Application of directed metallation in synthesis. Part 3: Studies in the synthesis of (±)-semivioxanthin and its analogues

The synthesis of several analogues of (±)-semivioxanthin including five thiophene analogues, using directed metalation are reported. The strategy consisted of the synthesis of functionalized naphthalene or benzo[b]thiophene as building blocks followed by annelation of the pyrone.     

Dihalodimethyltin(IV) complexes of 2‐(pyrazol‐1‐ylmethyl)pyridine

Reaction of dichloro‐ and dibromodimethyltin(IV) with 2‐(pyrazol‐1‐ylmethyl)pyridine (PMP) afforded [SnMe₂Cl₂(PMP)] and [SnMe₂Br₂(PMP)] respectively. The new complexes were characterized by elemental analysis and mass spectrometry and by IR, Raman and NMR (¹H, ¹³C) spectroscopies. Structural studies by X‐ray diffraction techniques show that the compounds consist of discrete units with the tin atom octahedrally coordinated to the carbon atoms of the two methyl groups in a trans disposition (Sn? C = 2.097(5), 2.120(5) Å and 2.110(6), 2.121(6) Å in the chloro and in the bromo compounds respectively), two cis halogen atoms (Sn? Cl = 2.4908(16), 2.5447(17) Å; Sn? Br = 2.6875(11), 2.7464(9) Å) and the two donor atoms of the ligand (Sn? N = 2.407(4), 2.471(4) Å and 2.360(5), 2.455(5) Å). In both cases, the Sn? N(pyridine) bond length is markedly longer than the Sn? N(pyrazole) distance. Copyright © 2003 John Wiley & Sons, Ltd.     

The adsorption of toluene on V-Sb oxides. Theoretical aspects

Toluene adsorption reactions on the (1 1 0) surface of VSbO₄ have been analyzed following the changes in the electronic structure of the hydrocarbon molecule and metal cation sites of the oxide using the Just Another Extended Hückel Molecular Orbital Program (JAEHMOP) code. The bonding character of these interactions has also been studied in the same theoretical framework. The calculations indicate that the exothermic hydrocarbon parallel interaction on Sb-V sites results in the weakening of one of the C-H bonds of the methyl fragment. This leads to a H-abstraction that involves the participation of a Sb-cation. Both methyl and phenyl fragments decrease their electronic population and so does the V-cation site. Most of these electrons are transferred to other V atoms in the bulk solid. As a result the LUMO of the toluene-oxide system fully populates. The analysis reveals that methyl-Sb bonding interactions mainly involve C_2px and H_1s orbitals with Sb_5s orbital, while non-bonding phenyl-V interactions involve C_2px orbitals with V_3dx²−y² orbital. This last interaction facilitates the desorption of the benzyl species after H-abstraction.     

Recent Developments in Synchrotron Mössbauer Reflectometry

Hyperfine Interactions - Synchrotron Mössbauer Reflectometry (SMR), the grazing incidence nuclear resonant scattering of synchrotron radiation, can be applied to perform depth-selective phase...     

复Finsler流形上的Koppelman-Leray-Norguet公式

利用不变积分核(Berndtsson核),复Finsler度量和联系于Chern-Finsler联络的非线性联络,研究复Finsler流形上具有逐块光滑C~((1))边界的有界域上(p,q)型微分形式的积分表示,得到了(p,q)型微分形式的Koppelman-Leray-Norguet公式和■-方程的解．作为应用,利用复Finsler度量和联系于Chern-Finsler联络的非线性联络,给出了Stein流形上具有逐块光滑C~((1))边界的有界域上(p,q)型微分形式的Koppelman- Leray-Norguet公式以及■-方程的解,并且得到了Stein流形上实非退化强拟凸多面体上(p,q)型微分形式的积分表示式和■-方程的解．     

Anisotropic alpha-emission in the223Ra decay chain

Anisotropic α-emission from nuclei in the decay chain from²²³Ra to²⁰⁷Tl has been observed using low temperature nuclear orientation in combination with high resolution α-detection at 4.2 K. Information on partial wave amplitudes as well as hyperfine interactions has been extracted.     

Turbulence modelling of the shear layers in the trailing edge region of a modern rear-loaded airfoil at incidence

After carefull analysis in a turbulent zero-pressure gradient flow, various simple algebraic turbulence models were applied to the almost separated flow on the upperside of an airfoil at incidence. The Johnson-King and Horton non-equilibrium (or rate equation) models give clearly improved results.     

An easy and fast way to determine the enantiomeric purity of substituted cyclanones

The determination of the enantiomeric purity of 2 or 3-substituted cyclanones, particularly cyclohexanones, is conveniently achieved by derivatisation into cyclic aminals with commercially available (R, R)-1,2-diphenylethylenediamine. The derivatisation procedure is directly done into the NMR tube, instantaneously, and ¹³C NMR allows an accurate measure of the ee.     

Lifetime study of high-spin states in 104,105In

In the neutron deficient isotopes _104,105In lifetimes of high spin states in the range from 0.5 ps to 600 ps have been measured in a coincidence recoil distance Doppler shift (RDDS) experiment. By combining the Doppler shift attenuation (DSA) and RDDS methods at few μm flight distances, the problem of delayed feeding has been avoided and very short lifetimes in the range 0.5–0.8 ps have been determined. Shell model calculations with strong restrictions for the neutron orbitals reveal good agreement with experimental level energies and still fair agreement for most measured B(M1) and B(E2) values. Received: 30 June 1998