Isobaric vapor-liquid equilibrium for binary systems containing benzothiophene

Isobaric vapor-liquid equilibrium (VLE) of the following systems was measured with a recirculation still: benzothiophene + dodecane at 99.6 kPa, benzothiophene + 1-dodecene at 100.1 kPa, and benzothiophene + 1-octanol at 100 kPa. All systems studied exhibit positive deviation from Raoult's law. A minimum temperature azeotrope was found in the systems benzothiophene + dodecane (x₁ = 0.491, P = 99.6 kPa, T = 484.72 K) and benzothiophene + 1-dodecene (x₁ = 0.185, P = 100.1 kPa, T = 484.45 K). No azeotropic behavior was found in benzothiophene + 1-octanol system at 100 kPa. The experimental results were correlated with the Wilson model and compared to COSMO-SAC predictive model. Liquid and vapor phase compositions were determined with gas chromatography. All measured data sets passed the thermodynamic consistency tests. The activity coefficients at infinite dilution are also presented.     

Uranyl(VI) complexes with a diaminobisphenol from eugenol and N-(2-aminoethyl)morpholine: Syntheses, structures and extraction studies

The syntheses and structural studies of an [O,N,O,N′]-type phenolic ligand [(N’,N’-bis(2-hydroxy-3-methoxy-5-(propen-2-yl)benzyl)-N-(2-aminoethyl)morpholine), (H₂L) and two new uranyl complexes of this ligand are described. The reaction between uranyl nitrate hexahydrate and H₂L in a 1:2 M ratio (M to H₂L) results in a uranyl complex of the formula [UO₂(HL)(NO₃)(H₂O)] (1). In the presence of a base (triethylamine), with the same molar ratio, the uranyl complex [UO₂(HL)₂]·2CH₃CN (2) is formed. The molecular structures H₂L, 1 and 2 were verified by X-ray crystallography. Both uranyl complexes are zwitterions with a neutral net charge. A comprehensive NMR-structural analyses of all compounds were performed in CDCl₃, DMSO-d₆ and pyridine-d₅. Complex 2 dissociates in all the studied NMR-solvents, forming a 1:1 complex and free ligand, but according to the spectra the formed complexes are not alike. The results of the ability of the ligand to extract the uranyl ion from water into dichloromethane are also presented.     

Synthesis of N-Monosubstituted Sulfondiimines by Metal-free Iminations of Sulfilimium Salts

Sulfondiimines are marginalized entities among nitrogen-containing organosulfur compounds, despite offering promising properties for applications in various fields including medicinal and agrochemical. Herein, we present a metal-free and rapid synthetic procedure for the synthesis of N-monosubstituted sulfondiimines that overcomes current limitations in their synthetic accessibility. Particularly, S,S-dialkyl substrates, which are commonly difficult to convert by existing methods, react well with a combination of iodine, 1,8-diazabicyclo[5.4.0]undec-7-en (DBU), and iminoiodinanes (PhINR) in acetonitrile (MeCN) to furnish the corresponding sulfondiimines in yields up to 85 % (25 examples). Valuable “free” NH-N′H-sulfondiimines can then be accessed by N-deprotection under mild reaction conditions. Several experimental observations suggest a mechanistic pathway diverging from the common radical-based iodine/iminoiodinane mechanism. Based on the experimental results in combination with data obtained by ¹H NMR spectroscopy, ESI mass spectrometry, and crystallographic analysis we propose a direct amination from PhINNs and a reaction path via a cationic iodonitrene.