Green Synthesis of Xanthenes: Utilizing Sulfonated Fructose as an Efficient and Eco-friendly Catalyst

Ali Kakeshpour

Department of Chemistry, University of Zabol, Zabol, Iran.

Ashraf Moradi *

Department of Chemistry, University of Zabol, Zabol, Iran.

Farzaneh Moradi

Department of Chemistry, University of Mazandaran, Babolsar, Iran.

*Author to whom correspondence should be addressed.


Abstract

The synthesis of xanthenes has garnered significant attention due to their extensive biological and therapeutic properties, including antibacterial, antiviral, and anti-inflammatory effects. Xanthenes are indispensable in organic synthesis and are also valued for their spectral properties as dyes in laser industries and fluorescent materials for detecting biological molecules. Despite various methods reported for xanthene synthesis, challenges such as low efficiency, lengthy reaction times, high catalyst requirements, and the use of hazardous organic solvents necessitate the development of more sustainable and efficient alternatives.

This study introduces sulfonated fructose as a novel, green catalyst for the condensation reactions of benzaldehyde, 2-naphthol, and dimedone to synthesize tetrahydrobenzo[a]xanthene-11-ones, and aldehyde and 2-naphthol to synthesize 14H-dibenzo[a,j]xanthenes. The sulfonation of fructose enhances its catalytic activity by increasing its acidity, stability, and selectivity, thus providing significant advantages over pure fructose. These include: 1. Higher Catalytic Activity: Enhanced acidity of sulfonated fructose reduces reaction times and increases yields. 2. Greater Stability: Increased stability of the catalyst leads to less degradation and a longer lifespan. 3. Compatibility with Green Chemistry: The use of less toxic and hazardous catalysts aligns with green chemistry principles, reducing environmental pollution. 4. Reduced Need for Toxic Solvents: Reactions can proceed under milder conditions using environmentally friendly solvents like water and ethanol. 5. Improved Selectivity: Sulfonic groups enhance the selectivity of reactions, resulting in fewer by-products and higher purity.

This innovative approach not only improves the efficiency and sustainability of xanthene synthesis but also demonstrates the economic and environmental benefits of using sulfonated fructose. The method offers straightforward operation, reduced costs, shorter reaction times, and easier purification, making it a valuable contribution to the field of green and sustainable chemistry.

Keywords: Agar catalyst, eco-friendly, organic synthesis, fructose sulfonated catalyst, xanthene synthesis, environmentally benign synthesis, biologically active compounds, pharmaceutical compounds


How to Cite

Kakeshpour, A., Moradi, A. and Moradi, F. (2024) “Green Synthesis of Xanthenes: Utilizing Sulfonated Fructose as an Efficient and Eco-friendly Catalyst”, Journal of Pharmaceutical Research International, 36(7), pp. 59–78. doi: 10.9734/jpri/2024/v36i77539.

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References

Jamison, James M et al. Potentiation of the antiviral activity of poly r (AU) by xanthene dyes. Cell Biology International Reports. 1990;14(12):1075-1084‏.

Chibale Kelly et al. Exploring the potential of xanthene derivatives as trypanothione reductase inhibitors and chloroquine potentiating agents. Tetrahedron. 2003; 59(13):2289-2296.

Knight C. Graham, and tracey stephens. xanthene-dye-labelled phosphatidylethanolamines as probes of interfacial ph. studies in phospholipid vesicles. Biochemical Journal. 1989; 258(3):683-687.

Ahmad Mohammad et al. Performance and photostability of xanthene and pyrromethene laser dyes in sol-gel phases. Journal of Physics D: Applied Physics. 2002;35(13):1473‏.

Bhowmik Benoy B, Papia Ganguly. Photophysics of xanthene dyes in surfactant solution. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2005;61(9): 1997-2003.‏

Walter B, Shelley. Fluorescent staining of elastic tissue with Rhodamine B and related xanthene dyes. Journal Histo Chemistry and Ceel Biology. 1969;20:244-249.

Tobita, Hiromi, et al. Extremely facile arene exchange on a ruthenium (II) complex having a novel bis (silyl) chelate ligand (9, 9-dimethylxanthene-4, 5-diyl) bis (dimethylsilyl)(xantsil). Organometallics. 1969;18.11(1999):2058-2060.

Wu Chung-Pu et al. Reversal of chloroquine resistance in plasmodium falciparum by 9H-xanthene derivatives. International Journal of Antimicrobial Agents. 2005;26(2):170-175‏.

Carr Albert A et al. Bis-basic-substituted polycyclic aromatic compounds. A new class of antiviral agents. 7. Bisalkamine esters of 9-oxoxanthene-2, 7-dicarboxylic acid, 3, 6-bis-basic ethers of xanthen-9-one, and 2, 7-bis (aminoacyl) xanthen-9-ones, -xanthenes, and-thioxanthenes. Journal of Medicinal Chemistry. 1976; 19(9):1142-1148‏.

Vartanyan RS. Synthesis and biological activity of uncondensed cyclic derivatives of piperidine. Pharmaceutical Chemistry Journal. 1984;18(11):736-749 .

