- Convenient one-pot synthesis of β-alkylthio acid derivatives from thioacetates and the corresponding α,β-unsaturated compounds
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Various β-alkylthio acid derivatives were prepared conveniently from thioacetates and α,β-unsaturated compounds through borohydride exchange resin (BER)-Pd catalyzed transesterification of thioacetates to the corresponding thiols and Michael addition of the resulting thiols to α,β-unsaturated compounds.
- Lee,Choi,Yoon
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- The Reaction of Electron-deficient Selenoaldehydes with Thiols
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Electron-poor selenoaldehydes, generated in-situ in refluxing toluene, reacted with thiols in the presence of triethylamine to give selenenyl sulfides, RSeSR'.The formation of a selenodisulfide, RSSeSR, was also evidenced.
- Duchenet, Virginie,Vallee, Yannick
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- A novel reduction of sodium alkyl thiosulfates using samarium metal without an activating agent in water
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A novel metallic samarium promoted reduction of sodium alkyl thiosulfates in the absence of an activating agent occurs to afford the corresponding disulfides with good yields in water at 90°C.
- Wang, Lei,Li, Pinhua,Zhou, Li
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- Facile solvent-free generation of disulfide dianion and its use for preparation of symmetrical disulfides
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A variety of symmetrical dialkyl disulfides were prepared from the reaction of alkyl halides, sodium hydroxide and elemental sulfur under solvent free conditions. The reaction proceeded very fast and produced the desired products in moderate to excellent isolated yields.
- Kiasat, Ali Reza,Mokhtari, Babak,Savari, Ali,Kazemi, Foad
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- ACTIVATION AND SYNTHETIC APPLICATIONS OF THIOSTANNANES. EFFICIENT CONVERSION OF THIOLS INTO DISULFIDES
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Various kinds of thiols are converted into the corresponding disulfides under mild conditions with the aid of alkoxystannane-ferric chloride.
- Sato, Tsuneo,Otera, Junzo,Nozaki, Hitosi
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- Selective, cofactor-mediated catalytic oxidation of alkanethiols in a self-assembled cage host
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A spacious Fe(ii)-iminopyridine self-assembled cage complex can catalyze the oxidative dimerization of alkanethiols, with air as stoichiometric oxidant. The reaction is aided by selective molecular recognition of the reactants, and the active catalyst is derived from the Fe(ii) centers that provide the structural vertices of the host. The host is even capable of size-selective oxidation and can discriminate between alkanethiols of identical reactivity, based solely on size. This journal is
- Da Camara, Bryce,Dietz, Philip C.,Chalek, Kevin R.,Mueller, Leonard J.,Hooley, Richard J.
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- A two in one approach: Renewable support and enhanced catalysis for sweetening using chicken feather bound cobalt(II) phthalocyanine under alkali free environment
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Poultry waste chicken feathers, an inexpensive and abundantly available material has been used as a renewable support for immobilizing a cobalt phthalocyanine catalyst. The synthesized heterogeneous cobalt(ii) phthalocyanine catalyst was used for the aerobic oxidation of mercaptans to the corresponding disulfides using ultrasonic irradiation under alkali free conditions. The significantly higher catalytic activity of the heterogeneous catalyst as compared to a homogeneous one can be attributed to the synergistic effect of the support matrix. In addition, the catalyst could easily be recovered and recycled for several runs without loss of activity, which makes the process greener and more cost-effective.
- Chauhan, Deepak K.,Patnam, Padma L.,Ganguly, Sudip K.,Jain, Suman L.
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- Water accelerated Sm/TMSCl reductive system: Debromination of vic- dibromides and reduction of sodium alkyl thiosulfates
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A simple and efficient method for the debromination of vic-dibromides to (E)-alkenes and reduction of sodium alkyl thiosulfates to disulfides promoted by Sm/TMSCl/H2O (trace) has been described.
- Xu, Xiaoliang,Lu, Ping,Zhang, Yongmin
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- Preparation of dialkyl disulfides via reduction of alkylthiocyanates with TiCl4/Sm system
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Dialkyl disulfides can be readily prepared in moderate to good yields via reduction of alkylthiocyanates with TiCl4/Sm system in THF at 0°C.
- Guo, Hongyun,Zhan, Zhuangping,Zhang, Yongmin
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- Preparation, structures, and physical properties of tetrakis(alkylthio) tetraselenafulvalene (TTCn-TSeF, n = 1-15)
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A series of tetrakis(alkylthio)tetraselenafulvalene compounds (TTC n-TSeF, n = 1-15) were prepared by a one-step reaction between dialkyl disulfide and tetralithiated TSeF. Molecular properties (redox potentials and optical absorptions in solution) and solid-state properties (thermal behaviors, electric conductivities, and molecular and crystal structures for n = 1 and 10) were studied. TTCn-TSeF compounds are weak electron donor molecules and characterized by small on-site Coulomb repulsion. TTC1-TSeF has a high-dimensional conduction network owing to the presence of highdimensional heteroatomic contacts, "Atomic-Wire Effect." The π-moieties of TTC10-TSeF were fastened by the alkyl chains ("Fastener Effect") to form π-columns and there are a variety of short heteroatomic contacts resulting in two dimensional electronic structure. Electrical conductivity exhibited peculiar enhancement for n = 1 and 7 ≤ n ≤ 14 owing to the presence of high-dimensional conduction paths. These compounds may manifest high carrier mobility, and are good candidates for the field-effect transistor channel based on the advantageous features: low dark conductivity, low donor ability, on-site Coulomb repulsion energy, high-dimensional π-electron structure, and high solubility in organic solvents.
