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DEVELOPMENT OF C-C BOND FORMING FUNCTIONALIZATION

C-C 键形成功能化的开发

基本信息

批准号：
08651013
负责人：
TANIGUCHI Yuki
金额：
$ 1.28万
依托单位：
KYUSHU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1996
资助国家：
日本
起止时间：
1996 至 1997
项目状态：
已结题

项目摘要

(I)DeveIopment of Novel Synthetic Method for the Synthesis of Amines by Aminomethylation of AIkanes Catalyzed by Copper AcetateTransition metal salts such as copper acetates catalyze the reaction of gaseous alkanes with N,N-dialkylmethylamine N-oxides in trifluoacetic acid (TFA) to afford N,N-dialkylaminomethylated alkanes in good yields. Aminomethylation reaction of propane with trimethylamine N-oxide gave N,N-dimethylisobutylamine as a single regioisomer together with isopropyl trifluoroacetate. Ethane reacts with trimethylamine N-oxide affording N,N-dimethylpropylamine as a sole product From the reaction of methane, methyl trifuoroacetate was obtained cxclusively.(2)Acetic Acid Synthesis from Methane and Carbon Monoxide by Rare Earth Catalyst SystemA new synthetic method of acetic acid in water has been developed from the carboxylation of methane with carbon monoxide using lanthanide catalysts. Ytterbium (III) acetate has been found to be the most active catalyst among the compounds of lanthanide series in the carboxylation reaction of methane with carbon monoxide. Sodium hypochlorite or hydrogen peroxide was used as oxidant in this reaction. Sodium hypochlorite exhibited the favorable activity than hydrogen peroxide in the reaction. The catalytic activity was improved by the addidon of transition metal salts such as manganese (II)acetate. The best result has been found at 0.1 ratio of manganese (II) acetate to ytterbium (III) acetate. The optimum reaction conditions (reaction temperature, 40. C ; time, 20h ; methane, 20atm ; carbon monoxide, 5atm) have been obtained.

过渡金属盐如醋酸铜催化气态烷烃与N，N-二烷基甲胺N-氧化物在三氟乙酸（TFA）中反应，以高产率得到N，N-二烷基氨甲基化烷烃。丙烷与氧化三甲胺发生氨甲基化反应，生成单一区域异构体N，N-二甲基异丁胺和三氟乙酸异丙酯。乙烷与N-氧化三甲胺反应，生成N，N-二甲基丙胺。甲烷与N-氧化三甲胺反应，生成三氟乙酸甲酯。（2）稀土催化剂体系下甲烷和一氧化碳合成乙酸开发了一种以甲烷和一氧化碳为原料，在稀土催化剂作用下进行羧化反应合成乙酸的新方法。乙酸镱（III）是镧系化合物中催化甲烷与一氧化碳羧化反应活性最高的催化剂。在该反应中使用次氯酸钠或过氧化氢作为氧化剂。次氯酸钠在反应中表现出比过氧化氢更好的活性。通过添加过渡金属盐如醋酸锰（II），提高了催化剂的活性。在醋酸锰（II）与醋酸镱（III）的比例为0.1时发现最佳结果。通过正交试验确定了最佳反应条件（反应温度40。反应温度20 ℃，反应时间20小时，甲烷20大气压，一氧化碳5大气压。