7-取代吲哚类化合物合成及官能团化研究进展

7-取代吲哚化合物是合成药物及精细化学品的重要中间体.本文综述了近15年金属Pd催化的7-取代吲哚化合物的制备方法,将其分成直接合成法和吲哚7位官能团化法两类,对每一类的反应过程和机理进行了详细介绍和评述.     

1-环丙基-7-氯-6-(1-哌嗪基)-4-氧-1,4-二氢-3-喹啉羧酸盐酸盐的熔化与离解性质研究

1－环丙基－7－氯－6－（1－哌嗪基）－4－氧－1，4－二氢－3－喹啉羧酸盐酸盐为环丙沙星合成中主要的杂质之一，研究其物化性质对于改善环丙沙星的结晶分离提纯具有重要意义。本文研究了1－环丙基－7－氯－6－（1－哌嗪基）－4－氧－1，4－二氢－3－喹啉羧酸盐酸盐的熔化，分解特性，溶解度与离子强度，温度和pH值的关系，并测定了该物质的离解常数，估算了该物质在水溶液中的活度积。     

Role of La2O3 in Pd-Supported Catalysts for Methanol Decomposition

Systems of Pd supported on various La₂O₃-modified -Al₂O₃ and CeO₂–Al₂O₃ catalysts were tested for catalytic methanol decomposition and characterized by means of XRD, BET, TPR, H₂-chemisorption and CO–FTIR. The addition of lanthanum significantly improved the selectivity of CO and H₂ for all the catalysts but showed a different influence on the catalytic activity in two systems. Methanol conversion decreased on La₂O₃-modified Pd/-Al₂O₃ catalysts, in line with the reduction of Pd dispersion, while the addition of La₂O₃ improved the dispersion of Pd and reinforced Pd–CeO₂ interaction for La₂O₃-modified Pd/CeO₂–Al₂O₃ catalysts, which resulted in a high production rate of CO and H₂. Thus, a synergistic effect between CeO₂ and La₂O₃ was observed on -Al₂O₃-supported Pd catalyst for methanol decomposition.     

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。     

A molecular level mechanism ofn-butane oxidation to maleic anhydride over vanadyl pyrophosphate

A molecular level mechanism is proposed for the highly selective 14-e^– oxidative transformation ofn-butane to maleic anhydride on the surface of vanadyl pyrophosphate. The mechanism suggests that the dimeric active sites assume at any given time, one of four possible interconvertible states which differ from each other in the number of available oxygen atoms and the formal oxidation states of the individual vanadium atoms. The relative ratios of active sites in each of the four possible states are dictated by the reaction conditions, the redox properties of the reacting gases and the structure of the vanadyl pyrophosphate active surface. A crucial feature of the mechanism is a pseudo-ozonide surface species formed by the interaction of a chemisorbed dioxygen molecule and an adjacent metal-oxo group. This unusual species is responsible for the initial activation of then-butane, which occurs when the chemisorbed dioxygen abstracts an H-atom from the alkane and the adjacent metal-oxo group reacts with the incipient alkyl radical to form an alkoxy group. The proposed mechanism is entirely consistent with literature reports describing the behaviour of (VO)₂P₂O₇ in flow, pulse and TAP reactors.     

Bioactive IL7-diphtheria fusion toxin secreted by mammalian cells

A number of targeted cytotoxic agents have been developed that selectively kill malignant or otherwise pathological cells. These engineered proteins consist of a potent cytotoxic element connected to a ligand domain that binds to specific molecules on the surface of the target cell. Several of these agents have shown promise in clinical trials and one is currently administered to patients. A significant technical obstacle that has impeded the development of some of these toxins is the difficulty of preparing certain recombinant proteins in properly folded forms. These fusion proteins have generally been produced in bacteria requiring them to be denatured and renatured in vitro. For some proteins this is an efficient process whereas for others it is not. We describe here a system to produce fusion toxins rapidly and efficiently by engineering mammalian cells to secrete them as properly folded molecules which can be purified in native form from cell culture medium. We have used this system to produce highly active preparations of DAB(389)-IL7, a molecule consisting of the catalytic and transmembrane domains of diphtheria toxin fused to interleukin 7. This system is generalizable and can be used to produce and evaluate rapidly fusion toxins incorporating novel or uncharacterized ligands.     

我国食品理化检验标准体系的发展趋势分析

GB/T5009体系是我国最重要的食品理化检验标准体系之一,历经多年的发展,现已日趋成熟。本文对现有的GB/T5009体系从组成、发展、特点及存在的问题进行了分析归纳,对未来食品理化检验标准体系的发展趋势进行了较为系统的总结。     

Sub-ambient cold-start emissions reduction using SwRI® PO x catalyst technology

This paper describes the application of SwRI’s cold-start PO _x catalyst technology to reduce cold-start hydrocarbon emissions from a US Tier 2 vehicle at −7 °C. A reduction in −7 °C (20 °F) cold-start hydrocarbons will help US Tier 2 vehicles meet the proposed EPA NMOG standards. Improvements in cold temperature hydrocarbon emissions would also be beneficial in many parts of Europe during the winter months. In this work, a total hydrocarbon reduction of 19% was realized at 24 °C, in line with previous results, but only up to 3% at −7 °C. Insufficient oxygen in the engine-out exhaust gas at −7 °C was determined to be the reason why the PO _x catalyst failed to significantly reduce HC emissions. Addition of supplemental oxygen to the exhaust during the cold-start, to simulate an adjustment in the engine calibration to less rich operation, resulted in a total hydrocarbon reduction of 18% with the PO _x catalysts in place, but no benefit when the PO _x catalysts were removed. Hence, the PO _x catalyst approach can be used to good effect, even under sub-ambient cold-start conditions.     

在线红外检测仪在头孢噻肟酸合成中的应用

利用在线红外检测仪ReactIRTM4000在线监测以7-氨基头孢烷酸(7-ACA)与2-甲氧亚氨基-2-(2-氨基-4-噻唑基)-硫代乙酸苯并噻唑酯(MEAM)为原料,用二甲基乙酰胺(DMA)作催化剂,一步合成头孢噻肟酸的实验过程,主要考察了反应时间对反应的影响。在最佳反应条件下(催化剂用量、反应物用量、结晶pH已经优化)头孢噻肟酸的合成摩尔收率超过98%。     

硝基-3-氧-3，4-二氢-2H-[1，4]苯并噁嗪-6-羧酸的合成

以4-羟基-3-硝基苯甲酸为原料,经酯化、醚化、还原合环、硝化、水解等5步反应,合成了两个未见文献报导的化合物7-硝基-3-氧-3,4-二氢-2H-[1,4]苯并噁嗪-6-羧酸和8-硝基-3-氧-3,4-二氢-2H-[1,4]苯并嗪-6-羧酸,其结构经IR、LC/MS、1HNMR和元素分析确证。