- Saito, Gunzi,Yoshida, Yukihiro,Murofushi, Hidenobu,Iwasawa, Naoko,Hiramatsu, Takaaki,Otsuka, Akihiro,Yamochi, Hideki,Isa, Kimio,Mineo-Ota, Eriko,Konno, Michiko,Mori, Takehiko,Imaeda, Ken-Ichi,Inokuchi, Hiroo
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- ACTIVATION AND SYNTHETIC APPLICATION OF THIOSTANNANES. EFFICIENT CONVERSION OF THIOL ACETATES INTO DISULFIDES
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Thiostannanes are obtained by treating alkoxystannanes with thiol acetates.Coupled with this reaction, the thiostannane methodology enables one-pot synthesis of disulfides from thiol acetate.
- Sato, Tsuneo,Otera, Junzo,Nozaki, Hitosi
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- Aerobic Oxidation of Thiols Catalyzed by Copper Nanoparticles Supported on Diamond Nanoparticles
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After purification by Fenton treatment, commercial diamond nanoparticles (NPs) are a suitable solid support for the deposition of Cu nanoparticles. Heating at 500°C under hydrogen proved to be a convenient annealing process for Fenton-purified diamond NPs that decreased the population of surface carboxylic acid groups and lead to samples with average Cu particle sizes of 3-4nm. The samples of Cu NPs supported on diamond NPs have been characterized by IR and X-ray photoelectron spectroscopy, as well as XRD and TEM. It was concluded that the samples contained Cu0 as well as CuI and CuII species. The resulting diamond-supported Cu NPs were highly active for the selective aerobic oxidation of aromatic thiols to the corresponding disulfides, whereas aliphatic thiols exhibited much lower reactivity because of some poisoning and catalyst deactivation produced by aliphatic thiols. The Cu catalysts used for thiophenol oxidation could be reused in four consecutive runs with 4% of decrease in the catalytic activity. This Cu catalyst exhibited similar catalytic activity, but is considerably more affordable, as an analogous diamond-supported Au catalyst.
- Dhakshinamoorthy, Amarajothi,Navalon, Sergio,Sempere, David,Alvaro, Mercedes,Garcia, Hermenegildo
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- Magnetic Fe3O4@MgAl-LDH composite grafted with cobalt phthalocyanine as an efficient heterogeneous catalyst for the oxidation of mercaptans
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Magnetically separable layered double hydroxide MgAl-LDH@Fe3O4 composite supported cobalt phthalocyanine catalyst was synthesized and used for the aerobic oxidation of mercaptans to corresponding disulfides under alkali free conditions. The catalyst exhibited excellent activity for the oxidation of mercaptans using molecular oxygen as an oxidant which can be effectively recovered by using an external magnetic field. In addition, the covalent immobilization of cobalt phthalocyanine to MgAl-LDH@Fe3O4 support prevents the leaching of the catalyst and improves its activity and stability.
- Kumar, Pawan,Gill, Kareena,Kumar, Sunil,Ganguly, Sudip K.,Jain, Suman L.
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- Preparation of disulfides by the oxidation of thiols using bromine
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Medium length aliphatic disulfides are easily synthesized via the bromine-oxidation of thiols in the absence of solvent. Bromine can also oxidize long aliphatic and aromatic thiols to disulfides in solution. All yields are quantitative.
- Wu, Xiaoming,Rieke, Reuben D.,Zhu, Lishan
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- Microwave-assisted synthesis of disulfides using tetrathiomolybdate: A step toward greener synthesis
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An eco-friendly, efficient, and rapid synthetic procedure for disulfides using benzyl triethyl ammonium tetrathiomolybdate through microwave irradiation of solid support adsorbed reactants is reported.
- Sidiq, Naheed,Bhat, Mohsin Ahmad,Khan, Khaliquz Zaman,Khuroo, Mohammad Akbar
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- Nitrosonium-catalyzed decomposition of S-nitrosothiols in solution: A theoretical and experimental study
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The decomposition of S-nitrosothiols (RSNO) in solution under oxidative conditions is significantly faster than can be accounted for by homolysis of the S-N bond. Here we propose a cationic chain mechanism in which nitrosation of nitrosothiol produces a nitrosated cation that, in turn, reacts with a second nitrosothiol to produce nitrosated disulfide and the NO dimer. The nitrosated disulfide acts as a source of nitrosonium for nitrosothiol nitrosation, completing the catalytic cycle. The mechanism accounts for several unexplained facets of nitrosothiol chemistry in solution, including the observation that the decomposition of an RSNO is accelerated by O2, mixtures of O 2 and NO, and other oxidants, that decomposition is inhibited by thiols and other antioxidants, that decomposition is dependent on sulfur substitution, and that decomposition often shows nonintegral kinetic orders.
- Zhao, Yi-Lei,McCarren, Patrick R.,Houk,Choi, Bo Yoon,Toone, Eric J.
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- Liquid-phase oxidation of thiols with chlorine dioxide
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The products and kinetics of the liquid-phase oxidation of 11 aliphatic and aromatic thiols with chlorine dioxide were studied at -10-+70 °C in organic media. The rate constants and activation parameters of the reaction were determined. The influence of the thiol structure on its reactivity was studied. A strong solvent effect on the reaction rate constant was found, and the reaction mechanism was proposed.
