Deuterium exchange of 4-pyrimidones and 4-pyrimidthiones

The hydrogen-deuterium exchange of H-2 in 4-pyrimidone, a number of 1- and 3-alkyl-4-pyrimidones and several of their thione analogs in deuterium oxide at moderate temperatures is reported. This reaction is apparently not susceptible to acid or base catalysis. Cations of the 4-pyrimidones were found not to exchange H-2 at all in acid media. Catalytic amounts of bases do not alter the exchange rates whereas more concentrated alkali decompose the pyrimidone. However, 1,4(3,4)-dihydro-1,3-dimethyl-4-oxopyrimidinium iodide (and its 6-methyl analog) exchange H-2 quite rapidly in neutral deuterium oxide, almost instantly when triethylamine is added as a catalyst, and very slowly in dilute solutions of deuterium chloride in deuterium oxide. Mechanisms are proposed to account for these phenomena.     

Als Beitrag zur Analytik von Organozinn-Stabilisatoren

Ohne Zusammenfassung     

Der Reaktionsmechanismus der allgemeinen Säure—Basen-Katalyse der Mutarotation der Glucose, 8. Mitt.: Die Aktivierungsenergie der heterogenen Kupfer-Katalyse der Glucose-Mutarotation (Kurze Mitteilung)

Ohne Zusammenfassung7. Mitt.:Hermann Schmid undG. Bauer, Mh. Chem.96, 1508 (1965); dort ältere Mitt. dieser Reihe zitiert.     

Pore size distributions in low‐k dielectric thin films from X‐ray porosimetry

X‐ray reflectivity has been used to determine the mass uptake of probe molecules in porous thin films supported on thick silicon wafers. The adsorption occurs by capillary condensation when the films are exposed to probe vapor at controlled partial vapor pressures. The probe solvent partial pressure was varied by mixing saturated air and dry air at constant temperature or by changing sample temperature at a constant vapor concentration. Pore size distribution in the films can be calculated from the probe uptake with typical porosimetric approaches such as the application of the Kelvin equation to convert partial pressure into pore size. For illustration, the pore size distribution of three different nanoporous thin films, the primary candidate of ultra‐low‐k interlevel dielectrics in the next generation of integrated circuit chips, was determined with this technique. These samples represent different generations of low‐k dielectrics developed by industry. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2170–2177, 2002     

(1-Adamantanethio)pyridines and tetrahydropyridines from the reaction of 1-adamantanethiol with pyridine I-oxide in acetic anhydride

The reaction of pyridine 1-oxide with 1-adamantanethiol in acetic anhydride produced a mixture of 2- and 3-(1-adamantanethio)pyridines, 1-aeetyl-2-(1-adamantanethio)-3-hydroxy-4-acetoxy-1,2,3,4-telrahydropyridine and the corresponding 3-acetoxyderivative. Pure substances were separated by means of column chromatography on alumina. The tetrahydropyridines were identified by means of their proton magnetic and mass spectra. 4-(1-Adamantanethio)pyridine was synthesized from 4-chloropyridinc and 1-adamantanethiol. The three isomeric (1-adamantanethio)-pyridines were, each, cleaved by concentrated hydrochloric acid to give 1-chloroadamantane and the corresponding pyridinethiol.