Tetraarylester der μ-Imidodiphosphorsäure und ihre Thioderivate — Strukturuntersuchungen

Tetraarylesters of μ-Imido-Diphosphoric Acid and its Thio Derivatives — Structure Investigations New O,O′,O″,O?-tetratolyl- and ditolyl-diphenylesters of the μ-imido-diphosphoric acid and its mono and dithio derivatives were synthesized, compared with the corresponding tetraphenylesters and investigated by ¹H, ¹³C, and ³¹P NMR spectroscopy and X-ray crystal structure analysis. Structures of the O,O′,O″,O?-tetrakis-(2-methyl-phenyl)-μ-imidodiphosphate, 1b , as well as of the corresponding ortho-, meta- and para-tolylesters of the μ-imido-monothiodiphosphoric acid ( 2a , 2b , 2c ) were determined. All the compounds form dimers via N? H…?O hydrogen bonds in the crystal as well as in nonpolar solvents. The distances around the phosphorus atoms rise with decreasing electronegativity of the phosphorus substituents. Signs of the ²J_{P? N? P} coupling constants were determined by ¹³C{¹H, ³¹P} triple resonance experiments for some compounds. These constants become more negative owing to substitution of a phosphoryl by a thiophosphoryl group.     

Substitution with retention in organoboranes and utilization of the phenomenon for a general synthesis of pure enantiomers

Organoboranes, readily available via the hydroboration of unsaturated organic compounds, exhibit a remarkable versatility in their reactions. The boron atom in these organoboranes can be readily converted into a wide variety of organic groups under very mild conditions, providing simple versatile syntheses of organic compounds. Exploration of these substitution reactions reveal that, with rare exceptions, the organoboranes transfer the alkyl group to other elements of synthetic interest with complete retention of stereochemistry. Recently we have discovered a method of synthesizing essentially optically pure organoborane intermediates. These optically active alkyl groups attached to boron can also be transferred with complete retention of optical activity. Consequently, it is now possible to achieve by a rational synthesis the preparation of almost any optically active compound with a chiral center, either R- or S-, in essentially 100% enantiomeric excess.     

Study of modified silicas by inverse gas chromatography part II: Influence of chain length on surface properties of silicas grafted withα−ω diols

Summary The surface properties of silicas modified with – diols having between 4 and 16 carbon atoms were investigated by inverse gas chromatography. It is shown, that the value of the dispersive component of the surface energy does not change monotonously: a minimum value is recorded when the surface is covered by a monolayer of methylene groups. Further, when measuring the adsorption enthalpies of polar probes, an alternation of their H values is observed: grafts having an odd number of carbon atoms systematically show higher H values than the others. A trans-trans configuration of the grafted chains which allows optimum interactions is proposed, suggesting a preferential diesterification reaction of both terminal hydroxyl groups of odd diols.     

Characteristics of vinyl iodide microwave plasma etching of GaAs/AlGaAs and InP/InGaAs heterostructures

Vinyl iodide (C₂H₃I) microwave discharges with additions of H₂ and Ar are found to provide faster etch rates than conventional CH₄/H₂/Ar discharges for InP, InGaAs, GaAs, and AlGaAs. This is a result of the relatively high volatilities of indium, gallium, and aluminum iodide species. The etched features are smooth and anisotropic over a wide range of do self-biases (–150 to –350 V), process pressures (1–20mTorr), and microwave powers (150–500 W). The polymer that forms on the mask during the plasma exposure can be readily removed in O₂ discharges. Electron spectroscopy for chemical analysis (ESCA) showed that the etched surfaces are slightly deficient in the group V elements under most conditions, but changes to the optical properties of the semiconductors are minimal. No defects are visible by transmission electron microscopy (TEM) in GaAs or InP samples etched at dc biases –250 V.     

à 3E态CH3N自由基的稳定性

观察到了CH_3N自由基Ã ~3E←X~3A_2体系317-272 nm的荧光激发谱, 特别讨论了振动激发的Ã 态的稳定性. 报导了v_3~′=6态的色散荧光和荧光时间谱, 该态在240 Pa下的寿命大约是80 ns. 实验表明Ã ~3E 态CH_3N自由基是稳定的, 势能面至少距振动基态4800 cm~(-1)内是束缚的, 异构化或预离解作用并不重要.     

