Systematic Studies on the Synthesis, Structures, and Properties of Aromatic Compounds Containing Heavier Group 14 Elements

含重14族芳香族化合物的合成、结构与性能的系统研究

• 批准号: 11304045
• 负责人: TOKITOH Norihiro
• 金额: $ 24.65万
• 依托单位: Kyoto University (2000-2001)Kyushu University (1999)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11304045/
• 关键词: steric protection; kinetic stabilization; silbenzene; 1-silanaphthalene; 2-silanaphthalene; 9-silaanthracene; germabenzene; 2-germanaphthalene; 芳香族化合物; ゲルマニウム

There has been no stable, neutral heteraaromatic compounds containing heavier group 14 elements, and their structures and properties have been revealed yet. In this Project, we studied on the synthesis of new type of heteraaromatic compounds containing a heavier group 14 element by taking advantage of an effective steric protection group, 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (Tbt), which is developed by us, and elucidated their structures and properties. Based on these results, we estimated the aromaticity of these compounds, systematically.We succeeded in the synthesis and isolation of the first stable silabenzene, 1-silanaphthalene, 2-silanaphthalene, 9-silaanthracene, germabenzene, and 2-germanaphthalene as stable crystals by taking advantage of Tbt group. The X-ray structural analyses, spectral data on NMR, UV/vis, and Raman spectroscopy, and theoretical calculations indicated that all these compounds are aromatic compounds as aromaticity these compounds showed the high reactivities to H_2O, alcohols, olefins, alkynes, ketones, and nitrile oxides and underwent ready addition of these reagents to the Si=C or Ge=C double-bond.We think that the new knowledge obtained in this project lays the foundations of the chemistry of heteraaromatic compounds containing heavier group 14 elements. We expect that novel properties and functions of heteraaromatic compounds containing heavier group 14 elements will be revealed on the basis of these results, showing the potential applicability and these chemistry will be applied to the synthesis of novel functional compounds and novel catalysis.

项目成果

Norihiro Tokitoh: "Formation of Antimony-Sulfur Double-Bond Compounds and Their Trapping with Nitrile Oxides"Heteroatom Chem.. 12. 244-249 (2001)

Norihiro Tokitoh：“锑硫双键化合物的形成及其与腈氧化物的捕获”Heteroatom Chem.. 12. 244-249 (2001)

Norihiro Taketh: "The Chemistry of Germanium-containing Heavy Ketone"Bull. Chem. Soc. Jpn.. 72. 1665-1684 (1999)

Norihiro Taketh：《含锗重酮的化学》牛。

Norihiro Tokitoh: "Recent Topics in the Chemistry of Heavier Congeners of Carbenes"Coord.Chem.Rev.. 210. 251-277 (2000)

Norihiro Tokitoh：“卡宾重同系物化学的最新主题”Coord.Chem.Rev.. 210. 251-277 (2000)

Renji Okazaki: "Heavy Ketones, the Heavier Element Congeners of a Ketone"Acc.Chem.Res.. 2000. 625-630 (2000)

Renji Okazaki：“重酮，酮的较重元素同系物”Acc.Chem.Res.. 2000. 625-630 (2000)

Takahiro Sasamori: "Novel Disproporitionation Reaction of Stable Stibabismuthene via 1,2,3,4-Distibadibismetane Derivative"Phosphorus, Sulfur and Silicon. 168-169. 413-416 (2001)

Takahiro Sasamori：“通过 1,2,3,4-Distibadibismetane 衍生物”磷、硫和硅进行稳定 Stibabismuthene 的新型歧化反应。