349-89-3

Basic information

• Product Name: 4-chlorobenzenesulfonyl fluoride
• Synonyms: 4-Chlorobenzenesulfonyl fluoride; benzenesulfonyl fluoride, 4-chloro-
• CAS NO: 349-89-3
• Molecular Formula: C₆H₄ClFO₂S
• Molecular Weight: 194.6112
• Mol File: 349-89-3.mol

Chemical Properties

• Boiling Point: 236.3°C at 760 mmHg
• Flash Point: 96.7°C
• Density: 1.473g/cm³
• Vapor Pressure: 0.0733mmHg at 25°C
• Refractive Index: 1.525
• CAS DataBase Reference: 4-chlorobenzenesulfonyl fluoride(CAS DataBase Reference)
• NIST Chemistry Reference: 4-chlorobenzenesulfonyl fluoride(349-89-3)
• EPA Substance Registry System: 4-chlorobenzenesulfonyl fluoride(349-89-3)

Safety Data

• Hazardous Substances Data: 349-89-3(Hazardous Substances Data)

Usage

Uses

Used in Pharmaceutical Industry:
4-Chlorobenzenesulfonyl fluoride is used as a synthetic intermediate for the production of various pharmaceuticals. Its ability to introduce the sulfonyl fluoride moiety into organic molecules makes it a valuable component in the synthesis of a range of medicinal compounds.
Used in Dye Industry:
In the dye industry, 4-chlorobenzenesulfonyl fluoride is utilized as a synthetic intermediate, contributing to the development of new dye products.
Used in Agrochemical Industry:
4-chlorobenzenesulfonyl fluoride is also employed as a synthetic intermediate in the agrochemical sector, playing a role in the creation of various agrochemical products.
Used in Organic Chemistry as a Reagent:
4-Chlorobenzenesulfonyl fluoride is used as a reagent in the synthesis of sulfonamides, which are an important class of compounds with applications as antimicrobial agents.
Used as a Fluorinating Agent:
In organic synthesis, 4-chlorobenzenesulfonyl fluoride serves as a fluorinating agent, facilitating the incorporation of fluorine into organic molecules, which can enhance their reactivity or stability.
Used in Specialty Resins and Polymers Production:
4-chlorobenzenesulfonyl fluoride has applications in the production of specialty resins and polymers, where it may contribute to the development of materials with unique properties.

Upstream product

• 98-60-2 4-chlorobenzenesulfonyl chloride 
• 108-90-7 chlorobenzene 
• 1142-19-4 4,4'-dichlorodiphenyl disulfide 
• 2725-55-5 di(4-chlorobenzenesulfonyl)amine 
• 1146-44-7 4,4'-dichlorophenyl thiosulfonate 
• 14752-66-0 sodium p-chlorobenzenesulphinate 
• 106-39-8 bromochlorobenzene 
• 873-77-8 (4-chlorphenyl)magnesium bromide 
• 637-87-6 1-Chloro-4-iodobenzene 
• 106-54-7 p-Chlorothiophenol 
• 1679-18-1 4-Chlorophenylboronic acid 
• 14204-31-0 2-(4-chlorophenylthio)isoindoline-1,3-dione 
• 98-66-8 4-chloro-benzenesulfonic acid 
• 673-41-6 p-chlorobenzenediazonium tetrafluoroborate 

