New synthetic method for orsellic acid type macrolides by intramolecular alkylation of protected cyanohydrin. The synthesis of (±)-zearalenone.

Zearalenone was synthesized by a general cyclization method of orsellic acid type macrolides having ketone moiety using the intramolecular alkylation of the protected cyanohydrin. This alkylation tolerates the presence of ester group and requires short reaction time.     

Synthesis of new layered-type and new mixed-layered-type bismuth compounds

Four new compounds, PbBi₂TiTaO₈F, PbBi₂TiNbO₈F, Bi₅Ti₂WO₁₄F, and Bi₇Ti₅O₂₀F, were prepared and identified by X-ray diffraction analysis. Two of them are new members of a family called layered bismuth compounds. The other two are new members of a family called mixed-layered bismuth compounds. Thermal properties of the new compounds were studied. Moreover, the possibility of the existence of other new members belonging to the family called mixed-layered bismuth compounds is discussed.     

Scale-up of wet kneading in a novel vertical high shear kneader

A novel multi-functional vertical high shear kneader has been developed and its performance in wet kneading has previously been reported [Watano et al., Chem. Pharm. Bull., 50(3), 341-345 (2002)]. In this study, scale-up of wet kneading in the novel vertical high shear kneader was conducted. Pharmaceutical excipients composed of lactose, cornstarch and micro-crystalline cellulose were used as powder samples. Kneading operations were conducted under various operating conditions and three different vessel scales. The dried pellets were then prepared by extruding the wet kneaded masses through a dome-type extruder and their drying by a fluidized bed. The physical properties such as strength and disintegration time of the dried pellets were evaluated. It was found that the properties of the dried pellets and their scale-up characteristics were well expressed by an agitation power per unit vessel volume and dimensionless Froude number.     

Simultaneous determination of tetrahydro-β-carbolines and β-carbolines

Summary Reversed-phase ion-pair HPLC with fluorimetric detectors connected in series was studied for the simultaneous determination of two tetrahydro--carbolines and two -carbolines. After additon of internal standards the samples were reacted with fluorescamine, and then subjected to serial extractions to remove their precursor (tryptamine) from the analytical system. This treatment not only suppressed the artefactual formation of tetrahydro--carbolines and -carbolines during analysis, but also effectively purified them. Under optimum conditions, using trifluoroacetic acid as counter ion, all analytes were separated within 14 min and without major interfering peaks. The quantitative ranges were 0.25–80.0 ng mL^–1 for both tetrahydro--carbolines and 0.1–30.0 ng mL^–1 for both -carbolines. Replicate spiking experiments showed that recovery from most of the samples tested was over 90% and the relative standard deviation ranged from 0.7 to 10.4% within and between assays. The proposed method was applicable to various materials such as soy sauce, vinegar, ketchup, tabasco, beer, wine, sake, whisky, brandy, cows' milk, coffee, cocoa, cheese, cigarette smoke and urine.     

The mineralization of CO32− ions on chitin- or chitosan- metal composite beads in water

The following dry composite beads (diameter 1.0-1-2 mm) were prepared: chitin-CaCO₃, chitosan-CaCl₂. chitosan-CuCl₂, partially N-acetylated chitosan-CuCl₂, chitosan-CuSO₄, chitosan-Fe₃O₄, chitin-SiO₂. Each of chitosan-CuCl₂, chitosan-CuSO₄ and chitin-CaCl₂ composite beads was treated in aqueous K₂CO₃ at room temperature to afford a mixture of metal carbonates and hydroxides on chitin or chitosan chain.     

New synthetic routes to optically active alpha-quaternary alpha-aryl amino acid derivatives via the diastereoselective Stevens and Sommelet-Hauser rearrangements

The Stevens rearrangement of N-allylic alpha-aryl amino acid-derived ammonium salts and the Sommelet-Hauser rearrangement of N-benzylic alpha-alkyl amino acid-derived ammonium salts are shown to proceed with remarkably high levels of diastereoselectivity. The methods presented in this work provide new routes to optically active alpha-quaternary alpha-aryl amino acid derivatives.     

