Design of Bowl-shaped Molecules and Their Application to the Stabilization of Highly Reactive Species

碗形分子的设计及其在高反应性物质稳定中的应用

基本信息

  • 批准号:
    06453062
  • 负责人:
  • 金额:
    $ 5.31万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for General Scientific Research (B)
  • 财政年份:
    1994
  • 资助国家:
    日本
  • 起止时间:
    1994 至 1995
  • 项目状态:
    已结题

项目摘要

In this study bowl-shaped molecules with calix [6] arene and cyclophane skeletons were designed and synthesized. First, the synthesis of some new bicyclic cyclophanes having some functional groups were carried out using an orcinol benzyl ether unit as a central bridge and a diphenylmethane unit as a peripheral ring. The structures of these cyclophanes were studied by NMR and X-ray crystallography to show that the diameter of their cavity is about 14@90. The thermolysis of a compound having a sulfoxide functionality in the cavity gave the first stable arenesulfenic acid. Second, bowl-shaped molecules having a calix [6] arene skeleton were synthesized using calix [6] arenes and 2,6-bis (bromomethyl) benzene derivatives with azide and t-butylthio substituents in the cavity and their structures were studied by NMR and X-ray crystallography. Here again, a stable arenesulfenic acid was synthesized by thermolysis of a sulfoxide. Both bromo and sulfenic acid derivatives were shown to have 1,2,3-alternate conformations. The photolysis of an azide derivative afforded unusual products derived from insertion of the intermediary nitrene into calixarene ring.
本研究设计并合成了具有杯[6]芳烃和环番骨架的碗状分子。首先,以地衣酚苄基醚单元为中心桥,二苯基甲烷单元为外环,合成了一些具有某些官能团的新型双环环番化合物。用核磁共振和X-射线结晶学研究了它们的结构,表明它们的空腔直径约为14@90。在腔内热分解具有亚硫氧基官能团的化合物,得到第一个稳定的芳磺酸。其次,以杯[6]芳烃和2,6-二(溴甲基)苯衍生物为原料,合成了具有杯[6]芳烃骨架的碗状分子,并用核磁共振和X-射线单晶对其结构进行了表征。在这里,我们又一次通过亚砜的热解合成了稳定的芳磺酸。溴酸衍生物和磺酸衍生物都具有1,2,3-交替构象。叠氮衍生物的光解产生了不寻常的产物,这是通过将中间体硝烯插入到杯芳烃环中而得到的。

项目成果

期刊论文数量(40)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
R.Okazaki: "Synthesis of Novel Lantern-Shaped Molecules Based on Resorcin[4]arene and m-Terphenyl Units" Tetrahedron Letters. 36. 7677-7680 (1995)
R.Okazaki:“基于间苯二酚[4]芳烃和间三联苯单元的新型灯笼形分子的合成”四面体快报。
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    0
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N.Tokitoh: "Synthesis and Crystal Structure of the First Stable Diaryl-germanethione" J.Am.Chem.Soc.115. 8855-8856 (1993)
N.Tokitoh:“第一个稳定的二芳基-锗硫酮的合成和晶体结构”J.Am.Chem.Soc.115。
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    0
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  • 通讯作者:
R.Okazaki: "Synthesis and Structure of a Bridged Calix [6] arene with a Sulfenic Acid Functionality in the Cavity" J. Org. Chem.61(in press). (1996)
R.Okazaki:“腔内具有磺酸官能团的桥接杯 [6] 芳烃的合成和结构”J. Org。
  • DOI:
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    0
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  • 通讯作者:
K.Goto: "Synthesis of a Stable Arenesulfenic Acid Bearing a Bowl-shaped Macrobicyclic Cyclophane Skeleton" Angew.Chem.(in press).
K.Goto:“带有碗形大双环环烷骨架的稳定芳烃磺酸的合成”Angew.Chem.(印刷中)。
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  • 影响因子:
    0
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  • 通讯作者:
R.Okazaki: "Abnormal Reaction of an Aryl Azide Confined in a Calix [6] arene Skeleton" J. Chem. Soc., Chem. Commun.1899-1900 (1995)
R.Okazaki:“限制在杯 [6] 芳烃骨架中的芳基叠氮化物的异常反应”J. Chem。
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    0
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OKAZAKI Renji其他文献

OKAZAKI Renji的其他文献

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{{ truncateString('OKAZAKI Renji', 18)}}的其他基金

Synthesis of Novel, Highly Reactive Sulfur-containing Species by Taking Advantage of Steric Protection
利用空间保护合成新型高活性含硫物质
  • 批准号:
    16550045
  • 财政年份:
    2004
  • 资助金额:
    $ 5.31万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Synthesis, Structure, and Reactivities of Doubly Bonded Compounds Between Heavier 14 Group Elements and Oxygen
较重 14 族元素与氧之间双键化合物的合成、结构和反应性
  • 批准号:
    12440182
  • 财政年份:
    2000
  • 资助金额:
    $ 5.31万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
Synthesis, Structure, and Reactivity of Stable Silabenzenes
稳定硅苯的合成、结构和反应活性
  • 批准号:
    10440184
  • 财政年份:
    1998
  • 资助金额:
    $ 5.31万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
Synthesis and Application of Novel Organosulfur Compounds
新型有机硫化合物的合成及应用
  • 批准号:
    08304037
  • 财政年份:
    1996
  • 资助金额:
    $ 5.31万
  • 项目类别:
    Grant-in-Aid for Scientific Research (A)
Synthesis of Stable Silaaromatic Compounds by Taking Advantage of Steric Protection
利用空间保护合成稳定的硅杂芳族化合物
  • 批准号:
    08454197
  • 财政年份:
    1996
  • 资助金额:
    $ 5.31万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
Reactive Organometallics of Non-transition Metals
非过渡金属反应性有机金属化合物
  • 批准号:
    05236102
  • 财政年份:
    1993
  • 资助金额:
    $ 5.31万
  • 项目类别:
    Grant-in-Aid for Scientific Research on Priority Areas
Syntheses and Properties of Novel Organic Compounds of Heavier 14,15, and 16 Group Elements
重14,15和16族元素的新型有机化合物的合成和性质
  • 批准号:
    04403005
  • 财政年份:
    1992
  • 资助金额:
    $ 5.31万
  • 项目类别:
    Grant-in-Aid for General Scientific Research (A)
Molecular Transformation Based on Design of Novel Reaction Environment
基于新型反应环境设计的分子转化
  • 批准号:
    02303003
  • 财政年份:
    1990
  • 资助金额:
    $ 5.31万
  • 项目类别:
    Grant-in-Aid for Co-operative Research (A)
Development and Application of New Steric Protection Group for Stabilization of Highly Reactive Organic Species
新型空间保护基团稳定高反应性有机物的开发与应用
  • 批准号:
    01470020
  • 财政年份:
    1989
  • 资助金额:
    $ 5.31万
  • 项目类别:
    Grant-in-Aid for General Scientific Research (B)

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合成刺激响应性环芳低聚物以控制客体分子的捕获和释放
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