- Yakupov,Shereshovets,Imashev,Ismagilov
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- Aerobic oxidation of thiols to disulfides using iron metal-organic frameworks as solid redox catalysts
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Aerobic oxidation of thiols to disulfides has been carried out using iron metal-organic frameworks (MOFs) as solid redox catalysts with very high yield and selectivity in acetonitrile under mild reaction conditions.
- Dhakshinamoorthy, Amarajothi,Alvaro, Mercedes,Garcia, Hermenegildo
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- HIGH OXIDIZING ACTIVITY OF 8-AZA-3,10-DIMETHYLISOALLOXAZINE (8-AZAFLAVIN)
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8-Azaflavin was synthesized for the first time, and it was found that 8-azaflavin is much more reactive (>1E4) than 3,10-dimethylisoalloxazine for oxidation of thiols in aqueous solution.Catalytic efficiency for disulfides synthesis was also examined under aerobic conditions.
- Yano, Yumihiko,Yatsu, Isao,Oya, Eiichi,Ohshima, Masashi
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- Reductive cleavage of S-S bond by samarium diiodide: A novel method for the synthesis of disulfides
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Samarium diiodide reductively cleaves the S-S bond of sodium alkyl thiosulfates to give the corresponding disulfides in moderate to good yields under mild and neutral conditions.
- Jia,Zhang,Zhou
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- Novel rearrangements of 2,3-dimercapto-1-propanol derivatives: Formation of dialkyl sulfide, dialkyl disulfide, and 1,2,3-tris(alkylthio)propane
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The base alkylation of 2,3-dimercapto-1-propanol with alkyl halides leads in good yield to 2,3-bis(alkylthio)-1-propanol and dialkyl sulfide. The reaction of 2,3-bis(alkylthio)-1-propanol with catalytic concentrated sulfuric acid proceeds with rearrangement to give 1,2,3-tris(alkylthio)propane and dialkyl disulfide. The rearrangement reaction takes place through a common intermediate thiaranium intermediate 8.
- Ong, Chi Wi,Chou, Yi Meen,Wang, Junn Nan
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- Electrochemical synthesis of organochalcogenides in aqueous medium
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The electrochemical preparation of telluride, selenide and sulfide ions was carried out in NaOH aqueous solution, using a two compartment cell. Organochalcogenides were prepared from halogenated compounds in a two-step procedure. The monochalcogenides were obtained as the major products in good yields.
- Ribeiro Neto, Pedro B.,Santana, Sonydelane O.,Levitre, Guillaume,Galdino, Danilo,Oliveira, Jadson L.,Ribeiro, Rogério T.,Barros, Maria E. S. B.,Bieber, Lothar W.,Menezes, Paulo H.,Navarro, Marcelo
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- A novel reduction of sodium alkyl thiosulfates with InCl 3(cat.)/Sm(0) system in aqueous media: Facile synthesis of disulfides
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A novel reduction of sodium alkyl thiosulfates. with InCl 3(cat.)/Sm(0) system in aqueous media has been developed, which generates the corresponding disulfides in good yields.
- Li, Pinhua,Wang, Lei,Yang, Yaner,Sun, Xinhua,Wang, Min,Yan, Jincan
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- Boron nitride nanoplatelets as a solid radical initiator for the aerobic oxidation of thiophenol to diphenyldisulfide
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Boron nitride (BN) nanoplatelets suspended in ethanol were obtained through the sonication of BN powders prepared through biopolymer-templated pyrolysis and air calcination of (NH4)3BO3-chitosan powders. AFM measurements indicate that BN nanoplatelets have an average height of 1.5 nm and length and width dimensions between 30 and 100 nm. BN nanoplatelets exhibit higher catalytic activity for the molecular oxygen-mediated oxidation of aromatic thiols to the corresponding disulfides than do boron and nitrogen-codoped graphene or commercial bulk hexagonal BN. The reaction scope includes substituted aromatic and heteroaromatic thiols, whereas aliphatic thiols are considerably less reactive. The hot filtration test and radical quenching by N-tert-butyl-α-phenylnitrone support an autoxidation mechanism involving thiyl radicals. BN nanoplatelets are deactivated during the course of the reaction owing to aggregation. The present study uncovers the activity of BN nanoplatelets used as an insoluble radical initiator of S-H bonds. Aerobics is fun: Boron nitride nanoplatelets prepared through pyrolysis and sonication demonstrate higher catalytic activity for the aerobic oxidation of thiophenol.
- Dhakshinamoorthy, Amarajothi,Primo, Ana,Esteve-Adell, Ivan,Alvaro, Mercedes,Garcia, Hermenegildo
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- Efficient and convenient oxidation of thiols to symmetrical disulfide with silica-PCl5/NaNO2 in water
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A very simple, environmentally benign, cost-effective, and efficient synthesis of disulfides from thiols using silica-PCl5/NaNO2 in aqueous medium has been described. The reaction was found to occur rapidly under mild conditions, and disulfides were obtained easily through a simple workup.
- Pathak, Uma,Pandey, Lokesh Kumar,Mathur, Sweta
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- Reactions of chlorine dioxide with organic compounds 2. Oxidation of thiols
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Oxidation of thiols with chlorine dioxide smoothly affords the corresponding disulfides.
- Lezna,Rubtsova,Kuchin
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- Fe(HSO4)3 and Fe(HSO4)3/DMSO as efficient, heterogeneous, and reusable catalyst systems for the oxidative coupling of thiols
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Fe(HSO4)3 has been used as a heterogeneous, efficient, and recyclable catalyst in ethanol for the selective oxidation of thiols to their corresponding disulfides. The same results were obtained under identical conditions using catalytic amounts of Fe(HSO4)3 in the presence of DMSO. Different types of aliphatic, aromatic, and heteroaromatic thiols have been used in the reaction, and in all cases the products were obtained in good to excellent yields.
