- Indium-catalyzed reductive sulfidation of aromatic carboxylic acids and aldehydes with elemental sulfur to prepare symmetrical benzyl sulfides
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Described herein is a direct approach to symmetrical thioethers from either aromatic carboxylic acids or aromatic aldehydes with elemental sulfur (S8) by using a reducing system combined with InI3 and 1,1,3,3-tetramethyldisiloxane (TMDS). This sulfidation does not require functionalized sulfur reagents, such as sulfides, disulfides, or metal sulfides, and it simultaneously forms two carbon-sulfur bonds in a single catalytic system. The coupling reaction of either aromatic carboxylic acids or aromatic aldehydes with elemental sulfur in the presence of a catalytic amount of InI3 and TMDS effectively produced the corresponding symmetrical benzyl sulfide derivatives.
- Miyazaki, Takahiro,Nishino, Kota,Yoshimoto, Shunsuke,Ogiwara, Yohei,Sakai, Norio
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Read Online
- Indium(III)-catalyzed reductive one-pot synthesis of thioethers from aromatic aldehydes and elemental sulfur
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Described herein is that a combination of InI3 and 1,1,3,3-tetramethyldisiloxane (TMDS) effectively promotes the reductive thioetherification from aromatic aldehydes with elemental sulfur (S8).
- Miyazaki, Takahiro,Nishino, Kota,Konakahara, Takeo,Sakai, Norio
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Read Online
- Synthesis method of dibenzyl sulfide
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As an important organic intermediate and a synthesis reagent, an organic sulfur compound also has unique pharmacological effects of resisting tumors, inflammation, bacteria and oxidation, preventing aging, preventing and treating cardiovascular diseases and the like. The patent develops a method for synthesizing dibenzyl sulfide without metal catalysis. In an acetonitrile solution, benzyl trifluoromethanesulfonic acid quaternary ammonium salt and sodium sulfide nonahydrate are used to synthesize dibenzyl sulfide in a wide substrate range with good to excellent yield through breakage of a carbon-nitrogen bond and generation of a carbon-sulfur bond. The method has the advantages of mild reaction conditions, simple operation, no metal, high yield, wide substrate applicability and the like.
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Paragraph 0008-0012; 0013-0015
(2021/02/06)
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- SULFUR EXTRUSION FROM DISULFIDES BY CARBENES
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The present invention relates to a method for preparing a compound T having a thioether group from a compound D having a disulfide group in the presence of a carbene.
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Page/Page column 17; 25-31
(2021/10/30)
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- Nanolayered cobalt-molybdenum sulphides (Co-Mo-S) catalyse borrowing hydrogen C-S bond formation reactions of thiols or H2S with alcohols
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Nanolayered cobalt-molybdenum sulphide (Co-Mo-S) materials have been established as excellent catalysts for C-S bond construction. These catalysts allow for the preparation of a broad range of thioethers in good to excellent yields from structurally diverse thiols and readily available primary as well as secondary alcohols. Chemoselectivity in the presence of sensitive groups such as double bonds, nitriles, carboxylic esters and halogens has been demonstrated. It is also shown that the reaction takes place through a hydrogen-autotransfer (borrowing hydrogen) mechanism that involves Co-Mo-S-mediated dehydrogenation and hydrogenation reactions. A novel catalytic protocol based on the thioetherification of alcohols with hydrogen sulphide (H2S) to furnish symmetrical thioethers has also been developed using these earth-abundant metal-based sulphide catalysts.
- Corma, Avelino,Sorribes, Iván
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p. 3130 - 3142
(2019/03/13)
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- Alkyl Sulfides as Promising Sulfur Sources: Metal-Free Synthesis of Aryl Alkyl Sulfides and Dialkyl Sulfides by Transalkylation of Simple Sulfides with Alkyl Halides
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A site-selective metal-free dealkylative approach to synthesize aryl alkyl and symmetrical dialkyl sulfides has been developed. This procedure is convenient and has wide functional group tolerance giving rise to sulfides carrying various alkyl chains from simple alkyl sulfides and alkyl halides in good to excellent yields. This transalkylation proceeds by an ionic mechanism via sulfonium intermediates and it was proposed that dimethylacetamide (DMAC) may participate in part to promote the reaction.
