Studies on the syntheses of heterocyclic compounds. CLXXIV. An approach to the synthesis of oxyacanthine and berbamine

Schotten-Baumann reaction of the amine (X) with 4-benzyloxy-3,4′-oxydiphenylacetyl chloride (XI) gave two amides, (XIIa) and (XIIb), which were cyclized to give the corresponding 3,4-dihydroisoquinolines, respectively. Methylation of the above 3,4-dihydro-isoquinolines, followed by hydrolysis, afforded the compounds having the same composition as berbamine (Ia) and oxyacanthine (Ib), whose structures are under examination.     

γ-Ray-induced polymerization of α-haloacrylic acids

The γ-ray induced polymerizations of α-chloroacrylic acid, mp 66°C, and α-bromo-acrylic acid, mp 72°C, were investigated in the temperature range from 35°C to 85°C. An analysis of polymerization kinetics was made, and results were similar to those reported in the literature for other vinyl monomers. On heating of the polymer obtained, elimination of hydrogen halide takes place, and intramolecular lactone formation is observed. The rate of lactone formation of poly(α-chloroacrylic acid) obtained in the solid-state polymerization was found to be higher than that in the liquid state, because a highly isotactic configuration of polymers, tends to be formed in the solid-state polymerization, and elimination of hydrogen chloride is facilitated with an isotactic 5₂ helix structure.     

High-Field and Multifrequency ESR Studies at KYOKUGEN in Osaka University

We have developed high-field and multifrequency (HFMF) electron spin resonance (ESR) apparatus for the magnetic fields up to 65 T at frequencies up to about 6 THz. In addition to this pulsed field ESR apparatus, we are making a multifrequency ESR apparatus with very high sensitivity in a static field. We report the results of ESR studies on BaCoV₂O₈ and NiGa₂S₄, followed by recent developments and future plans of our HFMF ESR apparatus.     

Reactions of 2-Pyridyl Substituted Phosphine Oxides and Phosphonium Salts with Organometallic Reagents and in Aqueous Media

Phosphine oxides bearing two or three 2-pyridyl groups react with organometallic reagents affording 2,2′-bipyridyl, 2-substituted pyridines and pyridine in good yields. Phosphonium salts and phosphine oxides, bearing at least two 2-pyridyl or substituted 2-pyridyl groups also give the corresponding 2,2′-bipyridyls and pyridines upon treatment with acid or neutral solvents such as water and alcohols in substantial yields. The 2,2′-bipyridyls are considered to be formed by ligand coupling within the pentacoordinated phosphorus intermediate formed incipiently during the reaction.     

Transverse mode control by manipulating gain distribution in a Yb:YAG ceramic thin disk

We demonstrated that transverse mode can be controlled by manipulating gain distribution in a Yb:YAG ceramic thin disk. Several elongated higher order transverse modes of a Hermite-Gaussian beam were observed when a straight-line-shaped gain region was created by using a diode laser output from an optical fiber. An orthogonally crossing pair of straight-line-shaped gain regions created with an additional optical fiber output resulted in the generation of a doughnut-shaped Laguerre-Gaussian beam. This implies that easy and quick switching of Hermite-Gaussian and Laguerre-Gaussian beams is possible without mechanical handling.     

Dark-spot formation by vector beams

Dark-spot formation is demonstrated by calculating electric-field distribution near the focus produced by focusing higher-order transverse-mode vector beams with radial and azimuthal polarizations in addition to Laguerre-Gaussian beams with linear and circular polarizations. The size of the dark spot in the radial direction varies from one beam to another, but the size in the axial direction is almost the same. The radially polarized TM02-mode beam is predicted to form a dark spot solely by an axial electric field.     

Novel synthesis of carbapenam by intramolecular attack of lactam nitrogen toward eta1-allenyl and eta3-propargylpalladium complex

When a THF solution of beta-lactam having propargyl phosphate was warmed in the presence of 5 mol % of Pd(2)(dba)(3) x CHCl(3), 20 mol % of a bidentate ligand, and sodium acetate (1.5 equiv) at 40 degrees C for 22 h, carbapenam was produced in high yield. In this reaction, the lactam nitrogen attacked the central carbon of a eta(3)-propargylpalladium complex, which was formed from propargyl phosphate and Pd(0).