- A NEW SYNTHESIS OF ORGANIC TRISULFIDES
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Thiols react with diimidazolylsulfide under mild conditions to give simmetrical trisulfides in good yield and high purity.
- Banerji, Asoke,Kalena, Govind P.
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- Electrochemical Synthesis of Organic Polysulfides from Disulfides by Sulfur Insertion from S8 and an Unexpected Solvent Effect on the Product Distribution
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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.
- F?hrmann, Jan,Hilt, Gerhard
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p. 11141 - 11149
(2021/06/09)
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- 3,4-Dichloro-1,2,5-thiadiazole: a commercially available electrophilic sulfur transfer agent and safe resource of ethanedinitrile
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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.
- Gorjian, Hayedeh,Khaligh, Nader Ghaffari
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- Redox Activation of Hydrogen Sulfide, Thiols, and Sulfur in Electrosynthesis of Organic Di- and Polysulfides
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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.
- Shinkar’,Smolyaninov,Kuzmin,Berberova
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p. 689 - 696
(2019/06/05)
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- Rhodium-catalyzed sulfur atom exchange reaction between organic polysulfides and sulfur
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RhH(PPh3)4 and cis-1,2-bis(diphenylphosphino)ethylene (dppv) catalyze the exchange of sulfur atoms between sulfur and organic polysulfides. The exchange of dialkyl trisulfides with sulfur proceeds at a high efficiency within 5 min at room temperature yielding a mixture of organic polysulfides.
- Arisawa, Mieko,Tanaka, Ken,Yamaguchi, Masahiko
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p. 4797 - 4800
(2007/10/03)
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- Fundamental reactivity of sulfur with organotins: Underexploited Ar-S bond formation under aqueous and aerobic conditions
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This work describes a comprehensive study on the reactivity of organotins with elemental sulfur for producing organosulfur compounds and Ar-S bonds. Elemental sulfur, fluoride ions and organotins reacted under aqueous, aerobic and almost neutral conditions to selectively generate disulfides, without forming thiols or thioethers (or sometimes trisulfides). Several parameters were examined in depth: organotins, carbon ligands, fluoride sources, temperatures, solvents and equivalents of sulfur.
- Gingras, Marc,Chabre, Yoann M.,Raimundo, Jean-Manuel
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p. 2052 - 2057
(2007/10/03)
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- Optimization of the synthesis of symmetric aromatic tri- and tetrasulfides
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The reaction of aromatic thiols with sulfur dichloride and sulfur monochloride to form the corresponding aromatic trisulfides, 2a-d, and tetrasulfides, 3a-d, has been optimized with respect to yield and purity. The use of pyridine as an amine base and the
- Zysman-Colman, Eli,Harpp, David N.
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p. 2487 - 2489
(2007/10/03)
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- Kaolinitic clay catalyzed reaction of sulfur monochloride with aromatics: An efficient and high yield synthesis of symmetrical disulfides
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Kaolinitic clay efficiently catalyses the reaction of sulfur monochloride with arenes to yield symmetrical 4,4′ arene disulfides in a single step under heterogeneous phase.
- Vyas, Renu,Chanda, Bhanu,Sudalai
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- Use of a sacriflcial-sulfur electrode in electroorganic chemistry. V. Formation of the sequence CSSSC from S and thiols or thiolates
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At a working potential of about +2.0 V (vs SCE) the carbon-sulfur electrode is a source of the electrogenerated cation S2+. In organic media, this electrophile reacts with thiols (or thiolates) to give a mixture of polysulfides of which the trisulfide is the main product. The reaction between electrogenerated Sy2- and alkyl halides is less selective. Elsevier,.
- Do, Quang Tho,Elothmani, Driss,Simonet, Jacques,Guillanton, Georges Le
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p. 273 - 281
(2007/10/03)
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- A Convenient Synthesis of 1,2-Dithietes and 1,2-Dithioxo Compounds Stabilized by Buttressing and Resonance Effects, Respectively, by Sulfuration of Alkynes with Elemental Sulfur
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Sulfuration of a series of alkynes by elemental sulfur was investigated.Alkynes carrying highly bulky substituents, 2,2,5,5-tetramethyl-3-hexyne (6a), 1,2-di-(1-adamantyl)ethyne (6b), 3,3-dimethyl-1-phenyl-1-butyne (6c), and 1-(1-adamantyl)-2-phenylethyne (6d), reacted with sulfur to give the corresponding stable 1,2-dithietes 7a-d in 46-65percent yields.Less hindered alkynes reacted with sulfur to afford 1,4-dithiins and thiophenes as the final products which were derived from the initial products, 1,2-dithietes, via their tautomerization to the corresponding 1,2-dithioxo compounds, while extremely congested alkynes failed to react with sulfur even under forcing conditions.On the other hand, ynamines, a typical electron-rich alkyne, 1-diethylamino-2-phenylthioethyne (6o), 1-diethylamino-2-phenylselenoethyne (6p), and tetraethylethynediamine (6q) were sulfurated under milder conditions to afford resonance-stabilized 1,2-dithioxo compounds 19o-q as the principal products.Mechanism of the formation of 1,2-dithietes, 1,2-dithioxo compounds, and other products is discussed.
