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.     

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.     

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.     

Measurements of the Refractive Index Increment on Hydroxyethyl Starch as a Basis for Absolute Molecular Weight Determinations

Solutions of hydroxyethyl starch are used as a blood plasma substitute. If their physiological efficiency is to be optimized, they need to be accurately characterized in terms of their molecular weight and its distribution. The absolute determination of molecular weight and molecular weight distribution by means of light scattering require a knowledge of the refractive index increment. Although numerous investigations of the refractive index increment of hydroxyethyl starch have already been published, the results vary significantly due to the use of different samples and the choice of different measuring parameters. There was therefore an urgent need to examine the extent to which the refractive index increment depends on molecular parameters, the experimental method used and the type of processing. Here it was found that different sample preparations result in different contents of solid matter, so that an exact determination of the quantity is required. Hydroxyethyl starches in the molecular weight range of about Mw = 200.000 g/mol and varying degrees of substitution between DS 0.38 and 0.50 which are regarded as optimal for clinical use give a refractive index increment of dn/dc^633nm = 0.146 = 0.005 cm³/g (solvent: H₂O/0.02% NaN₃; T = 25°C).     

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.     

纸质出版物的未来发展趋势

在变化的媒体世界中,宽带载体很快也参与了"围绕媒体内容的竞争",这对于从事印刷信息的企业也是如此.在新的条件下,把他们的品牌、甚至制作的内容以及多年的经验都运用在竞争的优势中.本文旨在介绍宽带的竞争,以激励德国出版业未来的发展情况.