110-81-6Relevant articles and documents
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Baldwin,Brown
, p. 1093 (1968)
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Hill,Wolfrom
, p. 1539 (1947)
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Universal Anticancer Cu(DTC)2 Discriminates between Thiols and Zinc(II) Thiolates Oxidatively
Xu, Luyan,Xu, Jialin,Zhu, Jingwei,Yao, Zijian,Yu, Na,Deng, Wei,Wang, Yu,Lin, Bo-Lin
, p. 6070 - 6073 (2019)
Aerobic organisms must rely on abundant intracellular thiols to reductively protect various vital functional units, especially ubiquitous zinc(II) thiolate sites of proteins, from deleterious oxidations resulting from oxidizing environments. Disclosed here is the first well-defined model study for reactions between zinc(II) thiolate complexes and copper(II) complexes. Among all the studied ligands of copper(II), diethyldithiocarbamate (DTC) displays a unique redox-tuning ability that enables copper(II) to resist the reduction by thiols while retaining its ability to oxidize zinc(II) thiolates to form disulfides. This work proves for the first time that it is possible to develop oxidants to discriminate between thiols and zinc(II) thiolates, alluding to a new chemical principle for how oxidants, especially universal anticancer Cu(DTC)2, might circumvent the intracellular reductive defense around certain zinc(II) thiolate sites of proteins to kill malignant cells.
Catalytic oxidation of thiols to disulfides with vanadyl acetylacetonate (VO(ACAC)2)
Raghavan,Rajender,Joseph,Rasheed
, p. 1477 - 1480 (2001)
Catalytic amounts of VO(acac)2 coupled with t-butylhydroperoxide chemoselectively oxidizes thiols to disulfides under mild reaction conditions and is generally useful for a wide variety of thiols.
C-S Bond Cleavage, Redox Reactions, and Dioxygen Activation by Nonheme Dicobalt(II) Complexes
Jana, Manish,Majumdar, Amit
, p. 617 - 632 (2018)
Synthesis and reactivity of a series of thiolate/thiocarboxylate bridged dicobalt(II) complexes were investigated in comparison with their carboxylate bridged analogues bearing free thiol/hydroxyl groups. Upon one-electron oxidation, complexes [Co2(N-Et-HPTB)(μ-SR1)](BF4)2 (R1 = Ph, 1a; Et, 1b; Py, 1c) and [Co2(N-Et-HPTB)(μ-SCOR2)](BF4)2 (R2 = Ph, 2a; Me, 2b) yielded [Co2(N-Et-HPTB)(DMF)2](BF4)3 (6) (DMF = dimethylformamide) along with the corresponding disulfides (where N-Et-HPTB is the anion of N,N,N′,N′-tetrakis[2-(1-ethylbenzimidazolyl)]-2-hydroxy-1,3-diaminopropane). Unlike the inertness of carboxylate bridged complexes [Co2(N-Et-HPTB)(μ-O2C-R3-SH)](BF4)2 (R3 = Ph, 3a; CH2CH2, 3b) and [Co2(N-Et-HPTB)(μ-O2CR4)](BF4)2 (R4 = Ph, 4a; Me, 4b; CH2CH2CH2OH, 5) toward O2, the bridging ethanethiolate in 1b was oxidized to yield a sulfinate bridged complex, [Co2(N-Et-HPTB)(μ-O2SEt)](BF4)2 (10). Detailed investigation of the synthetic aspects of 1a-1c led to the discovery of a C-S bond cleavage reaction and yielded the dicobalt(II) complexes [Co2(N-Et-HPTB)(SH)(H2O)](BF4)2 (8a), [Co2(N-CH2Py-HPTB)(SH)(H2O)](BF4)2 (8b) (where N-CH2Py-HPTB is the anion of N,N,N′,N′-tetrakis[2-(1-picolylbenzimidazolyl)]-2-hydroxy-1,3-diaminopropane)), and [Co2(N-Et-HPTB)(μ-S)](BF4) (9). Both 8a and 8b feature nonheme dinuclear Co(II) units containing a terminal hydrosulfide. The present study thus reports comparative redox reactions for a rare class of 16 dicobalt(II) complexes and introduces a selective synthetic strategy for the synthesis of unprecedented dicobalt(II) complexes featuring only one terminal hydrosulfide.
