Titanium (III) induced transformations of N,N-disubstituted hydroxylamines to imines and secondary amines

The reaction of N,N-disubstituted hydroxylamines with anhydrous TiCl3 gives the corresponding imines, while that with aqueous TiCl3 gives secondary amines.     

Dynamical properties of the vacuum in non-abelian field theories with and without supersymmetry

In QCD with massless quarks, the effective potential for the color singlet operator (F_μν^a)² can be constructed by the use of the trace anomaly equation and tells us that magnetic gluon condensation, 〈0|(F_μν^a)²|0〉 > 0, occurs. When the method is applied to supersymmetric QCD, however, it gives us a puzzle; the gluons condense with negative energy density, and supersymmetry is broken in a pathological manner with the appearance of a negatively normed Nambu-Goldstone fermion. Spurred on by this observation, we examine in detail the properties of the vacuum for the super (and ordinary) O(N) non-linear σ model in two dimensions for which a similar puzzling situation occurs with regard to the lagrangian condensate. We find, in particular, that (i) the chiral condensate plays a crucial role in resolving the puzzle and that (ii) it is the nature of the response of the lagrangian condensate to the test charge, not the sign or the magnitude of the condensate itself, that determines the phase of the system. Implications of these results for (super) QCD, including an unconventional possibility of “electric” gluon condensation, are discussed.     

Electrical resistivity and thermal conductivity of UP1−xSx

UP, US, and their solid solutions of several compositions were prepared, and the electrical resistivities of these samples were measured from liquid nitrogen temperature to 1000 K and the thermal diffusivities from 300 to 1000 K. It was shown that the resistivity of UP_1?xS_x at the paramagnetic region arose mainly from the scattering of conduction electrons by disordered spins localized at uranium ion sites. The resistivity of UP_0.4S_0.6 showed another anomaly below the transition temperature. A gentle hump of the thermal diffusivity of UP was observed at about 650 K. This was concluded to be due to the anomalous negative temperature coefficient of electrical resistivity observed above the Néel temperature up to about 550 K. The composition dependence of thermal conductivity of UP_1?xS_x was compared with that of UC_1?xN_x by separating the total conductivity into electronic and phonon contributions.     

Annealing effects in poly(vinylidene fluoride) as revealed by specific volume measurements,differential scanning calorimetry,and electron microscopy

Specimens of poly(vinylidene fluoride), crystal form II, annealed at different temperatures between 130 and 180°C were characterized by specific volume measurements, differential scanning calorimetry (DSC), and electron micróscopy. The degree of crystallinity calculated from the specific volume changed only by 15% i.e., from 50% to 65%. On the other hand, the melting behavior changed with annealing conditions. When a specimen was annealed above 170°C, two endothermic peaks appeared on either side of the annealing temperature. Results from DSC measurements made at different heating rates and electron microscopy showed that the two endotherms were caused by a bimodal distribution of lamellar thicknesses. The equilibrium melting point was found to be 210°C from the linear relation of the melting point and the annealing temperature. The equilibrium enthalpy and entropy of fusion were found to be 1.6 keal/mole and 3.3 eu/mole of repeat units by measurement on polymer–diluent mixtures. The surface free energy was found to be 5.1 kcal/mole of lamellar sequences from the plot of melting point versus reciprocal lamellar thickness obtained by electron microscopy. From a plot of enthalpy of fusion versus reciprocal lamellar thickness the surface enthalpy was found to be 20 keal/mole of lamellar sequences. These data lead to the estimate that a chain fold consists of about 30 repeat units.     

Self-assembled complexes of non-cross-linked amphiphilic polymeric ligands with inorganic species: highly active and reusable solid-phase polymeric catalysts

I present herein the development of highly active and reusable polymeric catalysts produced by self-assembly process of non-cross-linked amphiphilic polymeric ligands with inorganic species. Thus, PWAA 1 prepared from H3PW12O40 and poly[(N-isopropylacrylamide)-co-(acrylamide with ammonium salt)] is suitable for oxidation of alcohols, amines, and sulfides in aqueous hydrogen peroxide. PdAS 2 produced by self-organization of (NH4)2PdCl4 and poly[(N-isopropylacrylamide)10-co-diphenylphosphinostyrene] is an excellent recyclable catalyst for Suzuki-Miyaura reaction in water, water-organic solvent, and organic solvent. It is commercially available from Tokyo Kasei Kogyo (TCI). PdAS-V 3 assembled from (NH4)2PdCl4 and poly[(N-isopropylacrylamide)5-co-diphenylphosphinostyrene] provides recycling system of itself for Mizorogi-Heck reaction. TiSS 4 made from Ti(O-i-Pr)4 and poly(styryl-linked binaphtholate-co-styrene) promotes an enantioselective carbonyl-ene reaction as a recyclable catalyst.     

A novel rearrangement from eudesmanolide to adamantanone

A novel cyclization-skeletal rearrangement from a eudesmanolide, 3-desoxy-4β, 5αH-hexahydro-?-α-santonin(1) to an adamantanone, 2, 5, 9-trimethyltetracyclo [6. 3. 1. 0^1,6. 0^5,10]dodecan-11-one(2) was found to occur as the result of a most unusual reaction. The structure of 2 was elucidated by the X-ray diffraction method.     

X-ray crystal structure of a thiabenzene derivative

The first success of an X-ray analysis of a thiabenzene derivative, 1-benzoyl-2-methyl-2-thianaphthalene is described.