2987-53-3Relevant academic research and scientific papers
A rare cobalt(III) paramagnetic derivative incorporating 1-alkyl-2-[(o-thioalkyl)phenylazo]imidazole (SMeaaiNEt): EPR, redox and magnetic interpretation
Nandi, Soumendranath,Das, Kuheli,Datta, Amitabha,Roy, Suman,Garribba, Eugenio,Akitsu, Takashiro,Sinha, Chittaranjan
, p. 75 - 81 (2017)
The condensation of 1-alkyl-2-{(o-thioalkyl)phenylazo}imidazole (SMeaaiNEt), Co(ClO4)2, 6H2O and NaN3 in methanol affords a rare Co(III) paramagnetic complex [Co(SMeaaiNEt)(N3)3] (1). Single crystal X-ray diffraction study of complex 1 reveals that the Co(III) possesses a distorted octahedral environment. The EPR study interprets an unusual high-spin Co(III) species with configuration t2g4eg2 and S?=?2. The temperature dependent magnetic interpretation agrees with the existence of intermolecular antiferromagnetic coupling on the paramagnetic Co(III) center. A cyclic voltammetry study displays for complex 1 two quasi-reversible and one irreversible responses at the negative direction which may be assigned to different reduction systems. DFT computation using optimized geometry is governed to explain the electronic nature of cobalt derivative which is in accordance with the experimental evidence.
A Mild Heteroatom (O -, N -, and S -) Methylation Protocol Using Trimethyl Phosphate (TMP)-Ca(OH) 2Combination
Tang, Yu,Yu, Biao
, (2022/03/27)
A mild heteroatom methylation protocol using trimethyl phosphate (TMP)-Ca(OH)2combination has been developed, which proceeds in DMF, or water, or under neat conditions, at 80 °C or at room temperature. A series of O-, N-, and S-nucleophiles, including phenols, sulfonamides, N-heterocycles, such as 9H-carbazole, indole derivatives, and 1,8-naphthalimide, and aryl/alkyl thiols, are suitable substrates for this protocol. The high efficiency, operational simplicity, scalability, cost-efficiency, and environmentally friendly nature of this protocol make it an attractive alternative to the conventional base-promoted heteroatom methylation procedures.
Synthesis method of benzo[b] naphtho [2,3-d] thiophene
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Paragraph 0056-0062; 0103-0106, (2022/03/27)
The present invention discloses a method for synthesizing benzo [b] naphthio [2,3-d] thiophene, comprising the following steps: 2-aminobenzo [d] thiazole as a raw material, under the action of alkali and haloalkanes, to prepare 2- (methylthio) aniline; using 2- (methylthio) aniline to prepare (2-iophenyl) (methyl) thiane preparation of 1-iodo-2-(methylsulfonyl) benzene; using 1-iodo-2-(methylsulfonyl) benzene; using 1-iodo-2-(methylsulfonyl) Benzene and compound S5 were prepared to obtain 1-(2-(methyl sulfoxide phenyl)) naphthalene, and 1-(2-(methyl sulfoxidephenyl)) naphthalene was used to obtain benzo[b]naphthalene [2,3-d]thiophene. The present invention employs a green route to obtain high yield, high quality benzo [b] naphthalene [2,3-d] thiophene.
Ionic Reactivity of 2-Isocyanoaryl Thioethers: Access to 2-Halo and 2-Aminobenzothia/Selenazoles
Bao, Lan,Dong, Jinhuan,Hu, Junlin,Jia, Mengying,Liu, Xiaoli,Sun, Shaoguang,Xu, Xianxiu
, (2022/02/23)
An ionic cascade insertion/cyclization reaction of thia-/selena-functionalized arylisocyanides has been successfully developed for the efficient and practical synthesis of 2-halobenzothiazole/benzoselenazole derivatives. This synthetic protocol, incorporating a halogen atom when forming the five-membered ring of benzothia/selenazoles, is different from the existing ones, where halogenation of the preformed benzothia/selenazole precursors happens. Additionally, a facile access to 2-aminobenzothiazoles is also achieved by the one-pot cascade reaction of 2-isocyanoaryl thioethers, iodine, and amines.
Facile syntheses of 3-trifluoromethylthio substituted thioflavones and benzothiophenes via the radical cyclization
Wang, Lu,Wang, Huaiyu,Meng, Weidong,Xu, Xiu-Hua,Huang, Yangen
supporting information, p. 389 - 392 (2020/03/04)
3-CF3S substituted thioflavones and benzothiophenes were achieved via the reactions of AgSCF3 with methylthiolated alkynones and alkynylthioanisoles, respectively, promoted by persulfate. This protocol possesses good functional group tolerance and high yields. Mechanistic studies suggested that a classic two-step radical process was involved, which includes addition of CF3S radical to triple bond and cyclization with SMe moiety.
Copper-Catalyzed Methylthiolation of Aryl Iodides and Bromides with Dimethyl Disulfide in Water
Wang, Ying-Yu,Wu, Xiang-Mei,Yang, Ming-Hua
supporting information, (2020/07/20)
An efficient route to aryl methyl sulfides through the copper-catalyzed coupling reaction of aryl iodides or bromides with dimethyl disulfide in water is described. Electron-donating and electron-withdrawing functional groups in the substrates were tolerated, and the corresponding products were obtained in moderate to good yields.
