Preparation,structure, and unique thermal [2+2], [4+2], and [3+2] cycloaddition reactions of 4-vinylideneoxazolidin-2-one

The terminal allene C(alpha)=C(beta) bonds of 4vinylidene-2-oxazolidinone (2) readily undergo [2+2] cycloaddition with a wide variety of terminal alkynes, alkenes, and 1,3-dienes irrespective of their electronic nature under strictly thermal activation conditions (70-100 degrees C) and provide 3substituted (Z)-methylenecyclobutenes 6, 3substituted methylenecyclobutanes 7 and 8, and 3vinylmethylenecyclobutanes 9, respectively, in good to excellent yields. Alkenes react with 2 with complete retention of configuration. The [2+2] cycloaddition is concluded to proceed via a concerted [(pi(2s)+pi(2s))(allene) + pi(2s)] Hückel transition state on the basis of experimental evidences and quantum mechanical methods. Some highly polarized enones and nitrile oxide, on the other hand, react with 2 selectively at the internal C(4)=C(alpha) double bonds and give spiro compounds 10 and 11, respectively. The bent allene bonds (173-176 degrees) and the unique reactivity associated with 2 are attributed to a low-lying LUMO (C(alpha)=C(beta)) that is substantiated by a through-space sigma*(N-SO(2))-pi*(C(alpha)=C(beta)) orbital interaction.     

Development characteristics of fluctuating velocity field of drag-reducing surfactant solution flow in a duct

Development behavior of the fluctuating velocity of surfactant solution in a duct has been studied experimentally. The concentration of surfactants was kept constant at 1,000 ppm, mean velocity at 0.78 m/s and fluid temperature at 15 °C. Using laser Doppler velocimetry, the fluctuating streamwise velocity distributions at six cross sections, which ranged from 14 to 112 times of hydraulic diameter of the duct, were measured. From the results, the fluctuating structures of surfactant solution flow are observed to have structures different from that of turbulent water flow in the developing field. The wavelet analysis reveals that the high-level fluctuation of surfactant solution flow is characterized by periodicity rather than irregularity around the position where the fluctuation intensity takes a peak value and that the period and the scale of periodic flow structures are related to the relaxation times of the fluid. This indicates that the high-level fluctuation is deeply related to the elastic instability and has a different generation mechanism from that of turbulence observed in a Newtonian turbulent flow.     

Ultrabroadband (>2000 cm-1) multiplex coherent anti-Stokes Raman scattering spectroscopy using a subnanosecond supercontinuum light source

We have developed ultrabroadband (>2000 cm(-1)) multiplex coherent anti-Stokes Raman scattering (CARS) spectroscopy using a subnanosecond (sub-ns) microchip laser source. A photonic crystal fiber specifically designed for sub-ns supercontinuum (SC) generation has been used for obtaining ultrabroadband Stokes radiation, which enables us to achieve simultaneous vibrational excitation in the range from 800 to 3000 cm(-1). We have successfully obtained multiplex CARS spectra for several molecular liquids. Since the CARS system using the sub-ns SC is simple and compact, it can be easily applied to ultrabroadband multiplex CARS microspectroscopy.     

Synthesis of 1-hydrocarbon substituted cyclopropyl silyl ketones

The synthesis of cyclopropyl silyl ketones possessing a hydrocarbon group at 1-position of three-membered ring was investigated. The reaction of sulfoxonium ylide with α,β-unsaturated acylsilanes derived from α,β-unsaturated aldehydes did not afford the desired acylsilane derivatives. Instead, the corresponding silyl enol ethers were yielded exclusively. On the other hand, the Corey-Chaykovsky cyclopropanation of α-substituted α,β-unsaturated aldehydes proceeded well to give 1-substituted cyclopropyl aldehydes. The silyl substitution of formyl proton in the obtained aldehydes via umpolung of carbonyl group afforded the target acylsilanes.     

CO oxidation reaction on Pt(111) studied by the dynamic Monte Carlo method including lateral interactions of adsorbates

The dynamics of adsorbate structures during CO oxidation on Pt(111) surfaces and its effects on the reaction were studied by the dynamic Monte Carlo method including lateral interactions of adsorbates. The lateral interaction energies between adsorbed species were calculated by the density functional theory method. Dynamic Monte Carlo simulations were performed for the oxidation reaction over a mesoscopic scale, where the experimentally determined activation energies of elementary paths were altered by the calculated lateral interaction energies. The simulated results reproduced the characteristics of the microscopic and mesoscopic scale adsorbate structures formed during the reaction, and revealed that the complicated reaction kinetics is comprehensively explained by a single reaction path affected by the surrounding adsorbates. We also propose from the simulations that weakly adsorbed CO molecules at domain boundaries promote the island-periphery specific reaction.     

On homogeneous solutions of Einstein's field equations

In the first part of this paper we describe a formalism capable of finding all homogeneous solutions of Einstein's field equations with any arbitrary energy-impulse tensor. In the second part we find all homogeneous vacuum solutions.     

Photoinduced reactions—LXIX : The photochemical transposition of 2,6-di-t-butylphenols through their ketone tautomers

2,6-Di-t-butylphenol and its 4-substituted derivatives (1) have been shown to undergo novel photochemical transposition to isomeric phenols 2 and 3, being accompanied by de-t-butylation to give 4. Involvement of the triplet excited state of 1 was confirmed by sensitization and quenching experiments. Evidence is presented for the initial tautomerization of 1 to the ketonic tautomers which undergo further photochemical transformation to the products.