Marshall PN. The composition of Erythrosins, Fluorescein, Phloxine and Rose Bengal: a study using thin-layer chromatography and solvent extraction. The Histochemical Journal. 1976; 8(1976):487-499.

Rahmati, Abbas. A rapid and efficient method for the synthesis of 14H-dibenzo [α. j] xanthenes, aryl-5H-dibenzo [bi] xanthene-5, 7, 12, 14-(13H)-tetraone and 1, 8-dioxo-octahydroxanthenes by acidic ionic liquid. Chinese Chemical Letters. 2010;21(7):761-764‏.

Jones WM, Marshall DE, Walker PC. The flow of dilute aqueous solutions of macromolecules in various geometries. II. Straight pipes of circular cross-section. Journal of Physics D: Applied Physics. 1976;9(5):735‏.

Das Biswanath et al. An efficient and convenient protocol for the synthesis of novel 12-aryl-or 12-alkyl-8, 9, 10, 12-tetrahydrobenzo [a] xanthen-11-one derivatives. Synlett. 2007;20:3107-3112.‏

Mahdavinia, Gholam Hossein, et al. Ultrasound-promoted greener synthesis of aryl-14-H-dibenzo [a, j] xanthenes catalyzed by NH4H2PO4/SiO2 in water. Ultrasonics Sonochemistry. 2009;16(1):7-10.

CHU, Hui-Yuan et al. Catalytic Synthesis of 14-Alkyl (aryl)-14H-dibenzo [a, j] xanthene Compounds by the H2SO4 loaded coal based activated carbon as solid acid catalyst under solvent-free condition. Chinese Journal of Organic Chemistry. 2009;29(10):1637.‏

Menchen Steven M., et al. Sulfonated diarylrhodamine dyes. U.S. Patent No. 6,583,168. 24 Jun; 2003.

a) Seyyedhamzeh, Mozhdeh, Peiman Mirzaei, Ayoob Bazgir. Solvent-free synthesis of aryl-14H-dibenzo [a, j] xanthenes and 1, 8-dioxo-octahydro-xanthenes using silica sulfuric acid as catalyst." Dyes and Pigments 76.3 (2008): 836-839 b) Shaterian, Hamid Reza, Majid Ghashang, and Asadollah Hassankhani. One-pot synthesis of aryl 14H-dibenzo [a, j] xanthene leuco-dye derivatives.Dyes and Pigments. 2008;76(2):564-568‏.

Wang, Rui-Zhi, Li-Feng Zhang, Zhen-Shui Cui. Iodine-catalyzed synthesis of 12-aryl-8, 9, 10, 12-tetrahydro-benzo [a] xanthen-11-one derivatives via multicomponent reaction. Synthetic Communications®. 2009;39(12):2101-2107.

a) Mishra, Garima, et al. Traditional uses, phytochemistry and pharmacological properties of Moringa oleifera plant: An overview. Der Pharmacia Lettre. 2011;2(3):141-164‏

b) Mishra, Poonam, Sanjay Mishra. Study of antibacterial activity of Ocimum sanctum extract against gram positive and gram negative bacteria. American journal of food technology; 2011.

c) Mishra, Bhuwan B, Vinod K Tiwari. Natural products: An evolving role in future drug discovery. European Journal of Medicinal Chemistry. 2011;46(10):4769-4807.

Bigdeli, Mohammad A, Majid M Heravi, Gholam Hossein Mahdavinia. Silica supported perchloric acid (HClO4-SiO2): A mild, reusable and highly efficient heterogeneous catalyst for the synthesis of 14-aryl or alkyl-14-H-dibenzo [a, j] xanthenes. Journal of Molecular Catalysis A: Chemical. 275.1-2. 2007;25-29‏

a) Hirano, Takashi et al. Controls on the carbon balance of tropical peatlands. Ecosystems. 2009;12:873-887‏.

b) Hirano, Keisuke, Jack R Porter. Asymptotics for statistical treatment rules. Econometrica. 2009;77(5):1683-1701‏.

Mirjalili, Bi Bi Fatemeh, Abdolhamid Bamoniri, Ali Akbari. BF3· SiO2: An efficient alternative for the synthesis of 14-aryl or alkyl-14H-dibenzo [a, j] xanthenes. Tetrahedron Letters. 2008;49(45):6454-6456

Dabiri, Minoo, et al. Eco-friendly and efficient one-pot synthesis of alkyl-or aryl-14H-dibenzo [a, j] xanthenes in water. Bioorganic & Medicinal Chemistry Letters. 2008;18(1):436-438.

Liang HU et al. Analysis of small molecular selenium species in serum samples from mercury-exposed people supplemented with selenium-enriched yeast by anion exchange-inductively coupled plasma mass spectrometry. Chinese Journal of analytical Chemistry. 2011;39(4):466-470‏.

Heravi Majid M et al. On water: Rapid Knoevenagel condensation using sodium pyruvate. Letters in Organic Chemistry. 2006;3(4):297-299‏.

pasha ma, jayashankara vp, ramachandraswamy n. simple and efficient procedure for the one‐pot synthesis of β‐acetamido‐β‐aryl‐propiophenones by molecular iodine–catalyzed tandem reaction. Synthetic Communications. 2007; 37(9):1551-1556.

