Synthesis of 5-phenyl-2,3,8,9-tetramethoxy-11H-indeno[1,2-c]isoquinoline

A novel approach to the title compound 10 starting with a conveniently available cinnamic acid is proposed. It involves a Friedel-Crafts reaction followed by the synthesis of the amide and subsequent cyclodehydration via a Bischler-Napieralski reaction.     

Catalytic combustion of ethyl acetate over ceria-promoted platinum supported on Al2O3 and ZrO2 catalysts

Platinum-supported catalysts prepared by impregnation of mixed CeO₂/Al₂O₃ and CeO₂/ZrO₂ oxides using the sol-gel method were characterized and used in the combustion of ethyl acetate. In each series, the effect of CeO₂ loading (3 and 5 wt%) was studied. Characterization data from the studied catalysts (specific area measurements, hydrogen chemisorption, programmed temperature reduction (TPR), X-ray diffraction (XRD), photoelectron spectra (XPS) and transmission electron microscopy (TEM)) revealed significant changes in porosity and metal dispersion in each series. The catalytic activity of the solids, evaluated in the total combustion of ethyl acetate, exhibited a positive effect with the addition of Ce in the zirconia series whereas no significant changes was observed in the alumina series.     

Conformational analysis of 1,2,3,4-tetrahydroisoquinolines

Ring and nitrogen inversion account for the conformational equilibria of 3-phenyl-1, 2,3, 4-tetrahydroiso-quinolines. In order to quantitate the relative contribution of each conformer to the equilibrium, we undertook a molecular mechanics study on several substituted 3-phenyl-1, 2, 3, 4-tetrahydroisoquinolines. Predictions from calculations were checked against cmr chemical shift data. No boat conformation contributed significantly to the equilibrium. A general result of our calculations is that in all cases the 3-phenyl group in the equatorial position is strongly favored (by at least 2.50 kcal/mole). For 3-phenyl-1, 2, 3, 4-tetrahydroisoquinolines without substitution at nitrogen, N-H in equatorial position is preferred over the axial conformer, although the energy difference between both is always small (0.30–1.10 kcal/mole). For the cis-1,3-disubstituted compounds the le'3e conformers are the only species present (at least 99.8%). The calculated energy differences between the la′3a conformer and the le′3e conformer are always large (3.80–6.10 kcal/mole for the NHe conformers and 3.60–3.80 kcal/mole for the NHa conformers). The lack of a γ_1a upfield shift at C3 also points to the preference for the pseudoequatorial-equatorial conformer. For N-methyl-3-phenyl-1,2,3,4-tetrahydroisoquinoline a preference for the NMe group in the equatorial position is predicted (0.60–2.00 kcal/mole). The small downfield shift at C4 (γ_Na = 0.5 ppm) is consistent with the equatorial NMe preference. For the cis-1,2,3-trisubstituted compounds no significant γ_1a effect at C3 (γ_1a = -0.2 and 1.0 ppm) or γ_Na effect at C4 (γ_Na = 0.1 and 0.4 ppm) is observed. For these compounds, deformations due to steric congestion are evidenced by the deviation from the values of the C4a-C8a-Cl-N and C4a-C4-C3-N torsional angles, as compared to less crowded 3-phenyl-1,2,3,4-tetrahydroisoquinolines. Here the heterocyclic ring adopts a distorted half-chair conformation.     

Crystal chemistry and thermal behavior of metal salts and complexes of unsaturated dicarboxylic acids: aquabis(hydrogen itaconato)barium(II), [Ba(C5H5O4)2(OH2)]

[Ba(C₅H₅O₄)₂(OH₂)] is monoclinic, C2/c, with a = 4.472(1), b = 13.312(3), c = 22.236(5) Å, = 92.90(1)°, Z = 4, and D _m = 2.06 g cm^–3. The barium atom is 10-coordinate with Ba—O distances in the range 2.749(2)–2.989(2) Å. The material suffers a complex decomposition process upon heating at temperatures between 25 and 600°C in dynamic nitrogen and static air atmospheres. FT-IR and gas chromatography analyses indicate that water, CO, CO₂, methane, ethane, ethylene, propane, propylene, and butane, are evolved during the heating process, leaving a residue of BaCO₃. ¹H-NMR spectra of a sample heated at 200°C, showed isomerization of barium itaconate to barium methylmaleate.     

