Cyano-phosphorylation of aldehydes catalyzed by a nucleophilic N-heterocyclic carbene

The first method for cyano-phosphorylation of aldehydes with diethyl cyanophosphonate in the presence of N-heterocyclic carbene prepared from 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride and KOt-Bu, as a nucleophilic catalyst, is described.     

Neodolabelline,a methyl migrated dolabellane-type diterpene from the okinawan soft coral clavularia koellikeri

A new diterpene named neodolabelline (5), having a methyl migrated dolabellane-type skeleton, was isolated from the stoloniferan soft coral Clavularia koellikeri, together with clavukerins (trinor-sesquiterpenes) and bicyclo-germacrene, and the absolute configuration was determined.     

A bridged triptycene-intramolecular diels-alder reaction of 16,19-dimethoxy-[2](9,10)anthraceno[2]paracyclophane

A bridged triptycene was obtained by intramolecular cycloaddition reaction of 16,19-dimethoxy[2](9,10)anthraceno[2]paracyclophane followed by acid-catalyzed elimination of methanol. Internal strain in this molecule was disclosed by X-ray crystallographic analysis.     

Five new steroidal glycosides,pregnedioside-A, -B,and their three monoacetates,from an Okinawan soft coral of Alcyonium sp.

Five new pregnene-type steroidal glycosides, named pregnedioside -a ($\text{1}$), 4′-O-acetyl-pregnedioside-a ($\text{2}$), 3′-O-acetyl-pregnedioside-a ($\text{3}$), pregnedioside-b ($\text{5}$), and 4′-O-acetyl-pregnedioside-b ($\text{6}$), were isolated from an Okinawan soft coral of Alcyonium sp. and their structures were elucidated. These are rare examples of steroidal gylcosides from soft coral.     

Mössbauer spectroscopic study of γ-ray irradiated potassium borate glasses

Potassium borate glasses denoted by the formula xK₂O · (100 ? x)B₂O₃ · 7Fe₂O₃ were irradiated with ⁶⁰Co-γ-rays at room temperature. Mössbauer parameters for the irradiated glasses containing alkali equal to or higher than 20 mole% showed that the s-electron density at the iron nucleus increased without any change of the steric configuration of oxygen atoms around the iron nucleus. The increase of s-electron density was ascribed to electron transfer from the nonbridging oxygen to the iron nucleus. The presence of the nonbridging oxygen was also confirmed by the irradiation effect of the borate glass (x = 30) prepared using the enriched isotope of ⁵⁷Fe₂O₃. Mössbauer parameters for the irradiated glass suggest that the newly observed Fe²⁺ ions are in tetrahedral symmetry.     

ESR study of linear aliphatic oligoesters under γ-irradiation. I. Paramagnetic species produced in the material by irradiation at 77°K

Paramagnetic species produced in a series of linear aliphatic oligoesters $ [\bond;{\rm O}\bond;({\rm CH}_{\rm 2} {\rm )}_m\bond;{\rm O}\bond;{\rm CO}\bond;({\rm CH}_{\rm 2} {\rm )}_n\bond;{\rm CO\rlap{--} ]}_P $ by γ-irradiation at 77°K was investigated by an ESR method. A predominant doublet observed immediately after γ-irradiation, which has hyperfine splitting of 20–23 gauss, is attributed to a radical anion III. Slight decay of this radical anion is observed by illuminating the sample with visible light at 77°K. A small amount of the radical anion is converted to double triplet, which is assigned to ? (ES)? CH? CH₂? (where ES denotes the ester group), from the result of heat treatment. The conformational angles for the two β-protons in the (6,2) oligoester are determined to be θ₁ = θ₂ = 30°.     

Resonance Raman spectra of 15N enriched metallooctaethylorphyrins. Characterization of the oxidation state marker bands of hemoproteins

Resonance Raman spectra of ¹⁵N enriched metallooctaethylporphyrins [M(OEP) ? ¹⁵N₄] [M = Ni²⁺, Fe³⁺ (high spin), and Fe³⁺ (low spin)] were observed. Polarized Raman lines corresponding to the oxidation state marker band of hemoproteins were observed at 1377 (Ni), 1369 (Fe high spin) and 1372^?1 (Fe low spin) which were shifted to lower frequency from those of the ¹⁴N compounds by 6, 5, and 6 cm^?1, respectively. The vibrational mode for this band was shown to include an appreciable contribution of the C_αN symmetric stretching vibration and to be associated with ca. 0.01 Å of in-phase displacement of the four pyrrole nitrogens toward the metal ion.     

Nano-matrix structure formed by graft-copolymerization of styrene onto natural rubber

Nano-matrix structure was formed by graft-copolymerization of styrene onto urea-deproteinized natural rubber (U-DPNR) latex. The grafted U-DPNR was characterized by FT-IR spectroscopy, ¹H NMR spectroscopy and transmission electron microscopy. Conversion and grafting efficiency of styrene were more than 90% under the best condition of the graft-copolymerization. In transmission electron micrograph of film specimen stained by OsO₄, it was found that natural rubber particle of about 0.5 μm in diameter was dispersed in polystyrene matrix of about 15 nm in thickness. The conversion and grafting efficiency for the grafted U-DPNR were compared with those for a control sample prepared from enzymatic deproteinized natural rubber (E-DPNR) with styrene.     

LASER PHOTOLYSIS STUDIES OF SUPEROXIDE ADDUCTS OF COBALT(II) AND ZINC(II) PORPHYRINS IN DIMETHYLFORMAMIDE

Abstract— Photochemistry of superoxide adducts of cobalt(II) and zinc(II) porphyrins has been studied by laser photolysis. It was found that the former in dimethlformamide photodissociates the superoxide anion radical, O₂^-, with the quantum yield of 0.5 ± 0.05 at the excitation wavelenths 355 and 532 nm, and the latter gives flurescence and the triple state without giving rise to the photodissociation of O₂^-     

High-molecular-weight polyterephthalamide by direct polycondensation reaction in the presence of poly(ethylene oxide)

Polyterephthalamides of high molecular weight (η_inh up to 1.9) were obtained by the direct polycondensation reaction of terephthalic acid and aromatic diamines in the presence of poly(ethylene oxide) (PEO) with triphenyl phosphite in a N-methylpyrrolidone (NMP)–pyridine solution that contained lithium chloride. The molecular weights of the polymers produced varied with the amount and molecular weight of PEO, which showed maximum values when PEO with a molecular weight of 2.0 × 10⁴?5.0 × 10⁵ was used in a concentration of about 0.5 wt % in the solvent. The polycondensation reaction was significantly affected by the level of pyridine in a mixed solvent of NMP and pyridine and by the concentration of the lithium chloride added.