Furan derivatives. Part 10. Synthesis of cyclohepta[cd]benzofuran

Cyclohepta[cd]benzofuran 2 was synthesized by heating (5-oxo-5H-benzocyclohepten-4-yloxy)acetic acid 16 with sodium acetate in acetic anhydride or by photocyclization of 16 in acetonitrile. Several reactions of cyclohepta[cd]benzofuran 2 were examined. Protonation of 2 with trifluoroacetic acid occurred at the 2-position to give a tropylium ion 17 . Catalytic hydrogenation of 2 with palladium on charcoal proceeded smoothly to give tetrahydrocyclohepta[cd]benzofuran 18 . The Diels-Alder reaction of 2 with tetracyano-ethylene produced an adduct 19 . Formylation of 2 with phosphorus oxychloride and dimethylformamide occurred easily at the 2-position to afford compound 20 . Cyclohepta[cd]benzofuran 2 has both properties of heptafulvene and benzofuran.     

Furan derivatives. Part 12 . Synthesis of 2,5-dioxacyclohepta[jkl]-as-indacenes

A variety of 2,5-dioxacyclohepta[jkl]-as-indacenes 5, 7–14 were synthesized as a new heterocycle by the treatment of diethyl (5,9-dioxobenzocyclohepten-1,4-diyloxy)diacetates 4a-e with potassium hydroxide or sodium hydride in dioxane. The mechanism of furan-ring formation from 4a-e was discussed.     

A study on the reaction between chlorine trifluoride gas and glass-like carbon

The reaction between glass-like carbon (GC) and chlorine trifluoride (ClF₃) gas was investigated with weight measurements, surface analysis, and gas desorption measurements, where the ClF₃ gas is used for the in situ cleaning of tubes in silicon-related fabrication equipment. From Auger electron spectroscopy and X-ray photoelectron spectroscopy measurements, a carbon mono-fluoride, –(CF)_n–, film near the surface of GC is considered to be grown onto the GC surface above 400 °C by the chemical reaction with ClF₃, and this thickness of the fluoride film depends on the temperature. The grown fluoride film desorbs by annealing in a vacuum up to 600 °C. Although GC is apparently etched by ClF₃ over 600 °C, the etch rate of GC is much lower than that of SiC and quartz.     

Experimental investigation on reversal of secondary Bjerknes force between two bubbles in ultrasonic standing wave

The direction of the secondary Bjerknes force between a free bubble and an attached bubble was experimentally investigated. The behavior of the two bubbles in an ultrasonic standing wave of 27 kHz was observed using an imaging system with a high-speed video camera. It was demonstrated experimentally that the direction of the force reversed at a specific separation distance between the two bubbles, which was defined as the threshold distance. The threshold distance changed with the radius of the attached bubble. In addition, a theoretical calculation was performed using a previously derived model that coupled the vibrations of two free bubbles [Ida, Phys. Lett. A 297, 210-217 (2002)]. The experiment data for the threshold distance qualitatively agreed with the theoretical predictions, except when the separation distance was very small. Then, it was discovered that the free bubble became trapped near the attached bubble when the separation distance between the two bubbles was very small. This indicated that a stable equilibrium point for the separation distance exists that cannot be predicted by the theoretical model.     

Rapid breakdown mechanisms of open air nanosecond dielectric barrier discharges

The discharge initiation mechanism of nanosecond dielectric barrier discharges in open air has been clarified with time-dependent measurement of the discharge electric field by electric-field-induced coherent Raman scattering and optical emission. Our experimental observations have revealed that, in the prebreakdown phase of a nanosecond dielectric barrier discharge, the externally applied fast-rising electric field is strongly enhanced near the cathode due to large accumulation of space charge, which then strongly enhances ionization near the cathode. Once a sufficiently large number of ionizations take place, the location of peak ionization forms a front and propagates toward the cathode with strong optical emission, which establishes the discharge. This process is essentially different from the well-known Townsend mechanism for slower discharges.     

Synthesis of 7‐acetyloxy‐3,7‐dimethy1‐7,8‐dihydro‐6H‐isochromene‐6,8‐dione and its analogues

7‐Alkanoyloxy‐3,7‐dimefhyl‐7,8‐dihydro‐6H‐isochromene‐6,8‐diones 12‐15 were synthesized in 69‐16% yields from the reaction of 2,4‐dihydroxy‐3‐methyl‐6‐(2‐oxopropyl)benzaldehyde 11 with p‐toluenesulfonic acid in various carboxylic acids such as acetic acid, propionic acid, butyric acid and heptanoic acid followed by oxidation with lead tetraacetate. On the other hand, (±)‐daldinin A 5 (oleate) was not obtained using oleic acid as a medium. In the cases of heptanoic acid and oleic acid, esters 16 and 17 were produced in 23 and 9% yields, respectively. 6,8‐Dihydroxy‐3,7‐dimethyl‐2‐benzopyrylium p‐toluenesulfonate 31 is considered as the intermediate for the production of 12‐15. Overall yields of isochromenes 12‐15 were 26‐6% starting from 2‐methylresorcinol for seven steps.     

Electrostatic energies stored in dipolar films and analysis of decaying process of a large surface potential of Alq3 films

The decaying process of a large surface potential of as-deposited Alq₃ film was analyzed with consideration of electrostatic energies stored in the film. The analysis includes the cooperative molecular field effect and it shows that the derived equilibrium condition of dipolar films with electron traps supports the concept of the alignment of Fermi-level of metal and surface Fermi-level of dipolar films. The potential decay of Alq₃ films on Al electrodes by photo-exposure is explained due to detrapping of trapped electrons that are immediately transported to the injected electrodes along with the disordering of polar structure of Alq₃ films.     

Fluorescence-based temperature sensing using erbium-doped optical fibers with 1.48 μm pumping

Temperature sensing using 1.54 μm fluorescence at the transition between the energy levels⁴I_15/2 (ground state) and⁴I_13/2 generated in an erbium-doped fiber with 1.48 μm pumping is proposed. The fluorescence has a peculiar spectral profile that possesses two peaks around 1.530 μm and 1.552 μm wavelengths. The temperature-dependent fluorescence is investigated in the temperature range between -50°C and 90°C. The power ratio between the two peaks increases with an increase in temperature. The sensitivity of the ratio is 0.007/°C on average in the measured temperature range. The total fluorescence power and the absorption loss at λ = 1480 nm in the fiber decrease as the temperature increases. Optical fiber temperature sensing immune from the fluctuation in pumping power can be performed using the peak power ratio and/or the absorption loss.     

Crystal Structure of the Isopropylzinc Alkoxide of Pyrimidyl Alkanol: Mechanistic Insights for Asymmetric Autocatalysis with Amplification of Enantiomeric Excess

Asymmetric amplification during self‐replication is a key feature that is used to explain the origin of homochirality. Asymmetric autocatalysis of pyrimidyl alkanol in the asymmetric addition of diisopropylzinc to pyrimidine‐5‐carbaldehyde is a unique example of this phenomenon. Crystallization of zinc alkoxides of this 5‐pyrimidyl alkanol and single‐crystal X‐ray diffraction analysis of the alkoxide crystals reveal the existence of tetramer or higher oligomer structures in this asymmetric autocatalytic system.