A convenient method for the preparation of α-vinylfurans by phosphine-initiated reactions of various substituted enynes bearing a carbonyl group with aldehydes

α-Vinylfurans were obtained by phosphine-initiated cyclization of various enynes bearing a carbonyl group at the ene end in the presence of various aldehydes, in moderate to high yields. The reaction may consist of 1,6-addition of phosphine to the enynes, ring closure, and Wittig reaction between the ylid resulting from cyclization and an aldehyde. Thus, various aldehydes were able to be used in the reaction. The reaction was influenced greatly by the substituents at the acetylene position (R¹) and the α-position of the carbonyl group (R³).     

Collection of iron(III) from homogeneous aqueous solutions on membrane filters using Chromazurol B with Triton X-100.

A membrane filtration method was examined concerning the effective collection of iron(III) from a homogeneous aqueous solution with Chromazurol B (CAB), one of the triphenylmethane dyes, as a precipitating reagent in the presence of a non-ionic surfactant, polyethylene glycol mono[4-(1,1,3,3-tetramethylbutyl)phenyl]ether (Triton X-100). A formed blue Fe(III)-CAB complex was collected as a precipitate on a membrane filter by filtration under suction from a homogeneous aqueous solution in the pH range over about 2. The original solution was prepared at a concentration ratio of CAB to Fe(III) of to 10, and that of Triton X-100 to CAB of 10 to 100. It was then adjusted to a pH value of between 1.0 and 6.5. A linear relationship (r = 0.999) was obtained between the initial concentration and the found one of Fe(III) in the range of 2.0 x 10(-5) to 4.0 x 10(-4) mol dm(-3) at a fixed concentration ratio of CAB to Fe(III) of 3 and that of Triton X-100 to CAB of 20. This membrane filtration with CAB and Triton X-100 may be utilized for the separation of Fe(III) as a background species.     

Surfaces which contain helical geodesics

LetM be a complete smooth surface of constant mean curvature in the Euclidean 3-space. If there exists two helical geodesics onM through each point ofM, thenM is either a plane, a sphere, or a circular cylinder.     

Asymmetric interaction of optically active polymers with asymmetric small molecules. IV. Effect of hydrophobic groups on asymmetric interaction

In order to investigate the mechanism of the asymmetric interaction between optically active polymers and small molecules, optically active copolymers of N-acrylyl L-amino acids(N-acrylyl-L -phenylalanine, N-acrylyl-L -tryptophan, and N-acrylyl-L -leucine, respectively) and N,N′-hexamethylene diacrylylamide were synthesized, and interaction of these polymers with the optical isomers of phenylalanine and tryptophan was investigated. In the interaction of these acidic polymers with amino acids performed at pH 5.0, significant difference in amount of adsorption between the D and L isomers of amino acids were observed, and the L form of amino acids was adsorbed preferentially. The interaction between optically active small molecules was also investigated: these results showed a similarity to the results for interaction between optically active polymers and amino acids. In some instances of asymmetric interaction the influence of hydrophobic interaction between a polymer and substrate was clearly perceived. The stereoselective effects on the asymmetric interaction are discussed.     

Reversible formation of F+-centers over platinum promoted sulfated zirconia upon hydrogen treatment

Reversible formation of F⁺-centers was observed over platinum promoted sulfated zirconia in the presence and absence of hydrogen. The intensity of ESR signal of F⁺-centers was increased by treatment in He stream and it was decreased rapidly by supply of hydrogen in gas phase. This behavior seems to be related to proton spillover.     

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.     

An intramolecular diels-alder approach to quassinoids—a stereoselective construction of a-aromatic klaineanone

Thermolysis of a benzocyclobutene derivative ($\text{20}$) prepared from norcamphor produced stereoselectively a tetracyclic compound ($\text{2}$), which was converted to a lactone ($\text{21}$) having correct stereochemistry at C₇, C₈, C₉, C₁₁, C₁₃, and C₁₄ positions of (±)-klaineanone.     

The synthesis of isoquinoline alkaloid and its related compounds using alanine derivatives as chiral auxiliaries

Chiral 1-substituted isoquinoline derivatives, which were obtained by the reaction using alanine derivatives as chiral auxiliaries, were transformed to (S)-2,3,9,10,11-pentamethoxyhomoprotoberberine (7) and a synthetic intermediate for O-methylkreysigine (9) in good yields and high stereoselectivity. The corresponding chiral allyl derivative of isoquinoline was transformed to a pyrrolidinoisoquinoline (16) in a highly enantioselective manner.     

Stability and vibrational spectra of toroidal isomers of C 240

To study the thermodynamic and mechanical stability of toroidal isomers of C ₂₄₀, we use a semi-empirical tight-binding theory and calculate their electronic structure, cohesive energy and vibrational spectra within the harmonic approximation. From these, we deduce their free energy at temperatures up to 1500K. The results are also compared to the isomer with icosahedral symmetry. Finally, we discuss within this approach, their stability and abundance.     

Tandem base-promoted ring-opening/Brook rearrangement/allylic alkylation of O-silyl cyanohydrins of beta-silyl-alpha,beta-epoxyaldehyde: scope and mechanism

Metalated O-silyl cyanohydrins of beta-silyl-alpha,beta-epoxyaldehyde have been found to serve as functionalized homoenolate equivalents by a tandem sequence involving base-promoted ring opening of the epoxide, Brook rearrangement, and alkylation of the resulting allylic anion. On the basis of mechanistic studies involving competitive experiments using the diastereomeric cyanohydrins, we propose a reaction pathway involving a silicate intermediate 36 formed by a concerted process via an anti-opening of the epoxide followed by the formation of an O-Si bond.