Synthesis of σ-π conjugated non-linear optical materials by olefin metathesis

烯烃复分解合成σ-π共轭非线性光学材料

• 批准号: 10650773
• 负责人: KAWAI Tadashi
• 金额: $ 2.37万
• 依托单位: TOKYO METROPOLITAN UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10650773/
• 关键词: metathesis; cross-metathesis; non-linear optical material; σ-π conjugated materials; π-conjugated materials; vinylarenes; vinylferrocene; vinylsilanes; vinylsilane; オレフィンメタセシス; クロスメタセシス; ビニル芳香族化合物; ヘテロダイマー; Re_2O_7-Al_2O_3(レニア-アルミナ)触媒; σ-π共役

σ-π hybrid conjugated molecules have been expected as new organic materials with optical non-linearities with high transparency. Poly (silylene-vinylene) s are one of these candidates.Syntheses of poly (silylene-vinylene) s by olefin metathesis were attempted for the first time. New compounds, oligo (silylene-vinylene) s (dimer〜oligomer) of linear type were synthesized by self-metathesis of tetravinylsilane and dimethyldlvinylsilane, and 1,4-bis(dimethylvinylsilyl) benzene using Re_2O_7-Al_2O_3 catalyst under mild reaction conditions. It was found they are σ-π hybrid conjugated molecules with high transparency, but higher oligomer and polymer could not be obtained. The spectroscopic studies revealed that their optical nonlinearities are weak.Ferrocene is known as one of interesting compounds with optical non-linearities.Novel selective synthesis of π -conjugated molecules with various interesting functional group by cross-metathesis were attempted for the two systems over Grubbs and Schrock catalyst. (1) Cross-metathesis of various kinds of vinylarene and vinylhetroaromatics with 1 -octene, and (2) Cross-metathesis reactions between vinylferrocene and a series of vinylarene. Self -metathesis of vinylferrocene was not occurred, but Interestingly cross-metathesis proceeded to yield heterodimer (cross-metathesis product) with high selectivity (73-100 %) in the presence of the Schrock catalyst. The mechanism of selective heterodimer formation was proposed.

σ-π杂化共轭分子有望成为具有光学非线性和高透明度的新型有机材料。聚(硅撑-亚乙烯基)是这些候选者之一。首次尝试通过烯烃复分解合成聚(硅撑-亚乙烯基)。以Re_2O_7-Al_2O_3为催化剂，在温和的反应条件下，通过四乙烯基硅烷和二甲基二乙烯基硅烷与1,4-双(二甲基乙烯基硅烷基)苯的自复分解合成了线性型低聚(亚硅基-亚乙烯基)(二聚体〜低聚物)。结果发现它们是σ-π杂化共轭分子，具有较高的透明度，但无法得到更高的低聚物和聚合物。光谱研究表明它们的光学非线性很弱。二茂铁被认为是具有光学非线性的有趣化合物之一。在Grubbs和Schrock催化剂上，尝试通过交叉复分解两种体系选择性合成具有各种有趣官能团的π共轭分子。 （1）各种乙烯基芳烃、乙烯基杂芳烃与1-辛烯的交叉复分解反应；（2）乙烯基二茂铁与一系列乙烯基芳烃的交叉复分解反应。乙烯基二茂铁的自复分解没有发生，但有趣的是，在 Schrock 催化剂存在下，交叉复分解继续产生具有高选择性（73-100%）的异二聚体（交叉复分解产物）。提出了选择性异二聚体形成的机制。

项目成果

Tadashi KAWAl, Masako KOMAKI, Tomokazu IYODA: "Cross-metathesis of vinyl aromatic heterocycls with 1-octene in the presence of a Schrock catalyst"J.Mol.Catalysls A : Chemical. (印刷中). (2002)

Tadashi KAWAl、Masako KOMAKI、Tomokazu IYODA：“在 Schrock 催化剂存在下乙烯基芳族杂环与 1-辛烯的交叉复分解”J.Mol.Catalysls A：化学（2002 年出版）。

Tadashi KAWAI, Yasue SHIDA, Hirohisa YOSHIDA, Jiro ABE and Tomokazu IYODA: "Cross-metathesis of vinyl aromatic heterocycles : Comparison of Grubbs catalsyt and Schrock catalyst"J. Mol. Catalysis A : Chemical. (in press).

Tadashi KAWAI、Yasue SHIDA、Hirohisa YOSHIDA、Jiro ABE 和 Tomokazu IYODA：“乙烯基芳香杂环的交叉复分解：Grubbs 催化剂和 Schrock 催化剂的比较”J。

Tomohiro YASUDA, Jiro ABE, Tomokazu IYODA and Tadashi KAWAI: "Selective synthesis of 1-aryl-2-ferrocenylethylene by cross-methesis"Chem. letters. 812-813 (2001)

Tomohiro YASUDA、Jiro ABE、Tomokazu IYODA 和 Tadashi KAWAI：“通过交叉复分解选择性合成 1-芳基-2-二茂铁基乙烯”Chem.

Tadashi KAWAI, Masako KOMAKI and Tomokazu IYODA: "Cross-metathesis of vinyl aromatic heterocycles with 1-octene in the presence of a Schrock catalyst"J. Mol .Catalysis A : Chemical. (in press).

Tadashi KAWAI、Masako KOMAKI 和 Tomokazu IYODA：“在 Schrock 催化剂存在下乙烯基芳香杂环与 1-辛烯的交叉复分解”J.

T.KAWAI. et al.: "Acyclic diene metathesis (ADMET) of vinylsilanes over Re_2O_7-Al_2O_3 catalyst"J.Mol.Catalysis A : Chemical. 140. 287-292 (1990)

川井。