A simple synthesis of 2-arylbenzothiazoles and its application to palladium-catalyzed Mizoroki-Heck reaction

A variety of 2-arylbenzothiazoles were prepared by the direct reaction of 2-aminobenzenethiol and aryl aldehydes by the aid of activated carbon (Shirasagi KL or Darco^® KB) under oxygen atmosphere. 2-Pyridylbenzothiazole, thus obtained, was proved to work as an efficient ligand in palladium-catalyzed Mizoroki-Heck reaction.     

Vibrational spectra and rotational isomerism of ethyl trichloroacetate

The IR and Raman spectra of ethyl trichloroacetate (E-TCA) and its deuterate (E-TCA-d₅) have been measured in the liquid, glassy and crystalline states. Vibrational assignment was made by referring to isotopic wavenumber-shift, characteristic group frequencies of related esters and with the aid of a normal coordinate calculation on E-TCA and E-TCA-d₅. It is suggested that in the liquid and glassy states there exist two molecular forms (trans—trans—trans and trans—trans—gauche) with regard to the internal rotations about the ClC---C---O---CH₂CH₃ axis, and that the former persists in the crystalline state. The band pairs of E-TCA and the other ethyl esters are discussed in relation to the nature and number of rotational axes, effect of the heavy trichloromethyl group, and enhancement of band intensity by vibrational coupling.     

Highly regioselective nucleophilic carbon-carbon bond formation on furans and thiophenes initiated by pummerer-type reaction

[reaction: see text] The reactions of (phenylsulfinyl)furans or -thiophenes with carbon nucleophiles in the presence of trifluoroacetic anhydride allowed the nucleophilic installation of carbon functional groups on the furan and thiophene nuclei with complete regioselectivity.     

A crack tip tracking algorithm for cohesive interface element analysis of fatigue delamination propagation in composite materials

A novel approach is proposed for the use of cohesive elements in the analysis of delamination propagation in composite materials under high-cycle fatigue loading. The method is applicable to delamination propagation within the Paris-law regime and is suitable for the analysis of three-dimensional structures typical of aerospace applications. The major advantages of the proposed formulation are its complete independence of the cohesive zone length – which is a geometry-dependent parameter – and its relative insensitivity to mesh refinement. This is only possible via the introduction of three nonlocal algorithms, which provide (i) automated three-dimensional tracking of delamination fronts, (ii) an estimation of direction of crack propagation and (iii) accurate and mesh-insensitive integration of strain energy release rate. All calculations are updated at every increment of an explicit time-integration finite element solution, which models the envelopes of forces and displacements with an assumption of underlying constant cyclic loading. The method was implemented as a user-defined subroutine in the commercial finite element software LS-Dyna and supports the analysis of complex three-dimensional models. Results are presented for benchmark cases such as specimens with central cut plies and centrally-loaded circular plates. Accurate predictions of delamination growth rates are observed for different mesh topologies in agreement with the Paris-laws of the material.     

Formation of octacalcium phosphates with co-incorporated succinate and suberate ions

Octacalcium phosphates (OCPs) co-incorporated with various molar ratios of succinate and suberate ions were synthesized by wet processing. The interplanar spacings of the (100) planes (d(100)) of OCPs formed in the presence of succinic acid (Suc) or suberic acid (Sub) were larger than those of OCPs formed without addition of a dicarboxylic acid to the reaction solvent. The increases in the interplanar spacings of the (100) planes were caused by substitution of HPO(4)(2-) by dicarboxylate ions. The OCPs with co-incorporated succinate and suberate ions, i.e. solid solutions of OCP with incorporated Suc and Sub, were formed by reactions in the presence of Suc and Sub. When the Suc/(Suc + Sub) values in the starting compositions were in the range 0.45-1.0, Suc was preferentially incorporated into the OCP. In contrast, when the Sub/(Suc + Sub) values in the starting compositions were in the range 0.60-1.0, Sub was preferentially incorporated into the OCP crystals.     

Scattering theory for the elastic wave equation in perturbed half-spaces

In this paper we consider the linear elastic wave equation with the free boundary condition (the Neumann condition), and formulate a scattering theory of the Lax and Phillips type and a representation of the scattering kernel. We are interested in surface waves (the Rayleigh wave, etc.) connected closely with situations of boundaries, and make the formulations intending to extract this connection.

The half-space is selected as the free space, and making dents on the boundary is considered as a perturbation from the flat one. Since the lacuna property for the solutions in the outgoing and incoming spaces does not hold because of the existence of the surface waves, instead of it, certain decay estimates for the free space solutions and a weak version of the Morawetz arguments are used to formulate the scattering theory.

We construct the representation of the scattering kernel with outgoing scattered plane waves. In this step, again because of the existence of the surface waves, we need to introduce new outgoing and incoming conditions for the time dependent solutions to ensure uniqueness of the solutions. This introduction is essential to show the representation by reasoning similar to the case of the reduced wave equation.

     

Effect of allylic CH(3-n)F(n) groups (n = 1-3) on pi-facial diastereoselection

[structure: see text]. Michael addition of various enolates toward gamma-CH(3-n)F(n)-alpha,beta-unsaturated ketones (n = 1-3) was proven to smoothly furnish the 1,4-adducts with high si face selectivities which monotonously decreased by reduction in the number of fluorines. Although the Felkin-Anh model correctly anticipates the present stereochemical outcome only with E-acceptors, the hyperconjugative stabilization of transition states by electron donation from the allylic substituents (the Cieplak rule) successfully explains the pi-facial preference of both acceptors at least in a qualitative level.     

Oxidative aromatization of 1,3,5-trisubstituted pyrazolines and Hantzsch 1,4-dihydropyridines by Pd/C in acetic acid

[formula: see text] 1,3,5-Trisubstituted pyrazolines and Hantzsch 1,4-dihydropyridines were converted to the corresponding pyrazoles and pyridines effectively by the treatment of a catalytic amount of Pd/C in acetic acid.