4262-10-6

Upstream product

• 4548-45-2 2-chloro-5-nitropyridine 
• 930-69-8 sodium thiophenolate 
• 108-98-5 thiophenol 
• 4487-59-6 2-bromo-5-nitropyridine 
• 882-33-7 diphenyldisulfane 
• 4551-15-9 phenylthiotrimethylsilane 

Downstream Products

• 69770-61-2 5-nitro-2-benzenesulfonyl-pyridine 
• 103983-07-9 6-(phenylthio)pyridin-3-amine 

Relevant academic research and scientific papers

Alkylation of Nitropyridines via Vicarious Nucleophilic Substitution

Electrophilic nitropyridines react with sulfonyl-stabilized carbanions to give products of C-H alkylation via vicarious nucleophilic substitution. The process consists of formation of the Meisenheimer-type adduct followed by base-induced β-elimination of the sulfinic acid (e.g., PhSO2H). Mechanistic studies reveal that in the latter step alkyl substituent and adjacent nitro group tend to planarize for effective stabilization of benzyl anion, and thus, adduct of hindered isopropyl carbanion remains stable toward elimination for steric reasons.

Efficient synthesis of unsymmetrical heteroaryl thioethers and chalcogenides by alkali hydroxide-mediated SNAr reactions of heteroaryl halides and dichalcogenides

An efficient alkali hydroxide-mediated SNAr reaction of heteroaryl halides has been developed for the practical synthesis of the useful unsymmetrical heteroaryl thioethers and chalcogenides. The usually odorless, easily available, lowly toxic, and easily stored and handled diorganyl dichalcogenides can be used as safer and convenient chalcogen nucleophile precursors and diverse unsymmetrical heteroaryl chalcogenides can be obtained in good to high yields by the method.

Sulfur-silicon bond activation catalysed by Cl/Br ions: Waste-free synthesis of unsymmetrical thioethers by replacing fluoride catalysis and fluorinated substrates in SNAr reactions

In contrast to conventional activation of Nu-SiR3 reagents by F ion attributed to the strong affinity of Si to F, S-Si activation can now be achieved using Cl/Br ions of TBAX as catalysts via formation of weaker X-Si bonds and Me3Si-X. This led to a waste-free synthesis of unsymmetrical thioethers via F-free SNAr reactions of activated (hetero)aryl halides and RS-SiMe3, with recovery of the useful Me3Si-X reagent in high yields. This journal is the Partner Organisations 2014.

Catalyst-free and base-free water-promoted SNAr reaction of heteroaryl halides with thiols

A simple and efficient route for the synthesis of biaryl sulfides have been developed in aqueous medium under base- and catalyst-free conditions. A wide variety of heteroaryl halides and thiols underwent SNAr reaction to provide diaryl sulfides in good to excellent yields. The remarkable key features of the reaction include the use of water as an inexpensive and environmentally benign reaction medium, absence of any additional reagent or catalyst, and easy isolation of the products. Georg Thieme Verlag Stuttgart.

Green chemical synthesis of 2-benzenesulfonyl-pyridine and related derivatives

A practical synthesis of 2-benzenesulfonylpyridine, 1, is described which is a key starting material for the manufacture of an investigational new drug candidate at Eli Lilly and Company. An optimized green chemical process was developed which features a novel tandem SNAr/oxidation under mild conditions to produce the target sulfone, 1, in 86% yield and>99% purity. In addition, this novel, environmentally friendly methodology was found to be general for the synthesis of substituted aromatic pyridyl sulfides and sulfones.

Nucleophilic substitutions at the pyridine ring. Conformational preference of the products and kinetics of the reactions of 2-chloro-3-nitro- and 2-chloro-5-nitro-pyridines with arenethiolates

The reactions of 2-chloro-3-nitropyridine 1 and 2-chloro-5-nitropyridine 2 with arenethiolates 3a-i result in arylthio-dechlorination to give 2-arylthio-3-nitropyridines 4a-i and 2-arylthio-5-nitropyridines 5a-i. A 1H NMR study and AM1 calculat