Conformational effects in 3-halotetrahydropyrans

The conformational equilibria of 3-chloro- and 3-bromotetrahydropyran were measured by NMR and IR spectroscopy using model 2-alkyl-5-halotetrahydropyrans. The 3-chloro compound was 76·2% equatorial in carbon tetrachloride and 58·5% in acetonitrile and the 3-bromo compound 85% equatorial in carbon tetrachloride. The conformational equilibrium is discussed in terms of dipole, electronic and van der Waals effects.     

Application of the Ester Enolate Claisen Rearrangement in the Synthesis of Amino Acids Containing Quaternary Carbon Centers

Ester enolate Claisen rearrangement of highly substituted amino acid allylic esters 4 allows for the synthesis of sterically demanding amino acids 5 with beta-quaternary carbon centers. Because of enolate fixation by chelation, the rearrangement occurs in a highly diastereoselective fashion. The methodology is suitable not only for glycine derivatives but also for allylic esters of various amino acids. In this case amino acids with two vicinal quaternary carbon centers are created. With unsymmetrically substituted allylic esters like 4k-n the rearrangement proceeds with a high degree of diastereoselectivity.     

Regio- and Stereoselective Reactions of 17-Phenyl-18,19,20-trinorprostaglandin F(2)(alpha) Isopropyl Ester

Novel prostaglandin F(2)(alpha) derivatives, functionalized at C13 and C14, have been prepared. 17-Phenyl-18,19,20-trinorprostaglandin F(2)(alpha) isopropyl ester [(15S)-1] and its epimer [(15R)-1] were stereoselectively epoxidized, using Sharpless conditions, to produce each of the four diastereomeric epoxides (15S)-2, (15S)-3, (15R)-2, and (15R)-3. Treatment of the four epoxides with LiOH stereospecifically-produced the pentahydroxy substituted analogues 12 and 13. Alternatively, epoxides 2 and 3were allowed to react with thiophenolate ion. The attack of the sulfur nucleophile on the epoxide occurred at either C13 or C14 depending on the stereochemistry of the epoxide and of C15.     

Ultraviolet protection factors for clothing: an intercomparison of measurement systems

In recent years the need to standardize measurement protocols for quantifying the degree of ultraviolet radiation (UVR) protection provided by clothing has led to the introduction of a number of standards around the world. To date, these standards have specified spectral measurements of UVR transmission by clothing and fabrics. Development of a standard test method has become an important part of the testing process, and this article presents results from an intercomparison involving 10 independent testing laboratories and 11 different UVR transmission measurement instruments. In addition to comparing the measured ultraviolet protection factors (UPF), this intercomparison also incorporates detailed scan results from all 10 laboratories and highlights differences in performance of the various instruments in different wavelength regions. Careful examination of these differences can indicate where changes to the systems could be made to allow improvements both in equipment performance and in agreement of the final results. The variability in the measurements of UPF in this study suggest that the protection categories in standards may need to be broadened.     

The MPE/UCB far-infrared imaging Fabry-Perot interferometer (FIFI)

FIFI is an imaging spectrometer with two or three Fabry-Perot interferometers (FPI) in series for airborne astronomical observations in the far-infrared range (=40...200m). It employs 5×5 arrays of photoconducting detectors and offers spectral resolutions as small as 2km/s. Resolution and bandwidth can be set over a wide range to match a variety of astronomical sources. Cryogenic optics minimizes thermal background radiation and provides for in-flight step tunable spatial resolution. At 158 m wavelength the background-limited NEP is 3 × 10^-15W/Hz at 40 km/s resolution and with two FPI's; with three FPI's the expected NEP is 10^-15WHz at 5 km/s resolution.The frequency-chopping mode of the high-resolution Fabry-Perot allows for line detection in extended objects. Absolute internal flux calibration ensures adequate flat fielding of the array elements.     

Small Scale Models Subjected to Buried Blast Loading Part I: Floorboard Accelerations and Related Passenger Injury Metrics with Protective Hulls

Small scale models representing key vehicle structural elements, including both floorboards and bottom-mounted, downward V-shape hulls in various configurations, have been manufactured and subjected to a range of buried blast loading conditions. By varying surface stand-off distance and depth of burial for several hull and structure configurations, the input-scaled response of aluminum full-scale vehicle floorboards has been quantified using high speed stereo-vision. Specifically, the maximum vertical acceleration on the floorboard and the corresponding Head Injury Criterion (HIC₁₅) are quantified as metrics to assess the severity of the blast event. Results show standard V-shaped hulls provide essential blast mitigation, with reductions in floorboard measurements up to 47X in maximum acceleration and HIC₁₅. Though variations in protective hull geometry provide modest reductions in the severity of a floorboard blast event, results also show that personnel on typical floorboard structures during blast loading events will incur unacceptable shock loading conditions, resulting in either serious or fatal injury. A more appropriate design scenario would be to consider situations that employ frame-mounted passenger seating to reduce the potential for injury. A second set of experiments will be presented in Part II that focuses on frame motions and accelerations when steel frames and steel structures are employed with various frame connections and coatings for frame blast mitigation.     

A Straightforward Synthesis of Polyketides via Ester Dienolate Matteson Homologation

Application of ester dienolates as nucleophiles in Matteson homologations allows for the stereoselective synthesis of highly substituted α,β-unsaturated δ-hydroxy carboxyl acids, structural motifs widespread found in polyketide natural products. The protocol is rather flexible and permits the introduction of substituents and functionalities also at those positions which are not accessible by the commonly used aldol reaction. Therefore, this ester dienolate Matteson approach is an interesting alternative to the “classical” polyketide syntheses.