Crystal structure of triaquamaleatostrontium(II) monohydrate, [Sr(C4H2O4)(OH2)3]·H2O

[Sr(C₄H₂O₄)(OH₂)₃]·H₂O is monoclinic, P2₁/n, witha=11.476(2),b=7.027(1),c=12.344(2) Å, =115.74(3)°,V=896.67 ų,Z=4. The Sr atom is surrounded by nine oxygen atoms which come from four different maleate anions and three water molecules. The Sr–O distances range from 2.546(2) to 2.808(2) Å. The C–O distances are equal within the standard deviation 1.263(3) to 1.258(3) Å). In the maleate anion, the planes that contain the carboxylate groups form an angle of 74.44(9)°. Both carboxylate groups deviate significantly from planarity. The different coordination modes of the carboxylate group and the extensive hydrogen bonding present are responsible for the polymeric nature of the structure.     

Spectroscopic analysis of imidazolidines. Part II: 1H NMR spectroscopy and conformational analysis of 1,2 and 1,3‐diarylimidazolidines

¹H NMR spectra of a series of 1,2 and 1,3‐diarylimidazolidines are analyzed and correlated with their conformational features. Results were interpreted on the basis of chemical shifts and coupling constants of hydrogen atoms and confirmed by ID nOe difference experiments. 1,3‐Diarylimidazolidines ( 1–7 ) show a fast inversion of the N‐aryl nitrogen in all studied cases. 1,2‐Diaryl‐3‐methyl (or benzyl) imidazolidines ( 8–13 ) display a preferential conformation with a transoid orientation of N₃ and C₂ substituents.     

Stereoselective oxidative addition of benzenethiol to idene in the presence of ovoalbumin

The oxidative addition of benzenethiol to indene in the presence of ovoalbumin produces only one isomer on the surface of the protein,trans-anti-2-phenylsulfinyl-1-indanol. This reaction may be considered as a biomimetic model of detoxification of certain hydrocarbons by the liver.

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Stereoselektive oxydative Anlagerung von Thiophenol an Inden in Gegenwart von Ovoalbumin (Kurze Mitteilung)

Zusammenfassung Durch die oxydative Anlagerung von Thiophenol an Inden in Gegenwart von Ovoalbumin bildet sich nur ein Isomer an der Oberfläche des Proteins, dastrans-anti-2-Phenylsulfinyl-1-Indanol. Diese Reaktion kann als ein biomimetisches Modell der Entgiftung von gewissen Kohlenwasserstoffen durch die Leber betrachtet werden.

     

Nonlinear functional analysis and optimal economic growth

A problem of existence and characterization of solutions of optimal growth models in many sector economies is studied. The social utility to be optimized is a generalized form of a preference depending additively on consumption at the different dates of the planning period. The optimization is restricted to a set of admissible growth paths defined by production-investment-consumption relations described by a system of differential equations. Sufficient conditions are given for existence of a solution in a Hilbert space of paths, without convexity assumptions on either the utilities or the technology, using techniques of nonlinear functional analysis. A characterization is given of the utilities which are continuous with respect to the Hilbert space norm. Under convexity assumptions a characterization is also given of optimal and efficient solutions by competitive prices.     

Low reheating temperature and the visible sterile neutrino

We present here a scenario, based on a low reheating temperature T(R)<100 MeV at the end of (the last episode of) inflation, in which the coupling of sterile neutrinos to active neutrinos can be as large as experimental bounds permit (thus making this neutrino "visible" in future experiments). In previous models this coupling was forced to be very small to prevent a cosmological overabundance of sterile neutrinos. Here the abundance depends on how low the reheating temperature is. For example, the sterile neutrino required by the Liquid Scintillator Neutrino Detector result may not have any cosmological problem within our scenario.