Electrochemical Fixation of Carbon Dioxide by the Use of Fluidized Electrochemical Cell-Synthesis of Useful Organic Carboxylic Acids

使用流化电化学电池电化学固定二氧化碳-合成有用的有机羧酸

基本信息

批准号：
07555580
负责人：
TOKUDA Masao
金额：
$ 2.37万
依托单位：
HOKKAIDO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1997
项目状态：
已结题

项目摘要

The purpose of this research project is to develop an efficient preparation method of synthetically useful carboxylic acids by electrochemical fixation of carbon dioxide to organic substrates using fluidized electrochemical cell.1.Synthesis of Unsaturated Carboxylic Acids by Electrochemical Carboxylation Using a Reactive-metal Anode-Electrochemical carboxylation of allylic halides, propargylic halides, vinyl halides, vinyl triflates, and 1,4-dibromo-2-bromomethyl-2-butene in the presence of atmospheric carbon dioxide using a reactive-metal anode gave, respectively, alpha, beta-unsaturated acids, beta-keto carboxylic acids, and 3-methylene-4-pentenoic acid in high yields and in high regioselective manners.2.Efficient Synthesis of the Precursor of Anti-inflammatory Agents-Efficient synthesis of alpha, beta-unsaturated acids by electrochemical carboxylation of aryl-substituted vinyl bromides was successfully applied to a synthesis of the precursor of anti-inflammatory agents such as ibuprofen, naproxen, flurbiprofen, cicloprofen, and ketoprofen.3.Electrochemical Carboxylation Using Fluidized Electrochemical Cell-Fluidized electrochemical cell was newly made by us and used in the electrochemical carboxylation. Various reaction conditions such as flow rate of CO_2, temperature, electricity passed, and current density were examined in the electrochemical carboxylation of cinnamyl bromide. Electrochemical carboxylation of various organic halides under optimum conditions gave the corresponding carboxylic acids, including ibuprofen and its precursor, in good yields. Advantages in the use of the fluidized electrochemical cell are that the electrochemical carboxylations can be carried out in higher yields and selectivities, and at higher current densities than those of the usual one-compartment cell.

本研究项目的目的是开发一种通过使用流化电化学电池将二氧化碳电化学固定到有机底物上来有效制备合成有用的羧酸的方法。1.使用活性金属阳极电化学羧化合成不饱和羧酸烯丙基卤化物、炔丙基卤化物、乙烯基卤化物、乙烯基三氟甲磺酸酯和1,4-二溴-2-溴甲基-2-丁烯在大气二氧化碳存在下使用活性金属阳极分别产生α、β-不饱和酸、β-酮基羧酸和3-亚甲基-4- 2.抗炎剂前体的高效合成——电化学法高效合成α,β-不饱和酸芳基取代乙烯基溴的羧化成功应用于布洛芬、萘普生、氟比洛芬、环洛芬、酮洛芬等抗炎药前体的合成。 3.流化电化学池的电化学羧化-流化电化学池是我公司最新研制的。我们并用于电化学羧化。考察了肉桂基溴电化学羧化过程中CO_2流量、温度、通电量、电流密度等不同反应条件。在最佳条件下，各种有机卤化物的电化学羧化反应以良好的产率生成相应的羧酸，包括布洛芬及其前体。使用流化电化学电池的优点是电化学羧化可以以比通常的单室电池更高的产率和选择性以及更高的电流密度进行。