Highly (Z)-selective synthesis of beta-monosubstituted alpha,beta-unsaturated cyanides using the peterson reaction

[reaction: see text] The Peterson reaction between (t-BuO)Ph(2)SiCH(2)CN and various aldehydes furnishes the corresponding beta-monosubstituted alpha,beta-unsaturated cyanides with high Z selectivity (Z:E = 92:8 to >98:2).     

Enhanced indoor radon concentration by using radon-rich well water in a Japanese wooden house in Fukuoka, Japan

Summary Radon measurements were carried out in a Japanese wooden house built on granitic geology, where radon-rich well water is used. Atmospheric radon concentrations were measured over one year with passive integrated radon monitors. The monitors were distributed at several locations in the house and were replaced every two months. In order to confirm the diurnal variation and heterogeneous distribution of radon, short-term measurements were carried out accordingly. Radon, its decay products and terrestrial gamma-radiations were measured in this survey. From the long-term measurement, the radon concentration in the house ranged from 14 to 184 Bq^. m^-3with an arithmetic mean of 45 Bq^. m^-3. A radon concentration of 184 Bq^. m^-3was observed in the bathroom in spring (March-May) though the radon level was normal in the living room and bedroom. In order to characterize the house, similar measurements were conducted in several surrounding houses. There was a significant difference in radon concentration between the investigated houses. There was a spatial distribution of the radon concentration and the highest value was found in the bathroom. Radon and its decay products concentrations varied with time, which increased from midnight to morning whereas they decreased during daytime. Although the radon concentration in tap water was 1 Bq^. l^-1, a high level of 353 Bq^. l^-1was found in the well water.While well water was being used, the indoor radon concentration near the bathroom increased rapidly with a maximum value of 964 Bq^. m^-3. It is clear that the use of well water enhanced the radon level around the bathroom.     

Ambident reactivity of the thiocyanate anion revisited: can the product ratio be explained by the hard soft acid base principle?

Laser flash photolysis and stopped-flow methods have been employed to determine the kinetics of the reactions of benzhydrylium ions with both termini of the thiocyanate ion. In contrast to previous investigations which reported sulfur/nitrogen ratios of k(S)/k(N) = 2-10 for the reactions of carbocations with SCN(-), values of k(S)/k(N) = 10(3)-10(4) are now derived from absolute rate constants. This discrepancy is explained by the fact that the data determined in this investigation are the first which refer to activation-controlled attack of carbocations at both termini of the thiocyanate ion, while previous reactivity ratios included diffusion-controlled reactions. It is concluded that the selectivities of the reactions of carbocations with the thiocyanate ion cannot be explained by the hard soft acid base principle.     

Absolute stereochemistries and total synthesis of (+)-arisugacins A and B, potent, orally bioactive and selective inhibitors of acetylcholinesterase

In the current studies, we used the Kakisawa-Kashman modification of the Mosher NMR method to determine the complete absolute stereochemistry of arisugacins. We also report the convergent total synthesis of (+)-arisugacins A and B by a sequence including (i) ruthenium complex-catalyzed asymmetric reduction of the cyclohexenone derivative; (ii) stereoselective construction of the arisugacin skeleton by a Knoevenagel-type reaction of an α,β-unsaturated aldehyde derivative with production of a 4-hydroxy-2-pyrone derivative as a key reaction; and (iii) stereoselective dihydroxylation to give the diol derivative, followed by deoxygenation. Accordingly, we defined the absolute structures of arisugacins A and B as 4a-(R),6a-(R),12a-(R), and 12b-(S). Finally, we characterized the bioactivities of the synthetic intermediates to understand the structure-activity relationships of the arisugacins.     

Evaluation of thyroid scintigraphy in small animals

Thyroid scintigraphy in rats and mice with 99mTc and 123I was attempted to examine whether this modality might be used in small animals and to describe the possibilities of its application in examining experimentally produced thyroid diseases. A human gamma camera with a pinhole collimator improved for small animals was used for imaging. Thyroid images with 99mTc were obtained 20 minutes after injection and those with 123I were 24 hours after administration. All the scintigrams, although those obtained from mice with 99mTc displayed overlapped salivary gland images, demonstrated sufficiently clear images in size and shape, which showed that thyroid scintigraphy in small animals should be applicable in examining experimentally produced thyroid diseases.     

