Fluoromethyl-2,4,6-trinitrophenylsulfonate: A New Electrophilic Monofluoromethylating Reagent

Abstract

Fluoromethyl-2,4,6-trinitrophenylsulfonate has been prepared for the first time and qualified as a simple to use monofluoromethylating reagent. Its molecular structure in the solid state has been determined by single-crystal X-ray diffraction studies. This reagent proves to be effective for the electrophilic introduction of a CH2F group into selected chalcogen and nitrogen nucleophiles. Monofluoromethyl derivatives of various bifunctional N,O-nucleophiles have been synthesized using fluoromethyl-2,4,6-trinitrophenylsulfonate. Due to the good crystallizing properties of the anion, the fluoromethylated products as well as side products that are difficult to identify by nuclear magnetic resonance spectroscopy can readily be characterized by X-ray crystallographic techniques.

Synthesis and Reactivity of Trifluoromethylthiophosphonium Salts†

“…Furthermore, the P—S bond length of compound 6a was slightly longer than those of benzylthiophosphonium salt 7 (2.050(1) Å) [ 28 ] and fluoromethylthiophosphonium salt 8 (2.076(1) Å). [ 29 ] This was due to the great reduction of the n‐σ* interaction from sulfur to phosphorus atom induced by the strong electron‐withdrawing effect of trifluoromethyl group.…”

The synthetic versatility of fluoroiodomethane: recent applications as monofluoromethylation platform

“…60 By using fluoroiodomethane, the same author recently described the synthesis and characterization of fluoromethyl-2,4,6-trinitrophenylsulfonate, as a suitable reagent for the introduction of the monofluoromethyl moiety into chalcogen and nitrogen nucleophiles (Scheme 17). 61…”

Fluoroiodomethane: A CH2F‐Moiety‐Delivering Agent Suitable for Nucleophilic‐, Electrophilic‐, and Radical‐Harnessed Operations

“…[82] A similar rationale has been applied by Karaghiosoff for preparing the electrophilic agent fluoromethyl-2,4,6-trinitrophenyl sulfonate, able to transfer the CH 2 F group to substrates such as carbonic acid amides, phosphorous chalcogenides, and amino groups embodied in aromatic ketones (e. g. Michler-type and ketone and dipyridyl ones) (Scheme 25). [83] Accordingly, through the reaction of picryl chloride with sodium metabisulfite -followed by acidic hydrolysis to the corresponding sulfonic acid -a silver sulfonate was obtained in the presence of AgNO 3 . Therefore, upon fluoromethylation with fluoroiodomethane in DCM, the final fluoromethyl sulfonate was produced as a microcrystalline solid.…”

“…Michler‐type and ketone and dipyridyl ones) (Scheme 25). [83] Accordingly, through the reaction of picryl chloride with sodium metabisulfite – followed by acidic hydrolysis to the corresponding sulfonic acid – a silver sulfonate was obtained in the presence of AgNO 3 . Therefore, upon fluoromethylation with fluoroiodomethane in DCM, the final fluoromethyl sulfonate was produced as a microcrystalline solid.…”