Synthesis of N-alkoxycarbonyl and N-carboxamide derivatives of anti-inflammatory oxindoles

The synthesis of N-alkoxycarbonyl and N-carboxamide derivatives of anti-inflammatory oxindoles is described. These compounds, sought as potential prodrugs of the parent anti-inflammatory agents, were obtained by ring opening of the oxadiazine dione intermediates formed by the treatment of 1-unsubstituted 3-acyloxindoles with chlorocarbonyl isocyanate.     

Rates of convex approximation in non-hilbert spaces

This paper deals with sparse approximations by means of convex combinations of elements from a predetermined “basis” subsetS of a function space. Specifically, the focus is on therate at which the lowest achievable error can be reduced as larger subsets ofS are allowed when constructing an approximant. The new results extend those given for Hilbert spaces by Jones and Barron, including, in particular, a computationally attractive incremental approximation scheme. Bounds are derived for broad classes of Banach spaces; in particular, forL _p spaces with 1<p<∞, theO (n ^−1/2) bounds of Barron and Jones are recovered whenp=2. One motivation for the questions studied here arises from the area of “artificial neural networks,” where the problem can be stated in terms of the growth in the number of “neurons” (the elements ofS) needed in order to achieve a desired error rate. The focus on non-Hilbert spaces is due to the desire to understand approximation in the more “robust” (resistant to exemplar noise)L _p, 1 ≤p<2, norms. The techniques used borrow from results regarding moduli of smoothness in functional analysis as well as from the theory of stochastic processes on function spaces.     

THE TRANS → CIS PHOTOISOMERIZATION OF PROTONATED RETINYL SCHIFF BASES

Schiff bases were prepared from all- trans -retinal (I) and pyrrolidine perchlorate (II) and from I and n-butyl amine, protonated with anhydrous hydrogen chloride gas, Ill. Initial quantum yields of trans → cis photoisomerization (Φ°PI) were determined and primary photoproducts and product ratios were measured in aerated methanol. Φ°PI of all- trans -III is independent of excitation energy. All analyses were made using high-pressure liquid chromatographic (LC) methods. It was necessary to hydrolize the Schiff bases to corresponding retinals prior to LC analysis.     

Rapid measurement of leucine-specific activity in biological fluids by ion-exchange chromatography and post-column ninhydrin detection.

Commonly used methods for the measurement of leucine-specific activity use either high-performance liquid chromatography (HPLC) and pre-column derivatization or conventional ion-exchange chromatography. These are time-consuming, labor-intensive, relatively costly procedures, requiring high concentrations of radioactivity for accuracy. The present paper describes a method for the measurement of plasma leucine-specific activity using HPLC equipment, a large-bore ion-exchange column and post-column ninhydrin detection. With this method, determination of leucine concentration and leucine radioactivity was found to be linear (r2 greater than 0.999) over physiological ranges for both standards and deproteinized plasma. The intra- and inter-assay coefficients of variation for leucine concentrations were 1.4 and 2.7%, respectively. The intra- and inter-assay coefficients of variation for leucine-specific activities were 1.5 and 1.9%, respectively. The automated method is relatively fast (injection to injection time approximately 45 min), economical and capable of accurately assessing relatively small amounts of radioactivity.     

Synthesis and Structures of Polyphenylphenanthrenes

1,2,3,4,5,6,7,8-Octaphenylphenanthrene ( 4 ) and decaphenylphenanthrene ( 5 ) were prepared by very short syntheses (two or three steps) from tetraphenylfuran and polybrominated benzene derivatives. The X-ray structures of compounds 4 and 5 show them to be quite crowded, with the phenanthrene cores twisted by about 40° due to the clash of the C4 and C5 phenyl groups. Compound 4 was resolved by chromatography on a chiral support, and its free energy of activation for racemization was determined to be 24.6 kcal mol⁻¹ at 40 °C. Computational studies indicate that compound 5 has a racemization barrier approximately 6 kcal mol⁻¹ lower than 4 , and thus 5 would not be configurationally stable at room temperature.     

The dithiolene ligand and tetrathiafulvalene precursor molecules 4,5‐bis(bromomethyl)‐1,3‐dithiol‐2‐one and 4,5‐bis[(dihydroxyphosphoryl)methyl]‐1,3‐dithiol‐2‐one

The crystal structures of 4,5‐bis(bromomethyl)‐1,3‐dithiol‐2‐one, C₅H₄Br₂OS₂, (I), and 4,5‐bis[(dihydroxyphosphoryl)methyl]‐1,3‐dithiol‐2‐one, C₅H₈O₇P₂S₂, (II), occur with similar unit cells in the same monoclinic space group. Both molecules reside on a twofold symmetry axis coincident with the C=O bond, so that the substituents in the 4‐ and 5‐positions project above and below the plane of the 1,3‐dithiol‐2‐one ring. In both structures, the molecules align themselves in a head‐to‐tail fashion along the b axis, and these rows of molecules then stack, with alternating directionality, along the c axis. For (II), an extensive network of intermolecular hydrogen bonds occurs between molecules within the same stack and between adjacent stacks. Each –CH₂P(O)(OH)₂ group participates in four hydrogen bonds, twice as donor and twice as acceptor.     

Tetrahydroberberine,a pharmacologically active naturally occurring alkaloid

Tetrahydroberberine (systematic name: 9,10‐dimethoxy‐5,8,13,13a‐tetrahydro‐6H‐benzo[g][1,3]benzodioxolo[5,6‐a]quinolizine), C₂₀H₂₁NO₄, a widely distributed naturally occurring alkaloid, has been crystallized as a racemic mixture about an inversion center. A bent conformation of the molecule is observed, with an angle of 24.72 (5)° between the arene rings at the two ends of the reduced quinolizinium core. The intermolecular hydrogen bonds that play an apparent role in crystal packing are 1,3‐benzodioxole –CH₂...OCH₃ and –OCH₃...OCH₃ interactions between neighboring molecules.