Intramolecular meerwein reactions of the anthraquinone system. Synthesis,X-ray structural analysis and spectroscopic properties of anthra[9,1-bc:10,5-b'c']tetrahydrodipyran derivatives

Meerwein reactions of 1,5-anthraquinone bis(diazonium hydrogen sulfate) with sufficiently activated olefins, such as acrylonitrile, acrylic esters, methacrylonitrile and its esters, styrene and α-methylstyrene yielded derivatives of the new heterocyclic system anthra[9,1-bc:10,5-b'c']-2,3,7,8-tetrahydrodipyran. Isolation of derivatives was realized and yields enhanced by using dimethyl methylphosphonate as reaction medium. Compounds 5–18 were isolated as mixtures of diastereomers, some of which were separated by crystallization. Proof of structure and stereochemistry was obtained for some of the compounds by X-ray crystallographic analysis. The ¹H- and ¹³C-nmr data provided further support. Surprisingly large chemical shift differences between some of the proton signals of isomers were observed although the two asymmetric centers are far apart through bonds and through space. The mechanism of formation is explained on the basis of redox modulation of a charge transfer complex in which the aliphatic radical attacks the oxygen atom of the anthraquinone. It is proposed to classify this new type of reaction as an intramolecular Meerwein reaction.     

Azo initiators for the preparation of hydroxyl-terminated polybutadienes

Azo compounds such as di(4-hydroxybutyl)-2,2′-azobisisobutyrate, di(3-hydroxybutyl)-2,2′-azobisisobutyrate, di(2-hydroxypropyl)-2,2′-azobisisobutyrate, and di(2-hydroxyethyl)-2,2′-azobisisobutyrate were prepared and used as initiators for the preparation of hydroxyl-terminated polybutadienes (HTPBs) of molecular weight (M?_n) ranging from 2000 to 7500 and functionality between 1.90 and 3.0. The polymers were prepared by free-radical solution polymerization in dioxane and toluene. The polymers obtained were characterized for their molecular weight, hydroxyl number, functionality, and instrinsic viscosity.     

Modellrechnungen zum Dendriten-Wachstum in partiell-kristallinen Hochpolymeren

Zusammenfassung Überstrukturen in partiell-kristallinen Thermoplasten liegen oft in Gestalt von Sphärolithen vor. Es wird versucht, ihre Entstehung auf behindertes Dendritenwachstum zurückzuführen. Die durch das Simulationsmodell beschriebenen Strukturen werden mit experimentell beobachteten verglichen.

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Superstructures in partial-crystalline thermoplastics often show the shape of spherulites. The reason of this can be a handicapped growth of dendrites. The structures obtained by a simulation model are compared with those obtained by experiments.

     

Photocycloadditions to 3-phenyl-1,2-benzisothiazole

Photocycloaddition reactions of 3-phenyl-1,2-benzisothiazole alkenes yield derivatives of 2,3-dihydro-1,4-benzothiazepine in one step reactions. The photoadditions are both regio and stereospecific.     

Untersuchungen an reagenzien zur photometrischen zinnbestimmung

The formation of complexes between tin(IV) and o-diphenols, and o-hydroxyquinones, has been studied spectrophotometrically. Simple o-hydroxyquinones do not react with tin(IV), chloranilic acid gives an SnR₂ complex, and o-diphenols give SnR₃ complexes. The reactions of tin(IV) with hydroxyxanthene dyes to give coloured products were considered for their possible analytical utility: the pH range, absorption spectrum, solubility and composition of the complexes were investigated, and the stability constants determined. Analytical procedures have been developed for tin and checked for precision and sensitivity: gallein and hydroxyhydroquinonephthalein (dihydroxyfluorescein) are to be recommended.