Lithiation and electrophilic substitution of 8-chlorodibenz[b,f][1,4]-oxazepine-10-tert-butylcarbamate: The preparation of novel fused heterocyclic derivatives of 8-chlorodibenzoxazepine

Lithiation of 8-chlorodibenz[b,f][1,4]oxazepine-10-tert-butylcarbamate ( 1 ) is described. Electrophilic substitution of the resulting N-Boc dibenzoxazepine α- lithioamine 2 with ketones, aldehydes, nitriles, iso-cyanates and imines, followed by an in-situ cyclization, gave fused carbamates 5–26 , fused 2H-imidazol-2-ones 27–29 , fused hydantoins 30–32 , and fused ureas 33–35 , respectively, in 11–66% yield.     

Development of combinatorial chemistry methods for coatings: high-throughput adhesion evaluation and scale-up of combinatorial leads

Coupling of combinatorial chemistry methods with high-throughput (HT) performance testing and measurements of resulting properties has provided a powerful set of tools for the 10-fold accelerated discovery of new high-performance coating materials for automotive applications. Our approach replaces labor-intensive steps with automated systems for evaluation of adhesion of 8 x 6 arrays of coating elements that are discretely deposited on a single 9 x 12 cm plastic substrate. Performance of coatings is evaluated with respect to their resistance to adhesion loss, because this parameter is one of the primary considerations in end-use automotive applications. Our HT adhesion evaluation provides previously unavailable capabilities of high speed and reproducibility of testing by using a robotic automation, an expanded range of types of tested coatings by using the coating tagging strategy, and an improved quantitation by using high signal-to-noise automatic imaging. Upon testing, the coatings undergo changes that are impossible to quantitatively predict using existing knowledge. Using our HT methodology, we have developed several coatings leads. These HT screening results for the best coating compositions have been validated on the traditional scales of coating formulation and adhesion loss testing. These validation results have confirmed the superb performance of combinatorially developed coatings over conventional coatings on the traditional scale.     

Efficient conversion of substituted aryl thioureas to 2-aminobenzothiazoles using benzyltrimethylammonium tribromide

The reaction of molecular bromine (Br2) with arylthioureas is known to produce 2-aminobenzothiazoles (Hugerschoff reaction). We show here that benzyltrimethylammonium tribromide (1, PhCH2NMe3Br3), a stable, crystalline organic ammonium tribromide (OATB), can be readily utilized as an alternative electrophilic bromine source. It is easier to control the stoichiometry of addition with an OATB, which minimizes aromatic bromination caused by excess reagent. We have developed a direct procedure from isothiocyanates and amines using tetrabutylammonium thiocyanate (Bu4NSCN) and PhCH2NMe3Br3 to afford functionalized 2-aminobenzothiazoles.     

The fate of the hydroxyalkoxy radical in the OH‐initiated oxidation of isoprene

Rate constants for several intermediate steps in the OH‐initiated oxidation of isoprene were determined using laser‐photolysis/laser‐induced fluorescence of OH radicals at total pressures between 3 and 4 Torr at 295 K. The rate constant for decomposition of the hydroxyalkoxy radical was determined to be (3.0 ± 0.5) × 10⁴ s^?1 in this pressure range, which is in fair agreement with previous work. The presence of a prompt alkoxy decomposition pathway was also investigated and found to contribute less than 10% to the total hydroxyalkoxy radical decomposition. The rate constant for the reaction of the hydroxyperoxy radical with NO was determined to be (2.5 ± 0.5) × 10^?11 cm³ molecule^?1 s^?1, which is moderately higher than previously reported. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 255–261, 2002     

Anomalous Stereochemistry in the Wittig Reaction Induced by Nucleophilic Groups in the Phosphonium Ylide

Abstract

Reaction of ylides from 3–9 with benzaldehyde show that carboxylate and oxido functionalities proximate to the ylide center promote anomalously high E stereoselectivity in alkene formation. Through the use of α-deuterated ylides 12–14, an internal “trans-selective Wittig” mechanism was ruled out as a principal source of exaggerated E alkene production.     

