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Development of Novel Synthetic Methods of (Polyfluoro) silanes and Their Application to Creation of Functional Materials

（多氟）硅烷新合成方法的发展及其在功能材料制造中的应用

基本信息

批准号：
09450331
负责人：
KOMATSU Mitsuo
金额：
$ 8.96万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1998
项目状态：
已结题

项目摘要

In this project are investigated development of new methods for synthesis of (polyfluoro)silanes, which bear more than two different functional groups, and their application to creation of functional materials such as heterocycles and organic silicon polymers. Major results obtained are summarized below.1) Selective and efficient synthesis of a variety of hydrobromosilanes with high yields were achieved by treatment of hydrosilanes with copper bromide(II)/ copper iodide(I). Selective bromination of (polyhydro)silanes and (polyhydro)-disilanes were also successful.2) Highly efficient novel methodology for generation of azomethine ylides, typical 1,3-dipolar intermediates, utilizing di- or trifluorosilanes was found. Thus azaallyl anions or alpha-silylimines were treated with the fluorosilanes at room temperature to give azomethine ylides, which readily cycloadded to dipolaro-philes to afford various heterocycles.3) Treatment of alpha-silylimidates, or in-situ generated imidates from alpha-silylamides, with trifluorosilanes caused generation of azomethine ylide intermediates even at room temperature and their cycloadditions afforded a variety of heterocycles.4) To develop silicon-containing polymeric materials, synthetic methods of poly(silylenephenylene)s bearing Si-Cl and Si-F bonds were established. Various functional groups were introduced onto silicon atoms by nucleophilic displacement of the halogen moieties. Among them, a polymer containing ethynylphenyl functionality showed excellent heat-resistant ability.5) Several silicon-bridged bithiophenes were unprecedently synthesized via difluorosilane derivatives and this class of compounds are good candidates for electron-transportaing materials.

在该项目中，研究了具有两个以上不同官能团的（多氟）硅烷合成新方法的开发，及其在创建杂环和有机硅聚合物等功能材料中的应用。主要研究成果如下：1)通过溴化铜(II)/碘化铜(I)处理氢硅烷，实现了多种氢溴硅烷的选择性、高效合成，且收率高。 (多氢)硅烷和(多氢)-乙硅烷的选择性溴化也取得了成功。2) 发现了利用二氟硅烷或三氟硅烷生成偶氮甲碱叶立德（典型的1,3-偶极中间体）的高效新方法。因此，在室温下用氟硅烷处理氮杂烯丙基阴离子或α-甲硅烷基亚胺，得到偶氮甲碱叶立德，其容易环加成到亲偶极子上以提供各种杂环。3)用三氟硅烷处理α-甲硅烷基亚胺酯或由α-甲硅烷基酰胺原位生成的亚胺酯，引起偶氮甲碱的生成即使在室温下也能生成叶立德中间体，并且它们的环加成提供了多种杂环。4)为了开发含硅聚合物材料，建立了带有Si-Cl和Si-F键的聚(亚硅基亚苯基)的合成方法。通过卤素部分的亲核置换将各种官能团引入到硅原子上。其中，含有乙炔基苯基官能团的聚合物表现出优异的耐热能力。5)通过二氟硅烷衍生物前所未有地合成了几种硅桥联噻吩，此类化合物是电子传输材料的良好候选者。