- Eshghi,Bakavoli,Moradi,Davoodnia
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- Simple method for the preparation of symmetrical alkyl and aryl disulfides with alkyl sulfonyl halides in nitrogenous base
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In the present study, the reaction of thiols with alkyl sulfonyl halides was carried out in a nitrogenous base to compare the reactivity of -SH with that of -OH, which, however, led to the formation of disulfides. The reaction achieved as a result offers the use of an inexpensive reagent, quantitative yields of the product, and simplicity for the formation of the S-S bond. Copyright Taylor & Francis Group, LLC.
- Ali, Firdous Imran,Hashmi, Imran Ali,Siddiqui, Bina S.,Rasheed, Munawwer
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- A new reagent for the efficient synthesis of disulfides from alkyl halides
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Benzyltriethylammonium tetracosathioheptamolybdate [(C6H5CH2N(Et)3)6Mo 7S24] has been found to be a superior sulfur transfer reagent for the conversion of alkyl halides to the corresponding disulfides in excellent yields under very mild reaction conditions.
- Polshettiwar, Vivek,Nivsarkar, Manisha,Acharya, Jyotiranjan,Kaushik
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- Reductive cleavage of C - S bond by samarium diiodide: A novel method for the synthesis of disulfides and thiolesters
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Disulfides were obtained by the reaction of thiocyanates with equivalent SmI2. Smarium thiolates were generated by the reaction of an equivalent of thiocyanates with two equivalents of SmI2, and then reacted smoothly with acyl chlorides to give thiolesters.
- Jia, Xueshun,Zhang, Yongmin,Zhou, Zunjun
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- Application of Bulky NHC-Rhodium Complexes in Efficient S-Si and S-S Bond Forming Reactions
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The efficient and straightforward syntheses of silylthioethers and disulfides are presented. The synthetic methodologies are based on new rhodium complexes containing bulky N-heterocyclic carbene (NHC) ligands that turned out to be efficient catalysts in thiol and thiol-silane coupling reactions. These green protocols, which use easily accessible reagents, allow obtaining compounds containing S-Si and S-S bonds in solvent-free conditions. Additionally, preliminary tests on coupling of mono- and octahydro-substituted spherosilicates with selected thiols have proved to be very promising and showed that these catalytic systems can be used for the synthesis of a novel class of functionalized silsesquioxane derivatives.
- Bo?t, Ma?gorzata,?ak, Patrycja
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p. 17579 - 17585
(2021/11/18)
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- Antimony(V) and Tin(IV) Complexes with Redox-Active O,N,O-Donor Ligand in the Electrosynthesis of Symmetrical Disulfides
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Abstract: Reactions of electrochemically generated antimony(V) and tin(IV) complex species containing a tridentate O,N,O-donor ligand with various thiols were studied. Among main group metal complexes with N,N-bis(2-hydroxy-di-3,5-tert-butylphenyl)amine (CatH2–NH–CatH2), compounds [Me2Sn(Cat-N-SQ)] (I), [Et2Sn(Cat-N-SQ)] (II), [Ph2Sn(Cat-N-SQ)] (III), [(c-C6H11)2Sb(Cat-N-Cat)] (IV), and [Ph3Sb(Cat-NH-Cat)] (V) are the most active, able to mediate the oxidation of thiols (1-hexanethiol, cyclohexanethiol, and 4-methoxythiophenol), to symmetrical disulfides were identified. The anodic activation of Sb(V) and Sn(IV) complexes involves organic ligands and gives rise to intermediates that react with thiols. During the mediated electrosynthesis, the initial complex species is regenerated in solution. The use of metal complex mediators decreases the anodic overvoltage of the thiol oxidation in comparison with direct electrochemical synthesis. The yields of products depend on complex and thiol structures or ratio. The highest efficiency in the electrocatalytic reactions was found for the [Ph3Sb(Cat-NH-Cat)] complex, which should be used for the synthesis of disulfides.
- Berberova, N. T.,Lavrent’ev, V. A.,Ryabukhin, Yu. I.,Shinkar’, E. V.,Smolyaninov, I. V.
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p. 341 - 346
(2021/06/07)
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- Natural gallic acid catalyzed aerobic oxidative coupling with the assistance of MnCO3 for synthesis of disulfanes in water
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The formation of S-S bonds has great significance and value in synthetic chemistry and bioscience. To pursue a sustainable approach for such a synthesis, an aerobic oxidative coupling method for the efficient preparation of organic disulfanes, using a low-toxic natural gallic acid as an organocatalyst, inexpensive MnCO3 as a cocatalyst, O2 as the terminal oxidant and water as the solvent, has been successfully developed. Such metal-organic cooperative catalytic protocol provided an access to various symmetrical and unsymmetrical disulfanes in up to 99% yield. Gram scale synthesis with practical convenience and low loading of catalysts further illustrates the practicability of our method.
