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

• 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
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08640692/
• 关键词: Organic Sulfur Compound; Cyclic Unsaturated Compound; Tetrathiocin; Disulfide Bond; Crystal Structure; Ring Expansion Reaction; 硫黄化合物; 分子軌道計算; 環化反応

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.

以顺式1，2-二硫醇二钠为原料，通过氧化反应成功地合成了环辛-1，5-二烯的sp^3碳上被硫原子取代的四硫辛（四硫环辛-3，7-二烯）1和八硫环十六碳-3，7，11，1,5-四烯2。1的X射线结构呈扭曲型（近D_2对称），2的晶体结构呈笼形（近D_<2d>对称），并带有空腔。笼状结构表明化合物2有望成为一种具有两种配位位置（烯烃的π电子和硫原子上的孤对电子）的新型包合物。1的比较也进行了研究的基础上从头算分子轨道计算。1的扭曲构象被计算为在所有构象中具有最低的势能，并且最稳定的几何形状与1的X射线结构显示出良好的一致性。此外，稳定的几何形状被发现之间的1和相应的碳类似物（环辛-1，5-二烯）是不同的。四硫菌素1是热稳定的，即使在对二甲苯中3小时后也没有观察到分解。然而，化合物1在极性溶剂如乙腈/氯仿溶液中发生变化，即使在室温下也以良好的产率得到扩环产物2。还发现化合物1对辐射不稳定，甚至对室内光也不稳定。1在苯溶液中辐照，与双环化合物一起形成橡胶状黄色聚合物。

项目成果

T.Shimizu, K.Iwata, H.Murakami, N.Kamigata: "Synthesis, Structures, and Reactivities of Sulfur-Containing Cycloalkenes" Phosphorus, Sulfur, Silicon, and the Related Elements. 120-121. 457-458 (1997)

T.Shimizu、K.Iwata、H.Murakami、N.Kamigata：“含硫环烯烃的合成、结构和反应性”磷、硫、硅和相关元素。

T.Shimizu,K.Iwata,N.Kamigata,S.Ikuta: "Conformational Strains of(Z.Z)-,(E,Z)-and(E,E)-1,2,5,6-Tetrathiacycloocta-3,7-dienes based on ab initio Molecular Orbital Calculations" J.Chem.Res.(M). 1997(2). 344-354 (1997)

T.Shimizu、K.Iwata、N.Kamigata、S.Ikuta：“(Z.Z)-,(E,Z)-和(E,E)-1,2,5,6-Tetrathiacycloocta-3的构象菌株，

T.Shimizu, K.Iwata, N.Kamigata: "Crystal Structures and Properties of Cyclic Polyenes Possessing Disulfide Units" Angew.Chem.,Int.Ed.Engl.35(20). 2357-2359 (1996)

T.Shimizu、K.Iwata、N.Kamigata：“具有二硫化物单元的环状多烯的晶体结构和性质”Angew.Chem.，Int.Ed.Engl.35(20)。

T,Shimizu, K.Iwata, M.Kondo, S.Kitagawa, N.Kamigata: "meso-3,3'-Bi(1,2,4-trithiacyclohex-5-enyl)" Acta Cryst.C53. 748-749 (1997)

T，Shimizu，K.Iwata，M.Kondo，S.Kitakawa，N.Kamigata：“meso-3,3-Bi（1,2,4-trithiacyclohex-5-enyl）”Acta Cryst.C53。

T.Shimizu,N.Kamigata,et al.: "meso-3,3'-Bi(1,2,4-trithiacyclohex-5-enyl)" Acta Cryst.C53. 748-749 (1997)

T.Shimizu,N.Kamigata,et al.：“meso-3,3-Bi(1,2,4-trithiacyclohex-5-enyl)”Acta Cryst.C53。