989-39-9Relevant academic research and scientific papers
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.
Chemistry of Sulfenic Acids. 3. Studies of Sterically Hindered Sulfenic Acids Using Flash Vacuum Pyrolysis
Davis, Franklin A.,Jenkins, Robert H.,Rizvi, Syed Q. A.,Yocklovich, Steven G.
, p. 3467 - 3474 (2007/10/02)
Flash vacuum pyrolysis (FVP) of sulfoxides containing β-hydrogen atoms affords sulfenic acids (RSOH) in good concentration under conditions where they are stable.The application of this technique to the synthesis and study of sterically hindered sulfenic acids 12a-e is described.The principal or primary reaction of simple sulfenic acids prepared in this manner is dehydration to thiosulfinates 13 (eq 1).Steric inhibition to dehydration (eq 1) appears to only be of importance for 2-methyl-2-propanesulfenic acid (12a) which was trapped in good yield with methyl propiolate to afford 16a. 2,4,6-Tri-tert-butylbenzenesulfenic acid (12e) appears to be destabilized as a consequence of interaction between the SOH and adjacent tert-butyl groups.In the pyrolysis section of the apparatus, 12e decomposes to phenol 21 and aryl radical 22, which reacts further.Thermolysis of sulfoxides generates the sulfenic acids 12a-e in very low concentration at any one time.The products of sulfenic acids generated in this way result from secondary reactions of the corresponding thiosulfinates.