- Song, Lijuan,Li, Wenhao,Duan, Wenxue,An, Jichao,Tang, Shanyu,Li, Longjia,Yang, Guanyu
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supporting information
p. 1432 - 1438
(2019/03/26)
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- Visible-light-induced metal and reagent-free oxidative coupling of: Sp 2 C-H bonds with organo-dichalcogenides: Synthesis of 3-organochalcogenyl indoles
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Here, a unique visible-light-induced method for the organochalcogenation of the sp2 C-H bonds of indoles and aniline has been presented using diaryl dichalcogenides (S, Se, and Te) and oxygen as an oxidant avoiding a photocatalyst, base, catalyst, and reagent in acetone at room temperature. This benign protocol allows one to access a wide range of 3-arylselenylindoles, 3-arylthioindoles and even 3-aryltelluroindoles with good to excellent yields. Various functionalities namely, methoxy, and halo either on indoles or aryl dichalcogenides showed amenability to the developed reaction. Furthermore, thiocyanation of the sp2 C-H bonds of indoles has been accomplished by this visible light induced method. A mechanistic understanding by UV-visible, EPR spectroscopy, and cyclic voltammetry suggests that light induces electron transfer from the electron rich arene to oxygen providing an arene radical cation and a superoxide radical anion. Subsequently, reaction of the radical cation with aryl dichalcogenides provides a diaryl chalcogenyl cation which upon removal of protons gave unsymmetrical 3-indolyl aryl chalcogenides.
- Rathore, Vandana,Kumar, Sangit
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supporting information
p. 2670 - 2676
(2019/06/03)
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- Base-controlled Fe(Pc)-catalyzed aerobic oxidation of thiols for the synthesis of S-S and S-P(O) bonds
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Fe(Pc)-Catalyzed aerobic oxidation of thiols for the synthesis of disulfides has been developed under mild reaction conditions. In addition, an aerobic oxidative cross-dehydrogenative coupling (CDC) reaction of thiols with P(O)-H compounds (H-phosphonates and H-phosphine oxide) for the formation of S-P(O) bonds has been demonstrated under the Fe(Pc) catalysis system with a base additive. Control experiments revealed that the use of a base (DIPA) in this system controls the synthetic pathways in which thiophosphates are formed.
- Huang, Hai,Ash, Jeffrey,Kang, Jun Yong
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p. 4236 - 4242
(2018/06/21)
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- Photo-induced thiol coupling and C-H activation using nanocrystalline lead-halide perovskite catalysts
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The use of photon energy to promote chemical transformations offers versatile control of reaction kinetics and progress. Over the past decade, many photoactive transition-metal complexes and organic chromophores were developed to catalyze chemical transformations, enabling a myriad of reactions and compounds that were previously inaccessible via traditional synthetic methods. Here, we demonstrate the photocatalytic oxidative coupling of organic thiols using cesium lead halide perovskite nanocrystals as photocatalysts. The photo-catalyzed thiol coupling reactions selectively produced symmetric and unsymmetrical disulfides in high yields (68-96% isolated yields). Additionally, we discovered a perovskite-catalyzed phosphonylation of tertiary amines via visible-light-mediated cross-dehydrogenative coupling reaction, and obtained good isolated yields (50-96%). The variety of visible-light-induced photocatalytic processes that perovskite nanocrystals are capable of, coupled with their facile preparation, easily tunable redox potentials, high catalytic efficiency and reusability, presents great opportunities for their future applications in green and sustainable organic synthesis.
- Wu, Wen-Bin,Wong, Ying-Chieh,Tan, Zhi-Kuang,Wu, Jie
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p. 4257 - 4263
(2018/08/24)
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- An Organodiselenide with Dual Mimic Function of Sulfhydryl Oxidases and Glutathione Peroxidases: Aerial Oxidation of Organothiols to Organodisulfides
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A novel organodiselenide, which mimics sulfhydryl oxidases and glutathione peroxidase (GPx) enzymes for oxidation of thiols by oxygen and hydrogen peroxide, respectively, into disulfides has been presented. The developed catalyst oxidizes an array of organothiols into respective disulfides in practical yields by using aerial O2 to avoid any reagents/additives, base, and light source. The synthesized diselenide also catalyzes the reduction of hydrogen peroxide into water by following the GPx enzymatic catalytic cycle with a reduction rate of 49.65 ± 3.7 μM·min-1.
- Rathore, Vandana,Upadhyay, Aditya,Kumar, Sangit
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supporting information
p. 6274 - 6278
(2018/10/05)
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- Reusable cobalt-phthalocyanine in water: Efficient catalytic aerobic oxidative coupling of thiols to construct S-N/S-S bonds
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A new aerobic oxidative coupling of thiols in water to construct sulfenamides or disulfides was developed, utilizing cobalt(ii)phthalocyanine-tetra-sodium sulfonate as the catalyst and O2 as the oxidant. The mother liquor could be recycled up to 20 times with negligible loss of activity and only a minor decrease of product yield.
- Dou, Yingchao,Huang, Xin,Wang, Hao,Yang, Liting,Li, Heng,Yuan, Bingxin,Yang, Guanyu
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supporting information
p. 2491 - 2495
(2017/07/17)
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- Synthesis and in vitro biological evaluation of thiosulfinate derivatives for the treatment of human multidrug-resistant breast cancer
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Organosulfur compounds derived from Allium vegetables have long been recognized for various therapeutic effects, including anticancer activity. Allicin, one of the main biologically active components of garlic, shows promise as an anticancer agent; however, instability makes it unsuitable for clinical application. The aim of this study was to investigate the effect of stabilized allicin derivatives on human breast cancer cells in vitro. In this study, a total of 22 stabilized thiosulfinate derivatives were synthesized and screened for their in vitro antiproliferative activities against drug-sensitive (MCF-7) and multidrug-resistant (MCF-7/Dx) human adenocarcinoma breast cancer cells. Assays for cell death, apoptosis, cell cycle progression and mitochondrial bioenergetic function were performed. Seven compounds (4b, 7b, 8b, 13b, 14b, 15b and 18b) showed greater antiproliferative activity against MCF-7/Dx cells than allicin. These compounds were also selective towards multidrug-resistant (MDR) cells, a consequence attributed to collateral sensitivity. Among them, 13b exhibited the greatest anticancer activity in both MCF-7/Dx and MCF-7 cells, with IC50 values of 18.54±0.24 and 46.50±1.98 μmol/L, respectively. 13b altered cellular morphology and arrested the cell cycle at the G2/M phase. Additionally, 13b dose-dependently induced apoptosis, and inhibited cellular mitochondrial respiration in cells at rest and under stress. MDR presents a significant obstacle to the successful treatment of cancer clinically. These results demonstrate that thiosulfinate derivatives have potential as novel anticancer agents and may offer new therapeutic strategies for the treatment of chemoresistant cancers.