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Wakui,T. et al.
, p. 3081 - 3082 (1978)
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Lecher,Siefken
, p. 2598 (1926)
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Synthesis, structure and DFT study of asymmetrical NHC complexes of cymantrene derivatives and their application in the dehydrogenative dimerization reaction of thiols
Fraser, Roan,van Rooyen, Petrus H.,de Lange, Jurgens,Cukrowski, Ignacy,Landman, Marilé
, p. 11 - 22 (2017)
Asymmetrical NHC complexes of cymantrene and methylcymantrene have been synthesised through the photochemical substitution of carbonyl ligands in the presence of the imidazol-2-ylidene salts. The carbene substituents have been varied between compact (L1) and bulky (L2 and L3) substituents to produce an array of differently sized carbene ligands. The solid state crystal structures of three of the complexes confirmed the bonding pattern of the ligand towards available metal centres and an in-depth DFT study provided insight into electronic and steric aspects. Application of the Extended Transition State coupled with Natural Orbitals for Chemical Valence (ETS-NOCV) energy decomposition technique indicated various NOCV channels for each Mn–L bond (L?=?3-ethyl-1-methylimidazolylidene carbene, triphenylphosphine or acetonitrile), describing the density and energy changes of specific (σ and π) attributes of each bond. N-heterocyclic carbenes of cymantrene derivatives and their triphenylphosphine-substituted analogue are equivalent σ-donors, with 53% and 56%, respectively, of the total binding energy originating from σ-donation. However, NHC complexes show considerably less π character in the metal-carbene bond. Hydrogen interactions in the NHC complexes were also identified in the ETS-NOCV calculations and provided quantification of the hydrogen interactions witnessed in the solid state structures. Calculated Wiberg bond indices, bond dissociation enthalpies, percentage buried volumes and percentage sigma and pi-bonding characteristics quantified the bonding and electronic aspects of the ligand-metal interactions within the complex.
Heterogeneous photocatalytic degradation of disulfoton in aqueous TiO 2 suspensions: Parameter and reaction pathway investigations
Chen, Ming-Hung,Chen, Chiing-Chang,Wu, Ren-Jang,Lu, Chung-Shin
, p. 380 - 390 (2013)
The photocatalytic degradation of organophosphorus insecticide disulfoton is investigated by having titanium dioxide (TiO2) as a photocatalyst. About 99% of disulfoton is degraded after UV irradiation for 90 min. The effects of the solution pH, catalyst dosage, light intensity, and inorganic ions on the photocatalytic degradation of disulfoton are also investigated, as well as the reaction intermediates which are formed during the treatment. Eight intermediates have been identified and characterized through a mass spectra analysis, giving insight into the early steps of the degradation process. To the best of our knowledge, this is the first study reporting the degradation pathways of disulfoton. The results suggest that possible transformation pathways may involve in either direct electron or hole transfer to the organic substrate. The photodegradation of disulfoton by UV/TiO2 exhibits pseudo-first-order reaction kinetics and a reaction quantum yield of 0.267. The electrical energy consumption per order of magnitude for photocatalytic degradation of disulfoton is 85 kWh/(m3 order).
Nature of 2?/1?* Three-Electron-Bonded Chlorine Adducts to Sulfoxides
Kishore, Kamal,Asmus, Klaus-Dieter
, p. 7233 - 7239 (1991)
Reaction of sulfoxide radical cations, R2SO.+, with chloride ions in acidic aqueous solutions (pH * electron.The same species is formed upon oxidation of sulfoxides by Cl2*, although only with relatively low rate constants.The measured λmax are 390, 400, and 410 nm for the R2SO...Cl species with R = Me, Et, and n-Pr, respectively.Equilibrium constants for R2SO.+ + Cl- R2SO...Cl have been determined to be 560, 600, and 575 M-1, for the same respective series of species (error limit +/- 20percent).It is considered that our three-electron-bonded species is identical with an electronically not further specified chlorine-atom adduct to sulfoxide, R2SO(Cl)., observed earlier in sulfoxide-containing solutions of carbon tetrachloride and dichloromethane.The R2SO...Cl exhibit oxidizing properties and are shown to oxidize, for example organic sulfides and disulfides (rate constants on the order of 108 M-1 s-1) or SCN- (rate constants on the order of 109 M-1 s-1).The optical and kinetic results are discussed in light of the electronic properties of the radical species.