Substoichiometric precipitation of silicon as barium fluorosilicate

Distillation and substoichimetric precipitation for silicon have been developed for the determination of trace amounts of silicon. It is based on substoichiometric precipitation as barium fluorosilicate and the distillation of silicon tetrafluoride. The separation has been applied for the determination of silicon in gallium arsenide and NBS steel as standard reference material.     

exo- and enantioselective cycloaddition of azomethine ylides generated from N-alkylidene glycine esters using chiral phosphine-copper complexes

High diastereo- and enantioselectivities were obtained for the asymmetric 1,3-dipolar cycloaddition of azomethine ylides generated from N-alkylideneglycine esters with dipolarophiles using chiral phosphine-copper complexes as catalysts. Whereas the cycloaddition of azomethine ylides catalyzed by metal salts generally afforded endo-adducts as the predominant product, the present method is the first example of an exo-selective cycloaddition. [reaction: see text]     

Synthesis of (-)-aphanorphine using aryl radical cyclization

[structure: see text] The synthesis of (-)-aphanorphine was achieved by using Bu(3)SnH-mediated aryl radical cyclization of 1-benzyloxycarbonyl-2-(2-bromo-4-methoxyphenylmethyl)-2-methoxycarbonyl-4-(phenylthiomethylene)pyrrolidine, leading to exclusive formation of the 6-exo cyclization product.     

Slurry sampling techniques for the determination of lead in Bangladeshi fish samples by electrothermal atomic absorption spectrometry with a metal tube atomizer

Ultrasonic slurry sampling electrothermal atomic absorption spectrometry with a metal tube atomizer has been applied to the determination of lead in Bangladeshi fish samples. The slurry sampling conditions, such as slurry stabilizing agent, slurry concentration, pyrolysis temperature for the slurried fish samples, particle size and ultrasonic agitation time, were optimized for electrothermal atomic absorption spectrometry with the Mo tube atomizer. Thiourea was used as the chemical modifier for the interference of matrix elements. The detection limit was 53 fg (3S/N). The determined amount of lead in Bangladeshi fish samples was consistent with those measured in the dissolved acid-digested samples. The advantages of the proposed methods are easy calibration, simplicity, low cost and rapid analysis.     

Copolymerization of butadiene and styrene with a gadolinium tricarboxylate catalyst

Homo- and copolymerizations of butadiene (BD) and styrene (St) were carried out by gadolinium catalysts having various tricarboxylate ligands [Gd(OCOR)₃: R = CH₃, CH₂Cl, CHCl₂, CCl₃, and CF₃], to investigate the effects of ligands and discuss the cis polymerization mechanism. Polymerization of BD with Gd(OCOR)₃—(i—Bu)₃Al—Et₂AlCl catalysts was carried out in hexane at 50°C. By each catalyst, poly(BD) having a high cis content (cis = 97–99%) in 22–85% yields for 2–24 h were obtained. The ligands with low pKa values increased the polymerization activity as follows: R of Gd(OCOR)₃: CF₃ > CCl₃ > CHCl₂ > CH₂Cl ～ CH₃. On the other hand, in the polymerization of St or copolymerization of BD and St under similar conditions, the highest activity was attained by a Gd(OCOCCI₃)₃- based catalyst. The difference in the optimum ligand among the homo- and copolymerization of BD and St was discussed on the basis of energy levels of the catalysts. In the copolymers of BD and St, the cis-1,4 content of the BD unit decreased with increasing St content. Furthermore, according to the diad analysis of copolymers (St content ～ 14.5 mol %) by ¹³C NMR spectroscopy, the low cis value of the BD unit was observed in the St-BD diad (cis/trans/vinyl = 24/53/23), while the high cis value of the BD unit remained in the BD-BD diad (cis/trans/vinyl = 89/10/1). These results suggest that the terminal BD unit is controlled by the cis configuration by the coordination between the penultimate cis vinylene unit and the gadolinium metal catalyst, whereas the presence of the penultimate St unit interferes with cis polymerization of the terminal BD unit. The difference in the coordination mechanism in the course of polymerization between rare earth metal and transition metal catalysts such as the Ni(acac)₂ and Co(acac)₃-based catalyst was also discussed. © 1995 John Wiley & Sons, Inc.