Stereoselective Ring Opening of Electronically Excited Cyclohexa-2, 4-dienones: Cause and effect

The two conformers of a cyclohexa-2, 4-dienone with different substituents at C(6) on irradiation are believed to undergo ring opening stereospecifically affording a mixture of two configurationally isomeric diene-ketenes (and descendents thereof)- Exceptions are generally found for those dienones with one C and one O substituent or even with two C substituents, if one of them carries a polar group at a site able to interact through space with the ring C?O group. In these cases, only one of the two anticipated diene-ketenes (and descendents thereof) is produced. A thorough investigation of the photochemistry of a series of structurally different cyclohexa-2, 4-dienones on analytical as well as on preparative scale extends our mechanistic knowledge of the various routes from diene-ketenes into a variety of compound classes. Novel compound classes accessible to diene-ketenes are seven-membered carbocycles (by intramolecular aldolization of the zwitterion of appropriately substituted, transiently formed diene-(N, O)-ketene acetals) and β-lactams (by Staudinger reaction).     

Transitivity is neither hereditary nor finitely productive

We construct a transitive space that is the union of two subspaces homeomorphic to the (non-transitive) Kofner plane. Moreover, we show that the product of two transitive spaces need not be transitive. Finally, we observe that results of E.K. van Douwen establish that, under b = c, there exists a locally countable locally compact non-transitive zero-dimensional space. It follows that under b = c neither a locally transitive nor a compact space need be transitive.     

Rationale Tschebyscheff-Approximation über unbeschränkten Intervallen

Summary We consider rational best approximations to functions real-valued and continuous on closed unbounded intervals of the extended real numbers. The error of the best approximation is characterized by an alternant, whose length may be different from the well-known number for a bounded interval. Besides some exceptional cases the best approximation is unique.     

Über enolisierte Derivate der Chlorophyllreihe. 132-Desmethoxycarbonyl-173-desoxy-132,173-cyclochlorophyllid a-enol und eine Methode zur Einführung von Magnesium in porphinoide Ligandsysteme unter milden Bedingungen. (Vorläufige Mitteilung)

Enol derivatives in the chlorophyll series. 13²-Desmethoxycarbonyl-17³-desoxy-13²,17³-cyclochlorophyllide a-enol and a method for the introduction of magnesium into porphinoid ligands under mild conditions Magnesium transfer from the iodo-magnesium salt of 3,5-di-t-butyl-4-hydroxy-toluene (BHT) into methyl pheophorbide a is a fast process in methylenechloride/ether solution at ambient temperature. This procedure for the introduction of magnesium into labile chlorin ligands has made possible the preparation of a crystalline 13², 17³-cyclochlorophyllide a-enol. Concomitant use of the lithium salt of BHT facilitates the more critical insertion of magnesium into methyl bacteriopheophorbide a. The preparative success of these magnesium transfers depends crucially upon the solvent system used. Under conditions where the complexation of methyl pheophorbide a with iodo-magnesium-BHT is essentially complete within 2 minutes at 12° in methylenechloride/ether solution, strong inhibition of the magnesium transfer is observed by cosolvents such as pyridine, dimethylacetamide, dioxan or tetrahydrofuran.     

Quality assurance in pesticide residue analysis

Summary During the last few years, the Working Group Pesticide Residues of the Food Chemistry and Forensic Chemistry Division of the Gesellschaft Deutscher Chemiker (German Chemical Society) has organised six laboratory performance tests on the analysis of pesticide residues in which numerous laboratories were involved. In these tests the choice of the analytical methods for the examination of fats or vegetable substrates was free. Organochlorine pesticides in concentrations of over 0.01 mg/kg were mostly readily identified, whereas in the analysis of organophosphorus residues often only the classic compounds (parathion, diazinon, etc.) were reported. Many a false positive result could have been avoided by using more adequate methods for confirmatory analysis. The quantitative results, however, were generally quite reliable and were mostly within the official acceptable dispersion range. It can be concluded that the performance of a residue laboratory is by no means constant, and that it is necessary to assess regularly the quality of the analytical results by participating in such interlaboratory tests.

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Qualitätssicherung bei Rückstandsanalysen von PflanzenschutzmittelnErfahrungen aus Ringversuchen

     

Large Scale Bioprocess for the Production of Optically Pure <Emphasis Type="Italic">L</Emphasis>-Carnitine

Summary. A competitive production method using the biotransformation of 4-butyrobetaine to enantiomerically pure L-carnitine was developed and scaled-up by Lonza. The process produces L-carnitine in 99.5% yield, and >99.9% enantiomeric excess (ee). Continuous and discontinuous processes were developed but the fed-batch process was found to be economically the most favourable process mode.