6317-78-8

Upstream product

• 90-90-4 (4-bromophenyl)(phenyl)methanone 
• 930-69-8 sodium thiophenolate 
• 1144-74-7 4-nitrobenzophenone 
• 111278-46-7 C₁₉H₁₄N₂OS 
• 10442-39-4 tetra-n-butylammonium cyanide 
• 591-50-4 iodobenzene 
• 345-83-5 4-fluorobenzophenone 
• 4551-15-9 phenylthiotrimethylsilane 
• 611-95-0 4-carboxybenzophenone 
• 108-98-5 thiophenol 
• 134-85-0 4-chlorobenzophenone 
• 111278-47-8 C₁₃H₉N₃S 
• 71-43-2 benzene 

Downstream Products

• 85554-39-8 diphenylmethane 
• 127855-24-7 (4-benzoylphenyl)diphenylsulfonium hexafluoroantimonate 

Relevant academic research and scientific papers

Aryl thioether compound and preparation method thereof

The invention discloses an aryl thioether compound and a synthesis method thereof, wherein an aryl carboxylic acid and a mercaptan (phenol) are used as main raw materials, and a nickel catalyst is prepared. Under the action of the phosphine ligand and the additive, the aryl carboxylic acid and the thiol (phenol) react in an organic solvent, and after the reaction is finished, the corresponding aryl thioether is obtained. The method has the advantages of low cost, high yield, simple and convenient operation, no pollution and the like, and has potential industrial application prospects. The method provides a cheap and green way for preparation of aryl thioether compounds.

Nickel Phosphite/Phosphine-Catalyzed C-S Cross-Coupling of Aryl Chlorides and Thiols

A method for the coupling of aryl chlorides and thiophenols using an air-stable nickel(0) catalyst is described. This thioetherification procedure can be effectively applied to a range of electronically diverse aryl/heteroaryl chlorides without more expensive metal catalysts such as palladium, iridium, or ruthenium. This investigation also illustrates both, a variety of thiol coupling partners and, in certain cases, the use of Cs2CO3.

Efficient synthesis of unsymmetrical diaryl thioethers via TBAF-mediated denitrative substitution of nitroarenes with PhSTMS under mild and neutral conditions

Tetrabutylammonium fluoride (TBAF) effectively facilitated a denitrative substitution reaction of electron-deficient nitroarenes with phenylthiotrimethylsilane (PhSTMS) under mild and base-free neutral conditions at room temperature, providing a practical and efficient synthesis of useful unsymmetrical diaryl thioethers. Nitroarenes bearing ortho- and para-positioned electron-withdrawing groups are the most reactive substrates, indicating that this reaction most possibly proceeded via the nucleophilic aromatic substitution (SNAr) mechanism.

Microwave-promoted TBAF-catalyzed SNAr reaction of aryl fluorides and ArSTMS: An efficient synthesis of unsymmetrical diaryl thioethers

Microwave irradiation was found to promote tetrabutylammonium fluoride catalyzed nucleophilic aromatic substitution of aryl fluorides and arylthiotrimethylsilanes, affording high yields of unsymmetrical diaryl thioethers efficiently under mild, transition-metal- and base-free conditions. Microwave showed unusual improvement on the reaction in not only the conditions and reaction rate, but also in selectivity and substrate scope. Georg Thieme Verlag Stuttgart - New York.

TBAF-catalysed facile synthesis of unsymmetrical diaryl thioethers via mild SNAr reactions

By using tetrabutylammonium fluoride as the catalyst, the synthesis of unsymmetrical diaryl thioethers could be easily achieved in high yields via a mild nucleopilic aromatic substitution reaction of aryl fluorides and phenylthiotrimethylsilane.

