Reaction of silyl ketene acetals with epoxides: a new method for the synthesis of γ-butanolides

Titanium tetrachloride promoted reaction of silyl ketene acetals with epoxides, followed by acidic work-up, affords butanolides in moderate/good yields. With epihalohydrins the reaction is regioselective and occurs at the less substituted end of the epoxide; the γ-haloalkyl-γ-butanolides thus obtained can be further transformed into various products.     

Influence of the H/F replacement on the homoaromaticity of homotropylium ion: a GIAO/DFT theoretical study

The problem of homoaromaticity in mono-, di- and polyfluorinated- homotropylium cations is addressed by the B3LYP/6-311++G** DFT method. The energetic, structural and magnetic criteria are used for this purpose. They convincingly show that the ground state equilibrium species are aromatic, or in other words that the homoaromaticity is preserved by the (poly)fluorination. In contrast, a considerable decrease in the aromatic stabilization is observed in the transition structures (TS). According to the NICS(0) index, they vary form strongly antiaromatic, via weakly and non-aromatic to slightly aromatic transition states. However, the hierarchy of the aromaticity in fluorinated homotropylium ions predicted by NICS(0) is completely unrelated to that obtained by using the energy criterion assuming a kinetic definition of aromaticity. On the other hand the latter is closely related to geometric parameters of the equilibrium and transition structures.     

Short-step synthesis of tamoxifen and its derivatives via the three-component coupling reaction and migration of the double bond

The anti-tumor agent, tamoxifen, is easily synthesized by the successive allylation of benzaldehyde and the Friedel-Crafts alkylation reaction of anisole with the intermediary homoallyl silyl ethers, followed by the migration of the double bond to form the desired tetra-substituted ethylenes. Several derivatives of tamoxifen are also produced according to a similar synthetic strategy.     

Quantum Hall effect in back-gated InAs/GaSb heterostructures under a tilted magnetic field

We investigate the quantum Hall effect (QHE) in the InAs/GaSb hybridized electron–hole system grown on a conductive InAs substrate which act as a back-gate. In these samples, the electron density is constant and the hole density is controlled by the gate-voltage. Under a magnetic field perpendicular to the sample plane, the QHE appears along integer Landau-level (LL) filling factors of the net-carriers, where the net-carrier density is the difference between the electron and hole densities. In addition, longitudinal resistance maxima corresponding to the crossing of the extended states of the original electron and hole LLs make the QHE regions along integer-ν_net discontinuous. Under tilted magnetic fields, these R_xx maxima disappear in the high magnetic field region. The results show that the in-plane magnetic field component enhances the electron–hole hybridization and the formation of minigaps at LL crossings.     

Growth process of TiC clusters from Ti nanoparticles with evaporated carbon layer

Titanium carbide formation by the solid–solid reaction on the surface of Ti nanoparticles was studied in situ using a high-resolution transmission electron microscope with a heating stage. The cross-sectional image of the Ti surface was clearly observed. Vacuum-deposited carbon covered the whole the surface of Ti nanoparticles in spite of the partly evaporation on the nanoparticle surface. The diffusion of the carbon atoms inside the Ti nanoparticles depended on the size of the nanoparticles. When the Ti nanoparticle diameter was less than 30 nm, carbon atoms diffused into the Ti nanoparticle and formed TiC. The superstructure of the Ti nanoparticles was observed, which revealed the growth process of TiC to be the diffusion of carbon atoms. For Ti nanoparticles with diameter larger than 30 nm it was observed that diffusion of Ti atoms into the carbon layer was dominant, which resulted in formation of TiC in the carbon layer at the surface of Ti nanoparticles.     

Dihydropyridine-based MCRs. New reaction pathways in the interaction with ethyl glyoxalate and non-aromatic amines

The Lewis acid-catalyzed interaction of dihydropyridines with ethyl glyoxalate and primary aliphatic amines yields, depending on the reaction conditions, bicyclic aminals or rearranged tetrahydropyridines in one-pot multicomponent reactions.     

Equilibrated thermodesorption studies of adsorption of n-hexane and n-heptane on zeolites Y, ZSM-5 and ZSM-11

Gravimetric measurements of thermodesorption of n-hexane and n-heptane were performed under quasi-equilibrium conditions. Differential thermodesorption profiles for ZSM-5 and ZSM-11 showed two peaks, but for Y zeolites, only one thermodesorption peak was observed. A model function, derived from the Langmiur adsorption model, was fitted to the experimental data, and the model parameters (the adsorption entropy and enthalpy) were estimated. The two-step desorption profiles observed for ZSM-5 and ZSM-11 were attributed to the commensurate freezing effect, i.e. a transition in the adsorbed phase resulting in ordering of the adsorbed molecules in the zeolite channels. The results observed for ZSM-11 indicate that the zigzag channels typical for ZSM-5 micropore system are not necessary for this transition to occur.     

Characterization of Cds clusters in zeolite-A grown in alkaline solution

CdS clusters were synthesized in A type zeolite by reaction in alkaline aqueous solution at temperatures from 30 to 70 °C. The optical properties of the samples were studied by diffuse reflectance and photoluminescence spectroscopy. Their crystalline structure and morphology were studied by X-ray diffraction and by transmission and scanning electron microscopy. We found that at lower temperatures the CdS clusters are encapsulated in the zeolite cages. We compared the properties of these clusters with those encapsulated in the cages of zeolites X and Y, prepared by similar methods. CdS clusters smaller than the CdS exciton diameter are also formed outside the cages in the zeolite matrix. The size of these clusters increases with temperature producing a red-shift of the absorption edge in the optical absorption spectra.     

Limits of tangents and minimality of complex links

We show that the complex link of a large class of space germs (X,x₀) is characterized by its “simplicity”, among the Milnor fibres of functions with isolated singularity on X. This amounts to the minimality of the Milnor number, whenever this number is defined. Such a phenomenon has been first pointed out in case (X,x₀) is an isolated hypersurface singularity, by Teissier (Cycles évanescents, sections planes et conditions de Whitney, in: Singularités à Cargèse 1972, Asterisque, Nos. 7 et 8, Soc. Math. France, Paris, 1973, pp. 285-362).