Cyclopalladation of N,N,N′,N′-tetramethylisophthalthioamide

Summary N,N,N,N-Tetramethylisophthalthioamide (Hmpt) was cyclopalladated with PdCl₂ in hot dimethylsulphoxide to give [PdCl(mpt)]. The structure was determined by X-ray analysis. The thioamide is metallated at C(2) to act as an S528-01C528-02S tridentate anionic ligand. There is appreciable steric repulsion between the benzene ring H(4, 6) and the dimethylamino groups. The hydrogens and the methyl groups mutually deviate from the coordination plane in opposite directions. The stability of the fused 5,5-membered chelate ring formed by the S528-03C528-04S ligand seems to overcome the steric hindrance. Derivatives were prepared by replacement of the chloride ion with iodide, diethyldithiocarbamate, 4-tert-butylpyridine, or tri-n-butylphosphine, and characterized spectroscopically. The S528-05C528-06S-fused chelate ring was maintained in these derivatives.     

An efficient synthetic method for macrocyclic ketones by intramolecular alkylation of protected cyanohydrins,and its application to the syntheses of muscone and exaltone

A simple synthetic method for macrocyclic ketones based on intramolecular alkylation of carbanion, generated from protected cyanohydrin is reported. Subsequent mild treatment with acid and base of the cyclized products leads to macrocyclic ketones in high yields. The reaction is rapid and irreversible, and hence required short reaction time. The method was successfully applied to the syntheses of cyclohexadecanone and trans-2-cyclopentadecenone as a precursor of (±)-muscone and exaltone.     

Bioavailable acyl-CoA: cholesterol acyltransferase inhibitor with anti-peroxidative activity: synthesis and biological activity of novel indolinyl amide and urea derivatives

We synthesized a series of indoline derivatives with an amide or urea moiety and examined their inhibitory effects on acyl-CoA:cholesterol acyltransferase (ACAT) activity, lipid-peroxidation and serum cholesterol levels in experimental animals. Among the derivatives synthesized, a series of N-(1-alkyl-4,6-dimethylindolin-7-yl)-2,2-dimethylpropanamides++ + potently inhibited rabbit intestinal ACAT activity and lipid-peroxidation of rat brain homogenate. The effect on ACAT activity was related to the length of the alkyl chain at the 1-position of indoline. N-(4,6-Dimethyl-1-octylindolindolin-7-yl)-2,2-dimethylpropanami de hydrochloride (55) showed inhibitory effects on intestinal and hepatic ACAT activity slightly weaker than those of YM-750, and an inhibitory effect on low density lipoprotein (LDL)-peroxidation similar to that of probucol. Compound 55 also reduced serum cholesterol at 10 mg/kg/d in hyperlipidemic rats and 20 mg/kg/d in normolipidemic hamsters. The plasma concentration of 55 reached 716 ng/ml in dogs (10 mg/kg, p.o.), which is an effective concentration against hepatic ACAT activity and LDL-peroxidation. In conclusion, compound 55 is a novel bioavailable ACAT inhibitor with anti-peroxidative activity and is thus a promising anti-atherosclerotic and anti-hyperlipidemic drug. Indoline proved to be a useful pharmacophore for molecular design of new anti-peroxidative drugs.     

Electrical conductivities of potassium ferrites doped with divalent metal oxide

The electronic and ionic conduction in three kinds of potassium ferrites with β-alumina structure was studied. Undoped ferrite, K₂O·6Fe₂O₃, prepared by sintering at 1400°C after prefiring a mixture of potassium carbonate and ferric oxide, was a mixed conductor with about 1% ionic conduction and predominantly electronic conduction. The nickel- or zinc-doped potassium ferrite showed decreasing conductivity in the range of a single phase as the content of dopant increased. Variations of the electronic conduction in the doped potassium ferrites were assigned to changes of ferrous ion concentration accompanied by structural changes in the spinel-like blocks. Potassium ion conductivities of the three sorts of samples were estimated from the total conductivities and the transport numbers obtained by dc-polarization technique and electrolysis method. The decreases of the ionic conductivities were explained by narrowing of the alkali-oxygen slot caused by doping.     

