Mechanism of BPh3-Catalyzed N-Methylation of Amines with CO2 and Phenylsilane: Cooperative Activation of Hydrosilane

BPh₃ catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO₂ and PhSiH₃; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C₆F₅)₃ shows little or no activity. ¹¹B NMR spectra suggested the generation of [HBPh₃]⁻. The detailed mechanism of the BPh₃-catalyzed N-methylation of N-methylaniline ( 1 ) with CO₂ and PhSiH₃ was studied by using DFT calculations. BPh₃ promotes the conversion of two substrates (N-methylaniline and CO₂) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N⁺CO₂⁻⋅⋅⋅BPh₃]. The carbamate and BPh₃ act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH₃ to generate [HBPh₃]⁻, which is used to produce key CO₂-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh₃]⁻ species.     

Hydrophobic Monomers Recognize Microenvironments in Hydrogel Microspheres during Free-Radical-Seeded Emulsion Polymerization

The three-dimensional structure of nanocomposite microgels was precisely determined by cryo-electron micrography. Several nanocomposite microgels that differ with respect to their nanocomposite structure, which were obtained from seeded emulsion polymerization in the presence of microgels, were used as model nanocomposite materials for cryo-electron micrography. The obtained three-dimensional segmentation images of these nanocomposite microgels provide important insights into the interactions between the hydrophobic monomers and the microgels, that is, hydrophobic styrene monomers recognize molecular-scale differences in polarity within the microgels during the emulsion polymerization. This result led to the formation of unprecedented multi-layered nanocomposite microgels, which promise substantial potential in colloidal applications.     

Potential formation and high density plasma production on the tandem mirror GAMMA 10

GAMMA 10 experiments have advanced in high density experiments after the last EPS Workshop where we reported high density plasma production by using an ion cyclotron range of frequency heating at a high harmonic frequency and neutral beam injection in the central cell. Recently a high density plasma was obtained with much improved reproducibility than before and without degradation of diamagnetic signal. The high density plasma was attained by adjusting the spacing of the conducting plates installed in the anchor transition regions. Dependencies of particle confinement time, ion energy confinement time and plasma confining potential on plasma density were obtained for the first time in the high density region. Presented at 5th Workshop “Role of Electric Fields in Plasma Confinement and Exhaust”, Montreus, Switzerland, June 23–24, 2002.     

Status of heavy element research using a gas-filled recoil separator at RIKEN

A gas-filled type of recoil separator for heavy element research was installed at an experimental hall of RIKEN Linear Accelerator facility to realize getting higher intensity of primary beam and long beam time. Performance of the separator was studied using target recoils and various nuclear reactions. The results show the high performance of the separator for heave element research. As an application of the GARIS, production and identification of an isotope of the 110th element ²⁷¹[110] have been performed using the ²⁰⁸Pb(⁶⁴Ni,1n)²⁷¹[110] reaction. Three decay chains coincide well both in decay times and energies with the ones reported by the group of SHIP experiment at GSI, Germany. Our results provide a confirmation of the synthesis of an isotope ²⁷¹[110] of element 110.     

Determination of biologically active substances in roasted coffees using a diode-array HPLC system.

We studied the simultaneous quantitative analysis of biologically active substances, such as nicotinic acid, trigonelline, caffeine, qunolinic acid and tannic acid and pyrogallic acid, in several roasted coffees by an HPLC/diode-array system with a home-made sol-gel and ODS-2 columns. A simple method for simultaneous quantitative analysis of biologically active substances in the coffee brew became feasible by an HPLC/diode-array system with a sol-gel column at a single wavelength of 210 nm. The most efficient condition of the Rs value was above 1.05 when two sol-gel columns were connected. In addition, the elution behavior of nicotinic acid in brew extracted from commercially available coffee beans suggests the thermal decomposition process during roasting, and indicated the maximum value for full city roasted coffee.     

On the Essential Self-Adjointness of Wick Powers of Relativistic Fields and of Fields Unitary Equivalent to Random Fields

The essential self-adjointness on a natural domain of the sharp-time Wick powers of the relativistic free field in two space-time dimension is proven. Other results on Wick powers are reviewed and discussed.     

Neutron activation analysis of iodine in soil

A simple pre-irradiation procedure for the separation of iodine from soil has been developed. A soil sample was heated in a quartz tube for 15 min at about 900 °C. The evaporated iodine was collected in activated charcoal, which was produced from phenol resin with low impurities. The charcoal, with sorbed iodine, was irradiated by neutrons and the¹²⁸I produced was measured. A successful elimination of the background radioactivity due to the matrix elements was possible with this separation procedure. The detection limit by this method for soil samples was about 0.1 mg/kg (dry). The method has been applied to analyze selected soil samples.     

Novel UV‐induced photografting process for preparing poly(tetrafluoroethylene)‐based proton‐conducting membranes

A novel process comprising the UV‐induced photografting of styrene into poly(tetrafluoroethylene) (PTFE) films and subsequent sulfonation has been developed for preparing proton‐conducting membranes. Although under UV irradiation the initial radicals were mainly generated on the surface of the PTFE films by the action of photosensitizers such as xanthone and benzoyl peroxide, the graft chains were readily propagated into the PTFE films. The sulfonation of the grafted films was performed in a chlorosulfonic acid solution. Fourier transform infrared and scanning electron microscopy were used to characterize the grafted and sulfonated membranes. With a view to use in fuel cells, the proton conductivity, water uptake, and mechanical properties of the prepared membranes were measured. Even through the degree of grafting was lower than 10%, the proton conductivity in the thickness direction of the newly prepared membranes could reach a value similar to that of a Nafion membrane. In comparison with γ‐ray radiation grafting, UV‐induced photografting is very simple and safe and is less damaging to the membranes because significant degradation of the PTFE main chains can be avoided. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2624–2637, 2007     

Discrimination of carbonyl groups of meso-α-diketones with Horner-Wadsworth-Emmons reagent of chiral binaphthyl esters

Asymmetric Horner-Wadsworth-Emmons reactions of selected meso-α-dicarbonyl compounds with chiral phosphonate reagents, which possessed axially dissymmetric 1,1′-bi-2- or 8-naphthol at the carboxylate moiety as a chiral auxiliary, were examined. The reactions proceeded smoothly with good chemical yields as well as with high diastereoselectivities. Z-olefins were preferentially formed, and it was found that the free hydroxy group at the 2′- or 8′-position on the naphthalene ring plays a crucial role in the high diastereoselectivity, probably due to a complex-induced proximity effect. Mechanistic considerations are also described.     

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Statistical Inference for Stochastic Processes -