Solvent-free and One-pot Facile Synthesis of 12-aryl-tetrahydrobenzo[α]xanthene-11-one Derivatives Promoted by Manganese (IV) oxide as Efficient Catalyst

Farzaneh Mohamadpour*

Young Researchers and Elite Club, Islamic Azad University, Shiraz, Iran

*Corresponding Author:
Farzaneh Mohamadpour
Young Researchers and Elite Club, Shiraz
Branch, Islamic Azad University, Shiraz, Iran.
Tel: +98-71-36191542
Fax: +98-71-36191542
E-mail: Mohamadpour.f.7@gmail.com

Received date: August 10, 2017; Accepted date: August 22, 2017; Published date: August 29, 2017

Citation: Mohamadpour F (2017) Solventfree and One-pot Facile Synthesis of 12-aryl-tetrahydrobenzo[α]xanthene-11-one Derivatives Promoted by Manganese (IV) oxide as Efficient Catalyst. Trends Green Chem. Vofl. 3 No. 1:7. doi: 10.21767/2471-9889.100020

 
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Abstract

One-pot three-condensation synthesis of 12-aryl-tetrahydrobenzo[α]xanthene- 11-one derivatives catalyzed by Manganese (IV) oxide as an efficient, mild and inexpensive catalyst under solvent-free conditions was studied. The method presented is a safe and eco-friendly approach for the multi-component synthesis of xanthene derivatives with many merits in comparison with other reported results including short reaction times, solvent-free conditions, good to high yields, facile reaction profiles and easy work up.

Keywords

Manganese (IV) oxide; One-pot procedure; 12-aryl-tetrahydrobenzo[α] xanthene-11-one derivatives; Solvent-free conditions; Simple work up

Introduction

Multi-component reactions (MCRs) [1-4] play an important role in combinatorial chemistry with high atom economy due to their ability to synthesize biologically active heterocyclic compounds. Xanthene derivatives possess a variety of pharmaceutical and biological activities. The compounds with xanthene derivatives ring systems are reported as antiplasmodial [5], antiviral [6], anti-inflammatory [7]. Besides, these heterocyclic molecules have been widely used as pH sensitive fluorescent materials for visualization of biomolecules [8,9], laser technology [10,11] and luminescent dyes [12].

In recent decades, a number of methodologies for preparation of these compounds have been reported that is including various catalysts [13-22]. Some of these methodologies have limitations such as difficult work-up, toxic and expensive catalysts, low yields, use of strongly acidic conditions and longtime reactions. Therefore, the development of facile method for the synthesis of xanthene derivatives is of great importance. In continuation of our research work on the synthesis of 12-aryltetrahydrobenzo[ α]xanthene-11-ones, herein we wish to report commercially available Manganese (IV) oxide (MnO2) as inexpensive, readily and mild catalyst, for the one-pot synthesis of 12-aryl-tetrahydrobenzo[α]xanthene-11-one derivatives by means of three-component domino reaction of β-naphthol, aryl aldehyde derivatives and dimedone. Efficient, readily and lowcost catalyst, good to high yields and short reaction times that makes our protocol alternative in comparison to some of the earlier reported methods. Furthermore, one of the source of environmental pollutions is the usage of organic solvents under reflux conditions and the need for column chromatography to purity the products. In this present work, the products were obtained through simple filtering with no need column chromatographic separation.

Experimental Methods

Melting points of all compounds were determined using an Electro thermal 9100 apparatus. Also, nuclear magnetic resonance, 1H NMR spectra were recorded on a Bruker DRX- 400 Avance instruments with CdCl3 as solvents (Figure 1). In this article, all reagents and solvents were purchased from Merck, Fluka and Acros chemical companies were used without further purification.

green-chemistry-products-clearly

Figure 1: The 1H NMR spectra of one of the products clearly indicated the formation of 9,9-dimethyl-12-(4-methoxyphenyl)-8,9,10,12- tetrahydrobenzo[a]xanthen-11-one (4m) in the presence of Manganese (IV) oxide.

General procedure for preparation of 12-aryltetrahydrobenzo[α]xanthene-11-one derivatives (4a-o)

A mixture of β-naphthol (1, 1.0 mmol), aromatic aldehyde derivatives (2, 1.0 mmol), dimedone (3, 1.0 mmol) and MnO2 (20 mol%) was heated at 90°C for appropriate time. After completion of the reaction (by thin layer chromatography TLC) the mixture was cooled to r.t. and ethanol was added and the precipitated was separated with filtration and solid was recrystallized from ethanol to afford the pure products (4a-o).The products have been characterized by melting points and 1H NMR spectroscopy. Spectra data of selected and known product are represented below:

9,9-dimethyl-12-(4-methoxyphenyl)-8,9,10,12-tetrahydrobenzo[a] xanthen-11-one(4m):

image

White solid; Yield: 82%; Melting point (Mp): 201-203°C.

1HNMR (400 MHz, CdCl3): 0.99 (3H, s, CH3), 1.12 (3H, s, CH3), 2.16- 2.35 (2H, m, CH2), 2.58 (2H, s, CH2), 3.71 (3H, s,OCH3), 5.68 (1H, s, CHAr), 6.72 (2H, d, J=8.4 Hz, ArH), 7.21-7.47 (5H, m, ArH), 7.85 (2H, t, J=9.2 Hz, ArH), 8.01 (1H, d, J=8.4 Hz, ArH).

