Studies on the Active Molecules Prepared by Accumulation and Amplification of the Transannular Interaction between Chalcogen Atoms

硫族原子跨环相互作用累积放大制备活性分子的研究

基本信息

批准号：
07404035
负责人：
FURUKAWA Naomichi
金额：
$ 22.27万
依托单位：
University of Tsukuba
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1997
项目状态：
已结题

项目摘要

In this studies, it was described the preparation of the dications having 2-center-2-electron [2c-2e] system and highcoordinated dications having 3-center-4-electron [3c-4e] bonds using organic compounds bearing multiple-chalcogen atoms arranged in space. The dications of [2c-2e] substituted by alkyl and benzyl groups at the chalcogen atoms were found to be quite reactive, and their formation was either undetected or detected only by low temperature ^1H-and ^<13>C-nmr spectroscopy. These dications once formed undergo facile dealkylation to afford N-alkyl acetamides which are trapped by CH_3CN used as a solvent together with thia-sulfonium salts in high yields. The mechanism for this dealkylation is rationally explained to proceed via an S_Nl-type substitution mechanism. On the other hand, the photolysis of the monooxides, mono-N-tosylsulfilimines and mono-S-ylides of naphtho [1,8-de] -1,3-dithiin provided the corresponding ketones, N-imines and olefins quantitatively. The photolysis re … More actions may proceed via the activation of the S-S interaction of these compounds. As to the highcoordinated [3c-4e] dication species, 1-phenyl 2,6-dimethylthiomethylphenyl tellurides were converted to the telluranes on oxidation. Similarly, 1,11-methanoseleno- [or-thio] diselenocin (or dithiocin) afforded the corresponding selenurane (or sulfurane) compounds on treatment of the diselenocin (or dithiocin) with one electron oxidant such as NOBF_4. These [3c-4e] hypervalent dications can be converted readily to the starting tris-selenides (or sulfides) by reducing the dications. In these oxidation-reduction reactions of the trisselenides (or sulfides), these compounds show molecular hysteresis during oxidation-reduction. The dications were stable enough to be isolated and their structures were determined by X-ray crystallographic analysis. The ab initio MO-calculation of these compounds reveal the charge-distribution among the atoms in the hypervalent molecules which was discussed with their reactivities. Less

在这项研究中，描述了使用带有多硫属元素的有机化合物制备具有2-中心-2-电子[2c-2e]体系的双阳离子和具有3-中心-4-电子[3c-4e]键的高配位双阳离子发现在硫族原子上被烷基和苄基取代的[2c-2e]的原子具有相当的反应性，并且它们的形成要么未被检测到，要么被检测到。仅通过低温1 H-和13 C-核磁共振光谱检测到这些双阳离子一旦形成就容易脱烷基化以提供N-烷基乙酰胺，其被用作溶剂的CH_3CN与硫锍盐一起以高收率捕获。这种脱烷基化的机制被合理地解释为通过 S_Nl 型取代机制进行。另一方面，一氧化物的光解作用，单-N-甲苯磺酰亚胺和萘并[1,8-de]-1,3-二噻英的单-S-叶立德定量地提供相应的酮、N-亚胺和烯烃。光解反应可以通过活化进行。这些化合物的S-S相互作用。对于高配位的[3c-4e]阳离子物种，1-苯基2,6-二甲硫基甲基苯基碲化物。类似地，1,11-亚硒代-[或-硫代]二硒代辛（或二硫辛）在用一种电子氧化剂（例如二硫代辛）处理时得到相应的硒烷（或硫烷）化合物。 NOBF_4。这些[3c-4e]超价二价化合物可以很容易地转化为起始三硒化物（或在三硒化物（或硫化物）的这些氧化还原反应中，这些化合物在氧化还原过程中表现出分子滞后现象，足以被分离，并且通过X射线晶体分析确定了它们的结构。这些化合物的从头计算 MO 计算揭示了超价分子中原子之间的电荷分布，并对其反应性进行了讨论。