A green and efficient process for the synthesis of Benzothiazinones using Phosphate fertilizers MAP, DAP and TSP as heterogeneous catalysts

Abstract

The aim of this work is to prove the efficiency of the Phosphate fertilizers mono-ammonium phosphate (MAP), di-ammonium phosphate (DAP) and triple-super phosphate (TSP) as a “green” heterogeneous catalysts for the synthesis of 2-aryl-2H-benzo[b][1,4]thiazin-3(4H)-ones via the C-S and C-N coupling process of gem-dicyano epoxide with α-aminothiophenol. To optimize the reaction conditions, the synthesis was conducted with a range of solvents, catalyst amounts and catalyst particle sizes. Also, the potential recyclability of the catalysts was confirmed by running the reaction using the recycled catalyst.

Keywords

• Heterogeneous catalyst,phosphate fertilizer,MAP,DAP,TSP

Supporting Institution

University of Ibn Tofail

References

1. 1. Xiong L, Gao C, Shi Y-J, Tao X, Rong J, Liu K-L, et al. Identification of a new series of benzothiazinone derivatives with excellent antitubercular activity and improved pharmacokinetic profiles. RSC Adv. 2018;8(20):11163–11176. DOI: 10.1039/C8RA00720A.
2. 2. Armenise D, Muraglia M, Florio MA, De Laurentis N, Rosato A, Carrieri A, et al. 4H-1, 4-Benzothiazine, Dihydro-1, 4-benzothiazinones and 2-Amino-5-fluorobenzenethiol Derivatives: Design, Synthesis and in vitro Antimicrobial Screening. Arch Pharm (Weinheim). 2012;345(5):407–416. DOI: 10.1002/ardp.201100309.
3. 3. Zhang P, Li S, Gao Y, Lu W, Huang K, Ye D, et al. Novel benzothiazinones (BTOs) as allosteric modulator or substrate competitive inhibitor of glycogen synthase kinase 3β (GSK-3β) with cellular activity of promoting glucose uptake. Bioorg Med Chem Lett. 2014;24(24):5639–5643. DOI: 10.1016/j.bmcl.2014.10.078.
4. 4. Stößel A, Schlenk M, Hinz S, Küppers P, Heer J, Gütschow M, et al. Dual targeting of adenosine A2A receptors and monoamine oxidase B by 4 H-3, 1-benzothiazin-4-ones. J Med Chem. 2013;56(11):4580–4596. DOI: 10.1021/jm400336x.
5. 5. Kumar M, Sharma K, Samarth RM, Kumar A. Synthesis and antioxidant activity of quinolinobenzothiazinones. Eur J Med Chem. 2010;45(10):4467–4472. DOI: 10.1016/j.ejmech.2010.07.006.
6. 6. Borate HB, Maujan SR, Sawargave SP, Chandavarkar MA, Vaiude SR, Joshi VA, et al. Fluconazole analogues containing 2H-1, 4-benzothiazin-3 (4H)-one or 2H-1, 4-benzoxazin-3 (4H)-one moieties, a novel class of anti-Candida agents. Bioorg Med Chem Lett. 2010;20(2):722–725. DOI: 10.1016/j.bmcl.2009.11.071.
7. 7. Kamel MM, Ali HI, Anwar MM, Mohamed NA, Soliman AM. Synthesis, antitumor activity and molecular docking study of novel Sulfonamide-Schiff’s bases, thiazolidinones, benzothiazinones and their C-nucleoside derivatives. Eur J Med Chem. 2010;45(2):572–580. DOI: 10.1016/j.ejmech.2009.10.044.
8. 8. Berwaldt GA, Gouvêa DP, da Silva DS, das Neves AM, Soares MS, Azambuja JH, et al. Synthesis and biological evaluation of benzothiazin-4-ones: a possible new class of acetylcholinesterase inhibitors. J Enzyme Inhib Med Chem. 2019;34(1):197–203. DOI: 10.1080/14756366.2018.1543286.

9. 9. Ghailane T, Balkhmima RA, Ghailane R, Souizi A, Touir R, Touhami ME, et al. Experimental and theoretical studies for mild steel corrosion inhibition in 1 M HCl by two new benzothiazine derivatives. Corros Sci. 2013;76:317–324. DOI: 10.1016/j.corsci.2013.06.052.
10. 10. Willardsen JA, Dudley DA, Cody WL, Chi L, McClanahan TB, Mertz TE, et al. Design, synthesis, and biological activity of potent and selective inhibitors of blood coagulation factor Xa. J Med Chem. 2004;47(16):4089–4099. DOI: 10.1021/jm0497491.
11. 11. Makarenko SV, Kovalenko KS, Vershinina YS, Berestovitskaya VM. One-pot synthesis of substituted 1, 3-benzothiazole and 1, 4-benzothiazinone from dibromonitroacrylates. Russ J Org Chem. 2014;50(1):83–86. DOI: 10.1134/S1070428014010163.
12. 12. Chen D, Wu J, Yang J, Huang L, Xiang Y, Bao W. Cascade syntheses of aza [2, 1-b][1, 3]-benzothiazinone heteropolycyclic compounds from cyclic thiourea catalyzed by Cu (I). Tetrahedron Lett. 2012;53(52):7104–7107. DOI: 10.1016/j.tetlet.2012.10.088.
13. 13. Huang W-S, Xu R, Dodd R, Shakespeare WC. Facile synthesis of 1, 4-benzothiazin-3-ones from Cu-catalyzed coupling of 2-iodoanilines and 2-mercaptoacetate. Tetrahedron Lett. 2013;54(38):5214–5216. DOI: 10.1016/j.tetlet.2013.07.059.
14. 14. Sharifi A, Ansari M, Darabi HR, Abaee MS. Synergistic promoting effect of ball milling and KF–alumina support for the green synthesis of benzothiazinones. Tetrahedron Lett. 2016;57(5):529–532. DOI: 10.1016/j.tetlet.2015.12.078.
15. 15. Ghailane T, Saadouni M, Boukhris S. Regio-controlled synthesis of 1, 4-benzothiazinones. Heterocycles. 2011;83(2):357–363.
16. 16. Bahammou I, Esaady A, Boukhris S, Ghailane R, Habbadi N, Hassikou A, et al. Direct use of mineral fertilizers MAP, DAP, and TSP as heterogeneous catalysts in organic reactions. Mediterr J Chem. 2016;5(6):615–623. DOI: 10.13171/mjc56/01607062219-souizi.
17. 17. Merroun Y, Chehab S, Ghailane T, Boukhris S, Ghailane R, Habbadi N, et al. An effective method to synthesize 2, 3-dihydroquinazolin-4 (1H)-One using phosphate fertilizers (MAP, DAP and TSP) as green heterogeneous catalysts. J Turk Chem Soc Sect Chem. 2018;5(1):303–316.
18. 18. Zimou O, Malek B, Elhallaoui A, Ghailane T, Ghailane R, Boukhris S, et al. Valorization of the Phosphate Fertilizers Catalytic Activity in 1-(Benzothiazolylamino) Methy l-2-Naphthol Derivatives Synthesis. Bull Chem React Eng Catal. 2019;14(2):238. DOI: 10.9767/bcrec.14.2.2976.238-246.