Amination of octafluoronaphthalene in liquid ammonia: 2,6- and 2,7-Diaminohexafluoronaphthalenes selective preparation

Monoamination of octafluoronaphthalene by liquid ammonia affords 2-aminoheptafluoronaphthalene mainly (isolated yield 85-90%). Diamination of octafluoronaphthalene or amination of 2-aminoheptafluoronaphthalene affords a mixture of isomeric 1,6-, 1,7-, 2,6-, and 2,7-diaminohexafluoronaphthalenes with considerable prevalence of the 2,7-isomer (∼70%), thus being the first example of the predominant substitution at position 7 in 2-substituted polyfluoronaphthalenes. The 2,7/2,6 ratio of 2-X-heptafluoronaphthalene (X = ⁻NH, NH₂ and NHAc) amination diminishes with the decrease of electron-donating effect of the substituent; 2,7-diaminohexafluoronaphthalene forms in the reactions of 2-aminoheptafluoronaphthalene or octafluoronaphthalene with excess of NaNH₂ in liquid ammonia and 2,6-diaminohexafluoronaphthalene—in the reaction of 2-acetylamidoheptafluoronaphthalene with liquid ammonia followed by acetylamido group hydrolysis. The method of the selective preparation of these diamines based on the reversible transformation of amino group and a convenient technique of their high purity isolation by complexation with crown ether have been elaborated.     

Light scattering in a finite multi-particle system

We use the discrete dipole approximation (DDA) to perform electromagnetic scattering calculations of particles in a 3D volume. We adjust the spacing between the particles to change the volume densities of the scattering systems from approximately 10% to 100%. For very large volume densities, e.g. >50%, it is difficult to assign unambiguously whether the system is composed of a single heterogeneous particle or of multiple particles. Our calculations demonstrate optical effects attributable to multiple scattering in systems having volume densities as high as ～90%. This suggests that heterogeneities within naturally occurring particle systems can produce multiple-scattering effects. We also see evidence of very deep negative polarization branches (NPBs) (～?6%) that may have implications in interpreting polarization phase curves of cometary circumnuclear halos.     

Efficient synthesis of chalcone-4′-sulfonyl chlorides and fluorides

A library of 4′-chloro- and 4′-fluorosulfonyl-substituted chalcones was prepared via the aldol-type condensation reactions of 4-acetylbenzene-1-sulfonyl halides with various aromatic aldehydes, either in absolute ethanol or glacial acetic acid, in the presence of dry HCl. This represents the first examples of chalcone sulfonyl halides in which the phenone ring bears one of these functional groups. The reactivity of the chalcone sulfonyl halides were strongly dependent on the styrene ring substituents; sulfonyl chlorides reacted with most nucleophiles (e.g. amines, alcohols), while sulfonyl fluorides reacted only with charged nucleophiles (e.g. phenolates).     

Spectral localization in the hierarchical Anderson model

We prove that a large class of hierarchical Anderson models with spectral dimension has only pure point spectrum.

     

The NQR picture of electronic phase separation in the lanthanum–barium cuprates

We report the results of Cu and La NQR investigations of the spin and charge separation in La_2−xBa_xCuO₄ compounds. For Ba doping inducing the low-temperature tetragonal phase our Cu–NQR measurements revealed three inequivalent Cu sites in CuO₂ planes. In terms of the stripe-phase picture we assign them to the charged stripe, to its neighborhood and to the AF correlated regions free of holes correspondingly. The last site corresponds to the ordered Cu magnetic moment of 0.29μ_B.     

Environment‐Adopting Surfaces with Reversibly Switchable Morphology

Two‐component polymer brushes (polystyrene and poly(2‐vinylpyridine)) were synthesized by grafting from the surface of Si‐wafers. The brushes are sensitive to the surrounding medium, and their morphology and composition of the top of a brush can be switched upon exposure to different solvents. Thus surface energetic states and roughness of the film can be precisely tuned.     

A representative of p,p,p-trihalogenylides: synthesis and structure

The representative of P,P,P-trichloroylides-5-methyl-2-phenyl-4-(trichlorophosphoranylidene)-2,4-dihydro-3H-pyrazol-3-one-was synthesized. Its constitution was confirmed by 1H, 13C, and 31P NMR spectroscopy and by X-ray analysis. Some chemical properties were studied and compared with ones of P,P,P-trimethylylide-5-methyl-2-phenyl-4-(trimethylphosphoranylidene)-2,4-dihydro-3H-pyrazol-3-one. DFT calculations of the model molecules were carried out.     

Effect of the orientation of the optic axis on simulated scattering matrix elements of small birefringent particles

We study how the orientation of the optic axis affects single-scattering properties for small, birefringent calcite particles simulated using DDSCAT 7.1.1. We consider two irregular model particles, a flake and a rhomboid, in either a (i)?fixed or (ii)?random orientation. Simulations are performed for three volume-equivalent radii of 0.1, 0.45, and 1.0?μm. For each target, we repeat the computations for three sets of orientations of the optic axis. When a fixed spatial orientation of the target is considered, the simulations are significantly affected by the orientation of the optic axis. However, the effect is considerably weaker when assuming the same targets in random spatial orientation.