Bisaryldithiophosphonic Acids: Synthesis and Their Reactions with Organyl Chlorosilanes,Germanes, Stannanes,and Plumbanes

A method of synthesizing arylbisdithiophosphonic acids was developed by the reaction of 2,4-diaryl 1,3,2,4-dithiadiphosphetane-2,4-disulfides with tri(ethylene glycol) and 1,4-butandiol in anhydrous benzene suspension under mild conditions. The arylbisdithiophosphonic acids thus obtained were transformed into the corresponding diammonium salts. New bis(triorganylgermyl), stannyl and plumbyl, and cyclic diphenylsilyl and diphenylplumbyl derivatives of arylbisdithiophosphonic acids were prepared from the reactions of diammonium salts of the corresponding acids with triorganylchlorogermane, chlorostannane, chloroplumbane, diphenyldichlorosilane, and diphenyl dichloroplumbane.     

Synthesis and surface-active properties of the fatty acid N-methylethylolamides and their phosphate derivatives

N-Methylethylolamides have been synthesized on the basis of vegetable oils (corn, coconut, canola, olive, cotton-seed, and palm) and modified with orthophosphoric acid. The structure of the synthesized N-methylethylolamides and their phosphate derivatives has been identified by IR and NMR spectroscopies. Surface activity of the N-methylethylolamides and their derivatives at the water–air border has been determined and their colloidal-chemical parameters (maximum surface excess concentration and minimum area per molecule at the aqueous solution–air interface, surface pressure at the critical micellization concentration (CMC), standard thermodynamic parameters of adsorption and micellization) have been calculated. The character of influence of the surfactants structure on their colloidal-chemical parameter has been clarified. The petroleum-collecting and petroleum-dispersing capacities of the synthesized surfactants have been studied on the surface of the water of various mineralization degrees.     

The Reaction of 2-Ethoxy-3-Phenylbenzo[D]-1,3, 2-Oxazaphosphorin-6-One with α-Ketocarboxylic Acid Esters: Synthesis of Benzo[d]-1,3,2-Oxazaphosphepine Derivatives

Abstract

The reactions of 2-ethoxy-3-phenylbenzo[d]-1,3,2-oxazaphosphorin-6-one with R-carbonylcarboxylic acids ethyl esters (R = CF₃, Ph, and Me) lead to the formation of seven-membered heterocycles, 2-ethoxy-9-ethoxycarbonyl-2,8-dioxo-3-phenyl-9-R-benzo[d]-1,3,2-oxazaphosphepines.     

Electronic Excitation of [(μ4‐η2‐alkyne)Rh4(CO)8(μ‐CO)2]: An In Situ UV/Vis Spectroscopy,Spectral Reconstruction and DFT Study

Reactions of three alkynes, namely, 1‐heptyne, 3‐hexyne and 1‐phenyl‐1‐butyne, with [Rh₄(CO)₉(μ‐CO)₃] are performed in anhydrous hexane under argon atmosphere with multiple perturbations of alkynes and [Rh₄(CO)₉(μ‐CO)₃]. The reactions are monitored by in situ UV/Vis spectroscopy, and the collected electronic spectra are further analyzed with the band‐target entropy minimization (BTEM) family of algorithms to reconstruct the pure component spectra. Three BTEM estimates of [(μ₄‐η²‐alkyne)Rh₄(CO)₈(μ‐CO)₂], in addition to that of [Rh₄(CO)₉(μ‐CO)₃], are successfully reconstructed from the experimental spectra. Time‐dependent density functional theory (TD‐DFT) predicted spectra at the PBE0/DGDZVP level are consistent with the corresponding BTEM estimates. The present study demonstrates that: 1) the BTEM family of algorithms is successful in analyzing multi‐component UV/Vis spectra and results in good spectral estimates of the trace organometallics present; and 2) the subsequent DFT/TD‐DFT methods provide an interpretation of the nature of the electronic excitation and can be used to predict the electronic spectra of similar transition organometallic complexes.