In situ ESR of CrH-ZSM-5 up to 500°C in flowing gas containing O2, H2O,CCl4, NO,NO2, and C3H6

A flow cell was used for the in situ ESR monitoring of the state and reactivity of chromium ions in Cr-ZSM-5. Calcination of Cr(NO₃)₃/NH₄-ZSM-5 in air at 500°C is accompanied by migration of chromium ions inside the zeolitic channels and stabilization ofisolated Cr⁵⁺ cations near lattice A1³⁺ ions. Calcination of Cr-ZSM-5 at 750°C leads to a gradual disappearance of the isolated Cr⁵⁺ cations and formation of -Cr₂O₃ microcrystals. All the Cr⁵⁺ cations are accessible to gas-phase molecules: O₂ strongly broadens the dipole-dipole signal; H₂O sorption increases the local crystal field symmetry; admission of CCl₄ results in a small change of the Cr⁵⁺ local coordination; strongly stabilized complexes on Cr-ZSM-5 are observed upon sorption of either NO or NO₂. The sorption of C₂H₆ on Cr-ZSM-5 at 20°C is accompanied by a gradual reduction of the Cr⁵⁺ sites. At 500°C in [C₃H₆ + O₂ + He] flow, even at a large excess of oxidant, the reduction of a noticeable part of Cr⁵⁺ ions takes place. At 400°C, in the same gas mixtures, a deeper reduction of Cr⁵⁺ occurs. Closer to stoichiometric conditions, in a [C₃H₆ + NO + He] flow with 120% excess of oxidant the Cr⁵⁺ is completely reduced at 500°C. The oxidation of propene is accompanied by coke deposition on the surface of the catalyst. The implications of the results are discussed.     

6，7-二氢-5H-环戊烷并[b]吡啶

6,7-二氢-5H-环戊烷并[b]吡啶主要用于药物、杀菌剂和抗菌剂的研究,也被广泛应用于制备植物保护剂和合成树脂、防老剂以及塑料制品等。目前因其被作为第四代抗生素头孢匹罗的侧链而成为研究者竞相开发的热点。6,7-二氢-5H-环戊烷并[b]吡啶有实用价值的合成方法主要有N-羟基邻苯二甲酰胺法、丙烯醛法和己二酸二乙酯法。丙烯醛法中6,7-二氢-5H-环戊烷并[b]吡啶的收率为87.4%,具有较好的开发前景。     

End-capped polystyrene with 8-hydroxyquinoline group by ATRP method

8-Hydroxyqunioline end-capped polystyrene was prepared through atom transfer free radical polymerization (ATRP) with 8-(5-chloromethyl) quinolyl acetate as initiator. The results indicated that this polymerization is a first order reaction with respect to monomer conversion. The molecular weight increased linearly with monomer consumption and very narrow distribution of molecular weight was obtained (polydispersity index less than 1.2). The FT-IR and NMR results show that the 8-hydroxyquinloine group was chemically bonded to the polymer end and there is nearly one 8-hydroxyquinoline group in per polymer chain. All those data show that polymerization of styrene at such conditions displayed living characters. The polymer with 8-hydroxyqquinoline end group reacted with triethylaluminum to form polymeric light-emitting complex and single layer LED was prepared by common spin-coating method. The peak wavelength of LED based on synthesized polymeric complex was around 570 nm.     

On the preparation and properties of CuZSM-5 catalysts for NO decomposition

Equilibrium exchange isotherms were determined for the exchange of Cu²⁺ with NaZSM-5 at varying Cu(Ac)₂ concentrations in solutions of constant volume and zeolite weight. At low Cu²⁺ levels the solid scavenged all the copper ions. When copper could be detected in the equilibrated solutions, overexchange was observed. The extent of overexchange was higher at pH 6 than at pH 4. These results were analyzed in relation to catalytic activity.On leave from the Central Institute for Chemistry, Hungarian Academy of Sciences, H1525 Budapest, Hungary.     