- Choi, Keun Soo,Akiyama, Isao,Hoshino, Masamatsu,Nakayama, Juzo
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p. 623 - 629
(2007/10/02)
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- SYNTHESIS OF DISULPHIDES AND TRISULPHIDES via ORGANOSILICON COMPOUNDS
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Silyl sulphides 2a-b smoothly react with thiolsulphinates 1a-c and thiolsulphonates 6a-c to give unsymmetrical disulphides under mild conditions and in very good yields.The "neutral" conditions used allow one to avoid any side reactions and subsequent randomization of the products.When bis(trimethylsilyl)sulphide, 8, is used, symmetrical trisulphides may be obtained under the same experimental conditions.
- Capozzi, Giuseppe,Capperucci, Antonella,Degl'Innocenti, Alessandro,Duce, Rosa Del,Menichetti, Stefano
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p. 421 - 426
(2007/10/02)
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- SILICON IN ORGANOSULFUR CHEMISTRY. Part 1. SYNTHESIS OF TRISULPHIDES
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The reaction of bis(trimethylsilyl)sulphide with thiosulphinates in an inert solvent under neutral and mild conditions gives symmetrical alkyl- or aryl-trisulphides.
- Capozzi, Giuseppe,Capperucci, Antonella,Degl'Innocenti, Alessandro,Duce, Rosa Del,Menichetti, Stefano
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p. 2991 - 2994
(2007/10/02)
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- THE REACTION OF t-BUTYL HYPOCHLORITE WITH THIOCARBONYL COMPOUND - A CONVENIENT METHOD FOR THE TRANSFORMATION
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The reaction of t-butyl hypochlorite with different thiocarbonyl compounds has been studied.Primary thioamides 1a-c give 1,2,4-thiadiazole derivatives.N-Phenylthiourea 4a gives 5-imino-4-phenyl-3-phenylamino-4,5-dihydro-1,2,4-thiadiazoline 15.Secondary and tertiary thioamides 2a-d, N-methyl-2-thiopyrrolidinone 3, N,N'-dicyclohexylthiourea 4b, N,N,N'-trimethylthiourea 4c, 5-ethyl-5-phenylthiobarbituric acid 5, xanthione 7a, Mischler's thioketone 7b, thiocoumarin 8, O-ethylthiobenzoate 9, O,O-diphenylthiocarbonate 10, di-p-tolyl and o-phenylene trithiocarbonates 11 and 12 have all afforded the oxigen analogues.N,N-Dimethyl-S-phenyldithiocarbonate 6 produces a mixture of di-, tri-, and tetrasulfides.A mechanism for the transformation is suggested in accordance with the Hard and Soft Acids and Bases (HSAB) principle.
- El-Wassimy, M.T.M.,Jorgensen, K.A.,Lawesson, S.-O.
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p. 1729 - 1734
(2007/10/02)
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- REACTION OF N,N'-THIONYLDIIMIDAZOLE WITH THIOLS: A SULFUR TRANSFER REACTION
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Reaction of N,N'-thionyldiimidazole with thiols effects the formation of disulfides and trisulfides.These results are rationalized by assuming that the thiols react with N,N'-thionyldiimidazole to produce the disulfides and N,N'-thiobisimidazole which subsequently reacts with the starting thiols to give the trisulfides.
- Ogata, Masaru,Matsumoto, Hiroshi,Shimizu, Sumio
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p. 955 - 958
(2007/10/02)
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- Desulfurization of Organic Trisulfides by Tris(dialkylamino)phosphines. Mechanistic Aspects
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Tris(dialkylamino)phosphines effect a rapid desulfurization of trisulfides to disulfides under mild conditions.The reaction mechanism involves a bimolecular process, proceeding by the rate-determining formation of a phosphonium salt intermediate.The central sulfur atom of a diaryl trisulfide is removed in the process, while a dialkyl trisulfide loses a terminal sulfur atom to the aminophosphine.
- Harpp, David N.,Ash, David K.,Smith, Roger A.
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p. 5155 - 5160
(2007/10/02)
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