Gold(III) complexes with imidazole,benzoxazole, purine and pyrimidine derivatives

Summary The synthesis and characterization of Au^III complexes with several heterocyclic ligands are reported. The compounds have general formula [AuX₃(L)], where L =N-methylimidazole (N-MeIz),N-ethylimidazole (N-EtIz),N-propylimidazole (N-PrIz), benzoxazole (BO), 2-methylbenzoxazole (2-MeBO), 2,5-dimethylbenzoxazole (2,5-diMeBO), 2-amino-pyrimidine (2-APm), 4(6) -hydroxy-pyrimidine [4(6)-hydrPm] or hypoxanthine (Hypox) and X = Cl or Br. Elemental analysis, conductivity measurements and spectral studies were used for the characterization of the complexes. A square-planar geometry withN-bonded heterocyclic ligands is suggested.     

Simultaneous determination of neodymium, erbium and holmium in rare earth mixtures with 2-phenyltrifluoroacetone and octylphenol poly(ethyleneglycol) ether by third-derivative spectrophotometry

The complexes of the rare earth metals with 2-phenyltrifluoroacetone in the presence of TX-100 are reported. The characteristic absorbances of neodymium, holmium and erbium complexes can be increased by factors of 8.5, 31 and 15 respectively, compared to those of the cholrides. The third-derivative spectra have been used to eliminate the interference of cerium, and the sensitivities are increased again by factors of 7.4, 5.5 and 6.5. A method for the direct determination of neodymium, erbium and holmium in rare earth mixtures is proposed.     

Synthesis and Conformational Analysis of the Multidrug Resistance-Reversing Agent Hapalosin and Its Non-N-methyl Analog

Hapalosin was initially synthesized by macrolactonization, and a second synthesis was achieved by cycloamidation. In both syntheses, three of the five stereocenters in hapalosin were established by two Brown allylboration reactions. The synthesis of the non-N-Me analog of hapalosin involved chelation-controlled reduction of a gamma-amino-beta-keto ester and cycloamidation. In CDCl(3) at 25 degrees C, synthetic hapalosin exists as a 2.3:1 mixture of conformers, while its non-N-Me analog exists only as a single conformer. (1)H,(1)H-NOESY and computation reveal that the configuration of the amide bond is responsible for the conformations of the two compounds. The major conformer of hapalosin is found to be an s-cis amide, the minor conformer an s-trans amide, and the non-N-Me analog an s-trans amide. Applying distance constraints to protons that exhibit NOESY correlations, computation shows that the major conformer of hapalosin and the non-N-Me analog have very different conformations. By contrast, the minor conformer of hapalosin and the non-N-Me analog have very similar conformations.     

Chemical Reactions and Kinetics of the Carbon Monoxide Coupling in the Presence of

The chemical reactions and kinetics of the catalytic coupling reaction of carbon monoxide to diethyl oxalate were studied in the presence of hydrogen over a supported palladium catalyst in the gaseous phase at the typical coupling reaction conditions. The experiments were performed in a continuous flow fixed-bed reactor. The results indicated that hydrogen only reacts with ethyl nitrite to form ethanol, and kinetic studies revealed that the rate-determining step is the surface reaction of adsorbed hydrogen and the ethoxy radical (EtO-). A kinetic model is proposed and a comparison of the observed and calculated conversions showed that the rate expressions are of rather high confidence.     

Epoxide networks as model networks

Summary The equilibrium mechanical behaviour of weak diepoxide-monoepoxide-diamine networks, prepared with an excess of diamine and measured in the rubbery state, was compared with theoretical predictions obtained by using the theory of branching processes. The experimental equilibrium moduli fit well the shape of theoretical curves over a broad range of crosslinking density regardless of whether the contribution by trapped entanglements is considered or not. The data fit equally well the theoretical dependence for the front factor A = 1 without entanglement contribution and forA = (f _e - 2)/f _e , (f _e is the average effective functionality of a junction) with an entanglement contribution based on the contact probability between any two units within elastically active network chains (Langley).Dedicated to Prof. Dr.G. Rehage on the occasion of his 60th birthday.With 5 figures     

Quark-diagram estimates ofCP violation in two-body baryonicB_d^0 - \bar B_d^0 decays

CP violation in partial-decay-rate asymmetries are examined for some two-body baryonic decays of \(B_d^0 - \bar B_d^0 \) system. We discuss two feasible experimental circumstances: the symmetrice ⁺ e ^? collisions (i) on theZ ⁰ resonance to produce incoherent \(B_d^0 \bar B_d^0 \) states, and (ii) just above the ?(4S) resonance to produceC=even \(B_d^0 \bar B_d^0 \) states. Using the quark-diagram scheme, we estimate the branching ratios of those decays, and the numbers ofb \(\bar b\) pairs needed for testing theCP-violating effects for 3σ signature. We find that the promising channels may beB _d ⁰ , \(\bar B_d^0 \to p\bar p\) , \(\Delta ^ + \bar \Delta ^ - \) , \(p\bar \Delta ^ - \) , \(\Delta ^ + \bar p\) , \(n\bar n\) , \(\Delta ^0 \bar \Delta ^0 \) , \(n\bar \Delta ^0 \) , \(\Delta ^0 \bar n\) , \(\Sigma _c^ + \bar \Sigma _c^ - \) , \(\Lambda _c^ + \bar \Lambda _c^ - \) , \(\Sigma _c^ + \bar \Lambda _c^ - \) , \(\Lambda _c^ + \bar \Sigma _c^ - \) , \(\Sigma _c^0 \bar \Sigma _c^0 \) , \(\Xi _c^0 \bar \Xi _c^0 \) , which should be interesting for experimental observation.     

Two singular integrals containing a partial wave of the two-body coulomb T-matrix

The operatorsT _C,l E+i0)[–G ₀(E+i0)]^1–i andT _C,l(E+i)G ₀[–iG ₀(E+i)]ⁱ acting on spaces of Hölder continuous, differentiable and analytic functions are investigated. The results of their action are expressed in terms of explicit singular factors and terms and Hölder (differentiable, analytic) functions. The most singular part of these operators is shown to be determined by a simple functional.     

Highly regioselective construction of spirocycles via phosphine-catalyzed [3 + 2]-cycloaddition

A direct entry to spirocycles with low to moderate regioselectivity was achieved by triphenylphosphine-catalyzed [3 + 2]-cycloaddition of active exo-methylenecycles (1) and ethyl 2,3-butadienoate (2). The regioselectivity of the reaction was greatly improved by using the bulky tert-butyl ester of the 2,3-butadienoate (5). The regioselectivity of the reaction was further enhanced by using the tert-butyl 2-butynoate as the substrate. This protocol provided an efficient entry to the skeleton of spirocarbocycles, especially spiro[4.n]alkanes.