cas 368-43-4, BENZENESULFONYL FLUORIDE | Articles data

Articles about 368-43-4Total 44 be found

Article title
Article abstract
Author
Journal number and time
Download

-
-
Seel et al.
p. 437
(1978)
Read Online

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.).
Bui, Tien Tan,Tran, Van Hieu,Kim, Hee-Kwon
supporting information
p. 341 - 347
(2021/10/14)

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.
Cornella, Josep,Magre, Marc
p. 21497 - 21502
(2022/01/03)

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.
Mao, Runze,Bera, Srikrishna,Turla, Aurélya Christelle,Hu, Xile
supporting information
p. 14667 - 14675
(2021/09/18)

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.
Louvel, Dan,Chelagha, Aida,Rouillon, Jean,Payard, Pierre-Adrien,Khrouz, Lhoussain,Monnereau, Cyrille,Tlili, Anis
supporting information
p. 8704 - 8708
(2021/05/17)

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.
-
Paragraph 0908-0912; 0914; 0916-0917; 0919-0922; 0924-0927

(2021/04/29)

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.
-
Paragraph 0130-0163

(2021/01/12)

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.
Zhao, Shiyu,Guo, Yong,Su, Zhaoben,Wu, Chengying,Chen, Wei,Chen, Qing-Yun
supporting information
p. 1225 - 1232
(2021/05/04)

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.
Pérez-Palau, Marina,Cornella, Josep
supporting information
p. 2497 - 2500
(2020/03/11)

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).
Cornella, Josep,Wang, Lin
supporting information
p. 23510 - 23515
(2020/10/29)

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]?.
Kaupp, M.,Müller, R.,Pr?hm, P.,Riedel, S.,Schattenberg, C. J.,Schmid, J. R.,Sonnenberg, K.,Steinhauer, S.,Vo?nacker, P.
supporting information
p. 16002 - 16006
(2020/07/20)

Phosphorus(III)-Mediated, Tandem Deoxygenative Geminal Chlorofluorination of 1,2-Diketones
Tetrasubstituted carbon containing two different halogen substituents was constructed in a single-step operation by utilizing the carbene-like reactivity of dioxaphospholene through the tandem reaction of electrophilic and nucleophilic halogenating reagents. It was crucial to devise non-dealkylatable phosphoramidite, which enabled the efficient formation of geminal chlorofluorides from various 1,2-diketones with (PhSO2)2NF and n-Bu4NCl. In addition, selective functionalization of the chlorine substituent was demonstrated, and the absence of halogen scrambling was confirmed.
Choi, Garam,Chung, Won-Jin,Hwang, Sunjoo,Jang, Hanna,Kim, Ha Eun
p. 4190 - 4195
(2020/06/27)

Facile Access to AgOCF3 and Its New Applications as a Reservoir for OCF2 for the Direct Synthesis of N?CF3, Aryl or Alkyl Carbamoyl Fluorides
The development of innovative fluorination strategies is greatly dependent also on the availability, safety and practicability of available fluorinating reagents. We herein show a straightforward and quantitative strategy for the preparation of valuable AgOCF3 at room temperature and showcase its performance in trifluoromethoxylations or as reservoir for O=CF2. This enabled the direct, practical and safe synthesis of valuable N-alkyl/aryl and N?CF3 carbamoyl fluorides from secondary amines and isothiocyanides, respectively. Our mechanistic data indicate that AgOCF3 does not liberate O=CF2 until it is activated by a nucleophilic co-reagent, reinforcing the stability of the salt under our new preparation strategy.
Bouayad-Gervais, Samir,Scattolin, Thomas,Schoenebeck, Franziska,Turksoy, Abdurrahman
supporting information

(2020/02/11)

