Catalysis Letters

, Volume 142, Issue 8, pp 1020–1025 | Cite as

Multiple Oxo-Vanadium Schiff Base Containing Cyclotriphosphazene as a Robust Heterogeneous Catalyst for Regioselective Oxidation of Naphthols and Phenols to Quinones

  • Praveen K. Khatri
  • Suman L. Jain


Grafting of multiple oxo-vanadium Schiff base moieties to cyclotriphosphazene provided an efficient and recyclable heterogeneous catalyst for the regioselective oxidation of naphthols and phenols to quinones by using t-butylhydroperoxide as oxidant. One of the main advantages of the developed catalyst was the presence of multiple oxo-vanadium moieties in close proximity which made the developed catalyst more active as compared to its homogeneous oxo-vanadium Schiff base. After the reaction, the catalyst was easily recovered from the reaction mixture by simple filtration and reused for five runs without loss in activity.

Graphical Abstract


Cyclotriphosphazene Vanadium Oxidation Naphthol Quinone 



We thank Director, IIP for his kind permission to publish these results. We thank Analytical Sciences Division, IIP for IR, elemental analysis and Dr. JK Gupta for TGA analysis.


  1. 1.
    Leadbeater NE, Marco M (2002) Preparation of polymer-supported ligands and metal complexes for use in catalysis. Chem Rev 102:3217–3274CrossRefGoogle Scholar
  2. 2.
    Burgess K (2000) Solid phase organic synthesis. Wiley, New YorkGoogle Scholar
  3. 3.
    Allcock HR (2003) Chemistry and applications of polyphosphazenes. Wiley-VCH, New YorkGoogle Scholar
  4. 4.
    Gleria M, De Jaeger R (2004) Applicative aspects of poly(organophosphazenes). Nova Science Publishers, New YorkGoogle Scholar
  5. 5.
    Allen CW (1991) Regio- and stereochemical control in substitution reactions of cyclophosphazenes. Chem Rev 9:119–135CrossRefGoogle Scholar
  6. 6.
    Gall M, Breza M (2009) QTAIM study of transition metal complexes with cyclophosphazene-based multisite ligands I: zinc(II) and nickel(II) complexes. Polyhedron 28:521–524CrossRefGoogle Scholar
  7. 7.
    Chandrasekhar V, Nagendran S (2001) Phosphazenes as scaffolds for the construction of multi-site coordination ligands. Chem Soc Rev 30:193–203CrossRefGoogle Scholar
  8. 8.
    Uslu A, Guvenaltın S (2010) The investigation of structural and thermosensitive properties of new phosphazene derivatives bearing glycol and amino acid. Dalton Trans 39:10685–10691CrossRefGoogle Scholar
  9. 9.
    Allcock HR, Brennan DJ, Graaskamp JM, Parvez M (1986) Reactions between phosphazenes and organosilicon compounds: synthesis and molecular structure of methylsilane- and methylsiloxane-cyclotriphosphazenes. Organometallics 5:2434–2446CrossRefGoogle Scholar
  10. 10.
    Allcock HR, Connolly MS, Sisko JT, Al-Shali S (1988) Effects of organic side group structures on the properties of poly(organophosphazenes). Macromolecules 21:323–324CrossRefGoogle Scholar
  11. 11.
    Allcock HR, Brennan DJ (1988) Organosilicon derivatives of cyclic and high polymeric phosphazenes. J Organomet Chem 341:231–239CrossRefGoogle Scholar
  12. 12.
    Rao MR, Gayatri G, Kumar A, Sastry GN (2009) Cyclotriphosphazene ring as a platform for multiporphyrin assemblies. Chem Eur J 15:3488–3492CrossRefGoogle Scholar
  13. 13.
    Khatri PK, Singh B, Jain SL, Sinha AK, Sain B (2011) Cyclotriphosphazene grafted silica: a novel support for immobilizing the oxo-vanadium Schiff base moieties for hydroxylation of benzene. Chem Commun 47:1610–1612CrossRefGoogle Scholar
  14. 14.
    Shimizu M, Orita H, Hayakawa T, Takehira K (1989) A convenient synthesis of alkyl-substituted p-benzoquinones from phenols by a H2O2/heteropolyacid system. Tetrahedron Lett 30:471–474CrossRefGoogle Scholar
  15. 15.
