100-53-8Relevant articles and documents
Tris(2-Carboxyethyl)phosphine (TCEP) for the reduction of sulfoxides, sulfonylchlorides, N-oxides, and azides
Faucher, Anne-Marie,Grand-Maitre, Chantal
, p. 3503 - 3511 (2003)
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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.
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.
Electromediators in synthesis of sulfur organic compounds based on hydrogen sulfide and thiols
Okhlobystin,Okhlobystina,Shinkar',Berberova,Eremenko
, p. 302 - 306 (2010)
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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.
Rearrangement of O,S-Dialkyl Dithiocarbonates to S,S-Dialkyl Dithiocarbonates Catalyzed by Tricaprylmethylammonium Chloride
Degani, Iacopo,Fochi, Rita,Regondi, Valeria
, p. 149 - 151 (1981)
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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.
Microwave-assisted synthesis of thioamides with elemental sulfur
Milen, Matyas,Abranyi-Balogh, Peter,Dancso, Andras,Keglevich, Gyoergy
, p. 33 - 41 (2012)
Thioamides are prepared in moderate-to-good yields from the benzylamines or benzylamine derivatives by treatment with elemental sulfur under microwave and solvent-free conditions at 170.C in 15 min.
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Broadbent,Whittle
, p. 3587 (1959)
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Brindle,Liard
, p. 1480 (1975)
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Dicobalt Octacarbonyl Catalyzed Conversion of Benzylic Alcohols to Thiols, Hydrocarbons, and Esters Using Hydrogen Sulfide and Carbon Monoxide
Alper, Howard,Sibtain, Fazle
, p. 3306 - 3309 (1988)
The first examples of a homogeneous, metal complex catalyzed conversion of alcohols to thiols are reported, using hydrogen sulfide and catalytic quantities of dicobalt octacarbonyl.If ethanol is employed as one of the components of the reaction medium, th
Biomimetic thiolate alkylation with zinc pyrazolylbis(thioimidazolyl)borate complexes
Ibrahim, Mohamed M.,He, Guosen,Seebacher, Jan,Benkmil, Boumahdi,Vahrenkamp, Heinrich
, p. 4070 - 4077 (2005)
The NS2ZnX coordination in thiolate-alkylating zinc enzymes is reproduced in (tripod)ZnX complexes with substituted pyrazolylbis(thioimidazolyl)borate tripod ligands. Intermediate (tripod)Zn nitrates and perchlorates are converted into (tripod) Zn thiolates, including the biologically relevant homocysteinate. Methylation with CH3I converts these to (tripod)ZnI and the corresponding thioethers CH3SR, including methionine. A kinetic investigation has shown the alkylations to be intramolecular SN2 processes that take place at the zinc-bound thiolates. They are considerably faster for the (NS2)Zn thiolates than for the (N2S)- and (N3)Zn-thiolates with similar pyrazolylborate-derived tripod ligands, in agreement with Nature's choice of an NS2 donor set for zinc. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.
A rapid and efficient cleavage of organic disulfides to mercaptans using ZrCl4/NaBH4
Purushothama Chayr,Rajaram,Iyengar
, p. 3905 - 3911 (2000)
A practical and cheaper reagent system ZrCl/NaBH4 is used for the reductive cleavage of organic disulfides to mercaptans under mild conditions, in excellent yields.
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Chadaeva et al.
, (1972)
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Rate and Equilibrium Constants for the Reaction of Thiolate Ions with Dibenzo-1,2-dithiin and Naphtho-1,2-dithiole 1,1-Dioxides
Boduszek, Bogdan,Kice, John L.
, p. 2055 - 2060 (1982)
In aqueous dioxane the cyclic thiosulfonate dibenzo-1,2-dithiin 1,1-dioxide (1) reacts rapidly with thiolate ions and undergoes opening of the thiosulfonate ring (eq 2), forming disulfide 3a.Acidification of solutions of 3a with carboxylic acid buffers of appropiate pH leads to facile reversal of ring-opening reaction and the quantitative regeneration of 1.Since this reversal of ring opening is not acid-catalyzed, it must take place via a simple intramolecular displacement of RS- by the sulfinate (SO2-) group present in 3a and is therefore the microscopic reverse of the ring-opening reaction.Rate constants have been determined for both ring opening (kRS) and reversal of ring opening (k-RS) for a series of alkanethiolates of varying pKa.From these data one may also calculate the equilibrium constant, Keq(=kRS/k-RS), for reaction of each thiolate with 1.From comparison of the log Keq's with previously determined equilibrium constants for reaction of cyanide and sulfite ions with 1 one obtains quantitative information on the thermodynamics of reactions of the type ArSSR + CN- = ArSCN + RS- and ArSSR + SO32- = ArSSO3- + RS- that should be of considerable value for predicting the magnitude of equilibrium constants for cyanide-disulfide and sulfite-disulfide equilibria.Plots of log Keq, log KRS, and log k-RS vs. the pKa of RSH reveal that βeq=1.25, βRS=0.26, and β-RS=-0.99.These β values show that the transition state for eq 2 is quite unsymmetrical, with a structure Δ-...S-SO2δ-> where the RS-S bond is only ca. 20percent formed.The βRS and β-RS values are compared with the β values for several other previously studied displacements involving disulfides.The reaction of naphthol-1,2-dithiole 1,1-dioxide (2) with thiolates behaves in a fashion analogous to that of the reaction of RS- with 1.Comparison of Keq, kRS, and k-RS for an equilibrium involving 2 and a thiolate with those for the corresponding thiolate reacting with 1 allows one to assess how a change from a six- to a five-membered thiosulfonate ring influences Keq, kRS, and k-RS.The major effects are that k-RS is much larger and Keq is considerably smaller.
