Development of Electro Recyclable System by Use of Ruthenium Compound as a Redox Reagent

使用钌化合物作为氧化还原试剂开发电可回收系统

• 批准号: 63850172
• 负责人: TORII Sigeru
• 金额: $ 5.44万
• 依托单位: Okayama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B).
• 财政年份: 1988
• 资助国家: 日本
• 起止时间: 1988 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-63850172/
• 关键词: 1, 3-Dichloroacetone; Ruthenium Tetraoxide; Indirect Electrooxidation; Two-Layer Electrolysis; System Halohydrin; Cyclohexane-1, 4-dione; Double Mediatory; D-Glucose Diacetonide; アミノ酸; D-グルコ-スアセトニド; 1.3-ジクロロアセトン; ハロケトン; 活性ハロゲン種; 二酸化ルテニウム; レド

A practically viable procedure for the oxidation of 1, 2 ; 5, 6-0-indirect isopropylidene-alpha-D-glucofuranose to the corresponding ulose has been developed by using the indriect electrooxidation method with two redox couples of RuO_4/RuO_2 and [Cl^+]/Cl^-. The conditions were optimized as follows : an aqueous phase at pH ca. 10 ; a mixture of carbon tetrachloride and tert-butyl alcohol (ca. 9 : 1 v/v) as an organic phase ; current densities at 10-40 mA/cm^2 ; temperature at 20-40 ^0 ; the use of 2 mol% of RuO_2.2H_2O. Thus, the electrolysis under the above conditions afforded the desired ulose in 90% yield. The method was successfully applied to a facile synthesis of isopropyl 3-amino-4-cyclohexyl-2-hydroxybutanoate from D-glucose diacetonide with chiral integrity of the C (4), C (5) carbons.The synthesis of 1, 3-dichloroacetone which is one of the most important synthetic intermediates in the production of N^2-sulfamoyl-3- [[(2-guanidino-4-thiazolyl) methyl] thio] -propionamidine (a … More histamine H_2 recepter) was investigated. The conditions for the indirect electrooxidation of 1, 3-dichloro-2-propanol were optimized in detail by examining various factors. Thus, the electrolysis of 1, 3-dichloro-2-propanol was carried out in an AcOEt-aqueous NaCl (2 : 3 V/V) system buffered at pH 3-4 in a divided cell as 0-5 ^OC, giving the desired ketone in 96% yield and, consequently, hence the formation of 1, 1, 3-trichloroacetone was suppressed to less than 1%. The method has proven to be useful for the oxidation of cyclohexane-1, 4-diol to cyclohexane-1, 4-dione, an important intermediate for electronics material such as TCNQ.In conclusion, as a result of the present Developmental Scientific Research, the ruthenium mediated indirect electrooxidation method can be extended, in a preparative scale, to the oxidation of a variety of alcohols including halohydrins and carbohydrates through making a proper choice of various factors, in particular, an electrolysis cell, pH value, and electrolysis medium. Less

采用RuO_4/RuO_2和[Cl~+]/Cl~-两个氧化还原对的间接电氧化法，建立了1，2；5，6-0-间接亚丙基-α-D-呋喃葡萄糖氧化成相应果糖的可行方法。优化的条件为：水相pH约为10，有机相为四氯化碳和叔丁醇(体积比约为9：1)，电流密度为10~40 mA/cm~2，温度为20~40℃，RuO_2.2H_2O的摩尔分数为2%。因此，在上述条件下电解得到所需的果糖，产率为90%。以手性C(4)、C(5)碳为原料合成了3-氨基-4-环己基-2-羟基丁酸异丙酯。1，3-二氯丙酮的合成是合成N^2-磺酰基-3-[[(2-胍-4-噻唑基)甲基]硫代]-丙酰胺(a…)的重要中间体之一更多的组胺H_2受体)。通过考察各种因素，对1，3-二氯-2-丙醇的间接电氧化条件进行了详细的优化。因此，1，3-二氯-2-丙醇在乙酸乙酯-氯化钠水溶液(2：3V/V)体系中进行，在pH为3-4的分槽中作为0-5oC缓冲，得到所需的酮，产率为96%，因此，1，1，3-三氯丙酮的生成被抑制到1%以下。该方法对环己烷-1，4-二醇氧化成环己烷-1，4-二酮是一种重要的电子材料中间体，如TCNQ。总之，由于目前的发展科学研究，通过适当选择电解槽、pH值和电解介质，Ru介导的间接电氧化法可以在制备规模上扩展到包括卤代醇和碳水化合物在内的各种醇的氧化。较少

项目成果

Sigeru TORII: "Indirect Electrooxidation by Using Ruthenium Tetraoxide and Chloride Ion as Recycling Mediators.Optimization for the Oxidation of DiisopropylideneーDーglucose to the Ulose" Bulletin of the Chemical Society of Japan. 62. 2108-2110 (1989)

Sigeru TORII：“使用四氧化钌和氯离子作为回收介体的间接电氧化。二异丙叉-D-葡萄糖氧化成 Ulose 的优化”日本化学学会公报 62. 2108-2110 (1989)。

Hideo Tanaka: Tetrahedron Letters. 30. (1989)

田中秀夫：四面体字母。

Sigeru TORII: "Comprehensive Organic Synthesis,Volume 7,3.7.Addition Reactions with Formation of CarbonーHalogen Bonds" Pergamon Press, 14 (1991)

Sigeru TORII：“综合有机合成，第 7 卷，3.7. 形成碳-卤素键的加成反应” Pergamon Press，14 (1991)

Sigeru TORII: "Organic Electroctrochemistry.An Introduction and a Guide.Synthetiec and Mechanistic Aspects of Anodic Reactions of Organic Compounds Classified by Electrophors.14.Carboxylic Acids" Dekker, 46 (1991)

Sigeru TORII：“有机电化学。简介和指南。按电泳分类的有机化合物阳极反应的合成和机理方面。14.羧酸” Dekker，46 (1991)

T. INOKUCHI: ""A Selective and Efficient Method for Alcohol Oxidations Mediated by N-Oxoammonium Salts in Combination with Sodium Bromite"" J. ORG. CHEM.55. 462-466 (1990)

T. INOKUCHI：“一种选择性且有效的由 N-氧铵盐与亚溴酸钠结合介导的醇氧化的方法”J. ORG。