Synthese von Benzo[b]thioxanthenen

Synthesis of Benzo[b]thioxanthenes Benzo[b]thioxanthenes, heterocyclic compounds related to tetracenes and tetracyclines can be obtained by the reaction of 2H-benzo[b]thiete ( 1 ) and 1,4-naphthoquinones ( 3a–g ). The primary cycloadducts 4a–g undergo an autoxidation process leading to the quinones 6a–g . The dihydroxy compound 4e shows an additional isomerization by a tetrafold H transfer ( 4e → 5e ′). Another preparative route to benzo[b]thioxanthenes makes use of the cycloadditon reaction of 1 and 1,4-epoxynaphthalenes ( 7a–d ). The primary adducts can be transformed to the title compounds by catalytic dehydration processes ( 8a–d → 9a-d ). An alternate regioselective opening of the oxygen bridge can be performed by the action of trimethyliodosilane ( 8a → 10a ). Methylation of 9a furnishes the sulfonium salt 14a which rearranges in a strongly alkaline medium to 16a ; in the presence of oxygen ketone 17a is generated.     

Liquid circulation in columns due to bubble drift

The profiles of liquid velocity and gas hold-up in convection cells of bubble columns were calculated numerically. Development of a circulation cell was calculated from momentum and mass balances. Breakdown of the circulation cell was calculated taking into account the drift motion of bubbles ascending in accordance with the velocity gradient of the liquid. A limit of stability for the development of circulation cells has been obtained.     

Measurement of radiation emitted from thin vaporizing liquid films for the calculation of surface temperature

Evaporation of liquid films, not subjected to motion, and with a starting thickness of 1 mm, was tested. Solvents dichloromethane and ethanol were used as liquids. Surface temperature during evaporation was measured in a non-intrusive way using pyrometry. The employed pyrometer was calibrated against a black body radiant. Measurement accuracy in the region of the ambient temperature is 0.2 K. Since any principal stray radiation is always measured along with the thermal radiation emitting from the liquid film, the measurement results are at first distorted. A correction calculation is described. With this, the various proportions of stray radiation can be subsequently calculated. In order to do this, the dimensions of the test equipment and the spectral data of the evaporating solvents must be taken into account. The quantity of stray radiation depends mainly on the properties of the surface onto which the liquid film is applied, as well as on the spectral transmissivity of the liquid. This was measured for every tested liquid according to wavelength and layer thickness. Where the spectral transmissivity of a liquid is low, a correction calculation of the measured surface temperature is not necessary, while a high level of accuracy is still retained.     

Acylierung von Heterocyclen mit Kohlensäurederivaten. I. Kinetik und Mechanismus der Reaktion von 2-Aminobenzimidazolen mit Arylcyanaten

Acylation of Heterocycles with Carbonic Acid Derivatives. I. Kinetics and Mechanism of the Reaction of 2-Aminobenzimidazoles with Aryl Cyanates The second order rate constants for the reaction of 2-amino-benzimidazoles (2-ABI) with aryl cyanates forming 2-amino-benzimidazole aryl ester imide 3 have been determined in dependence on substituent effects by u. v. measurements. The results are interpreted by a six-membered cyclic transition state in which the electrophilic attack of the cyanate on the endocyclic N atom is catalyzed by an H bridge interaction of the exocyclic amino group of 2-ABI with the OCN group.     

Spaltung von 1,2,4-Thiadiazol-3-onen mit Triphenylphosphan: Triphenylphosphonio-thioimidazolate und ihre Folgereaktionen

Fission of 1,2,4-Thiadiazol-3-ones by Triphenylphosphane: gewidinet Triphenylphosphonio Thioimidazolates and Their Consecutive Reactions Treatment of benzimidazo[1,2-d][1,2,4]thiadiazol-3(2H)-ones ( 1 ) and imidazo[1,2-d]-[1,2,4]thiadiazol-3(2H)-ones ( 17 ) with triphenylphosphan leads to the liberation of isocyanate and the formation of triphenylphosphonio-thiobenzimidazolat ( 4 ) and triphenylphosphonio-thioimidazolat ( 18 ), respectively. 2,4-Diphenyl-5-phenylimino-1,2,4-thiadiazol-3-one ( 23 ) is desulfurized with Ph₃P and decomposed into phenyl isocyanate and diphenylcarbodiimide whereas the N-unsubstituted imino-thiadiazol-3-one ( 25 ) is attacked at the exocyclic imino group by Ph₃P to give the N-phosphoranylidene thiourea ( 26 ). The structure of 4 can be rationalized as a dynamic system between polar and apolar valence isomeres. Reactions of 1 and 17 with cyanates, isocyanates, carbon disulfide, acetic anhydride, amines, benzyl chloride, grignard compounds, and CH acidic compounds are described.     

Zur Radikalischen Copolymerisation ungesättigter Isocyanate mit Vinylchlorid

On the Free Radical Copolymerization of Unsaturated Isocyanates with Vinylchloride The free radical copolymerization of vinyl-, isopropenyl- and p-vinyl-phenylisocyanate with vinylchloride in mass and tetrahydrofurane solution at 50°C is investigated. The incorporation of the isocyanate monomers in the copolymers is favoured. These monomers effect a great decrease of the rate of copolymerization and a crosslinking of the formed homo- and copolymers, whose extent depends on the kind and the quantity of the incorporated monomers. The crosslinking is caused by the forming of isocyanurate units.     

在机床研发中基于职能单位的产品开发理论与实践

通过调查得知,包括虚拟现实技术在机床制造中应用可能性的应用方法、策略和工具在产品开发中的现状.对调查结果进行了讨论,考虑到研究理论的可移植性和对企业内部实战的依赖性.讨论的结果为基础研究领域的命题"基于职能单位的产品开发"提供结论.