13C- and 1H-NMR. Spectra of ortho-benzoquinones. On the assignment problem in 13C spectra

¹³C- and ¹H-NMR. spectra of ortho-benzoquinone 1 and its methyl derivatives have been analysed. By means of heteronuclear double resonance experiments it is shown that assignments given in the literature for the olefinic carbon resonances of 1 and of a series of substituted ortho-benzoquinones have to be inverted. ¹³C-carbonyl frequencies of various six-membered cyclic ketones are presented.     

Enzymatic synthesis of 7-deoxy-N-acetylneuraminic acid and 7-O-methyl-N-acetylneuraminic acid

7-Deoxy-N-acetylneuraminic Acid and 7-O-methyl-N-acetylneuraminic acid were synthesized through the sialic acid aldolase-catalyzed aldol addition reactions of 4-deoxy-N-acetyl-D-mannosamine and 4-O-methyl-N-acetyl-D-mannosamine, respectively, with pyruvate. The obtained sialic acids will be used as probes for the investigation of the unusual mechanism of a novel sialidase from leech.     

Determination of 1-vinyl-2-pyrrolidone in human serum by high-performance liquid chromatography

Summary A simple method is described which allows the quantification of 1-vinyl-2-pyrrolidone (NVP) in human serum. NVP is extracted from serum with diethylether and determined with HPLC/UV-detection. 1-Cyclohexyl-2-pyrrolidone serves as an internal standard. The detection limit is 0.1 mg/l. The method has shown that NVP can enter the organisms of workers occupationally exposed to this substance.     

Synthesis and Odor of Chiral Partial Structures of Khusimone. Part 1

Khusimone (1), one of the main odor-donating compounds of vetiver oil is subject of the following study on structure/odor relationship. The omittance of the ethano bridge of the tricyclic khusimone leads to a bicyclic system. The stereoselective approach to this degraded structure is described, and the olfactory properties are studied. The key step of the synthesis of the hydrindane nucleus is based on a highly diastereoselective conjugate addition to a chiral oxo-cyclopentene-2-carboxylate.     

Solvothermal Synthesis, Crystal Structure, and Properties of the First Zinc Containing Thioantimonate(III) [Zn( tren)] 2Sb 4S 8·0.75 H 2O

Yellow crystals of the title compound were obtained under solvothermal conditions reacting elemental Zn, Sb, and S in a solution of tris(2-aminoethyl)amine (=tren) and water. The compound crystallises in the monoclinic space group P2₁/c with a=13.0247(7), b=22.308(2), c=12.1776(6) Å, and =105.352(6)°. In the structure of [Zn(tren)]₂Sb₄S₈·0.75 H₂O two [Zn(tren)]²⁺ cations are bound to the [Sb₄S₈]^4– anion via S atoms. The Zn²⁺ ions are in a trigonal bipyramidal environment of four N atoms of the tetradentate tren ligand and one S atom of the [Sb₄S₈]^4– anion. The anion is formed by SbS₃ and SbS₄ units which share common corners and edges. The interconnection mode yields three different non-planar Sb₂S₂ heterorings. The shortest intermolecular Sb–S distance amounts to about 3.7Å, and taking this long separation into account undulated chains running along [001] are formed with the water molecules residing in the pocket-like cavities. Upon heating the compound decomposes in one step starting at about 240°C. The final decomposition product was identified as ZnS and Sb₂S₃ by X-ray powder diffractometry. Additionally, spectroscopic data as well as synthetic procedures for [Zn(tren)]₂Sb₄S₈·0.75 H₂O are reported.     

Inter- and intra-annular proton exchange in gaseous benzylbenzenium ions (protonated diphenylmethane)

Two distinct proton exchange reactions occur in metastable gaseous benzylbenzenium ions, generated by isobutane chemical ionization of diphenylmethane and four deuterium-labelled analogues. Whereas the proton ring-walk at the benzenium moiety is fast giving rise to a completely random intraannular proton exchange, the interannular proton exchange is surprisingly slow and competes with the elimination of benzene. A kinetic isotope effect of k_H/k_D= 5 has been determined for the interannular proton transfer, and a particularly high energy barrier of 50–75 kJ mol^?1 has been estimated. These observations are attributed to steric restrictions of the ring-to-ring proton transfer in benzylbenzenium ions and contrasted to the fast interannular proton exchange in the higher homologues.     

VNCl2(Pyridin)2 Synthese,IR-Spektrum und Kristallstruktur

VNCl₂(Pyridine)₂; Synthesis, I. R. Spectrum, and Crystal Structure VNCl₂(Pyridine)₂ is formed from the cyclothiazeno-vanadium(IV) complex [VCl(N₃S₂)(Pyridine)₂]₂ · 2 CH₂Cl₂ in boiling toluene in form of brown-red, hydrolysis sensitive crystal. It was characterized by its I.R. spectrum and an X-ray crystal structure determination. VNCl₂(Pyridine)₂crystallizes in the orthorhombic space group Pccn with four formula units per unit cell (668 observed independent reflexions, R = 0.055). Lattice constants: a = 1550, b = 924, c = 832 pm. Monomer molecules are situated on twofold rotation axes. They are stacked along the V?N axis to form columns V?N…V. The short VN bond of 160 pm corresponds to a triple bond, whereas the V…N distance of 256 pm indicates a weak interaction. The V? N(Pyridine) and V? Cl bond lengths are 213.0 and 233.5 pm, respectively.     

Optisch aktive übergangsmetall-komplexe XX. Optisch aktive cyclopentadienyl-perfluoropropyl-kobalt-komplexe mit zweizähnigen schiff-basen

In the reaction of C₅H₅ Co(C₃F₇)(CO)I with the Schiff base NN′, derived from S-(-)-?-phenylethylamine and pyridine carbaldehyde-2, the salt [C₅H₅Co(C₃F₇)NN′]⁺ I^? (Ia,b) is formed, which can be transformed to [C₅H₅ Co(C₃F₇)NN′]⁺ PF₆^? (IIa,b). The sodium salt Na⁺ [NN″]^? of the Schiff base, derived from S-(-)-α-phenylethylamine and pyrrol carbaldehyde-2, in the reaction with C₅H₅ C0(C₃F₇)(CO)I yields the neutral complex C₅H₅ Co(C₃F₇)NN″ (IIIa,b). The diastereoisomeric pairs IIa,b and IIIa,b are separated by fractional crystallisation and chromatography respectively into the optically pure components which differ in their ¹H NMR spectra. The IR, UV, CD, mass spectra and optical rotations of the new compounds IIa, IIb, IIIa and IIIb are compared.