权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

Development of New Processes for the Introduction of Heteroatoms and their Synthetic Applications

杂原子引入新工艺的开发及其合成应用

基本信息

批准号：
05555240
负责人：
SONODA Noboru
金额：
$ 9.22万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Developmental Scientific Research (B)
财政年份：
1993
资助国家：
日本
起止时间：
1993 至 1994
项目状态：
已结题

项目摘要

Radical reactions between organic dichalcogenides and carbon-carbon unsaturated compounds have been investigated precisely. Based on the relative reactivities of organic dichalcogenides and chalcogen-centered radicals, it has become apparent that two different chalcogeno-groups can be introduced simultaneously into a variety of carbon-carbon multiple bonds with excellent selectivity. Upon irradiation with the light of wavelength over 300 nm, the reaction of acetylenes with organic disulfides and diselenides takes place smoothly to provide the corresponding thioselenation products regioselectively. Similar additions can be employed with allenes and 1,3-dienes, affording beta-selenoallylic sulfieds and gamma- (selenomethyl) -allylic sulfides, respectively, in good yields. With vinylcyclopropanes, thioselenation via ring-opening of cyclopropane occurs to give gamma- (selenomethyl) allylic sulfides. With enynes, thioselenation via radical cyclization is demonstrated successfully. In additi … More on, novel mixed systems of organic dichalcogenides, i.e., a disulfide-ditelluride mixed system and a diselenide-ditelluride mixed system have been developed. Both systems require the irradiation with light of wavelength over 400nm, because UV or near UV light causes the decomposition of the products bearing a photo-sensitive C-Te bond. From acetylenes are thus obtained beta-thio-and beta-selenovinylic tellurides, respectively. With allenes and 1,3-dienes, however, the desired thiotelluration products are not formed at all, but instead dithiolation products are obtained. Further investigation on this disulfide-ditelluride-allene system leads to successful development of a novel telluride-catalyzed dithiolation reaction of allenes with disulfides. Similary, a selenide-catalyzed dithiolation of 1,3-dienes to give 1,4-dithiolation products are disclosed. Both systems has enabled the efficient dithiolation of allenes and 1,3-dienes, which is difficult to be attained by using a disulfide single system. Less

研究了有机二烃类化合物与碳-碳不饱和化合物之间的自由基反应。基于有机二卤化物和硫族中心自由基的相对反应性，很明显，两个不同的硫族基团可以同时引入到各种碳-碳多键中，具有很好的选择性。在波长超过300 nm的光照下，乙炔与有机二硫化物和二硒化物的反应顺利进行，得到相应的硫代选择性产物。类似的加成可用于烯烃和1，3-二烯，分别以良好的产率分别得到β-硒烯丙基硫化物和伽马-(硒甲基)-烯丙基硫化物。在乙烯基环丙烷中，通过环丙烷的开环反应进行硫代硒化合成γ-(亚硒甲基)烯丙基硫化物。在烯炔类化合物中，通过自由基环化反应成功地实现了硫醚化反应。此外，…此外，还开发了新的有机二氢碳化物混合体系，即二硫化物-二碲酸盐混合体系和二硒醚-二碲碳化物混合体系。这两个体系都需要波长超过400 nm的光照射，因为紫外光或近紫外光会导致带有光敏C-Te键的产品分解。因此，从乙炔中分别得到β-硫代和β-亚硒酸碲化物。然而，对于烯烃和1，3-二烯，根本没有形成所需的硫代化产物，而是得到了二硫代化产物。通过对该体系的进一步研究，成功地开发了一种新型的碲化物催化的二硫代烯与二硫化物的二硫代化反应。类似地，公开了一种硒催化的1，3-二烯二硫代化得到1，4-二硫代化产物。这两个体系都能有效地实现二硫代烯和1，3-二烯的二硫代化反应，这是使用二硫键单一体系难以实现的。较少