Ring opening of unprotected aziridines by zinc selenolates in a biphasic system

A set of chiral β-seleno amines were prepared by the ring-opening reaction of unprotected aziridines. Under acid conditions diaryl or dialkyl diselenides were reduced by zinc and treated with unprotected aziridines to produce the desired products in good yields. Chiral β-telluro amine was also obtained using this method.     

Sparse p-version BEM for first kind boundary integral equations with random loading

We consider the weakly singular boundary integral equation on a deterministic smooth closed curve with random loading g(ω). Given the kth order statistical moment of g, the aim is the efficient deterministic computation of the kth order statistical moment of u. We derive a deterministic formulation for the kth statistical moment. It is posed in the tensor product Sobolev space and involves the k-fold tensor product operator . The standard full tensor product Galerkin BEM requires unknowns for the kth moment problem, where N is the number of unknowns needed to discretize Γ. Extending ideas of [V.N. Temlyakov, Approximation of functions with bounded mixed derivative, Proc. Steklov Inst. Math. (1989) vi+121. A translation of Trudy Mat. Inst. Steklov 178 (1986)], we develop the p-Sparse Grid Galerkin BEM to reduce the number of unknowns from to .     

Approximation by Shepard type pseudo-linear operators and applications to Image Processing

Recently, it has been shown that sum and product are not the only operations that can be used in order to define concrete approximation operators. Several other operations provided by fuzzy sets theory can be used. In the present paper, pseudo-linear approximation operators are investigated from the practical point of view in Image Processing. We study max–min, max–product Shepard type approximation operators together with Shepard operators based on pseudo-operations generated by an increasing continuous generator. It is shown that in several cases these outperform classical approximation operators based on sum and product operations.     

Chemo-regioselectivity in heterogeneous catalysis: competitive routes for C = O and C = C hydrogenations from a theoretical approach

The usual empirical rule stating that the C=C bond is more reactive than the C=O group for catalytic hydrogenations of unsaturated aldehydes is invalidated from the present study. Density functional theory calculations of all the competitive hydrogenation routes of acrolein on Pt(111) reveals conversely that the attack at the C=O bond is systematically favored. The explanation of such catalytic behavior is the existence of metastable precursor states for the O-H bond formation showing that the attack at the oxygen atom follows a new preferential mechanism where the C=O moiety is not directly bonded with the Pt surface atoms, hence yielding an intermediate pathway between Langmuir-Hinshelwood and Rideal-Eley general types of mechanisms. When the whole catalytic cycle is considered, our results reconcile with experimental studies devoted to hydrogenation of acrolein on Pt, since the desorption step of the partially hydrogenated product (unsaturated alcohol versus saturated aldehyde) plays a key role for the selectivity.     

Efficient synthesis of novel NK1 receptor antagonists: selective 1,4-addition of grignard reagents to 6-chloronicotinic acid derivatives

A new efficient synthesis of two novel classes of NK1 receptor antagonists, among them befetupitant and netupitant, starting from 6-chloronicotinic acid is described. The introduction of the o-tolyl substituent at C4 of the pyridine ring was achieved by a one-pot selective 1,4-Grignard addition/oxidation sequence to 6-chloronicotinic acid or a derivative of it. The scope of this addition/oxidation sequence was examined. It was also shown that the carboxylic function can be converted to a methyl amino group by a Hofmann rearrangement followed by reduction. Furthermore, a new high-yielding synthesis of 2-(3,5-bistrifluoromethylphenyl)-2-methyl propionic acid based on the carbonylation of the tertiary alcohol obtained by Grignard addition of 3,5-bis(trifluoromethyl)bromobenzene to acetone was established.     

A novel method for quantification of sulfolane (a metabolite of busulfan) in plasma by gas chromatography–tandem mass spectrometry

The role of busulfan (Bu) metabolites in the adverse events seen during hematopoietic stem cell transplantation and in drug interactions is not explored. Lack of availability of established analytical methods limits our understanding in this area. The present work describes a novel gas chromatography-tandem mass spectrometric assay for the analysis of sulfolane (Su) in plasma of patients receiving high-dose Bu. Su and Bu were extracted from a single 100 μL plasma sample by liquid-liquid extraction. Bu was separately derivatized with 2,3,5,6-tetrafluorothiophenolfluorinated agent. Mass spectrometric detection of the analytes was performed in the selected reaction monitoring mode on a triple quadrupole instrument after electronic impact ionization. Bu and Su were analyzed with separate chromatographic programs, lasting 5?min each. The assay for Su was found to be linear in the concentration range of 20-400?ng/mL. The method has satisfactory sensitivity (lower limit of quantification, 20?ng/mL) and precision (relative standard deviation less than 15?%) for all the concentrations tested with a good trueness (100?±?5?%). This method was applied to measure Su from pediatric patients with samples collected 4?h after dose 1 (n?=?46), before dose 7 (n?=?56), and after dose 9 (n?=?54) infusions of Bu. Su (mean?±?SD) was detectable in plasma of patients 4?h after dose 1, and higher levels were observed after dose 9 (249.9?±?123.4?ng/mL). This method may be used in clinical studies investigating the role of Su on adverse events and drug interactions associated with Bu therapy.     

One-nucleon removal cross-sections for 17, 19C and 8, 10B

One-neutron removal cross-sections ( ) of ^{17, 19}C in various targets at about 900 MeV/nucleon, and one-proton removal cross-sections ( ) of ^{8, 10}B at about 1400 MeV/nucleon were measured using the fragment separator FRS at GSI. A significant increase of for ¹⁹C compared to its neighbors was observed. The same behavior was found for for the neutron-deficient nucleus ⁸B compared to the stable isotope ¹⁰B. These results support a one-neutron halo structure in ¹⁹C and a one-proton halo in ⁸B. Received: 26 July 2000 / Accepted: 11 January 2001     

[Mo12O40P][C44H38P2][CoC10H10] * 3(C3H7NO): A quasi-ternary intercluster compound

Binary intercluster compounds (IC) can be reduced to basic structure types of ionic solids. We examined the validity of this concept for ternary compounds, on the example of a quasi-ternary intercluster compound made from a Keggin anion ([PMo₁₂O₄₀]^3?), an organic cation (o-xylylenebis(triphenylphosphonium)), and a complex (cobaltocenium). The new compound and its two related quasi-binary IC were investigated by X-ray diffractometry, examined for intermolecular interactions such as hydrogen-bonding, π–, or van der Waals-interactions, and evaluated for possible reductions to basic structure types.     

Phosphorus Containing Tri-and Hexamacrocycles

Abstract

Multisite receptors containing more than two macrocyclic cavities. despite of the fact that their syntheses, most often, require sophisticated pathways, arc of very high interest since they may allow new insights into ion channel transfer, ion conduction.[1] We report here a method which combine simple reactions, high yields (80%), with easily prepared starting reagents[2], of two new polymacrocyclic system, a tri-(r) and an hexamacrocyck(II). They were obtained by a condensation reaction between 4-formylbenzo-15-crown-5 (3 or 6 quiv, respectively) and phosphouihydrazide (1 equiv.) or hexahydrazide (1 equiv.) in tetrahydrofuran.