- Liu, Ting,Qiu, Renhua,Zhu, Longzhi,Yin, Shuang-Feng,Au, Chak-Tong,Kambe, Nobuaki
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supporting information
p. 3833 - 3837
(2018/12/05)
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- Indium-catalyzed direct conversion of dibenzyl ethers to dibenzyl sulfides using elemental sulfur and a hydrosilane and its application to the preparation of benzyl selenides
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Described herein is a catalytic system composed of an indium(III) compound, a hydrosilane and an easily handled form of elemental sulfur (S8) that effectively and directly catalyzes the sulfidation of dibenzyl ethers to produce dibenzyl sulfides. This system could also be applied to selenium in a straightforward conversion to dibenzyl selenides.
- Sakai, Norio,Takada, Koji,Katayama, Masahiro,Ogiwara, Yohei
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supporting information
p. 791 - 793
(2018/06/12)
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- Indium-catalyzed direct preparation of dibenzyl sulfides from benzyl alcohols and elemental sulfur with a hydrosilane and its application to the preparation of dibenzyl selenide
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We describe how a reducing system composed of InI3 and a hydrosilane efficiently and directly introduce elemental sulfur into the structure of dibenzyl sulfides via a nucleophilic substitution of benzyl alcohols. Also, we describe the application of this reducing system in the direct preparation of a dibenzyl selenide derivative with selenium.
- Miyazaki, Takahiro,Katayama, Masahiro,Yoshimoto, Shunsuke,Ogiwara, Yohei,Sakai, Norio
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supporting information
p. 676 - 679
(2016/01/26)
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- Phase-vanishing method with gas evolution and its application to organic synthesis
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Using a phase-vanishing (PV) system, hydrogen, oxygen, and hydrogen sulfide generated in situ from CaH2, KO2, and P2S5, respectively, were directly reacted with substances in the organic phase to afford the desired products. The selective synthesis of sulfides and disulfides was achieved with the evolution of H2S gas via tuning the bases used in the PV method. Using this PV system, reactions with hazardous gaseous reagents can be carried out easily and safely in a common test tube.
- Matake, Ryosuke,Niwa, Yuki,Matsubara, Hiroshi
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p. 672 - 675
(2016/01/26)
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- Dithiooxamide as an Effective Sulfur Surrogate for Odorless High-Yielding Carbon-Sulfur Bond Formation in Wet PEG200 as an Eco-Friendly, Safe, and Recoverable Solvent
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In this study, we have employed dithiooxamide, a solid, odorless, and commercially available compound, as a sulfur surrogate for the preparation of dialkyl sulfides from available alkyl halides in high yields. This sulfur transfer agent was also used for a copper-catalyzed high-yielding preparation of diaryl sulfides from their available aryl halides and for the preparation of thia-Michael adducts in high yields. All the reactions were performed under odorless conditions in wet PEG200 (PEG = polyethylene glycol), which is an eco-friendly, safe, and recoverable solvent. The protocols were easily applicable to large-scale operation.
- Firouzabadi, Habib,Iranpoor, Nasser,Gorginpour, Forough,Samadi, Arash
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supporting information
p. 2914 - 2920
(2015/05/04)
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- Convenient and robust one-pot synthesis of symmetrical and unsymmetrical benzyl thioethers from benzyl halides using thiourea
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A series of symmetrical and unsymmetrical benzyl thioethers have been synthesised using a one-pot reaction from benzyl halides and thiourea. This procedure avoids the isolation or handling of malodorous thiols and generates high yields of benzyl thioether
- Eccles, Kevin S.,Elcoate, Curtis J.,Lawrence, Simon E.,Maguire, Anita R.