A Facile Synthesis of Symmetrical Alkanesulfonothioic S-Alkyl Esters (S-Alkyl Alkanethiosulfonates)
Freeman, Fillmore,Keindl, Monica C.
, p. 913 - 915 (1983)
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Chadaeva et al.
, (1975)
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Reaction of Mono- and Dihaloalkanes with Mixed Solutions of Chalcogens in Alkaline Reductive Systems
Deryagina,Grabel'nykh,Mamaseva
, p. 711 - 714 (2003)
Sufur-selenium, sulfur-tellurium, selenium-tellurium, and sulfur-selenium-tellurium mixtures readily dissolve in the hydrazine hydrate-alkali system to form chalcogenide anions. Alkylation of the latter with ethyl bromide results in preferential formation
First experimental evidence for the formation of a silicate anion by intramolecular addition of a persulfoxide to a trimethylsiloxy group
Clennan, Edward L.,Dillon, David L.
, p. 6827 - 6830 (1998)
The photooxidation of an α-trimethylsiloxysulfide has been studied. The reaction generates a persulfoxide which can be trapped by diphenylsulfoxide, decompose to generate triplet oxygen and substrate, or rearrange to a silicate product via a silicate intermediate.
Oxidation of diethyl disulfide with atmospheric oxygen in the presence of 1,3-dimethylimidazolium dimethyl phosphate
Krivoborodov, E. G.,Mezhuev, Ya. O.,Novikova, E. P.,Zanin, A. A.
, p. 986 - 989 (2020)
Oxidation of diethyl disulfide with atmospheric oxygen at 363 К in the presence of 1,3-dimethylimidazolium dimethyl phosphate is described. On the basis of the 1Н, 31Р, and 13С NMR data, it is shown that oxidation of diethyl disulfide results in ethyl sulfonates. Formation of ethyl alcohol, which is a product of a side reaction of ethyl sulfonate hydrolysis, probably, catalyzed by the 1,3-dimethylimidazolium cation, was detected using HPLC and 1Н and 13С NMR.
Otera,Okawara
, p. 335 (1969)
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Young
, p. 812 (1937)
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A STUDY OF THE PRODUCTS FROM THE HETEROGENEOUS CATALYTIC OXIDATION OF MERCAPTAN
Radin, A. N.,Danyushevskii, V. Ya.,Bodganov, V. S.,Kadentsev, V. I.,Lafer, L. I.,et al.
, p. 1652 - 1655 (1985)
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METHOD FOR OXIDATION OF SULFUR-CONTAINING COMPOUNDS
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Paragraph 0137-0140; 0143, (2021/10/30)
Various embodiments disclosed relate to a method of oxidizing sulfur-containing compounds. The method involves contacting a sulfur-containing compound with a helmet phthalocyaninato-type catalyst in the presence of an oxidant. The present invention also provides a method of removing undesired sulfur-containing compounds from a fluid, such as natural gas, crude oil or an aqueous waste stream.
Mechanism of electrochemical reduction of 5-thio derivatives of 2(5H)-furanone
Latypova,Chmutova,Kurbangalieva,Yanilkin
, p. 313 - 327 (2019/04/25)
The anionoid elimination of the substituent from position 5 of the lactone ring is the predominant pathway of electrochemical reduction of 5-arylsulfanyl- and 5-arylsulfonyl-3,4-dichloro-2(5H)-furanones in acetonitrile. The contribution of the competing elimination of the chloride ion increases on going to 3,4-dichloro-5-ethylsulfanyl-2(5H)-furanone. An experimental criterion based on the morphology of cyclic voltammograms was proposed for identification of a particular pathway of electroreduction of 2(5H)-furanone derivatives.
