368-43-4

Basic information

• Product Name: BENZENESULFONYL FLUORIDE
• Synonyms: Phenylsulfonyl fluoride;BENZENESULFONYL FLUORIDE;BENZENESULPHONYL FLUORIDE;Benzenesulphonyl fluoride 99%;Benzenesulphonylfluoride99%;Benzenesulfonic acid fluoride;Benzenesulfonyl fluoride,99%;Benzenesulfonyl fluoride, 99% 5GR
• CAS NO: 368-43-4
• Molecular Formula: C₆H₅FO₂S
• Molecular Weight: 160.17
• EINECS: 206-707-2
• Product Categories: Organic Building Blocks;Sulfonyl Halides;Sulfur Compounds
• Mol File: 368-43-4.mol

Chemical Properties

• Boiling Point: 207-208 °C(lit.)
• Flash Point: 189 °F
• Appearance: /
• Density: 1.333 g/mL at 25 °C(lit.)
• Vapor Density: 5.52
• Vapor Pressure: 40.5mmHg at 25°C
• Refractive Index: n20/D 1.492(lit.)
• Sensitive: Moisture Sensitive
• BRN: 2206835
• CAS DataBase Reference: BENZENESULFONYL FLUORIDE(CAS DataBase Reference)
• NIST Chemistry Reference: BENZENESULFONYL FLUORIDE(368-43-4)
• EPA Substance Registry System: BENZENESULFONYL FLUORIDE(368-43-4)

Safety Data

• Hazard Codes: C
• Statements: 20/21/22-34
• Safety Statements: 26-27-36/37/39-45
• RIDADR: UN 3265 8/PG 2
• WGK Germany: 3
• RTECS: DB8940000
• TSCA: Yes
• HazardClass: 8
• PackingGroup: III
• Hazardous Substances Data: 368-43-4(Hazardous Substances Data)

Usage

Uses

Used in Chemical Synthesis:
Benzenesulfonyl fluoride is used as a reagent in the chemical synthesis of α-sulfonyl phosphonates. It is particularly effective in the direct sulfonylation of lithiated alkyl phosphonates, which are important intermediates in the preparation of various organic compounds.
Used in Mass Spectrometry:
In the field of analytical chemistry, benzenesulfonyl fluoride has been employed in the study of gas-phase fluorine migration reactions of radical cations. This research has been conducted using electron ionization tandem mass spectrometry, providing valuable insights into the compound's chemical behavior and properties.
Used in Pharmaceutical Industry:
Benzenesulfonyl fluoride is also utilized in the pharmaceutical industry as a protecting group for amines and alcohols during organic synthesis. Its selective reactivity and ease of removal make it a preferred choice for protecting functional groups in the synthesis of complex molecules, including drugs and drug candidates.
Used in Research and Development:
Due to its unique chemical properties, benzenesulfonyl fluoride is often used in research and development for the synthesis of novel compounds and the investigation of various chemical reactions. It serves as a valuable tool for chemists in understanding reaction mechanisms and developing new synthetic routes.

Safety Profile

A poison by intraperitoneal route. Slightly irritating to sbn. Flammable when exposed to heat or flame. It can react vigorously with oxihzing materials. To fight fire, use water, foam, CO2, water spray or mist, dry chemical. When heated to decomposition it emits toxic fumes of Fand SO,. See also FLUORIDES and SULFATES.

InChI:InChI=1/C6H5F3Si/c7-10(8,9)6-4-2-1-3-5-6/h1-5H

Upstream product

• 98-09-9 benzenesulfonyl chloride 
• 98-11-3 benzenesulfonic acid 
• 71-43-2 benzene 
• 17067-71-9 tri-(pentafluoro phenyl) phenyl silane 
• 7789-21-1 fluorosulphonic acid 
• 712-48-1 chlorodiphenylarsine 
• 3204-68-0 benzyldimethylphenylammonium chloride 
• 882-33-7 diphenyldisulfane 
• 203126-16-3 phenyltetrafluoro-λ⁶-sulfanyl chloride 
• 108-86-1 bromobenzene 
• 81431-98-3 2-cyanophenylisothiocyanate 
• 1197209-25-8 trifluoromethyl benzenesulfonate 
• 98-13-5 Phenyltrichlorosilane 
• 657-98-7 Benzolsulfinsaeurefluorid 

