100-53-8Relevant articles and documents
Electromediators based on the Ni(II) and Cr(III) complexes with the redox-active ligands in the synthesis of sulfur-containing organic compounds
Okhlobystin,Smolyaninov,Okhlobystina,Berberova,Koldaeva, Yu. Yu.,Abdulaeva
, p. 33 - 36 (2013)
The chromium(III) tris-o-semiquinolate complex Cr(LSQ) 3 (LSQ is 3,6-di-tert-butyl-o-semiquinone) and the monoanionic paramagnetic nickel(II) complex [n-Bu4N][Ni(L S SQ)(L S DT)] (L S SQ is o-thiosemiquinone, L S DT is benzene-1,2-dithiolate) are considered as electromediators of hydrogen sulfide oxidation in the presence of various organic substrates (hex-1-ene, oct-1-ene, benzene, toluene, and benzoic acid). It is revealed that the electrolysis of hydrogen sulfide at the oxidation potential of the mediators in the presence of the substrates affords the corresponding aliphatic and aromatic thiols in a yield of 62-75%.
Insight into the Mechanism of Reversible Ring-Opening of 1,3-Benzoxazine with Thiols
Urbaniak, Tobias,Soto, Marc,Liebeke, Manuel,Koschek, Katharina
, p. 4050 - 4055 (2017)
The reversible ring-opening addition and fragmentation reaction of p-cresol-based N-phenylbenzoxazine with aliphatic and aromatic thiols was investigated in solvent-mediated and solvent-free reactions. Independently of the used thiol, N-phenylbenzoxazine and the thiols reacted to equilibrium with comparable amounts of reactants and products in aprotic solvent, whereas in protic solvent almost full conversions were reached. In contrast, thiol reactivity was a crucial factor in solvent-free reactions yielding fast and complete conversions for a more acidic thiol and balanced equilibrium concentrations in case of thiols with high pKa values. The strong influence of thiols with low pKa values emphasizes the relevance of the protonation step in the ring-opening reactions of 1,3-benzoxazines with thiols in absence of solvents where acidity predominates nucleophilicity. The reverse reactions, namely adduct dissociation and benzoxazine recovery, were successfully conducted at elevated temperatures and reduced pressure facilitated by the removal of the formed thiols yielding up to 95% recovered 1,3-benzoxazine. These results provide deeper understanding of the reversible ring-opening reaction mechanism of 1,3-benzoxazine with thiols.
New organic single crystal of (benzylthio)acetic acid: Synthesis, crystal structure, spectroscopic (ATR-FTIR, 1H and 13C NMR) and thermal characterization
Sienkiewicz-Gromiuk, Justyna,Tarasiuk, Bogdan,Mazur, Liliana
, p. 65 - 71 (2016)
(Benzylthio)acetic acid (Hbta) was synthesized with 78% yield from benzyl chloride and thiourea as substrates. Well-shaped crystals of Hbta were grown by slow solvent evaporation technique from pure methanol. The compound was investigated by single-crystal X-ray and powder diffraction techniques and was also characterized by other analytical methods, like ATR-FTIR, 1H and 13C NMR and TG/DSC. The acid molecule adopts bent conformation in the solid state. The crystal structure of Hbta is stabilized by numerous intermolecular interactions, including O-H···O, C-H···O, C-H···S and C-H···π contacts. Thermal decomposition of the obtained material takes place above 150 °C.
Synthesis of thiols via palladium catalyzed methanolysis of thioacetates with borohydride exchange resin
Choi,Yoon
, p. 2655 - 2663 (1995)
Various thiols are prepared quantitatively from the corresponding thioacetates via Pd catalyzed methanolysis with borohydride exchange resin under a mild and neutral conditions. One-pot synthesis of thiols from alkyl halides through the formation of alkyl thioacetates using thioacetate exchange resin followed by methanolysis is also described.
Tris(3-hydroxypropyl)phosphine (THPP): A mild, air-stable reagent for the rapid, reductive cleavage of small-molecule disulfides
McNulty, James,Krishnamoorthy, Venkatesan,Amoroso, Dino,Moser, Michael
, p. 4114 - 4117 (2015)
Tris(3-hydroxypropyl)phosphine (THPP) is demonstrated to be a versatile, water-soluble and air-stable reducing agent, allowing for the rapid, irreversible reductive cleavage of disulfide bonds in both aqueous and buffered aqueous-organic media. The reagent shows exceptional stability at biological pH under which condition it permits the rapid reduction of a wide range of differentially functionalized small-molecule disulfides.
Template effects of vesicles in dynamic covalent chemistry
Bravin, Carlo,Hunter, Christopher A.
