Synthesen von Heterocyclen, 146. Mitt.: Zur Synthese polymerer Indigofarbstoffe mit potentiellen Halbleitereigenschaften

Zusammenfassung Die Darstellung von polymeren Indigofarbstoffen (PI) nach dem Verfahren vonZiegler undKappe ^{2, 3} wird beschrieben. Ausgehend von Benzidin (1 a) und Tolidin (1 b) erhält man so diePI 6 a bzw.6 b. In analoger Weise wird aus Tetrahydrochinoxalin (7), der N,N-überbrücktePI 12 gewonnen.

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Syntheses of heterocycles, CXLVI: The synthesis of polymeric indigos with potential semiconductor properties

The synthesis of polymeric indigos (PI) according to the procedure ofZiegler andKappe ^{2, 3} is described. Starting with benzidine (1 a) or tolidine (1 b) thePI 6 a and6 b, resp., are obtained. In a similar way the N,N-bridgedPI 12 is synthesized from tetrahydroquinoxaline (7).

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Aus den Dissertationen vonH. G. Foraita undL. F. Werner, Universität Graz, Januar bzw. Juni 1963.     

Cyclocopolymerization of dicyclic dienes and maleic anhydride to fused ring systems

The cyclocopolymerization of maleic anhydride and four 1,5- and 1,6-dienes (bicyclopentene, bicyclohexene, dicyclopentenyl ether, and dicyclohexenyl ether) and one tetraene (quartercyclopentene) is described. Soluble, low molecular weight copolymers were obtained from all five compounds. Their compositions approach 2:1 copolymer ratios. Fused ring structures are proposed as the main repeating units. Among the compounds listed, bicyclopentene copolymerized most easily and gave good conversions for monomer ratios of 2:1. Quartercyclopentene and dicyclopentyl ether, the other five-membered ring compounds, also polymerized to good-to-fair yields. However, a monomer ratio of about 4:1 was required to obtain conversions comparable to a 2:1 maleic anhydride—bicyclopentene polymerization. The six-membered systems, bicyclopentene and dicyclopentenyl ether, gave consistently low conversions, even with a 4:1 monomer ratio. The influence of the initiator system, initiator concentration, and reaction medium was studied on copolymerizations of bicyclopentene. Best results were obtained in acetic anhydride with azobisisobutyronitrile as the initiator.     

The electronic structure of FeO 4 2− , RuO4, RuO 4 − , RuO 4 2− and OsO4 by the HFS-DVM method

The electronic structures of FeO ₄ ^2? , RuO₄, RuO ₄ ^? , RuO ₄ ^2? and OsO₄ have been investigated using the Hartree-Fock-Slater Discrete Variational Method. The calculated ordering of the valence orbitals is 2t ₂, 1e, 2a ₁, 3t ₂ andt ₁ with thet ₁ orbital as the highest occupied. The first five charge transfer bands are assigned as:t ₁→2e(v ₁), 3t ₂→2e(v ₂),t ₁→4t ₂(v ₃), 3t ₂→4t ₂(v ₄) and 2a ₁→4t ₂(v ₅). It is suggested that ad-d transition should be observed at 1.5 eV in RuO ₄ ^? and RuO ₄ ^2? .     

Diffusion of flux lines in a random potential

A liquid of flux lines in a random superconductor is considered. We find spontaneous breaking of a continous internal symmetry from averaging over the random potential. A corresponding Goldstone mode describes diffusion of the flux lines. The diffusion coefficient vanishes if we exceed a critical strength of randomness. This is accompanied by a divergent correlation length. An interpretation of the behavior is a freezing transition of the flux liquid into a glass-like state.     

Synthesen von Heterocyclen, 104. Mitt.: Zur Chemie des 6-Chlor-4-hydroxy-2-oxopyran-3-carbonsäurechlorids

Zusammenfassung Es wird die Reaktion der 6-Chlor-4-hydroxy-2-oxo-pyran-carbonsäure (2) und ihres Säurechlorids (1) gegenüber aromatischen Aminen untersucht. Während mit Anilin Substitution des Pyrons erfolgt, kommt es bei der Umsetzung mit Anisidin oder Toluidin durch Ringöffnung zur Bildung von Acetondicarbonsäureaniliden.

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The reaction of 6-chloro-4-hydroxy-2-oxo-pyran-carboxylic acid (2) and its acid chloride (1) with aromatic amines is investigated. With aniline substitution of the pyron occurs, while treatment with anisidine or toluidine leads to acetone-dicarboxylic-anilides by ring cleavage.

     

All massless,scalar fields with trivialS-matrix are wick-polynomials

We extend a result about non-interacting fields given by Buchholz and Fredenhagen. Consider a massless, scalar field ø in 3 + 1 dimensional space-time which does not interact. The corresponding Hilbert space is assumed to be the FockspaceH of the free massless fieldA. This implies — as we show in the first part — that alln-point-functions are rational functions of their arguments. In the second part we use this fact to construct a symmetric, traceless tensorfield ^1...n, relatively local to the original field ø, and connecting the vacuum with the one particle states. In the last part we prove ^1...n to be relatively local to the free fieldA.     

Synthesen von Heterocyclen, 79. Mitt.: Über Reaktionen mit Ketensäurechloriden

Zusammenfassung Monosubstituierte Malonsäurechloride reagieren mit Nitrilen bzw. Isocyanaten zu 1,3-Oxazinen¹. Malonylchlorid setzt sich mit den gleichen Reaktionspartnern sowie mit Phenylsenföl in einer komplizierteren Reaktionsfolge zu bicyclischen Pyrono-1,3-oxazinen^1–3 um.

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Monosubstituted malonyl chlorides react with nitriles and isocyanates to 1.3-oxazines. Malonyl chloride itself reacts with nitriles, isocyanates, and iso-thiocyanates in a complicated manner yielding bicyclic pyrono-1.3-oxazines.

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Herrn KollegenA. Wacek, Techn Hochschule Graz, mit den besten Wünschen zum 70. Geburtstag.     

An Efficient Strategy to Orthogonally Protected (R)- and (S)-alpha-Methyl(alkyl)serine-Containing Peptides via a Novel Azlactone/Oxazoline Interconversion Reaction

A novel strategy for the synthesis of (R)- and (S)-alpha-methyl(alkyl)serine-containing peptides is presented. Using (S)-phenylalanine cyclohexylamide 6 as chiral auxiliary, the optically pure azlactones (R)- and (S)-2 were synthesized via a novel azlactone/oxazoline interconversion reaction (Figures 3 and 6). These azlactones constitute fully protected and activated synthetic equivalents of (R)- and (S)-alpha-methylserine and can be directly incorporated into peptides without further protective group manipulations. Like other alpha,alpha-dialkylated glycines, optically pure alpha-alkylserines can be used to stabilize beta-turn and alpha-helical conformations in short peptides.     

Zur Chemie derMeldrums?ure, 3. Mitt. Synthesen von Heterocyclen, 188. Mitt.

Thermolysis ofMeldrum acid in the presence of cycloalkanones leads to dioxaspiro-alkanediones (3 a–c) by the elimination of acetone. With increasing temperature an additional dehydratation is observed and with two moles ofMeldrum acid pyrano-cycloalkano-pyranediones (6 a–b) are formed. The reaction of dialkylMeldrum acids with cyclic 1,3-diones is investigated.