Moment characterization of localized orbitals

The parallel between orbital first and second electric moments and statistical first and second central moments is noted. Three measures of orbital spatial distribution in terms of their moments are proposed, and applied to the LMO's in a series of ten-electron hydrides. Consistent differences between bond and lone pair distributions are found. Using the statistical interpretation, for each LMO an effective solid angle around the central atom is postulated.     

Molecular orbital studies on the conformation of GABA (γ-aminobutyric acid)

In distinction to Extended Hückel Theory which predicts as the most stable conformation of free zwitterionic GABA a totally extended form, PCILO and SCF ab initio studies show that the intrinsically preferred conformation of the isolated molecule is a highly folded one, resulting from strong interactions between the two charged ends. Computations are also carried out for hydrated GABA in the supermolecule approach allowing moreover for the flexibility of binding of some of the water molecules of the first hydration shell. They predict the coexistence in solution of a large number of conformations showing different degrees of folding (or extension), a result confirmed by recent NMR studies. This and a number of similar results show that we have to adapt our thinking on the role of conformations in pharmacological activity to this situation, which was frequently obscured by the more abundant results of X-ray crystallography yielding a single conformation.     

Stereochemistry of cyclic ether formation—II : Intramolecular cyclisation of secondary aliphatic alcohols to tetrahydrofuran-type ethers

The mechanism and stereochemistry of δ-C atom functionalisation in the reactions of secondary straight-chain aliphatic alcohols with lead tetraacetate, ceric ammonium nitrate, and heavy metal (Pb⁴⁺, Hg²⁺, Ag⁺) salts (AcO)^?1, O^2?, CO₃^2?-halogen (I₂, Br₂, Cl₂) combinations are discussed. By demonstrating the intermediacy of 5-bromo-2-hexanol, it was confirmed that the dark silver oxidebromine induced cyclisation of 2-hexanol (and alcohols in general) involves (as the other hypohalite reactions) intramolecular 1,5-hydrogen abstraction by alkoxy radicals and formation of δ-bromohydrins. A novel and simple procedure for obtaining tetrahydrofurans from alcohols by way of the hypochlorite reaction, using silver or mercuric salts and chlorine, is described.     

Liquid chromatography of benzene derivatives on a porous methacrylate copolymer containing epoxy groups

Summary The retention of benzene derivatives with nonpolar and polar substituents on a porous methacrylate copolymer containing epoxy groups using both nonpolar and polar eluents was investigated. When n-hexane is used as the eluent, the retention of n-alkylbenzenes and polymethylbenzenes is weaker than that of benzene. In the case of benzene derivatives containing polar functional groups their capacity ratios (k) on this porous polymer increases approximately linearly with the increase of the adsorbate molecules dipole moment. The retention characteristics of the methacrylate copolymer were compared with that of a styrene-divinylbenzene copolymer and silica gels with a hydroxylated surface and with a surface modified by chemically bonded alkylsilyl groups.     

丙烯气相直接环氧化Au/TiO2催化剂的研究

在H2和O2共存条件下，金催化剂催化丙烯气相直接环氧化反应是近年来发展起来的一种新型环氧丙烷(PO)合成技术．本文采用沉积沉淀法制备了一系列Au／TiO2催化剂，考察了反应溶液的pH值、Au负载量、沉淀剂以及焙烧温度等因素对催化剂丙烯环氧化催化性能的影响．结果表明制备条件对催化性能有明显影响：反应溶液的pH值为7．5及Au负载量为2．4％时所得催化剂活性最好；当以Na2CO3、NaOH等含Na^ 物质作为沉淀剂时，催化性能明显优于Li^ 、K^ 等其它碱金属离子；400℃焙烧制得的催化剂活性较好，在50℃低温反应条件下，环氧丙烷得率可达1．3％．HRTEM结果表明，催化剂中Au组分高度分散于载体表面，且随着焙烧温度的增加Au粒因发生聚集而变大，从而影响了催化剂的活性．表面XPS分析证实，活性较好的Au／TiO2催化剂中活性组分Au除部分呈氧化态外，主要是以金属态的形式存在．