Arenesulfonyl Fluoride Synthesis via Copper-Catalyzed Fluorosulfonylation of Arenediazonium Salts
We report herein a general and practical copper-catalyzed fluorosulfonylation reaction of a wide range of abundant arenediazonium salts to smoothly prepare various arenesulfonyl fluorides using the 1,4-diazabicyclo[2.2.2]octane-bis(sulfur dioxide) adduct as a convenient sulfonyl source in combination with KHF2 as an ideal fluorine source and without the need for additional oxidants. Interestingly, the electronic character of the arene ring in the starting arenediazonium salts has a significant impact on the reaction mechanistic pathway.
Liu, Yongan,Yu, Donghai,Guo, Yong,Xiao, Ji-Chang,Chen, Qing-Yun,Liu, Chao
supporting information
p. 2281 - 2286
(2020/03/13)

NFSI/KF mediated mild and chemoselective interconversion of aryl TBDMS ethers to their benzene sulfonate
A one pot protocol for the transformation of aryl TBDMS ethers to corresponding benzene sulfonate esters using NFSI (N-flurobenzenesulfonimide)/KF is described. In situ generation of benzenesulfonyl fluoride directs chemoselective cleavage of aryl silyl ethers over alkyl silyl ethers. Electron withdrawing substituent's on aryl ring provided better yield than donating groups. Protecting groups and sensitive functionalities are well tolerated in this methodology. Thus, commercially available inexpensive reagents, mild reaction conditions and step economy are the advantages of this method.
Dond, Bharat D.,Thore, Shivaji N.
supporting information

(2020/02/06)

Method for efficiently preparing sulfuryl fluorides compound by catalytic fluorination
The invention belongs to the technical field of the chemical synthesis, and particularly relates to a method for efficiently preparing a sulfuryl fluorides compound by catalytic fluorination. The provided method for efficiently preparing the sulfuryl fluorides compound by the catalytic fluorination comprises the following steps: enabling a sulfonyl chlorides compound to react with a hydroge fluoride under the action of a catalyst of a sulfonic acids derivative, to obtain the sulfuryl fluorides compound. A novel catalytic technology is provided, and the method has extensive substrate applicability. Efficient catalytic efficiency and yield are expressed.
-
Paragraph 0079; 0080; 0081; 0082

(2019/05/22)

Sulfonyl Fluoride Synthesis through Electrochemical Oxidative Coupling of Thiols and Potassium Fluoride
Sulfonyl fluorides are valuable synthetic motifs for a variety of applications, among which sulfur(VI) fluoride exchange-based "click chemistry" is currently the most prominent. Consequently, the development of novel and efficient synthetic methods to access these functional groups is of great interest. Herein, we report a mild and environmentally benign electrochemical approach to prepare sulfonyl fluorides using thiols or disulfides, as widely available starting materials, in combination with KF, as an inexpensive, abundant and safe fluoride source. No additional oxidants nor additional catalysts are required and, due to mild reaction conditions, the reaction displays a broad substrate scope, including a variety of alkyl, benzyl, aryl and heteroaryl thiols or disulfides.
Laudadio, Gabriele,Bartolomeu, Aloisio De A.,Verwijlen, Lucas M. H. M.,Cao, Yiran,De Oliveira, Kleber T.,No?l, Timothy
supporting information
p. 11832 - 11836
(2019/08/26)

Facile one-pot synthesis of sulfonyl fluorides from sulfonates or sulfonic acids
A facile cascade process for directly transforming the abundant and inexpensive sulfonates (or sulfonic acids) to the highly valuable sulfonyl fluorides was developed. This new protocol features mild reaction conditions using readily available and easy-to-operate reagents. A diverse set of sulfonyl fluorides was prepared facilitating the enrichment of the sulfonyl fluoride library.
Jiang, Ying,Alharbi, Njud S.,Sun, Bing,Qin, Hua-Li
p. 13863 - 13867
(2019/05/17)

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.
Lee, Cayo,Ball, Nicholas D.,Sammis, Glenn M.
supporting information
p. 14753 - 14756
(2019/12/23)

