Cyclisierungsreaktionen zu Pyrano[3,2-c]pyridinen und pyrano[3,2-c]chinolinen unter Verwendung von Ethoxymethylen-malodinitril bzw.-cyanessigester Synthesen mit Nitrilen, 50. Mitt. pyrano[3,2-c]quinolines with ethoxymethylene-malonitrile and-ethyl cyanoacetate,resp.

Reaction of ethoxymethylene-malonitrile and ethoxymethyleneethyl cyanoacetate, resp., with 4-hydroxy-2-pyridones (1a–b) and 4-hydroxy-2-quinolones (3a–b) leads to 2,5-dioxo-5,6-dihydro-2 H-pyrano[3,2-c]pyridine-(2a–d) and 2,5-dioxo-5,6-dihydro-pyrano[3.2-c]quinoline-derivatives (4a–d), resp.2a–d and4a–d exhibit remarkable visible fluorescence. Absorption- and emmission-data in different solvents are reported.     

Thianaphthenoyltrifluoroacetone as an analytical reagent: The keto-enol tautomerism of the 2- and 3-isomers of thianaphthenoyltrifluoroacetone

Summary The keto-enol tautomerism of the 2- and 3-isomers of thianaphthenoyltrifluoroacetone has been studied and the results explained by considering the relative negativities of the 2- and 3-position of thianaphthene. The results of the comparison of the keto-enol tautomerism of 3-thianaphthenoyltrifluoroacetone to that of 2-thenoyltrifluoroacetone in 80% benzene-20% ethanol may explain in part the greater sensitivity of the former in trace metal analysis.

---

Zusammenfassung Die Keto-Enol-Tautomerie der 2- und 3-Isomeren des Thianaphthenoyltrifluoracetons wurde untersucht und mit der relativen Negativität der 2- und 3-Stellung des Thianaphtens zu erklären versucht. Der Vergleich der Keto-Enol-Tautomerie von II mit der des 2-Thenoyltrifluoracetons in BenzolÄthanol (80+20) könnte eine Erklärung für die größere Sensitivität von II bei der Spurenmetallanalyse bieten.

     

Through-space delocalized water-soluble paracyclophane bichromophores: new fluorescent optical reporters

Conjugated polymers and oligomers can serve as highly responsive fluorescent reporters for biosensor applications. However, their optical properties in aqueous media are highly dependent upon environmental conditions. The structure of the paracyclophane framework provides a platform for designing optical reporters that show little sensitivity to surfactants, and thus is well-suited for fluorescent assays. The permanent intramolecular delocalization through the paracyclophane core dominates intermolecular perturbations in spontaneously formed aggregates.     

Arylesters of alkylsulfonic acids in sediments Part III of organic compounds as contaminants of the Elbe River and its tributaries

Sediments from the Elbe River and from its major tributaries are shown to be contaminated with arylesters of alkylsulfonic acids. Here we report on the structure elucidation and quantification of aryl esters of alkylsulfonic acids. Chromatographic separation and mass spectrometric properties are discussed. Congener-specific analyses revealed a highly similar pattern throughout the area investigated. Alkylsulfonic acid phenylesters were present at almost all sampling locations. Amounts ranged from 33 000 μg/kg near the industrial region of Bitterfeld to 15 μg/kg in wadden sea sediments. Concentrations of alkylsulfonic acid cresylesters were between 10–40% of the phenylesters, and fell below the detection limit only in the Elbe estuary. The presence of aryl esters of alkylsulfonic acids in all sediment samples analyzed indicates a widespread distribution of these compounds in the environment. Previous literature described these compounds erroneously as phenoxyalkanes. Received: 5 August 1997 / Accepted: 21 August 1997     

[(C6H5)3P]2Ni(Me3Si?CC?SiMe3). Darstellung,Eigenschaften und Struktur des ersten stabilen Nickel(0)-Komplexes von Bis-trimethylsilylacetylen

