644-32-6Relevant articles and documents
Thiylation of functionalized electrophiles with sulfur in basic reductive systems
Deryagina,Russavskaya,Grabel'nykh
, p. 346 - 349 (2004)
Functionalized electrophiles, specifically acetyl chloride, benzoyl chloride, chloroacetylchloride, benzenesulfonyl chloride, and N,N,4-trichlorobenzenesulfonamide, were brought into reaction with sulfur in the systems hydrazine hydrate-NaOH and sodium sulfide-water-ethanol. The efficiencies of these systems were compared. The reaction of chloroacetyl chloride with sulfur in the system hydrazine hydrate-base afforded new types of polymeric compounds, poly[(diacylhydrazine)polysulfides]. The reaction mechanisms were discussed.
Transformation of Thioacids into Carboxylic Acids via a Visible-Light-Promoted Atomic Substitution Process
Fu, Qiang,Liang, Fu-Shun,Lou, Da-Wei,Pan, Gao-Feng,Wang, Rui,Wu, Min,Xie, Kai-Jun
supporting information, p. 2020 - 2024 (2022/03/31)
A visible-light-promoted atomic substitution reaction for transforming thiocacids into carboxylic acids with dimethyl sulfoxide (DMSO) as the oxygen source has been developed, affording various alkyl and aryl carboxylic acids in over 90% yields. The atomic substitution process proceeds smoothly through the photochemical reactivity of the formed hydrogen-bonding adduct between thioacids and DMSO. A DMSO-involved proton-coupled electron transfer (PCET) and the simultaneous generation of thiyl and hydroxyl radicals are proposed to be key steps for realizing the transformation.
Visible Light-Induced Amide Bond Formation
Song, Wangze,Dong, Kun,Li, Ming
supporting information, p. 371 - 375 (2019/11/29)
A metal-, base-, and additive-free amide bond formation reaction was developed under an organic photoredox catalyst. This green approach showed excellent functional selectivity without affecting other functional groups such as alcohols, phenols, ethers, esters, halogens, or heterocycles. This method featured a broad substrate scope, good compatibility with water and air, and high yields (≤95%). The potential utilities were demonstrated by the synthesis of important drug molecules such as paracetamol, melatonin, moclobemide, and acetazolamide.
Amide Synthesis from Thiocarboxylic Acids and Amines by Spontaneous Reaction and Electrosynthesis
Tang, Li,Matuska, Jack H.,Huang, Yu-Han,He, Yan-Hong,Guan, Zhi
, p. 2570 - 2575 (2019/06/13)
Amide bond formation is one of the most important basic reactions in chemistry. A catalyst-free approach for constructing amide bonds from thiocarboxylic acids and amines was developed. The mechanistic studies showed that the disulfide was the key intermediate for this amide synthesis. Thiobenzoic acids could be automatically oxidized to disulfides in air, thioaliphatic acids could be electro-oxidized to disulfides, and the resulting disulfides reacted with amines to give the corresponding amides. By this method, various amides could be easily synthesized in excellent yields without using any catalyst or activator. The successful synthesis of bioactive compounds also highlights the synthetic utility of this strategy in medicinal chemistry.
Visible light driven amide synthesis in water at room temperature from Thioacid and amine using CdS nanoparticles as heterogeneous Photocatalyst
Das, Sudipto,Ray, Shounak,Ghosh, Abhisek Brata,Samanta, Partha Kumar,Samanta, Suvendu,Adhikary, Bibhutosh,Biswas, Papu
, (2017/12/28)
Highly efficient photocatalytic thioacid mediated amide synthesis at room temperature using CdS nanoparticles as photocatalyst was observed under a household 30?W CFL in water. The operationally mild reaction was tolerant to a number of functional group substitutions on amine and could be scaled up to gram. This heterogeneous photocatalyst was extremely stable and could easily be recovered by simple centrifugation for at least six recycling reactions without any significant loss of catalytic performance. The possible reaction mechanism for the photocatalytic thioacid mediated amide synthesis over the CdS semiconductor has also been proposed on the basis of experimental observations.
