|Budget Amount *help
¥29,000,000 (Direct Cost: ¥29,000,000)
Fiscal Year 1991: ¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 1990: ¥4,000,000 (Direct Cost: ¥4,000,000)
Fiscal Year 1989: ¥22,000,000 (Direct Cost: ¥22,000,000)
|Keywords||alkylidene episulfides / thioally iron complexes / zirconocene dichloride / di-t-butylethanethial / 1, 2, 3, 4, 5-pentathiepane / 1, 2, 3-selenadiazole / thiadigermirane / silthiane / アレンエピスルフィド / βーチオアリル / チオアリル鉄トリカルボニル錯体 / チオアリルカチオン / 金属カルボニル / チオルテニウムクラスタ- / 1,2,3ーセレナジアゾ-ル / 硫黄 / 1,2,3ーブタトリエン / シクロドデカヘキサエン / ペンタスルフィド / 2原子硫黄 / エピスルフィド / シクロペンテンチオン / チオキシアリル / 1、2ージチオン / 1、2、3ーセレナジアゾ-ル / 1、2ージセレネタン|
The strain alkylidene episulfides were synthesized by carbene and alkylidene carbene addition to thiocarbonyl compounds. Thermal, photochemical and acid catalyzed reactions have been extensively investigated, and the transition metal promoted reaction results in the first isolation of thioally iron and ruthenium tricarbonyl complexes. The reaction of germylene with thioketene gave 3alkylidenethiagermirane. Thiagermetane is extremely sensitive toward oxygen as well as sulfur to yield corresponding ring expansion products. Zirconocene has been generated by various method. Addition of n-BuLi to zirconocene dichloride at -78ﾟC under agron followed by introduction of di-t-butylthioketene and work up with IO%HCI gave di-t-butylethanethial and its isomer, di-t-butylethenethiol. The intermediate, zirconocene thioacyl complex was formed in a moderated yield. Sulfurization of alkylideneallene was easily performed by heating with excess of elemental sulfur in DMF at 110o to give the corresponding allene episulfide. On the other hand, sulfurization of 1, 2, 3-butatriene with elemental sulfur gave 1, 2, 3, 4, 5-pentathiepane derivative as yellow crystals. On the other hand, 1, 2, 3-butatriene with selenium in the presence of DBU gave 1, 2, 5-triselenepane derivatives. Sulfurization of fused 1, 2, 3-selenadiazole with elemental sulfur at 120ﾟC gave nonathiacycloundecene, 1, 2, 3-trithiole. Photolysis or thermolysis of hexamesitylcyclotrigennane with elemental sulfur produced the thiadigermirane along with dithiadigermetane. On the other hand, the trihydrosilane bearing bulky substituent reacts with elemental sulfur and selenium to give the cage molecule such as adamantane type silthiane. All new compounds were characterized by NMR.