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

通过卡宾和亚烷基卡宾与硫代羰基化合物的加成反应合成了亚烷基环硫化物。热，光化学和酸催化反应已被广泛研究，和过渡金属促进的反应的结果在第一次分离的硫代烯丙基铁和钌三羰基配合物。锗烯与硫代烯酮反应生成3-亚烷基硫锗烷。硫锗烷对氧和硫极其敏感，产生相应的扩环产物。二茂锆的生成方法有多种。在-78 ° C下，在Agron下，将n-BuLi加入到二氯二茂锆中，然后引入二叔丁基硫代烯酮，并用10% HCl处理，得到二叔丁基乙硫醇及其异构体二叔丁基乙硫醇。中间体二茂锆硫代酰基络合物以适度的产率形成。亚烷基联二烯在DMF中与过量的单质硫在110 ℃下加热容易地进行硫化，得到相应的联二烯环硫化物。另一方面，用元素硫硫化1，2，3-丁三烯得到1，2，3，4，5-五硫杂环庚烷衍生物，为黄色晶体。另一方面，在DBU存在下，1，2，3-丁三烯与硒反应生成1，2，5-三硒杂环庚烷衍生物。稠合的1，2，3-硒二唑与元素硫在120 ℃硫化得到九硫杂环十一烯，1，2，3-三硫杂环戊烯.六均三甲苯基环三萜烷与元素硫的光分解或热分解产生硫代二锗烷沿着产生二硫代二锗烷。另一方面，带有大体积取代基的三氢硅烷与元素硫和硒反应，得到笼状分子，如金刚烷型硅硫烷。所有新化合物均经核磁共振谱表征。

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.