Trans-selective γ-arylation of macrocyclic N-picolinoylcycloalkylamines through palladium-catalyzed methylene sp3 carbon–hydrogen bond activation

While numerous stereoselective methylene β- and γ-carbon–hydrogen activation reactions are reported, there are no examples of trans-selective γ-carbon–hydrogen activation of cyclic compounds. Herein I report the first trans-selective palladium-catalyzed γ-arylation of N-picolinoylcycloalkylamine with aryl iodides. Trans-arylation of macrocyclic N-picolinoylcyclododecylamine proceeded to give trans-3-aryl-N-picolinoylcyclododecylamine as a sole mono-arylated product in up to 85% yield. Other, larger substrates were also applicable to trans-arylation, albeit with lower efficiency. The picolinoyl group of the trans-arylated product was easily removed with zinc and diluted hydrochloric acid.     

Single-phase heat transfer characteristics of concentric-tube thermosyphon

An experimental study has been conducted to evaluate the influence of the presence of inner tube and the Rayleigh number on free convective heat transfer in an open thermosyphon. Water and fluorocarbon R-11 refrigerant as the working fluids were utilized. Heat transfer results using the concentric geometry were given for modified Rayleigh number from 3.6×10² to 4.1 × 10⁷ which encompasses the regions of similarity, impeded and boundary layer flow conditions. It was found that the presence of the inner tube markedly increases the overall heat transfer coefficient of open thermosyphon by a factor as large as 2 to 10 in the turbulent impeded and boundary layer regimes.

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Wärmeübergang in einem Thermosyphon aus konzentrischem Rohr bei einphasiger Strömung

Zusammenfassung Es wurde experimentell untersucht, wie der Einbau eines Innenrohres und wie die Rayleigh-Zahl auf die freie Konvektion in einem offenen Thermosyphon, gefüllt mit Wasser oder dem Kältemittel R 11, einwirkt. Der untersuchte Bereich bei konzentrischer Geometrie lag bei modifizierten Rayleigh-Zahlen von 3,6 · 10² bis 4,1 · 10⁷ und umfaßte damit die Regionen der Grenzschichtströmung. Es ergab sich, daß der Einbau eines Innenrohres den Gesamtwärmeübergang eines offenen Thermosyphons im Bereich der behinderten turbulenten Strömungen und Grenzschichtströmungen um den Faktor 2 bis 10 steigert.

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Nomenclature a inner radius of heated tube, D/2 - A_in sectional space area of inner tube, d _i ² /4 - A_an sectional space area of annulus, (D^2-d ₀ ² )/4 - C_p specific heat - d_i inner diameter of inner tube - d₀ outer diameter of inner tube - D inner diameter of heated tube - g gravitational acceleration - L tube length of thermosyphon - Nu_a Nusselt number based on inner radius of heated tube - Nu_r Nusselt number based on equivalent heattransfer radius - Nu_x Nusselt number, defined in equation (1) - Pr Prandtl number, defined in equation (3) - q heat flux from heated tube - r equivalent heat-transfer radius, defined in equation (4) - Ra_a modified Rayleigh number based on inner radius of heated tube - Ra_r modified Rayleigh number based on equivalent heat-transfer radius - Ra_x modified Rayleigh number, defined in equation (2) - T_e temperature of entrance-fluid - T_w temperature of heated surface - T temperature difference between heated wall and entrance-fluid, T_w-T_e Greek Symbols coefficient of volumetric expansion - thermal diffusivity - thermal conductivity - viscosity - kinematic viscosity     

Reduction of ion thermal diffusivity associated with the transition of the radial electric field in neutral-beam-heated plasmas in the large helical device

Recent large helical device experiments revealed that the transition from ion root to electron root occurred for the first time in neutral-beam-heated discharges, where no nonthermal electrons exist. The measured values of the radial electric field were found to be in qualitative agreement with those estimated by neoclassical theory. A clear reduction of ion thermal diffusivity was observed after the mode transition from ion root to electron root as predicted by neoclassical theory when the neoclassical ion loss is more dominant than the anomalous ion loss.     

Alignment of atomic autoionizing states created by slow Na++He collisions

Ejected-electron spectra have been measured for collisions of He-atoms with Na⁺-ions, whose impact energy ranged from 1.7 to 7.0 keV. The ion impact-energy dependence of the angular-differential cross-section of the ejected electrons has been investigated for an aligned autoionizing state Na**(2p ⁵ 3s ^{2 2} P), which has been created by charge transfer from the He-atoms. The alignment of the autoionizing state Na**(2p ⁵ 3s ^{2 2} P) is discussed in relation to the scattering angles of the Na⁺-ions. A complete longitudinal alignment has been observed with respect to the quasimolecular axis.     

A critical analysis of the glass-forming ability of alloys

Several empirical rules have been proposed during the past few years to synthesize bulk metallic glasses. But, the real reasons for the improved glass-forming ability of these alloys are still not clear and the ability to design alloy compositions to enable synthesis of larger diameter rods has not improved. The present work conducts a critical analysis of the existing data in terms of the different glass-forming criteria and concludes that the available parameters cannot satisfactorily predict the GFA and explain all the observed data. Reasons for this failure have been suggested.     

Biosorption of chromium(VI) and arsenic(V) onto methylated yeast biomass

Yeast biomass was methylated in a 0.1 M HCl methyl alcohol solution at room temperature and the methylated yeast (MeYE) was applied to the adsorptive separation of Cr(VI) and As(V) anions from aqueous solutions. At near-neutral pH, while Cr(VI) and As(V) anions were scarcely adsorbed onto unmethylated yeast biomass, the amounts adsorbed increased with increasing methylation degree. The amount of Cr(VI) adsorbed onto MeYE was almost constant at pH 4-6 and decreased with increasing pH above pH 6. The amount of As(V) adsorbed onto MeYE was rather lower than that of Cr(VI) and it had a peak at about pH 7. A metal-binding model was used to describe the adsorption characteristics of Cr(VI) and As(V) on MeYE. The results showed that MeYE has two different types of adsorption sites. The saturated amount of Cr(VI) and As(V) adsorbed onto MeYE having methylation degree 0.94 was 0.55 mmol g(-1).     

Synthesis and in vitro antifungal activities of novel triazole antifungal agent CS-758.

Synthesis and in vitro antifungal activities of a novel triazole antifungal agent CS-758 (former name, R-120758) are described. The minimum inhibitory concentrations (MICs) of a series of dioxane-triazole compounds related to R-102557 were examined. Variation of the length of the chain between the dioxane ring and the phenyl ring revealed that the linkage with two double bonds is the most preferable. When a cyano group was introduced to the C4 position on the benzene ring, MICs improved further. A fluorine atom was introduced to obtain CS-758. The MICs of CS-758 surpassed those of fluconazole and itraconazole against Candida, Aspergillus and Cryptococcus species. The precursor (E,E)-aldehyde was synthesized stereoselectively from 3-fluoro-4-methylbenzonitrile using the Horner-Wadsworth-Emmons reaction.     

Heat-transfer characteristics from a bundle of horizontal tubes immersed in aggregative fluidized bed

Experiments were performed to study the effect of air fluidization velocity, particle diameter, tube diameter, and pitch between tubes on heat-transfer coefficient for a bundle of horizontal tubes immersed in an aggregative fluidized bed. Not only horizontal but also vertical distributions of the heat-transfer coefficients within the bundle were also extensively determined. The heat-transfer coefficient and its maximum value were found to be dependent on the particle diameter, the air fluidization velocity, and the gap between the tubes in the bundle. The proposed correlation for the maximum heat-transfer coefficient was in good agreement with the present results.