4-(6′甲基苯并噻唑-2′-偶氮)-3,5-二氨基吡唑与钯显色反应的研究和应用

对6种苯并噻唑偶氮吡唑化合物的分析特性进行了探讨,着重研究了4—(6′—甲基苯并噻唑-2′-偶氮)-3,5-二氨基吡唑(MBTAP)与钯离子显色反应的光度性质。在非离子表面活性剂 Brij35存在下与钯离子形成橙红色的配合物。适宜的 pH 值范围为9.0～10.5.配合物的最大吸收波长为510nm,表观摩尔吸光系数为3.01×10~4L·mol~(-1)·cm~(-1)。钯在0～14μg/25mL,范围内服从比尔定律.显色体系可稳定11h。在柠檬酸存在下可消除 Fe~(3+)、Co~(2+)、Cu~(2+)、Ni~(2+)等离子的干扰。     

Structural significance of the alkyl substituent at the C-4 of (+)-trans-verbenyl acetate in sex pheromonal activity of the American cockroach

The significance of the alkyl group at the C-4 of (+)-trans-verbenyl acetate, which is the sex pheromone mimic of the American cockroach, was investigated. Seven alcohols possessing an ethyl, propyl, or dimethyl group at this position of the 6,6-dimethylbicyclo[3.1.1]heptane skeleton were synthesized and evaluated by behavioral assay. All of the alcohols were inactive, while three of four acetates of the 2-alcohols induced sexual behavior in male cockroaches at the 0.02 or 0.5 mg dosage level, either of which is many orders of magnitude higher than the threshold level of the natural sex pheromones (10^–8 mg). Among the acetates, the compounds with a methyl group or an -oriented ethyl group at C-4 showed the highest activity. The results are discussed in terms of spatial requirements of the molecules for interactions with the receptor.Studies on the sex pheromone mimic of the American cockroach, (+)-trans-verbenyl acetate. Part VIII. For Part VII, seeComp. Biochem. Physiol.,70A: 229–234 (1981).     

Platyphylloside: Metabolism and digestibility reductionin vitro

The metabolism of platyphylloside [(5S)-5-hydroxy-1,7-bis-(4-hydroxyphenyl)-3-heptanone-5-O--d-glucopyranosidel]—known to reduce digestibility—was studiedin vitro in sheep rumen liquor. Platyphylloside is hydrolyzed to 5-hydroxy-3-platyphyllone [(5S)-5-hydroxy-1,7-bis-(4-hydroxyphenyl)-3-heptanone], which is reduced to centrolobol [1,7-bis-(4-hydroxyphenyl)-3-heptanol], via 3-platyphyllone [7-bis-(4-hydroxyphenyl)-3-heptanone]. The digestibility-reducing effect was shown to be correlated with the concentration of centrolobol.     

2-氯-5-氯甲基-1,3-噻唑提纯新方法

2-氯-5-氯甲基-1,3-噻唑(CCMT)是一种重要的农药中间体。介绍了以1-异硫氰酸基-2-氯-2-丙烯和氯气反应制备2-氯-5-氯甲基-1,3-噻唑的方法,并重点介绍了通过合成2-氯-5-氯甲基噻唑盐酸盐的方法进行产品提纯的新方法,产品含量大于99%,提纯收率95%。     

药物中间体3,5-二甲氧基-邻苯二甲酸酐的合成及表征

以3,5-二甲氧基苯甲酸甲酯为原料经过羟烷基化反应、酯交换反应、水解反应、脱羧反应、氧化反应、脱水反应来合成3,5-二甲氧基-邻苯二甲酸酐这一中间体,每步反应的收率均在90%以上。通过差热分析、红外、质谱、核磁等分析手段对合成的化合物的结构表征,结果表明,所合成的化合物的结构、性能指标与目标要求一致。     

Kinetic modelling of the catalytic conversion of synthesis gas

A kinetic study for the one-step conversion of synthesis gas to gasoline on a ZnO–Cr₂O₃–ZSM-5 catalyst is described. On this catalyst, three reactions are involved in the overall transformation of synthesis gas: the methanol synthesis, the conversion of methanol to hydrocarbons and the water–gas shift reaction. Under the operating conditions selected for the study, it was found that the water–gas shift was at equilibrium and the methanol was completely converted to hydrocarbons. Consequently, it was postulated that the kinetics of the limiting reaction step, the methanol synthesis on the ZnO–Cr₂O₃ component, was the one that controls the overall reaction rate. Three kinetic model equations describing the rate of synthesis gas conversion on the bifunctional catalyst, were considered to fit the data of the experimental runs performed in a Berty well-mixed reactor. Those equations were derived under very special conditions where the methanol decomposition term could be neglected. It was also observed that in the kinetic equations a term involving the fugacity of CO₂ was required to predict the rate properly. The catalyst deactivation was also taken into account in the analysis.