Chemistry of Spontaneous Alkylation of Methimazole with 1,2-Dichloroethane

Spontaneous S-alkylation of methimazole (1) with 1,2-dichloroethane (DCE) into 1,2-bis[(1-methyl-1H-imidazole-2-yl)thio]ethane (2), that we have described recently, opened the question about its formation pathway(s). Results of the synthetic, NMR spectroscopic, crystallographic and computational studies suggest that, under given conditions, 2 is obtained by direct attack of 1 on the chloroethyl derivative 2-[(chloroethyl)thio]-1-methyl-1H-imidazole (3), rather than through the isolated stable thiiranium ion isomer, i.e., 7-methyl-2H, 3H, 7H-imidazo[2,1-b]thiazol-4-ium chloride (4a, orthorhombic, space group Pnma), or in analogy with similar reactions, through postulated, but unproven intermediate thiiranium ion 5. Furthermore, in the reaction with 1, 4a prefers isomerization to the N-chloroethyl derivative, 1-chloroethyl-2,3-dihydro-3-methyl-1H-imidazole-2-thione (7), rather than alkylation to 2, while 7 further reacts with 1 to form 3-methyl-1-[(1-methyl-imidazole-2-yl)thioethyl]-1H-imidazole-2-thione (8, monoclinic, space group P 2₁/c). Additionally, during the isomerization of 3, the postulated intermediate thiiranium ion 5 was not detected by chromatographic and spectroscopic methods, nor by trapping with AgBF₄. However, trapping resulted in the formation of the silver complex of compound 3, i.e., bis-{2-[(chloroethyl)thio]-1-methyl-1H-imidazole}-silver(I)tetrafluoroborate (6_, monoclinic, space group P 2₁/c), which cyclized upon heating at 80 °C to 7-methyl-2H, 3H, 7H-imidazo[2,1-b]thiazol-4-ium tetrafluoroborate (4b, monoclinic, space group P 2₁/c). Finally, we observed thermal isomerization of both 2 and 2,3-dihydro-3-methyl-1-[(1-methyl-1H-imidazole-2-yl)thioethyl]-1H-imidazole-2-thione (8), into 1,2-bis(2,3-dihydro-3-methyl-1H-imidazole-2-thione-1-yl)ethane (9), which confirmed their structures.     

Preparation of Hierarchical Porous Activated Carbon from Banana Leaves for High-performance Supercapacitor: Effect of Type of Electrolytes on Performance

We demonstrate a facile efficient way to fabricate activated carbon nanosheets (ACNSs) consisting of hierarchical porous carbon materials. Simply heating banana leaves with K₂CO₃ produce ACNSs having a unique combination of macro-, meso- and micropores with a high specific surface area of ∼1459 m² g⁻¹. The effects of different electrolytes on the electrochemical supercapacitor performance and stability of the ACNSs are tested using a two-electrode system. The specific capacitance (C_sp) values are 55, 114, and 190 F g⁻¹ in aqueous 0.5 M sodium sulfate, organic 1 M tetraethylammonium tetrafluoroborate in acetonitrile, and pure ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF₆]) electrolytes, respectively. The ACNSs also shows the largest potential window of 3.0 V, the highest specific energy (59 Wh kg⁻¹) and specific power (750 W kg⁻¹) in [BMIM][PF₆]. A mini-prototype device is prepared to demonstrate the practicality of the ACNSs.     

Diels-Alder reactions in pyridinium based ionic liquids

Diels-Alder reactions have been investigated in pyridinium based ionic liquids. These solvents are found to be more effective compared to the organic solvent studied, in enhancing the reaction rate and product yields. Recycled ionic liquids also gave excellent results.     

The use of potassium alkynyltrifluoroborates in Mannich reactions

Potassium alkynyltrifluoroborates react with amines and salicylaldehydes in the presence of benzoic acid to generate highly functionalized amines. Ionic liquids such as butylmethylimidazolium tetrafluoroborate (BmimBF₄) are suitable solvents for the reaction.     

Novel photo-induced oxidative cyclization of 1,3-dimethyl-5-(1-arylmethylidene)pyrimidine-2,4,6(1,3,5H)-triones: synthesis and properties of areno[5,6]pyrano[2,3-d]pyrimidine-2,4(1,3H)-dionylium ions and their photo-induced autorecycling oxidizing reaction toward some amines

Novel photo-induced oxidative cyclization was accomplished to synthesize areno[b]pyrimido[5,4-e]pyran-2,4(1,3H)-dionylium ions 13a-c⁺·ClO₄⁻. Furthermore, 13a-c⁺·BF₄⁻ and their phenyl-substituted derivatives 19a,b⁺·BF₄⁻ were alternatively synthesized by the reaction of salicylaldehyde and its naphthyl derivatives with barbituric acids and subsequent treatment with aq. HBF₄. Structural characteristics of 13a-c⁺ and 19a,b⁺ were clarified on inspection of the UV-vis and NMR spectral data as well as X-ray crystal analyses. The electrochemical properties were studied by the CV measurement. In a search for reactivity, reactions of 13a-c⁺·BF₄⁻ with some nucleophiles, hydride, benzylamine, and H₂O, were also carried out. The photo-induced autorecycling oxidation reactions of 13a-c⁺·BF₄⁻ toward some amines under aerobic conditions were carried out to give the corresponding imines (isolated by converting to the corresponding 2,4-dinitrophenylhydrazones) in 643-3600% yield (recycling number of 13a-c⁺·BF₄⁻: 6.4-36.0).     

