Synthesis and Reactivity of Cyclic Unsaturated Compounds Substituted by 16 Group Elements

16族元素取代环状不饱和化合物的合成及反应活性

基本信息

批准号：
08640692
负责人：
SHIMIZU Toshio
金额：
$ 0.83万
依托单位：
TOKYO METROPOLITAN UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1996
资助国家：
日本
起止时间：
1996 至 1997
项目状态：
已结题

项目摘要

Tetrathiocin (tetrathiacycloocta-3,7-diene) 1, substituted by sulfur atoms at the sp^3 carbons of cycloocta-1,5-diene, and octathiacyclohexadeca-3,7,11,15-tetraene 2 were synthesized successfully by oxidation of cis-disodium ethene-1,2-dithiolate. The X-ray structure of 1 showed the twist form (nearly D_2 symmetry), and the crystal structure of 2 was found to have cage geometry (nearly D_<2d> symmetry) possessing a cavity. The cage structure indicates that the compound 2 is expected to become a new inclusion compound with two types of coordination site (pi-electrons of the olefins and lone pairs on the sulfur atoms). A comparison of 1 was also studied based on ab initio MO calculations. The twist conformer of 1 was calculated to have the lowest potential energy among all the conformers, and the most stable geometry showed good agreement with the X-ray structure of 1. Furthermore, stable geometries were found to be different between 1 and corresponding carbon analogue (cycloocta-1,5-diene). Tetrathiocin 1 was thermally stable and no decomposition was observed even in refluxing p-xylene after 3 h. However, compound 1 changed in polar solvent, such as acetonitrile/chloroform solution, even at room temperature to give the ring expansion product 2 in good yield. Compound 1 was also found to be unstable toward irradiation, even room light. Irradiation of 1 in a benzene solution, a rubber-like yellow polymer was formed together with bicyclic compound.

四磷酸蛋白（四磷酸3,7-7-二烯）1，用硫原子取代，在Cycloocta-1,5-二烯的Sp^3碳中，八脂蛋白二氧化碳-3,7,7,1115-泰恩2成功地通过了氧化度，由氧化度合成。 1的X射线结构显示出扭曲形式（几乎是D_2对称性），发现2的晶体结构具有具有空腔的笼几何（几乎D_ <2d>对称性）。笼子结构表明化合物2有望成为具有两种类型的配位位点的新纳入化合物（硫化原子上的烯烃和孤对的Pi-Electrons）。还根据从头算机计算进行了比较1的比较。计算出1的扭曲构象异构体在所有构象异构体中具有最低的势能，最稳定的几何形状与1的X射线结构非常吻合。此外，发现稳定的几何形状在1之间且相应的碳模拟（cycloocloocta-1,5-二烯）之间有所不同。四硫素1是热稳定的，即使在3小时后回流P-二甲苯中也没有观察到分解。但是，即使在室温下，也可以在室温下以良好的产量给环膨胀产物2变化，例如乙腈/氯仿溶液，例如乙腈/氯仿溶液。还发现化合物1对辐照，甚至是房间的光线不稳定。在苯溶液中辐照1，与双环化合物一起形成橡胶状的黄色聚合物。