Organic phosphorus compounds. IV. Asymmetric 4-(benzothiazol-2-yl)benzylphosphonates as potent calcium antagonistic vasodilators

Various asymmetric or cyclic ester derivatives of the phosphonic acid moiety in the calcium antagonist fostedil (KB-944) were synthesized. The coronary vasodilator activity of these compounds was assessed by Langendorff's method. Among them, the ethyl isopropyl ester 12 showed the most potent activity, which was comparable to that of fostedil.     

Aurilide, a cytotoxic depsipeptide from the sea hare Dolabella auricularia: isolation, structure determination, synthesis, and biological activity

The bioassay-guided fractionation of the cytotoxic constituents of the Japanese sea hare Dollabella auricularia led to the isolation of aurilide (1), a 26-membered cyclodepsipeptide. The gross structure of 1 was established by spectroscopic analysis including 2D NMR techniques. The absolute stereostructure was determined by chiral HPLC analysis of acid hydrolysates of 1 and by the enantioselective synthesis of a degradation product arising from a dihydroxylated fatty acid portion. The enantioselective synthesis of 1 was achieved in 12% overall yield (16 steps) and confirmed the absolute stereostructure of 1. The cytotoxicity of 1 was evaluated using a synthetic sample, which was found to exhibit potent cytotoxicity against HeLa S₃ cells with an IC₅₀ of 0.011 μg/mL. Further biological and pharmacological studies of 1 have been carried out by using synthetic 1.     

Photopolymerization of methyl methacrylate in the presence of tertiary amines

The sensitization effect of tertiary amines on the photopolymerization of methyl methacrylate was studied. N,N-Dimethylbenzylamine, triethylamine, and N,N-dimethylaniline increased the rate of polymerization in this order, but pyridine did not show any effect. A free-radical mechanism was confirmed by the tacticity of polymer, the retarding effect of hydroquinone, and the copolymer composition with styrene. On the basis of the detailed kinetics of the sensitized polymerization and the ultraviolet spectra of the reaction mixtures, a sensitization mechanism is proposed, in which the excited monomer and the amine form a complex and generate an initiating radical.     

A practical asymmetric synthesis of trans-4,5-benzhydrindan-1-ones as a precursor of A-nor B-aromatic steroidal compounds

The enantio-controlled synthesis of trans-4,5-benzhydrindan-1-ones was achieved by means of a stereoselective [4+2] cycloaddition of o-quinodimethanes generated by a thermal cleavage of benzocyclobutene derivatives as a key step. The chiral substrates of the thermal reaction were synthesized by a diastereoselective Grignard addition to the chiral O-isopropylideneglyceroketones connected to a benzocyclobutene ring, which were simply prepared from D-mannitol as a chiral source. This approach can provide a new efficient access to A-nor B-aromatic steroidal compounds.     

Crystal structures of n-alkanes with branches of different size in the middle

We synthesized four branched n-alkane samples C35-C1, C35-C4, C35-C6, and C35-C4Ph with the same number of carbons as the main chain, n = 35, to which the methyl, butyl, hexyl, and butyl phenyl groups were respectively attached at the middle, and also the corresponding linear homologue of C35, and studied their crystalline structures from DSC, IR, and Raman spectroscopy, X-ray diffraction measurement, and computer simulation. Solid-solid phase transitions characteristic of linear alkane C35 are not observed for any branched alkanes, and their melting temperatures Tm are lowered to 325.2, 318.5, 314.3, and 314.1K, respectively. Main chains of branched alkane molecules are not folded, irrespective of length and chemical structure of branches, but are extended to take the planar zigzag form in the solid state. The branches of C35-C4 and C35-C6 are also aligned inside the crystal in the extended form. Data analyses on solution-grown crystallized samples reveal that, with increasing the branch length, their crystal structures transform from polymorphic forms of the orthorhombic (P2(1)2(1)2(1)) and the triclinic (P) for C35-C1 and C35-C4 to the unique triclinic form for C35-C6 and C35-C4Ph, so as to minimize extra surface energy invoked by introduction of long branches.     

Pinacol coupling reaction of beta-halo-alpha,beta-unsaturated aldehydes promoted by TiI4

The pinacol reaction of beta-halogenated alpha,beta-unsaturated aldehydes was promoted by titanium tetraiodide to give coupling products in good yields with high dl-selectivity. Subsequent reduction with H(2)/Pd-C gave saturated vic-diols in good yields. Heck coupling reaction enabled the displacement of halogens with vinyl groups without the loss of stereochemical integrities. [reaction: see text]     

Flow-injection determination of 9,10-phenanthrenequinone with catalytic photometric detection

A catalytic photometric method with a flow-injection system is described for the determination of 9,10-phenanthrenequinone. It is based on the catalytic effect of 9,10-phenanthrenequinone on the redox reaction of 1,2-dinitrobenzene with formaldehyde under alkaline conditions. 9,10-Phenanthrenequinone at the 5.0 x 10(-8)-5.0 x 10(-6)M level can be determined at a rate of 20 samples/hr. The detection limit is 1.0 x 10(-8)M (40 pg in a 10-microl injection).     

Alkyl chain branching in ethylene–vinyl acetate copolymer

Ethylene–vinyl acetate copolymers contain two kinds of side chains: acetoxy branches originating from incorporated vinyl acetate and alkyl branches. The alkyl branching was determined by infrared analysis after converting the ethylene–vinyl acetate copolymer to a hydrocarbon polymer by three steps: hydrolysis, iodation with hydriodic acid containing red phosphorus, and reductive hydrogenation with lithium aluminum hydride. It was found that physical properties such as stiffness were dependent both on the degree of alkyl chain branching and on vinyl acetate content.     

Liposomes prepared from synthetic amphiphiles. I. Their technetium labeling and stability

In order to apply liposomes prepared from synthetic amphiphiles containing amino acid residues to radiopharmaceuticals, their labeling with 99Tc or 99mTc and stability in saline or in serum were investigated. These liposomes were highly labeled by embedding stearylamine-diethylenetriamine pentaacetic acid as a ligand of technetium. The labeling was more efficient at pH 7.0 than at pH 4.0 or 8.5. Among these technetium-labeled liposomes tested, liposomes containing the alanine residue were stable in saline or in 50% serum at 37 degrees C for at least 24 h, in contrast to liposomes (phosphatidylcholine: cholesterol = 1:1 molar ratio) whose stability had been enhanced by adding cholesterol.     

XPS study of one-dimensional compounds: TiS3

X-Ray photoelectron spectra of TiS₃ with a one-dimensional structure were measured. TiS₃ may be regarded as Ti⁴⁺(S₂)^2?S^2? with pairs of S atoms (S₂) and isolated S atoms. The spectra of the sulfur core-levels are assigned by comparison with those of TiS₂, where all S atoms are largely separated. The binding energy of the S₂ pairs is found to be 1.4 eV higher than that of the isolated S atoms, which is consistent with the larger negative charge of the isolated atoms. The structures of the valence band of TiS₃ are discussed in terms of a molecular orbital scheme for the S₂ pairs.