Electroreductive intermolecular coupling of phthalimides with aldehydes: application to the synthesis of alkylideneisoindolin-1-ones

The electroreduction of N-methyl, N-p-anisyl, and N-unsubstituted phthalimides with aldehydes in the presence of chlorotrimethylsilane and triethylamine gave intermolecularly coupled products, 3-hydroxy-3-(1-hydroxyalkyl)isoindolin-1-ones. The coupling products were reduced with Et₃SiH/BF₃·Et₂O to 3-(1-hydroxyalkyl)isoindolin-1-ones, which were dehydrated to alkylideneisoindolin-1-ones. From N-unsubstituted phthalimides, Z-isomers of alkylideneisoindolin-1-ones were obtained stereospecifically.     

The Unit-Subduced-Cycle-Index Methods and the Characteristic-Monomial Method. Their Relationship as Group-Theoretical Tools for Chemical Combinatorics

Among the four methods of the unit-subduced-cycle-index (USCI) approach, the subduced-cycle-index (SCI) method and the partial-cycle-index (PCI) method have been discussed by using adamantane of T _d -symmetry as a probe for enumeration problems, where USCIs are derived on the basis of permutaion representations, coset representations (CRs) and marks. After the examination of the SCIs and PCIs, Pólya's theorem that is a standard method of chemical combinatorics has been derived from the USCI approach. As another approach, a new method called the characteristic-monomial (CM) method has been developed by virtue of charactereistic monomials (CMs). The CMs have been derived from Q-conjugacy representations and Q-conjugacy characters, which have been related to irreducible representations and irreducible characters of the standard repertoire of chemical group theory. The two approaches have been compared to discuss group-theoretical tools for chemical combinatorics on a common basis.     

Highly enantioselective synthesis of atropisomeric anilide derivatives through catalytic asymmetric N-arylation: conformational analysis and application to asymmetric enolate chemistry

In the presence of (R)-DTBM-SEGPHOS-Pd(OAc)(2) catalyst, N-arylation (aromatic amination) of various o-tert-butylanilides with p-iodonitrobenzene proceeds with high enantioselectivity (88-96% ee) to give atropisomeric N-(p-nitrophenyl)anilides having an N-C chiral axis in good yields. Atropisomeric anilide products highly prefer to exist as the E-rotamer which has trans-disposed o-tert-butylphenyl group and carbonyl oxygen. The application of the present catalytic enantioselective N-arylation to an intramolecular version gives atropisomeric lactam derivatives with high optical purity (92-98% ee). The reaction of the lithium enolate prepared from the atropisomeric anilide and lactam products with various alkyl halides gives alpha-alkylated products with high diastereoselectivity (diastereomer ratio = 13:1 to 46:1).     

Phase relationship and dynamics of anisotropic gelation of carboxymethylcellulose aqueous solution

Anisotropic gelation of carboxymethylcellulose (CMC) in aqueous NaOH sandwiched between two circular cover glasses by immersing it in aqueous CaCl₂ has been studied. In the course of dialysis, gelation and phase separation occurred simultaneously to make turbid stripes arranged radially. The time course of the gel layer width was well expressed in scaled linear plots predicted by a theory based on “moving boundary picture” at low CMC concentrations. On the other hand, at high CMC concentrations, the time course was expressed by a two-stage dynamics. The time course did not depend on the initial thickness of the CMC solution and the diameter of the cover glasses, whereas the rate of gelation decreased with increasing CMC concentration. It was attributed to the change in the calcium cation concentration required for forming the gel in the process. The universality and the individuality of the present system in the gelation dynamics are discussed.     

ɛ‐TiO,a Novel Stable Polymorph of Titanium Monoxide

For the Ti/O system, three titanium monoxide (TiO) phases (α, β, and γ) with defective NaCl‐type structures and a high‐temperature hexagonal phase (H) have been known for decades. In this work, single crystals of a novel polymorph, ?‐TiO, were synthesized by using a bismuth flux. X‐ray diffraction (XRD) revealed a hexagonal crystal structure (a=4.9936(3) Å, c=2.8773(2) Å, P 2m) that is isotypic with ?‐TaN. While the Ti atoms are surrounded by trigonal prismatic (sixfold coordination) and trigonal planar (threefold coordination) arrangements of O atoms, the O atoms are found in a pseudo‐square‐pyramidal arrangement of Ti atoms. First‐principles calculations of the formation enthalpy and the electron and phonon density of states and crystal orbital Hamilton population (COHP) analysis revealed that ?‐TiO is more stable than α‐TiO, which had previously been regarded as the most stable phase at low temperatures.     

The burning rate’s effect on the flame length of weak fire whirls

This paper discusses why the visibly-determined flame length of a weak fire whirl increases as compared with the corresponding pool fire without spin. Here, a fire whirl is called weak when the pure aerodynamic effect of flow circulation has a negligible influence on the flame length. Split cylinders were used to apply a flow circulation to a 3-cm-diameter methane burner flame and a 3-cm-diameter ethanol pool fire. After applying the flow circulation, the flame length of the ethanol pool fire increased about three times, while little change was observed in the flame length of the methane burner flame. The difference is explained by the fact that the burning rate of the methane burner flame was fixed constant, whereas that of the ethanol pool fire increased due to the increased heat input to the fuel surface caused by a change in flame shape pushed toward the fuel surface. The experimental observations thus demonstrate that the burning-rate effect can significantly increase the flame length even under a weak circulation condition. Computational fluid dynamics (CFD) simulations were conducted to understand the detailed flow structure of a fire whirl. An analytical model was then developed based on the experimental observations and CFD calculations; the predicted relationship between the flame height and the burning rate agreed with experimental data.     

Polarimetry of short-pulse gamma rays produced through inverse Compton scattering of circularly polarized laser beams

We have developed a polarimetry of ultrashort pulse gamma rays based on the fact that gamma rays penetrating in the forward direction through a magnetized iron carry information on the helicity of the original gamma rays. Polarized, short-pulse gamma rays of (1.1+/-0.2)x10(6)/bunch with a time duration of 31 ps and a maximum energy of 55.9 MeV were produced via Compton scattering of a circularly polarized laser beam of 532 nm off an electron beam of 1.28 GeV. The first demonstration of asymmetry measurements of short-pulse gamma rays was conducted using longitudinally magnetized iron of 15 cm length. It is found that the gamma-ray intensity is in good agreement with the simulated value of 1.0x10(6). Varying the degree of laser polarization, the asymmetry for 100% laser polarization was derived to be (1.29+/-0.12)%, which is also consistent with the expected value of 1.3%.