, p. 9122 - 9125 (2020)
Vesicle lipid bilayers have been employed as templates to modulate the product distribution in a dynamic covalent library of Michael adducts formed by mixing a Michael acceptor with thiols. In methanol solution, all possible Michael adducts were obtained in similar amounts. Addition of vesicles to the dynamic covalent library led to the formation of a single major product. The equilibrium constants for formation of the Michael adducts are similar for all of the thiols used in this experiment, and the effect of the vesicles on the composition of the library is attributed to the differential partitioning of the library members between the lipid bilayer and the aqueous solution. The results provide a quantitative approach for exploiting dynamic covalent chemistry within lipid bilayers. This journal is
Hydrolysis and aminolysis of alkyl xanthate esters and cellulose analogues
Humeres, Eduardo,Soldi, Valdir,Klug, Marilene,Nunes, Mauricea,Oliveira, Celia M.S.,Barrie, Patrick J.
, p. 1050 - 1056 (1999)
The hydrolysis and aminolysis of a series of S-substituted O-alkylxanthate esters was studied in 20% v/v aqueous methanol at 35°C. The pH-rate profiles of the hydrolyses showed water and hydroxide-ion-catalyzed reactions. The reaction of 2,4-dinitrophenyl cellulose xanthate (CelXDNP) and p-nitrobenzyl cellulose xanthate (CelXNB) with polyalanine and lysozyme produced a covalent bond between the polypeptide and the cellulose matrix, as shown by solid-state 13C NMR. However, the nature of the bonding could not be identified. The reaction of nucleophiles (H2O, OH-, RNH2) and xanthic esters was consistent with an addition-elimination mechanism through a tetrahedral intermediate. Bronsted plots against the pKa of the nucleophile (βnu) or the nucleofuge of the substrate (βlg) were used to characterize the rate-determining step. The pKa values of the nucleophiles ranged between -1.74 and 15.74, and for the nucleofuges, they were in the range of 10.50-0.92. For nucleophiles with pKa values up to about 10, βlg was 0.10-0.15, and βnu changed from 0.48 to 0.35 for the strongest electron-withdrawing nucleofuge. It was concluded that the water-catalyzed hydrolyses, and also aminolyses with moderately basic amines, occur with rate-determining formation of the tetrahedral intermediate. For strong bases such as hydroxide ion, the disappearance of the intermediate becomes the slowest step. The reaction of cellulose xanthic esters with external nucleophiles as hydroxide ion and amines shows simple first-order kinetics and is slower than alkyl or sugar xanthates, probably due to the diffusion effect through the tight cybotactic region of cellulose.
Thermal reactions of dibenzyl disulfide and dibenzyl sulfide with metals: A new route to trans-stilbene and dibenzyl
Voronkov,Panova,Timokhina,Gromkova
, p. 1043 - 1045 (2004)
A procedure was developed for preparing stilbene by thermal desulfuring of dibenzyl disulfide and dibenzyl sulfide with metals (Fe, Zn). The major product of the similar reaction of dibenzyl disulfide with copper is dibenzyl.
New Birch Type Reduction. Halogen or Halides-Activated Reduction of Disulfides to Thiols with Aluminium in Liquid Ammonia
Sato, Ryu,Akaishi, Ryouichi,Goto, Takehiko,Saito, Minoru
, p. 773 - 774 (1987)
Aromatic and aliphatic disulfides were reduced to the corresponding thiols in high yields by new halogen or halides-activated Birch type reduction with aluminium in liquid ammonia.
Cyclic Sulfenyl Thiocarbamates Release Carbonyl Sulfide and Hydrogen Sulfide Independently in Thiol-Promoted Pathways
Pluth, Michael D.,Steiger, Andrea K.,Zhao, Yu
, (2019)
Hydrogen sulfide (H2S) is an important signaling molecule that provides protective activities in a variety of physiological and pathological processes. Among the different types of H2S donor compounds, thioamides have attracted attention due to prior conjugation to nonsteroidal anti-inflammatory drugs (NSAIDs) to access H2S-NSAID hybrids with significantly reduced toxicity, but the mechanism of H2S release from thioamides remains unclear. Herein, we reported the synthesis and evaluation of a class of thioamide-derived sulfenyl thiocarbamates (SulfenylTCMs) that function as a new class of H2S donors. These compounds are efficiently activated by cellular thiols to release carbonyl sulfide (COS), which is quickly converted to H2S by carbonic anhydrase (CA). In addition, through mechanistic investigations, we establish that COS-independent H2S release pathways are also operative. In contrast to the parent thioamide-based donors, the SulfenylTCMs exhibit excellent H2S releasing efficiencies of up to 90percent and operate through mechanistically well-defined pathways. In addition, we demonstrate that the sulfenyl thiocarbamate group is readily attached to common NSAIDs, such as naproxen, to generate YZ-597 as an efficient H2S-NSAID hybrid, which we demonstrate releases H2S in cellular environments. Taken together, this new class of H2S donor motifs provides an important platform for new donor development.
