Efficient synthesis of ferrocenylenones by Friedel-Crafts acylation with EtAlCl2-Me3Al

Efficient synthesis of ferrocenylenones using a Friedel-Crafts acylation reaction is described. Acryloyl, methacryloyl, crotonoyl, cinnamoyl, and β-methylcrotonoyl chlorides react with ferrocene in the presence of a Lewis acid (EtAlCl₂ or EtAlCl₂-Me₃Al) to give the corresponding ferrocenylenones (acryloyl, methacryloyl, crotonoyl, cinnamoyl, and methylcrotonoylferrocenes) in good isolated yields. Besides ferrocenylenones, chloroactylferrocene is also synthesised by this method.     

The effect of Cu substitution on the A1g mode of La0.7Sr0.3MnO3 manganites

We report on the first Raman data of Cu substituted La_1−ySr_yMn_1−xCu_xO₃ (0≤x≤0.10 and 0.17≤y≤0.3, accordingly in order to have the same Mn⁴⁺/[Mn⁴⁺+Mn³⁺] ratio), collected in the frequency range 100-900 cm⁻¹ and at room temperature, with parallel (e_i∥e_s) and crossed (e_i⊥e_s) polarizations of the incident (e_i) and scattered (e_s) light. Spectra were fitted with a Drude-Lorentz model, and peaks at 190-220 and 430 cm⁻¹, together with two broad structures centered at near 500 and 670 cm⁻¹, have been found. We also have observed that the A_1g mode is substantially shifted with increasing Cu substitution. The A_1g phonon shift is a linear function of the tolerance factor t and the rhombohedral angle α_r, thus following the structural changes of the MnO₆ octahedra in the system.     

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.     

Discrete Sturm–Liouville problems, Jacobi matrices and Lagrange interpolation series

The close relationship between discrete Sturm–Liouville problems belonging to the so-called limit-circle case, the indeterminate Hamburger moment problem and the search of self-adjoint extensions of the associated semi-infinite Jacobi matrix is well known. In this paper, all these important topics are also related with associated sampling expansions involving analytic Lagrange-type interpolation series.     

Reaction of SbPO4 with lithium in non-aqueous electrochemical cells: preliminary study and evaluation of its electrochemical performance in anodes for lithium ion batteries

SbPO₄, a phosphate with a layered structure, was tested as an electrode material for lithium cells spanning the 3.0-0.0 V range. Two main electrochemical processes were detected as extensive plateaus at ca. 1.6 and 0.7 V in galvanostatic measurements. The first process was found to be irreversible, thus excluding a potential intercalation-like mechanism for the reaction and being better interpreted as a decomposition reaction leading to the formation of elemental Sb. This precludes the use of this compound as a cathodic material for lithium cells. By contrast, the process at 0.7 V is reversible and can be ascribed to the formation of lithium-antimony alloys. The best electrochemical response was obtained by cycling the cell at a C/20 discharge rate over the voltage range 1.25-0.25 V. Under these conditions, the cell delivers an average capacity of 165 Ah/kg—a value greater than those reported for other phosphates—upon successive cycling.     

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.