Über die Phosphidierung des Nickels durch Phosphortrichlorid

On the Phosphidation of Nickel by Phosphorus Trichloride The phosphidation of nickel sheets by phosphorus trichloride vapor of 30 and 50 Torr has been studied kinetically by gravimetric means in the temperature range of 400–650°C in hydrogen atmosphere. The phosphidation proceeded generally according to the parabolic rate law. The parabolic rate constant increased with an increase of temperature, and its temperature dependence yielded the activation energies of about 33 and 47 kcal/mole for 400–550 and 550–650°C, respectively. X-ray and electron microprobe analyses showed that surfaces of the specimens phosphidized are made up of mixtures of Ni₂P and Ni₆P₅, and that at the phosphide/metal interface the compound Ni₂P is formed. The experiments using argon as carrier gas resulted in the formation of both the phosphides and the chlorides, and this fact could be explained in terms of thermodynamics.     

Determination of sultopride and tiapride in serum by gas chromatography using a surface ionisation detector

A sensitive and selective method has been developed for the determination of sultopride and tiapride in serum using gas chromatography with a surface ionisation detector. No interfering peaks from endogenous substances were observed. The method showed good reproducibility and accuracy, and the standard curve was linear up to 2 micrograms/ml with a correlation coefficient of 0.999. This method is applicable to pharmacokinetic studies and therapeutic drug monitoring of sultopride and tiapride.     

A New Synthetic Route to (±)-Perhydrohistrionicotoxin

Starting from ethyl 2-cyclohexen-1-carboxylate ( 3 ) the total synthesis of the perhydrohistrionicotoxin intermediate 23 was achieved in 25% overall-yield. The two key steps involve a positionally specific addition of HOBr to the oxime-olefin 7 and the alkylation of bromooxime 17 with 1-lithio-1-butyne. The latter represents a novel method for stereospecific and position-specific introduction of a nucleophilic butyl equivalent in α-position to a ketonic carbonyl group.     

Synthesis of aromatic polyamides by 1-hydroxybenzotriazole-catalyzed polycondensation of active aromatic diesters with aromatic diamines

Catalytic actions of various additives were studied in the polycondensation of di(4-nitrophenyl) isophthalate with bis(4-aminophenyl) ether in N-methyl-2-pyrrolidone, and 1-hydroxybenzotriazole (HOBt) was found to be a highly effective catalyst that yielded high-molecular-weight polyamide. In addition to the polycondensation of the 4-nitrophenyl ester, the polymerization of negatively substituted phenyl esters like di(2,4,5-trichlorophenyl) isophthalate was also accelerated by HOBt. For the HOBt-catalyzed aminolysis of esters a bifunctional concerted mechanism that involves an eight-membered transition state was proposed.     

Synthesis of poly(benzoxazole)s by direct polycondensation of dicarboxylic acids with 3,3′-dihydroxybenzidine dihydrochloride using phosphorus pentoxide/methanesulfonic acid as condensing agent and solvent

A convenient method for the synthesis of poly(benzoxazole)s of high molecular weights has been developed. These polymers were prepared readily by direct polycondensation of aromatic dicarboxylic acids containing phenyl either structure with 3,3′-dihydroxybenzidine dihydrochloride using phosphorus pentoxide/methanesulfonic acid (PPMA) as condensing agent and solvent. Polycondensations proceeded fast and was completed within 5 h at 140°C and produced poly(benzoxazole)s with inherent viscosities up to 4.6 dL/g. Model compound work was performed in detail to demonstrate the feasibility of the reaction for polymer formation. The thermogravimetry of the aromatic poly(benzoxazole)s showed 10% weight loss in air and nitrogen at 450–505°C and 465–535°C, respectively.     

Hydrothermal Synthesis of Mo-Based Oxide Catalysts and Selective Oxidation of Alkanes

Mo-V-M(=Al, Ga, Bi, Sb and Te)–O mixed oxide catalysts were synthesized hydrothermally for the first time, characterized structurally, and tested for ethane and propane oxidation after activation by various ways. These catalysts were black solids of rod-shaped (fiber like) crystals, which had a layer structure in the direction of fiber axis and a high dimensional arrangement of metal octahedra in the cross-section plane. These fresh crystalline materials became active for catalytic oxidation of alkanes after heat-treatment at 600 °C and subsequent grinding in order to increase exposed plane of the cross-section. The resulting catalysts were very active for an oxidative dehydrogenation of ethane with 80% of the ethylene selectivity in the reaction temperature range of 300 to 400 °C and also showed about 50% selectivity to acrylic acid in the propane oxidation. Multi-functional character which derived from the high dimensional structure of the catalysts and mechanism of the selective alkane oxidation were discussed.     

Fused silica capillary tube isotachophoresis using a multichannel photodiode array detector

Isotachophoresis carried out in a 0.25 mm i.d. fused-silica capillary tube yielded high resolution, compared with that in a fluorinated ethylene-propylene polymer tube. The use of an ultraviolet-visible multichannel spectrophotometer with photodiode array as detector together with a cross flow cell (volume 0.01 μl) was investigated. The system was successfully applied to the analysis of cationic dyes such as neutral red, bismarck brown, and basic fuchsine.     

Structural change of water by gelation of curdlan suspension

Phase transition of water restrained by curdlan suspension annealed at a temperature from 20 to 110°C was investigated by differential scanning calorimetry (DSC). The melting temperature of water restrained by annealed curdlan discontinuously decreased at around 60°C, while the amount of bound water calculated from enthalpy of melting increased at 60°C, regardless of water content. Using a highly sensitive DSC, curdlan suspension with various concentrations was studied. It was found that an endothermic transition was observed at ca. 58°C in a wide range of concentrations. The transition observed at 60°C is thermo-reversible and both temperature and transition enthalpy are constant even after gel formation. Well equilibrated suspension at a temperature lower than 60°C formed no gel.