Cheng Ying et al. Interaction of aryloxychlorocarbenes with acetylenedicarboxylate: Novel formation of polyfunctional butadienes and 8-oxatricyclo [3.2. 1.02. 4] oct-6-enes. The Journal of Organic Chemistry. 2005;70(12):4840-4846.

Jin Tong-Shou et al. Ultrasound-assisted synthesis of 2-amino-2-chromenes with cetyltrimethylammonium bromide in aqueous media. Ultrasonics Sonochemistry. 2004;11(6):393-397.

Shaterian Hamid Reza, Kobra Azizi, Nafiseh Fahimi. Phosphoric acid supported on alumina (H 3 PO 4/Al 2 O 3) as an efficient and reusable catalyst for the one-pot synthesis of benzoxanthene pigments. Research on Chemical Intermediates. 2014;14:1403-1414.

Reddi Mohan Naidu, Kalla, et al. Design, synthesis and antiviral potential of 14-aryl/heteroaryl-14 H-dibenzo [a, j] xanthenes using an efficient polymer-supported catalyst. Molecules. 2012;17(6): 7543-7555.

Kumar Anil, et al. Design, synthesis and antiviral potential of 14-aryl/heteroaryl-14H-dibenzo [a, j] xanthenes using an efficient polymer-supported catalyst. Molecules (Basel, Switzerland). 2012; 17(6):7543-7555.

Sheshmani, Shabnam. Catalytic application of two novel sandwich-type polyoxometalates in synthesis of 14-substituted-14 H-dibenzo [a, j] xanthenes. Journal of Chemical Sciences. 2013;125: 345-351

Moradi, Ashraf, Reza Heydari, Malek Taher Maghsoodlou. Agar: A novel, efficient, and biodegradable catalyst for the one-pot three-component and green synthesis of 2, 3-dihydroquinazolin-4 (1 H)-one, 4 H-pyrimidobenzothiazole and 2-aminobenzothiazolomethylnaphthol derivatives. Research on Chemical Intermediates. 2015;41:7377-7391.

Sahu P, RSC Adv. 2013;3:9854.

(d) PK Sahu, PK Sahu, SK Gupta, DD Agarwal, Ind. Eng. Chem. Res. 2014; 53:2085.

Hazeri N, Maghsoodlou MT, Mir F, Kangani M, Saravani H, Molashahi E. An efficient one-pot three-component synthesis of tetrahydrobenzo [b] pyran and 3, 4-dihydropyrano [c] chromene derivatives using starch solution as catalyst. Chinese Journal of Catalysis. 2014;35(3):391-395.

Kakeshpour Ali, Moradi Ashraf, Maghsoodlou Malek Taher, Moradi Farzaneh. A Novel Efficient and Biodegradable Natural Catalyst and Bio Based Solvents for the Green One Pot Three Component Synthesis of Tetrahydrobenzo[B]pyran and 3,4-Dihydropyrano[C]chromenes. Journal of Pharmaceutical Research International. 2024;36:13-26.

Nandi Ganesh Chandra et al. An efficient one-pot synthesis of tetrahydrobenzo [a] xanthene-11-one and diazabenzo [a] anthracene-9, 11- dione derivatives under solvent free condition. Tetrahedron 2009; 65(34):7129-7134‏.

Sheu Joen‐Rong. Pharmacological effects of rutaecarpine, an alkaloid isolated from Evodia rutaecarpa. Cardiovascular Drug Reviews. 1999;17(3): 237-245.‏

Gao, Shijay, Chen Hsuan Tsai, Ching-Fa Yao. A simple and green approach for the synthesis of tetrahydrobenzo [a]-xanthen-11-one derivatives using tetrabutyl ammonium fluoride in water. Synlett 2009; 06:949-954‏.

a) Zolfigol, Mohammad, Ahmad RezaáMoosavi-Zare. WCl6 as an efficient, heterogeneous and reusable catalyst for the preparation of 14-aryl-14 H-dibenzo [a, j] xanthenes with high TOF. RSC advances 2.9. 2012;3618-3620.

b) Moosavi-Zare, Ahmad Reza, et al. Condensation of 2-naphtol with arylaldehydes using acetic acid functionalized ionic liquids as highly efficient and reusable catalysts. Chinese Journal of Catalysis 35.4. 2014;573-578.

Firouzabadi H, Iranpoor N, Sobhani S, Gassamipour S. Magnesium triflate [Mg(OTf)2] a highly stable, non-hygroscopic and a recyclable catalyst for the high yielding preparation of diethyl α-trimethylsilyloxyphosphonates from diethyl α-hydroxyphosphonates by HMDS under solventless conditions. Journal of Organometallic Chemistry. 2004;689:3197-3202.

Naimi-Jamal MR, Mashkouri S, Sharifi A. An efficient, multicomponent approach for solvent-free synthesis of 2-amino-4H-chromene scaffold. Mol. Divers. 2010; 14:473