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Application to New Molecular Design : Synthesis and Properties of Strained Heterocyclic Compounds

新分子设计的应用：应变杂环化合物的合成与性能

基本信息

批准号：
01430006
负责人：
ANDO Wataru
金额：
$ 18.56万
依托单位：
Tsukuba University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (A)
财政年份：
1989
资助国家：
日本
起止时间：
1989 至 1991
项目状态：
已结题

项目摘要

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.

以硫代羰基化合物为原料，用卡宾和烷基基卡宾加成合成了烷基亚二硫代化合物。热、光化学和酸催化反应已被广泛研究，过渡金属促进的反应首次分离出硫代铁和钌三羰基配合物。丁二烯与硫烯反应得到3烷基乙基丁二烯。硫代甲烷对氧和硫极为敏感，产生相应的扩环产物。锆石新世的生成方法多种多样。将n-BuLi加入到二氯化锆中，温度为-78ºC，然后引入二丁基硫烯，再以IO%的HCI加成，得到二丁基乙烷及其异构体二丁基乙烷醇。中间产物锆新世硫酰基络合物以中等产率生成。用过量的单质硫在110℃的DMF中加热，可以很容易地使烷基二烯硫化，得到相应的二硫化烯。另一方面，1,2,3 -丁腈与单质硫的硫化得到1,2,3,4,5 -五硫代烷衍生物为黄色晶体。另一方面，1,2,3 -丁烯与硒在DBU存在下得到1,2,5 -三烯烷衍生物。将1,2,3 -硒二唑与单质硫在120℃下硫化，得到1,2,3 -三硫唑。六烷基环三烯醚与单质硫的光解或热解产生二硫代三烯烷和二硫代三烯烷。另一方面，承载大体积取代基的三氢硅烷与单质硫和硒反应得到金刚烷型硅烷等笼状分子。所有新化合物都通过核磁共振进行了表征。