Batch‐ and Continuous‐Flow Aerobic Oxidation of 14‐Hydroxy Opioids to 1,3‐Oxazolidines—A Concise Synthesis of Noroxymorphone

14‐Hydroxymorphinone is converted to noroxymorphone, the immediate precursor of important opioid antagonists, such as naltrexone and naloxone, in a three‐step reaction sequence. The initial oxidation of the N‐methyl group in 14‐hydroxymorphinone with in situ generated colloidal palladium(0) as the catalyst and molecular oxygen as the terminal oxidant constitutes the key transformation in this new route. This oxidation results in the formation of an unexpected oxazolidine ring structure. Subsequent hydrolysis of the oxazolidine under reduced pressure followed by hydrogenation in a packed‐bed flow reactor using palladium(0) as the catalyst provides noroxymorphone in high purity and good overall yield. To overcome challenges associated with gas–liquid reactions with molecular oxygen, the key oxidation reaction was translated to a continuous‐flow process.     

Modulation of the Thermoresponsive Behavior of Poly(N,N‐diethylacrylamide) via Cyclodextrin Host/Guest Interactions

The modulation of the cloud point of aqueous poly(N,N‐diethylacrylamide) solutions via the formation of supramolecular cyclodextrin complexes with hydrophobic end groups, namely adamantyl, tert‐butyl phenyl and azobenzene, synthesized via RAFT polymerization is described. The dependence of the apparent cloud points after cyclodextrin complexation is investigated with respect to the type and quantity of the guest end group, the polymer chain length and the cyclodextrin/end group ratio. Furthermore, the effect is reversed via the addition of guest molecules or via biocompatible enzymatic degradation of the cyclodextrins entire.

     

Determination of the minimum allowable operating temperature of stationary phases in capillary columns by inverse gas chromatography

A method was developed to determine the minimum allowable operating temperature (MiAOT) of wall coated open tubular capillary columns. Two polyethylene glycol and fourteen polysiloxanes phases with different side groups (methyl, phenyl, cyanopropyl, trifluoropropyl, n-octyl) and backbone stiffening units (tetramethyl-p-silphenylene, tetramethyl-p,p'-sildiphenylene ether, carborane) were investigated by inverse gas chromatography. A sigmoidal profile of temperature versus column efficiency was found for almost all phases, as the column efficiency increased with temperature. The MiAOT was defined as that temperature where the column efficiency is half of its original value at elevated temperatures. It was found that the MiAOT of a stationary phase is approx. 60 K higher than its glass transition temperature.     

Determination of cadmium and lead in beverages after leaching from pewter cups using graphite furnace atomic absorption spectrometry

Two simple methods have been developed to determine cadmium and lead in different kinds of beverages and vinegar leached from pewter cups produced in Brazil. Leaching experiments have been carried out with different solutions: beer, sugar cane spirit, red and white wine, vinegar and a 3% acetic acid solution. The solutions were kept in cups with and without solder for 24 h. Lead and cadmium have been determined using graphite furnace atomic absorption spectrometry with deuterium background correction. The limits of detection were 0.05 and 1.4 μg L⁻¹, and the characteristic mass was 1.0 pg and 19 pg for Cd and Pb, respectively. With the developed methods it was possible to determine accurately cadmium and lead by direct analysis in these liquids and to evaluate the leaching of these metals from pewter cups. The results presented in this work show that pewter cups are not cadmium- and lead-free; this point goes against the manufacturers’ declaration that their products are lead-free.     

Enantioselective synthesis of branched allylic esters via rhodium-catalyzed coupling of allenes with carboxylic acids

We report on the first intermolecular asymmetric catalytic regio- and enantioselective addition of carboxylic acids to terminal allenes to form valuable branched allylic esters, employing a rhodium(I)/(R,R)-DIOP catalyst system.     

Normal forms for real quadratic forms

We investigate the non-diagonal normal forms of a quadratic form on , in particular for n = 3. For this case it is shown that the set of normal forms is the closure of a 5-dimensional submanifold in the 6-dimensional Grassmannian of 2-dimensional subspaces of . Received: 27 June 2008