A study of the reactivity of S(VI)-F containing warheads with nucleophilic amino-acid side chains under physiological conditions
Sulfonyl fluorides (SFs) have recently emerged as a promising warhead for the targeted covalent modification of proteins. Despite numerous examples of the successful deployment of SFs as covalent probe compounds, a detailed exploration of the factors influencing the stability and reactivity of SFs has not yet appeared. In this work we present an extensive study on the influence of steric and electronic factors on the reactivity and stability of the SF and related SVI-F groups. While SFs react rapidly with N-acetylcysteine, the resulting adducts were found to be unstable, rendering SFs inappropriate for the durable covalent inhibition of cysteine residues. In contrast, SFs afforded stable adducts with both N-acetyltyrosine and N-acetyllysine; furthermore, we show that the reactivity of arylsulfonyl fluorides towards these nucleophilic amino acids can be predictably modulated by adjusting the electronic properties of the warhead. These trends were largely conserved when the covalent reaction occurred within a protein binding pocket. We have also obtained a crystal structure depicting covalent modification of the catalytic lysine of a tyrosine kinase (FGFR1) by the ATP analog 5′-O-3-((fluorosulfonyl)benzoyl)adenosine (m-FSBA). Highly reactive warheads were demonstrated to be unstable with respect to hydrolysis in buffered aqueous solutions, indicating that warhead reactivity must be carefully tuned to provide optimal rates of protein modification. Our results demonstrate that the reactivity of SFs complements that of more commonly studied acrylamides, and we hope that this work spurs the rational design of novel SF-containing covalent probe compounds and inhibitors, particularly in cases where a suitably positioned cysteine residue is not present.
Mukherjee,Debreczeni,Breed,Tentarelli,Aquila,Dowling,Whitty,Grimster
supporting information
p. 9685 - 9695
(2017/11/30)

One-pot palladium-catalyzed synthesis of sulfonyl fluorides from aryl bromides
A mild, efficient synthesis of sulfonyl fluorides from aryl and heteroaryl bromides utilizing palladium catalysis is described. The process involves the initial palladium-catalyzed sulfonylation of aryl bromides using DABSO as an SO2 source, followed by in situ treatment of the resultant sulfinate with the electrophilic fluorine source NFSI. This sequence represents the first general method for the sulfonylation of aryl bromides, and offers a practical, one-pot alternative to previously described syntheses of sulfonyl fluorides, allowing rapid access to these biologically important molecules. Excellent functional group tolerance is demonstrated, with the transformation successfully achieved on a number of active pharmaceutical ingredients, and their precursors. The preparation of peptide-derived sulfonyl fluorides is also demonstrated.
Davies, Alyn T.,Curto, John M.,Bagley, Scott W.,Willis, Michael C.
p. 1233 - 1237
(2017/02/10)

Catalyst-free radical fluorination of sulfonyl hydrazides in water
The first catalyst-free fluorination of sulfonyl hydrazides for the synthesis of sulfonyl fluorides has been developed via a free-radical pathway. This protocol presents a broad substrate scope and does not require any metal catalyst and additive. All these transformations proceed smoothly in water under mild conditions, which enables a straightforward, practical and environmentally benign fluorination for S-F bond formation.
Tang, Lin,Yang,Wen, Lixian,Yang, Xingkun,Wang, Zhiyong
p. 1224 - 1228
(2016/03/09)

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.
Lummer, Katrin,Ponomarenko, Maxim V.,R?schenthaler, Gerd-Volker,Bremer, Matthias,Beier, Petr
p. 79 - 83
(2014/01/06)

