1067641-60-4

Upstream product

• 14204-31-0 2-(4-chlorophenylthio)isoindoline-1,3-dione 
• 1679-18-1 4-Chlorophenylboronic acid 
• 4524-70-3 thiophosphoric acid S-(4-chlorophenyl) ester O,O'-diethyl ester 
• 1142-19-4 4,4'-dichlorodiphenyl disulfide 
• 106-54-7 p-Chlorothiophenol 

Downstream Products

• 5310-68-9 (4-chlorophenyl)pentafluoro-λ⁶-sulfane 
• 1584127-84-3 2-(4-chlorophenyltetrafluoro-λ 6-sulfanyl)ethynylbenzene 
• 312-64-1 2-fluoroethyl 4-chlorobenzenesulfonate 
• 1207989-49-8 2-fluoroethyl 4-chlorobenzenesulfinate 

Relevant academic research and scientific papers

AgBF4-Mediated Chlorine-Fluorine Exchange Fluorination for the Synthesis of Pentafluorosulfanyl (Hetero)arenes

We report a new protocol to form pentafluorosulfanyl (hetero)arenes via chlorine-fluorine exchange of (hetero)aryl tetrafluorosulfanyl chlorides by AgBF4. The method enables access to electron-deficient pentafluorosulfanyl(hetero)arenes, which are targets that are difficult to synthesize. Two advantages of AgBF4 are its ease of handling and stability. This would be a general transformation protocol.

Validation of Arylphosphorothiolates as Convergent Substrates for Ar-SF 4Cl and Ar-SF 5Synthesis

In this manuscript we describe the oxidative fluorination of aryl phosphorothiolates to access Ar-SF4Cl compounds. These compounds serve as precursors for the highly coveted Ar-SF5 compounds. The use of phosphorothiolates as starting materials permits access to Ar-SF4Cl from a wide variety of available starting materials, namely boronic acids, diazonium salts, aryl iodides, thiophenols, or simple arenes. The protocol has been demonstrated for 10 examples and showed good tolerance to various functional groups. Finally, we demonstrated that AgBF4 can be used as a fluorinating agent, affording good yields of an Ar-SF5.

A Unified Strategy for Arylsulfur(VI) Fluorides from Aryl Halides: Access to Ar-SOF3 Compounds

A convenient protocol to selectively access various arylsulfur(VI) fluorides from commercially available aryl halides in a divergent fashion is presented. Firstly, a novel sulfenylation reaction with the electrophilic N-(chlorothio)phthalimide (Cl-S-Phth) and arylzinc reagents afforded the corresponding Ar-S-Phth compounds. Subsequently, the S(II) atom was selectively oxidized to distinct fluorinated sulfur(VI) compounds under mild conditions. Slight modifications on the oxidation protocol permit the chemoselective installation of 1, 3, or 4 fluorine atoms at the S(VI) center, affording the corresponding Ar-SO2F, Ar-SOF3, and Ar-SF4Cl. Of notice, this strategy enables the effective introduction of the rare and underexplored -SOF3 moiety into various (hetero)aryl groups. Reactivity studies demonstrate that such elusive Ar-SOF3 can be utilized as a linchpin for the synthesis of highly coveted aryl sulfonimidoyl fluorides (Ar-SO(NR)F).

Making the SF5 Group More Accessible: A Gas-Reagent-Free Approach to Aryl Tetrafluoro-λ6-sulfanyl Chlorides

Modern pentafluorosulfanyl (SF5) chemistry has an Achilles heel: synthetic accessibility. Herein, we present the first approach to aryl-SF4Cl compounds (key intermediates in state-of-the-art aryl-SF5 synthesis) that overco

