Simple and Efficient Synthesis of Steroidal Hybrids of Estrogen and Vitamin D3

A simple and efficient synthesis of steroidal hybrids of estrogen and vitamin D₃ through modification of estrone (5) at position 16 of the steroid nucleus is described.     

A numerical study of heat island flows: Stationary solutions

We present two‐dimensional numerical simulations of a natural convection problem in an unbounded domain. The flow circulation is induced by a heat island located on the ground and thermal stratification is applied in the vertical direction. The main effect of this stably stratified environment is to induce the propagation of thermal perturbations in the horizontal direction far from the local thermal source. Numerical stationary solutions at Ra?10⁵ are computed in large elongated computational domains: convergence with respect to the domain sizes is investigated at different resolutions. On fine grids, with mesh size , a thermal sponge layer is added at the vertical boundaries: this local damping technique improves the convergence with respect to the domain length. Boussinesq equations are discretized with a second‐order finite volume scheme on a staggered grid combined with a second‐order projection method for the time integration. Copyright © 2008 John Wiley & Sons, Ltd.     

On the thermal anisotropy affecting transfers in a multilayer porous mediumSur l'effet de l'anisotropie thermique sur les transferts dans un milieu poreux multicouches

An analytical model for studying double-diffusive natural convection within a multilayer anisotropic porous medium is developed and validated with respect to a direct numerical silmulation. The studied domain is composed of two horizontal porous layers where the lower one is thermally anisotropic and is submitted to a uniform horizontal heat flux and a vertical mass flux. The assumption of parallel flow is validated and the effect of anisotropy on dynamic transitions is investigated. To cite this article: R. Bennacer et al., C. R. Mecanique 332 (2004).     

First-principles calculations of structural,electronic and thermal properties of Zn1−x Mg x S ternary alloys

Structural, electronic and thermal properties of Zn_1?x Mg _x S ternary alloys are studied by using the full potential-linearized augmented plane wave method (FP-LAPW) within the density functional theory (DFT). The Wu-Cohen generalized gradient approximation (WC-GGA) is used in this approach for the exchangecorrelation potential. Moreover, the modified Becke-Johnson approximation (mBJ) is adopted for band structure calculations. The dependence of the lattice constant, bulk modulus and band gap on the composition x showed that the first exhibits a small deviation from the Vegard’s law, whereas, a marginal deviation of the second from linear concentration dependence (LCD). The bowing of the fundamental gap versus composition predicted by our calculations agrees well with the available theoretical data. The microscopic origins of the gap bowing are explained by using the approach of Zunger and co-workers. Thermal effects on some macroscopic properties of Zn_1?x Mg _x S alloys are also investigated using the quasi-harmonic Debye model, in which the phononic effects are considered. As, this is the first quantitative theoretical prediction of the thermal properties of Zn_1?x Mg _x S alloys, no other calculated results and furthermore no experimental studies are available for comparison.     

Enantioselective total synthesis of cytotoxic taiwaniaquinones A and F

The first synthesis of cytotoxic (-)-taiwaniaquinone A and (-)-taiwaniaquinone F has been achieved through the intramolecular aldol condensation of a ketoaldehyde and the oxidative cleavage of an isopropylidene ketal.     

Room-temperature ionic liquids as new solvents for organic electrosynthesis. The first examples of direct or nickel-catalysed electroreductive coupling involving organic halides

Direct or Ni-catalysed electroreductive homocouplings of organic halides and couplings of organic halides with activated olefins are efficiently conducted by constant current electrolyses in an undivided cell in room-temperature ionic liquids as the solvent-electrolyte media.     

Expedient total syntheses of rhein and diacerhein via Fries rearrangement

Short and practical total syntheses of rhein (1) and diacerhein (2) have been achieved via a Fries rearrangement and bis-carbonylation strategy followed by cyclization in molten salt, starting from dibromoester 7.     

Experimental and theoretical push‐pull Chemo‐ and regioselectivity in 1,3‐Dipolar cycloaddition reactions: the case of benzotriazepin‐5‐one with mesitylnitrile oxide

A novel heterocyclic compound 3‐mesityl‐5‐methyl‐4,5,11,11a‐tetrahydro‐6H‐[1,2,4]oxadiazolo [5,4‐b][1,3,4]benzotriazépin‐6‐one 4 has been synthesised by a 1,3 dipolar cycloaddition (13DC) reaction of 1,3,4‐benzotriazepin‐5‐one 1 with mesitylnitrile oxide 3 . The reaction, beside its synthetic interest, has shown to be completely chemo‐ and regioselective. The structure of the compound was determined by X‐ray crystallography and analysed by spectral methods (NMR and mass spectrometry). The molecular mechanism for the reaction has been studied using quantum mechanical calculations at the B3LYP/6‐31G* theory level. Two mechanisms are possible for the formation of the cycloadduct 4 . The first one involves a 13DC reaction between 1 , as dipolarophile and 3 , as dipole. Analysis of the results indicates that it takes place along asynchronous concerted bond‐formation process with a very low polar character. The regioselectivity obtained from the calculations are in complete agreement with the unique formation of the cycloadduct 4 . The second mechanism is initiated by the nucleophilic attack of the N3 nitrogen of the tautomer form of 2 , to the C5 carbon of the nitrile oxide 3 to yield an amidoxime. However, the large energy involved in this addition prevents this mechanism. The large energy difference between the tautomers 1 and 2 , makes that only the C?N site of benzotriazepin‐5‐one 1 could act as a dipolarophile site. This fact makes the 13DC reaction to be chemoselective. The analysis of global electrophilicity of the reagents allows explaining the low polar character of these 13DC reactions. Copyright © 2007 John Wiley & Sons, Ltd.