Ring-opening reactions of halogenated N-aryl-1,2,3,4-tetrahydroisoquinoline and 2,3,4,5-tetrahydro-1H-2-benzazepine derivatives

Compounds 4a-4d, 4f and 10 were prepared and their ring-opening reactions with N-bromosuccinimide (NBS) investigated. Compounds 4a and 4b gave a mixture of products which did not contain any significant quantity of the corresponding aldehydes 5a and 5b whereas compounds 4c, 4d and 4f gave exclusively the aldehydes 5c, 5d and 5f respectively. Compound 10 similarly gave the aldehyde 11 when treated with NBS.     

Chemistry of the phenoxathiins and isosterically related heterocycles. XXXII . The synthesis of 2-azathianthrene and selected analogs

The synthesis of 2-azathianthrene ([1,4]benzodithiino[2,3-c]pyridine), the only remaining monoazathianthrene yet to be reported, is described. Attempts at the direct condensation of disubstituted pyridines with the dianion of 1,2-dimercaptobenzene were generally unsuccessful requiring that the alternative condensation of the dianion with disubstituted pyridine 1-oxides be employed. The title compound was characterized by physical means including ¹³C-nmr spectroscopy. One analog, 4-nitro-2-azathianthrene was also studied by X-ray crystallographic means; the molecule crystallized with two molecules in the asymmetric unit P2₁/n, a = 20.712(3), b = 7.8109(13), c = 13.720(2)Å, β = 107.880(11)°, Z = 8, the data refined to a final R = 0.051 for 3061 reflections. Dihedral angles between the planes of the phenyl rings were 135.00(13) and 132.52(13)° for the two independent molecules contained in the crystal. Close non? bonded S ?O intramolecular contacts were observed in both molecules between the sulfur and nitro-group oxygens. Both nitro groups are twisted out of the plane of the pyridine ring and are oriented at angles of 28.75 and 38.82° respectively.     

Benzannelated analogs of phenanthro[1,2-b]- and [2,1-b]thiophene: Synthesis and structural characterization by two-dimensional NMR and X-ray techniques

Syntheses of benzo[3,4]phenanthro[1,2-b]thiophene, benzo[3,4]phenanthro[2,1-b]thiophene and their 1-methyl analogs are reported as potential constituents of solvent refined coal liquids and for mutagenicity testing. The attempted synthesis of the 13-methyl analogs which gave the 11-methyl isomers is also described. Total assignments of the ¹H- and ¹³C-nmr spectra based on long range optimized heteronuclear protoncarbon two-dimensional chemical shift correlation are reported. Carbon assignments obtained for benzo[3,4]-phenanthro[1,2-b]thiophene using this approach were confirmed with a 125 MHz ¹³C–¹³C INADEQUATE spectrum. X-Ray crystal structures were determined for benzo[3,4]phenanthro[1,2-b]thiophene and 1-methyl-benzo[3,4]phenanthro[2,1-b]thiophene. Both molecules were helically distorted from planarity. Close intramolecular contacts between the bay region H1–H13 and ClMe-H13 of 2.03 and 2.28 Å, respectively, were responsible for the distortions. There were no close intermolecular contacts of <3.5Å. both molecules refined to an R value of <0.05.     

Experimental and theoretical electron density study of a highly twisted polycyclic aromatic hydrocarbon: 4-methyl-[4]helicene

Helicenes are molecules of considerable interest in view of their aromaticity which persists despite a marked departure from planarity and because of the extreme potency of some of their metabolites as tumor and mutation promoters. In this study, the electron density of 4-methyl-[4]helicene (or 4-methylbenzo[c]phenanthrene) is studied topologically with an emphasis on the fjord region since this region is where metabolic activation is initiated. The molecule consists of four fused aromatic rings that assume a twisted geometry. This geometry brings two hydrogen atoms into close proximity in the fjord region of the molecule accompanied by the appearance of an intramolecular C-Hdelta+...delta+H-C bond path (an interaction termed hydrogen-hydrogen or H- H bonding to distinguish it from dihydrogen bonding from which it is qualitatively distinct). In addition to the intramolecular H-H interaction, a number of intermolecular interactions are shown to be involved in the packing of this molecule in the crystalline state. The effect of the nonplanarity of the molecule on the local aromaticity of each ring is also discussed.     

