Pseudoguaiane-type sesquiterpenes and inhibitors on nitric oxide production from Dichrocephala integrifolia

Three new pseudoguaiane-type sesquiterpenes, dichrocepholides A-C, and two new pseudoguaiane-type sesquiterpene dimers, dichrocepholides D and E, were isolated from the aerial part of Dichrocephala integrifolia. Their stereostructures were determined on the basis of chemical and physicochemical evidence. In addition, the extract and its principal sesquiterpene constituent, parthenin, showed an inhibitory activity on nitric oxide (NO) production and on induction of inducible NO synthase.     

Heterometallic hexanuclear cluster with an S = 8 spin ground state: MnII[MnII(hfac)2]3[NiII(pao)3]2 (hfac- = hexafluoroacetylacetonate,pao- = pyridine-2-aldoximate)

The heterometallic Mn(II)(4)Ni(II)(2) title compound has been synthesized and characterized by X-ray crystallography. The compound consists of a Ni-Mn-Ni linear moiety, [[Ni-(mu-NO)(3)](2)-Mn], linked by oximate bridges and three Mn(II) hfac terminal units attached by oximate oxygens in a di-mu-oxo fashion, forming a novel heterometallic cluster: Mn[Mn(hfac)(2)](3)[Ni(pao)(3)](2) (1). Magnetic measurements reveal the antiferromagnetic nature of the oximate pathway between Mn(II) and Ni(II) metal ions, which imposes an unusual high-spin ground state (S = 8) for 1.     

Contrasteric stereochemical dictation of the cyclobutene ring-opening reaction by a vacant boron p orbital

Cyclobutene, having a pinacolatoboryl group at the 3-position, was prepared by the reaction of trimethyl borate with a cyclobutenyl anion, which was generated by reductive lithiation of 3-(phenylselenyl)cyclobutene. Its thermal ring-opening reaction provided (Z)-1-borylbuta-1,3-diene selectively despite the arising steric congestion. The contrasteric behavior was accounted for by assuming an electron-accepting interaction of the vacant boron p orbital with the distorted breaking sigma orbital in the inward transition state.     

Electrochemical characterization of negative electrodes consisting of surface-modified Zr0.9Ti0.1(Ni1.1Co0.1Mn0.5V0.2Cr0.1)x Laves-phase alloys

Laves-phase hydrogen storage alloy has a high potential for use as negative electrode material as alternative for the misch-metal-based material. In order to improve the energy density and the rate capability of negative electrode, chemical and mechanical modification of Lavesphase alloy with different stoichiometric ratios was carried out. Discharge capacity and high-rate dischargeabilty was evaluated by electrochemical methods and the characterization of Laves-phase alloy was made by X-ray diffraction, SEM observation and PCT measurement. The best result in discharge capacity could be obtained for stoichiometric Laves-phase alloy with a composition of Zr_0.9Ti_0.1Ni_1.1Co_0.1Mn_0.5V_0.2Cr_0.1 by boiling in 10 M KOH solution. On the other hand, the high-rate dischargeability was increased remarkably by introducing mechanical grinding before alkali treatment. The cause for improved performance was discussed on the basis of thermodynamic stability of metal hydride and changes in crystal structure and surface morphology influencing on diffusion coefficient and diffusion path length of hydrogen.     

Preparation of enol ethers by carbonyl olefination utilizing an alkoxymethyl chloride-titanocene(II) system

Aldehydes, ketones, esters and lactones are transformed into enol ethers or 1,2-dialkoxy-1-alkenes by treatment with organotitanium species prepared from alkoxymethyl chlorides and a titanocene(II) complex.     

A study on the conformation-anomeric effect-stereoselectivity relationship in anomeric radical reactions,using conformationally restricted glucose derivatives as substrates

We previously theorized that, since the stereoselectivity of anomeric radical reactions is significantly influenced by the kinetic anomeric effect, which can be controlled by restricting the conformation of the radical intermediate, the proper conformational restriction of the pyranose ring of the substrates would therefore make highly alpha- and beta-stereoselective anomeric radical reactions possible. This theory was based on our previous results of the anomeric radical reactions with d-xylose derivatives as the substrates. We herein report the anomeric radical deuteration reactions with the conformationally restricted 1-phenylseleno-d-glucose derivatives, 2g and 3g, restricted in a (4)C(1)-conformation by an O-cyclic diketal moiety, and 4g, 5g, 6g, 7g, and 8g, restricted in a (1)C(4)-conformation by bulky O-silyl protecting groups. The radical deuterations with Bu(3)SnD, using the (4)C(1)-restricted substrates 2g and 3g, afforded the corresponding alpha-products (alpha/beta = 98:2) highly stereoselectively, whereas the (1)C(4)-restricted substrate 6g, having a trigonal (sp(2)) carbon substituent, i.e., -CHO, at the 5-position, selectively gave the beta-products (alpha/beta = 0:100). Thus, the stereoselectivity was significantly increased by the conformational restriction and was completely inverted by changing the substrate conformation from the (4)C(1)-form to the (1)C(4)-form. On the other hand, the deuterations with the (1)C(4)-restricted substrates 4g and 5g showed that the 1,5-steric effect due to the tetrahedral carbon substituent (-CH(2)OTIPS or -CH(2)OH) at the 5-axial position dominantly prevented the hydride transfer from the beta-face competing with the kinetic anomeric effect. This study suggests that, depending on the restricted conformation of the substrates to the (4)C(1)- or the (1)C(4)-form, the alpha- or beta-products would be obtained highly stereoselectively via anomeric radical reactions of hexopyranoses.     

