15619-03-1Relevant articles and documents
Redox Activation of Hydrogen Sulfide, Thiols, and Sulfur in Electrosynthesis of Organic Di- and Polysulfides
Shinkar’,Smolyaninov,Kuzmin,Berberova
, p. 689 - 696 (2019)
A novel and efficient method for the synthesis of biologically active organic di-, tri- and tetrasulfides has been proposed. Different methods of redox activation of sulfur, hydrogen sulfide, and thiols in the reactions with organic compounds have been considered. Electrochemical initiation of the reactions of the mediator–H2S–S8 system with cyclohexane, methylcyclohexane, and benzene has occurred to the formation of polysulfides R2Sn (n = 2–4). The application of tetrabutylammonium bromide as a mediator of H2S oxidation has allowed to decrease the anodic overpotential of electrosynthesis. Di- and tetrasulfides have been obtained under anodic activation of the cycloalkanethiols (C5, C6) or thiophenol in the reaction with sulfur. Electroreduction of S8 in the presence of the same thiols has favored the formation of di- and trisulfides. The yield and the ratio of the R5Sn (n = 2–4) depend on the method of redox activation of the thiolating reagent.
Chromium(III) and indium(III) 3,6-di-tert-butyl-o-semiquinolate complexes as redox mediators of hydrogen sulfide oxidation in reactions with cycloalkanes
Berberova,Shinkar,Smolyaninov,Shvetsova,Sediki
, p. 578 - 582 (2017)
The electrochemical oxidation of the chromium(III) and indium(III) complexes with 3,6-di-tert-butyl-o-semiquinolate leading to the formation of active monocationic species is studied by cyclic voltammetry. The reactions of the latter with hydrogen sulfide generate the radical cation of H2S, whose fragmentation affords the proton and thiyl radical. These complexes are proposed for the first time as redox mediators for the one-pot thiolation of inert cycloalkanes C6–C8, which decreases the activation energy of hydrogen sulfide compared to that for direct electrochemical oxidation. The major products of cycloalkane functionalization involving H2S are thiols and organic di- and trisulfides. The yield of the synthesized compounds depends on the type of the mediator: the chromium(III) complex exhibits the highest efficiency in the electrocatalytic transformations.
3,4-Dichloro-1,2,5-thiadiazole: a commercially available electrophilic sulfur transfer agent and safe resource of ethanedinitrile
Gorjian, Hayedeh,Khaligh, Nader Ghaffari
, (2021/11/04)
3,4-Dichloro-1,2,5-thiadiazole is introduced as a safe and efficient sulfur transfer reagent. By applying this commercially available reagent, the symmetrical trisulfides and ethanedinitrile were simultaneously obtained by reacting various thiols with this reagent at room temperature. This reagent is non-toxic, inexpensive, and commercially available. In addition, no higher-order polysulfides were detected in all cases after the completion of the reaction. The short reaction times (20–50 min), excellent selectivity, and high yield of the trisulfides are some attractive merits of this reagent for the preparation of trisulfides. The reaction is one-pot, and isolation-purification of intermediates is not required. The procedure was readily scaled up to 5 grams. A mechanism is presented to explain the chemistry.
Electrochemical Synthesis of Organic Polysulfides from Disulfides by Sulfur Insertion from S8 and an Unexpected Solvent Effect on the Product Distribution
F?hrmann, Jan,Hilt, Gerhard
, p. 11141 - 11149 (2021/06/09)
An electrochemical synthesis of organic polysulfides through sulfur insertion from elemental sulfur to disulfides or thiols is introduced. The highly economic, low-sensitive and low-priced reaction gives a mixture of polysulfides, whose distribution can be influenced by the addition of different amounts of carbon disulfide as co-solvent. To describe the variable distribution function of the polysulfides, a novel parameter, the “absorbance average sulfur amount in polysulfides” (SAP) was introduced and defined on the basis of the “number average molar mass” used in polymer chemistry. Various organic polysulfides were synthesized with variable volume fractions of carbon disulfide, and the yield of each polysulfide was determined by quantitative 13C NMR. Moreover, by using two symmetrical disulfides or a disulfide and a thiol as starting materials, a mixture of symmetrical and asymmetrical polysulfides could be obtained.
Simple and green method for synthesis of symmetrical dialkyl disulfides and trisulfides from alkyl halides in water; PMOxT as a sulfur donor
Soleiman-Beigi, Mohammad,Mohammadi, Fariba
, p. 134 - 141 (2017/03/07)
An environmentally new, mild and efficient method has been developed for the synthesis of dialkyl disulfides and dialkyl trisulfides in aqueous conditions by a reaction between alkyl halides (and tosylate) and potassium-5-methyl-1,3,4-oxadiazole-2-thiolate (PMOxT) as a sulfur transfer reagent. The advantages of this method are that it occurs under mild reaction conditions, it is base free, it uses water as the solvent and it occurs in high yields. A variety of dialkyl disulfides and dialkyl trisulfides can be obtained in good to excellent yields up to 98%.
Redox mediators of hydrogen sulfide oxidation in reactions with cycloalkanes
Berberova,Shinkar',Smolyaninov,Pashchenko
, p. 295 - 298 (2016/01/12)
An indirect electrochemical method for thiolation of cycloalkanes C5-C7 has been suggested. The method is based on a new approach to activation of hydrogen sulfide by redox mediators.
Iron catalysed insertion of sulfur into the non-activated C-H bond
Balavoine,Barton,Gref,Lellouche
, p. 1883 - 1894 (2007/10/02)
The reaction of various sulfur reagents (S8, H2S, Na2S, NaHS) with cyclohexane under Gif(III), GoAgg(II) and GoAgg(III) conditions affords the usual oxidation products in competition with cyclohexyl di- and poly-sulfide formation. Other cyclic hydrocarbons behave similarly. The sulfation reactions are considered to be biomimetic for the enzymes isopenicillin N synthase and biotin synthase.