Investigation of water environments in a C18 bonded silica phase using 1H magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy

High resolution 1H magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra have been obtained on typical C18 bonded silicas used in chromatographic solid-phase extraction separations. It has been shown for the first time that water molecules distributed in distinct physico-chemical environments within the chromatographic system can be detected directly using a simple 1H MAS NMR measurement. The resonances assigned to water protons in differing physico-chemical environments have distinct chemical shifts, line widths, relaxation times (T1 and T2) and also exhibit temperature dependent coalescence behaviour. This novel MAS approach may lead to a better understanding of the environments of other analytes in mixtures during such separations.     

De novo structural prediction of transition metal complexes: application to technetium

De novo structural prediction of transition metal complexes is investigated. Technetium complexes are chosen given their importance in medical imaging and nuclear waste remediation and for the chemical diversity they display. A new conformational searching algorithm (LIGB) for transition metals is described that allows one to search for different conformational and geometric isomers within a single simulation. In the preponderance of cases, both conformational searching techniques (LIGB and high-temperature molecular dynamics/simulated annealing) provide comparable results, while LIGB is superior for macrocyclic complexes. A genetic algorithm-optimized PM3(tm) parametrization for Tc is compared with the standard implementation and found to yield a significant improvement in predictive ability for the most prevalent Tc structural motifs. The utility of a coupled molecular mechanics-semiempirical quantum mechanics protocol is demonstrated for very rapid, efficient, and effective de novo prediction of transition metal complex geometries.     

Atmospheric pressure chemical vapour deposition of fluorine‐doped tin(IV) oxide from fluoroalkyltin precursors

Perfluoroalkytin compounds R_(4−n)Sn(R_f)_n (R = Me, Et, Bu, R_f = C₄F₉, n = 1; R = Bu, R_f = C₄F₉, n = 2, 3; R = Bu, R_f = C₆F₁₃, n = 1) have been synthesized, characterized by ¹H, ¹³C, ¹⁹F and ¹¹⁹Sn NMR, and evaluated as precursors for the atmospheric pressure chemical vapour deposition of fluorine‐doped SnO₂ thin films. All precursors were sufficiently volatile in the range 84–136 °C and glass substrate temperatures of ca 550 °C to yield high‐quality films with ca 0.79–2.02% fluorine incorporation, save for Bu₃SnC₆F₁₃, which incorporated <0.05% fluorine. Films were characterized by X‐ray diffraction, scanning electron microscopy, thickness, haze, emissivity, and sheet resistance. The fastest growth rates and highest quality films were obtained from Et₃SnC₄F₉. An electron diffraction study of Me₃SnC₄F₉ revealed four conformations, of which only the two of lowest abundance showed close F Sn contacts that could plausibly be associated with halogen transfer to tin, and in each case it was fluorine attached to either the γ‐ or δ‐carbon atoms of the R_f chain. Copyright © 2005 John Wiley & Sons, Ltd.     

Volatility return intervals analysis of the Japanese market

We investigate scaling and memory effects in return intervals between price volatilities above a certain threshold q for the Japanese stock market using daily and intraday data sets. We find that the distribution of return intervals can be approximated by a scaling function that depends only on the ratio between the return interval τ and its mean 〈τ〉. We also find memory effects such that a large (or small) return interval follows a large (or small) interval by investigating the conditional distribution and mean return interval. The results are similar to previous studies of other markets and indicate that similar statistical features appear in different financial markets. We also compare our results between the period before and after the big crash at the end of 1989. We find that scaling and memory effects of the return intervals show similar features although the statistical properties of the returns are different.     

Quasicrystals in a monodisperse system

We investigate the formation of a two-dimensional quasicrystal in a monodisperse system, using molecular dynamics simulations of hard-sphere particles interacting via a two-dimensional square-well potential. We find that more than one stable crystalline phase can form for certain values of the square-well parameters. Quenching the liquid phase at a very low temperature, we obtain an amorphous phase. By heating this amorphous phase, we obtain a quasicrystalline structure with fivefold symmetry. From estimations of the Helmholtz potentials of the stable crystalline phases and of the quasicrystal, we conclude that the observed quasicrystal phase can be the stable phase in a specific range of temperatures.