Molecular Design and Development of New Synthetic Methods of Novel Thio-, Seleno-, Tellurocarboxylic Acid Derivatives

新型硫代、硒代、碲代羧酸衍生物的分子设计和新合成方法的开发

• 批准号: 06453127
• 负责人: KATO Shinzi
• 金额: $ 4.86万
• 依托单位: GIFU UNIVERSITY
• 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
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06453127/
• 关键词: Calcogenocarboxylic acids; Tellurocarboxylic acids; Metal salts; Selenoarsenation; Aromatic selenothioic acid S-esters; セレノカルボン酸; テルロカルボキシル基; セシウム塩

In recent years, much attention has been paid to a series of chalcogenocarboxylic acid derivatives because of their biological activity such as brain blocking agent as well as of industrial materials such as photo-sensitizing agents and additives to lubricants. However, in spite of these useful properties, only a limited number of fundamental data have been studied. Accordingly, the prime objective of the present research was to disclose their basic features from the synthetic and structural point of view. The results obtained through the present research are as follows.1.X-ray molecular structure analyzes of thio-, seleno-and tellurocarboxylic acid lithium, rubidium, and cesium salts were successful. The results have shown they adopt the structures where the metal resides on sulfur, selenium, or tellurium atom in a solid state.2.Tellurocarboxylic acid was generated at low temperature from the corresponding Cesium salts. The acids exist predominantly as a telluro form in nonpolar solvents, whereas the telluoxo form was a predominant species in polar solvents. The similar trends were also observed for thio- and selenocarboxylic acids3.Se-Arsanyl selenocarboxylates were found to undergo the addition reaction to conjugated terminal acetylenes with high regio- and stereoselectivity.4.The stability trends of a series of selenothioic acid S-esters have been disclosed.

近年来，由于具有脑阻断剂等生物活性，以及光敏剂、润滑剂添加剂等工业原料，一系列硫基羧酸衍生物受到了广泛的关注。然而，尽管有这些有用的特性，人们只研究了有限数量的基础数据。因此，本研究的主要目的是从综合和结构的角度揭示它们的基本特征。通过本研究得到的结果如下：1。对硫、硒和碲羧酸锂、铷和铯盐的x射线分子结构进行了成功的分析。结果表明，它们采用了金属在固体状态下驻留在硫、硒或碲原子上的结构。由相应的铯盐在低温下生成碲羧酸。这些酸在非极性溶剂中主要以碲酸形式存在，而在极性溶剂中以碲酸形式存在。在硫代羧酸和硒代羧酸中也观察到类似的趋势。硒-芳基硒化羧酸酯与共轭末端乙炔发生加成反应，具有较高的区域选择性和立体选择性。揭示了一系列亚硒酸s -酯的稳定性趋势。

项目成果

村井利昭: "Reaction of Selenothioic Acid S‐Alkyl Esters with Electron Ceficient Alkynes.Selective Synthesis of Cyclic Selenides and Acyclic Divinyl Selenides" Tetrahedron Lett.35. 8817-8820 (1994)

Toshiaki Murai：“硫代硫酸 S-烷基酯与缺电子炔烃的反应。环状硒化物和无环二乙烯基硒化物的选择性合成”Tetrahedron Lett.35 (1994)。

加藤晋二: "Thion (RCSOH),Selenon (RCSeOH) and Telluron Acids (RCTeOH) as Predominant Species" J.Am.Chem.Soc.(in press). (1996)

Shinji Kato：“硫离子 (RCSOH)、硒 (RCSeOH) 和碲酸 (RCTeOH) 作为主要物种”J.Am.Chem.Soc.（出版中）。

加藤晋二: "Tautomeric Equilibrium between Selenol and Selenoxo Forms of Selenocarboxylic Acid" J.Am.Chem.Soc.2195-2196 (1994)

Shinji Kato：“硒醇和硒代羧酸形式之间的互变异构平衡”J.Am.Chem.Soc.2195-2196 (1994)

加藤晋二: "Preparation of Bis(phosphine)-bis(selenocarboxylato)-nickel(II), Palldium(II)and platinum(II)complexes and their X-ray Crystal Structure Analysis" J.Chem. Soc. Dalton Trans. I. (in press). (1996)

Shinji Kato：“双（膦）-双（硒代羧基）-镍（II）、钯（II）和铂（II）络合物的制备及其X射线晶体结构分析”J.Chem Soc I。 （出版中）。

村井利昭: "Rhodium(II) Acetate Catalyzed Hydrosilylation of Enamides and N‐Vinylureas Leading to 1‐(Trialkyl)silylamine Derivatives" J.Chem.Soc.,Chem.Commun.2143-2144 (1994)

Toshiaki Murai：“乙酸铑 (II) 催化烯酰胺和 N-乙烯基脲的氢化硅烷化生成 1-(三烷基)甲硅烷基胺衍生物”J.Chem.Soc.,Chem.Commun.2143-2144 (1994)