Syntheses totales et etudes de lignanes biologiquement actifs—I : Application de la reaction d'ullmann a la synthese de biaryles precurseurs de lignanes bisbenzocyclooctadienes

Several biaryls bearing various substituents on both rings were synthesized in a preparative fashion, and in yields up to 88% by a technical improvement on the classical Ullmann reaction. All these biaryls bear reactive functional groups (i.e. formyl, methoxycarbonyl, dimethoxycarbonylpropyl and butanolidylmethyl) in both the o and o′ positions. The biaryls 9, 13, 21 and 26–33 are plausible synthons for bisbenzocyclooctadiene lignans such as schizandrin and steganacin.     

The crystal and molecular structure of 1,1,2,4,4,5-hexaphenyl-1,4-diphosphoniacyclohexadiene-2,5 dibromide

The crystal and molecular structure of 1,1,2,4,4,5-hexaphenyl-1,4-diphosphoniacyclohexadiene-2,5 dibromide has been determined by a single crystal, x-ray diffraction study using diffractometer data. The compound crystallizes in the space group P2₁/_c with unit cell constants a = 8.813(1), b = 36.736(4), c = 12.478(1) Å, and β = 120.91°(1). The structure was solved by the heavy atom method and refined by block-diagonal least-squares to a final R = 0.04 for the 2761 statistically significant reflections. The structure determination shows that the central phosphonium ring is a diene and not a delocalized structure as anticipated. The ring is in the boat conformation with the axial phenyl rings aligned essentially parallel to each other and 3.55 Å apart.     

Microelectrochemical sensors for in vivo brain analysis: an investigation of procedures for modifying Pt electrodes using Nafion

Various Nafion coating procedures were examined in order to design a simple and reproducible coating method to maximise permselective characteristics, and thus eliminate signals from electroactive interferents, in sensors designed for direct in vivo measurements in the brain. Interferents investigated included ascorbic acid (AA), the principal endogenous electroactive interferent present in the brain, and uric acid. Application of the Nafion (5% commercial solution) using a thermally annealing procedure involving 5 pre-coats, and 2 subsequent dip-bake layers resulted in elimination of interferent signals. It also produced complete blocking of the signal for the neurotransmitter dopamine. The optimum time and temperature for annealing was found to be 5 min at 210 degrees C. An examination of shelf life over two weeks indicated negligible AA interference over this period. Preliminary investigations with respect to the potential use of these Nafion-modified Pt electrodes in the design of implantable, first generation, peroxide detecting biosensors indicated that the modified electrode had no effect on O2 permeability but did produce a significant decrease in H2O2 sensitivity. While this may preclude their use in biosensor development they may be more suitable for detection of gaseous neurochemicals such as nitric oxide.     

Henry's law and diffusion constants of vinyl chloride in poly(vinyl chloride) at high temperature

The Henry's law and diffusion constants of vinyl chloride in poly(vinyl chloride) were determined at temperatures of 24, 90, 120, 150, and 170°C for weight fractions of vinyl chloride between 0.2 × 10^?3 and 0.8 × 10^?3. Above 90°C, Henry's law applies; values of the constant increase with temperature from 1.8 × 10² to 5.5 × 10² atm per unit weight fraction of dissolved vinyl chloride. The heat of desorption is about 15 kJ/mole. At 24°C, the nominal Henry's law constant was smaller than would have been obtained by extrapolating the values found at higher temperature. The diffusion constants increase with temperature from about 2 × 10^?13 to 3 × 10^?7 cm²/sec. The activation energy for diffusion is about 110 kJ/mole between 90 and 170°C. Although all values were determined in the absence of air, it is likely that they apply to polymer in air. They may, therefore, be used to calculate the vinyl chloride content in the gas above poly(vinyl chloride) under specific processing conditions.     

Asymmetric total synthesis of the antileukaemic lignan precursor (-)steganone and revision of its absolute configuration

A total synthesis of (-)steganone, correlating it with L-glutamic acid, shows it to have the opposite configuration to that assigned by Kupchan.     

Mass spectral rearrangements of N,N-bis(4′-arylthio-2′-butynyl)anilines and N,N-bis(4′-arylsulfonyl-2′-butynyl)anilines

The title compounds display unusual modes of fragmentation under electron impact. One of the dominant modes is the concerted elimination of the two arylthio and arylsulfonyl moieties followed by further extrusion of the C₆H₄ unit as a cumulene. No elimination of SO₂ is observed from any of the sulfones nor an expulsion of the C₄H₄ fragment. Such behavior contrasts strikingly with that of 1,4-diarylsulfonyl-2-butynes and of the 1,6-diarylsulfonyl-2,4-hexadiynes.     

Reactive intermediates in asymmetric cross-coupling catalysed by palladium P-N chelates

The palladium dibromide complexes of (S,R)-(1,1′-bis-diphenylphosphino)-2-ferrocencylthyldimethylamine and (S,R)-(1-diphenylphosphino)-2-ferrocenylethyldimethylamine have been reduced with dilithiocyclooctatetraene to form the corresponding Pd⁰ cyclooctatetraene complexes. Their reactions with E-4-methoxy-2′-bromophenylethene, and then benzylmagnesium chloride at −60 to −30°C, provide information on the structure of intermediates in asymmetric cross-coupling.     

Gas-phase copolymerization of sulfur dioxide and butene-1

Mixtures of sulphur dioxide and butene-1 have been polymerized in the gas phase to the 1:1 alternating copolymer by electron irradiation. The rate of polymerization, measured by the decrease in gas pressure, decreased with increase in temperature over the range ?20 to +30°C. The initial G(-monomer) values decreased from 500 to 50 giving an Arrhenius activation energy of ?30 kJ mol^?1. These results are consistent with a ceiling temperature-pressure relationship. The ceiling temperature is about 60°C lower than that observed previously in the liquid phase in accord with thermo-dynamic prediction.     

Analysis of partially resolved liquid chromatographic peaks using dynamic modeling with the kalman filter

Establishing a calibration model is an important part of any mathematical method for multi-component determination. Use of a calibration model based on single spectra is subject to error, because the model spectrum chosen may not be representative of the response over the full range of the calibration. Alternative calibration models require more time to establish calibration, an these may not be convenient for real-time determinations. A novel calibration method is reported for use with Kalman filters. The method, dynamic modeling, is based on the use of libraries of calibration spectra. The set of used to describe the model at any time is based on component concentrations, estimated for the multi-component mixture, as determined from the Kalman filter, so that several spectra can be used to best describe a varying response. Through application of the dynamic modelingt to simulated and real chromatograms, it is demonstrated that use of the method decreases estimation errors cause by model data mismatches, and that full benefit can be obtained from relatively small libraries.     

The isomerization of optically-active propargyl alcohols to terminal acetylenes.

The isomerization of optically-active secondary propargyl alcohols, RCHOHCC(CH₂)_nCH₃, to terminal acetylenic alcohols, RCHOH(CH₂)_n+1 C=CH, by potassium 3-aminopropylamide (KAPA) proceeds without loss of configuration at the hydroxy center.