Study on Generation and Characterization of Reactive Intermediates Possessing Selenooxo Group

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Recently, several methods have been reported for the conversion of carbonyl compounds to the corresponding selenocarbonyl compounds by the treatment with various selenating reagents possessing reactive metal-selenium bonds. However, the syntheses of the selenocarbonyl compounds have often been impeded by the difficulty of the preparation and the treatment of such selenating reagents. During our studies on the synthetic use of elemental selenium for the convenient syntheses of selenocarbonyl compounds, we have expected that the reaction of dihalomethanide ions and trihalomethanide ion with activated elemental selenium would afford some reactive species related to hitherto unknown selenocarbonyl compounds such as "selenocarbonyl halides" and "selenophosgenoids", respectively. We would like to describe the detail of the novel selenation reaction of the substrates. Treatment of dihalomethane derivatives, chloroform, or sodium trichloroacetate with elemental selenium in the presence of NaH and an excess amount of an amine gave the corresponding selenoamides, Selenoureas, and bis (N,N-dialkylselenocarbamoyl) triselenides in modest yields. These products were afforded from reactive intermediates related to "selenocarbonyl halides" and "selenophosgenoids" generated by the dichloromethanide ions and trichloromethanide ion with N-alkylated aminopolyselenide species (R2N- (Se) n-).