Adsorbed state of nitrogen on ruthenium catalysts: TPD and isotopic study

The adsorbed state of nitrogen on Ru catalysts was studied by a TPD technique combined with an isotopic technique. (1) A molecular and an atomic species on Ru powder, (2) a molecular and three atomic species on Raney-Ru, and (3) two molecular and probably three atomic species on Raney-Ru/K were identified, respectively. Relations between the adsorbed states and those reactivities for an isotopic equilibration reaction of N₂ were discussed.     

The Erd?s-Pósa property for vertex- and edge-disjoint odd cycles in graphs on orientable surfaces

We prove that for any orientable surface S and any non-negative integer k, there exists an integer f_S(k) such that every graph G embeddable in S has either k vertex-disjoint odd cycles or a vertex set A of cardinality at most f_S(k) such that G-A is bipartite. Such a property is called the Erd?s-Pósa property for odd cycles. We also show its edge version. As Reed [Mangoes and blueberries, Combinatorica 19 (1999) 267-296] pointed out, the Erd?s-Pósa property for odd cycles do not hold for all non-orientable surfaces.     

Stereoregularity of poly(alkyl α-chloroacrylates) and mechanism of isotactic polymerization

The catalytic activity of the complexes prepared by the reaction of Grignard reagents with ketones, esters, and an epoxide as polymerization catalysts of methyl and ethyl α-chloroacrylates was investigated. The modifiers which gave isotactic polymers were α,β-unsaturated ketones such as benzalacetophenone, benzalacetone, dibenzalacetone, mesityl oxide, and methyl vinyl ketone, and α,β-unsaturated esters such as ethyl cinnamate, ethyl crotonate, and methyl acrylate. Catalysts with butyl ethyl ketone, propiophenone, and propylene oxide as modifiers produced atactic polymers but no isotactic polymers. It was revealed that the complex catalysts having a structure ? C?C? O? MgX (X is halogen) gave isotactic polymers. The mechanism of isotactic polymerization was discussed. In addition, for radical polymerization of ethyl α-chloroacrylate, enthalpy and entropy differences between isotactic and syndiotactic additions were calculated to give ΔH_i^* ? ΔH_s^* = 910 cal/mole and ΔS_i^* ? ΔS_s^* = 0.82 eu.     

Preparation of 9-hydroxy grayanotoxin derivatives and their acute toxicity in mice

Novel 9alpha and 9beta-hydroxy grayanotoxin II derivatives were prepared by photo-sensitized oxygenation of iso-grayanotoxin II and oxidation of grayanotoxin II tetraacetate with selenium dioxide respectively. The lethal dosage of 9alpha and 9beta-hydroxy grayanotoxin II were lower than that of grayanotoxin II. In addition, the lethal dosage of 9beta-hydroxy-dihydro grayanotoxin II was higher than that of dihydro grayanotoxin II.     

Synthesis of a capillarisin sulfur-analogue possessing aldose reductase inhibitory activity by selective isopropylation

We describe the synthesis of 2-[(4-hydroxyphenyl)thio]-7-isopropoxy-5,6-dimethoxy-4H-chromen-4-one 2 from 3,4,5-trimethoxyphenol 6 via the key intermediate, 3-iodo-7-isopropoxy-5,6-dimethoxy-4H-chromen-4-one 3. An important feature of this synthetic scheme involves selective alkylation, which can be achieved by two different routes. One route involves the selective isopropylation of a triacetate derivative 4 under basic conditions. The second route employs the selective demethylation of a trimethoxy derivative 5 under acidic conditions followed by isopropylation. The product of these alternative routes, compound 3, is then converted to a capillarisin sulfur analogue 2 in a one-pot reaction via the imidazolyl intermediate 22.     

Side-chain liquid crystalline homo- and copolymethacrylates with a carbonate linkage between the benzylideneaniline mesogen and ethylene chain

Abstract

New liquid crystalline (LC) homo- and copolymethacrylates having a carbonate linkage between a benzylideneaniline mesogen and ethylene chain in the side chain were prepared by free radical polymerization of methacrylate derivatives comprising 4-cyano- and/or 4-methoxybenzylide-neaniline units using AIBN as an initiator. The structures of the polymers were characterized by FTIR, ¹HNMR, and elemental analyses. The LC properties were evaluated by differential scanning calorimetry (DSC), polarizing microscopic observation of textures and X-ray diffraction. These measurements showed that all the homo- and copolymers form nematic phases. The isotropization temperatures on composition exhibited a negative deviation from a linear relationship between them predicted by the Schroeder-Van Laar equation. This phenomenon might be caused mainly by an unusual geometry arising from a smaller bond angle in the carbonate linkage.