454-90-0Relevant articles and documents
Cross-Coupling through Ag(I)/Ag(III) Redox Manifold
Demonti, Luca,Mézailles, Nicolas,Nebra, Noel,Saffon-Merceron, Nathalie
supporting information, p. 15396 - 15405 (2021/10/12)
In ample variety of transformations, the presence of silver as an additive or co-catalyst is believed to be innocuous for the efficiency of the operating metal catalyst. Even though Ag additives are required often as coupling partners, oxidants or halide scavengers, its role as a catalytically competent species is widely neglected in cross-coupling reactions. Most likely, this is due to the erroneously assumed incapacity of Ag to undergo 2e? redox steps. Definite proof is herein provided for the required elementary steps to accomplish the oxidative trifluoromethylation of arenes through AgI/AgIII redox catalysis (i. e. CEL coupling), namely: i) easy AgI/AgIII 2e? oxidation mediated by air; ii) bpy/phen ligation to AgIII; iii) boron-to-AgIII aryl transfer; and iv) ulterior reductive elimination of benzotrifluorides from an [aryl-AgIII-CF3] fragment. More precisely, an ultimate entry and full characterization of organosilver(III) compounds [K]+[AgIII(CF3)4]? (K-1), [(bpy)AgIII(CF3)3] (2) and [(phen)AgIII(CF3)3] (3), is described. The utility of 3 in cross-coupling has been showcased unambiguously, and a large variety of arylboron compounds was trifluoromethylated via [AgIII(aryl)(CF3)3]? intermediates. This work breaks with old stereotypes and misconceptions regarding the inability of Ag to undergo cross-coupling by itself.
Preparation method of m-trifluoromethylphenol
-
Paragraph 0065-0066; 0082; 0084; 0086, (2018/03/26)
The invention discloses a preparation method of m-trifluoromethylphenol. A preparation method of the m-trifluoromethylphenol comprises the following steps of enabling m-trifluoromethylphenol and alkali metal hydroxide and/or alkali metal alcohol to hydrolyze in an alcohol solvent under the condition of existence of a copper complex catalyst, and acidifying a reaction solution; the copper complex catalyst is selected from one or multiple of 8-copper hydroxyquinoline, 2-methyl-8-copper hydroxyquinoline, 4-methyl-8-copper hydroxyquinoline, copper acetate, and copper acetylacetonate. The preparation method has the advantages that the raw materials which can be easily purchased in industry are used for reacting, the technology is simple, the post-treatment is easy, the conditions are relativelymoderate, the pollution to environment is smaller, the m-trifluoromethylphenol with higher purity can be prepared at higher yield rate, the cost is low, and the industrialization application is realized. (The formula is shown in the description.).
Application of Silicon-Initiated Water Splitting for the Reduction of Organic Substrates
Gevorgyan, Ashot,Mkrtchyan, Satenik,Grigoryan, Tatevik,Iaroshenko, Viktor O.
, p. 375 - 382 (2018/06/04)
The use of water as a donor for hydrogen suitable for the reduction of several important classes of organic compounds is described. It is found that the reductive water splitting can be promoted by several metalloids among which silicon shows the best efficiency. The developed methodologies were applied for the reduction of nitro compounds, N-oxides, sulfoxides, alkenes, alkynes, hydrodehalogenation as well as for the gram-scale synthesis of several substrates of industrial importance.