METHOD FOR PREPARING A POLYFLUORINATED COMPOUND

The present invention relates to a process for preparing a polyfluorinated compound of formula Ar-Ri(l), wherein Ar-Ri(l) is an aromatic ring system wherein R1 is selected from the group consisting of SF4CI, SF3, SF2CF3, TeFS, TeF4CF3, SeF3, IF2, SeF2CF3, and IF4, X2 is N or CR2, X3 is N or CR 3, X 4 is N or CR 4, X 5 is N or CR 5, X 6 is N or CR 6, and the total number of nitrogen atoms in the aromatic ring system is between 0 and 3, and if X 5 is CR 5 and X 6 is CR 6 R 5 and R 6 may form together a saturated or unsaturated five or six membered ring system comprising one or more nitrogen, wherein said five or six membered ring system may be substituted with one or more residues R 7 said process involving the following reaction step reacting a starting material selected from the group consisting of Ar2S2, Ar2Te2, Ar2Se2, ArSCF3, Arl, ArTeCF3, ArSeCF3, ArSCF3, and ArSCI, wherein Ar has the same definition as above, with trichloroisocyanuric acid (TCICA) of the formula (III) in the presence of the alkali metal fluoride (MF).

IF5 affects the final stage of the Cl-F exchange fluorination in the synthesis of pentafluoro-λ6-sulfanyl-pyridines, pyrimidines and benzenes with electron-withdrawing substituents

A difficult chlorine-fluorine (Cl-F) exchange fluorination reaction in the final stage of the preparation of pentafluoro-λ6-sulfanyl-(hetero)arenes having electron-withdrawing substituents has now been elucidated through the use of iodine pentafluoride. A major side-reaction of C-S bond cleavage was sufficiently inhibited by the potential interaction between F and I with a halogen bonding.

Silver-induced self-immolative Cl-F exchange fluorination of arylsulfur chlorotetrafluorides: Synthesis of arylsulfur pentafluorides

A novel strategy for the synthesis of arylsulfur pentafluorides by silver carbonate-induced Cl-F exchange fluorination of arylsulfur chlorotetrafluorides is reported. This fluorination does not require any exogenous fluoride sources. Rather, the reaction proceeds via the self-immolation of the substrate Ar-SF4Cl.

An improved method for the fluorination of arylsulfur chlorotetrafluorides to arylsulfur pentafluorides

A new method for the fluorination of arylsulfur chlorotetrafluorides to arylsulfur pentafluorides is described. The reaction is promoted by hydrogen fluoride generated from potassium hydrogen fluoride and trifluoroacetic acid which also serves as a solvent. The reaction is performed under mild conditions and uses substochiometric amounts of potassium hydrogen fluorides in certain cases. Recovery and reuse of trifluoroacetic acid was successfully demonstrated which makes this method safe, simple to use, and atom- and cost-effective.

Discovery of practical production processes for arylsulfur pentafluorides and their higher homologues, bis- and tris(sulfur pentafluorides): Beginning of a new era of "super-trifluoromethyl" arene chemistry and its industry

Various arylsulfur pentafluorides, ArSF5, have long been desired in both academic and industrial areas, and ArSF5 compounds have attracted considerable interest in many areas such as medicines, agrochemicals, and other new materials, since the highly stable SF5 group is considered a "super-trifluoromethyl group" due to its significantly higher electronegativity and lipophilicity. This article describes the first practical method for the production of various arylsulfur pentafluorides and their higher homologues, bis- and tris(sulfur pentafluorides), from the corresponding diaryl disulfides or aryl thiols. The method consists of two steps: (Step 1) treatment of a diaryl disulfide or an aryl thiol with chlorine in the presence of an alkali metal fluoride, and (step 2) treatment of the resulting arylsulfur chlorotetrafluoride with a fluoride source, such as ZnF2, HF, and Sb(III/V) fluorides. The intermediate arylsulfur chlorotetrafluorides were isolated by distillation or recrystallization and characterized. The aspects of these new reactions are revealed and reaction mechanisms are discussed. As the method offers considerable improvement over previous methods in cost, yield, practicality, applicability, and large-scale production, the new processes described here can be employed as the first practical methods for the economical production of various arylsulfur pentafluorides and their higher homologues, which could then open up a new era of "super-trifluoromethyl" arene chemistry and its applications in many areas.

METHODS FOR PREPARING FLUOROALKYL ARYLSULFINYL COMPOUNDS AND FLUORINATED COMPOUNDS THERETO

Novel preparative methods for fluoroalkyl arylsulfinyl compounds are disclosed. Fluorinated compounds as useful fluorinated compounds, intermediates, or builing blocks are disclosed. Useful applications of the fluoroalkyl arylsulfinyl compounds are shown.