63823-56-3

Upstream product

• 16118-29-9 4-Nitro-benzoesaeure-benzylthiolcarbonsaeure-anhydrid 
• 100-44-7 benzyl chloride 
• 62-23-7 4-nitro-benzoic acid 
• 100-53-8 phenylmethanethiol 
• 555-16-8 4-nitrobenzaldehdye 
• 6313-36-6 benzyl thiosulphate 
• 122-04-3 4-nitro-benzoyl chloride 

Downstream Products

• 100-02-7 4-nitro-phenol 
• 123-30-8 4-amino-phenol 
• 100-53-8 phenylmethanethiol 
• 154424-50-7 benzyl 4-nitrobenzenecarbodithioate 

Relevant academic research and scientific papers

Methanesulfonic anhydride-promoted sustainable synthesis of thioesters from feedstock acids and thiols

Abstract: An unprecedented metal-, halogen- and solvent-free, MSAA-promoted S-carbonylation of thiols with feedstock acids has been developed. This new transformation provides an efficient and atom-economic strategy for the synthesis of thioesters in a single operation from readily available and inexpensive starting materials. The reaction avoids the use of expensive and hazardous coupling reagents, bases and generates water as the only by-product, thus making this chemical synthetic process more viable, environment-friendly and contributing towards sustainable chemistry. Graphic abstract: [Figure not available: see fulltext.].

Water-soluble alkyne amide condensing agent as well as preparation method and application thereof

The invention discloses a water-soluble alkyne amide condensing agent and an application method of the water-soluble alkyne amide condensing agent in synthesis of amide, polypeptide, ester and thioester compounds. The alkyne amide condensing agent has good performance and can efficiently and conveniently promote formation of amide bonds and ester bonds, alpha-chiral centers of carboxylic acid is free of racemization in the reaction process, carboxylic acid activation and a subsequent amidation reaction can be performed spontaneously, and extra additives and catalysts are not needed. After amidation and esterification reactions are finished, reaction by-products and the excessive alkyne amide condensing agent can be converted into substances capable of being dissolved in water through treatment by a weakly-acidic aqueous solution, and then high-purity products can be obtained through extraction and/or recrystallization. The whole process is simple to operate, has the characteristics ofconvenience in purification, wide application range, economic performance and environmental protection, conforms to the direction of green chemistry in modernization, and has good application prospects.

Water-removable ynamide coupling reagent for racemization-free syntheses of peptides, amides, and esters

A novel ynamide coupling reagent, the by-product of which can be removed by water, was reported. It promotes the direct coupling between carboxylic acids and amines, alcohols or thiols to provide amides, peptides, esters and thioesters, respectively. No detectable racemization was observed for all the coupling reactions of carboxylic acids containing an α-chiral center. Importantly, a simple acidic aqueous work-up removed the by-product readily to afford pure coupling products in good to excellent yields without the use of column chromatography, thus making this method more environmentally benign, user friendly and cost-effective. The robustness of the water-removable ynamide coupling reagent was further exemplified by the racemization/epimerization-free synthesis of carfilzomib, in which no column chromatography purification was involved for the entire 12-step synthesis.

Microwave-assisted direct thioesterification of carboxylic acids

A one-pot synthesis of thioesters directly from carboxylic acids, N,N′-diphenylthiourea, triethylamine, and primary alkyl halides is described. Microwave-assisted heating and a catalytic amount of 4- (dimethylamino)pyridine (DMAP) further improved the yields. Both aromatic and aliphatic carboxylic acids were converted to the corresponding thioesters, and many functional groups were compatible with this reaction. Several possible reaction intermediates were investigated, and the quaternary ammonium salts, derived from alkyl halides and tertiary amines, were the intermediates to yield thioesters. A new reaction mechanism for this thioesterification is proposed.

Harnessing the catalytic behaviour of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP): An expeditious synthesis of thioesters

A novel, efficient, metal-, base- and acid-free straightforward protocol has been developed for the construction of useful thioesters. The immense catalytic potential of HFIP for promoting the thiocarbonylation of acyl halides and thiols is disclosed. HFIP was recovered with ease and reused for further reactions without any loss of reactivity. Both aryl and alkyl thiols bearing electron-donating and electron-withdrawing groups as well as aryl- and alkyl acyl halides worked well in this reaction. Inexpensive precursors, short reaction time, obviating workup, high atom economy, and gram-scale preparation are the significant features of the developed eco-friendly route for S-carbonylation of thiols.

N-heterocyclic carbene catalysed oxidative coupling of aldehydes with alcohols/thiols and one-pot oxidation/esterification of allylic alcohols

A versatile carbene-catalysed oxidation protocol involving N-heterocyclic carbene catalysts and 2,2,6,6-tetramethylpiperidine N-oxyl (TEMPO) is described for the synthesis of esters, cinnamic acids, and thioesters. A wide range of esters, thioesters, and cinnamic acids were obtained by metal-free coupling of aldehydes with aliphatic, allylic and aromatic alcohols, benzyl mercaptan, and water. In addition to the oxidative coupling of aldehydes with nucleophiles, dehydrogenation of saturated aldehydes and oxidation of allylic alcohols were found under our oxidative coupling conditions. Unlike other TEMPO-mediated oxidative esterification reactions, this reaction does not proceed through a TEMPO ester intermediate to form esters and thioesters. N-Heterocyclic carbene complexes catalyse various oxidative coupling reactions in the presence of TEMPO. A variety of α,β-unsaturated and saturated esters, and aromatic esters and thioesters were synthesised. Copyright

Substituted thiobenzoic acid S-benzyl esters as potential inhibitors of a snake venom phospholipase A2: Synthesis, spectroscopic and computational studies

4-Chlorothiobenzoic acid S-benzyl ester (I), 3-nitrothiobenzoic acid S-benzyl ester (II), 4-nitrothiobenzoic acid S-benzyl ester (III) and 4-methylthiobenzoic acid S-benzyl ester (IV) were prepared and characterized by 1H and 13C NMR, Mass spectrometry and IR spectroscopy. Quantum chemical calculations were performed with Gaussian 09 to calculate the geometric parameters and vibrational spectra. Phospholipase A2 (PLA2) was purified from Crotalus durissus cumanensis venom by molecular exclusion chromatography, followed by reverse phase-high performance liquid chromatography. Two studies of the inhibition of phospholipase A 2 activity were performed using phosphatidilcholine and 4-nitro-3-octanoyloxybenzoic acid as substrates, in both cases compound II showed the best inhibitory ability, with 74.89% and 69.91% of inhibition, respectively. Average percentage of inhibition was 52.49%. Molecular docking was carried out with Autodock Vina using as ligands the minimized structures of compounds (I-IV) and as protein PLA2 (PDB code 2QOG). The results suggest that compounds I-IV could interact with His48 at the active site of PLA2. In addition, all compounds showed Van der Waals interactions with residues from hydrophobic channel of the enzyme. This interaction would impede normal catalysis cycle of the PLA2.

NHC-catalyzed thioesterification of aldehydes by external redox activation

The NHC-catalyzed thioesterification of aromatic or aliphatic aldehydes with a range of thiols was developed in the presence of a stoichiometric amount of an organic oxidant. Among the oxidants examined, phenazine was shown to give the best results in terms of chemical yield and compatibility with thiols.