Results and Discussion

Recognizing the solvent free-based processes as eco-friendly methodology for the synthesis of organic compounds, we conceived the preparation of 12-aryl-tetrahydrobenzo[α] xanthene-11-one derivatives from the reaction between β-naphthol (1), aryl aldehyde derivatives (2) and dimedone (3) catalyzed by Manganese (IV) oxide (MnO2) (Scheme 1). In order to determine the optimal reaction conditions, we screened different amounts of MnO2 (5-25 mol%) at range of rt-100°C in the absence of solvent (Table 1) using β-naphthol, benzaldehyde and dimedone as a model reaction. When the amount of MnO2 was increased from 5 to 20 mol%, the yield of product was improved from 32 to 86% (Table 1, entries 2-5). However, when the amount of MnO2 was increased to 25 mol%, a remarkable increase in the yield of the product was not observed (Table 1, entry 12). Consequently, the amount of 20 mol% for MnO2 was selected as the optimized amount of the catalyst for this procedure. The reasonable results were observed when the reaction was performed at 90°C (Table 1, entry 5). The Increment of the temperature up to 100°C (Table 1, entry 11) didn’t significantly improve the reaction results. The efficiency of this protocol was examined by the reaction of a variety of aryl aldehydes with electron-donating and electronwithdrawing groups with β-naphthol and dimedone and the results are summarized in Table 2 (4a-o).

image
Entry MnO2 (mol%) Temperature (°C) Time (min) Isolated Yields (%)
1 Catalyst free 90 360 trace
2 5 90 65 32
3 10 90 35 55
4 15 90 20 74
5 20  90  15 86
6 20 rt 360 trace
7 20 40 90 26
8 20 60 65 43
9 20 70 40 65
10 20 80 20 71
11 20 100 15 87
12 25 90 15 88
aReaction conditions: β-naphthol (1.0 mmol); benzaldehyde (1.0 mmol); dimedone (1.0 mmol) and MnO2 was heated under various temperatures for the appropriate time.  

Table 1: Optimization of the reaction condition for the synthesis of 4aa.

imageEntry R Product Time (min) Isolated
Yields (%)
 Mp (°C)  Literature Mp (°C)
1 C6H5 4a 15 86 147-149 148-150 [17]
2 4-F- C6H4 4b 15 89 182-184 184-185 [13]
3 4-O2N-C6H4 4c 15 87 176-178 175-178 [19]
4 3-O2N-C6H4 4d 10 85 168-170 167-169 [13]
5 4-Br- C6H4 4e 25 77 183-186 184-186 [17]
6 3-Br- C6H4 4f 25 81 164-166 161-164 [19]
7 4-Me- C6H4 4g 15 88 170-172 171-173 [17]
8 3-Me- C6H4 4h 15 91 180-181 178-180 [16]
9 4- Cl-C6H4 4i 25 79 178-180 176-178 [17]
10 3- Cl-C6H4 4j 25 81 179-181 178-180 [22]
11 2- Cl-C6H4 4k 20 83 177-179 179-180 [20]
12 2, 4- Cl2-C6H3 4l 30 76 184-186 183-184 [22]
13 4-OMe- C6H4 4m 20 82 201-203 202-204 [17]
14 2-OMe- C6H4 4n 15 89 167-169 165-167 [22]
15 4-OH- C6H4 4o 25 78 220-222 222-223 [17]

Table 2: MnO2 catalyzed synthesis of 12-aryl-tetrahydrobenzo[α]xanthene-11-ones.

Comparison of catalytic ability some of catalysts reported in the literature for synthesis of 12-aryl-tetrahydrobenzo[α]xanthene- 11-one derivatives are shown in Table 3. This study reveals that MnO2 has shown its extraordinary potential to be an alternative inexpensive, readily and efficient catalyst for the one-pot synthesis of these biologically active heterocyclic compounds, in addition good to high yields and short reaction times under solvent-free conditions are the notable advantages this present methodology.

Entry Catalyst Conditions Time/Yield (%)  References
1 Fe3O4@SiO2-SO3H Solvent-free,110°C  30 min/95 [13]
2 NaHSO4/SiO2 CH2Cl2, Reflux  300 min/91 [14]
3 NO2-FePc/C EtOH, Reflux  30 min/91% [15]
4 DSIMHS Solvent-free,55°C 20 min/93 [17]
5 CAN Microwave irradiation,120°C  120 min/85 [18]
6 Sr(OTf)2 1,2-Dichloroethane,80°C  300 min/85 [21]
7 MnO2 Solvent-free, 90C 15 min/86  This work
aBased on the three-component reaction of β-naphthol (1.0 mmol); benzaldehyde (1.0mmol) and dimedone (1.0 mmol).  

Table 3: Comparison of catalytic ability some of catalysts reported in the literature for synthesis of 12- aryl-tetrahydrobenzo[α]xanthene-11-onesa.

Conclusion

Extremely facile and efficient procedure have been developed for the synthesis of 12-aryl-tetrahydrobenzo[α]xanthene- 11-one derivatives. One-pot three-component reaction of β-naphthol, aromatic aldehyde derivatives and dimedone in the presence of Manganese (IV) oxide (MnO2) as efficient, readily and inexpensive catalyst under solvent-free conditions provides these biologically active heterocyclic compounds. Operational simplicity, inexpensive catalyst, enhanced rates, short reaction times and good to high isolated yields of the pure products are notable advantages of this eco-friendly protocol.

Acknowledgments

We gratefully acknowledge financial support from the Young Researchers and Elite Club, Shiraz Branch, Islamic Azad University of Shiraz.

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