[(C₆H₅)₃P]₂Ni(Me₃Si? C?C? SiMe₃). Preparation, Properties, and Structure of the First Stable Nickel(0) Complex with Bis(trimethylsilyl)acetylene The title compound is the first example of a nickel(0) complex with bis(trimethylsilyl)acetylene and obtained from (ph₃P)₂Ni(C₂H₄) and bis(trimethylsilyl)acetylene in tetrahydrofuran. The complex is characterized by some reactions, the i.r. spectrum and by a structural analysis with the aid of X-ray diffraction data. (ph₃P)₂Ni(Me₃Si? C?C? SiMe₃) crystallizes monoclinic in the space group C2/c with four formula units per unit cell (2468 observed, independent reflexions, R = 0.038). The cell dimensions are a = 20.927, b = 13.812, c = 14.238 Å, α = γ = 90°, β = 91.02°. The molecules are monomer in crystalls. The molecule is planar with ligands arranged trigonally about the central atome but distorted to the tetrahedral complex.     

Rotational diffusion effects on absorbance measurements: limitations to the magic-angle approach.

Optical absorbance changes are commonly used to characterize intermediates which appear in the bleaching sequence of rhodopsin and in the photocycle of bacteriorhodopsin. Absorbance changes can be caused by an intermediate's rotational diffusion, and when this occurs it can distort absorbance changes due to the structural evolution of intermediates. Linear polarization of an optical probe source at 54.7 degrees (the magic angle) relative to the polarization direction of a linearly polarized actinic source has often been used to eliminate signals due to rotational diffusion. We used Jones calculus to investigate the validity of the magic-angle strategy. Taylor expansion of the result in powers of the absorbances of the bleached ground state and of the intermediates leads to a relatively simple expression which can be used to determine whether rotational contributions are likely under various experimental conditions. This expression shows that in first order no dichroism-dependent term appears in the absorbance measured at magic angle. In second order, however, linear dichroism contributes to signals. For the sequence of rhodopsin intermediates: rhodopsin hv----bathorhodopsin in equilibrium BSI----lumirhodopsin, where BSI is a recently discovered blue-shifted intermediate, we determined the magnitude of the dichroism signals to be, on average, less than 2% of the true absorbance change due to the intermediates themselves (and hence undetectable). Freedom from dichroism artifacts in this case results from the fact that the transition dipoles of these intermediates are similar to that of rhodopsin. Larger and certainly detectable dichroism signals are predicted to occur, even at the magic angle, for later intermediates which have transition dipole moments which differ significantly from that of rhodopsin.(ABSTRACT TRUNCATED AT 250 WORDS)     

Preparation of some complexes of the type (C6H5)3P[(CH3)2AsCH2CH(R)CH2As(CH3)2] M(CO)3 (M = Mo or W,R = H or C(CH3)3)

The title compounds, which contain six-membered chelate rings locked in the chair conformation, have been prepared by the reaction of (C₆H₅)₃P with the appropriate tetracarbonyl derivative in refluxing mesitylene.     

Triplet-triplet energy transfer in the tryptophyl-tyrosinate dipeptide

Direct evidence for intermolecular triplet-triplet energy transfer in the dipeptide tryptophyl-tyrosine is presented. The methods of steady state ODMR and transient ODMR yield rates for the triplet-triplet energy transfer process of order 10 s^?1.     

High-resolution field desorption mass spectrometry: Part VII. Explosives and Explosive Mixtures4

Standard explosives and technical mixtures of explosives have been investigated by field desorption mass spectrometry. The compounds investigated gave intense molecular ions or protonated molecules and structurally significant fragmentation. For comparison, the corresponding electron impact and chemical ionization mass spectrometry data are reported. Emission-controlled field desorption, photographic detection, and accurate mass measurements enabled the components of the technical mixtures to be identified. An example of the determination of an additive in a technical product by field desorption mass spectrometry and stable isotope dilution is given. The use of these techniques for quality control of explosives and for forensic investigations appears to be promising.     

Activated alpha-alkyl-alpha-arylacetic acid enantiomers for stereoselective thin-layer chromatographic and high-performance liquid chromatographic determination of chiral amines

The separation of racemic benoxaprofen into the two benoxaprofen enantiomers by preparative high-performance liquid chromatography and the application of the activated enantiomers as derivatization reagents for the simultaneous stereoselective determination of chiral amines in biological material is described. Activated (+)- and (-)-benoxaprofen are both shown to be very sensitive and stable chiral fluorescence markers, applicable to thin-layer chromatography as well as to high-performance liquid chromatography.