53847-74-8

Upstream product

• 15672-95-4 3,3-dimethylpropyl phenyl sulfide 
• 75924-63-9 C₁₂H₁₆HgS 
• 917-92-0 3,3-Dimethylbut-1-yne 
• 108-98-5 thiophenol 
• 36525-02-7 <(E)-3,3-dimethyl-1-butenyl>mercuric chloride 
• 882-33-7 diphenyldisulfane 
• 38442-51-2 tert-butylmercury chloride 
• 1822-73-7 phenylthioethylene 
• 61382-45-4 (E)-1-iodo-3,3-dimethyl-1-butene 
• 113034-93-8 9-(phenylthio)-9-borabicyclo<3.3.1>nonane 
• 26620-11-1 (E)-2-chlorovinylthiobenzene 
• 37530-86-2 1-phenylsulfonyl-2-(phenylthio)ethene 
• 13884-92-9 phenylthiomethyl triphenylphosphonium chloride 
• 630-19-3 pivalaldehyde 

Downstream Products

• 150312-11-1 (1,2-Dichloro-3,3-dimethyl-butylsulfanyl)-benzene 

Relevant academic research and scientific papers

Neighboring the effect in the oxidation of α-Stannyl phenyl vinyl sulfides

α-Stannyl vinyl sulfides were generally prepared by hydrostannylation of thioacetylenes catalyzed by Pd(PPh3)4. The regio- and stereochemistry of the products was determined unequivocally in three cases by X-ray crystallographic stru

The palladium-catalyzed cross-coupling reaction of 9-organothio-9-borabicyclo[3.3.1]nonanes with organic electrophiles: Synthesis of unsymmetrical sulfides

The synthesis of unsymmetrical sulfides was carried out in high yields by the palladium-catalyzed cross-coupling reaction of 9-organothio-9-borabicyclo[3.3.1]nonane (9-RS-9-BBN) with organic electrophiles, such as iodoarenes, 1-iodo-1-alkenes, allyl carbonate and propargyl carbonate. Iodoarenes and 1-iodo-1-atkenes were smoothly converted into the corresponding sulfides at 50 °C in the presence of PdC12(dppf) (3 mol%) and K3PO4 (3 equiv.) in DMF. In contrast, the cross-coupling reaction of 9-RS-9-BBN with allyl or propargyl carbonates occurred in DMF without the assistance of a base. Both reactions catalyzed by Pd(dba)2-dppf regioselectively produced allyl and allenyl sulfides in excellent yields. The scope and limitations of the reactions, as well as the effects of varying the reaction conditions, are discussed.

Reductive alkylation of electronegatively-substituted alkenes by alkylmercury halides

Photolysis of alkylmercury halides in the presence of electronegatively-substituted 1-alkenes yields adduct radicals [RCH2CH(EWG).] that in some cases react with RHgX to form RCH2CH(HgX)(EWG), e.g., EWG = (EtO)2PO or PhSO2. When the EWG is carbonyl or cyano, the resonance stabilized adduct radicals fail to react with the alkyl mercury halide. In these cases photolysis with RHgCl/KI in Me2SO leads to the adduct mercurial via reaction of the adduct radicals with RHgI2-. The reactions of tertiary-enolyl adduct radicals are inefficient with RHgX/KI, and disproportionation of the adduct radicals is the major reaction pathway. For secondary- or tertiary-adduct radicals the reductive alkylation products are formed in excellent yield by reaction with RHgCl and silyl hydrides in Me2SO solution in a process postulated to involve RHgH as an intermediate. The relative reactivities of a number of α,β-unsaturated systems toward t-Bu. have been measured by competitive techniques. The results demonstrate a high reactivity of s-cis enones relative to the s-trans conformers.

THE REACTION OF ALKYL PHENYL SULPHIDES WITH MANGANESE DIOXIDE AND ACETYL CHLORIDE

In a one-pot reaction, manganese dioxide in stoichiometric amounts and acetyl chloride transform alkyl phenyl sulphides into the corresponding 1-alkenyl phenyl sulphides; these latter products can be undergo chlorination of the double bond promoted by the

Free-Radical Reactions of Benzenethiol and Diphenyl Disulphide with Alkynes. Chemical Reactivity of Intermediate 2-(Phenylthio)vinyl Radicals

Reaction of benzenethiol at 100 deg C with neat alkyl- and dialkyl-acetylenes leads to virtually quantitative formation of isomeric mixtures of (E)- and (Z)-vinyl sulphide adducts in ratios which depend largely upon both the extent and the nature of alkyl substitution.Results are explained in terms of rapidly interconverting sp2-hybridized (E)- and (Z)-1-alkyl-2-(phenylthio)vinyl radical intermediates which can undergo hydrogen transfer from benzenethiol to an extent which is essentially dependent upon the steric hindrance of their cis-2-substituent.Consistent results are provided by related radical reactions of diphenyl disulphide with alkyl-substituted alkynes to afford varying amounts of 1,2-bis(phenylthio)ethylene adducts ascribable to SH2 reaction of the resulting 1-alkyl-2-(phenylthio)vinyl radicals with the disulphide present.Under analogous conditions benzenethiol and diphenyl disulphide react with phenylacetylenes to give vinyl sulphide or bissulphide adducts in a trans-stereoselective fashio.The findings are interpreted by suggesting, for the intermediate sp-hybridized 1-phenyl-2-(phenylthio)vinyl radicals, the occurrence of significant bonding interaction between the unpaired electron and the adjacent sulphur, which would essentially prevent attack of radical scavenger on the side cis to PhS.Evidence is also presented that 1-phenyl-2-(phenylthio)vinyl radicals can exhibit homolytic intramolecular cyclization reactions, leading to benzothiophene products to a comparatively much greater extent than the 1-alkyl-2-substituted analogues; however, 1-tert-butyl-2-(phenylthio)vinyl radical would represent a special case.

Reactions of Alkylmercurials with Heteroatom-Centered Acceptor Radicals

The relative reactivities of alkylmercury halides toward PhS., PhSe., or I. decrease drastically from R = tert-butyl to R = sec-alkyl to R = n-butyl, indicative that R. is formed in the rate-determining step in the attack of these radicals upon RHgCl.The alkyl radicals thus formed will enter into chain reactions in which a heteroatom-centered radical (A.) is regenerated from substrates such as RS-SR, ArSe-SeAr, ArTe-TeAr, PhSe-SO2Ar, Cl-SO2Ph; ZCH=CHA (A = Cl, I, SPh, SO2Ph); or PhCCHA (A = I, SPh, SO2Ph). β-Styrenyl (PhCH=CHA, Ph2C=CHA) and β-phenethynyl (PhCCA) systems with A = I, Br, SO2Ph also enter into chain reactions with mercury(II) salts with the ligands PhS, PhSe, PhSO2, or (EtO)2PO.The relative reactivities of a series of reagents toward t-Bu. and of PhCH=CHA, Ph2C=CHA, and PhCCA toward c-C6H11. are reported as well as the regioselectivity of t-Bu. attack observed for 1,2-disubstituted ethylenes (ZCH=CHA) with Z and A from the group Ph, Cl, Br, I, SO2Ph, SPh, Bu3Sn.Reactions of (E)- and (Z)-PhCH=CHI or MeO2CCH=CHI with t-Bu. or c-C6H11. occurred in a regioselective and stereospecific (retention) manner.Reactions of (E)- and (Z)-ClCH=CHCl occurred in a nonstereospecific manner in which the E/Z product ratio increased with the bulk of the attacking radical.A similar effect on the E/Z product ratios was observed for (Z)-MeO2CCH=CHCl.