Die Acidität von Silanolgruppen. Vorläufige Mitteillung

The intrinsic acidity constant K_int. of surface silanol groups has been determined by coulometric titration of silicagel at 25° in solutions of the constant ionic strength 0,1M consisting primarily of sodium perchlorate. The experimental data are consistent with      

The first bis(orotato–N,O) complex: Synthesis,crystal structure,spectroscopic and thermal characterization of (chaH)2[Cu(HOr–N,O)2(cha)] · 2H2O (cha = cyclohexylamine and HOr = orotate(2−))

The novel bis(cyclohexylaminium) cyclohexylaminebis(orotate–N,O)cuprate(II) dihydrate, (C₆H₁₅N)₂[Cu(C₅H₂N₂O₄)₂(C₆H₁₄N)] · 2H₂O, has been prepared and characterized by elemental analysis, magnetic measurements, FT-IR and UV–Vis spectroscopy, thermal analysis and X-ray diffraction. The Cu(II) complex crystallizes in the monoclinic space group P2₁/c. The copper atom in the five-coordinated (chaH)₂[Cu(HOr–N,O)₂(cha)] · 2H₂O is chelated by a deprotonated pyrimidine nitrogen atom and carboxylate oxygen atom as a bis(bidentate) ligand and the cyclohexylamine ligand completes the square-pyramidal coordination. The thermal decomposition of the complex has been predicted by the help of thermal analysis (TG, DTG and DTA).     

Iodine Oxidation of S-Trityl- and S-Acetamidomethyl-cysteine-peptides Containing Tryptophan: Conditions Leading to the Formation of Tryptophan-2-thioethers

Cystine peptides are conveniently prepared from S-acetamidomethyl- or S-trityl-protected cysteine derivatives by direct oxidation with iodine. Since the reaction proceeds through the formation of sulfenyl iodides, these highly reactive groups may substitute the indole ring of tryptophan residues, resulting in the formation of 2-thioethers. During the synthesis of the peptide hormone somatostatin, we investigated this possible side reaction. By-products of the tryptophan-2-thioether type can be produced under conditions which lead to a marked retardation of the disulfide bond formation. The largest amount of these compounds were formed when the oxidation was carried out in 90% aqueous trifluoroethanol. In model peptides in which tryptophan and cysteine residues were separated by 1 to 4 glycine residues, the ring size of the resulting thioether exerted a strong influence on the yield: in peptides with 1 and 2 glycines, only dimeric disulfides were formed. Incorporation of 3 and 4 glycine residues gave thioethers in yields of about 40% and 70% respectively. Conversely, under normal conditions of iodine oxidation, when disulfides are rapidly formed from the S-acetamidomethyl- or S-tritylcysteine residues, tryptophan-2-thioethers are produced only in insignificant amounts or not at all.     

Zweiwertige Wahrscheinlichkeitsfunktionen auf orthokomplementären Verbänden

Ohne Zusammenfassung     

Synthesis,Spectral, Thermal and Structural Characterization of mer‐Triaquaorotatoquinoxaline Cadmium(II) Dihydrate

The new orotate complex of cadmium(II) with quinoxaline, mer‐[Cd(HOr)(H₂O)₃(QX)]·2H₂O, was synthesized and characterized by elemental analysis, FT–IR spectroscopy, thermal analysis and single crystal X–ray diffraction techniques. The complex crystallizes in the triclinic system, space group . The Cd²⁺ ion exhibits a distorted octahedral coordination by one bidentate orotate, one monodentate quinoxaline and three aqua ligands. The uncoordinated water molecules link the orotate, quinoxaline and aqua ligands via O–H···O, O–H···N hydrogen bonds. Thus, an extensive network of hydrogen bonds stabilizes the crystal structure and form an infinitive three dimensional lattice. The decomposition reaction takes place in the temperature range 20–700 °C in the static air atmosphere.