Über Pseudocinchonin und das Verhalten von Hydrochlorcinchonin

Ohne ZusammenfassungEs sei mir gestattet, auch an dieser Stelle meinem hochverehrten Lehrer, Herrn Prof. Dr. Zd. H. Skraup, für das während meiner ganzen Studienzeit mir entgegengebrachte Interesse und Wohlwollen, sowie ganz besonders für die Unterstützung und Förderung bei Ausarbeitung der vorliegenden Dissertation herzlich und aufrichtig zu danken.     

Optimization of simulated moving bed plants with low efficient stationary phases: separation of fructose and glucose

An optimization procedure for simulated moving bed (SMB) plants with low efficient stationary phases is presented. The new aspect is that the desorbent consumption can be cut by 70% by running the plant with lower internal liquid flows and a corresponding larger switch time while the productivity is kept constant. This concept was validated by the separation of fructose and glucose in water on a calcium resin with an eight-column SMB plant. The separation can be predicted well by a true moving bed (TMB) and a simulated moving bed simulation. Adsorption isotherms were determined up to 300 kg/m3 for glucose and 500 kg/m3 for fructose from 25 to 80 degrees C. Experimental SMB runs were performed over a wide range of feed concentrations (10-350 kg/m3) and temperatures (25-80 degrees C). The strong influence of the delay volume is pointed out. For an experimental run with high feed concentration a complete set of data is presented. To reduce biological growth separation at 80 degrees C is recommended.     

Na5AlF2(PO4)2: Darstellung,Kristallstruktur und Ionenleitfähigkeit

Na₅AlF₂(PO₄)₂: Synthesis, Crystal Structure and Ionic Conductivity Two different procedures (precipitation from aqueous solution and solid state reaction) for the synthesis of hitherto unknown Na₅AlF₂(PO₄)₂ were optimized. The crystal structure was determined using diffractometer data (P3 , a = b = 10.483(1), c = 6.607(1) Å, MoKα, 1080 independent reflections, R_w = 0.025). PO₄-tetrahedra and AlO₄F₂-“octahedra” are connected via common vertices forming a twodimensionally extended heteropolyanion. Sodium is located in interconnected spacings of the [AlF₂(PO₄)₂]-part of the structure. Ionic conductivity as expected because of these structural features was affirmed experimentally.     

Study of feed temperature control of chromatography using computional fluid dynamics simulation

Recently preparative high-performance liquid chromatography (HPLC) has been used more and more frequently to separate drugs and natural substances. However, large-scale HPLC easily tends to reduce the yield and purity of the product. Hydrodynamic and heat factors play an important roles. Generally, in a large-scale HPLC column, the tracer profile inside column will take on a parabolic shape because of the distributor, which will impact the separation performance of the column. With the inlet temperature suitably lower than the wall temperature, this situation could be improved to some extent. In this work, some experiments were conducted using HPLC, with a column 10 cm in diameter to determine the optimal temperature difference between wall and inlet temperatures. The wall temperature was fixed at about 30 degrees C and the inlet temperature varied from 15 to 30 degrees C. The flow-rate of the eluent, methanol, was 300 ml/min. The experimental result was simulated using CFD software FLUENT 4.4.4. The simulated temperature field fitted the experimental one very well and the simulated flow, temperature and tracer distribution inside column could provide good explanation of separation performance under different conditions. In addition, the simulation could at least approximately predict the optimal temperature difference.     

Biologically active compounds through catalysis: efficient synthesis of N-(heteroarylcarbonyl)-N'-(arylalkyl)piperazines

A practical route for the synthesis of new biologically active 5-HT(2 A) receptor antagonists has been developed. In only three catalytic steps, this class of central nervous system (CNS) active compounds can be synthesized efficiently with high diversity. As the initial step, an anti-Markovnikov addition of amines to styrenes provides an easy route to N-(arylalkyl)piperazines, which constitute the core structure of the active molecules. Here, base-catalyzed hydroamination reactions of styrenes with benzylated piperazine proceeded in high yield even at room temperature. After catalytic debenzylation, the free amines were successfully carbonylated with different aromatic and heteroaromatic halides and carbon monoxide to yield the desired compounds in good to excellent yields. The two key reactions, base-catalyzed hydroamination of styrenes and palladium-catalyzed aminocarbonylation of haloarenes/heterocycles, showed tolerance towards various functional groups, thereby demonstrating the potential to synthesize a wide variety of new derivatives of this promising class of pharmaceuticals.     

Total Synthesis of Nominal Gobienine A

The lichen‐derived glycoconjugate gobienine A is structurally more complex than most glycolipids isolated from higher plants by virtue of the all‐cis substituted γ‐lactone substructure embedded into its macrocyclic frame. A concise entry into this very epimerization‐prone and hence challenging structural motif is presented, which relies on an enantioselective cyanohydrin formation, an intramolecular Blaise reaction, a palladium‐catalyzed alkoxycarbonylation, and a diastereoselective hydrogenation of the tetrasubstituted alkene in the resulting butenolide. This strategy, in combination with ring‐closing olefin metathesis for the formation of the macrocyclic perimeter, allowed the proposed structure of gobienine A ( 1 ) to be formed in high overall yield. The recorded spectral data show that the structure originally attributed to gobienine A is incorrect and that it is not the epimerization‐prone ester site on the butanolide ring that is the locus of misassignment; rather, the discrepancy must be more profound.     

A Hybrid Ring‐Opening Metathesis Polymerization Catalyst Based on an Engineered Variant of the β‐Barrel Protein FhuA

A β‐barrel protein hybrid catalyst was prepared by covalently anchoring a Grubbs–Hoveyda type olefin metathesis catalyst at a single accessible cysteine amino acid in the barrel interior of a variant of β‐barrel transmembrane protein ferric hydroxamate uptake protein component A (FhuA). Activity of this hybrid catalyst type was demonstrated by ring‐opening metathesis polymerization of a 7‐oxanorbornene derivative in aqueous solution.     

Arene Ruthenium(II) Complexes Bearing the κ-P or κ-P,κ-S Ph2P(CH2)3SPh Ligand

Neutral [Ru(η⁶-arene)Cl₂{Ph₂P(CH₂)₃SPh-κP}] (arene = benzene, indane, 1,2,3,4-tetrahydronaphthalene: 2a, 2c and 2d) and cationic [Ru(η⁶-arene)Cl(Ph₂P(CH₂)₃SPh-κP,κS)]X complexes (arene = mesitylene, 1,4-dihydronaphthalene; X = Cl: 3b, 3e; arene = benzene, mesitylene, indane, 1,2,3,4-tetrahydronaphthalene, and 1,4-dihydronaphthalene; X = PF₆: 4a–4e) complexes were prepared and characterized by elemental analysis, IR, ¹H, ¹³C and ³¹P NMR spectroscopy and also by single-crystal X-ray diffraction analyses. The stability of the complexes has been investigated in DMSO. Complexes have been assessed for their cytotoxic activity against 518A2, 8505C, A253, MCF-7 and SW480 cell lines. Generally, complexes exhibited activity in the lower micromolar range; moreover, they are found to be more active than cisplatin. For the most active ruthenium(II) complex, 4b, bearing mesitylene as ligand, the mechanism of action against 8505C cisplatin resistant cell line was determined. Complex 4b induced apoptosis accompanied by caspase activation.