Green Chemistry - Development of Environment Benain Oxidation

绿色化学-环境苯氧化的发展

• 批准号: 13640536
• 负责人: MIYOSHI Norikazu
• 金额: $ 1.92万
• 依托单位: Faculty of Integrated Arts and Sciences, University of Tokushima
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13640536/
• 关键词: Green Chemistry; An Environmentally Benign Reaction; Bismuth Trichloride; Hydrogen Peroxide; Oxidative Esterification; Chlorination; ビスマス化合物; 過酸化物; 過酸化水素; 酸化反応; ヒドロペルオキシド; ヘミアセタール

In the course of our continuous investigation of organic reactions utilizing bismuth compounds, we have been interested in oxidation reaction using bismuth compounds. Namely, we found that tributylbismuthine reacts with acid chlorides or carboxylic acids in hexane at room temperature under an oxygen atmosphere to give the corresponding butyl carboxylates in good yields. It was also found that aldehydes reacted smoothly with hydrogen peroxide in methanol at room temperature in the presence of a catalytic amount of bismuth trichloride to give the corresponding hydrogen peroxides.We have reported the oxidative esterification of aldehydes. Several aldehydes were treated with hydrogen peroxide in the presence of a catalytic amount of bismuth trichloride in refluxing methanol to give the corresponding methyl esters in high yields.This oxidative esterification was applied to the preparation of adipic acid from 2-hydroxycyclohexanone. When 2-hydroxycyclohexanone was reacted under the same reaction conditions, dimethyl adipate was obtained in good yield. Fortunately, we found that adipic acid was obtained when the reaction was tried without methanol.We have also reported the oxidative chlorination of ketones. Several ketones were treated with hydrogen peroxide in the presence of bismuth trichloride in refluxing methanol to give the corresponding α-chlorinated products in high yields.

在我们对利用铋化合物进行有机反应的不断研究过程中，我们对利用铋化合物进行氧化反应产生了兴趣。也就是说，我们发现三丁基铋在室温下，在氧气气氛下与正己烷中的酸性氯化物或羧酸反应，得到相应的丁基羧酸盐，收率很高。还发现，在室温下，在催化量的三氯化铋存在下，醛与甲醇中的过氧化氢反应顺利，生成相应的过氧化氢。我们已经报道了醛的氧化酯化反应。在催化量的三氯化铋存在下，用过氧化氢在回流甲醇中处理几种醛，得到相应的高收率甲酯。将氧化酯化反应应用于2-羟基环己酮制备己二酸。2-羟基环己酮在相同的反应条件下反应，得到了收率较高的己二酸二甲酯。幸运的是，我们发现在没有甲醇的情况下，反应得到了己二酸。我们也报道了酮类的氧化氯化反应。在有三氯化铋存在的条件下，用双氧水在回流甲醇中对几种酮类进行处理，得到相应的高收率α-氯化产物。

项目成果

R. Hiroi, N. Miyoshi, and M. Wada: "Organic Solvent-Free One-Pot Reduction of Imines Generated in situ from Aldehydes and Aniline by Tributyltin Hydride on Silica Gel"Chem. Lett.. 2002. 274-275 (2002)

R. Hiroi、N. Miyoshi 和 M. Wada：“通过硅胶上的氢化三丁基锡对醛和苯胺原位生成的亚胺进行有机无溶剂一锅还原”Chem。

T.Fukuma: "Water Accelerated Allylation of Aldehydes by Using Water Tolerant Grignard-Type Allylating Agents from Allylmagnesium Chloride and Various Metallic Salts"Chemistry Letters. 2002. 376-377 (2002)

T.Fukuma：“使用来自烯丙基氯化镁和各种金属盐的耐水格氏型烯丙基化剂水加速醛的烯丙基化”化学快报。

R.Hiroi: "Organic Solvent-Free One-Pot Reduction of Imines Generated in situ from Aldehydes and Aniline by Tributyltin Hydride on Silica Gel"Chemistry Letters. 2002. 274-275 (2002)

R.Hiroi：“通过硅胶上的氢化三丁基锡对醛和苯胺原位生成的亚胺进行有机无溶剂一锅还原”化学快报。

M.Wada: "Bismuth Trichloride Catalyzed Efficient Reductive Etherification of Carbonyl Compounds with Alcohols : A Novel Method for Preparation of Symmetrical and Unsymmetrical Ethers"Chemistry Letters. 2002. 248-249 (2002)

M.Wada：“三氯化铋催化羰基化合物与醇的高效还原醚化：一种制备对称和不对称醚的新方法”化学快报。

M. Wada, S. Nagayama, K. Mizutani, R. Hiroi, and N. Miyoshi: "Bismuth Trichloride Catalyzed Efficient Reductive Etherification of Carbonyl Compounds with Alcohols : A Novel Method for Preparation of Symmetrical and Unsymmetrical Ethers"Chem. Lett.. 2002.

M. Wada、S. Nagayama、K. Mizutani、R. Hiroi 和 N. Miyoshi：“三氯化铋催化羰基化合物与醇的高效还原醚化：一种制备对称和不对称醚的新方法”Chem。