Alkylperoxide, XXXVII1) Über die Bildung cyclischer Peroxide aus Mehrfachketonen

1.1.3.3-Tetraacetyl-propan addiert 2 Mol H2O2 unter Bildung von 4.4′-Methylen-bis-[3.5-dimethyl-1.2-dioxolan-diol-(3.5)] (1). Unter Saureeinwirkung entsteht aus Tetraacetylpropan mit 1 Mol H2O2 7-Acetyl-1.4.6-trimethyl-2.3.5.10-tetraoxa-tricyclo[4.3.1.04.9]decan (4). Aus 4 bildet sich mit H2O2 unter Saurekatalyse Perhydro-3.5.7a.8a-tetramethyl-bis-1.2-dioxolo-[3.4-b;4.3′-e]pyran-dihydroperoxid-(3.5) (5a). – 1.1.2-Triacetyl-athan bildet mit H2O2 1.4.6-Trimethyl-2.3.5.7.8-pentaoxa-tricyclo[4.2.2.04.9]decan (9). 3.4-Diacetyl-2.5-dimethylfuran addiert H2O2 zu 1.4.5.7-Tetramethyl-1.4-dihydro-furo[3.4-d][1.2]dioxin-dihydroperoxid-(1.4) (8a). Mit Benzoylimidazol lassen sich die Dihydroperoxider 5a und 8a zu den Benzoyl-Derivaten 5b und 8b benuoylieren. Alkyl Peroxides, XXXVII1). The Formation of Cyclic Peroxides by Reaction of Polyketones with Hydrogen Peroxide Reaction of tetraacetylpropane with 2 moles of H2O2 leads to the formation of 4,4′-methylene-bis[3,5-dimethyl-1,2-dioxolane-3,5-diol] (1), whereas in acidic solution at 60° with 1 mole H2O2,7-acetyl-1,4,6-trimethyl-2,3,5,10-tetraoxa-tricyclo[4,3,1,04.9]decane (4) is formed. 4 and an excess of H2O2 in acidic solution at 60° gives perhydro-3,5,7a,8a-tetramethyl-bis[1,2-dioxolo(3,4-b;4′,3′-e)-pyran]-3,5-dihydroperoxide (5a). – From 1,1,2-triacetylethane and H2O2 in presence of sulfuric acid one gets 1,4,6-trimethyl-2,3,5,7,8-pentaoxatricyclo[4,2,2,o4,9]-decane (9). From a mixture of 3,4-diacetyl-2,5-dimethylfuran, 2n H2SO4, and H2O2 1,4,5,7-tetramethyl-1,4-dihydrofuro[3,4-d][1,2]dioxin-1,4-dihydroperoxide (8a) crystallizes. The O-benzoyl derivatives of the dihydroperoxides 5a and 8a are prepared from benzoylimidazole.