Development of New Synthetic Reactions via C-H Bond Activation of Hydrocarbons such as Methane

通过甲烷等碳氢化合物的 C-H 键活化开发新的合成反应

• 批准号: 09355031
• 负责人: FUJIWARA Yuzo
• 金额: $ 17.73万
• 依托单位: KYUSHU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09355031/
• 关键词: Acetic acid from methane; Calcium chloride; Esterification; Cupric acetate; Palladium acetate; C-H bond activation; Aromatic compound; Olefin; メタンにより酢酸合成; 塩化カルシウム触媒; メタンのエステル化反応; 酢酸銅触媒; 芽香族化合物とオレフィンの反応; 酢酸パラジウム; 芽香族化合物とアルキンの反応; 芽香族置換アルケン

The following metal-catalyzed new synthetic reactions via C-H bond activation of hydrocarbons such as methane and aromatics have been discovered.1. Acetic Acid Synthesis from Methane and COCaC1ィイD22ィエD2 and VO(acac)ィイD22ィエD2 have been found to catalyze the reaction of methane and CO leading to acetic acid in almost quantitatively.2. Esterification of MethaneIt has been found that Cu(OAc) ィイD22ィエD2 and heteropolyacids such as HィイD25ィエD2PVィイD22ィエD2MOィイD210ィエD2OィイD240ィエD2 convert methane and trifluoroacetic acid to methyl trifluoacetate in high yields.3. Coupling of Aromatics to OlefinsThe Pd(OAc) ィイD22ィエD2/benzoquinone/t-BouOOH/AcOH-ACィイD22ィエD2O system has been found to catalyze the controlling reaction of olefins and aromatics to give aromatics-substituted olefins in high yield.4. Addition of Aromatics to AcetylenesThe Pd(OAc) ィイD22ィエD2/trifluoacetic acid system has been found to catalyze the addition of aromatics to C-C triple bonds to give aromatics-substituted olefins in high yields. This reaction also takes place intramolecularly to give heterocyclic compounds.

已发现以下金属催化的通过碳氢键活化甲烷和芳烃等碳氢化合物的新合成反应。 1．甲烷与COCaC1ィイD22ィエD2合成乙酸和VO(acac)ィイD22ィエD2几乎定量地催化甲烷和CO反应生成乙酸。2．甲烷的酯化反应发现Cu(OAc)ィイD22ィエD2与HィイD25ィエD2PVィイD22ィエD2MOィイD210ィエD2OィイD240ィエD2等杂多酸将甲烷和三氟乙酸转化为甲基三氟乙酸收率高。 3．芳烃与烯烃的偶联Pd(OAc)ィイD22ィエD2/苯醌/t-BouOOH/AcOH-ACィイD22ィエD2O体系可以催化烯烃与芳烃的控制反应，高产率地得到芳烃取代烯烃。 4．芳烃与乙炔的加成Pd(OAc)ィイD22ィエD2/三氟乙酸体系已被发现能够催化芳烃与C-C三键的加成，以高产率得到芳烃取代的烯烃。该反应也在分子内发生，生成杂环化合物。

项目成果

M.Asadullah: "Cobalt Catalyzed Carboxylation of Saturated Hydrocarbons with CO in the Presence of KィイD22ィエD2SィイD22ィエD2OィイD28ィエD2 and TFA under Mild Conditions"Tetrahed. Lett.. 40. 8867-8871 (1999)

M.Asadullah：“在温和条件下，在 KD22D2SD22D2OD28D2 和 TFA 存在下，饱和烃与 CO 的钴催化羧化”Tetrahed.. 40. 8867 -8871 (1999)

M. Asadullah: "Mg/K_< 2>S_< 2>O_< 8> Promoted Direct Carboxylation of Saturated Hydrocarbons with CO"Applied Organometallic Chemistry. 13. 539-547 (1999)

M. Asadullah：“Mg/K_< 2>S_< 2>O_< 8> 促进饱和烃与 CO 的直接羧化”应用有机金属化学。

C.Jia: "Highly Efficient Catalytic Activation of Aromatics C-H Bonds"Science. (in press).

C.Jia：“芳烃C-H键的高效催化活化”科学。

M.Asadullah: "Mg/KィイD22ィエD2SィイD22ィエD2OィイD28ィエD2-Promoted Direct Carboxylation of Saturated Hydrocarbons with CO"Applied Organometal. Chem.. 13. 539-547 (1999)

M.Asadullah：“Mg/KD22D2SD22D2OD28D2-促进饱和烃与 CO 的直接羧化”应用有机金属。 13. 539-547 (1999)

M.Asadullat: "Synthesis of Carboxylic Acids thyough the Fosmation of C-C Bond betwecn Saturated Hydrocarbons and CO in the presence of Mg/K_2S_2O_8/TFA System"Chemistry Letters. 6号. 449-450 (1999)

M.Asadullat：“在 Mg/K_2S_2O_8/TFA 系统存在下，通过饱和烃和 CO 之间的 C-C 键合成羧酸”，《化学快报》第 6 期。449-450 (1999)。