H3PW12O40: An Efficient and Green Catalyst for the Facile and Selective Oxidation of Sulfides to Sulfoxides, Applied to the Last Step of the Synthesis of Omeprazole

Document Type: Research Article

Authors

1 Department of Chemistry, Alzahra University, Tehran, I.R. IRAN

2 Department of Chemistry, School of Science, Alzahra University, Tehran, I.R. IRAN

3 Department of Chemistry, University of Mazandaran, Babolsar, I.R. IRAN

4 Department of Chemistry, Mashhad Branch, Islamic Azad University, Mashhad, I.R. IRAN

Abstract

Omeprazole, (6-methoxy-2-((4-methoxy-3,5-dimethylpyridin-2-yl)methylsulfinyl)-1H-benzimidazole is a well-established prescribed drug, exhibits proton pump inhibitor activity. In this work, a novel, facile, economical and selective oxidation approach using H3PW12O40 as Keggin type heteropolyacids along with H2O2 in the last step of the conventional synthesis of this compound as well as its derivatives under environmental-benign conditions, is reported. This protocol can bewell adopted for pilot plant scale giving a high pure pharmacopeia grade material. Our synthetic route involves the use of various heteropolyacids as heterogeneous catalysts. Due to the obtained results, it was concluded that Keggin type heteropolyacid , is an effective catalyst for this purpose. The optimized condition for the last step of this synthesis was applied to the synthesis of lansoprazole, pantoprazole, and rabeprazole.

Keywords

Main Subjects


[2] Tavish D.M., Buckley M.M., Heel R.C., Omeprazole. An Updated Review of its Pharmacology and Therapeutic Use in Acid-Related Disorders, Drugs, 1: 138-170 (1991).

[3] Shin J.M., Cho Y.M., Sachs G., Chemistry of Covalent Inhibition of the Gastric (H+‏, K+‏)-ATPase by Proton Pump Inhibitors, J. Am. Chem. Soc, 126: 7800–7811 (2004).

[4] Bhalerao D.S., Kondaiah G.M., Dwivedi N., Mylavarappu R.K., Reddy L.A., Roy A., Nagaraju G., Reddy P.P., Bhattacharya A., Bandichhor R., Novel Approach to the Synthesis of Omeprazole: An Antipeptic Ulcer Agent, Synth. Commun., 40: 2983-2987 (2010).

[6] Alminger T., Larsson H., Lindberg P., Sunden G., Novel Pharmacological Compounds, WO Patent No. 87/02668, (1987).

[7] Alminger T., Bergman R., Bundgaard H., Lindberg P., Sunden G., New Benzimidazole Derivatives
A Process for Production thereof and a Pharmaceutical Composition Containg the Same
, WO Patent No. 88/03921, (1988).

[8] Brandstrom A., Lindberg P., Sunden G., Therapeutically Active Fluoro Substituted Benzimidazoles, Processes for their Preparation as Well as their Use, WO Patent No. 91/09028, (1991).

[9] Von Unge S., Novel Ethoxy Carbonyl Oxymethyl Derivatives of Substituted Benzimidazoles, WO Patent No.9532957, (1995).

[10] a) Kowalski P., Mitka K., Kossowska K., Kolarska Z., Oxidation of Sulfides to Sulfoxides. Part 1: Oxidation Using Halogen Derivatives, Tetrahedron, 61: 1933-1953 (2004).

b) Shaabani A., Ganji N., Seyyedhamzeh M., Mofakham H., Cellulose Sulfuric Acid: As an Efficient Bio Polymer Based Catalyst for the Selective Oxidation of Sulfides and Thiols by Hydrogen Peroxide, Iran. J. Chem. Chem. Eng. (IJCCE), 33: 1-7 (2014)

[11] Kaczorowska K., Kolarska Z., Mitka K., Oxidation of Sulfides to Sulfoxides. Part 2: Oxidation by Hydrogen Peroxide, Tetrahedron, 62: 8315-8327 (2005).

[12] Wojaczynska E., Wojaczynski J., Enantioselective Synthesis of Sulfoxides, Chem. Rev., 110: 4303-4356 (2010).

[13] Ahmmed S., Kundu D., Siddiqui M.N., Metal Solvent Free Selective Oxidation of Sulfides to Sulfone Using Bifunctional Ionic Liquid [pmim]IO4, Tetrahedron Lett., 56: 335-337 (2010).

