A theoretical investigation of the enantioselective hydrogenation mechanism of α-ketoesters

The enantioselective hydrogenation of α-ketoesters to α-hydroxyesters over Pt/Al₂O₃ catalysts modified by cinchona alkaloids is an interesting model reaction for the investigation of heterogeneous catalysis capable of producing optically active products. The aim of the present theoretical study is to rationalize the interaction between protonated cinchona alkaloids (modifiers) and methyl pyruvate (substrate) by investigating the possible weak complexes formed by these two species. For this purpose we use molecular mechanics and the AM1 semiempirical method. The optimization leads to two stable forms of the complexes, where the substrate is bound to the modifier via hydrogen bonding between the oxygen of the α-carbonyl of pyruvate and the quinuclidine nitrogen of the alkaloid. In such complexes the methyl pyruvate is transformed into a half-hydrogenated species which can be adsorbed on the platinum surface and, after hydrogenation, leads to methyl lactate product. The results show that adsorption of the complex leading to (R)-methyl lactate is more favorable than that of the corresponding system yielding (S)-methyl lactate, which may be the key for the enantio-differentiation.     

Synthesis and absolute configuration of clemastine and its isomers (author's transl)]

Synthesis and Absolute Configuration of Clemastine and its Isomers. Condensation of 4-chloro-α-methylbenzhydrylalkohol ( 1 ) with 2-(2-chloroethyl)-1-methylpyrrolidine ( 2 ) gave an isomeric mixture of 2-[2-(p-chloro-α-methyl-=-phenylbenzyloxy)ethyl]-1-methylpyrrolidine ( 3 ) and 4-(p-chloro-=-phenylbenzyloxy)-1-methyl-hexahydroazepin ( 4 ). The separation of the four possible optically active isomers of 3 is described and their absolute configuration established by degradation to (R)- and (S)-1-methyl-2-pyrrolidineethanol ( 6 ), respectively, and by an X-ray cristallographic analysis of the quarternary methiodide of the isomer 3-A . Clemastine (3-A) is (+)-(2R)-2-[2-((αR)-(p-chloro-α-methyl-α-phenylbenzyloxy)ethyl)]-1-methylpyrrolidine.     

Identification of ochratoxin A in food samples by chemical derivatization and gas chromatography-mass spectrometry.

The contamination of foods with ochratoxin A can be determined very sensitively by high-performance liquid chromatography (HPLC) with fluorescence detection. A novel procedure is described to confirm OA-positive results quantitatively down to the HPLC detection limit of 0.1 ppb. For this, ochratoxin A in the sample extract is converted into its O-methylochratoxin A methyl ester derivative, which is identified subsequently by gas chromatography-mass spectrometry negative-ion chemical ionization and multiple ion detection modes using the hexadeuterated O-methyl-d3-ochratoxin A methyl-d3 ester derivative as internal standard for quantification. In the analysis of more than 60 contaminated samples, the procedure was found to be very accurate.     

Liquid chromatographic separation of the thyroid hormones

The liquid Chromatographic separation of 3,3',5-triiodothyronine, 3,3',5'-triiodothyronine, and thyroxine with a nonpolar stationary phase was studied as a function of pH, temperature, organic content of the mobile phase, and ionic strength using aqueous phosphate—acetonitrile, aqueous phosphate—methanol, and aqueous phosphate— n-propanol mobile phase systems. It was demonstrated that the quality of the thyroid hormone separations, as determined by normalized peak capacity values, was unchanged with temperature, remained relatively constant with increasing ionic strength, and was affected to the greatest extent by changes in pH and organic modifier content of the mobile phase. Chromatographic behavior of the compounds studied as a function of these variables was found to be consistent with existing Chromatographic theory and/or empirical observations. Recommended conditions are aqueous phosphate—methanol mobile phase, pH 2–5 (aqueous portion), and high temperature (60–70°C).     

Collisional depolarization of NO2 fluorescence as studied by Hanle effect measurements

We report on collisional depolarization of NO₂ fluorescence with use of Hanle effect (zero magnetic field level crossing) experiments. Single fine structure levels of NO₂ in several regions of the visible absorption spectrum predominantly near 593 nm and 514 nm are prepared by selective optical excitation and the depolarization of the fluorescence light versus a magnetic field is investigated. We find that the Hanle signal is in general a superposition of two Lorentzian shaped signals, each with a characteristic dependence on light intensity and NO₂ pressure. For NO₂ pressures >1 µ bar the collisional depolarization follows simple Stern-Volmer kinetics. However, an unusual pressure dependence is observed at NO₂ pressures <1 µ bar. In the same pressure range (<1 µ bar) we see also an unexpected resonance with significantly different properties as the Hanle signal.     

Chemistry of λ-2H-azaphosphirene metal complexes

In this review, important aspects of λ³-2H-azaphosphirene metal complexes are discussed in relation to synthesis, physical properties and synthetic applications; ab-initio calculations on relative energies of CH₂NP isomers and of λ³-2H-azaphosphirene metal complexes (Cr, Mo, W) are also presented. Currently, there are three routes to this unsaturated three-membered ring system, which are discussed in detail: two of them use a rearrangement of metal carbene complexes, whereas the other relies on [2+1] cycloaddition reactions of electrophilic terminal phosphanediyl complexes and carbonitriles. The structural data show characteristics of a very strained heterocyclic ring system, which partially helps to understand the reactivity of this heterocycle complex in solution. The synthetic potential of λ³-2H-azaphosphirene metal complexes is illustrated by selected examples, which demonstrate their ability to serve, under very mild conditions as precursor for various new building blocks, i.e. nitrilium phosphanylide complexes, electrophilic terminal phosphanediyl complexes and phosphavinyl-nitrene complexes.     

Activated alpha-alkyl-alpha-arylacetic acid enantiomers for stereoselective thin-layer chromatographic and high-performance liquid chromatographic determination of chiral amines

The separation of racemic benoxaprofen into the two benoxaprofen enantiomers by preparative high-performance liquid chromatography and the application of the activated enantiomers as derivatization reagents for the simultaneous stereoselective determination of chiral amines in biological material is described. Activated (+)- and (-)-benoxaprofen are both shown to be very sensitive and stable chiral fluorescence markers, applicable to thin-layer chromatography as well as to high-performance liquid chromatography.