Chiral distortion in a Mn(IV)(salen)(N3)2 derived from Jacobsen's catalyst as a possible conformation model for its enantioselective reactions

The Mn (IV)(salen)(N 3) 2 complex ( 3) from Jacobsen's catalyst is synthesized, and the X-ray crystal structures of 3 as well as the starting Mn (III)(salen)(N 3)(CH 3OH) complex ( 2) are determined in order to investigate the conformation of the high-valent Mn (IV)(salen) molecule in comparison with that of Mn (III)(salen). The asymmetric unit of the crystal of 3 contains four complexes, all of which adopt a nonplanar stepped conformation effectively distorted by the chirality of the diimine bridge. The asymmetric unit of 2 also contains four complexes. Two of them show a stepped conformation of a lesser degree, but the other two adopt a bowl-shaped conformation. Comparison of the structural parameters shows that the Mn center in 3 is coordinated from both sides by two external axial N 3 ligands with significantly shorter bond lengths, which could induce greater preference for the stepped conformation in 3. The CH 3CN solution of 3 shows circular dichroism with a significantly strong band at 275 nm as compared to 2, suggesting that 3 may adopt a more chirally distorted conformation also in solution. The circular dichroism spectrum of 3 is slightly altered with isodichroic points from 298 to 253 K and shows no further change at temperatures lower than 253 K, suggesting that the solution of 3 contains an equilibrium between two conformers, where a low-energy conformer with more chiral distortion is predominantly favored even at room temperature. Complexes 2 and 3 are thoroughly characterized using various techniques including cyclic voltammetry, magnetic susceptibility, UV-vis, electron paramagnetic resonance, (1)H NMR, infrared spectroscopy, and electrospray ionization mass spectrometry.     

Generation and detection of the radical cation and the dication derived from 4,9‐diethyl[1,4]dihydrodithiino[5,6‐f]benzotrithiole and its 5‐oxide

4,9‐Diethyl[1,4]dihydrodithiino[5,6‐f]benzotrithiole (DTBT) gave a radical cation, DTBT(•+), and a dication, DTBT(2+), on treatment with a single‐electron oxidizing reagent. Both compounds showed an ESR signal, whereas the dication, generated by this procedure, was silent for ¹H NMR. Hydrolysis of DTBT(2+) gave DTBT 1‐oxide (DTBT 1‐O) and 2‐oxide (DTBT 2‐O) together with DTBT and a mixture of several dioxides. A singlet‐state dication, DTBT(2+)‐S, which was generated upon treatment of DTBT 5‐oxide (DTBT 5‐O) with concentrated D₂SO₄, was detected by ¹H and ¹³C NMR. After 20 h, the NMR signals disappeared while the solution was active for ESR. The results suggest that (i) a species generated from DTBT by oxidation with the single‐electron oxidizing reagent is a triplet‐state dication, DTBT(2+)‐T, and (ii) DTBT(2+)‐S, initially generated, gradually isomerizes to DTBT(2+)‐T in the solution, and DTBT(2+)‐T forms a partial spin pair. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:394–401, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20445     

Comparative studies on 99mTc-pyrophosphate and 85Sr-chloride for skeletal imaging

In order to know the potential merits of 99mTc-pyrophosphate (99mTc-PYP) skeletal imaging, a comparative study was carried out by administering to the rabbit 85Sr-chloride (85Sr), classical bone-seeking agent, and 99mTc-PY simultaneously. Radioisotopic distribution was investigated as regards their deposition in the pelvic bones, and sharpness of the skeletal scintigrams, too. Both agents were remarkably affinitive to the skeletal system and there were remarkably differences in their temporal deposition pattern. Marked deposition was observed of either agent in the metaphyses. With 99mTc-PYP, the vertebral and costal systems were delineated symmetrically and each vertebral body was distinctly depicted as such 99mTc-PYP many possess the following merits over 85Sr; (1) owing to its physical properties, sufficiently large radioactivity of 99mTc-can be administered; (2) body burden of radiation absorption is reduced; (3) skeletal scintigrams of high quality are obtainable in a short period of time.     

Preliminary communicationPalladium-catalyzed carboxylation of aromatic compounds with carbon dioxide

Carbon dioxide has been found to react with aromatic compounds such as benzene, anisole, furane, and thiophene to give aromatic acids in modest yields with palladium(II) salts as catalysts. The addition of t-BuOOH increases the yield.