Palladium-Catalyzed 2-(Neopentylsulfinyl)aniline Directed C–H Acetoxylation and Alkenylation of Arylacetamides
Barysevich, Maryia V.,Laktsevich-Iskryk, Marharyta V.,Krech, Anastasiya V.,Zhabinskii, Vladimir N.,Khripach, Vladimir A.,Hurski, Alaksiej L.
supporting information, p. 937 - 943 (2020/02/25)
The 2-(neopentylsulfinyl)aniline directing group that promotes rapid palladium-catalyzed C–H acetoxylation and alkenylation of arylacetamides has been developed. The acetoxylation reaches completion within only 40 min at 100 °C and leads to the bis-functionalized products. Alternatively, the reaction can be carried out at room temperature, which is beneficial for sensitive substrates. For the alkenylation, we have developed a protocol in which easily available 1-substituted cyclopropanols were employed as equivalents of vinyl ketones.
Unusually Distorted Pseudo-Octahedral Coordination Environment around CoII from Thioether Schiff Base Ligands in Dinuclear [CoLn] (Ln = La, Gd, Tb, Dy, Ho) Complexes: Synthesis, Structure, and Understanding of Magnetic Behavior
Basak, Dipmalya,Leusen, Jan Van,Gupta, Tulika,K?gerler, Paul,Bertolasi, Valerio,Ray, Debashis
, p. 2387 - 2405 (2020/03/05)
The synthesis, structural characterization, and magnetic behavior of a new family of binuclear CoII-LnIII complexes of formula [LnIIICoIIL2(NO3)3]·H2O (Ln = La, 1; Gd, 2; Tb, 3; Dy, 4; Ho, 5; HL = 3-methoxy-N-(2-(methylsulfanyl)phenyl)salicylaldimine) have been reported. The chosen ligand system HL has adjacent soft ONS and hard OO binding pockets ideal for selective coordination of CoII and 4f metal ions. All the complexes 1-5 exhibit a CoII center in a highly distorted octahedral geometry with the LnIII centers in bicapped square-antiprism geometry. The unique distortion about the CoII center is introduced by the coordination of 4f metal ions in the hard OO coordination site. The distortion is further supported by the presence of -SMe groups giving an S donor atom which owing to its larger size can support large bond distances and angles. The geometry around the CoII centers is intermediate between meridional and facial geometric isomers. The magnetic properties of these complexes have been investigated by a "full model" approach using CONDON with the experimental magnetochemical analysis revealing ferromagnetic Co-Ln coupling in compounds 2-5. Ab initio calculations on the X-ray crystal structures of 1-5 paint a semiquatitative picture about the contribution of the individual anisotropic centers toward the overall magnetic properties of the compounds. Theoretical analysis predicts 1 and 2 as weak single-ion magnet (SIM) and single-molecule magnet (SMM) respectively with CoII being solely responsible for the complex anisotropy. In 2, JCoGd plays a crucial role in preserving the anisotropy contribution of Co by channelizing relaxation via a higher excited exchange doublet. Because of the inefficiency of JCoTb, JCoDy, and JCoHo in quenching single-ion Ln fragment transverse anisotropy and preserving CoII high axial anisotropy (favoring rhombicity), 3-5 lack SMM behavior.
Preparation method of o-aminothiophenol
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Paragraph 0033; 0038; 0040; 0042; 0044; 0046; 0048; 0052, (2020/12/30)
The invention provides a preparation method of o-aminothiophenol. The preparation method comprises the following steps: putting o-chloronitrobenzene into sodium methyl mercaptide, and performing heating under the action of a catalyst to carry out a methyl vulcanization reaction so as to prepare o-nitrophenyl dimethyl sulfide; putting o-nitrophenyl thioether into a solvent, and carrying out hydrogenation reduction to prepare o-aminobenzene thioether; and demethylating the o-aminothiophenol under the action of hydrobromic acid to obtain the o-aminothiophenol. The preparation method of o-aminothiophenol has the advantages of high yield and high product purity.
Identification of MsrA homologues for the preparation of (R)-sulfoxides at high substrate concentrations
Yang, Jiawei,Wen, Yuanmei,Peng, Liaotian,Chan, Yu,Cheng, Xiaoling,Chen, Yongzheng
, p. 3381 - 3388 (2019/04/01)
Here we report a methionine sulfoxide reductase A (MsrA) homologue with extremely high substrate tolerance and a wide substrate scope for the biocatalytic preparation of enantiopure sulfoxides. This MsrA homologue which was obtained from Pseudomonas alcaliphila (named paMsrA) showed good activity and enantioselectivity towards a series of aryl methyl/ethyl sulfoxides 1a-1k, with electron-withdrawing or electron-donating substituents at the aromatic ring. Chiral sulfoxides in the R configuration were prepared with approximately 50% of yield and up to 99% enantiomeric excess through the asymmetric reductive resolution of racemic sulfoxide catalyzed by the recombinant paMsrA protein. More importantly, kinetic resolution has been successfully accomplished with high enantioselectivity (E > 200) at initial substrate concentrations up to 320 mM (approximately 45 g L-1), which represents a great improvement in the aspect of the substrate concentration for the biocatalytic preparation of chiral sulfoxides.
