One-Pot Production of Substituted Anthraquinones via the Diene Synthesis in the Presence of Mo-V-P Heteropoly Acid Solutions

Abstract

Acid-catalytic 1,3-butadiene condensation with para-quinones followed by the obtained product oxidation may be performed in one stage as one-pot process, if assisted by the aqueous solutions of Mo-V-P heteropoly acids with a composition of HaPzMoyVxOb. 1,4-naphthoquinone (NQ) condensation with 1,3-butadiene in HPA solutions (brutto-composition H15P4Mo18V7O89 and H17P3Mo16V10O89) in the presence of hydrophylic organic solvents (acetone, 1,4-dioxane) provides 70% yield of 9,10-anthraquinone (AQ) containing no less than 90% AQ. In the same conditions reaction NQ with substituted 1,3-butadienes in the presence of the aqueous H17P3Mo16V10O89 (HPA-10) solution allows to prepare substituted AQ with yield up to 90% and purity up to 99%. The catalysts are regenerated by oxygen in separate stage and are reused.

Share and Cite:

Gogin, L. and Zhizhina, E. (2014) One-Pot Production of Substituted Anthraquinones via the Diene Synthesis in the Presence of Mo-V-P Heteropoly Acid Solutions. Modern Research in Catalysis, 3, 575-61. doi: 10.4236/mrc.2014.32008.

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1] Gorelik, M.V. (1983) Chemistry of Anthraquinones and Their Derivatives. Khimia, Moscow.
[2] (2005) Anthraquinone Dyes and Intermediates. In: Ullmann’s Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
[3] (2006) Anthraquinone. In: Kirk-Othmer Encyclopedia of Chemical Technology, 5th Edition, John Wiley & Sons, New York, 419-427.
[4] Ju, H.S., Ju, Y.J., Kim, J.E. and Won, J.I. (2001) Preparation of Napthoquinone and Anthraquinone Using Oxidizing Agent. KR Patent No. 2001004856.
[5] Ju, H.S., Ju, Y.J., Kim, J.E. and Won, J.I. (2000) Method of Manufacturing Anthraquinone from 1,4-Napthoquinone and 1,3-Butadiene. KR Patent No. 2000001821.
[6] (1942) Organic Syntheses. John Wiley & Sons, New-York.
[7] Kozhevnikov, I.V. (1998) Catalysis by Heteropoly Acids and Multicomponent Polyoxometal-lates in Liquid-Phase Reactions. Chemical Reviews, 98, 171-198. http://dx.doi.org/10.1021/cr960400y
[8] Zhizhina, E.G., Matveev, K.I. and Russkikh, V.V. (2004) 1,4-Naphtoand 9,10-Anthraquinone Catalytic Preparation by Diene Synthesis Reaction for Cellulose-Paper Industry. Khimiya v Interesakh Ustoichivogo Razvitiya, 12, 47-51.
[9] Zhizhina, E.G., Simonova, M.V., Odyakov, V.F. and Matveev, K.I. (2005) Catalytic Synthesis of 9,10-Anthraquinone in the Presence of Mo-V-Phosphoric Heteropoly Acids Solutions. Catalysis in Industry, 12-17.
[10] Zhizhina, E.G. and Odyakov, V.F. (2012) Aqueous Solutions of Mo-V-P Heteropoly Acids as Bifunctional Catalysts for Preparation of 9,10-Anthraquinone and Its Hydrogenated Derivatives. ChemCatChem, 4, 1405-1410.
http://dx.doi.org/10.1002/cctc.201200039
[11] Gogin, L.L., Zhizhina, E.G. and Pai, Z.P. (2013) Low-Waste One-Pot Process of Anthraquinone Production via Diene Synthesis in the Presence of Heteropoly Acids Solutions. Khimiya v Interesakh Ustoichivogo Razvitiya, 21, 123-127.
[12] Weygand-Hilgetag (1968) Methods of Experiment in Organic Chemistry. Khimia, Moscow.
[13] Odyakov, V.F., Zhizhina, E.G. and Maksimovskaya, R.I. (2008) Synthesis of Molybdovanadophos-Phoric Heteropoly Acid Solutions Having Modified Composition. Applied Catalysis A: General, 342, 126-130.
http://dx.doi.org/10.1016/j.apcata.2008.03.008
[14] Selling, A., Andersson, I., Grate, J.H. and Pettersson, L. (2000) A Potentiometric and (31P, 51V) NMR Study of the Aqueous Molybdovanadophosphate System. European Journal of Inorganic Chemistry, 2000, 1509-1521.
[15] Zhizhina, E.G., Odyakov, V.F. and Matveev, K.I. (1999) Thermochemical Study of Reduction and Oxidation Reactions of Molybdovanadophosphoric Heteropoly Acids in Aqueous Solutions. European Journal of Inorganic Chemistry, 1999, 1009-1014.
[16] Zhizhina, E.G., Simonova, M.V., Odyakov, V.F. and Matveev, K.I. (2004) Regeneration of Catalysts Based on Aqueous Solutions of Mo-V-P Heteropoly Acids. Khimiya v Interesakh Ustoichivogo Razvitiya, 6, 683-688.
[17] Kozhevnikov, I.V. and Matveev, K.I. (1982) Heteropoly Acids in Catalysis. Russian Chemical Reviews, 51, 1875-1896.

Copyright © 2024 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.