Oxidation of disulfides with electrophilic halogenating reagents: Concise methods for preparation of thiosulfonates and sulfonyl halides
The reaction of aromatic or benzylic disulfides with 2.5 equiv of Selectfluor in acetonitrile/water (10:1) at room temperature efficiently produced the corresponding thiosulfonates. Conversely, the reaction of disulfides with 6.5 equiv of Selectfluor or thiosulfonates with 4.5 equiv of Selectfluor in refluxing acetonitrile/water (10:1) provided sulfonyl fluorides in high yields. Accufluor and FP-T300 are also effective in preparing sulfonyl fluorides from disulfides under the similar reaction conditions. Sulfonyl chlorides or sulfonyl bromides were effectively obtained from the reaction of disulfides with 6 equiv of either N-chlorosuccinimide or N-bromosuccinimide in acetonitrile/water (10:1) at room temperature. Some other electrophilic chlorinating or brominating reagents are also able to be used instead of N-chlorosuccinimide or N-bromosuccinimide for the syntheses of sulfonyl halides from disulfides. These reactions of disulfides with electrophilic halogenating reagents are convenient methods to prepare thiosulfonates and sulfonyl halides.
Kirihara, Masayuki,Naito, Sayuri,Nishimura, Yuki,Ishizuka, Yuki,Iwai, Toshiaki,Takeuchi, Haruka,Ogata, Tomomi,Hanai, Honoka,Kinoshita, Yukari,Kishida, Mari,Yamazaki, Kento,Noguchi, Takuya,Yamashoji, Shiro
p. 2464 - 2471
(2014/04/03)

Preparation of α-Fluorobis(phenylsulfonyl)methane (FBSM)
-
Prakash, G.K. Surya,Shao, Nan,Wang, Fang,Ni, Chuanfa
p. 130 - 144
(2014/04/03)

Ascertaining the suitability of aryl sulfonyl fluorides for [18F]radiochemistry applications: A systematic investigation using microfluidics
Optimization of [18F]radiolabeling conditions and subsequent stability analysis in mobile phase, PBS buffer, and rat serum of 12 aryl sulfonyl chloride precursors with various substituents (electron-withdrawing groups, electron-donating groups, increased steric bulk, heterocyclic) were performed using an Advion NanoTek Microfluidic Synthesis System. A comparison of radiochemical yields and reaction times for a microfluidics device versus a conventional reaction vessel is reported. [18F]Radiolabeling of sulfonyl chlorides in the presence of competing nucleophiles, H-bond donors, and water was also assessed and demonstrated the versatility and potential utility of [18F]sulfonyl fluorides as synthons for indirect radiolabeling. Published 2013 by the American Chemical Society.
Matesic, Lidia,Wyatt, Naomi A.,Fraser, Benjamin H.,Roberts, Maxine P.,Pham, Tien Q.,Greguric, Ivan
p. 11262 - 11270
(2013/12/04)

Electrophilic fluorination of N,N-dimethylaniline, N,N-dimethylnaphthalen- 1-amine and 1,8-bis(dimethylamino)naphthalene with N-F reagents
Reaction of N,N-dimethylaniline, N,N-dimethylnaphthalen-1-amine and 1,8-bis(dimethylamino)- naphthalene (proton sponge) with 1-chloromethyl-4- fluorodiazonia-bicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor) and N-fluorobenzenesulfonimide (NFSI) h
Sorokin, Vladimir I.,Pozharskii, Alexander F.,Ozeryanskii, Valery A.
p. 67 - 72
(2013/11/06)

Oxidation of disulfides with Selectfluor: Concise syntheses of thiosulfonates and sulfonyl fluorides
The reaction of aromatic or benzylic disulfides with 2.5 equiv of Selectfluor in acetonitrile/water (10:1) at room temperature efficiently produced the corresponding thiosulfonates. On the other hand, the reaction of disulfides with 6.5 equiv of Selectfluor in refluxing acetonitrile/water (10:1) provided sulfonyl fluoride in high yields.
Kirihara, Masayuki,Naito, Sayuri,Ishizuka, Yuki,Hanai, Honoka,Noguchi, Takuya
experimental part
p. 3086 - 3089
(2011/06/26)

