Abstract
Oxidation of cycloolefins (cyclohexene, cyclooctene, and cyclododecene) with a 30% solution of hydrogen peroxide at 65 °C in the presence of heteropoly acids (HPA) H3PW12–x Mo x O40 (x = 0—12), which are precursors of active peroxo complexes, and phase transfer catalysts Q+Cl–, where Q+ is the quaternary ammonium cation containing C4—C18 alkyl groups or [C5H5NC16H33]+, was studied. The catalytic activity decreases in the HPA series: H3PW12O40 > H3PW9Mo3O40 > H3PW6Mo6O40 > H3PW3Mo9O40 > H3PMo12O40. The state of the H3PW12O40—I2I2 system was studied using UV, IR, and 31P NMR spectroscopies with variation of the [H2O2] : [HPA] ratio from 2 to 200 during cyclohexene epoxidation. Despite different catalytic precursors, the reaction proceeds through the same peroxo complex.
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References
A. H. Hains, Methods for the Oxidation Compounds, Academic, London, 1985, 108.
G. Strukul, Catalytic Oxidations with Hydrogen Peroxide as Oxidant, Kluwer, Dordrecht, 1992.
R. A. Sheldon, Stud. Sci. Catal., 1990, 55, 1.
C. Venturello, E. Alneri, and M. Ricci, J. Org. Chem., 1983, 48, 3831.
C. Venturello and M. Ricci, J. Org. Chem., 1986, 51, 1599.
D. C. Duncan, R. C. Chambers, E. Hecht, and C. L. Hill, J. Am. Chem. Soc., 1995, 117, 681.
Y. Ishii, K. Yamawaki, T. Ura, H. Yamada, T. Yoshida, and M. Ogawa, J. Org. Chem., 1988, 53, 3587.
C. Venturello, R. D'Aloisio, J. C. J. Bart, and M. Ricci, J. Mol. Catal., Ser. A, Chem., 1985, 32, 107.
T. Oguchi, Y. Sakata, N. Takeuchi, K. Kaneda, Y. Ishii, and M. Ogawa, Chem. Lett., 1989, 2053.
Y. Matoba, H. Inoue, Akagi Jun-ichi, T. Okabayashi, Y. Ishii, and M. Ogawa, Synth. Commun., 1984, 14, 865.
G. A. Tsigdinos, Top. Curr. Chem., 1971, 76, 1.
E. A. Nikitina, Geteropolisoedineniya [Heteropoly Compounds], Goskhimizdat, Moscow, 1962, 424 pp. (in Russian).
C. Aubry, G. Chottard, N. Platzer, J.-M. Bregeault, R. Thouvenot, F. Chauveau, C. Huet, and H. Ledon, Inorg. Chem., 1991, 30, 4409.
N. N. Kundo, Z. P. Pai, and E. A. Gutova, Zh. Prikl. Khim., 1987, 60, 1702 [J. Appl. Chem. USSR, 1987, 60 (Engl. Transl.)].
L. I. Kuznetsova, R. I. Maksimovskaya, M. A. Fedotov, and K. I. Matveev, Izv. Akad. Nauk SSSR, Ser. Khim., 1983, 733 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1983, 32 (Engl. Transl.)].
A. J. Bailey, W. P. Griffith, and B. C. Parkin, J. Chem. Soc., Dalton Trans., 1995, 1833.
G. A. Tolstikov, Reaktsii gidroperekisnogo okisleniya [Reactions of Hydroperoxide Oxidation], Nauka, Moscow, 1976, 200 pp. (in Russian).
E. V. Dehmlov, S. S. Dehmlov, Phase Transfer Catalysis, Verlag Chemie, Weinheim, 1983, 485 pp.
L. Salles, C. Aubry, R. Thouvenot, F. Robert, C. Doremieux-Morin, G. Chottard, H. Ledon, and Y. Jeannin, Inorg. Chem., 1994, 33, 871.
H. Furukawa, T. Nakamura, H. Inagaki, E. Nishikawa, C. Imai, and M. Misono, Chem. Lett., 1988, 877.
Kwan-Young Lee, K. Itoh, M. Hashimoto, N. Mizuno, and M. Misono, Stud. Surf. Sci. Catal., 1994, 82, 538.
C. D. Valentin, P. Gisdakis, I. V. Yudanov, and N. Rosch, J. Org. Chem., 2000, 65, 2996.
G. M. Varga, Jr., E. Papaconstantinou, and M. Pope, Inorg. Chem., 1970, 9, 662.
L. P. Kazanskii, Izv. Akad. Nauk SSSR, Ser. Khim., 1975, 499 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1975, 24 (Engl. Transl.)].
C. Venturello and R. D'Aloisio, J. Org. Chem., 1988, 53, 1553.a
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Timofeeva, M.N., Pai, Z.P., Tolstikov, A.G. et al. Epoxidation of cycloolefins with hydrogen peroxide in the presence of heteropoly acids combined with phase transfer catalyst. Russian Chemical Bulletin 52, 480–486 (2003). https://doi.org/10.1023/A:1023495824378
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DOI: https://doi.org/10.1023/A:1023495824378