Molecular Structure of 1,3,5-Tris (Trimethylstannyl) Benzene: An Electron Diffraction Study

The molecular structure of 1,3,5-tris (trimethylstannyl) benzene has been determined by gas-phase electron diffraction. The C — C bond length is in good agreement with that in benzene. In agreement with the somewhat electron-releasing character of the substituents, the endocyclic bond angles at the substituents are somewhat smaller than 120°. The mean value of Sn — C bond lengths is greater than that in tetraphenyltin and tetramethyltin. The SnMe₃ groups appear freely rotating around the C_aryl — Sn bonds. The following bond lengths (r _g) and bond angles were determined: (Sn — C)_mean 2.150 ± 0.007 Å, C — C 1.399 ± 0.005 Å, (C — H)_mean 1.105 ± 0.006 Å, < C — C(Sn) — C 117.7 ± 1.7º, < C_aryl — Sn — C_methyl 106.7 ± 0.7º < Sn — C — H 111.5 ± 0.9º.     

Thermisches Verhalten von Cyclopropa[c]chromenen

The Cyclopropa[c]chromenes 14 , trans-and cis- 15 , trans-and cis- 16 and 17 rearrange on heating > 200° in N, N-diethylaniline to give 2-alkyl-2H-chromenes 7, 8, 21, 22. The rate determining step of this rearrangement is the ‘homoelectrocyclic’ ring opening of the cyclopro-pa[c]chromenes to give ω-allyl-quinomethanes of type 4. These intermediates show fast [1,5s] and [1,7a] H-shifts, followed by electrocyclic ring closure. Deuterium labelling experiments are in agreement with this mechanism. The remarkable dependence of the rates of rearrangement with respect to the stereochemistry of the cyclopropa[c]chromenes (cf. table 2) suggests that in the first step only one of the two possible disrotatory modes of ring opening is involved.     

Hydration of acetylene on Cd2+ exchanged zeolites

The reaction takes place on Cd-containing Lewis sites, whereas the irreversible adsorption and condensation of product acetaldehyde on acidic OH groups of Cd-X, FAU catalyst results in deactivation. Preadsorbed ammonia moderates the deactivation, because it reacts with acetylene, and pyridine homologues are formed which block the accessible OH groups. Since in divalent cationic forms of clinoptilolite no OH groups are generated, Cd-clinoptilolite proved to be a catalyst of permanent activity.

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, Cd, — OH FAU, Cd-X. , .. , OH . OH, Cd- .

     

Comparative bioanalytical study of3H-deramciclane in dog plasma, using a gas chromatography-nitrogen-selective detection (GC-NPD), a new GC-radiochemical detection (GC-RD) and a liquid scintillation method

Summary A new, highly sensitive and selective gas chromatography method, using radiochemical detection (GC-DR) was developed for the selective determination of³H-labelled deramciclane and its N-desmethyl metabolite in dog plasma. Inter-day accuracy and precision, as well as system suitability of the GC-RD method was investigated during the method validation. The calibration curve was proved to be linear (r=0.9986) in a wide concentration range (13–1000 ngeqv mL⁻¹) The lower limit of quantitation (LLOQ) was 13.7 ngeqv mL⁻¹, and the limit of the detection (LOD) was 1 ngeqv mL⁻¹. Using this new GC-RD method, plasma levels of³H-labelled deramciclane and its metabolite were determined in dogs, after the administration of a single 10 mg kg⁻¹ oral dose. Pharmacokinetic curves and the calculated pharmacokinetic parameters were compared to those obtained using a previously elaborated gas chromatography-nitrogen selective detection method (GC-NPD) and to those obtained by measuring the plasma level of total radioactivity (liquid scintillation counting, LSC). Pharmacokinetic curves and the calculated pharmacokinetic parameters obtained with the two different gas chromatography detection methods (NPD and RD) showed good correlation. Comparison of these results to those acquired by total radioactivity measurement demonstrated that deramciclane was intensively metabolised. Moreover, the biological half-life (t ₁ ^2/β ) of the unknown metabolites proved to be more than a magnitude longer than the half-life of the parent compound or that of N-desmethyl metabolite. Presented at: Balaton Symposium on High-Performance Separation Methods, Siófok, Hungary, September 3–5, 1997.     

Filtering on manifolds

We coasider a partially observable diffusion process (x _t,y_t)t0 whose unobservable componentx _t lives on a submanifold M ofR ⁿ . We present some general conditions under which the conditional law ofx _t, given the observationsy _s ,s [0,t], admits a density w.r.t. a given measure on M. We characterize the analytical properties of this density by using appropriate Sobolev spaces.Research supported by the Hungarian National Foundation of Scientific Research No. 2290.     

Characterization of OV-1/FFAP-mixture coated glass capillary columns used for the separation of free fatty acids

As an alternative to acid pretreated UCON and FFAP capillaries for the analysis of wide-boiling free fatty acid mixtures, OV-1 : FFAP phase mixtures were used on high-temperature silylated inert glass capillary columns. The HETP-carrier gas velocity curves, peak asymmetry factors, coating efficiency, gas phase and stationary phase contributions to the mass transfer resistance were determined for various OV-1 : FFAP ratios. Mixed-phase capillaries showed optimum performance at a 2 : 1 OV-1 : FFAP ratio. The thermal and long-term stability of OV-1-stabilized FFAP columns surpassed those of the UCON and pure FFAP reference column used.     

Synthesis of vinca alkaloids and related compounds. 100. Stereoselective oxidation reactions of compounds with the aspidospermane and quebrachamine ring system. First synthesis of some alkaloids containing the epoxy ring

The first syntheses of the alkaloids (-)-mehranine (3), (+)-voaphylline/conoflorine (4), (+)-N(a)-methylvoaphylline/hecubine (5), and (-)-lochnericine (2) were achieved by stereoselective epoxidation starting from (-)-tabersonine (1), through intermediates with the aspidospermane and quebrachamine skeleton.     

Experiences and practical hints on using the DDRP method,illustrated by the example of the H2 + H reaction

By using the dynamically defined reaction path (DDRP) method and starting from various initial polygons, the intrinsic reaction coordinate (IRC) of the H₂ + H → H + H₂ reaction has been calculated. The numerical stability of the method is illustrated by the evolution phases of the reaction path. Techniques and experiences on the parameter choice and effects of the parameter values on the stability and computer time consumption are discussed. © John Wiley & Sons, Inc.     

Thermogravimetric studies on aluminium foils for electrolytic capacitors

Thermogravimetry was applied in studies of aluminium foils for electrolytic capacitors. Scanning electron microscopy, X-ray diffraction and surface area determination were also used in the interpretation of the results. Both the specific surface area and the capacity of the foils showed a linear relationship to the height of the oxidation step measured by TG, which was found suitable for following the processes of anodic oxidation and thermal treatment of the foils as well.     

Thermoanalytical study of nucleating effects in polypropylene composites

Nucleating and transcrystallization behaviour of additives in engineering PP composites and the effect of modified interfacial structure is the subject of this series of papers. The first part concentrates on polypropylene/liquid crystalline polyester blends. Increased crystallisation temperature and degree of crystallinity of polypropylene is characteristic to the blends containing different amount of LCP additive. Transcrystallization process governs the formation of crystalline structure in these systems in course of isothermal crystallisation at 132C. The nucleating effect of LCP gives rise to more uniform crystalline structure in the polypropylene phase.The financial support of the OTKA 014194 is acknowledged with gratitude.