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Basic Research for Establishment of Functionalized Organosilicon Chemistry

功能化有机硅化学建立的基础研究

基本信息

批准号：
07405043
负责人：
KOHEI Tamao
金额：
$ 12.42万
依托单位：
KYOTO UNIVERSITY
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

(1)Regioselective Synthesis of Polyfunctionalized AlkyloligosilanesHighly selective cross-coupling reactions promoted by lithium metal have been achieved between aminodichloromonosilanes and chlorosilanes or chlorodisilanes in THF to form the corresponding symmetrical and unsymmetrical aminotrisilanes in high yields. The amino group is converted to alkoxy group or fluorine.(2)Synthesis of Functionalized Siloles and Silole OligomersA series of 1,1-difunctionalized siloles have been synthesized from 1,1-diaminosiloles. Oligo (1,1-silole)s, silole oligomers catenated through silicons, have been synthesized as model compounds of poly (1,1-silole)s. Crystal structures and UV-vis spectra have been determined, in which tersilole and quatersilole have unique abdorption maxima around 280-290nm.(3)Synthesis and Structures of Tris [2-(dimethylamino) phenyl] silane and -germane CompoundsTris [2-(dimethylamino) phenyl] silane and -germane compounds were synthesized and charcterized by X-ray crastallography. Three 2-(dimethylamino) phenyl groups in the hydrosilane and hydrogermane encapsulate the hydrogen atom bonded to silicon and germanium, which results in the short Si-H and Ge-H bonds and an increase in the s character of the bonds. The silanol and germanol exist as monomers through the intramolecular hydrogen bonding between the hydroxy group and one of the amino groups.

（1）多官能化烷基低聚硅烷的区域选择性合成在金属锂的促进下，氨基二氯单硅烷与氯硅烷或氯二硅烷在THF中实现了高选择性的交叉偶联反应，高产率地合成了相应的对称和不对称氨基三硅烷。氨基被转化为烷氧基或氟。（2）功能化硅杂环戊烯和硅杂环戊烯低聚物的合成以1，1-二氨基硅杂环戊烯为原料合成了一系列1，1-双功能化硅杂环戊烯。低聚（1，1-噻咯）是通过硅链连接的噻咯低聚物，是聚（1，1-噻咯）的模型化合物。测定了它们的晶体结构和紫外-可见光谱，发现它们在280- 290 nm处有独特的吸收峰。（3）三[2-（二甲氨基）苯基]硅烷和三[2-（二甲氨基）苯基]-锗烷化合物的合成与结构合成了三[2-（二甲氨基）苯基]硅烷和三[2-（二甲氨基）苯基]-锗烷化合物，并用X射线晶体衍射对其结构进行了表征。氢化硅烷和氢化锗烷中的三个2-（二甲氨基）苯基包裹了与硅和锗键合的氢原子，这导致短的Si-H和Ge-H键，并增加了键的s特征。硅醇和锗醇通过羟基和氨基之间的分子内氢键作为单体存在。