Downstream Products

• 100-03-8 4-chlorobenzenesulfinic acid 
• 349-04-2 4-chloro-3-nitrobenzenesulfonyl fluoride 
• 6621-62-1 4-chloro-benzenesulfonic acid-(2,4-dichloro-phenyl ester) 
• 101079-89-4 4-chloro-benzenesulfonic acid-(2-chloro-ethyl ester) 
• 383-11-9 4-(trifluoromethylsulfonyl)chlorobenzene 
• 98-60-2 4-chlorobenzenesulfonyl chloride 
• 368-85-4 4-fluorobenzenesulfonyl fluoride 
• 864872-88-8 N-(1-{4-[2-(4-chloro-benzenesulfonyl)-benzenesulfonyl]-phenyl}-ethyl)-2,2,2-trifluoro-acetamide 
• 864872-97-9 N-(1-{4-[4-chloro-2-(4-chloro-benzenesulfonyl)-benzenesulfonyl]-phenyl}-ethyl)-2,2,2-trifluoro-acetamide 
• 864872-87-7 N-(1-{4-[2-(4-chloro-benzenesulfonyl)-4-trifluoromethyl-benzenesulfonyl]-phenyl}-ethyl)-2,2,2-trifluoro-acetamide 
• 864872-86-6 N-(1-{4-[2-(4-chloro-benzenesulfonyl)-4-cyclopentyloxy-benzenesulfonyl]-phenyl}-ethyl)-2,2,2-trifluoro-acetamide 
• 447460-28-8 N-(1-{4-[2-(4-chloro-benzenesulfonyl)-4-methoxy-benzenesulfonyl]-phenyl}-ethyl)-2,2,2-trifluoro-acetamide 
• 100709-81-7 4-chloro-benzolsulfynoic acid ; S-benzyl-thiuronium-salt 
• 97-09-6 4-Chloro-3-nitrobenzenesulfonamide 

Relevant articles and documents

Visible-Light-Mediated Synthesis of Sulfonyl Fluorides from Arylazo Sulfones

Sulfonyl fluorides are useful motifs for a wide range of applications in organic synthesis including sulfur (VI) fluoride exchange-based “click chemistry.” Herein, a visible-light-mediated synthesis of sulfonyl fluorides from arylazo sulfones is described. In the present study, K2S2O5 and N-fluorobenzenesulfonimide (NFSI) were used as the sulfonyl source and fluorinating agent, respectively, for visible-light-mediated fluorosulfonylation of arylazo sulfones to prepare various sulfonyl fluorides in 60–85% yield. This protocol is a synthetic approach to provide useful sulfonyl fluoride structures at room temperature. (Figure presented.).

Redox-Neutral Organometallic Elementary Steps at Bismuth: Catalytic Synthesis of Aryl Sulfonyl Fluorides

A Bi-catalyzed synthesis of sulfonyl fluorides from the corresponding (hetero)aryl boronic acids is presented. We demonstrate that the organobismuth(III) catalysts bearing a bis-aryl sulfone ligand backbone revolve through different canonical organometallic steps within the catalytic cycle without modifying the oxidation state. All steps have been validated, including the catalytic insertion of SO2 into Bi-C bonds, leading to a structurally unique O-bound bismuth sulfinate complex. The catalytic protocol affords excellent yields for a wide range of aryl and heteroaryl boronic acids, displaying a wide functional group tolerance.

Fluorination method

In order to overcome the problems of high cost and low stability of the existing fluorination reagents for preparing acyl fluoride, sulfonyl fluoride and phosphoryl fluoride compounds, the invention provides a fluorination method, which comprises the following operation steps of: adding a fluorination reagent into a substrate, wherein the fluorination reagent comprises cations M and anions, the anions are selected from one or more of perfluoropolyether chain carboxylic acid anions as shown in the specification: CF3(OCF2)nCO2, wherein n is selected from 1-10; the substrate comprises a carboxylic acid compound, a sulfonic acid compound, a phosphoric acid compound and a phosphine oxide compound; and carrying out fluorination reaction to obtain acyl fluoride, sulfonyl fluoride and phosphoryl fluoride products. According to the fluorination method provided by the invention, the perfluoropolyether chain carboxylate is used as a fluorination reagent, so that the dehydroxylation fluorination reaction of the carboxylic acid compound, the sulfonic acid compound and the phosphoric acid compound and the fluorination reaction of the phosphine oxide compound are realized, the product yield isrelatively high, and the fluorination method has relatively good universality for different substrates.

