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Heterogeneous catalyst SiO2–LaCl3·7H2O: characterization and microwave-assisted green synthesis of α-aminophosphonates and their antimicrobial activity

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Abstract

Silica-supported lanthanum (III) chloride (SiO2–LaCl3·7H2O) was prepared and characterized by infrared spectroscopy, X-ray diffraction analysis, scanning electron microscope, energy-dispersive X-ray spectroscopy, thermogravimetric analysis and differential thermal analysis techniques. The catalytic activity of this silica-supported lanthanum (III) chloride was investigated in a one-pot three-component Kabachnik-Fields reaction. A library of new α-aminophosphonates was prepared employing various benzothiazole and thiadiazole amines, different substituted aldehydes and diethylphosphite under solvent-free conditions using conventional/microwave methods with good to excellent yields (85–97%). The advantages of this catalyst are that it is environmentally benign, economically inexpensive, and easy to prepare, gives high yields and high purity is less time-consuming, offers easy purification is reusable and enables products to be obtained by simple recrystallization without column chromatography.

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References

  1. Corma A, Garcia A (2003) Lewis acids: from conventional homogeneous to green homogeneous and heterogeneous catalysis. Chem Rev 103:4307–4365

    Article  CAS  Google Scholar 

  2. Narsaiah AV, Nagaiah K (2003) An efficient knoevenagel condensation catalyzed by LaCl3·7H2O in heterogeneous medium. Synthetic Comm 33:3825–3832

    Article  CAS  Google Scholar 

  3. Venkateswarlu Y, Kumar SR, Leelavathi P (2013) Facile and efficient one-pot synthesis of benzimidazoles using lanthanum chloride. Org Med Chem Lett 3:1–8

    Article  Google Scholar 

  4. Shinde AH, Srilaxmi M, Satpathi B, Sharada DS (2014) A highly efficient synthesis of imidazo-fused polyheterocycles via Groebke–Blackburn–Bienayme reaction catalyzed by LaCl3·7H2O. Tetrahedron Lett 55:5915–5920

    Article  CAS  Google Scholar 

  5. Madhava G, Rasheed S, Ramana KV, Subba Rao D, Naresh K, Naga Raju C (2014) LaCl3.7H2O: an efficient catalyst for the synthesis of phosphinates (Michaelis–Arbuzov reaction) under neat conditions and their potential antimicrobial activity. J Chem Sci 126:117–125

    Article  Google Scholar 

  6. Shaik TB, Chennamsetty S, Devineni SR, Shaik NR, Mundla ND, Raj Kumara JP, Chamarthi NR (2014) Catalyst-free green synthesis of urea and thiourea derivatives of tetramethylguanidine (TMG) and evaluation of biological activity. Bul Chem Com 46:724-730.

  7. Phillips MA, Fletterick R, Rutter WJ (1990) Arginine 127 stabilizes the transition state in carboxypeptidase. J Biol Chem 265:20692–20698

    Article  CAS  Google Scholar 

  8. Kalla RMN, Choi JS, Yoo JW, Byeon SJ, Heo MS, Kim I (2014) Synthesis of 2-amino-3-cyano-4H-chromen-4-ylphosphonates and their anticancer properties. Eur J Med Chem 76:61–66

    Article  CAS  Google Scholar 

  9. Atherton FR, Hassal CH, Lambert RW (1986) Synthesis and structure-activity relationships of antibacterial phosphonopeptides incorporating (1-aminoethyl)phosphonic acid and (aminomethyl)phosphonic acid. J Med Chem 29:29–40

    Article  CAS  Google Scholar 

  10. Green D, Patel G, Elgendy S (1993) The facile synthesis of O, O-dialkyl 1-aminoalkanephosphonates. Tetrahedron Lett 34:6917–6920

    Article  CAS  Google Scholar 

  11. Maier L (1990) Organic phosphorus compounds. Synthesis and properties of 1-amino-2-arylethylphosphonic and phosphinic acids as well as phosphine oxides. Phosphorus Sulfur Silicon Relat Elem 53:43–67

