On the Preparation of 2‐Substituted Cephalosporins,Part 2

Cephalosporin sulfoxides 1 and 2 containing an enone‐ or dienone‐type moiety at position 2 were treated with 2,3‐dimethylbuta‐1,3‐diene or diethyl azodicarboxylate to synthesize, in Diels? Alder reactions, the new cephalosporin derivatives 4 and 5 with a cyclic substituent (Scheme 1). Under the same conditions, ethyl diazoacetate and diazomethane reacted differently: while reactions of 1 and 3 with the former lead to compounds 7 – 10 corresponding to the 1,3‐dipolar cycloaddition route (Scheme 2), diazomethane produced only enol ethers 12 and 13 , respectively (Scheme 3). This difference could be rationalized by assuming two different reaction pathways: an orbital‐symmetry‐controlled concerted cycloaddition and an ionic one.     

Ring expansion of steroid oxethans into hihydrooxazines

In tha case of oxethans condensed in an appropriate steric position to the sterane skeleton, the formation of six-membered dihydrooxazines has been observed with aliphatic or aromatic acid nitriles in the presence of Lewis acids, involving thus ring expansion.     

Maximization of separation efficiency in capillary electrophoretic chiral separations by means of mobility-matching background electrolytes

It has been predicted, both theoretically and by computer simulation, that in capillary electrophoresis the electromigration-dispersion-induced peak broadening can be eliminated by matching the mobilities of the analyte and the background electrolyte co-ion. Though mobility matching can be achieved by invoking multiple secondary chemical equilibria in the background electrolyte — such as protonation or complexation - to change the mobility of the co-ion, this approach is not feasible when the composition of the background electrolyte is dictated by the need to achieve a certain separation selectivity. In this paper, a background electrolyte preparation principle is outlined which decouples the dual roles of the background electrolyte, namely the buffering function and the mobility matching function, by ascribing the buffering function solely to the counter-ion (a conjugate acid or conjugate base) and the mobility matching function solely to the co-ion (a strong electrolyte). The power of this approach is demonstrated by solving difficult enantiomer separations.     

Flavonoids. 41. Stereospecific synthesis of 2,3-dihydro-c-3-substituted-t-3-methyl-r-2-phenyl-4H-1-benzopyran-4-ones

The synthesis of 2,3-dihydro-t-3-mesyloxy-c-3-methyl-r-2-phenyl-4H-1-benzopyran-4-one (1) is described. The reaction of mesylate 1 with various nucleophiles, first of all O- and N-nucleophiles, yields the corresponding 2,3-dihydro-c-3-substituted-t-3-methyl-r-2-phenyl-4H-1-benzopyran-4-ones 2b, 7b, 9, 10, 12, 14 and 18 . Azide 14 is a useful intermediate for the synthesis of flavonoids 15–17 .     

The relationship between the structures of Cu(II) complexes and their chemical transformations

The structures of compounds M ₂ ^I M^II(SEO₄)₂ (M^I=K, Tl; M^II=Cu and Ni), were studied using IR, electronic and EPR spectra. The results indicate a hexacoordination of both central atoms, and a bridging function of selenato groups, the mode of their coordination varies with M^I and M^II. The compound Tl₂Cu(SeO₄)₂ was prepared also in the amorphous glassy form, although with partial decomposition. It is presumed that in the homogeneous smaragd-green material -Cu-O-Cu-, -Cu-OSeO₂-Cu- and -Cu-OSeO₃-Cu- bridges are present simultaneously. The course of the thermal decomposition of the studied compounds depends on the nature of the M^I and M^II cations. According to powder X-ray patterns, the decomposition products do not contain individual oxides. Nearly complete removal of selenium was observed in the decomposition of hydrated ammonium double selenates of Ni(II) and Cu(II).

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Zusammenfassung Mittels IR-, Elektronen- und EPR-Spektren wurden die Strukturen der Verbindungen M ₂ ^I M^II (SeO₄)₂ mit M^I=K und Tl sowie M^II=Cu and Ni bestimmt. Die Ergebnisse zeigen eine Hexakoordination beider Zentralatome und eine Brückenfunktion der Selenatgruppen, deren Koordination sich mit M^I und M^II ändert. Die Verbindung Tl₂Cu(SeO₄)₂ wurde, wenn auch unter geringen Zerfalles, auch in einer amorphen Glasform hergestellt. Es wird angenommen, daß in den Smaragdgrün-Stoffen gleichzeitig-Cu-O-Cu-, -Cu-OSeO₂-Cu- und -Cu-OSeO₃-Cu- Brücken vorkommen. Der Verlauf der thermischen Zersetzung der untersuchten Verbindungen hängt von der Art der M^I und M^II-Kationen ab. In Bezugnahme auf Röntgenpulverdiffraktionsaufnahmen enthalten die Zersetzungsprodukte keine getrennten Oxide. Beim Zerfall von hydratierten Ammoniumdoppelselenaten von Ni(II) und Cu(II) wurde eine fast vollständige Abgabe von Selen beobachtet.

