Tetraarylester der μ-Imidodiphosphorsäure und ihre Thioderivate — Strukturuntersuchungen

Tetraarylesters of μ-Imido-Diphosphoric Acid and its Thio Derivatives — Structure Investigations New O,O′,O″,O?-tetratolyl- and ditolyl-diphenylesters of the μ-imido-diphosphoric acid and its mono and dithio derivatives were synthesized, compared with the corresponding tetraphenylesters and investigated by ¹H, ¹³C, and ³¹P NMR spectroscopy and X-ray crystal structure analysis. Structures of the O,O′,O″,O?-tetrakis-(2-methyl-phenyl)-μ-imidodiphosphate, 1b , as well as of the corresponding ortho-, meta- and para-tolylesters of the μ-imido-monothiodiphosphoric acid ( 2a , 2b , 2c ) were determined. All the compounds form dimers via N? H…?O hydrogen bonds in the crystal as well as in nonpolar solvents. The distances around the phosphorus atoms rise with decreasing electronegativity of the phosphorus substituents. Signs of the ²J_{P? N? P} coupling constants were determined by ¹³C{¹H, ³¹P} triple resonance experiments for some compounds. These constants become more negative owing to substitution of a phosphoryl by a thiophosphoryl group.     

De novo synthesis of 4'-ethoxy nucleoside analogues

Butenolides 5a and 13 were used as optically active templates in the de novo synthesis of 4'-disubstituted nucleoside analogues. The butenolides were reduced and acylated in situ to give acetates 10 and 14. Vorbrüggen coupling gave the protected nucleoside analogues 11 and 15. Reduction of 11 gave 4'-ethoxy-2',3'-dideoxythymidine (6) and deprotection of 15 gave 4'-ethoxy-2',3'-dideoxydidehydrothymidine (7). The cis-dihydroxylation of a variety of butenolides occurred with the major product formed from oxidation of the beta-face.     

Über die CH-Bestimmung in schwefelhaltigen Verbindungen

Zusammenfassung Verschiedene schwefelhaltige Verbindungen ergeben zu hohe Kohlenstoffwerte. Dieser Fehler kann behoben werden, indem die Einwaage im Verbrennungsschiffchen mit vorbehandeltem Cerdioxid abgedeckt oder vermischt wird.

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CH determination in containing compounds sulfur

Summary Various sulfur-containing compounds yield carbon values which are too high. This error can be eliminated by covering or mixing the aliquot in combustion boats with pretreated cerium dioxide.

     

An Analytical Method for the Separation and Determination of As(III) and As(V) in Seepage and Acid Mine Drainage Water

To avoid changes in the original As species distribution in natural water after sampling, a method of immediate separation of As(V) by anion exchange at the sampling site was developed. The procedure consists of two steps. The total concentration of arsenic is determined in one part of the water sample acidified on site. Another part of the water samples is pressed through a column filled with an anion exchanger. The As(III) species that is not redox-stable remains in the effluent of the sorbents column and can be analyzed with conventional methods after stabilization by addition of conc. HNO₃. As(V) is sorbed by the exchanger material. The As(V) concentration can be calculated as the difference between As_sol and As(III), neglecting very low contents of methylated species. Oxidation of Fe(II) by air followed by co-precipitation of arsenic with iron hydroxide was applied in field experiments to minimize the As concentration in seepage and mining water.     

C2-Symmetric 4,4′,5,5′-Tetrahydrobi(oxazoles) and 4,4′,5,5′-Tetrahydro-2,2′-methylenebis[oxazoles] as Chiral Ligands for Enantioselective Catalysis Preliminary Communication

The synthesis of a series of enantiomerically pure, C₂-symmetric 4,4′,5,5′-tetrahydro-2,2′-methylenebis[oxazoles] and 4,4′,5,5′-tetrahydro-2,2′-bi(oxazoles) is reported. Copper complexes with anionic tetrahydromethylenebis[oxazole] ligands are efficient catalysts for the enantioselective cyclopropane formation from olefins and diazo compounds (up to 96% ee in the reaction of styrene with menthyl diazoacetate). Tetrahydrobi(oxazole)iridium(I) complexes were found to catalyze transfer hydrogenations of aryl alkyl ketones with i-PrOH (up to 91% ee). Tetrahydrobi(oxazole)palladium complexes can be used as enantioselective catalysts for allylic nucleophilic substitution (up to 77% ee in the reaction of PhCH?CHCH(OAc)Ph with NaHC(COOMe)₂).     

Structure and Properties of Ethene Copolymers Synthesized by Metallocene Catalysts

Abstract

The microstructure of ethylene copolymers based on 1-hexene, 1-octene, and norbornene as comonomers was studied and related to its melting, crystallization, and glass transition behavior as well as to tensile strength.     

Quantitative Medium-Resolution NMR Spectroscopy Under Non-Equilibrium Conditions,Studied on the Example of an Esterification Reaction

Medium-resolution nuclear magnetic resonance spectroscopy is a promising tool for the monitoring of liquid reactions. For process analytical applications, the requirements of robustness and insensitivity of the spectrometer in relation to high temperatures and pressures are challenging. Within this study, a flow probe using a glass dewar is presented. Temperatures of flowing samples up to 130 °C and pressures up to 40 bar were successfully applied, and the corresponding temperature loss of the flowing sample at 2 ml min^?1 was <2.4 °C at 130 °C. Furthermore, if the process requires a measurement in a non-equilibrium state of magnetization, a comprehensive data treatment is given. For this purpose, the influences of the flow and T ₁ of the substances under investigation are studied in detail on the example of a homogeneously catalyzed esterification. In addition, data analysis schemes were designed such that the experiments directly revealed mole fractions from the spectra. Limited spectral resolutions and low signal-to-noise ratio still did not obstruct quantitative interpretation of the experiments.