Zur Reaktion von atomarem Wasserstoff mit 1-Olefinen

About the Reaction of Atomic Hydrogen with 1-Olefines . Chemical activated reaction paths of the C₂ C₈-l-olefines, initiated by atomic hydrogen, have been studied using an isothermal flow-system (298 K, 130 Pa) with electrical discharge. In the reaction mixtures homologeous series of 1-olefines and n-alkanes were found which are identical with those of cycloolefine systems described previously [1, 2]. The reactions of the 1-olefines are analysed and discussed in detail and compared to the cycloolefine reactions.     

Zur Bildung von Ethoxy-hydrochinazolinon durch Reaktion von Estercarbonylsauerstoff mit Cyan-enamin

Formation of Ethoxyhydroquinazolinone by Attack of an Estercarbonyloxygen at a Cyano Group By the reaction of ethyl-2-oxo-cyclohexanecarboxylate with cyan amide 4-ethoxyhexahydroquinazolin-2-one (12) is formed. Butyl-2-oxo-cyclopentanecarboxylate and cyan amide yield butyl-3-cyanamino-cyclopent-1-en-carboxylate (14) . 2-Oxocyclohexane-carboxamide (1) and ethyl-cyanoacetate form with sodiumhydroxide 4-cyano-octahydroisoquinolin-1, 3-dione (17) and with ammonium acetate ethyl cyclohexylidene-cyanoacetate-2-carboxamide (18) . 18 and ammonia, hydrazine, or cyclohexylamine form the salts of cyanohydroquinazolindione 20a–c , respectively.     

Reaktion von methylenaktiven Nitrilen und Cyanamid mit acylierten Enaminen

Reaction of Methylene Active Nitriles and Cyanamide with Acylated Enamines The addition products from enamines onto isocyanates and isothiocyanates, i.e. substituted β-aminoacrylo amides 1 and thioamides 2 , react with malononitrile to yield the 6-amino-1-aryl-5-cyano-pyridin-2-ones 3 and -thiones 4 among them 5,6,7,8-tetrahydroisoquinolin-1-ones and -thiones. From ethyl cyanoacetate the 5-cyano-6-hydroxy-pyridin-2-ones 7 and from benzoyl acetonitrile the 6-phenyl-pyridin-2-ones 8 are formed. The replacement of malononitrile by cyanamide yields the 2-amino-3-aryl-pyrimidin-4-ones 5 and -thiones 6 among them 5,6,7,8-tetrahydroquinazolin-4-ones and -thiones. The not isolated β-acyl enamines derived from enamines and acid chlorides react with malononitrile or cyanamide to form the pyridin-2-ones 14 or pyrimidin-2-ones 15 caused by Dimroth-rearrangement.     

Zur Reaktion von Dicyclopentadiendiepoxid mit Acrylsäure

On the Reaction of Dicyclopentadiene Diepoxide with Acrylic Acid The esterification of dicyclopentadiene diepoxide as a bifunctional epoxide with acrylic acid was investigated. The influence of solvent polarity, reaction temperature and the catalytic system used are discussed. It was found, that the reaction rate increased with increasing solvent polarity. By using tertiary amines as catalysts, only a small catalytic effect was observed. On the contrary, a good catalytic effect was achieved with Lewis-acids. By means of FeCl₃, a vinylester containing epoxide groups and CC-double-bonds is obtained, which polymerizes via various mechanisms.     

Kinetik und Mechanismus der Reaktion von Arylisocyanaten mit Alkylhydroperoxiden

Kinetics and Mechanism of the Reaction of Aryl Isocyanates with Alkyl Hydroperoxides Sec-alkyl peroxycarbamates, prepared from phenyl isocyanate and sec-alkyl hydroperoxides, are instable at normal temperatures and decompose to yield ketones, carbon dioxide and aniline which reacts further to diphenylurea. The reactions of phenyl isocyanate with tetraline hydroperoxide, t-butyl hydroperoxide, aniline, and tert.-butanol in dioxane have been studied kinetically and the catalytic constants of diazabicyclooctane, triethylamine, and stannous octoate as catalysts have been determined. Rate constants of the reactions with hydroperoxides decrease with increasing hydroperoxide concentration caused by association of the catalyst with the hydroperoxide. Compared to their basicities, alkyl hydroperoxides are very reactive towards isocyanates.