Study on Generation and Characterization of Reactive Intermediates Possessing Selenooxo Group

• Project/Area Number: 07651044
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Iwate University
• Principal Investigator: TAKIKAWA Yuji Iwate University Faculty of Engineering, Professor, 工学部, 教授 (00003848)
• Co-Investigator(Kenkyū-buntansha): SHIMADA Kazuaki Iwate University Faculty of Engineering, Associate Professor, 工学部, 助教授 (10142887)
• Project Period (FY): 1995 – 1996
• Project Status: Completed (Fiscal Year 1996)
• Budget Amount: ¥2,100,000 (Direct Cost: ¥2,100,000); Fiscal Year 1996: ¥400,000 (Direct Cost: ¥400,000); Fiscal Year 1995: ¥1,700,000 (Direct Cost: ¥1,700,000)
• Keywords: Selenophosgen / Selenoacyl halide / Dihalomethanide ion / Selenoamide / Selenourea / Reactive Species / Selenooxo Group / セレノオキソ化合物 / 含セレン活性化学種

Research Abstract

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-).

Research Products

• [Publications] Kazuaki Shimada, Minoru Yamaguchi, Tohru Sasaki, Kenji Ohnishi, Yuji Takikawa: "A Willgerodt-Kindler Type Selenation of Dihalomethane Derivatives, Chloroform, and Sodium Trichloroacetate by Treating with a Base, Elemental Selenium, and Amine" Bull. Chem. Soc. Jpn.69(8). 2235-2242 (1996)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Kazuaki Shimada, Minoru Yamaguchi, Tohru Sasaki, Kenji Ohnishi, and Yuji Takikawa: "A Willgerodt-KIndler Type Selenation of Dihalomethane Derivatives, Chloroform, and Sodium Trichloroacetate by Treating eith a Base, Elemental Selenium, and an Amine" Bulletin of the Chemical Society of Japan. 69(8). 2235-2242 (1996)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Kazuaki Shimada Minoru Yamaguchi Tohru Sasaki Kenji Ohnishi Yuji Takikawa: "A Willgerodt-Kindler Type Selenation of Dihalomethane Derivatives,Chloroform,and Sodium Tricloroacetate by Treating with a Base,Elemental Selenium,and an Amine" Bull. Chem. Soc. Jpn.69(8). 2235-2242 (1996)