A convenient, one-pot procedure for the preparation of acyl and sulfonyl fluorides using Cl3CCN, Ph3P, and TBAF(t -BuOH) 4
Various carboxylic acids were converted into acyl fluorides in excellent yields by treatment with trichloroacetonitrile, triphenylphosphine, and TBAF(t-BuOH)4 at room temperature. The reaction was applicable to the preparation of acid-sensitive amino acid fluorides without deprotection or rearrangement
Kim, Joong-Gon,Jang, Doo Ok
experimental part
p. 3049 - 3052
(2011/02/25)

METHODS FOR PRODUCING ARYLSULFUR PENTAFLUORIDES
Novel methods for preparing arylsulfur pentafluorides are disclosed. Arylsulfur halotetrafluoride is reacted with a fluoride source under hydrous conditions to form an arylsulfur pentafluoride. The purification method is also disclosed.
-
Page/Page column 33-34

(2010/04/03)

2,7-Substituted indoles
The present invention provides a compound of the formula: a pharmaceutically acceptable salt or a prodrug thereof, where R1, R2, R3, R4, and n are those defined herein. The present invention also provides compositions comprising, methods for using, and methods for preparing Compound of Formula I.
-
Page/Page column 12

(2010/11/30)

Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 12. Extrusion of Ph3P from sulfonyl ylides and reactivity of the resulting sulfonyl carbenes
Twelve sulfonyl stabilised phosphorus ylides have been prepared and their behaviour upon flash vacuum pyrolysis at 600°C has been examined. Examples with an arylsulfonyl substituent undergo loss of Ph3PO to give intractable products but those with an arylmethylsulfonyl substituent separately lose Ph3P and SO2 to give products consistent with the intermediacy of sulfonyl carbenes. X-Ray structure determinations of one ylide from each series show a more significant P-O non-bonding interaction in the first case, providing some explanation for the different thermal reactivity.
Aitken, R. Alan,Drysdale, Martin J.,Ferguson, George,Lough, Alan J.
p. 875 - 880
(2007/10/03)

Preparation of halogeno(pentafluorophenyl)silanes (C6F5)nSiX4-n (X=F, Cl and Br; N=2, 3) from pentafluorophenyl(phenyl)silanes (C6F5)nSiPh4-n
Halogeno(pentafluorophenyl)silanes (C6F5)nSiX4-n (X=F, Cl and Br; n=2, 3) were prepared in good yields from the corresponding phenylsilanes (C6F5)nSiPh4-n by reactions with the electrophiles aHF, FSO3H, HCl-AlCl3 or with AlX3 (X=Cl, Br)-halogenated hydrocarbons. The relative leaving ability of the organyl groups (C6F5, C6H5, Me) bonded to the silicon atom and the strength of the electrophilic reagent are discussed.
Frohn,Lewin,Bardin
p. 233 - 240
(2007/10/03)

α-Fluorination of methyl phenyl sulfoxide and related compounds by molecular fluorine: A novel method for the introduction of fluorine into sulfoxides bearing α-H atoms
Direct formation of α-fluorosulfones from sulfoxides bearing α-H atoms merely by reaction with molecular fluorine (5% F2/N2) is reported, and a novel non-Pummerer-type mechanism is proposed for this α-fluorination reaction.
Toyota, Akemi,Ono, Yoshinori,Chiba, Jun,Sugihara, Takumichi,Kaneko, Chikara
p. 703 - 708
(2007/10/03)

