20875-34-7Relevant articles and documents
Preparation of Propargylic Sulfinates and their [2,3]-Sigmatropic Rearrangement to Allenic Sulfones
Tata, Rama Rao,Hampton, Carissa S.,Harmata, Michael
supporting information, p. 1232 - 1241 (2017/04/11)
The scope of the [2,3]-sigmatropic rearrangement of propargylic sulfinates to allenic sulfones by silver catalysis was expanded. A series of new propargylic sulfinate esters was generated from a variety of aromatic and heteroaromatic sulfonyl chlorides an
Discovery of 4-tert-butyl-2,6-dimethylphenylsulfur trifluoride as a deoxofluorinating agent with high thermal stability as well as unusual resistance to aqueous hydrolysis, and its diverse fluorination capabilities including deoxofluoro-arylsulfinylation with high stereoselectivity
Umemoto, Teruo,Singh, Rajendra P.,Xu, Yong,Saito, Norimichi
supporting information; experimental part, p. 18199 - 18205 (2011/03/18)
Versatile, safe, shelf-stable, and easy-to-handle fluorinating agents are strongly desired in both academic and industrial arenas, since fluorinated compounds have attracted considerable interest in many areas, such as drug discovery, due to the unique effects of fluorine atoms when incorporated into molecules. This article describes the synthesis, properties, and reactivity of many substituted and thermally stable phenylsulfur trifluorides, in particular, 4-tert-butyl-2,6-dimethylphenylsulfur trifluoride (Fluolead, 1k), as a crystalline solid having surprisingly high stability on contact with water and superior utility as a deoxofluorinating agent compared to current reagents, such as DAST and its analogues. The roles of substiuents on 1k in thermal and hydrolytic stability, fluorination reactivity, and the high-yield fluorination mechanism it undergoes have been clarified. In addition to fluorinations of alcohols, aldehydes, and enolizable ketones, 1k smoothly converts non-enolizable carbonyls to CF2 groups, and carboxylic groups to CF3 groups, in high yields. 1k also converts C(=S) and CH3SC(=S)O groups to CF2 and CF3O groups, respectively, in high yields. In addition, 1k effects highly stereoselective deoxofluoro-arylsulfinylation of diols and amino alcohols to give fluoroalkyl arylsulfinates and arylsulfinamides, with complete inversion of configuration at fluorine and the simultaneous, selective formation of one conformational isomer at the sulfoxide sulfur atom. Considering the unique and diverse properties, relative safety, and ease of handling of 1k in addition to its convenient synthesis, it is expected to find considerable use as a novel fluorinating agent in both academic and industrial arenas.
PREPARATION AND SPECTRAL PROPERTIES OF SYMMETRICAL S-ARYL ARENESULFONOTHIOATES (THIOSULFONATES)
Freeman, Fillmore,Bartosik, Lisa G.,Bui, Nghe Van,Keindl, Monica C.,Nelson, Eric L.
, p. 375 - 386 (2007/10/02)
Arenesulfinyl chlorides (4-XC6H4S(O)Cl; X = H, CH3, F, Cl, Br) react with activated zerovalent zinc in benzene at 6 to 8 deg C to give symmetrical S-aryl arenesulfonothioates (thiosulfonates) in good to excellent yields. 2- and 3-substituted arenesulfinyl chlorides (X=Cl, CH3) give a mixture of products (disulfide, thiosulfinate, and/or thiosulfonate). 2,4,6-Triisopropylbenzenesulfinyl chloride reacts with zinc in 1,2-dimethoxyethane to give S-(2,4,6-triisopropylphenyl) 2,4,6-triisopropylbenzenesulfinothioate and bis(2,4,6-triisopropylphenyl) disulfide.Possible mechanisms for the reaction, the 1H and 13C NMR spectra and the chemical ionization and electron impact mass spectra of the thiosulfonates are discussed.The para carbon substituent chemical shifts (Cp-SCS) for the thiosulfonates and for symmetrical diaryl disulfides have been subjected to several dual substituent parameter (DSP) correlations. Key Words: S-aryl-arenesulfonothioates (thiosulfonates); arenesulfinyl chlorides; 1H and 13C NMR; mass spectrometry; substituent shift parameters.