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Wood,Bost
, p. 1011 (1937)
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Solid Supported Reagents and Reactions. Part 21.1 Rapid and Clean Synthesis of Thiols from Halides Using Polymer-supported Hydrosulfide
Bandgar, Babasaheb P.,Pawar, Sanjay B.
, p. 212 - 213 (1998)
A variety of thiols are prepared from corresponding halides using polymer-supported hydrosulfide in excellent yields. Isolation of pure products by simple filtration and evaporation is an important feature of this method.
A preparative scale reduction of alkyl disulfides with tributyl phosphine and water
Ayers, Joshua T.,Anderson, Shelby R.
, p. 351 - 358 (1999)
A series of alkyl disulfides has been shown to be reduced by tributyl phosphine at room temperature. The resulting thiols were then acylated in the same pot and isolated in good yields. This sequence is convenient and is a practical option for the preparation of gram quantities of thiol or thioester from the corresponding disulfide.
A NEW, HIGHLY EFFICIENT METHOD FOR THE CONVERSION OF ALCOHOLS TO THIOLESTERS AND THIOLS
Volante, R. P.
, p. 3119 - 3122 (1981)
Various alcohols were converted to their corresponing thiolacetates by treatment with triphenylphosphine and diisopropyl azodicarboxylate in the presence of thiolacetic acid.The overall conversion was both highly efficient (89-99percent yields) and stereoselective (99.5percent inversion).
Phosphorus Pentasulfide Mediated Conversion of Primary Carbamates into Thiols
Maurya, Chandra Kant,Gupta, Pradeep Kumar
, p. 1649 - 1651 (2017)
In this paper, we report a method for the conversion of primary carbamates into thiols in the presence of phosphorus pentasulfide (P 2 S 5) in refluxing toluene. Presently, no method exists in the literature for conversion of carbamates into thiols and, to the best of our knowledge, it is the first report for this type of conversion. This method presents an indirect route for the conversion of alcohols into thiols via their carbamate derivatives that may be useful in the total synthesis of compounds containing a thiol functionality.
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Bittell,J.E.,Speier,J.L.
, p. 1687 - 1689 (1978)
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Photoactive Metal-Organic Frameworks for the Selective Synthesis of Thioethers: Coupled with Phosphine to Modulate Thiyl Radical Generation
Guo, Zhifen,Liu, Xin,Bai, Rong,Che, Yan,Chi, Yanhong,Guo, Chunyi,Xing, Hongzhu
supporting information, p. 8672 - 8681 (2021/06/28)
Metal-organic framework (MOF) materials are intriguing photocatalysts to trigger radical-mediated chemical transformations. We report herein the synthesis and characterization of a series of isomorphic MOFs which show a novel structure, wide visible-light absorption, high chemical stability, and specific redox potential. The prepared MOFs were explored for the photoinduced single-electron oxidation of thiol compounds, generating reactive thiyl radicals to afford thioethers via a convenient thiol-olefin reaction. Importantly, we provide a widely applicable strategy by combing a photoactive MOF with phosphine to modulate the generation of thiyl radical in the reaction, thereby producing a single product of the thioether without the formation of a disulfide byproduct due to the dimerization of thiyl radicals. The photocatalytic reaction takes advantage of this strategy, showing great generality where tens of thiols and olefins have been examined as coupling partners. In addition, the strategy has also been demonstrated to be effective for the reactions catalyzed by other MOFs. Mechanism studies reveal that the selective synthesis of C-S products relies on a synergy between the photoinduced generation of a thiyl radical over the MOF and the in situ cleavage of S-S bond into a S-H bond by phosphine. It is notable that the synthesized MOFs show advanced performance in comparison with classical MOFs. The work not only provides a series of novel MOF photocatalysts that are capable of photoinduced thiol-olefin coupling but also indicates the great potential of MOFs for photochemical transformations mediated by reactive radicals.
Catalytic Hydrogenation of Thioesters, Thiocarbamates, and Thioamides
Luo, Jie,Rauch, Michael,Avram, Liat,Ben-David, Yehoshoa,Milstein, David
supporting information, p. 21628 - 21633 (2021/01/11)
Direct hydrogenation of thioesters with H2 provides a facile and waste-free method to access alcohols and thiols. However, no report of this reaction is documented, possibly because of the incompatibility of the generated thiol with typical hydrogenation catalysts. Here, we report an efficient and selective hydrogenation of thioesters. The reaction is catalyzed by an acridine-based ruthenium complex without additives. Various thioesters were fully hydrogenated to the corresponding alcohols and thiols with excellent tolerance for amide, ester, and carboxylic acid groups. Thiocarbamates and thioamides also undergo hydrogenation under similar conditions, substantially extending the application of hydrogenation of organosulfur compounds.
