112498-21-2

Upstream product

• 1121-30-8 1-hydroxy-2(1H)-pyridinethione 
• 2637-34-5 2-Sulfanylpyridine 
• 104-81-4 4-Methylbenzyl bromide 
• 589-18-4 4-Methylbenzyl alcohol 
• 109-09-1 2-chloropyridine 
• 109-04-6 2-bromo-pyridine 
• 2637-34-5 pyridine-2-thione 
• 104-82-5 4-Methylbenzyl chloride 

Downstream Products

• 97522-59-3 C₁₄H₁₁NOS 
• 112498-12-1 2-((4-methylbenzyl)sulfinyl)pyridine 
• 29335-87-3 2-(4-methyl-benzyl)-pyridine 

Relevant academic research and scientific papers

Promoting Effect of Crystal Water Leading to Catalyst-Free Synthesis of Heteroaryl Thioether from Heteroaryl Chloride, Sodium Thiosulfate Pentahydrate, and Alcohol

It is observed the crystal water in sodium thiosulfate pentahydrate (Na2S2O3·5H2O) can promote its multicomponent reaction with heteroaryl chlorides and alcohols, providing a facile, green, and specific synthesis of unsymmetrical heteroaryl thioethers via one-step formation of two C-S bonds under catalyst-, additive-, and solvent-free conditions. Mechanistic studies suggest that the crystal water in Na2S2O3·5H2O is crucial in generating the key thiol intermediates and byproduct NaHSO4, which then catalyzes the dehydrative substitution of alcohols with thiols to afford thioethers.

Efficient Generation of C–S Bonds via a By-Product-Promoted Selective Coupling of Alcohols, Organic Halides, and Thiourea

A metal- and base-free three-component coupling of alcohols, heteroaryl halides, and thiourea has been developed for direct and selective synthesis of heteroaryl thioethers. This method can be easily scaled up to the gram scale and extended to dialkyl thioethers, heteroaryl selenides, benzothiazoles, and some antimycobacterially-active thioethers. Mechanistic studies revealed that a by-product-promoted in situ C–O activation of alcohols to more reactive alkyl halides and slow release of the thiol and alkyl halide intermediates are the key to the high selectivity and success of the reaction. (Figure presented.).

Enantioselective Sulfoxidation Catalyzed by a Bisguanidinium Diphosphatobisperoxotungstate Ion Pair

The first enantioselective tungstate-catalyzed oxidation reaction is presented. High enantioselectivities were achieved for a variety of drug-like phenyl and heterocyclic sulfides under mild conditions with H2O2, a cheap and environmentally friendly oxidant. Synthetic utility was demonstrated through the preparation of (S)-Lansoprazole, a commercial proton-pump inhibitor. The active ion-pair catalyst was identified to be bisguanidinium diphosphatobisperoxotungstate using Raman spectroscopy and computational studies.

Versatile C(sp2)?C(sp3) Ligand Couplings of Sulfoxides for the Enantioselective Synthesis of Diarylalkanes

The reaction of chiral (hetero)aryl benzyl sulfoxides with Grignard reagents affords enantiomerically pure diarylalkanes in up to 98 % yield and greater than 99.5 % enantiomeric excess. This ligand coupling reaction is tolerant to multiple substitution patterns and provides access to diverse areas of chemical space in three operationally simple steps from commercially available reagents. This strategy provides orthogonal access to electron-deficient heteroaromatic compounds, which are traditionally synthesized by transition metal catalyzed cross-couplings, and circumvents common issues associated with proto-demetalation and β-hydride elimination.

Antimycobacterial Agents. 1. Thio Analogues of Purine

Thio analogues of purine, pyridine, and pyrimidine were prepared based on the initial activity screening of several analogues of these heterocycles against Mycobacterium tuberculosis (Mtb). Certain 6-thio-substituted purine analogues described herein showed moderate to good inhibitory activity. In particular, two purine analogues 9-(ethylcarboxymethyl)-6-(decylthio)-9H-purine (20) and 9-(ethylcarboxymethyl)-6-(dodecylthio)-9H-purine (21) exhibited MIC values of 1.56 and 0.78 μg/mL respectively against the Mtb H37Rv strain. N9-Substitution apparently enhances the antimycobacterial activity in the purine series described herein.

