Iodine(III)‐Catalyzed Rearrangements of Imides: A Versatile Route to α,α‐Dialkylated α‐Hydroxy Carboxylamides

A tertiary hydroxy group α to a carboxyl moiety comprises a key structural motif in many bioactive substances. With the herein presented metal‐free rearrangement of imides triggered by hypervalent λ³‐iodane, an easy and selective way to gain access to such a compound class, namely α,α‐disubstituted‐α‐hydroxy carboxylamides, was established. Their additional methylene bromide side chain constitutes a useful handle for rapid diversification, as demonstrated by a series of further functionalizations. Moreover, the in situ formation of an iodine(III) species under the reaction conditions was proven. Our findings clearly corroborate that hypervalent λ³‐benziodoxolones are involved in these organocatalytic reactions.     

Meeting infinitely many cells of a partition once

We investigate several versions of a cardinal characteristic defined by Frankiewicz. Vojtáš showed , and Blass showed . We show that all the versions coincide and that is greater than or equal to the splitting number. We prove the consistency of and of . Received: 2 October 1996 / Revised version: 22 May 1997     

TERAHERTZ QUALITY CONTROL OF POLYMERIC PRODUCTS

We report on experiments that evaluate the potential of terahertz (THz) time-domain spectroscopy (TDS) for quality control of polymeric compounds. We investigate specimens out of a polyethylene compound with silver-coated titanium dioxide nanospheres and a glass-fiber reinforced epoxy composite. We further examine an industrial polymer product produced by injection molding. Our data demonstrates that THz imaging is a powerful tool for contactless quality control in the polymer industry.     

LiTiCl3: Synthesis and thermal behaviour

LiTiCl₃ is obtained as one example within an ample solid solution, Li_24–2nTi_nCl₂₄ (?4?n?10), by synpropotionation of TiCl₃ and Ti in the presence of LiCl (2:1:3 molar ratio) in sealed tantalum tubes at 750°C. It crystallizes with the inverse spinel-type structure according to (Li_0.67)^[4](Li_0.67Ti_1.33)^[4]Cl₄ with, at 25°C, a = 1048.62(4) pm, space group Fd3m. Thermal expansion is linear with α = 4.85 × 10^?5K^?1 up to about 300°C and thereafter, when the migration of Li⁺ from tetrahedral to octahedral interstices becomes increasingly important, it exhibits a relative decrease resulting, finally, in the phase transition to a NaCl-type structure that is observed for the first time at about 575°C.     

Stereochemie von Metallocenen, 13. Mitt.: Optisch aktive Derivate des Methylcymantrens: Darstellung,Rotationsdispersion und konfigurative Korrelation

Zusammenfassung Optisch aktive Methylcymantren-- und--carbonsäuren wurden durch Racematspaltung ihrer Phenäthylaminsalze erhalten. Bei der Umwandlung in die entsprechenden Acetyl- bzw. Vinyl-methylcymantrene treten charakteristische Drehwertänderungen auf. Aus diesen, vor allem aber aus der Rotationsdispersion, ließ sich auf Grund von Konformationsanalysen und Vergleichen zwischen offenkettigen und cyclischen Verbindungen sowie mit analogen Methylferrocenderivaten für die -substituierten Produkte mit großer Sicherheit die absolute Konfiguration ableiten: (1S) für (+)-Methylcymantren--carbonsäure und ihre Folgeprodukte. Dieser Befund wurde durch kinetische Racematspaltung des Anhydrides der racem. Säure mit (–)--Phenäthylamin gestützt.

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Optically active methylcymantrene-- and--carboxylic acids were obtained by resolution of their salts with -phenethylamine. Upon transformation into the corresponding acetyl and vinyl methylcymantrenes, characteristic shifts of the optical rotation are observed. From these data, and especially from the rotatory dispersions, on the basis of conformational analyses and comparisons between open chain and cyclic compounds as well as with analogous methylferrocene derivatives, the absolute configurations of the -substituted products could be deduced with reasonable probability: (1S) for (+)-methylcymantrenecarboxylic acid and its subsequent products. This result was supported by kinetic resolution of the anhydride of the racemic carboxylic acid with (–)--phenethylamine.

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