Addition compounds of nucleophiles and 3-ethylthio-6-oxo-6H-1,2-dithiolo[4,3-c]1,2-dithiolium tetrafluoroborate. Synthesis of 3H,6H-1,2-dithiolo[4,3-c]1,2-dithiole-3-one-6-thione

Summary A smooth method of synthesizing 3H, 6H-1,2-dithiolo[4,3-c]1,2-dithiole-3,6-dithione (3), and also its partial desulfuration to yield 3H, 6H-1,2-dithiolo[4,3-c]1,2-dithiole-3-one-6-thione (4) is presented. The ethylation product5 of the monothione4 reacts with various nucleophilic reagents to form remarkably stable adducts. The adducts of5 with methanol,tert-butyl mercaptan, and with aniline could be isolated and characterized by their¹H-NMR spectra.

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Anlagerungsverbindungen von Nukleophilen an 3-Ethylthio-6-oxo-6H-1,2-dithiolo[4,3-c]1,2-dithioliumtetrafluoroborat. Synthese von 3H,6H-1,2-Dithiolo[4,3-c]1,2-dithiol-3-on-6-thion

Zusammenfassung Eine glatte Synthese für 3H,6H-1,2-Dithiolo[4,3-c]1,2-dithiol-3,6-dithion (3) und für dessen partielle Entschwefelung zu 3H,6H-1,2-Dithiolo[4,3-c]1,2-dithiol-3-on-6-thion (4) wird angegeben. Das Ethylierungsprodukt5 des Monothions4 reagiert mit unterschiedlichen Nukleophilen zu bemerkenswert stabilen Addukten. Die Addukte mit Methanol,tert.-Butylmercaptan und mit Anilin wurden isoliert und durch ihr¹H-NMR-Spektrum charakterisiert.

     

The Electrochemistry of Vitamin B12 in Ionic Liquids and Its Use in the Electrocatalytic Reduction of Vicinal Dibromoalkanes

We present the first electrochemical study in ionic liquid media of cyanocobalamin (vitamin B₁₂), a biologically important molecule, and show its suitability as catalyst in the electroreduction of dibromoalkanes.     

Selective Thioacetalization of Aldehydes Catalyzed by Aqueous Zinc Tetrafluoroborate

Abstract

A wide range of cyclic dithioacetals are prepared from the corresponding aldehydes in the presence of aqueous solution of zinc tetrafluoroborate.     

Liquid–liquid equilibria of ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate and sodium citrate/tartrate/acetate aqueous two-phase systems at 298.15 K: Experiment and correlation

Binodal curves of the aqueous 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF₄) + sodium citrate (Na₃C₆H₅O₇), [Bmim]BF₄ + sodium tartrate (Na₂C₄H₄O₆) and [Bmim]BF₄ + sodium acetate (NaC₂H₃O₂) systems have been determined experimentally at 298.15 K. The Merchuk equation was used to correlate the binodal data. The effective excluded volume (EEV) values obtained from the binodal model for these three systems were determined. The binodal curves and EEV both indicate that the salting-out abilities of the three salts follow the order: Na₃C₆H₅O₇ > Na₂C₄H₄O₆ > NaC₂H₃O₂. The liquid–liquid equilibrium (LLE) data were obtained by density determination and binodal curves correlation of these systems. Othmer–Tobias and Bancraft, and Setschenow equations were used for the correlation of the tie-line data. Good agreement was obtained with the experimental tie-line data with both models.     

Direct Electrochemistry of Myoglobin in a Nafion‐Ionic Liquid Composite Film Modified Carbon Ionic Liquid Electrode

In this paper two kinds of ionic liquids (ILs) were used for the construction of a myoglobin (Mb) electrochemical biosensor. Firstly a hydrophilic ionic liquid of 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIMBF₄) was used as binder to prepare a carbon ionic liquid electrode (CILE), then a Nafion and hydrophobic ionic liquid of 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIMPF₆) composite film was applied on the surface of the CILE. The direct electrochemistry of Mb in the Nafion‐BMIMPF₆/CILE was achieved with the cathodic and anodic peak potentials located at ?0.345 V and ?0.213 V (vs. SCE). The formal potential (E°′) was located at ?0.279 V, which was the characteristic of Mb Fe^III/Fe^II redox couples. The electrochemical behaviors of Mb in the Nafion‐ionic liquid composite film modified CILE were carefully investigated. The Mb modified electrode showed good electrocatalytic behaviors to the reduction of trichloroacetic acid (TCA) and NaNO₂. Based on the Nafion‐BMIMPF₆/Mb/CILE, a new third generation reagentless biosensor was constructed.