Study on Generation and Characterization of Reactive Intermediates Possessing Selenooxo Group

最近，已报道了几种方法，通过各种具有反应活性的金属-硒键的硒试剂处理，将羰基化合物转化为相应的硒羰基化合物。然而，由于硒试剂的制备和处理的困难，硒羰基化合物的合成常常受到阻碍。在元素硒的合成应用研究中，我们预计二卤代甲基稀土离子和三卤代甲基稀土离子与活化的元素硒反应将分别产生一些与迄今未知的硒羰基化合物有关的活性物种，如“硒羰基卤化物”和“硒磷化合物”。我们想要描述新的底物的硒反应的细节。二卤代甲烷衍生物、氯仿或三氯乙酸钠在NaH和过量胺的存在下与元素硒反应，以适量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N-烷基氨基多硒物种(R2N-(Se)n-)的二氯甲烷离子和三氯甲烷离子生成的与“硒羰基卤化物”和“硒磷化合物”有关的反应中间体提供的。

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-).