[15] Afrasiabi R., Jalilian F., Yadollahi B., Solvent Free Oxidation of Sulfides to Sulfones by H2O2 in the Presence of Chromium Substituted Polyoxometalate as Catalyst, Inorg. Chem. Commun., 50: 113-116 (2014).

[18] Heravi M.M., Fard M.V., Faghihi Z., Heteropoly Acids-Catalyzed Organic Reactions in Water: Doubly Green Reactions, Green Chem. Lett. Rev., 6: 282-300 (2013).

[19] Heravi M.M., Sadjadi S., Recent Developments in Use of Heteropoly Acids, Their Salts and Polyoxometalates in Organic Synthesis, J. Iran. Chem. Soc., 6: 1-54, (2009).

b) Sadjadi S., Heravi M.M., Recent Advances in Applications of POMs and Their Hybrids in Catalysis, Cur. Org. Chem., 20: 1404-1444 (2016).

c) Heravi M.M., Sodeh S., Hekmatshoar R., Oskooie H.A., Keggin-Type Heteropoly Acids-Catalyzed One Pot Oxidation-Trimerization of Alcohols into 2,4,6-Trisubstituted-1,3,5-Trioxanes, Iran. J. Chem. Chem. Eng. (IJCCE), 28: 131-136 (2009).

[20] Timofeeva M.N., Acid Catalysis by Heteropoly Acids, Appl. Catal. A: General, 256: 19-35 (2003).

[21] Heravi M.M., Sadjadi S., Oskoole, H.A., Hekmatshoar R., Bamoharram F.F., The Synthesis of Coumarin-3-Carboxylic Acids and 3-Acetyl-coumarin Derivatives Using Heteropoly Acids as Heterogeneous and Recyclable Catalysts, Catal. Commun., 9: 470-474 (2008)

b) Heravi, M.M., Sadjadi S.,Hekmatshoar R., Oskooie H.A., Keggin-Type Heteropolyacids-Catalyzed One Pot Oxidation-Trimerization of Alcohols into 2,4,6-Trisubstituted-1,3,5-Trioxanes, Iran. J. Chem. Chem. Eng. (IJCCE), 28:131-136 (2009).

[26] Avrutov I., Mendelovici M., Finkelstein N., Processes for the Production of Substituted 2-(2-Pyridylmethyl) sulfinyl-1H-benzimidazoles, US Patent No. 20040138466, (2004).

[28] Sathicq A.G., Romanelli G.P., Palermo V., Heterocyclic Amine Salts of Keggin Heteropoly Acids Used as Catalyst for the Selective Oxidation of Sulfides to Sulfoxides, Tetrahedron Lett., 49: 1441-1444 (2008).

[29] Palermo V., Sathicq A.G., Vazquez P.G., Selective Oxidation of Sulfides to Sulfoxides Using Modified Keggin Heteropoly Acids as Catalyst, Phosphorus, Sulfur, Silicon Relat. Elem., 189: 1423-1432 (2014).

[30] Heravi M.M., Sadjadi S., Haj N.M., Oskooie H.A., Bamoharram F.F., Role of Various Heteropolyacids in the Reaction of 4-Hydroxycoumarin, Aldehydes and Ethylcyanoacetate, Catal. Commun., 10: 1643-1664 (2006).

[31] Sadjad, S., Heravi M.M., Recent Advances in Applications of POMs and Their Hybrids in Catalysis, Current Org. Chem., 20: 1404-1444 (2016).

[33] Matsuishi N., Takeda H., Iizumi K., Murakami K., Hisamitsu A., Imidazo[4,5-b] pyridine Compounds, Process for Preparing Same and Pharmaceutical Compositions Containing Same, EP Patent No.0254588 A1, (1988)

[36] Hekmatshoar R., Sajadi S., Heravi M.M., H14[NaP5W30O110] as a Heterogeneous Recyclable Catalyst for the air Oxidation of Thiols under Solvent Free Conditions, Molecules, 12: 2223-2228 (2007).

[37] Lefebvre F., Liu-Cai F.X., Auroux A., Microcalorimetric Study of the Acidity of Tungstic Heteropolyanions, J. Mater. Chem., 4: 125-131 (1994).

[38] Kozhevnikov I.V., Advances in Catalysis by Heteropoly Acid, Russ. Chem. Rev., 56: 811–825 (1987).

[39] Misono M., Heterogeneous Catalysis by Heteropoly Compounds of Molybdenum and Tungsten, Catal. Rev. Sci. Eng., 29: 269-321 (1987).