Synthesis of Highly Functionalized 1-Azadienes and Ketenimines

Summary. The 1:1 reactive intermediate generated by the addition of alkyl isocyanides to dialkyl acetylenedicarboxylates was trapped by fairly strong NH-acids such as carbazole, indole, or pyrrole to yield highly functionalized 1-azadienes and ketenimines.     

Insights into sticking of radicals on surfaces for smart plasma nano-processing

In reactive plasma processing, species produced in the plasma reach the surface of a substrate and cause etching, deposition and surface modification through surface reactions. These reactions are characterized by the densities and energies of species incident on the surfaces. In order to realize nano-scale plasma processing, important species for plasma processing have been identified and characterized, and their behavior, not only in the gas phase, but also on the surface, have been clarified and controlled. One of the most critical parameters for insights into surface reaction kinetics of radicals is sticking and surface loss probability. On the basis of radical densities measured by various methods, the sticking and surface reaction loss probabilities have been compiled, and they enable the quantitative understanding of the kinetics of radicals on the surface in the plasma. In this article, the sticking and surface reaction loss probabilities measured thus far are reviewed focusing on fluorocarbon gas, silane gas and methane gas based plasma processes. The establishment of a smart plasma process and the development of an autonomous production device with control of radicals on the basis of insights into the surface reactions for nano-scale plasma processing are presented.     

中药柴胡中K、Ca、Zn、Fe和Mn含量测定及清除自由基机制分析

研究了柴胡中金属元素的作用为治疗呼吸系统疾病提供依据.选取柴胡粉碎、干燥至恒重,采用HNO3-HClO4湿法消化,用原子吸收分光光度计测定宏量元素钙、钾和微量元素铁、锰、锌的含量.测定结果表明,柴胡中含有丰富的金属元素.用原子吸收分光光度法测定中草药中金属元素含量,方便迅速.结果准确,测定结果为临床上合理利用柴胡清除自由基、预防和治疗呼吸系统疾病提供科学依据,也为大力开发、利用中药柴胡提供了有用的数据.     

Di-radical dinuclear copper complex: synthesis,structure, and magnetic properties

The reaction of Cu(Ac)₂·4H₂O with 2-[(3,5-dichloro-2-hydroxy-benzylidene)-amino]-2hydroxymethyl-propane-1,3-diol (H₄L) and 4,4′-bipyridyl-N,N′-dioxide (4,4′-bipy-NO) in DMF under solvothermal conditions leads to the formation of a di-radical dinuclear copper complex [Cu₂(4,4′-bipy-NO)(dcdmap)₄] (1) (dcdmap is the anion of 2,4-dichloro-6dimethylaminomethyl-phenol, synthesized by an in situ reaction). Compound 1 was characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. Complex 1 displays dominant anti-ferromagnetic interaction between oxyradicals and copper ion and oxyradical.     

Electronic spectrum of dibiphenylene-ethene radical anion

The electronic absorption spectrum for the dibiphenylene-ethene radical anion ( ), generated electrochemically in dimethylsulfoxide solutions, is reported. Based on calculations by the LCAO-MO method in theHückel approximation and on the analysis of the band positions it is suggested that in the molecule two planar fluorenylidene fragments are twisted (60°) about the central C=C bond.

---

Das Elektronenabsorptionsspektrum des Dibiphenylen-Radikalanions (Kurze Mitteilung)

Zusammenfassung Das Dibiphenylenethen-Radikalanion ( ) wurde elektrochemisch hergestellt und das Elektronenabsorptionsspektrum aufgenommen. Auf Grund von LCAO-MO Berechnungen in derHückel-Annäherung und der Analyse der Bandenlagen wird nahegelegt, daß im -Molekül zwei planare Fluorenyliden-Fragmente ca. 60° um die zentrale C=C-Bindung verdrillt angeordnet sind.

     

Charge transfer complexes and cation radical salts of azino-diselenadiazafulvalene

The synthesis and the redox behaviour of electroactive donor molecules incorporating an azino spacer group between a benzoselenazole core and another heterocyclic moiety, either a benzoselenazole one or a thiazole one, are reported. Neutral complexes were obtained with TCNQ and, for the first time with dithiadiazafulvalene or diselenadiazafulvalene derivatives, cation radical salts by electrocrystallization. Crystal structures data of these complexes are presented and their geometries compared with those deduced from theoretical calculations.     

Aminomethylation of organic halides promoted by zinc in protic medium

Organic halides undergo smooth aminomethylation by secondary amines and aqueous formaldehyde promoted by metallic zinc under copper(I) catalysis. Good to excellent yields are obtained with primary, secondary, and tertiary iodides, allylic, propargylic, and benzylic bromides and with α-bromoesters. In most cases, DMSO is the best solvent, but dioxane is preferable for some more reactive halides. Additional experiments with radical quenchers and promoters and the use of ‘radical clocks’ indicate a stepwise reaction mechanism initiated by the attack of an alkyl radical to iminium ion.     

Effect of alcohol sources on synthesis of single-walled carbon nanotubes

The effect of oxidant species forming an alcohol molecule for hot-filament chemical vapor deposition (HFCVD) on single-walled carbon nanotubes (SWCNTs) growth has been investigated. To use a graphite rod as a filament for HFCVD to decompose alcohol sources, contamination-free sample surface can be obtained and SWCNTs are successively and densely grown at a lower temperature than those by conventional thermal CVD. It is found that the higher the molecule number of alcohol among CH₃OH, C₂H₅OH, and 2-C₃H₇OH is, the lower the initial growth rate of SWCNTs is. As for CH₃OH, diameter distribution of SWCNTs is dynamically changed with the growth time passed, and a negative growth rate is observed at the later stage of growth. The growth kinetics depending on the alcohol sources is discussed on the basis of a capability of the oxidant species to burn away SWCNTs and deactivation of Co catalysts used for the growth.     

关于绝对半素环和绝对半素根

本文了绝对半素环的概念，研究了绝对半素与与半素环及素环之间的关系，讨论了由全体绝对半素环类决定的上根－－绝对半半素根及其性质。     

A facile route to highly functionalized ketenimines

Summary A one-pot synthesis of highly functionalized ketenimines by reaction of alkyl isocyanides with dialkyl acetylenedicarboxylates in presence of 1,3-diphenylpropan-1,3-dione is reported.

---

Ein einfacher Weg zu hochfunktionalisierten Keteniminen

Zusammenfassung Es wird eine Eintopfsynthese hochfunktionalisierter Ketenimine durch Reaktion von Isocyaniden mit Dialkylacetylendicarboxylaten in Gegenwart von 1,3-Diphenylpropan-1,2-dion beschrieben.