14372-66-8

Upstream product

• 333-20-0 potassium thioacyanate 
• 90-04-0 2-methoxy-phenylamine 
• 540-72-7 sodium thiocyanide 
• 100-66-3 methoxybenzene 
• 5720-06-9 2-Methoxyphenylboronic acid 
• 2290-65-5 trimethylsilyl isothiocyanate 
• 7677-24-9 trimethylsilyl cyanide 
• 38452-13-0 1-methylsulfinyl-2-methoxybenzene 
• 1147550-11-5 ammonium thiocyanate 
• 492-95-5 2-methoxyphenyldiazonium tetrafluoroborate 

Downstream Products

• 33174-74-2 2,2 dithiobis(benzonitrile) 
• 1097193-02-6 1-[(difluoromethyl)thio]-2-methoxybenzene 

Relevant academic research and scientific papers

Straightforward Access to Thiocyanates via Dealkylative Cyanation of Sulfoxides

Thiocyanates, versatile building blocks in organic synthesis, are shown to be easily accessible via an interrupted Pummerer reaction of sulfoxides. This facile dealkylative functionalization proceeds under mild conditions through electrophilic activation of the sulfoxide partner. The resulting thiocyanate itself can serve as a handle for diversification in a straightforward one-pot procedure.

An electrochemical method for deborylative seleno/thiocyanation of arylboronic acids under catalyst- And oxidant-free conditions

An electrochemical deborylative seleno/thiocyanation of arylboronic acids has been well established to synthesize the corresponding aryl seleno/thiocyanates with good functional group tolerance under ambient conditions. A gram-scale reaction has been performed to highlight the advantages of the protocol. Preliminary mechanistic studies indicate that the oxidation of the seleno/thiocyanate anion occurs prior to that of the arylboronic acid substrate in galvanostatic mode, and that free radicals are involved in the process.

Electrochemical ipso-Thiocyanation of Arylboron Compounds

An operationally simple electrochemical method for the transition-metal-free ipso-thiocyanation of arylboronic acids and aryl trifluoroborates has been developed. The SCN electrophile is generated in situ by anodic oxidation of thiocyanate anions, which avoids formation of salt waste and prevents unwanted side reactions arising from chemical oxidants. The reaction proceeds regiospecifically, and the scope extends to non-activated aromatic systems. (Figure presented.).

One-pot synthesis of (ethoxycarbonyl)difluoromethylthioethers from thiocyanate sodium and ethyl 2-(trimethylsilyl)-2,2-difluoroacetate (TMS-CF2CO2Et)

An efficient one-pot cascade methodology for the synthesis of (ethoxycarbonyl)difluoromethyl thioethers is described. Benzyl, allyl, alkyl halides or diazonium salts as the starting materials together with thiocyanate sodium and TMS-CF2CO2Et in the presence of CsF or NaOAc afford a variety of the fluoroalkylthiolated products in moderate to good yields.

Synthesis of difluoromethyl thioethers from difluoromethyl trimethylsilane and organothiocyanates generated in situ

A copper-CF2H complex generated in situ from copper thiocyanate and TMS-CF2H smoothly converts organothiocyanates into valuable difluoromethyl thioethers. This reaction step can be combined with several thiocyanation methods to one-pot protocols, allowing late-stage difluoromethylthiolations of widely available alkyl halides and arenediazonium salts. This strategy enables the introduction of difluoromethylthio groups - a largely unexplored substituent with highly promising properties - into drug-like molecules. A copper-CF2H complex generated in situ from copper thiocyanate and TMS-CF2H smoothly converts organothiocyanates into valuable difluoromethyl thioethers. This reaction step can be combined with several thiocyanation methods to one-pot protocols, allowing late-stage difluoromethylthiolations of widely available alkyl halides and arenediazonium salts.

A mild copper-catalyzed aerobic oxidative thiocyanation of arylboronic acids with TMSNCS

A facile and efficient transformation of arylboronic acids to their corresponding aryl thiocyanates has been successfully developed. Based on the CuCl-catalyzed oxidative cross-coupling reaction between arylboronic acids and trimethylsilylisothiocyanate (TMSNCS) under oxygen atmosphere, the transformation can be readily conducted at ambient temperature. The newly-developed protocol provided a competitive synthetic approach to aryl thiocyanates that can tolerate a broad range of reactive functional groups and/or strong electron-withdrawing groups.

Synthesis of aryl thiocyanates via copper-catalyzed aerobic oxidative cross-coupling between arylboronic acids and KSCN

A new protocol for the preparation of aryl thiocyanates by the cross-coupling reaction of arylboronic acids with KSCN salt is described. The coupling reaction was catalyzed by 20 mol% of copper acetate in the presence of 2.0 equivalents 4-methylpyridine serving both as ligand and base under 0.2 MPa of molecular oxygen. A variety of arylboronic acids, including those with substituents at ortho position, were suitable under the reaction conditions. Georg Thieme Verlag Stuttgart · New York.

Novel process for generating useful electrophiles from common anions using Selectfluor fluorination agent

In the present work, the electrophile equivalents C1+, Br+, SCN+, and NO2+ are generated from their respective sodium, potassium, and in some cases ammonium salts (M+X-) by reaction with Selectfluor electrophilic fluorination agent in acetonitrile solution at room temperature. These generated electrophilic species subsequently react in situ with a variety of aromatic substrates containing one or more substituent groups including H, F, C1, CH3, COOH, C(O)CH3, NO2, and OR′ and NR′R″ where R′ and R″ are H or CH3. The resulting substitution products are, in most cases, isolable as pure compounds in high yield. Variations in the process include the use of other anions, electrophilic fluorination agents, and solvents.

Preparation of arylthiocyanates using N,N′-dibromo-N,N′-bis(2, 5-dimethylbenzenesulphonyl) ethylenediamine and N,N-dibromo-2,5- dimethylbenzenesulphonamide in the presence of KSCN as a novel thiocyanating reagent

N-Bromosulphonamides, synthesized via direct bromination of sulphonamides, react with several types of arene substrates in the presence of KSCN to afford aryl thiocyanates. The method appears to be generally applicable to benzenoid substrates with a wide

Improved procedure to aryl thiocyanates: A new synthetic application of dry arenediazonium o-benzenedisulfonimides

Aryl thiocyanates 3 (22 examples) were easily prepared by reaction of dry arenediazonium o-benzenedisulfonimides 1 and sodium thiocyanate (2) in anhydrous acetonitrile at room temperature (20-25 °C) in the presence of copper powder (Procedure A) and at 50 °C or room temperature without the metal catalyst (Procedure B). The yields were from very good to excellent in Procedure A (average yield = 83%), and from modest to excellent in Procedure B (average yield = 63%). In comparison with the thiocyanod-ediazoniation carried out under traditional Sandmeyer-type conditions, the yields of 3 were higher and the isothiocyanate isomers were formed only in traces. Moreover, the results obtained in the absence of copper confirm the role of the anion of salts 1 as an electron transfer agent.