- Roseblade, Ariane,Ung, Alison,Bebawy, Mary
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p. 1353 - 1368
(2017/10/10)
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- Method for preparing disulfide bond containing compound by using TEMPO catalyst through aerobic oxidation
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The invention discloses a method for preparing a disulfide bond containing compound by using a TEMPO catalyst through aerobic oxidation. The method comprises the following steps: adding R-SH, R'-SH and TEMPO into a solvent, and performing heating reflux in an aerobic environment, thereby preparing R-S-S-R'. The method achieves oxidative coupling reaction of thiophenol and mercaptan in the absence of transition metal and is high in yield, good in selectivity and free of over-oxidized product; for aliphatic mercaptan which is relatively poor in activity, the problem of oxidation can be solved by adding copper salt as a promoter, the yield is relatively high, and the reaction is greatly affected by a substitute group; the catalyst is easy to obtain, the reaction condition is gentle, and the method is applicable to large-scale production.
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Paragraph 0061-0069; 0117; 0118; 0119; 0120
(2016/10/07)
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- A [...] analogs, its preparation process and its application
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The invention discloses a largazole analogue which contains alkyl disulfide side chains and is represented by formula I, and a preparation method and applications thereof. The largazole analogue possesses relatively high antineoplastic activity and selectivity, can be used for development of antitumor drugs. Raw materials of the largazole analogue are cheap and easily available; and the preparation method is simple, and is a method suitable for industrialization. R in formula represents an alkyl group containing 1 to 8 carbon atoms.
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Paragraph 0150-0153
(2016/10/08)
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- Dynamic disulfide metathesis induced by ultrasound
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The reversible metathesis of disulfide bonds is generally induced by a combination of a reducing agent and base or by irradiation with ultraviolet light. Here we report that ultrasound irradiation is suitable for generating clean equilibrium mixtures of disulfides within one hour or one day, depending on the sonication source. Preliminary mechanistic investigations suggest that the solvent plays an active role in producing initiator radicals.
- Fritze, Urs F.,Von Delius, Max
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supporting information
p. 6363 - 6366
(2016/05/24)
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- Haloacid/dimethyl sulfoxide-catalyzed synthesis of symmetrical disulfides by oxidation of thiols
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A novel method is developed for the oxidation of thiols to the corresponding disulfides using 20 mol % haloacid (HBr or HI) in combination with dimethyl sulfoxide. A tentative mechanism is proposed for the oxidation. In addition to the advantages of cost-effectiveness, simple processes, and broad functional group tolerance, the exclusive formation of disulfides is the principle reward of this methodology while compared to known methods that further oxidize disulfides to S-oxides and other byproducts.
- Natarajan, Palani,Sharma, Himani,Kaur, Mandeep,Sharma, Pooja
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supporting information
p. 5578 - 5582
(2015/09/21)
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- Design, synthesis, and biological evaluation of largazole derivatives: Alteration of the zinc-binding domain
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A new series of largazole analogues in which the side chain was replaced with disulfide groups were synthesized, and their biological activities were evaluated. Compound 8 bearing an octyl moiety showed much better selectivity for HDAC1 over HDAC7 than largazole (320-fold). Structure-activity relationships suggested that the length in the disulfide chain of largazole is important for the selectivity toward HDAC1 over HDAC7.
- Su, Jinyue,Qiu, Yatao,Ma, Kun,Yao, Yiwu,Wang, Zhen,Li, Xianling,Zhang, Dayong,Tu, Zhengchao,Jiang, Sheng
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p. 7763 - 7769
(2014/12/10)
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- Biodegradable Polymers with Sulfenamide Bonds for Drug Delivery Applications
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The present invention provides polysulfenamides and methods of making same.
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Paragraph 0089
(2014/04/18)
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- S-Acylation of aliphatic and aromatic thiols with carboxylic acids and their esters over solid acid catalysts in the gas phase at temperatures above 200 °c
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Benzenethiol is reacted with acetic acid in a hydrogen stream over [(Mo6Cl8)Cl4(H2O) 2]·6H2O. Catalytic activity of the clusters appears above 200 °C, yielding S-phenyl thioacetate. The selectivity is 98% at 300 °C. Niobium, tantalum, and tungsten halide clusters with the same octahedral metal framework also catalyze the reaction. Benzoic acid and aliphatic carboxylic acids afford the corresponding S-phenyl carbothioates by reaction with benzenethiol. Aliphatic thiols are also S-acylated to yield the corresponding S-alkyl carbothioates. When carboxylic esters are applied to the reaction with benzenethiol over [(Nb6Cl12)Cl 2(H2O)4]·4H2O at 450 °C, the sterically unhindered moiety of the ester is incorporated into the products: S-phenyl thioacetate or methyl phenyl sulfide is obtained selectively. A Br?nsted acid site developed on the cluster complex by thermal activation is the active site of the catalyst. Hence, solid acids such as silica-alumina, zeolites, and heteropoly acids that are stable above 200 °C also catalyze these reactions.
