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Relevant academic research and scientific papers

A mild and fast photocatalytic trifluoromethylation of thiols in batch and continuous-flow

S-CF3 bonds are important structural motifs in various pharmaceutical and agrochemical compounds. However, their preparation remains a major challenge in synthetic organic chemistry. Here, we report the development of a mild and fast photocatalytic trifluoromethylation of thiols. The combination of commercially available Ru(bpy)3Cl2, visible light and inexpensive CF3I gas proved to be an efficient method for the direct trifluoromethylation of thiols. The protocol is demonstrated on a wide range of aromatic, hetero-aromatic and aliphatic substrates in both batch and continuous microflow (32 examples, 52-98% yield). Process intensification through continuous microflow application resulted in a 15-fold increase in production rate (0.25 mmol min-1) due to improved gas-liquid mass transfer, enhanced irradiation as well as convenient handling of the gaseous CF3 source. Furthermore, the efficiency of the flow process allowed to reduce the amount of CF3I (1.1 equivalent) to reach full conversion. This journal is

Process for the preparation of perhaloalkylthioethers

The present invention relates to a process for the preparation of perhaloalkylthioethers by bringing a perhaloalkyl halide, preferably a bromide or an iodide, into contact with a disulphide in the presence of zinc and of sulphur dioxide or of a dithionite or of a hydroxymethanesulphinate or of a formate anion and sulphur dioxide.

Reactions of Bromotrifluoromethane and Related Halides. Part 12. Transformation of Disulfides into Perfluoroalkyl Sulfides in the Presence of Sulfoxylate Anion Radical Precursors

Perfluoroalkyl sulfides are prepared by reaction of perfluoroalkyl halides with disulfides in the presence of sulfoxylate anion radical precursors.Aliphatic, aromatic and heteroaromatic disulfides bearing cyano, ester and amino functional groups have been employed; a variety of perhalogenoalkanes can also be employed, e.g.CF3(CF2)nI, CF3Br, CF2Br2, CF2BrCl, CFCl3 and CF2ClCFCl2.The most convenient sulfoxylate anion radical precursor for this reaction is formed by a combination of sodium formate and sulfur dioxide.

Chemistry of Halogenoperfluoroalkanes> Synthesis of Fluorinated Ethers and Thioethers via Radical or Anionic Intermediates

Condensation of bromotrifluoromethane with potassium thiophenoxides in DMF is performed under pressure (2-3 atm) in a glass apparatus.Inhibition by nitrobenzene shows that a SRN1 mechanism is involved in the formation of aryl trifluoromethyl sulfides.Dichlorodifluoromethane itself reacts through a similar process to give aryl chlorodifluoromethyl sulfides.Condensation of 1,1,2-trichlorotrifluoroethane with potassium thiophenoxide or phenoxide occurs even in the presence of nitrobenzene.The formation of aryl 2,2-dichloro-1,1,2-trifluoroethyl sulfides or ethers can be explained by a chain carbanionic mechanism.

PERFLUOROALKYLATION OF THIOLS. EVIDENCE FOR A RADICAL CHAIN PROCESS

Perfluoroalkyl sulfides are formed from primary or secondary perfluoroalkyl iodides and aromatic or alphatic thiolates without UV irradiation.Perfluoroalkyl radicals are intermediates as demonstrated by inhibition and trapping studies.