    Article  CAS  Google Scholar 

  12. Allen MC, Fuhrer W, Tuck B (1989) Renin inhibitors. Synthesis of transition-state analog inhibitors containing phosphorus acid derivatives at the scissile bond. J Med Chem 32:1652–1666

    Article  CAS  Google Scholar 

  13. Reddy GCS, Rani CR, Reddy MVN, Reddy CS (2014) An elegant microwave assisted one-pot synthesis of di(a-aminophosphonate) pesticides. Arch Pharm Chem Life Sci 347:819–824

    Article  Google Scholar 

  14. Srinivasulu D, Bhaskara Reddy MV, Rajasekhar D, Balaji M, Naga Raju C (2013) Design, synthesis and antimicrobial activity of α-aminophosphonates of quinoline and their molecular docking studies against DNA gyrase A. Lett Drug Des Discov 10:967–976

    Article  CAS  Google Scholar 

  15. Ambica KS, Taneja SC, Hundal MS, Kapoor KK (2008) One-pot synthesis of α-aminophosphonates catalyzed by antimony trichloride adsorbed on alumina. Tetrahedron Lett 49:2208–2212

    Article  CAS  Google Scholar 

  16. Mitragotri SD, Pore DM, Desai UV, Wadgaonkar PP (2008) Sulfamic acid: an efficient and cost-effective solid acid catalyst for the synthesis of α-aminophosphonates at ambient temperature. Catal Commun 9:1822–1826

    Article  CAS  Google Scholar 

  17. Naidu KR, Kumar Reddy KRK, Vinod Kumar Ch, Naga Raju C, Sharma DD (2009) A facile catalyst-free pudovik reaction for the synthesis of α-amino phosphonates. S Afr J Chem 62:185–188

    CAS  Google Scholar 

  18. Veeranarayana Reddy M, Dindulkar SD, Jeong YT (2011) BF3·SiO2-catalyzed one-pot synthesis of α-aminophosphonates in ionic liquid and neat conditions. Tetrahedron Lett 52:4764–4767

    Article  Google Scholar 

  19. Chandrasekhar S, Jaya Prakash S, Jagadeshwar V, Narsihmulu Ch (2001) Three component coupling catalyzed by TaCl5–SiO2: synthesis of α-amino phosphonates. Tetrahedron Lett 42:5561–5563

    Article  CAS  Google Scholar 

  20. Maghsoodlou MT, Khorassani SMH, Heydari R, Hazeri N, Sajadikhah SS, Rostamizadeh M, Keishams L (2010) Silica supported polyphosphoric acid (PPA-SiO2): an efficient and reusable heterogeneous catalyst for the one-pot synthesis of α-amino phosphonates. Turk J Chem 34:565–570

    CAS  Google Scholar 

  21. Maghsoodlou MT, Khorassani SMH, Heydari R, Hazeri N, Sajadikhah SS, Rostamizadeh M (2011) An efficient and simple synthesis of α-amino phosphonates as ‘drug like’ molecules catalyzed by silica-supported perchloric acid (HClO4–SiO2). Arabian J Chem 4:481–485

    Article  CAS  Google Scholar 

  22. Sobhani S, Falatooni ZM, Honarmard M (2014) Synthesis of phosphoric acid supported on magnetic core–shell nanoparticles: a novel recyclable heterogeneous catalyst for Kabachnik-Fields reaction in water. RSC Adv 4:15797–15806

    Article  CAS  Google Scholar 

  23. Subba Rao D, Srinivasulu D, Rajasekhar D, Naga Raju C (2013) CeCl37H2O-SiO2: Catalyst promoted microwave assisted neat synthesis, antifungal and antioxidant activities of α-diaminophosphonates. Chin Chem Lett 24:759–763