- Nagashima, Sayoko,Yamazaki, Hitomi,Kudo, Kentaro,Kamiguchi, Satoshi,Chihara, Teiji
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p. 332 - 338
(2013/07/26)
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- Rhodium-catalyzed synthesis of 2,3-diaryl-1,4-diketones via oxidative coupling of benzyl ketones using α-thioketone oxidizing reagent
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RhH(PPh3)4 and 1,2-bis(diphenylphosphino)benzene (dppBz) catalyzed the oxidative coupling reaction of aryl benzyl ketones giving 2,3-diaryl-1,4-diketones in high yields. 3,3-Dimethyl-1-methylthio-2-butanone was used as the oxidizing
- Arisawa, Mieko,Li, Guangzhe,Yamaguchi, Masahiko
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supporting information
p. 1298 - 1301
(2013/03/13)
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- New class of biodegradable polymers formed from reactions of an inorganic functional group
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Although numerous small molecules have been synthesized with sulfenamide bonds (R2N-SR), this is the first report of the synthesis of polysulfenamides. These polymers are readily synthesized at room temperature using secondary diamines and dithiosuccinimides. The dithiosuccinimides were readily synthesized in one step by the reaction of dithiols such as HS(CH 2)6SH with N-chlorosuccinimide. The resulting dithiosuccinimides were either recrystallized or readily purified by chromatography on silica gel and required no special handling. The conversions of polymerization ranged from 95 to 98%, and the molecular weights of the polymer reached as high as 6300 g mol-1. The sulfenamide bond was very stable in organic solvents, and no degradation was observed under atmospheric conditions in C6D6 for 30 days. In contrast, the sulfenamide bond readily decomposed in less than 12 h in D2O. Polysulfenamides were fabricated into micrometer-sized particles loaded with dye and endocytosed into JAWSII immature dendritic and HEK293 cells. Polysulfenamides represent a new class of polymers that are readily synthesized, stable in aprotic solvents, and readily degrade in water.
- Yoo, Jun,Kuruvilla, Denison J.,D'Mello, Sheetal R.,Salem, Aliasger K.,Bowden, Ned B.
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p. 2292 - 2300
(2012/06/29)
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- Transformation of thiols to disulfides by epolactaene and its derivatives
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In this paper we report a disulfide formation of thiols induced by epolactaene and its derivatives. We previously reported the disulfide formation of N-acetylcysteine methyl ester by epolactaene in a 1:1 MeOH/0.5 M NaHCO 3 aq solution. The present studies reveal that the disulfide formation proceeds under mild conditions such as in PBS at pH 7.3, suggesting that epolactaene may induce disulfide formation of cellular thiols. This compound induces the disulfide formation of several thiols in a 1:1 MeOH/0.5 M NaHCO3 aq solution at room temperature. Moreover, our results show that the acyl side-chain of epolactaene greatly influences the products of the reaction. We analyzed the reaction mechanism by using thiolysis products of epolactaene derivatives and propose a new reaction mechanism.
- Kuramochi, Kouji,Sunoki, Takashi,Tsubaki, Kazunori,Mizushina, Yoshiyuki,Sakaguchi, Kengo,Sugawara, Fumio,Ikekita, Masahiko,Kobayashi, Susumu
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experimental part
p. 4162 - 4172
(2011/08/09)
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- Inexpensive, one-pot synthesis of unsymmetrical disulfides using 1-chlorobenzotriazole
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A new synthesis of unsymmetrical disulfides is described. The reaction of a thiol R1SH with 1-chlorobenzotriazole (BtCl) at -78 °C in DCM affords a high-yielding conversion to R1SBt without appreciable formation of the symmetrical disulfide R1SSR1. R1SBt is then reacted with R2SH to form the unsymmetrical disulfide in a one-pot sequence with green character that avoids the use of toxic and harsh oxidizing agents. The methodology has been developed for synthesis of various types of disulfides.
- Hunter, Roger,Caira, Mino,Stellenboom, Nashia
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p. 8268 - 8271
(2007/10/03)
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- Synthesis of disulfides containing a corrinoid head group for preparation of self-assembled monolayers
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The synthesis of three novel alkane disulfides with head-groups derived from vitamin B12, 14a, 14b and 15, is described. Self-assembled monolayers on gold are prepared from the symmetrical disulfide 15, bearing two cobyrinate head groups. The coating of the gold surface is analyzed by TOF-SIMS and ESCA measurements. Georg Thieme Verlag Stuttgart.
- Mendon?a, Joana,Luginbühl, Reto,Siegenthaler, Hans,Keese, Reinhart
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p. 1901 - 1904
(2007/10/03)
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- Synthesis of Nonsymmetric Dialkyl Disulfides and Their Use as Extreme-Pressure Additives for Lubricating Oils
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A series of nonsymmetric dialkyl disulfides were synthesized in the reaction of alkylmercaptans with alkyl halides in an alkaline alcohol solution in the presence of elemental sulfur and catalytic amounts of 1-(N,N-dimethylaminomethyl)-1,2,4-triazole. It was shown that nonsymmetric dialkyl disulfides synthesized by the novel procedure possess antiscuff properties and can be used as high-performance additives for lubricating oils.
