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Catalytic Olefin Epoxidation With H 2 O 2 in Supercritical CO 2 . Synergic Effect by Hexafluoroacetone and Manganese‐Porphyrins
Author(s) -
Campestrini Sandro,
Tonellato Umberto
Publication year - 2001
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/1615-4169(20011231)343:8<819::aid-adsc819>3.0.co;2-y
Subject(s) - chemistry , cyclooctene , catalysis , hydrogen peroxide , manganese , hexafluoroacetone , supercritical fluid , decomposition , olefin fiber , supercritical carbon dioxide , inorganic chemistry , photochemistry , organic chemistry
The heterogeneous oxidation of cyclooctene with hydrogen peroxide catalyzed by manganese 5,10,15,20‐tetrakis(2′,6′‐dichlorophenyl)porphyrinate, in the presence of hexafluoroacetone hydrate as co‐catalyst, has been studied in supercritical carbon dioxide, at 40 °C and 20 MPa. Under proper conditions, a complete olefin conversion may be obtained with the formation of cyclooctene oxide as the sole product. Fixation by hexafluoroacetone into its perhydrate derivatives provides a useful system to solubilize hydrogen peroxide in supercritical carbon dioxide, and to hamper catalyst bleaching and oxidant decomposition. Moreover, in the presence of both manganese‐porphyrin and hexafluoroacetone, the reaction rates are enhanced. Among the factors that may increase yields and rate of conversion, the use of a Teflon‐coated steel reactor rather than an uncoated one proved to be quite relevant, thus indicating the occurrence of a parasite radicaldecomposition of hydrogen peroxide promoted by steel reactor walls.