCatalyst (mol%)SolventTemperature (°C)Time (min)Yield 3a (%) b
a Reaction conditions: dimedone (2 mmol), benzaldehyde (1 mmol); b Isolated yields.
Table 2. Preparation of 1,8-dioxo-octahydroxanthenea derivatives using Fe@SBA-15 as catalyst.
Table 2. Preparation of 1,8-dioxo-octahydroxanthenea derivatives using Fe@SBA-15 as catalyst.
EntryAldehydeTime (min)Yield (%) aMP (°C)Literature MPRef.
Reaction conditions: dimedone (2 mmol), aldehyde (1 mmol), 0.001 mmol catalyst, 80 °C; a Isolated yield.
Table 3. Comparative performance of FeNP@SBA-15 with literature reported catalytic systems.
Table 3. Comparative performance of FeNP@SBA-15 with literature reported catalytic systems.
EntryCatalystCatalyst Loading (mol%)T (°C)Time (min)Yield (%)Ref.
1FeNP@SBA-150.1803099This study
2Silica-Supported Preyssler nanoparticles0.5Reflux3 h93[30]
5Fe2(SO4)3·7H2O101201.5 h86[52]
6p-Toluene Sulfonic Acid30803099[53]
7CuS quantum dots0.006 gr80695[55]
Table 4. Reuses of the supported FeNP catalyst in the reaction of benzaldehyde with dimedone.
Table 4. Reuses of the supported FeNP catalyst in the reaction of benzaldehyde with dimedone.
Run No. a123456789101112
Yield (%) b999999999898989797969492
a Reaction conditions: benzaldehyde (5.0 mmol) and dimedone (10.0 mmol), supported FeNP@SBA-15 (0.005 mmol, 0.167g) at 80 °C for 30 min; b Isolated yields.

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Rajabi, F.; Abdollahi, M.; Diarjani, E.S.; Osmolowsky, M.G.; Osmolovskaya, O.M.; Gómez-López, P.; Puente-Santiago, A.R.; Luque, R. Solvent-Free Preparation of 1,8-Dioxo-Octahydroxanthenes Employing Iron Oxide Nanomaterials. Materials 2019, 12, 2386.

AMA Style

Rajabi F, Abdollahi M, Diarjani ES, Osmolowsky MG, Osmolovskaya OM, Gómez-López P, Puente-Santiago AR, Luque R. Solvent-Free Preparation of 1,8-Dioxo-Octahydroxanthenes Employing Iron Oxide Nanomaterials. Materials. 2019; 12(15):2386.

Chicago/Turabian Style

Rajabi, Fatemeh, Mohammad Abdollahi, Elham Sadat Diarjani, Mikhail G. Osmolowsky, Olga M. Osmolovskaya, Paulette Gómez-López, Alain R. Puente-Santiago, and Rafael Luque. 2019. "Solvent-Free Preparation of 1,8-Dioxo-Octahydroxanthenes Employing Iron Oxide Nanomaterials" Materials 12, no. 15: 2386.

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