One-Pot Two-Step Synthesis of Aryl Sulfur Compounds by Photoinduced Reactions of Thiourea Anion with Aryl Halides

(Equation presented) The photoinduced reactions of aryl halides with the thiourea anion afford arene thiolate ions in DMSO. These species without isolation, and by a subsequent aliphatic nucleophilic substitution, S RN1 reaction, oxidation, or protonation, yield aryl methyl sulfides, diaryl sulfides, diaryl disulfides, and aryl thiols with good yields (50-80%). This is a simple and convenient approach which involves the use of the commercially available and inexpensive thiourea in a one-pot two-step process for the synthesis of aromatic sulfur compounds.

CONCERNING THE MECHANISM OF DISPLACEMENT OF NITRO GROUPS FROM ACTIVATED AROMATIC SYSTEMS

The photostimulated reactions of p-nitrobenzophenone and p-nitrobenzonitrile with a variety of nucleophiles have been investigated.Displacement of the nitro group is observed in all cases.The rates of the reactions were measured by FT-IR.The rates were slowed by substances such as sulfur, air, Galvinoxyl and p-benzoquinone.In several cases rates of loss of starting material were monitored by quenching the reaction mixtures and isolating product and starting material.These reactions also showed inhibition of their rates in the presence of inhibitors.These results indicate that the reactions are chain processes.It is concluded that the substrates are converted into their corresponding radical anions which then react with the nucleophiles in a bimolecular displacement reaction.The alternate mechanism, which involves dissociation of the radical anions, is precluded because they are known not to dissociate. Key words: Stable radical anions, nucleophilic displacements

AN SRN1 APPROACH TO SOME AROMATIC NITRILES VIA DIAZOSULFIDES

Diazosulfides 1 react with excess tetrabutylammonium cyanide in Me2SO under photon (sunlamp) or electron (Pt cathode) stimulation to give the corresponding nitriles.The results are interpreted on the basis of an SRN1 mechanism involving the (phenylthio)azo as nucleofugal group.

A CONVENIENT SRN1 SYNTHESIS OF AROMATIC NITRILES FROM DIAZONIUM SALTS VIA DIAZOSULFIDES

Properly substituted diazosulfides XC6H4-N=N-SPh (1) (either isolated or generated in situ from arenediazonium tetrafluoroborates and sodium benzenethiolate) react with tetrabutylammonium cyanide, in Me2SO under photon or electron stimulation, leading to nitriles XC6H4CN (2).Satisfactory yields of 2, comparable with those of the Sandmeyer reaction, are obtained when X= 3- or 4-CF3, 2-, 3-, or 4-CN, 4-F, 4-MeCO, 3-MeO, 4-NO2, 4-PhCO, and 4-PhSO2.For different reasons, the reaction practically fails as a useful nitrile synthesis when X= H, 4-MeO, 2-, or 3-NO2.The collected evidences agree well with the intervention of an SRN1 mechanism to which diazosulfides 1, given their easy reducibility followed by a prompt fragmentation of the C-N and N-S bonds, are convenient participating substrates.An important consequence of the mechanism involved is the behaviour of bromo and chloro derivatives (1: X= Br, Cl) which lead, through the contemporaneous introduction of two cyano functionalities, to more than satisfactory yields of the corresponding dicyanobenzenes.

Electrochemically Induced Aromatic Substitution. The 2-Nitropropane Anion, a Powerful Nucleophile in SRN1 Aromatic Substitution

In contrast with previous reports, the 2-nitropropane anion reacts readily with aryl radicals in the context of aromatic SRN1 processes.This is shown in the examples of 4-bromobenzophenone and iodobenzene under electrochemical stimulation.The substitution products do not, however, result from the simple addition of the 2-nitropropyl anion on the aryl radical.The ensuing anion radical is indeed unstable, cleaving off a nitrite ion and thus leading to the cumene derivative as the main substitution product.Comparison of reactivity with diethyl phosphite and thiophenoxide ions shows that the 2- nitropropane anion is a quite powerful nucleophile in aromatic SRN1 reactions.