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Unexpected cleavage of thiacalix[4]arene sulfoxides

机译:意外的硫屈绝裂解[4]芳烃亚砜

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摘要

Thiacalix[4] arenes having one bridge oxidized to a sulfoxide moiety can react with organolithium reagents to form cleaved structures which are otherwise difficult to access. Cleavage of the macrocyclic skeleton is independent of the starting conformation as proven by the same product obtained from the corresponding cone, partial cone or 1,3-alternate derivatives. Quenching of the crude reaction mixture with D2O allowed elucidation of the mechanism which is based on the ligand exchange of the sulfoxide functionality. The general applicability of this reaction was demonstrated using the corresponding distal or proximal disulfoxide derivatives, while the quenching of the reaction mixture using various electrophiles allowed the isolation of the corresponding mono-and di-substituted oligomers. The structure of the unexpected product (a tetrameric derivative) was assigned by single crystal X-ray crystallography.
机译:具有氧化成亚砜部分的一座桥的硫克氏菌[4]可以与有机锂试剂反应以形成难以进入的切割结构。 宏环骨架的切割与由来自相应锥形,部分锥体或1,3-交替衍生物获得的相同产物的开始构象无关。 用D2O淬火粗反应混合物允许阐明基于亚砜官能度的配体交换的机制。 使用相应的远端或近端二氧化氧化酯衍生物对该反应的一般适用性进行说明,而使用各种电泳的反应混合物淬火允许分离相应的单氧和二取代的低聚物。 通过单晶X射线晶体学分配意外产品(四聚衍生物)的结构。

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  • 来源
    《RSC Advances》 |2017年第84期|共8页
  • 作者单位

    Univ Chem &

    Technol Prague Dept Organ Chem Tech 5 Prague 16628 6 Czech Republic;

    UCTP Solid State Dept Prague 16628 6 Czech Republic;

    Univ Chem &

    Technol Prague Dept Organ Chem Tech 5 Prague 16628 6 Czech Republic;

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  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 化学;
  • 关键词

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