N-halogeno compounds. Part 18. 1-Alkyl-4-fluoro-1,4-diazoniabicyclo [2.2.2] octane salts: User-friendly site-selective electrophilic fluorinating agents of the N-fluoroammonium class
Methods of synthesis are described for a range of 1-alkyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane salts [R-N+(CH2CH2)3N+-F (X-)2, where R = CH3, CH2Cl, C2H5, CF3CH2, C8H17 and (X-)2 = (TfO-)2, (BF4-)2, (PF6-)2, (TfO-, BF4-), (TfO-, PF6-), (TfO-, FSO3-)] by direct fluorination (with neat F2 at ≤20 mmHg or F2-N2 blends at 1 atm pressure) of monoquaternary salts of 1,4-diazabicyclo[2.2.2]octane [R-+N(CH2CH2)3N X-] or their 1:1 adducts with boron trifluoride, phosphorus pentafluoride, or sulfur trioxide in acetonitrile at ca - 35°C. The results of site-selective electrophilic fluorination of diethyl sodio(phenyl)malonate [→ PhCF(CO2Et)2], 1-morpholinocyclohexene (→ 2-fluorocyclohexanone), phenol (→ 2- and 4-FC6H4OH), 1- and 2-hydroxynaphthalene (→ 2- and 4-FC10H6OH, and 1-FC10H6OH and 1,1-difluoro-2-oxo-1,2-dihydronaphthalene, respectively), acetanilide (→ 2- and 4-FC6H4NHCOCH3), anisole (→ 2- and 4-FC6H4OCH3) and sodium benzenesulfinate (→ PhSO2F) with these N-fluoroammonium salts are presented.
Banks, R. Eric,Besheesh, Mohamed K.,Mohialdin-Khaffaf, Suad N.,Sharif, Iqbal
p. 2069 - 2076
(2007/10/03)

Sulfonation of Aromatic Compounds in HSO3F-SbF5
-
Tanaka, Mutsuo,Souma, Yoshie
p. 3738 - 3740
(2007/10/02)

TRIS(DIALKYLAMINO)SELENONIUM HALIDES
Tris(dialkylamino)selenonium halides are formed in the reaction of N-trimethylsilyldialkylamines with the corresponding selenium tetrahalides.Tris(dialkylamino)selenonium chlorides react under mild conditions with carboxylic acids and their halides, phosphorus trichloride, and fluorosulfuranes to give amides, tris(dialkylamino)chlorophosphonium chlorides, and tris(dialkylamino)sulfonium pentafluoroselenates.
Markovskii, L. N.,Tovstenko, V. I.,Martynyuk, E. G.,Pashinnik, V. E.,Shermolovich, Yu. G.
p. 422 - 425
(2007/10/02)

TRIS(MORPHOLINO)SELENONIUM FLUORIDE
-
Markovskii, L. N.,Tovstenko, V. I.,Martynyuk, E. G.,Pashinnik, V. E.,Shermolovich, Yu. G.,Iksanova, S. V.
p. 1185 - 1186
(2007/10/02)

Cross-interaction Constants as a Measure of the Transition-state Structure. Part 1. The Degree of Bond Formation in Nucleophilic Substitution Reactions
The kinetic of seven reaction series in methanol involving halides as leaving groups and aromatic amines as nucleophiles are reported.Analyses of various Hammett ρ values, especially the cross-interaction constants ρXY between substituents X in the nucleophile and Y in the substrate, are used to characterize the transition-state structure for the nucleophilic substitution reactions.The degree of bond formation in the transition state as measured by /ρXY/ indicated that the reactions can be classified into two groups according to the magnitude of the cross-interaction constants; the fluoride series gave larger /ρXY/ values indicating a greater degree of bond formation, under the same reactants condition, compared with other series with relatively good leaving groups, e.g.Cl-, Br-, and -OSO2C6H5.When, however, a non-conjugative intervening group such as CO or CH2 is present between the reaction centre and the benzene ring of a reactant, the cross-interaction constant is reduced by a factor of ca. 2, demonstrating the fall-off of the susceptibility of the reaction centres to substituent changes.
Lee, Ikchoon,Shim, Chang Sub,Chung, Soo Young,Kim, Hyung Yoon,Lee, Hai Whang
p. 1919 - 1924
(2007/10/02)

