Novel synthesis of the ocular age pigment A2-E: new method for substituted pyridine synthesis via azaelectrocyclization

[reaction: see text] The formal synthesis of the ocular age pigment A2-E was achieved by the efficient one-pot preparation of the substituted pyridine, which involves the aza-6pi-electrocyclization of the Schiff base derived from (E)-3-carbonyl-2,4,6-trienal followed by oxidation.     

Pulse radiolysis of 4,4'-bipyridyl aqueous solutions at elevated temperatures: spectral changes and reaction kinetics up to 400 degrees C

The spectral changes as well as the reaction kinetics of the transient species of 4,4'-bipyridyl (4,4'-bpy) have been experimentally investigated by pulse radiolysis techniques up to 400 degrees C. The results show that the transient species such as OH adduct 4,4'-bpyOH*, monoprotonated electron adduct 4,4'-bpyH*, and doubly protonated electron adduct 4,4'-bpyH2+* have 15-20 nm blue shifts from room temperature to 400 degrees C. For a deaerated neutral solution of 4,4'-bpy in the presence of tert-butyl alcohol, ethanol, or NaCOOH, the doubly protonated electron adduct is the main transient species at room temperature. But at temperatures > 350 degrees C, a monoprotonated form, the N-hydro radical 4,4'-bpyH*, becomes predominant. Interestingly, at room temperature, CO2-* could not efficiently react with 4,4'-bpy, but the reaction was accelerated with increasing temperature; at 350 degrees C, this reaction completed within 2 mus. Using an alkaline solution (pH = 11.5) of 4,4'-bpy in the presence of tert-butyl alcohol, we studied the N-hydro radical 4,4'-bpyH* from room temperature to 400 degrees C at 25 MPa. An estimation of the temperature-dependent G(e(aq)-) at 25 MPa agrees with our previous result with methyl viologen as a scavenger.     

A New Type of Photorearrangement of γ-Hydroxy-α, β, δ, ε-dienone

A new type of photorearrangement of the γ-hydroxy-α, β, δ, ε-dienone, vomifoliol acetate ( 2 ) to the diketone 4 is described, and its facile rearrangement is compared with that of desoxyvomifoliol acetate ( 3 ).     

Improvement of corrosion resistance of carbon steel using chemical vapor deposition from the mixture of Mo(CO)6 and Cr(CO)6 with an ArF-excimer laser

The corrosion resistance of carbon steel has been improved by the deposition from the mixture of Mo(CO)₆ and Cr(CO)₆ as well as from each carbonyl alone with an ArF-excimer laser (193 nm). The corrosion resistance attained by coating with the films from the mixture is higher than from Mo(CO)₆ alone, while lower than from Cr(CO)₆ alone. While the corrosion resistance increases with beam intensity monotonically over the range 4–25 MW cm^–2 for the deposition from Cr(CO)₆ alone, it tends to decrease slightly above 15 MW cm^–2 for the deposition from Mo(CO)₆ alone and from the mixture. SEM (Scanning Electron Microscope) photographs show that the films from each carbonyl and their mixture consist of small grains that are more densely packed at higher beam intensities. The comparison of the film thickness evaluated from sputtering time to remove the films with that from direct observation with SEM suggests that the density of the film increases with beam intensity. In the films deposited from the mixture, molybdenum is preferentially incorporated from the gas phase. Present name: Department of Quantum Engineering and Systems Science     

1,5]-H shift of aldehyde hydrogen in dienal compounds to produce ketenes

In 3-ethoxycarbonyl-2,4-dienal compounds, a thermal [1,5]-H shift of aldehyde hydrogen easily proceeded to produce the corresponding vinyl ketenes due to the remarkable substituent effect caused by the C3 ester group. The produced ketenes were captured by an alcohol and olefins to afford the corresponding esters and four-membered ring compounds, respectively.     

Total synthesis of manoalide and seco-manoalide

The first synthesis of manoalide and seco-manoalide from methyl 7,8-dihydro-β-ionylidene acetate was achieved in high yield by the new method utilizing regiospecific singlet oxygen oxidation of 3-alkenyl-5-trimethylsilylfuran to β-alkenyl-γ-hydroxybutenolide.     

The Synthesis of Damascenone and β-Damascone and the possible mechanism of their formation from carotenoids

A brief synthesis of damascenone ( 5 ) from the acetylenic diol 2 and also that of β-damascone ( 8 ) from β-ionol, resembling the biogenetic synthesis, are described. A possible mechanism for the formation of damascenone from neoxanthin is proposed.     

Pulse radiolysis study on free radical scavenger edaravone (3-methyl-1-phenyl-2-pyrazolin-5-one)

The reactions between edaravone and various one-electron oxidants such as (*)OH, N(3)(*), Br(2)(-), and SO(4)(-), have been studied by pulse radiolysis techniques. The transient species produced by the reaction of edaravone with (*)OH radical shows an absorption band with lambda(max)=320 nm, while the oxidation by N(3)(*), Br(2)(-), SO(4)(-) and CCl(3)OO(*) results in an absorption band with lambda(max)=345 nm. Different from the previous reports, the main transient species by the reaction of edaravone with (*)OH radical in the absence of O(2) is attributed to OH-adducts. At neutral condition (pH 7), the rate constants of edaravone reacting with (*)OH, N(3)(*), SO(4)(-), CCl(3)OO(*), and e(aq)(-) are estimated to be 8.5x10(9), 5.8x10(9), 6x10(8), 5.0x10(8) and 2.4x10(9)dm(3)mol(-1)s(-1), respectively. From the pH dependence on the formation of electron adducts and on the rate constant of edaravone with hydrated electron, the pK(a) of edaravone is estimated to be 6.9+/-0.1.     

Transient absorption measurement system using pulsed energetic ion

This article reports a highly sensitive transient absorbance measurement system using pulsed energetic ions. The ions were pulsed by a beam chopper, which was synchronized with the cyclotron, and accelerated to the desired energy around 18 MeV/u. H, He, C and Ne ions can be used for the transient absorption measurement. The optical system can measure an absorbance smaller than 1.0×10⁻⁴ in the wavelength range of 400–740 nm.