Cultural influences on sex differentials in mathematics aptitude and achievement

Results of mathematics testing of 14‐year‐olds and college freshmen in the West Bank indicate more substantial variation on the basis of cultural factors than on the basis of gender. In particular, no significant difference in the mathematical abilities of men and women appeared in the college group.     

Modulable and Highly Diastereoselective Carbometalations of Cyclopropenes

The copper‐catalyzed carbomagnesiation reaction of cyclopropenyl esters 1 leads to various substituted cyclopropanes species 3 in good yields with very high diastereoselectivities. The reaction proceeds through a syn‐chelated carbomagnesiation reaction and could be extended to various cyclopropenylmethyl ester derivatives 5 . The potential of this approach was illustrated by the preparation of two consecutive all‐carbon quaternary stereocenters. However, the carbometalation reaction needs to be performed at temperature ranging from ?35 to ?20 °C to avoid subsequent fragmentation reaction into stereodefined β,γ‐nonconjugated unsaturated esters 4 . Alternatively, the carbocupration reaction with organocopper species could also be performed to leads to configurationally stable cyclopropyl copper species 2[Cu] . Additionally, when the Lewis acid character of the copper center is decreased (i.e., RCuCNLi), the reaction proceed with an anti‐selectivity. The diastereodivergent behavior of these organometallic species is of synthetic interest, since both diastereomers syn‐ 3 and anti‐ 3 can be obtained, at will, from the same precursor cyclopropenyl esters 1 .     

Theoretical study on the reaction of hydrogen atoms with aniline

The reaction of aniline with hydrogen atom is investigated herein using the hybrid meta-DFT functional of BB1 K. Hydrogen atom is found to preferentially add at an ortho position. However, the fate of the o-(C₆H₅NH₂)H adduct is found to be solely the deactivation of the initial addition channel. The rate constant for the abstraction channel (C₆H₅NH₂ + H → C₆H₅NH + H₂) is fitted by the expression 1.10 × 10⁻¹¹ exp(−4,200/T) cm³ molecule⁻¹ s⁻¹. Our calculated rate constant for the abstraction channel agrees very well with the available experimental measurements. Satisfactory agreement is found between calculated and experimental measurements for the displacement channel (C₆H₅NH₂ + H → C₆H₆ + NH₂). Our detailed analysis for the corresponding displacements in toluene and phenol suggests that the three systems exhibit similar behavior with regard to the relative importance of abstraction and displacement channels.     

Molecular structure and barriers to internal rotation of α-naphthalenesulfonyl chloride: a study by gas-phase electron diffraction and quantum chemical calculations

α-Naphthalenesulfonyl chloride, α-NaphSC, was studied by gas-phase electron diffraction (GED) and quantum chemical calculations (HF/6-311 + G**, HF/aug-cc-pVDZ, B3LYP/cc-pVDZ, B3LYP/cc-pVTZ, B3LYP/aug-cc-pVDZ, B3LYP/aug-cc-pVTZ, MP2/cc-pVDZ, and MP2/cc-pVTZ). The calculations predict the existence of two conformers with C ₁ (I) and C _s (II) symmetries. The most stable conformer I has an enantiomer. The experimental data of α-NaphSC obtained at 370(5) K could be best fitted by a C ₁ symmetry model indicating that only this form exists in the gas-phase. In this model the C_α–S–Cl plane deviates from the perpendicular orientation relative to the plane of the naphthalene skeleton. Under the applied experimental conditions, the mole fraction of a second less stable conformer II of α-NaphSC predicted by calculations is no more than 1 %. The following geometrical parameters of conformer I were obtained from the experiment (Å and °; uncertainties are in parentheses): r _h1(C–H) = 1.082(6), r _h1(C–C)_cp = 1.407(3), r _h1(C–S) = 1.764(5), r _h1(S–O)_av = 1.425(3), r _h1(S–Cl) = 2.051(5), ∠C–C_α–C = 122.5(1), ∠C_α–S–Cl = 101.5(10); C9–C1–S–Cl = 71.4(21). The calculated barriers to internal rotation of the sulfonyl chloride group exceed considerably the thermal energy values corresponding to the temperatures of the GED experiments. Natural bond orbitals analysis of the electron density distribution was carried out to explain the peculiarities of the molecular structure of the studied compound and the deviation from the structures of β-NaphSHal molecules and their benzene analogs.     

The Coagulation Impact of 50% Epoxidised Natural Rubber Chain in Ethylene Carbonate-Plasticized Solid Electrolytes

In this research, thin, soft and flexible free standing films can be obtained from poly (methyl methacrylate) (PMMA)/50% epoxidised natural rubber (ENR 50)/lithium triflate (LiCF₃SO₃) blends. However, phase separation is observed on the surface of the films which indicates that the blending is not homogeneous. The blend became more homogeneous when ethylene carbonate (EC) plasticizer is introduced into the blend system. However, the anti-plasticization effect of EC on ENR 50 occurs at lower concentration of EC at which the rubber became coagulated due to immiscibility of the rubber with EC plasticizer during solution casting. These ENR 50 coagulates can be observed as large solid structures in the Field Emission Scanning Electron Microscope (FESEM) micrographs of the EC-plasticized rubber-based electrolytes. The presence of these coagulates, hinder the migration of lithium ions in the system and also trap the lithium ions within the coil. This in turn reduced the number of free lithium ions that contribute to the ionic conduction. As a result, the conductivity of the un-plasticized PMMA/ENR 50/LiCF₃SO₃ film dropped drastically by two orders of magnitude.     

Dynamical shape gradient for the Navier–Stokes system

This Note deals with the sensitivity analysis of a newtonian incompressible fluid driven by the Navier–Stokes equations with respect to the dynamic of the fluid domain boundary. The structure of the gradient with respect to the velocity of the domain for a given cost function is established. This result is obtained using new shape derivation tools for Eulerian functionals and the Min–Max derivation principle. To cite this article: R. Dziri et al., C. R. Acad. Sci. Paris, Ser. I 338 (2004).     

Asymmetric Catalytic Preparation of Polysubstituted Cyclopropanol and Cyclopropylamine Derivatives

The catalytic asymmetric carbometalation of cyclopropenes followed by either an electrophilic oxidation or amination reaction provides a unique approach to the formation of diastereomerically pure and enantiomerically enriched cyclopropanol and cyclopropylamine derivatives, respectively.