Copper-catalyzed three-component reaction of arylhydrazine hydrochloride, DABSO, and NFSI for the synthesis of arenesulfonyl fluorides

This paper reports a convenient copper-catalyzed three-component conversion of arylhydrazine hydrochlorides to arenesulfonyl fluorides in good yields under mild conditions, using 1,4-diazabicyclo [2.2.2]octane bis(sulfur dioxide) (DABSO) as a sulfonyl source andN-fluorobenzenesulfonimide (NFSI) as a fluorine source based on a radical sulfur dioxide insertion and fluorination strategy. Notably, arylhydrazine hydrochloride is used as a safe precursor of aryl radicals.

Metal-Free Visible-Light Synthesis of Arylsulfonyl Fluorides: Scope and Mechanism

The first metal-free procedure for the synthesis of arylsulfonyl fluorides is reported. Under organo-photoredox conditions, aryl diazonium salts react with a readily available SO2 source (DABSO) to afford the desired product through simple nucleophilic fluorination. The reaction tolerates the presence of both electron-rich and -poor aryls and demonstrated a broad functional group tolerance. To shed the light on the reaction mechanism, several experimental techniques were combined, including fluorescence, NMR, and EPR spectroscopy as well as DFT calculations.

Deoxyfluorination of Carboxylic, Sulfonic, Phosphinic Acids and Phosphine Oxides by Perfluoroalkyl Ether Carboxylic Acids Featuring CF2O Units

The deoxyfluorination of carboxylic, sulfonic, phosphinic acids and phosphine oxides is a fundamentally important approach to access acyl fluorides, sulfonyl fluorides and phosphoric fluorides, thus the development of inexpensive, stable, easy-to-handle, versatile, and efficient deoxyfluorination reagents is highly desired. Herein, we report the use of potassium salts of perfluoroalkyl ether carboxylic acids (PFECA) featuring CF2O units as deoxyfluorination reagents, which are generated mainly as by-products in the manufacture of hexafluoropropene oxide (HFPO). The synthesis of acyl fluorides, sulfonyl fluorides and phosphoric fluorides can be realized via carbonic difluoride (COF2) generated in situ from thermal degradation of the PFECA salt.

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).

Synthesis of Sulfonyl Fluorides from Sulfonamides

A simple and practical synthesis of sulfonyl fluorides from sulfonamides is reported. The method capitalizes on the formation of the sulfonyl chloride by virtue of the reaction of Pyry-BF4 and MgCl2, and subsequent in situ conversion to the more robust and stable sulfonyl fluoride by the presence of KF. The mild conditions and high chemoselectivity of the protocol enable the late-stage formation of sulfonyl fluorides from densely functionalized molecules.

Nickel(II)-Catalyzed Synthesis of Sulfinates from Aryl and Heteroaryl Boronic Acids and the Sulfur Dioxide Surrogate DABSO

We report a redox-neutral Ni(II)-catalyzed sulfination of readily available aryl and heteroaryl boronic acids. Using the combination of commercially available, air-stable NiBr2·(glyme), a commercially available phenanthroline ligand, and DABSO, boronic acids are efficiently converted to the corresponding sulfinate salts, which can be further elaborated to valuable sulfonyl-containing groups, including sulfones, sulfonamides, sulfonyl fluorides, and sulfonate esters. The catalyst loading can be reduced to 2.5 mol ?% on a gram scale. This practically simple protocol tolerates an unprecedented range of pharmaceutically relevant and electron-poor (hetero)aryl boronic acids, allowing the direct synthesis of active pharmaceutical ingredients.

One-pot fluorosulfurylation of Grignard reagents using sulfuryl fluoride

Herein, we report a new method for the one-pot syntheses of sulfonyl fluorides. Addition of an alkyl, aryl, or heteroaryl Grignard to a solution of sulfuryl fluoride at ambient temperature affords the desired sulfonyl fluorides in 18-78% yield. Furthermore, this method is applicable for in situ sequential reactions, whereby the Grignard reagent can be converted to the corresponding diarylsulfone, sulfonate ester, or sulfonamide in a one-pot process.