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Ultrasound-assisted reaction of 1,4-naphthoquinone with anilines through an EDA complex

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Abstract

Naphthoquinone amino derivatives exhibit interesting physicochemical properties and a wide range of biological activities with potential medicinal applications. A clean, fast and simple method for the preparation of phenylamino-1,4-naphthoquinones is presented by the reaction of naphthoquinone (NQ) and anilines under ultrasound irradiation (US). Anilino derivatives were synthesized in good yields and shorter reaction times in comparison with the conventional method. This ultrasound procedure can be applied to the preparation of naphthoquinone derivatives with anilines containing electron-donor substituents (2-OMe, 4-OMe, 4-Me and 4-OEt) or halogen or electron-withdrawing substituents (4-F, 4-Cl, 4-Br, 3-F, 3-Cl, 3-Br, 4-Ac). This procedure was also applied to the reaction of anilines with 2,3-dichloro-1,4-naphthoquinone (DCNQ). A reaction mechanism involving an EDA complex is proposed based on NMR experiments and previous studies about solid/solid reactions.

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References

  1. Riffel A, Medina LF, Stefani V, Santos RC, Bizani D, Brandelli A (2002) In vitro antimicrobial activity of a new series of 1,4-naphthoquinones. Braz J Med Biol Res 35:811–818. https://doi.org/10.1590/S0100-879X2002000700008

    Article  PubMed  CAS  Google Scholar 

  2. Ball MD, Bartlett MS, Shaw M, Smith JW, Nasr M, Meshnik SR (2002) Activities and conformational fitting of 1,4-naphthoquinone derivatives and other cyclic 1,4-diones tested in vitro against Pneumocystis carin. Agents Chemother 45:1473–1479. https://doi.org/10.1128/AAC.45.5.1473-1479.2001

    Article  Google Scholar 

  3. Bittner S, Gorohovsky S, Lozinsky E, Shames AI (2000) EPR study of anion radicals of various N-quinonyl amino acids. Amino Acids 19:439–449. https://doi.org/10.1007/s007260070022

    Article  PubMed  CAS  Google Scholar 

  4. Medina LFC, Stefani V, Brandelli A (2006) An unusual reduction on the quinonoid ring of 5-amino-8-hydroxy-1,4-naphthoquinone by Staphylococcus aureus. Lett Appl Microbiol 42:381–385. https://doi.org/10.1111/j.1472-765x.2006.01863.x

    Article  PubMed  CAS  Google Scholar 

  5. Biot C, Bauer H, Schirmer RH, Davioud-Charret E (2004) 5-Substituted tetrazoles as bioisosteres of carboxylic acids. bioisosterism and mechanistic studies on glutathione reductase inhibitors as antimalarials. J Med Chem 47:5972–5983. https://doi.org/10.1021/jm0497545

    Article  PubMed  CAS  Google Scholar 

  6. Mantyla A, Garnier-Rautio JT, Nevalainen T, Vepsalainen J, Koskinen A, Croft SI, Jarvinen T (2004) Synthesis, in vitro evaluation, and antileishmanial activity of water-soluble prodrugs of buparvaquone. J Med Chem 47:188–195. https://doi.org/10.1021/jm030868a

    Article  PubMed  CAS  Google Scholar 

  7. Tandon VK, Yadav DB, Maurya HK, Chaturvedi AK, Shukla PK (2006) Design, synthesis, and biological evaluation of 1,2,3-trisubstituted-1,4-dihydrobenzo[g]quinoxaline-5,10-diones and related compounds as antifungal and antibacterial agents. Bioorg Med Chem 14:6120–6126. https://doi.org/10.1016/j.bmc.2006.04.029

    Article  PubMed  CAS  Google Scholar 

  8. Leyva E, López LI, García de la Cruz RF, Espinosa-González CG (2016) Synthesis and studies of the antifungal activity of 2-anilino-/2,3-dianilino-/2-phenoxy- and 2,3-diphenoxy-1,4-naphthoquinones. Res Chem Int 43:1813–1827. https://doi.org/10.1007/s11164-016-2732-3