Reaction of Thiocarboxylic Acids with N-tert-Butyl-2-halo-2-methylpropanimines
Khairullin,Gazizov,Kirillina, Yu. S.,Ivanova, S. Yu.,Bashkirtseva, N. Yu.,Karimova
, p. 111 - 113 (2018/07/29)
Reaction of N-tert-butyl-2-chloro-2-methylpropanimine with thiocarboxylic acids has proceeded by two routes, one involving nucleophilic substitution of the chlorine atom in the primary iminium salt by acylthio group, and another via reduction of its catio
Reaction of N-tert-butyl-2-haloaldimines with thiolcarboxylic acids
Khairullin,Gazizov,Kirillina, Yu. S.,Gazizova,Khayarov, Kh. R.
, p. 2736 - 2738 (2017/12/26)
The reactions of N-tert-butyl-2-chloroaldimine with thiolcarboxylic acids occurs along two pathways: nucleophilic substitution of chlorine in the primary iminium salt by acylmercapto group and reduction of the C–Cl bond in the iminium cation. The reaction
3,6-Di(pyridin-2-yl)-1,2,4,5-tetrazine (pytz) mediated metal-free mild oxidation of thiols to disulfides in aqueous medium
Samanta, Suvendu,Ray, Shounak,Ghosh, Abhisek Brata,Biswas, Papu
, p. 39356 - 39363 (2016/06/01)
Thiols are efficiently oxidized to disulfides (RSSR) in the presence of 3,6-di(pyridin-2-yl)-1,2,4,5-tetrazine (pytz) in aqueous medium, as well as in the absence of a solvent under mild and metal-free conditions. A broad range of alkyl, aryl and heterocyclic symmetrical disulfides can be easily obtained in almost quantitative yields. The X-ray single crystal structure of 2-aminocyclopent-1-ene-1-carbothioic dithioperoxyanhydride (disulfide obtained from 2-aminocyclopentene-1-dithiocarboxylic acid, ACDA) is reported. The reaction mechanism has been studied thoroughly. It is shown that the reaction proceeds through the formation of an organosulphur radical. Pytz interacts with thiol to accept one electron and produces an organosulphur radical. Pytz ultimately accepts two electrons to form H2pytz and is capable of oxidizing 2 equivalents of thiols.
Potassium Thioacids Mediated Selective Amide and Peptide Constructions Enabled by Visible Light Photoredox Catalysis
Liu, Hongxin,Zhao, Liyun,Yuan, Yunfei,Xu, Zhifang,Chen, Kai,Qiu, Shengxiang,Tan, Haibo
, p. 1732 - 1736 (2016/03/15)
A remarkable visible-light-promoted photoredox catalytic methodology involved with amines and eco-friendly potassium thioacids for amide formation was uncovered. This approach can mimic the natural coenzyme acetyl-CoA to selectively acylate amines without affecting other functional groups such as alcohols, phenols, esters, among others. The developed strategy may hold great potential for a comprehensive display of biologically interesting peptide synthesis and amino acid modification through a diacyl disulfide intermediate.
Phosphorothioate anti-sense oligonucleotides: The kinetics and mechanism of the generation of the sulfurising agent from phenylacetyl disulfide (PADS)
Scotson, James L.,Andrews, Benjamin I.,Laws, Andrew P.,Page, Michael I.
, p. 8301 - 8308 (2016/09/09)
The synthesis of phosphorothioate oligonucleotides is often accomplished in the pharmaceutical industry by the sulfurisation of the nucleotide-phosphite using phenylacetyl disulfide (PADS) which has an optimal combination of properties. This is best achieved by an initial 'ageing' of PADS for 48 h in acetonitrile with 3-picoline to generate polysulfides. The initial base-catalysed degradation of PADS occurs by an E1cB-type elimination to generate a ketene and acyldisulfide anion. Proton abstraction to reversibly generate a carbanion is demonstrated by H/D exchange, the rate of which is greatly increased by electron-withdrawing substituents in the aromatic ring of PADS. The ketene can be trapped intramolecularly by an o-allyl group. The disulfide anion generated subsequently attacks unreacted PADS on sulfur to give polysulfides, the active sulfurising agent. The rate of degradation of PADS is decreased by less basic substituted pyridines and is only first order in PADS indicating that the rate-limiting step is formation of the disulfide anion from the carbanion.