- Kirichenko,Khanov,Ibragimov,Glazunova,Kirichenko,Dzhemilev
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p. 428 - 430
(2007/10/03)
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- Method for preparing aromatic diphenyl thioethers
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The invention concerns a method for preparing aromatic diphenyl thioethers. More particularly the invention concerns the preparation of 4-chloro-4′-thiomethyldiphenylether. The inventive method for preparing an aromatic diphenyl thioether is characterised in that it consists in reacting in an aqueous medium a diazonium salt of an aromatic diphenyl compound with a disulphide sulphur compound, in the presence of an efficient amount of a coupling catalyst.
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- The kinetics and mechanism of the reaction between diphenylcarbonyl oxide and mercaptans
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The kinetics of the reaction between diphenylcarbonyl oxide Ph2COO and several mercaptans was studied by pulsed photolysis. At 295 K in acetonitrile, the absolute rate constants (k6, dm3 mo1-1 s-1) for the reaction between Ph2COO and RSH changed from 4.64 × 105 for n-butylmercaptan to 1.52 × 108 for thiophenol. The major molecular products of the oxidation of mercaptans RSH were the corresponding disulfides RSSR. The dependences of the logarithm of the rate constant on substituent inductive parameters (σ*) and mercaptan acidity pKa were obtained. The reaction mechanism was discussed.
- Krupin,Nazarov,Khursan,Komissarov
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p. 1888 - 1892
(2007/10/03)
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- A kinetic study of S-nitrosothiol decomposition
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Under anaerobic conditions S-nitrosothiols 1a-e undergo thermal decomposition by homolytic cleavage of the S-N bond; the reaction leads to nitric oxide and sulfanyl radicals formed in a reversible manner. The rate constants, k1, have been determined at different temperatures from kinetic measurements performed in refluxing alkane solvents. The tertiary nitrosothiols 1c (k1(69°C) = 13 × 10-3 min-1) and 1d (k1(69°C) 91 × 10-3 min-1) decomposed faster than the primary nitrosothiols 1a (k1(69°C) = 3.0 × 10-3 min-1) and 1b (k1(69°C) = 6.5 × 10-3 min-1). The activation energies (E#= 20.5 - 22.8 Kcal mol-1) have been calculated from the Arrhenius equation. Under aerobic conditions the decay of S-nitrosothiols 1a-e takes place by an autocatalytic chain-decomposition process catalyzed by N2O3. The latter is formed by reaction of dioxygen with endogenous and/or exogenous nitric oxide. The autocatalytic decomposition is strongly inhibited by removing the endogenous nitric oxide or by the presence of antioxidants, such as pcresol, β-styrene, and BHT The rate of the chain reaction is independent of the RSNO concentration and decreases with increasing bulkiness of the alkyl group; this shows that steric effects are crucial in the propagation step.
- Grossi, Loris,Montevecchi, Pier Carlo
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p. 380 - 387
(2007/10/03)
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- Preparation of disulfides by the oxidation of thiols using trichloroisocyanuric acid
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Thiols are readily oxidized to disulfides by a solution of pyridine, water, benzoic acid and trichloroisocyanuric acid in acetonitrile and methylene chloride.
- Zhong,Guo
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p. 1825 - 1828
(2007/10/03)
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- Alkyl- and Arylthiodediazoniations of Dry Arenediazonium o-Benzenedisulfonimides. Efficient and Safe Modifications of the Stadler and Ziegler Reactions to Prepare Alkyl Aryl and Diaryl Sulfides
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The reaction between dry arenediazonium o-benzenedisulfonimides 1 and sodium thiolates in anhydrous methanol represents an efficient and safe procedure, of general validity, for the preparation of unfunctionalized or variously functionalized alkyl aryl and diaryl sulfides. As a rule, the reaction temperature was maintained at 0-5°C for the alkylthiodediazoniations and at room temperature (20-25°C) for the arylthiodediazoniations. The sulfide yields are generally high; of the 63 considered examples, 43 gave yields greater than 80% and 13 were between 70% and 80%. Lower yields were obtained only when sterically hindered diazonium salts or thiols were used. A good amount of the o-benzenedisulfonimide (8) was always recovered from the reactions and could be reused to prepare salts 1. The copious experimental data collected in homogeneous conditions have offered several starting points for the study of the mechanism of these reactions.
- Barbero, Margherita,Degani, Iacopo,Diulgheroff, Nicola,Dughera, Stefano,Fochi, Rita,Migliaccio, Mara
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p. 5600 - 5608
(2007/10/03)
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- Skeletal reorganization of mercaptoacetaldehyde dialkyl acetal in acid: formation of disulphide, 1,2-bis(mercapto)ethylene and 1,1,2-tris(mercapto)ethane derivatives
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The reaction of mercaptoacetaldehyde dialkyl acetals 1a-c in the presence of sulfuric acid, polyphosphoric acid and zinc chloride is described. Other than the disulfide reported previously, new compounds 1,2-bis-(mercapto)ethylene, 1,2,3-tris-(mercapto)ethane and 1,2-bis-(mercapto)methane have been isolated for the first time.
- Ong, Chi Wi,Yen, Sin Fei,Chou, Yi Meen
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p. 601 - 605
(2007/10/03)
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- Hydrotalcite clay-catalysed air oxidation of thiols
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Hydrotalcite is an efficient catalyst for air oxidation of a variety of aromatic, aliphatic and alicyclic thiols in hexane, affording the corresponding disulfides in excellent to quantitative yields under mild and neutral conditions.
- Hirano, Masao,Monobe, Hiroyuki,Yakabe, Sigetaka,Morimoto, Takashi
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p. 374 - 375
(2007/10/03)
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