Structures of moracins E,F, G,and H,new phytoalexins from diseased mulberry

The structures and antifungal activity of four new mulberry phytoalexins, designated as moracins E, F, G, and H, are described.     

The interaction of oxygen with TiC(001): photoemission and first-principles studies

High-resolution photoemission and first-principles density-functional slab calculations were used to study the interaction of oxygen with a TiC(001) surface. Atomic oxygen is present on the TiC(001) substrate after small doses of O(2) at room temperature. A big positive shift (1.5-1.8 eV) was detected for the C 1s core level. These photoemission studies suggest the existence of strong O<-->C interactions. A phenomenon corroborated by the results of first-principles calculations, which show a CTiTi hollow as the most stable site for the adsorption of O. Ti and C atoms are involved in the adsorption and dissociation of the O(2) molecule. In general, the bond between O and the TiC(001) surface contains a large degree of ionic character. The carbide-->O charge transfer is substantial even at high coverages (>0.5 ML) of oxygen. At 500 K and large doses of O(2), oxidation of the carbide surface occurs with the removal of C and formation of titanium oxides. There is an activation barrier for the exchange of Ti-C and Ti-O bonds which is overcome only by the formation of C-C or C-O bonds on the surface. The mechanism for the removal of a C atom as CO gas involves a minimum of two O adatoms, and three O adatoms are required for the formation of CO(2) gas. Due to the high stability of TiC, an O adatom alone cannot induce the generation of a C vacancy in a flat TiC(001) surface.     

Structure of the active sites of Co-Mo Hydrodesulfurization catalysts as studied by magnetic susceptibility measurement and NO adsorption

The elucidation of a molecular structure of the active sites (i.e., the Co-Mo-S phase) of Co-Mo hydrodesulfurization catalysts has received extensive attention. In the present study, we unambiguously determined, for the first time, the NO adsorption behavior and magnetic property of the Co-Mo-S phase by preparing unique Co-Mo/Al(2)O(3) catalysts (CVD-Co/MoS(2)/Al(2)O(3)), in which all the Co atoms are present as the Co-Mo-S phase. The catalysts were characterized by NO adsorption (pulse technique and FTIR), Co K-edge XANES, and the magnetic susceptibility and effective magnetic moment of Co. Nitric oxide molecules were adsorbed on 33% of the Co atoms in CVD-Co/MoS(2)/Al(2)O(3) after sulfidation and on only half of the Co atoms even after an H(2)-treatment of the sulfided catalyst at 573-673 K. The Co atoms in CVD-Co/MoS(2)/Al(2)O(3) exclusively exhibited an antiferromagnetic property, indicating that even-numbered Co atoms are interacting with each other in the Co-Mo-S phase. A Co-Mo/Al(2)O(3) catalyst, prepared by a conventional impregnation technique, was composed of the antiferromagnetic Co sulfide species as observed in CVD-Co/MoS(2)/Al(2)O(3) in addition to Co(9)S(8). On the basis of the NO adsorption behavior and magnetic property, it is empirically proposed that the structure of the Co-Mo-S phase is represented as a Co sulfide dinuclear cluster located on the edge of MoS(2) particles. The magnetic property of Co/Al(2)O(3) sulfide catalysts depended on the preparation method.     

Studies of poly-yne polymers containing transition metals in the main chain : VI. Synthesis of nickel-poly-yne polymers by alkynyl ligand exchange using a copper(I) catalyst.

Reactions of trans-bis(Tri-n-butlphosphine)diethynylnickel(Ia) with 1-alkynes in the presence of an amine complex of a copper(I) salt as a catalyst give quantitatively alkynyl ligand exchange products. By this method, complex(Ia) reacts with appropriate α,ω-diethynyl compounds to afford high molecular weight linear polymers in good yields. This procedure provides a convenient route to such nickel-poly-yne polymers.