    Article  CAS  Google Scholar 

  9. Kutyrev AA (1991) Nucleophilic reactions of quinones. Tetrahedron 47:8043–8065. https://doi.org/10.1016/s0040-4020(01)91002-6

    Article  CAS  Google Scholar 

  10. Leyva E, Schmidke-Sobeck SJ, Loredo-Carrillo SE, Magaldi-Lara DA (2014) Spectral and structural characterization of 2-(fluorophenylamino)- and 2-(nitrophenylamino)-1,4-naphthoquinone derivatives. J Mol Struct 1068:1–7. https://doi.org/10.1016/j.molstruc.2014.03.044

    Article  CAS  Google Scholar 

  11. Leyva E, López LI, Loredo-Carrillo SE, Rodríguez-Kessler M, Montes-Rojas A (2011) Synthesis, spectral and electrochemical characterization of novel 2-(fluoroanilino)-1,4-naphthoquinones. J Fluorine Chem 132:94–101. https://doi.org/10.1016/j.jfluchem.2010.12.001

    Article  CAS  Google Scholar 

  12. Leyva E, López LI, Moctezuma E, de Lasa H (2008) A bentonitic clay assisted method for the preparation of 2-(R-anilino)-1, 4-naphthoquinones. Top Catal 49:281–287. https://doi.org/10.1007/s11244-008-9088-x

    Article  CAS  Google Scholar 

  13. Leyva E, Baines KM, Espinosa-González CG, Magaldi-Lara DA, Loredo-Carrillo SE, de Luna-Méndez TA, López L (2015) 2-(Fluoro) and 2-(methoxyaniline)-1,4-naphthoquinones. Synthesis and mechanism and effect of fluorine substitution on redox reactivity and NRM. J Fluorine Chem 180:152–160. https://doi.org/10.1016/j.jfluchem.2015.08.016

    Article  CAS  Google Scholar 

  14. Lisboa CS, Santos VG, Vaz BG, de Lucas NC, Eberlin MN, Garden SJ (2011) C–H functionalization of 1,4-naphthoquinone by oxidative coupling with anilines in the presence of a catalytic quantity of copper(II) acetate. J Org Chem 76:5264–5273. https://doi.org/10.1021/jo200354u

    Article  CAS  Google Scholar 

  15. Aguilar-Martínez M, Cuevas G, Jiménez-Estrada M, González I, Lotina- Hennsen B, Macías-Ruvalcaba N (1999) An experimental and theoretical study of the substituent effects on the redox properties of 2-(R-phenyl)amino-1,4-naphthalenediones in acetonitrile. J Org Chem 64:3684–3694. https://doi.org/10.1021/jo990186o

    Article  PubMed  Google Scholar 

  16. Pokhrel N, Vabbina PK, Pala N (2016) Sonochemistry: science and engineering. Ultrason Sonochem 29:104–128. https://doi.org/10.1016/j.ultsonch.2015.07.023

    Article  PubMed  CAS  Google Scholar 

  17. Bretanha LC, Teixeira VE, Ritter M, Siqueira GM, Cunico W, Pereira CMP, Freitag RA (2011) Ultrasound-promoted synthesis of 3-trichloromethyl-5-alkyl(aryl)-1,2,4-oxadiazoles. Ultrason Sonochem 18:704–707. https://doi.org/10.1016/j.ultsonch.2010.09.016

    Article  PubMed  CAS  Google Scholar 

  18. Srivastava RM, Filho RAWN, da Silva CA, Bortoluzzi A (2009) First ultrasound-mediated one-pot synthesis of N-substituted amides. Ultrason Sonochem 16:737–742. https://doi.org/10.1016/j.ultsonch.2009.04.006

    Article  PubMed  CAS  Google Scholar 

  19. Duarte A, Cunico W, Pereira CMP, Freitag RA, Siqueira GM (2010) Ultrasound promoted synthesis of thioesters from 2-mercaptobenzoxa(thia)zoles. Ultrason Sonochem 17:281–283. https://doi.org/10.1016/j.ultsonch.2009.08.004

