Exploitation of New Synthetic Reactions via C-H Bond Activation by Transition Metal Catalysts

通过过渡金属催化剂活化 C-H 键开发新的合成反应

基本信息

批准号：
07455363
负责人：
FUJIWARA Yuzo
金额：
$ 4.74万
依托单位：
KYUSHU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

项目摘要

Our research on this project has discovered and developed the following two new synthetic reactions : 1) carboxylation of arenes with CO by palladium catalysts under very mild conditions, and 2) aminomethylation of alkanes with methyl-tert-amine N-oxides by copper catalysts.1. Carboxylation of Arenes with CO by Palladium Catalysts under Very Mild Conditions(1) The Pd (OAc)_2 catalyzed carboxylation reaction of aromatic compounds such as benzene, toluene, anisole, chlorobenzene, and naphthalene with CO in the presence of trifluoroacetic acid and K_2S_2O_8, to give the corresponding aromatic carboxylic acids in high yields under the vary mild conditions (1 atm CO,room temperature) has been discovered.(2) The reaction proceeds electrophilically with o, p-orientation when an electron-releasing group is attached to the benzene ring.2. Aminomethylation of Alkanes with Methyl-tert-amine N-oxides by Copper Catalysts(1) The Cu (OAc)_2/K_2S_2O_8/CF_3 COOH system has been found to cause the aminomethylation reaction of alkanes (10 atm) with methyl-tert-amine N-oxidess at 150ﾟC to give the corresponding amines in high yields.(2) Reactions of propane and ethane with trimetjylamine N-oxide gives N,N'-dimethylisobutylamine and N,N'-dimethylpropylamine, respectively. But methane remains unreacted under the present reaction conditions and the work is underway.

我们对该项目的研究发现并开发了以下两个新的合成反应：1）在非常轻微的条件下通过钯催化剂与CO的羧基化和2）2）用铜催化剂用甲基 - 胺N-氧化物烷基化烷基化的烷基化。 Carboxylation of Arenes with CO by Palladium Catalysts under Very Mild Conditions(1) The Pd (OAc)_2 catalyzed carboxylation reaction of aromatic compounds such as benzene, toluene, anisole, chlorobenzene, and naphthalene with CO in the presence of trifluoroacetic acid and K_2S_2O_8, to give the corresponding aromatic carboxylic acids in high在不同的温和条件下（1 ATM CO，室温）的产量。（2）当将电子释放组附在苯环上时，反应以O，P取向进行电动进行。2。通过铜催化剂（1）Cu（OAC）_2/K_2S_2S_2O_8/CF_3 COOH系统已发现烷基氨基胺与甲基胺N-氧化物的氨基甲基化（1）已发现COOH系统可导致甲基甲基甲基氨基甲基反应（10 atm）与甲基 - tert-tert-amine N-氧化物的氨基甲基化反应（10 atm）。丙烷和其他与三酰胺N-氧化物的反应分别为N，N'-二甲基异丁胺和N，N'-二甲基丙酰胺。但是在当前反应条件下，甲烷仍未反应，并且正在进行工作。