TRANSITION METAL-CATALYZED FANCTIONALIZATION REACTION OF ALKANES IN SUPERCRITICAL FLUID

（1）新的催化系统已经被测试为液体阶段的甲烷部分氧化。它发现了一种含有异丁二烯/K2 S2 O 8/（CF 3CO）2 O/CF 3COOH催化剂系统转换甲基到甲基三氟乙酸酯的痕迹，其含量为95%的甲基乙酸酯。反应的激活能量估计为27.9千卡/摩尔。（2）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。甲烷（5大气压）与CO （20大气压）在80-D1-D1C为93%的甲烷提供20小时的醋酸。其他含V2 O3、V2 O 5和NaVO 3和各种vajium的异丁二烯化合物如H5 PV 2 Mo 10 O 40、H4 PVW 11 O 40和H5 SiVW 11 O 40，也如催化剂。（3） As a catalyst of the above two reactions， VO（OCOCF3）3 complex was isolated。这个新的催化系统已经对超临界碳二氧化物中甲烷的碳氧化和氧化进行了测试。我们发现这种钒复合物不受超临界碳二氧化物的影响，而且没有催化活性对产品产生影响。（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。关于89.55在这次反应中发生了螺旋桨的转换Arrhenius和Eyring Plots所确定的螺旋反应的激活参数。

(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.