Medicinal foodstuffs. XVII. Fenugreek seed. (3): structures of new furostanol-type steroid saponins, trigoneosides Xa, Xb, XIb, XIIa, XIIb, and XIIIa, from the seeds of Egyptian Trigonellafoenum-graecum L

Six new furostanol-type steroid saponins called trigoneosides Xa, Xb, XIb, XIIa, XIIb, and XIIIa were isolated from the seeds of Egyptian Trigonella foenum-graecum L. (Leguminosae) together with six known furostanol-type steroid saponins: trigoneosides Ia, Ib, and Va, glycoside D, trigonelloside C, and compound C. The structures of trigoneosides Xa, Xb, Xlb, XIIa, Xllb, and XIIIa were determined on the basis of chemical and physicochemical evidence as 26-O-beta-D-glucopyranosyl-(25S)-5alpha-furostane-2alpha+ ++,3beta,22xi,26-tetraol 3-O-alpha-L-rhamnopyranosyl(1-->2)-,beta-D-glucopyranoside, 26-O-beta-D-glucopyranosyl-(25R)-5alpha-furostane-2 alpha,beta,22xi,26tetraol 3-O-alpha-L-rhamnopyranosyl(l -->2)-beta-D-glucopyranoside, 26-O-beta-D-glucopyranosyl-(25R)-5alpha-furostane2alpha++ +,beta,22xi,26-tetraol 3-O-beta-D-xylopyranosyl(l -->4)-beta-D-glucopyranoside, 26-O-beta-D-glucopyranosyl-(25S)-furost-4-ene-3beta,22xi,26- triol 3-O-Ca-L-rhamnopyranosyl(1-->2)-beta-D-glucopyranoside, 26-O-beta-D-glucopyranosyl-(25R)-furost-4-ene-3beta,22xi+ ++,26-triol 3-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D-glucopyranoside, and 26-O-beta-D-glucopyranosyl(25S)-furost-5-ene-3beta,22xi,26-t riol 3-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D-glucopyranosyl (1-->3)-beta-D-glucopyranosyl(1--4)]-beta-D-glucopyranoside, respectively.     

Synthesis of Optically Active Vasicinone Based on Intramolecular Aza-Wittig Reaction and Asymmetric Oxidation(1)

Both optical isomers of a quinazoline alkaloid, vasicinone, were synthesized by two different methods. The first method used (3S)-3-hydroxy-gamma-lactam as a chiral synthon, which was, after O-TBDMS protection, o-azidobenzoylated followed by treatment with tri-n-butylphosphine to afford (S)-(-)-vasicinone via the tandem Staudinger/intramolecualr aza-Wittig reaction. The second method utilized asymmetric oxygenation of deoxyvasicinone with (1S)-(+)- or (1R)-(-)-(10-camphorsulfonyl)oxaziridine (the Davis reagent), respectively. The aza-enolate anion of deoxyvasicinone was treated with (S)-(+)-reagent to afford (R)-(+)-vasicinone in 71% ee, while the reaction with (R)-(-)-reagent gave (S)-(-)-vasicinone in 62% ee. The optical purity was analyzed by HPLC on specially modified cellulose as a stationary phase. These results provided a facile method to prepare both optical isomers of vasicinone and confirmed the recently reversed stereochemistry of natural (-)-vasicinone.     

Voltammetry at partially covered electrodes: Part III. Faradaic impedance measurements at model electrodes

Faradaic, impedances at model electrodes partially covered with a photoresist layer have been studied theoretically and experimentally. Equations for the faradaic impedance are derived based on the theoretical model and approach described in Part I of this series of papers. Experimental data for the hexacyanoferrate system at various model electrodes give excellent agreement, with theoretical predictions for the diffusion impedance behavior, and the applicability of the derived equations to the estimation of the degree of coverage and the size of the active regions is confirmed. Furthermore, the application of such model electrodes to the kinetic study of electrode reactions with high heterogeneous charge transfer rates is suggested.     

1H-NMR Relaxation of Water Molecules in the Aqueous Microcrystalline Cellulose Suspension Systems and Their Viscosity

An intensive study for aqueous microcrystalline cellulose (MCC) suspensions was carried out in view of the relationship between a viscosity and a 1H spin-spin relaxation time (T2) of water. An investigation was carried out for four suspension systems with the different particle size distributions. The proton mole ratio () of bound water against MCC particles and T2 of bound water (T2,b) were evaluated from the T2 values obtained by Carr-Purcell- Meiboom-Gill (C.P.M.G) method and those by solid echo method, respectively. As a result of these analyses, the T2,b value for the aqueous MCC suspension was evaluated as 5 × 10–3 s and it was found that the system having a larger tended to show a higher viscosity. By relating the above results to the observation of the suspensions by an optical microscope, it was concluded that a network formed by MCC particles plays an important role in generating a high viscosity of MCC suspension, and that an averaged mobility of water molecules is sensitively affected by the network structure.