Methyl trifluoropyruvate in the Pictet-Spengler reaction

Condensation of methyl trifluoropyruvate with 2-(3,4-dimethoxyphenyl)ethylamine, tryptamine, and (D, L)-tryptophan yielded 1-methoxycarbonyl-1-trifluoromethyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline, 1-methoxycarbonyl-1-trifluoromethyl-1,2,3,4-tetrahydro-9H-pyrido[3,4-b]indole, and Z-1-methoxycarbonyl-1-trifluoromethyl-3-carboxy-1,2,3,4-tetrahydro-9H-pyrido[3,4-b]indole, respectively. The Z configuration of the latter was determined by x-ray structural analysis.A. N. Nesmayanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow, Russia. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1831–1836, August, 1992.     

甲烷在Mo/HZSM-5催化剂上的脱氢聚合反应

对不同Mo含量的Mo／HZSM－5催化剂的结构进行了表征，并对这些催化剂的甲烷非氧气氛下的转化反应进行了考察．催化剂的BET比表面积及酸性随Mo含量的增加而降低，当Mo含量大于5％时，Mo对ZSM－5分子筛的晶型有影响，并出现MoO3物相．甲烷在700℃时可高选择性地生成苯和乙烯，最佳Mo含量大约为2％．纯的MoO3或HZSM－5上该反应几乎不进行，因此，可能是分散的钼氧离子和分子筛的酸中心是甲烷转化的活性中心，只有二者的协同作用才能促进甲烷的转化．反应后催化剂中的钼物种被还原了．催化剂上的积炭可能是催化剂失活的主要原因之一，烧炭后催化剂活性基本恢复．     

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.     

Polarographic behaviour of salicylaldehyde-2-pyridylhydrazone and its copper(II) complex

The polarographic behaviour of salicylaldehyde-2-pyridylhydrazone (SAPH) has been studied in aqueous buffer solution containing 40% ethanol using DC and DP polarographic methods. In the pH range 1.8–7.5 the observed single irreversible reduction wave is assigned to the splitting of the N-N bond and reduction of C=N centre. In alkaline medium, a second wave appears at a more negative potential due to the reduction of the salicylaldehyde which is formed by hydrolytic decomposition of the SAPH molecule. The effect of pH on the limiting current andE _1/2 as well as the reduction mechanism are discussed and compared with similar compounds. The kinetic parameters of the electrode reaction have been calculated.The analytical properties of the copper(II)-SAPH system is described. The complex gave rise to a single irreversible well-defined wave (E _1/2=–0.58 V at pH=5.2). The reaction process is diffusion controlled. A method is suggested for the determination of Cu(II) in presence of different metal ions as the difference in theirE _1/2 values is sufficient for the purpose.This work is taken partly from the M. Sc. Thesis of Jamal S. Shalabi     

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.     

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.     

Composition of <Emphasis Type="Italic">Carlina acanthifolia</Emphasis> Root Essential Oil

The root of Carlina acanthifolia All. (Asteraceae) contained 1.0% of essential oil (expressed in g per 100 g of dried plant material). Using GC and GC/MS, nine components were identified (100% of total oil). The structure of benzyl 2-furylacetylene (carlina oxide), which is the principal component of the oil (91.5%), was spectrometrically identified. __________ Published in Khimiya Prirodnykh Soedinenii, No. 4, pp. 331–332, July–August, 2005.     

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．     

煅烧温度对TiO2/SiO2混合氧化物表面酸量的影响

采用共沉淀法制备了高钛含量的复合氧化物TiO2／SiO2．用BET、XRD、FT-IR和正胺吸附等分析手段，研究了煅烧温度对TiO2／SiO2表面酸量的影响．研究发现，随着煅烧温度的升高，TiO2／SiO2表面羟基密度、比表面积逐渐减少，TiO2晶粒尺寸变大，造成TiO2／SiO2表面酸量降低．当煅烧温度达到600℃到800℃之间，表面酸量基本不再改变．     

Thermody namic functions of 1,2-alkanediols in dilute aqueous solutions

The heat capacities of binary aqueous solutions of 1,2-ethanediol, 1,2-propanediol and 1,2-butanediol were measured at temperatures ranging from 283.15 to 338.15 K by differential scanning calorimetry. The partial molar heat capacities at the infinite dilution were then calculated for the respective alkanediols. For 1,2-ethanediol or 1,2-propanediol, the partial molar heat capacities at the infinite dilution of increased with increasing temperature. In contrast, the partial molar heat capacities of 1,2-butanediol at the infinite dilution decreased with increasing temperature. Heat capacity changes by dissolution of the alkanediols were also determined. Heat capacity changes caused by the dissolution of 1,2-ethanediol or 1,2-propanediol were increase with increasing temperature. On the other hand, heat capacity changes caused by the dissolution of 1,2-butanediol are decrease with increasing temperature. Thus our results indicated that the structural changes of water caused by the dissolution of 1,2-butanediol differed from that of the two other alkanediols. This revised version was published online in July 2006 with corrections to the Cover Date.