Study on Generation and Characterization of Reactive Intermediates Possessing Selenooxo Group

最近，已经报道了几种通过用具有反应性金属-硒键的硒化试剂处理将羰基化合物转化为相应的硒羰基化合物的方法。然而，硒代羰基化合物的合成常常受到制备和处理这类硒化试剂的困难的阻碍。在研究硒在合成硒羰基化合物中的应用时，我们曾预期二卤甲烷离子和三卤甲烷离子与活化的硒反应，将分别产生一些与未知的硒羰基化合物有关的活性物种，如“硒羰基卤化物”和“类硒膦酸盐”。我们想描述的新的硒化反应的基板的细节。在NaH和过量的胺存在下，用元素硒处理二卤甲烷衍生物、氯仿或三氯乙酸钠，以适度的产率得到相应的硒酰胺、硒脲和双（N，N-二烷基硒氨基甲酰基）三硒醚。这些产物是由二氯甲烷离子和三氯甲烷离子与N-烷基化氨基多硒化物物种（R2 N-（Se）n-）生成的与“硒代羰基卤化物”和“类硒代磷酸盐”相关的反应中间体得到的。

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-).