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.

(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烷烃的产量良好。丙烷与三甲胺N-氧化物的氨基甲基化反应将N，N-二甲基异生酰胺作为单个区域异构体以及异丙基三氟乙酸酯一起。乙烷与三甲胺N氧化物反应，从甲烷的反应中获得N，N-二甲基丙酰胺作为唯一产物，从而获得甲基三氟乙酸甲酯，可获得甲基三氟乙酸酯。（2）乙酸从甲烷和一氧化甲烷和碳一氧化碳合成的乙烷与稀土催化剂中的碳酸氧化物合成的氧化物合成的碳酸氧化物合成的碳酸氧化物合成，该方法是从碳酸氧化碳酸盐中开发的。灯笼催化剂。在甲烷与碳一氧化碳的羧化反应中，乙酸乙酸酯（III）乙酸盐（III）是最活跃的催化剂。在该反应中，次氯酸钠或过氧化氢用作氧化剂。在反应中，次氯酸钠比过氧化氢表现出有利的活性。过渡金属盐（例如乙酸锰（II））的Addidon改善了催化活性。最好的结果是以0.1的比率为0.1，乙酸锰与乙酸苯甲酸酯（III）。已经获得了最佳反应条件（反应温度为40。C；时间为20H；甲烷，20atm；一氧化碳，5ATM）。