    Article  Google Scholar 

  24. Rajasekhar D, Subba Rao D, Srinivasulu D, Naga Raju C, Balaji M (2013) Microwave assisted synthesis of biologically active α-aminophosphonates catalyzed by nano-BF3·SiO2 under solvent-free conditions. Phosphorus Sulfur Silicon Relat Elem 188:1017–1025

    Article  CAS  Google Scholar 

  25. Subba Rao D, Rasheed S, Thaslim Basha SK, Naga Raju C, Naresh K (2013) SiO2/ZnCl2 catalyzed α-aminophosphonates and phosphonated N-(substituted phenyl) sulfonamides of 2-aminothiophene: synthesis and biological evaluation. Der Pharma Chemica 5:61–74

    Google Scholar 

  26. Radha Rani C, Bhatnagar I, Gangireddy CSR, Syama SC, Suresh Reddy C (2013) Green synthesis of α-aminophosphonate derivatives on a solid supported TiO2–SiO2 catalyst and their anticancer activity. Arch Pharm Chem Life Sci 346:667–676

    Article  Google Scholar 

  27. Maghsoodlou MT, Khorassani SMH, Hazeri N, Rostamizadeh M, Sajadikhah SS, Shahkarami Z, Maleki N (2009) An efficient synthesis of α-amino phosphonates using silica sulfuric acid as a heterogeneous catalyst. Heteroat Chem 20:316–318

    Article  CAS  Google Scholar 

  28. Mulla SAR, Pathan MY, Chavan SS, Gample SP, Sarkar D (2014) Highly efficient one-pot multi-component synthesis of α-aminophosphonates and bis-α-aminophosphonates catalyzed by heterogeneous reusable silica supported dodecatungstophosphoric acid (DTP/SiO2) at ambient temperature and their antitubercular evaluation against Mycobacterium Tuberculosis. RSC Adv 4:7666–7672

    Article  CAS  Google Scholar 

  29. Barry AL (1976) The antimicrobial susceptibility test: principle and practices, edsIllus lea and Febiger, Philadelphia, PA USA, p 180

  30. Bauer AW, Kirby WMM, Sherris JC, Turck M (1996) Antibiotic susceptibility testing by a standardized single disk method. Am J Clin Pathol 45:493–496

    Article  Google Scholar 

  31. Sarker SD, Nahar L, Kumarasamy Y (2007) Microtitre plate-based antibacterial assay incorporating resazurin as an indicator of cell growth, and its application in the in vitro antibacterial screening of phytochemicals. Methods 42:321–324

    Article  CAS  Google Scholar 

  32. Ahmed N, Siddiqui ZN (2014) Sulphated silica tungstic acid as a highly efficient and recyclable solid acid catalyst for the synthesis of tetrahydropyrimidines and dihydropyrimidines. J Mol Catal A Chem 387:45–56

    Article  CAS  Google Scholar 

  33. Guo-Cai Z, Fu-ping L, Ming-Gui X (2003) Mechanism of chlorinating lanthanum oxide and cerium oxide with ammonium chloride. Trans Nonferrous Met Soc China 13:1454–1458

    Google Scholar 

Download references

Acknowledgments

The author, SK. Thaslim Basha expresses a deep sense of gratitude to University Grant Commission for awarding SRF and financial support. The authors also thank IIT Madras for providing spectroscopic and analytical data. This work was also supported by the National Research Foundation of Korea (NRF) Grant funded by the Korea government (NRF-2019R1A2C1003735 and NRF-2020R1A6A1A03043435).

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Correspondence to Reddi Mohan Naidu Kalla, Sung Chul Hong or Chamarthi Naga Raju.

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Basha, S.K.T., Kalla, R.M.N., Varalakshmi, M. et al. Heterogeneous catalyst SiO2–LaCl3·7H2O: characterization and microwave-assisted green synthesis of α-aminophosphonates and their antimicrobial activity. Mol Divers 26, 2703–2715 (2022). https://doi.org/10.1007/s11030-021-10360-x

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