A practical synthesis of alpha-aryl methyl ketones via a transition-metal-free Meerwein arylation

We report herein a simple, scalable, transition-metal-free approach to the synthesis of alpha-aryl methyl ketones from diazonium tetrafluoroborate salts under mild conditions. This methodology uses easily accessible and nontoxic starting material and was applied to the multi-kilogram-scale preparation of 1-(3-bromo-4-methylphenyl)propan-2-one.     

Synthesis and Chemical and Electrochemical Characterization of Fe-S Carbonyl Clusters. X-ray Crystal Structures of [N(PPh(3))(2)](2)[Fe(5)S(2)(CO)(14)] and [N(PPh(3))(2)](2)[Fe(6)S(6)(CO)(12)

A reinvestigation of the redox behavior of the [Fe(3)(&mgr;(3)-S)(CO)(9)](2)(-) dianion led to the isolation and characterization of the new [Fe(5)S(2)(CO)(14)](2)(-), as well as the known [Fe(6)S(6)(CO)(12)](2)(-) dianion. As a corollary, new syntheses of the [Fe(3)S(CO)(9)](2)(-) dianion are also reported. The [Fe(5)S(2)(CO)(14)](2)(-) dianion has been obtained by oxidative condensation of [Fe(3)S(CO)(9)](2)(-) induced by tropylium and Ag(I) salts or SCl(2), or more straightforwardly through the reaction of [Fe(4)(CO)(13)](2)(-) with SCl(2). The [Fe(6)S(6)(CO)(12)](2)(-) dianion has been isolated as a byproduct of the synthesis of [Fe(3)S(CO)(9)](2)(-) and [Fe(5)S(2)(CO)(14)](2)(-) or by reaction of [Fe(4)(CO)(13)](2)(-) with elemental sulfur. The structures of [N(PPh(3))(2)](2)[Fe(5)S(2)(CO)(14)] and [N(PPh(3))(2)](2)[Fe(6)S(6)(CO)(12)] were determined by single-crystal X-ray diffraction analyses. Crystal data: for [N(PPh(3))(2)](2)[Fe(5)S(2)(CO)(14)], monoclinic, space group P2(1)/c (No. 14), a = 24.060(5), b = 14.355(6), c = 23.898(13) ?, beta = 90.42(3) degrees, Z = 4; for [N(PPh(3))(2)](2)[Fe(6)S(6)(CO)(12)], monoclinic, space group C2/c (No. 15), a = 34.424(4), b = 14.081(2), c = 19.674(2) ?, beta = 115.72(1) degrees, Z = 4. The new [Fe(5)S(2)(CO)(14)](2)(-) dianion shows a "bow tie" arrangement of the five metal atoms. The two Fe(3) triangles sharing the central Fe atom are not coplanar and show a dihedral angle of 55.08(3) degrees. Each Fe(3) moiety is capped by a triply bridging sulfide ligand. The 14 carbonyl groups are all terminal; two are bonded to the unique central atom and three to each peripheral iron atom. Protonation of the [Fe(5)S(2)(CO)(14)](2)(-) dianion gives reversibly rise to the corresponding [HFe(5)S(2)(CO)(14)](-) monohydride derivative, which shows an (1)H-NMR signal at delta -21.7 ppm. Its further protonation results in decomposition to mixtures of Fe(2)S(2)(CO)(6) and Fe(3)S(2)(CO)(9), rather than formation of the expected H(2)Fe(5)S(2)(CO)(14) dihydride. Exhaustive reduction of [Fe(5)S(2)(CO)(14)](2)(-) with sodium diphenyl ketyl progressively leads to fragmentation into [Fe(3)S(CO)(9)](2)(-) and [Fe(CO)(4)](2)(-), whereas electrochemical, as well as chemical oxidation with silver or tropylium tetrafluoroborate, in dichloromethane, generates the corresponding [Fe(5)S(2)(CO)(14)](-) radical anion which exhibits an ESR signal at g = 2.067 at 200 K. The electrochemical studies also indicated the existence of a subsequent one-electron anodic oxidation which possesses features of chemical reversibility in dichloromethane but not in acetonitrile solution. A reexamination of the electrochemical behavior of the [Fe(3)S(CO)(9)](2)(-) dianion coupled with ESR monitoring enabled the spectroscopic characterization of the [Fe(3)S(CO)(9)](-) radical monoanion and demonstrated its direct involvement in the generation of the [Fe(5)S(2)(CO)(14)](n)()(-) (n = 0, 1, 2) system.     

Similarity analysis and exact solutions for a general discrete two-velocity model of Boltzmann equation

Summary This paper concerns with the similarity analysis for a general discrete two-velocity model of the Boltzmann equation introduced by Illner [12]. We find the general groups of invariance and we get some exact solutions, recovering general results which contain either solutions extensively described in the literature or undiscovered ones.

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Sommario In questa nota si applica l'analisi dei gruppi infinitesimi di trasformazione ad un modello generale discreto a due velocità dell'equazione di Boltzmann introdotto da Illner [12]. Si trovano i più generali gruppi di invarianza e si ottengono alcune soluzioni esatte, ritrovando risultati generali che contengono sia soluzioni ampiamente descritte in letteratura che nuove soluzioni.

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Work supported by the C.N.R. through the G.N.F.M.     

