Synthesis of Anti-Inflammatory α-Arylalkanoic Acids by 1,2-Aryl Shift. New Synthetic Methods (42)

α-Arylalkanoic acids have acquired importance as anti-inflammatory agents and are now in great demand on the pharmaceutical front. Hence, the need has arisen for new and improved, economical synthetic procedures suitable for their preparation and manufacture on an industrial scale. For many years the synthetic approach to this class of compounds was restricted to the Willgerodt and Darzen reactions. More recently, several methods have been developed which are based on the 1,2-aryl shift in acetals of α-functionalized alkyl aryl ketones. This new approach starts from the oxythallation of alkyl aryl ketones first described by Taylor and McKillop in 1971. Asymmetric syntheses of some important arylakanoic acids have also been developed on this basis. The highly toxic thallium salts may be replaced, inter alia, by catalytically effective metal salts.     

NMR relaxation and micro-imaging study of polystyrene in concentrated cyclohexane solution

¹³C-relaxation times of polystyrene (PS) in its θ solvent, cyclohexane, are measured at different temperatures. A two-step model for the dissolution is proposed. Swelling of the polymer below the θ temperature is eventually the dispersion of the side group phenyl rings only. While above the θ temperature, complete dissolution is the dispersion of the main chain at a molecular level. The results of T₁(C) are confirmed by¹H-NMR imaging. NMR and its imaging are powerful twls to study the dynamic behavior of dissolution process of polymers in their θ solvents. Project supported by the National Key Projects for Fundamental Research “Macromolecular condensed state”, the State Science and Technology Commission of China.     

6-硫杂-13-氧杂二环[9.3.0]-3,8-二炔十四烷的合成及核磁共振鉴定

以３，４－二（４′－甲磺酰氧－２′－丁炔基）四氢呋喃或６－硫杂－３，８－二炔－１，１１－二羟甲基环十一烷为原料合成了二环化合物６－硫杂－１３－氧杂二环［９．３．０］－３，８－二炔十四烷。通过１ＨＮＭＲ，１３ＣＮＭＲ，ＩＲ及ＭＳ进行了结构鉴定。     

3-烷基-N-甲基-2-吡咯烷酮的结构鉴定及NMR研究

本文测定了七个N-甲基-3-烷基-2-吡咯烷酮的¹³C、¹H-NMR、IR和质谱,确定了各化合物的结构,并对谱线进行了归属。同时总结出烷基取代对吡咯烷酮的影响及吡咯烷酮对烷基化学位移的影响的¹³C谱两组经验取代参数。     

A Mössbauer study of hyperfine interaction in the systems Co x Mn3−x−y Fe y O4 and Ni x Mn3−x−y Fe y O4

A Mössbauer study of systems Co _x Mn_3?x?y Fe _y O₄ and Ni _x Mn_3?x?y Fe _y O₄ for values ofx=0·1, 0·5, 1·0 andy ranging from 0·1 to 2·0 in steps of 0·2 have been made. At room temperature samples fory values ranging in between 0·1 to 0·5 exhibit paramagnetic behaviour while all spectra for values ofy between 0·6 to 0·8 show relaxation effects. Well-defined hyperfine Zeeman spectra are observed for all the samples withy>0·8 and resolved in two sextets corresponding to octahedral and tetrahedral site symmetries and a central doublet probably due to the presence of super-paramagnetic particles in the system. The hyperfine field at⁵⁷Fe nucleus reduces with decreasing iron cobalt and nickel concentration. These observations have been explained in terms of site preference of cations and exchange interactions.     

A new hierarchy system on the basis of a “Master” Boltzmann equation for microscopic density

It is shown that Boltzmann's equation written in terms of microscopic density (namely the unaveraged Boltzmann function) has a wider range of validity as well as finer resolvability for fluctuations than the conventional Boltzmann equation governing Boltzmann's function. In fact the new Boltzmann equation for ideal gases has implications as a microscopically exact continuity equation like Klimontovich's equation for plasmas, and can be derived without invoking any statistical concepts, e.g., distribution functions, or molecular chaos. The Boltzmann equation in the older formalism is obtained by averaging this equation only under a restricted condition of the molecular chaos. The new Boltzmann equation is seen to contain information comparable with Liouville's equation, and serves as a master kinetic equation. A new hierarchy system is formulated in a certain parallelism to the BBGKY hierarchy. They are shown to yield an identical one-particle equation. The difference between the two hierarchy systems first appears in the two-particle equation. The difference is twofold. First, the present formalism includes thermal fluctuations that are missing in the BBGKY formalism. Second, the former allows us to formulate multi-time correlations as well, whereas the latter is restricted to simultaneous correlation. These two features are favorably utilized in deriving the Landau-Lifshitz fluctuation law in a most straightforward manner. Also, equations describing the nonequilibrium interaction between thermal and fluid-dynamical fluctuations are derived.     

(1)H and (13)C NMR studies of asymmetrically substituted bis- and tris-Tröger's bases

The (1)H and (13)C NMR spectra of two stereoisomeric bis-Tr?ger's bases and four stereoisomeric tris-Tr?ger's bases asymmetrically substituted on the external aromatic rings were recorded and the corresponding signals assigned. The relative configuration of the stereogenic units has been unequivocally determined on the basis of homoallylic couplings and NOE experiments.     

Structure of the products of condensation of hydroxylamine with trifluoromethyl-beta-diketones: assignments of the diastereotopic protons of the 4-methylene group in 5-hydroxy-5-trifluoromethyl-delta2-isoxazolines

The combined use of 1H NMR spectroscopy with theoretical calculations of chemical shifts (GIAO) and coupling constants (B3LYP/6-311 ++G**) of a 5-hydroxy-5-trifluoromethyl-Delta2-isoxazoline has enabled solving the problem of the assignments of the diastereotopic protons in this compound. This result has been extended to 5-hydroxy-5-trifluoromethyl-Delta2-pyrazolines and the corresponding 5-trichloromethyl derivatives.     

Noninterpolatory Hermite subdivision schemes

Bivariate interpolatory Hermite subdivision schemes have recently been applied to build free-form subdivision surfaces. It is well known to geometric modelling practitioners that interpolatory schemes typically lead to ``unfair" surfaces--surfaces with unwanted wiggles or undulations--and noninterpolatory (a.k.a. approximating in the CAGD community) schemes are much preferred in geometric modelling applications. In this article, we introduce, analyze and construct noninterpolatory Hermite subdivision schemes, a class of vector subdivision schemes which can be applied to iteratively refine Hermite data in a not necessarily interpolatory fashion. We also study symmetry properties of such subdivision schemes which are crucial for application in free-form subdivision surfaces.

A key step in our mathematical analysis of Hermite type subdivision schemes is that we make use of the strong convergence theory of refinement equations to convert a prescribed geometric condition on the subdivision scheme--namely, the subdivision scheme is of Hermite type--to an algebraic condition on the subdivision mask. The latter algebraic condition can then be used in a computational framework to construct specific schemes.

     

R-analogue of the Burnside ring of profinite groups and free Lie algebras

Let R be a finite-dimensional torsion-free special λ-ring. In this paper we generalize the results in Dress and Siebeneicher (Adv. in Math. 70 (1988) 89; 78 (1989) 1) by constructing R-analogue of the Burnside ring of profinite groups . In particular, we remark that the (Grothendieck) Lie-module denominator identity of free Lie algebras in Oh (Necklace rings and logarithmic functions, preprint, KIAS, 2003) is closely related to the canonical isomorphism between and Grothendieck's ring of formal power series with coefficients in R and constant term 1.