Neutron dosimetric measurements in shuttle and MIR

Detector packages consisting of thermoluminescence detectors (TLD), nuclear emulsions and plastic track detectors were exposed at identical positions inside MIR space station and on shuttle flights inside Spacelab and Spacehab during different phases of the solar cycle. The objectives of the investigations are to provide data on charge and energy spectra of heavy ions, and the contribution of events with low-energy deposit (protons, electrons, gamma, etc.) to the dose, as well as the contribution of secondaries, such as nuclear disintegration stars and neutrons. For neutron dosimetry 6LiF (TLD600) and 7LiF (TLD700) chips were used both of which have almost the same response to gamma rays but different response to neutrons. Neutrons in space are produced mainly in evaporation and knock-on processes with energies mainly of 1-10 MeV and up to several 100 MeV, respectively. The energy spectrum undergoes continuous changes toward greater depth in the attenuating material until an equilibrium is reached. In equilibrium, the spectrum is a wide continuum extending down to thermal energies to which the 6LiF is sensitive. Based on the difference of absorbed doses in the 6LiF and 7LiF chips, thermal neutron fluxes from 1 to 2.3 cm-2 s-1 are calculated using the assumption that the maximum induced dose in TLD600 for 1 neutron cm-2 is 1.6 x 10(-10) Gy (Horowitz and Freeman, Nucl. Instr. and Meth. 157 (1978) 393). It is assumed that the flux of high-energy neutrons is at least of that quantity. Tissue doses were calculated taking as a mean ambient absorbed dose per neutron 6 x10(-12) Gy cm2 (for a10 MeV neutron). The neutron equivalent doses for the above-mentioned fluxes are 52 micro Gy d-1 and 120 micro Gy d-1. In recent experiments, a personal neutron dosimeter was integrated into the dosimeter packages. First results of this dosimeter which is based on nuclear track detectors with converter foils are reported. For future measurements, a scintillator counter with anticoincidence logic is under development.     

Radiation measurements on the Mir Orbital Station

Radiation measurements made onboard the MIR Orbital Station have spanned nearly a decade and covered two solar cycles, including one of the largest solar particle events, one of the largest magnetic storms, and a mean solar radio flux level reaching 250 x 10(4) Jansky that has been observed in the last 40 years. The cosmonaut absorbed dose rates varied from about 450 microGy day-1 during solar minimum to approximately half this value during the last solar maximum. There is a factor of about two in dose rate within a given module, and a similar variation from module to module. The average radiation quality factor during solar minimum, using the ICRP-26 definition, was about 2.4. The drift of the South Atlantic Anomaly was measured to be 6.0 +/- 0.5 degrees W, and 1.6 +/- 0.5 degrees N. These measurements are of direct applicability to the International Space Station. This paper represents a comprehensive review of Mir Space Station radiation data available from a variety of sources.     

Determination of charge states of single swift heavy projectiles by high-energy delta-electrons

The effective charge state is an important particle parameter which is required for the calculation of many effects concerning the interaction between radiation and matter such as an estimate of the radial dose of swift heavy projectiles, stopping power and so on. A new method for the determination of effective charge states of heavy ions is based on the measurement of the number of high-energy delta-electrons which are ejected from a target by the penetrating ion. These electrons are detectable with a CCD-detector and their number can be correlated to the effective charge state of the projectile for known particle velocities. This method is even applicable to operation with single swift heavy ions within statistical bounds.     

Investigation of proton-proton short-range correlations via the 12C(e,e'pp) reaction

We investigated simultaneously the 12C(e,e'p) and 12C(e,e'pp) reactions at Q2=2 (GeV/c)2, xB=1.2, and in an (e, e'p) missing-momentum range from 300 to 600 MeV/c. At these kinematics, with a missing momentum greater than the Fermi momentum of nucleons in a nucleus and far from the delta excitation, short-range nucleon-nucleon correlations are predicted to dominate the reaction. For (9.5+/-2)% of the 12C(e,e'p) events, a recoiling partner proton was observed back-to-back to the 12C(e,e'p) missing-momentum vector, an experimental signature of correlations.     

Influence of thermal and thermo-mechanical treatment

Two lipids with similar melting ranges but of different composition were analyzed using differential scanning calorimetry and X-ray diffraction. The lipids were processed via extrusion or were tempered at different temperatures; they were analyzed directly after extrusion and after storage at 40°C. Precirol ATO 5® showed high sensitivity to storage time and varied temperature exposure. Extrusion showed only marginal influences on the solid state. Melting peaks were narrower and shifted to higher temperatures in comparison to the untreated powder. Dynasan 114® was more robust, changes in the solid state could only be shown for samples treated above the melting range. Thus, Dynasan 114® is more appropriate for solid lipid extrusion of pharmaceutical products.