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M ₂ ^I Mⁱⁱ(SeO₄)₂, ⁱ — , , ⁱⁱ , - , . , - ^{i ii}. Tl₂Cu(SeO₄)₂ , . , ----, --OSeO₂- -Cu-OSeO₃-u-. ^{i ii}. , . .

     

Synthesis of a single-isomer sulfated beta-cyclodextrin carrying nonidentical substituents at all of the C2, C3, and C6 positions and its use for the electrophoretic separation of enantiomers in acidic aqueous and methanolic background electrolytes. Part 2: Heptakis(2-O-methyl-6-O-sulfo) cyclomaltoheptaose

The sodium salt of heptakis(2-O-methyl-6-O-sulfo)cyclomaltoheptaose (HMS), the second single-isomer, sulfated beta-CD carrying nonidentical substituents at all of the C2, C3, and C6 positions, has been synthesized, analytically characterized, and used for the capillary electrophoretic separation of the enantiomers of a group of 23 weak base analytes in acidic aqueous and methanolic BGEs. HMS interacted strongly with only about half of the analytes studied. The good separation selectivities and favorable normalized EOF mobilities allowed for rapid, efficient separation of the enantiomers of 19 of the 23 weak base analytes in the aqueous BGEs, often with separation selectivity values complimentary to those obtained with other single-isomer sulfated CDs. HMS did not prove to be as good a resolving agent in acidic methanolic BGEs as its counterpart, heptakis(2-O-methyl-3-O-acetyl-6-O-sulfo)cyclomaltoheptaose.     

Effect of feed zone width on product purity in preparative-scale,continuous free-flow isoelectric focusing separation of enantiomers

The effects of the increased width of the sample feed stream upon the purity of the collected fractions were examined in the continuous free-flow isoelectric focusing separation of the enantiomers of dansyl-tryptophan. Compared to the reference separation obtained with a narrow feed stream introduced through the central sample feed port of the continuous free-flow isoelectric focusing separation unit, the final pH gradient, the position of the enantiomer band centroids and the values of the cumulative product recoveries and cumulative product purities remained essentially identical as the width of the feed band of the racemic sample dissolved in the carrier ampholyte was increased up to the full width of the separation chamber suggesting that the current, limiting practice of narrow, central feed bands can be safely abandoned and dilute feedstock solutions can be utilized in preparative-scale isoelectric focusing enantiomer separations.     

Unprecedented cyclisations of calix[4]arenes under the Mitsunobu protocol. Part 3: Thiacalix[4]crowns versus dimers

Intermolecular couplings versus intramolecular ring closures were observed in the reaction of p-tert-butylthiacalix[4]arene and diethylene glycols affording dimers 2 and/or the inherently chiral 1,2-thiacalix[4]crown-3 derivatives 5 under the Mitsunobu protocol. The enantiomeric separation of 5a was achieved by chiral HPLC. The reaction of thiacalix[4]monocrowns 1 with diethylene glycols failed to give crowned thiacalix-tubes 7, instead biscrowns 8 were formed. Partially alkylated double thiacalix[4]arenes 10, 11 were obtained via the base promoted alkylations of a thiacalixarene dimer 2a containing diethyleneoxy linkers.     

Comparative thermogravimetric study of chlorinations of hematite and wustite

The reactions of hematite and wustite with Cl₂, COCl₂, CO+Cl₂ and gaseous CCl₄ were studied by thermogravimetry, X-ray diffraction and computer-assisted thermodynamic calculations. During the chlorination of hematite, only gaseous products were formed. The apparent activation energies were calculated from the isothermal TG curves. The chlorination of wustite involves the formation and transformation of a series of solid chloride products. FeCl₂(s), FeCl₃(s) and FeOCl(s) were found as intermediates during chlorination with Cl₂ or Cl₂+CO, while only FeCl₂(s) was detected in reactions with COCl₂ oe CCl₄. The chlorinations of the iron oxides with various agents were compared, and the differences in reactivity sequences were established.

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Zusammenfassung Die Reaktionen von HÄmatit und Wustit mit Cl₂, COCl₂, CO+Cl₂ and gasförmigen CCl₄ wurden thermogravimetrisch und röntgendiffraktometrisch untersucht. Thermodynamische Berechnungen wurden mit Computern ausgeführt. Bei der Chlorierung von HÄmatit entstehen nur gasförmige Reaktionsprodukte. Die scheinbaren Aktivierungsenergien wurden aus isothermen TG-Kurven berechnet. Bei der Chlorierung von Wustit wird eine Reihe von festen Chloriden gebildet. FeCl₂(s), FeCl₃(s) und FeOCl(s) treten bei der Chlorierung mit Cl₂ oder Cl₂ + CO als intermediÄre Produkte auf, wÄhrend bei Reaktionen mit COCl₂ oder CCl₄ nur FeCl₂(s) nachgewiesen wurde. Die verschiedenen Chlorierungsmittel wurden hinsichtlich ihrer Wirksamkeit miteinander verglichen und in einer entsprechenden Reihenfolge eingeordnet.

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Cl₂, COCl₂, CO+Cl₂ CCl_{2 4} , , . . . . Cl₂ Cl₂ + CO , FeCl₂, FeCl₃ FeOCl, COCl₂ CCl₄ — FeCl₂. .