A congested Ru(dps)2 or Ru(dprs)2 core (dps = di-2-pyridyl sulfide; dprs = di-2-pyrimidinyl sulfide) promotes sulfur inversion of N,S-chelate thioethers containing CH2R and 2-pyridyl or 2-pyrimidinyl groups

The thioethers L [L = 4-methylbenzyl 2-pyridyl sulfide (L1), 4-chlorobenzyl 2-pyridyl sulfide (L2), 3-chlorobenzyl 2-pyridyl sulfide (L3), 1,4-bis(2-pyridylthiomethyl)benzene (L4), 4- methylbenzyl 2-pyrimidinyl sulfide (L5), and 4-chlorobenzyl 2-pyrimidinyl sulfide (L6)], containing a CH2R group bonded to the sulfur atom, were prepared and characterized. Compounds L1, L2, L3, and L4 reacted with cis-Ru(N,N-dprs)2Cl2 or cis-Ru(N,N-dps)2Cl2 (dprs = di-2-pyrimidinyl sulfide, dps = di-2-pyridyl sulfide) leading to the complexes [Ru(N,N-dprs)2(N,S-L)][PF6]2 and [Ru(N,N-dps)2(N,S-L)][PF6]2. Similar products were obtained from [Ru(N,N-dps)2(NO2)(NO)][PF6]2 and L5 or L6. As a consequence of the L ligand N,S-chelation, all the complexes contain the four-membered ring RuSCN(Ru-N). Since the ruthenium and sulfur atoms are stereogenic centres, with Δ and Λ, and R and S configurations, respectively, they led to four isomers, including the enantiomers. NMR investigations show that the sulfur inversion produces an exchange between the diastereoisomers ΔR and ΔS, as well as Lambda;S and Lambda;R. The one-dimensional band-shape analysis of the exchanging methylene proton signals showed that the inversion barriers (ΔG?298 κ) for the dprs complexes are in the 54.9-53.8 kJ mol-1 range, with the two invertomers exhibiting similar abundance. Substitution of dprs with dps affects the relative invertomer population leaving the magnitude of ΔG?298 κ (52.0-50.6 kJ mol-1) practically unchanged. Conversely, the substitution of the pyridine thioethers (L1, L2) with pyrimidine thioethers (L5, L6) influences the inversion barriers, and ΔG?298 κ values of 47.5 and 47.0 kJ mol-1 were found for [Ru(N,N-dps)2(N,S-L5)][PF6]2 and [Ru(N,N- dps)2(N,S-L6)][PF6]2, respectively. An intramolecular mechanism without any bond rupture is suggested on the basis of the ΔS? values (negative or close to zero) and the NMR spectra, temperature -reversible and concentration-independent. The contemporary presence of the congested Ru(N,N-dps)2 or Ru(N,N-dprs)2 core and sterically demanding N,S-coordinated thioether ligands is invoked to explain the low energy barrier of the process. This hypothesis is also corroborated by the different behaviour observed for the complex [Ru(bipy)2(N,S-L1)][PF6]2.

Conversion of Hydroxyl Groups in Alcohols to Other Functional Groups with N-Hydroxy-2-thiopyridone, and Its Application to Dialkylamines and Thiols

The radical decarboxylation reaction of N-alkoxyoxalyloxy-2-thiopyridone which was prepared by the reaction of alcohol, oxalyl chloride, and N-hydroxy-2-thiopyridone was studied both in the absence and presence of olefinic compounds.The same reactions with olefinic and acetylenic alcohols gave the corresponding lactone derivatives.On the other hand the unsymmetrical alkyl 2-pyridyl disulfides were obtained by the same reaction with aliphatic thiols.