    Saladino R, Neri V, Mincione E, Filippone P (2002) Selective oxidation of phenol and anisole derivatives to quinones with hydrogen peroxide and polymer-supported methylrhenium trioxide systems. Tethaedron 58:8493–8500CrossRefGoogle Scholar
  16. 16.
    Zalomaeva OV, Sorokin AB (2006) Access to functionalized quinones via the aromatic oxidation of phenols bearing an alcohol or olefinic function catalyzed by supported iron phthalocyanine. New J Chem 30:1768–1773CrossRefGoogle Scholar
  17. 17.
    Cooksey CJ, Land EJ, Riley PA (1996) A simple one-pot preparation of 4-alkoxy and 4-alkyl thio-catechols and o-benzoquinones. Org Prep Proced Int 28:463–467CrossRefGoogle Scholar
  18. 18.
    Zalomaeva OV, Kholdeeva OA, Sorokin AB (2007) Preparation of 2-methyl-1,4-naphthoquinone (vitamin K3) by catalytic oxidation of 2-methyl-1-naphthol in the presence of iron phthalocyanine supported catalyst. Comptes Rendus Chimie 10:598–603CrossRefGoogle Scholar
  19. 19.
    Magdziak D, Rodriguez AA, Van De Water RW, Pettus TRR (2002) Regioselective oxidation of phenols to o-quinones with o-iodoxybenzoic acid (IBX). Org Lett 4:285–288CrossRefGoogle Scholar
  20. 20.
    Verma S, Jain SL, Sain B (2011) An efficient biomaterial supported bifunctional organocatalyst (ES-SO3-C5H5NH+) for the synthesis of β-amino carbonyls. Org Bio Chem 9:2314–2318CrossRefGoogle Scholar
  21. 21.
    Verma S, Jain SL, Sain B (2011) Starch immobilized Ru-containing ionic liquid catalyzed oxidative cyanation of tertiary amines with hydrogen peroxide. ChemCatChem 3:1329–1332CrossRefGoogle Scholar
  22. 22.
    Kumar S, Verma S, Jain SL, Sain B (2011) Thiourea dioxide (TUD): a robust organocatalyst for oxidation of sulfides to sulfoxides with TBHP under mild reaction conditions. Tetrahedron Lett 52:3393–3396CrossRefGoogle Scholar
  23. 23.
    Verma S, Nandi M, Modak A, Jain SL, Bhaumik A (2011) Novel organic–inorganic hybrid mesoporous silica supported oxo-vanadium Schiff base for selective oxidation of alcohols. Adv Synth Catal 353:1897–1902CrossRefGoogle Scholar
  24. 24.
    Singhal S, Jain SL, Sain B (2009) An efficient aerobic oxidative cyanation of tertiary amines with sodium cyanide using vanadium based systems as catalysts. Chem Commun 17:2371–2372CrossRefGoogle Scholar
  25. 25.
    Ando R, Yagyu T, Maeda M (2004) Characterization of oxo-vanadium (IV) Schiff-base complexes and those bound on resin, and their use in sulfide oxidation. Inorg Chim Acta 357:2237–2244CrossRefGoogle Scholar
  26. 26.
    Ratnikov MO, Farkas LE, McLaughlin EC, Chiou G, Choi H, Khalafy SHE, Doyle MP (2011) Dirhodium-catalyzed phenol and aniline oxidations with T-HYDRO. Substrate scope and mechanism of oxidation. J Org Chem 76:2585–2593CrossRefGoogle Scholar
  27. 27.
    Moriarty RM, Prakash O (2001) Oxidation of phenolic compounds with organohypervalent iodine reagents. Org React 57:327–416Google Scholar
  28. 28.
    Suresh S, Skaria S, Ponrathnam S (1996) Polymer-supported vanadium salt as a catalyst for the oxidation of phenols. Synth Commun 26:2113–2117CrossRefGoogle Scholar
  29. 29.
    Luo HB, Xie YY (2003) Regioselective oxidation of phenols to o-quinones with Dess-Martin periodinane(DMP). Chin Chem Lett 14:555–556Google Scholar
  30. 30.
    Egusquiza G, Romanelli G, Cabello C, Botto C, Thomas H (2008) Phenol and naphthol oxidation to quinones with hydrogen peroxide using vanadium- substituted Keggin heteropolyacid as catalyst. Catal Commun 9:45–50CrossRefGoogle Scholar
  31. 31.
    Romanelli G, Villabrille P, Vázquez P, Cáceres C, Tundo P (2008) Phenol and naphthol oxidation to quinones with hydrogen peroxide using vanadium-substituted Keggin heteropoly acid as catalyst. Lett Org Chem 5:332–335CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2012

Authors and Affiliations

  1. 1.Chemical Sciences DivisionCSIR-Indian Institute of PetroleumDehradunIndia

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