    Article  PubMed  CAS  Google Scholar 

  20. Neelgund GM, Kulkairni AS, Bundi ML (2004) EDA complexes of 2,3-dichloro-1,4-naphthoquinone with some substituted anilines. Monatsh Chem 135:343–355. https://doi.org/10.1007/s00706-003-0128-8

    Article  CAS  Google Scholar 

  21. Nagendrappa RR, Jayadevappa ES (1975) Donor–acceptor equilibria involving para-benzoquinone and 1,4-naphthoquinone as acceptors and N-methyl-anilines and N,N-dimethyl-anilines as donors. Indian J Chem 13:1173–1176

    CAS  Google Scholar 

  22. Sieveking I, Thomas P, Estévez JC, Quiñones N, Cuéllar MA, Villena J, Espinosa-Bustos C, Fierro A, Tapia RA, Maya D, López-Muñoz R, Cassels BK, Estévez RJ, Salas CO (2014) 2-Phenylaminonaphthoquinones and related compounds: synthesis, trypanocidal and cytotoxic activities. Bioorg Med Chem 22:4609–4620. https://doi.org/10.1016/j.bmc.2014.07.030

    Article  PubMed  CAS  Google Scholar 

  23. Satheshkumar A, Kuppanagounder PE (2012) Spectroscopic and theoretical studies on the nucleophilic substitution of 2,3-dichloronaphthoquinone with para-substituted anilines in solid state via initial charge transfer complexation. Spectrochim Acta A 98:378–383. https://doi.org/10.1016/j.saa.2012.08.056

    Article  CAS  Google Scholar 

  24. Prachayasittikul V, Pingaew R, Worachartcheewan A, Nantasenamat C, Prachayasittikul S, Ruchirawat S, Prachayasittikul V (2014) Synthesis, anticancer activity and QSAR study of 1,4-naphthoquinone derivatives. Eur J Med Chem 84:247–263. https://doi.org/10.1016/j.ejmech.2014.07.024

    Article  PubMed  CAS  Google Scholar 

  25. Satheshkumar A, Ganesh K, Elango P (2014) Charge transfer facilitated direct electrophilic substitution in phenylaminonaphthoquinones: experimental, theoretical and electrochemical studies. New J Chem 38:993–1003. https://doi.org/10.1039/c3nj01228j

    Article  CAS  Google Scholar 

  26. Kim YS, Park SY, Lee HJ, Suh ME, Schollmeyer D, Lee CO (2003) Synthesis and cytotoxicity of 6,11-dihydro-pyrido- and 6,11-dihydro-benzo[2,3-b]phenazine-6,11-dione derivatives. Bioorg Med Chem 11:1709–1714. https://doi.org/10.1016/s0968-0896(03)00028-2

    Article  PubMed  CAS  Google Scholar 

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Acknowledgements

Financial support by CONACyT (Grant No. 155678) is gratefully acknowledged. All authors kindly acknowledge The National Laboratory for Characterization of Physicochemical Properties and Molecular Structure, CONACyT (Grant NO. 123732) for the instrumentation time provided.

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Authors and Affiliations

  1. Facultad de Ciencias Químicas, Universidad Autónoma de San Luis Potosí, Manuel Nava No. 6, Zona Universitaria, C.P. 78210, San Luis Potosí, S.L.P., Mexico

    Elisa Leyva, Agobardo Cárdenas-Chaparro, Silvia E. Loredo-Carrillo, Lluvia I. López & Fernanda Méndez-Sánchez

  2. Departamento de Química, Universidad de Guanajuato, Noria Alta s/n, C.P. 36000, Guanajuato, GTO, Mexico

    Antonio Martínez-Richa

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  1. Elisa Leyva
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  2. Agobardo Cárdenas-Chaparro
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  4. Lluvia I. López
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Correspondence to Elisa Leyva.

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1H NMR spectra for products 3a-3v 1.29MB

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Leyva, E., Cárdenas-Chaparro, A., Loredo-Carrillo, S.E. et al. Ultrasound-assisted reaction of 1,4-naphthoquinone with anilines through an EDA complex. Mol Divers 22, 281–290 (2018). https://doi.org/10.1007/s11030-018-9820-9

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  • DOI: https://doi.org/10.1007/s11030-018-9820-9

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