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experimental part
p. 216 - 228
(2010/10/03)
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- Araliphatic sulfonium and their use
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Sulfonium salts of the formulae I to IV STR1 in which A is C1 -C12 alkyl, C3 -C8 cycloalkyl, C4 -C10 cycloalkylalkyl, phenyl which is unsubstituted or mono- or polysubstituted by C1 -C8 alkyl, C1 -C4 alkoxy, halogen, nitro, phenyl, phenoxy, alkoxycarbonyl having 1-4 C atoms in the alkoxy radical or acyl having 1-12 C atoms, Ar, Ar1 and Ar2, independently of one another, are each unsubstituted or mono- or polysubstituted phenyl, or naphthyl which is unsubstituted or mono- or polysubstituted each arylene is an unsubstituted or mono- or polysubstituted phenylene or unsubstituted or mono- or polysubstituted naphthylene and Q? is SbF6-, AsF6- or SbF5 OH- are valuable curing agents and curing accelerators in the heat-curing of cationically polymerizable compounds, preferably epoxy resins.
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- Cobalt carbonyl catalyzed reaction of mercaptans with Schiff bases and carbon monoxide
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Thiophenols and p-methylbenzyl mercaptan react with Schiff bases and carbon monoxide in benzene, in the presence of cobalt carbonyl, to give amides as the pricipal products.These amides arise from cleavage of the carbon-nitrogen double bond of the reactant imine.The reaction is applicable to a variety of Schiff bases (i.e. aliphatic, benzylic, aromatic).Thioesters and olefins are usually obtained as reaction by-products.
- Antebi, Shlomo,Alper, Howard
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p. 2010 - 2012
(2007/10/02)
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- Desulfurization of benzylic mercaptans by triiron dodecacarbonyl under acidic and biphasic conditions
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The biphasic reaction of benzylic mercaptans with triiron dodecacarbonyl, 48-50% tetrafluoroboric acid, and benzene affords desulfurized products in good to excellent yields. This reaction is superior to that effected in the presence of sodium dodecylbenzenesulfonate, a phase transfer agent for acidic processes.
- Alper, Howard,Sibtain, Fazle
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p. 225 - 229
(2007/10/02)
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- COBALT CARBONYL CATALYZED REACTIONS OF DISULFIDES: CARBONYLATION TO THIOESTERS AND DESULFURIZATION TO SULFIDES.
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Aromatic and benzylic disulfides react with carbon monoxide and a catalytic amount of cobalt carbonyl to give thioesters and carbonyl sulfide, while the presence of t-butyl peroxide results in the formation of sulfides in high yields.
- Antebi, Shlomo,Alper, Howard
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p. 2609 - 2612
(2007/10/02)
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- PHASE TRANSFER CATALYZED DESULFURIZATION REACTIONS
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Mercaptans react with triiron dodecarbonyl or dicobalt octacarbonyl, under phase transfer catalysis conditions, to give hydrocarbons in good yields.
- Alper, Howard,Sibtain, Fazle,Heveling, Josef
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p. 5329 - 5332
(2007/10/02)
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- Nucleophilic Substitution on 4-Methylbenzyl Thiocyanate with Nucleophiles
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The reactions of 4-methylbenzyl thiocyanate (1) with several nucleophiles have been investigated.Compound 1 possesses three electrophilic sites, i.e., benzylic carbon, sulfur and cyano carbon, to receive nucleophilic attack.PhS- and CN- which have HOMO's of high energy levels appear to attack preferentially the sulfur atom.MeO- was found to attack preferably the cyanide carbon, while amines which have HOMO's of low energy levels prefer benzylic carbon to attack.The nucleophilic substitution on the sulfur or the cyanide carbon generates CN- or p-xylene-α-thiolate anion, strong nucleophiles, as the primary products, which then initiate the complex secondary reactions.The selective reactivities of three attacking sites for nucleophiles in 1 have been rationalized in terms of MO theory.
- Oae, Shigeru,Yamada, Norihiro,Fujimori, Ken,Kikuchi, Osamu
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p. 248 - 256
(2007/10/02)
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- Preparation of arylsulphonium salts
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A process for the production of an arylsulphonium salt, comprising reacting an aromatic compound of the formula in which Ar is an aromatic radical with a sulphoxide of the formula STR1 in which R1 and R2 each independently is an aliphatic or aromatic radical or, together, a divalent radical, in the presence of hydrogen fluoride. The products are known and can be converted to arylthioethers which are intermediates for other known syntheses.
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