TRANSITION METAL-CATALYZED FANCTIONALIZATION REACTION OF ALKANES IN SUPERCRITICAL FLUID

过渡金属催化超临界流体中烷烃的官能化反应

基本信息

批准号：
10650835
负责人：
TANIGUCHI Yuki
金额：
$ 2.24万
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：
1998
资助国家：
日本
起止时间：
1998 至 1999
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10650835/
关键词：
ALKANE METHANE VANADIUM TRIFLUOROACETIC ACID ACETIC ACID CARBOXYLATION SUPERCRITICAL CO2 C-H結合活性化

项目摘要

(1) The new catalytic system has been examined for the partial oxidation of methane in liquid phase. It was found that the vanadium containing heteropolyacids/K2S2O8/(CF3CO)2O/CF3COOH catalyst system converts methane to methyl trifluoroacetate along with a trace amount of methyl acetate in a 95% yield based on methane. The activation energy of the reaction was estimated to be 27.9 kcal/mol.(2) The VO(acac)2(acac=2,4-pentanedionato) catalyst in the presence of K2S2O8 and CF3COOH has been found to efficiently transform methane and CO to acetic acid selectively. The reaction of Methane (5 atm) with CO (20 atm) at 80ィイD1゜ィエD1C for 20 h gives acetic acid in 93% yield based on methane. Other vanadium compounds such as V2O3, V2O5, and NaVO3 and various vanajium-containing heteropolyacids such as H5PV2Mo10O40, H4PVW11O40, and H5SiVW11O40 also work as catalysts.(3) As a catalyst of the above two reactions, VO(OCOCF3)3 complex was isolated. This new catalytic system has been examined for the carboxylation and oxidation of methane in supercritical carbon dioxide. It was found that this vanadium complex is insoluble to supercritical carbon dioxide and has no catalytic activity affording no product.(4) Cobalt (II) acetate (Co(OAc)2) has been found to be an efficient catalyst for the carboxylation reaction of saturated hydrocarbons with CO to yield the corresponding carboxylic acids in high yields in the presence of K2S2O8 and CF3COOH. About 89.55 conversion of propane is obtained in this reaction. The activation parameters of the reaction of propane have been determined by Arrhenius and Eyring plots.

(1)对新型催化体系进行了液相甲烷部分氧化实验，发现含钒杂多酸/K2S2O8/(CF3CO)2O/CF3COOH催化剂体系将甲烷转化为三氟乙酸甲酯，并伴有微量的三氟乙酸甲酯。基于甲烷，乙酸甲酯的产率为 95%。反应的活化能估计为27.9 kcal/mol。 (2) VO(acac)2(acac=2,4-pentanedionato)催化剂在K2S2O8和CF3COOH存在下可以有效地选择性地将甲烷和CO转化为乙酸。 5 atm) 与 CO (20 atm) 在 80D1D1C 下反应 20 小时，得到乙酸以甲烷计，其他钒化合物如V2O3、V2O5和NaVO3以及各种含钒杂多酸如H5PV2Mo10O40、H4PVW11O40和H5SiVW11O40也可用作催化剂。 (3) VO作为上述两个反应的催化剂。 (OCOCF3)3复合物被分离出来。对超临界二氧化碳中甲烷的羧化和氧化进行了研究，发现该钒络合物不溶于超临界二氧化碳，并且没有催化活性，无法产生产物。(4) 乙酸钴(II) (Co(OAc))。 2) 已被发现是饱和烃与CO发生羧化反应的有效催化剂，在K2S2O8存在下以高产率产生相应的羧酸该反应中丙烷的转化率约为89.55。丙烷反应的活化参数已通过阿伦尼乌斯图和艾林图确定。