Synthesis of 2-methyl-1,4-naphthoquinone (vitamin K3) using the nanostructured gold catalysts in acetic acid and supercritical carbon dioxide

Preparation of 2-methyl-1,4-naphthoquinone (vitamin K3) by oxidation of 2-methylnaphthalene and 2-methyl-1-naphthol using the nanostructured gold catalysts supported on hypercrosslinked polystyrene (5 % Au/SPS) was investigated. The effect of temperature on the oxidation process was studied; the attempt was made for replacement of the standard solvent – acetic acid to an environmentally friendly supercritical carbon dioxide. It is found that the use of supercritical CO2 is high (near 100 %), selectivity of the oxidation of 2-methyl-1- naphthol to the desired product is stored, wherein the conversion is increased on 10–15 %. Oxidation of 2-methylnaphthalene using supercritical CO2 leads to a drastic reduction of conversion and selectivity to the desired product, resulting from the fact that under these conditions peracetic acid (main oxidant) is formed. The possibility of using gold nanostructured catalysts for selective oxidation of 2-methyl-1-naphthol and 2-methylnaphthalene in 2-methyl-1,4-naphthoquinone (99 and 58% respectively).

1. Kholdeeva O.A., Zalomaeva O.V., Sorokin A.B., Ivanchikova I.D., Pina C.D., Rossi M. // Catal. Today. 121 (2007) 58.

2. Zalomaeva O.V., Kholdeeva O.A., Sorokin A.B. // Comptes Rendus Chimie. 10 (2007) 598.

3. Patriarche G.J., Lingane J.J. // Analytica Chimica Acta. 49 (1970) 241.

4. Yamazaki S. // Tetrahedron Letters. 42 (2001) 3355.

5. Narayanan S., Murthy R., Reddy K.M., Premchander N. // Applied Catalysis A: General. 228 (2002) 161.

6. Eremin D.V., Petrov L.A. // Optimization of Conditions for Preparing Vitamin K3 by Oxidation of 2-Methylnaphthalene with Chromium Trioxide in Acid Solutions. Russian Journal of Applied Chemistry. 2009. Vol. 82. № 5. P. 866–870.

7. Beller M., Feng Shi, Man Kin Tse // Selective oxidation of naphthalene derivatives with ruthenium catalysis using hydrogen peroxide as terminal oxidant. Journal of Molecular Catalysis A: Chemical. 270. 2007. P. 68—71.

8. Oscar A. Anunziata, Liliana B. Pierella, Andrea R. Beltramone // Synthesis of menadione over selective oxidation zeolites // Journal of Molecular Catalysis A: Chemical. 149. 1999. P. 255—261.

9. Симонова М.В., Жижина Е.Г. Получение витамина К3 по реакции диенового синтеза в растворах

10. Mo-V-фосфорных гетерополикислот // Химия в интересах устойчивого развития. 2005. Т. 13. С. 479—482.

11. Anunziata O.A., Pierella L.B., Beyer H.K., Nagy J.B. Studies in Surface Science and Catalysis, Elsevier. 1995.

12. Vol. 94. Р. 574.

13. Kowalski J, Peoszyeska J., Sobkowiak A. Catalysis Communications. 4 (2003) 603.

14. Murahashi S.-I., Fujii A., Inubushi Y., Komiya N.: Synthesis of 2-substituted quinones, vitamin K3, and vitamin K1 from p-cresol. BF3·OEt2-catalyzed methyl migration of 4-tertbutyldioxycyclohexadienones. Tetrahedron Letters. 51 (2010) 2339—2341.

15. Быков А.В., Коняева М.Б., Демиденко Г.Н., Матвеева В.Г., Тямина И.Ю., Сульман Э.М. Физико-химические исследования полимерстабилизированных платиновых катализаторов энантиоселективного гидрирования кетонов // Катализ в промышленности. 2012. № 4. С. 67—72.

16. Tsyurupa M.P., Blinnikova Z.K., Proskurina N.A., Pastukhov A.V., Pavlova L.A., Davankov V.A. Hypercrosslinked polystyrene: The first nanoporous polymeric material // Nanotechnologies in Russia. 2009. Т. 4. № 9—10. С. 665—675.

17. Selvaraj M., Kandaswamy M., Park D.W., Ha C.S. Catal. Today. 2010. 158(3—4). Р. 377—384.

18. Strukul G., Somma F., Ballarini N., Cavani F., Frattini A., Guidetti S., Morselli D. Applied Catalysis A: General. 356 (2009) 162.

19. Jessop P.G. The Journal of Supercritical Fluids. 38 (2006) 211.

20. Isaacs N.S., Keating N.J. Chem. Soc., Chem. Commun. 876 (1992).

21. Отто М. Современные методы аналитической химии. М: Техносфера, 2004. Т. 2. 288 с.

22. Anunziata O.A., Beltramone A.R., Cussa J. Applied Catalysis A: General. 270 (2004) 77.

23. Anunziata O.A., Pierella L.B., Beltramone A.R. Journal of Molecular Catalysis A: Chemical. 149 (1999) 255.