Downstream Products

• 593-53-3 Methyl fluoride 
• 33419-26-0 1,1-bis-benzenesulfonyl-ethane 
• 3112-85-4 methylphenylsulfonate 
• 3406-02-8 bis(phenylsulfonyl)methane 
• 92-52-4 biphenyl 
• 127-63-9 diphenyl sulphone 
• 515-46-8 Ethyl benzenesulfonate 
• 36635-63-9 ((isocyanomethyl)sulfonyl)benzene 
• 61035-59-4 1,1,1,3,3,3-hexafluoropropan-2-yl benzenesulfonate 
• 420-56-4 trimethylsilyl fluoride 
• 84224-41-9 (Z)-(1-Propenyl)-benzolsulfonat 
• 84224-40-8 (E)-(1-Propenyl)-benzolsulfonat 
• 84224-42-0 (2-Methyl-1-propenyl)-benzolsulfonat 
• 84224-46-4 (2-Methyl-1-cyclohexen-1-yl)-benzolsulfonat 

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.).

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.

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.

Synthesis of Sulfones and Sulfonyl Derivatives using Sodium (tert-butyldimethylsilyl)oxymethanesulfinate

The present invention relates to a method for manufacturing a sulfone and sulfonyl derivative compound using sodium (tert-butyldimethylsilyl)oxymethanesulfinate, which is a novel organic sulfin salt, wherein the novel organic sulfin salt has good stability, environmental friendliness and economy, and is easy to handle, and thus significantly reduces the amount of transition metal catalysts and the amount of organic sulfin salts used when introducing aryl or alkenyl. Also, alkylation, arylation, amination, and fluorination are all possible during secondary functionalization. Therefore, the present invention can be usefully used in preparation and mass production of various kinds of sulfones and derivatives thereof including asymmetric sulfone derivatives.

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.

Copper-Catalyzed Intermolecular Functionalization of Unactivated C(sp3)-H Bonds and Aliphatic Carboxylic Acids

Intermolecular functionalization of C(sp3)-H bonds and aliphatic carboxylic acids enables the efficient synthesis of high value-added organic compounds from readily available starting materials. Although methods involving hydrogen atom transfer have been developed for such functionalization, these methods either work for only activated C(sp3)-H bonds or bring in a narrow set of functional groups. Here we describe a Cu-catalyzed process for the diverse functionalization of both unactivated C(sp3)-H bonds and aliphatic carboxylic acids. The process is enabled by the trapping of alkyl radicals generated through hydrogen atom abstraction by arylsulfonyl-based SOMO-philes, which introduces a large array of C, N, S, Se, and halide-based functional groups. The chemoselectivity can be switched from C-H functionalization to decarboxylative functionalization by matching the bond dissociation energy of the hydrogen atom transfer reagent with that of the target C-H or O-H bond.

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.

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.

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).

Improved Access to Organo-Soluble Di- and Tetrafluoridochlorate(I)/(III) Salts

A facile one-pot gram-scale synthesis of tetraalkylammonium tetrafluoridochlorate(III) [cat][ClF4] ([cat]=[NEt3Me]+, [NEt4]+) is described. An acetonitrile solution of the corresponding alkylammonium chloride salt is fluorinated with diluted fluorine at low temperatures. The reaction proceeds via the [ClF2]? anion which is structurally characterized for the first time. The potential application of [ClF4]? salts as fluorinating agents is evaluated by the reaction with diphenyl disulfide, Ph2S2, to pentafluorosulfanyl benzene, PhSF5. The CN moieties in acetonitrile and [B(CN)4]? are transferred in CF3 groups. Exposure of carbon monoxide, CO, leads to the formation of carbonyl fluoride, COF2, and elemental gold is dissolved under the formation of tetrafluoridoaurate [AuF4]?.