Alumina carbonyl epoxidation

Cyclododecene may be prepared from 1,5,9-cyclododecatriene by the catalytic reduction with Raney nickel and hydrogen diluted with nitrogen, with nickel sulfide on alumina, with cobalt, iron, or nickel in the presence of thiophene, with palladium on charcoal, with palladimn chloride in the presence of water, with palladium on barium sulfate, with cobalt acetate in the presence of cobalt carbonyl, and with cobalt carbonyl and tri- -butyl phosphine. It may also be obtained from the triene by reduction with lithium and ethylamine, by disproportionation, - by epoxidation followed by isomerization to a ketone and WoliT-Kishner reduction, and from cyclododecanone by the reaction of its hydrazone with sodium hydride. ... 

Epoxides (see also a,(3-Epoxy alcohols, etc., Glycidic acids, esters, nitriles) From alkenes by epoxidation Dimethyldioxirane, 120 Fluorine-Acetonitrile, 135 Potassium peroxomonosulfate, 259 From carbonyl compounds Alumina, 14... 

Support for the new mechanism was provided by trapping the intermediate with methyl iodide to give epoxide 133. The structure of this compound was indicated by IR absorption at 1646 cm- (2-quinolone carbonyl) and by the NMR spectrum. The epoxide was converted readily into the diol balfourolone (135) on alumina chromatography or by treatment with 2 N sodium hydroxide at 20° the mild conditions and the failure of 2,4-dimethoxyquinoline epoxides (e.g., 109) to react under similar conditions suggest that this reaction occurs through formation of O-methylbalfourodinium salt (134) and subsequent nucleophilic attack at the 2-position rather than by direct reaction of hydroxide ion on the epoxide ring. Epoxide 133 is the presumed intermediate in reaction of 4-methoxy-... 

---