The Combination of Potassium Fluoride and Calcium Fluoride: A Useful Heterogeneous Fluorinating Reagent
The combination of potassium fluoride and calcium fluoride was found to be an effective and practical solid reagent for the fluorination of various organic chlorides and bromides under mild conditions.
Ichihara, Junko,Matsuo, Toshiya,Hanafusa, Terukiyo,Ando, Takashi
p. 793 - 794
(2007/10/02)

ENHANCED EFFECT OF SPRAY-DRIED POTASSIUM FLUORIDE ON FLUORINATION
Spray-dried potassium fluoride was found to be much less hygroscopic and much more effective as a fluorinating agent than usual calcine-dried potassium fluoride.Organic compounds containing an activated halogen atom were readily fluorinated in acetonitrile with spray-dried potassium fluoride.
Ishikawa, Nobuo,Kitazume, Tomoya,Yamazaki, Takashi,Mochida, Yoshiharu,Tatsuno, Toshio
p. 761 - 764
(2007/10/02)

KINETICS OF THE TRANSFORMATIONS OF AROMATIC SULFO DERIVATIVES TO ACID HALIDES IN CHLORO- AND FLUOROSULFONIC ACID MEDIA
The pseudofirst-order rate constants for the formation of the corresponding sulfonic acid halides (keff) from sulfo derivatives with the general formula RC6H4SO3X, where X = NH2, Cl, F, and R = H, p-Cl, p-NO2, and m-NO2, were measured by GLC in fluorosulfonic and chlorosulfonic acids.The effect of substituents in the benzene ring on the rate of the transformations of the sulfo derivatives into the halides is similar to the previously investigated effect of substituents on the rate of solvolysis of substituted benzenesulfonyl halides in 100percent sulfuric acid (ρ -4).Com parison of the ratios of the keff values for the transformations of the sulfonamides in chlorosulfonic and fluorosulfonic acids and also the sulfonyl fluorides in 100percent sulfuric acid and chlorosulfonic acid with the ratios of the acidities of the respective media shows that these reactions have acid-catalytic character.The sulfonyl chlorides and sulfonamides in 100percent sulfuric acid are solvolyzed to a significant degree with the participation of H2S2O7.
Ivanov, S. N.,Gnedin, B. G.
p. 1909 - 1914
(2007/10/02)

Arylsulfur(VI) Trifluoride Oxides by F2-Addition to Sulfinic Fluorides
The hitherto unknown compounds of the type: arylsulfur(VI) trifluoride oxides (2a: Ar = Ph; 2b: Ar = p-FC6H4) are obtained by direct F2-addition to the sulfinic fluorides 1a and b.The fixed trigonal-bipyramidal ligand arrangement is documented by 19F and 13C1H NMR data.In glass vessels, 2a, b readily undergo decomposition catalyzed by HF to give the corresponding sulfonic fluorides 3a, b.Action of BF3 on 2a by abstraction of fluoride yields the difluorophenylsulfoxonium salt 4a, that on dry distillation with NaF re-liberates 2a.
Ruppert Ingo
p. 1047 - 1052
(2007/10/02)

KINETIC INVESTIGATION OF THE S-FLUORINATION OF ARENESULFINATES WITH PERCHLORYL FLUORIDE
The effect of substituents and solvents on the kinetics of S-fluorination of sodium arenesulfinates with perchloryl fluoride was investigated.Alternative fluorination mechanisms were examined, and it was found that the mechanism is SN2 substitution at the fluorine atom.
Vigalok, I. V.,Petrova, G. G.,Lukashina, S. G.,Vigalok, A. A.,Levin, Ya. A.
p. 1239 - 1243
(2007/10/02)

Process for preparing sulfonic acid fluorides
Sulfonic acid fluorides are prepared by reacting sulfonic acid halides with inorganic fluorides in an organic-aqueous phase. The reaction is carried out in the presence of catalytic amounts of an amine or an onium salt.
-
(2008/06/13)