Adaptive behaviour of the spinal cord in the transition from quiet stance to walking

Background

Parkinson??s disease is characterized by a continuous loss of neurons within the substantia nigra (SN) leading to a depletion of dopamine. Within the adult SN as a non-neurogenic region, cells with mainly oligodendrocytic precursor characteristics, expressing the neuro-glial antigen-2 (NG2) are continuously generated. Proliferation of these cells is altered in animal models of Parkinson??s disease (PD). Exercise and environmental enrichment re-increase proliferation of NG2⁺ cells in PD models, however, a possible mechanistic role of dopamine for this increase is not completely understood. NG2⁺ cells can differentiate into oligodendrocytes but also into microglia and neurons as observed in vitro suggesting a possible hint for endogenous regenerative capacity of the SN. We investigated the role of dopamine in NG2-generation and differentiation in the adult SN stimulated by physical activity and environmental enrichment.

Results

We used the 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP)-model for dopamine depletion and analysed newborn cells in the SN at different maturation stages and time points depending on voluntary physical activity, enriched environment and levodopa-treatment. We describe an activity- induced increase of new NG2-positive cells and also mature oligodendrocytes in the SN of healthy mice. Running and enriched environment refused to stimulate NG2-generation and oligodendrogenesis in MPTP-mice, an effect which could be reversed by pharmacological levodopa-induced rescue.

Conclusion

We suggest dopamine being a key regulator for activity-induced generation of NG2-cells and oliogodendrocytes in the SN as a potentially relevant mechanism in endogenous nigral cellular plasticity.     

A Note on the analytic solutions of the Camassa–Holm equation

In this Note we are concerned with the well-posedness of the Camassa–Holm equation in analytic function spaces. Using the Abstract Cauchy–Kowalewski Theorem we prove that the Camassa–Holm equation admits, locally in time, a unique analytic solution. Moreover, if the initial data is real analytic, belongs to $H^s(\mathbb{R})$ with $s>3/2$, $6u_0{6}_{L^1}<\infty$ and $u_0?u_{0xx}$ does not change sign, we prove that the solution stays analytic globally in time. To cite this article: M.C. Lombardo et al., C. R. Acad. Sci. Paris, Ser. I 341 (2005).     

Wave features of a hodograph-like transformation for quasilinear hyperbolic systems

We study the properties of a variables transformation for a 2×2 quasilinear hyperbolic nonhomogeneous system of first order, related to wave propagation. The considered variables transformation transforms characteristic curves of the original system, into characteristic curves of the transformed system. We make use of this property to study the propagation of weak discontinuities (acceleration waves) compatible with the quasilinear system (1.1). Finally a special class of rate-type media is considered and asymptotic solutions are investigated.

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Sommario Si studiano le proprietà di una trasformazione di variabili per un sistema quasilineare iperbolico del primo ordine non omogeneo. La trasformazione considerata trasforma curve caratteristiche del sistema originale in curve caratteristiche del sistema trasformato. Utilizzando queste proprietà si studia la propagazione delle onde di discontinuità (onde di accelerazione) compatibile con il sistema quasilineare iperbolico considerato e si cercano soluzioni asintotiche.

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This work was supported by the C.N.R. through the G.N.F.M. and partially under contract No. 88. 01855.01.     

Curved domain walls dynamics driven by magnetic field and electric current in hard ferromagnets

The propagation of curved domain walls in hard ferromagnetic materials is studied by applying a reductive perturbation method to the generalized Landau–Lifshitz–Gilbert equation. The extended model herein considered explicitly takes into account the effects of a spin-polarized current as well as those arising from a nonlinear dissipation.     

The Dirichlet problem for second order elliptic equations with coefficients in the Stummel class in unbounded domains

In this note we prowe existence and unicity of solution of a Dirichlet problem for second order elliptic operator in the divergence form, with the coefficients of the lower order terms belonging to a variant of the Stummel-Kato class, in an unbounded domain, extending the works [6] and [2].

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Sunto In questa nota proviamo un Teorema di esistenza e unicità per la soluzione di un problema di Dirichlet relativo ad un operatore ellittico del secondo ordine in forma di divergenza, con i coefficienti dei termini di ordine inferiore appartenenti ad una variante dello spazio di Stummel-Kato, in un dominio non limitato, estendendo i lavori [6] e [2].

     

Study of morphological hysteresis in <Emphasis Type="Italic">partially immiscible</Emphasis> polymers

The morphology evolution of two systems of partially immiscible polymers, differing in miscibility, is investigated by means of rheological experiments and optical microscopy. For each system, two concentrations, 10% and 20%, are used. For immiscible systems, a hysteresis zone, defined by coalescence and breakup, exists where the average drop radius is not a unique function of the shear rate. We investigate whether the findings also apply to partially immiscible polymers. The average radii at different shear rates, measured with rheology, are compared to model predictions. The hysteresis zone, if present, is indeed affected by the polymeric system, the concentration and the flow history applied. Coalescence evolution is measured for three different step-downs in shear rate. For both 10% systems, the resulting average radii show a rather high scattering and do not match the theoretical predictions. For the 20% concentrations, the average experimental drop sizes seem independent of the magnitude of the step-down, at least during a certain period of time. Thereafter, it experiences a sudden, in the time scale of the experiments unbounded, increase in size that is more pronounced for the higher step-downs. Deviations of the experimental data from theoretical predictions are attributed to the partially immiscible character of the systems, yielding enhanced coalescence which, in turn, can induce confinement effects.