Hydrogenation without a transition-metal catalyst: on the mechanism of the base-catalyzed hydrogenation of ketones

The hydrogenation of unsaturated organic substrates such as olefins and ketones is usually effected by homogeneous or heterogeneous transition-metal catalysts. On the other hand, a single case of a transition-metal-free and purely base-catalyzed hydrogenation of ketones was reported by Walling and Bollyky some 40 years ago. Unfortunately, the harsh reaction conditions (ca. 200 degrees C, >100 bar H(2), potassium tert-butoxide as base) limit the substrate spectrum of this reaction to robust, nonenolizable ketones such as benzophenone. We herein present a mechanistic study of this process as a basis for future rational improvement. The base-catalyzed hydrogenation of ketones was found to be irreversible, and it shows first-order kinetics with respect to the substrate ketone, hydrogen, and catalytic base. The rate of the reaction depends on the type of alkali ion present (Cs > Rb - K > Na > Li). Using D(2) instead of H(2) revealed a rapid base-catalyzed isotope exchange/equilibration between the gas phase and the solvent as a concomitant reaction. The degree of deuteration of the product alcohols did not indicate a significant kinetic isotope effect. It is proposed that both ketone reduction and isotope exchange proceed via similar six-membered cyclic transition states involving the H(2)(D(2))-molecule, the alkoxide base, and the ketone (solvent alcohol in the case of isotope exchange). Mechanistic analogies are pointed out which apparently exist between the base-catalyzed hydrogenation of ketones studied here and the Ru-catalyzed asymmetric ketone hydrogenation developed by Noyori. In both cases, heterolysis of the hydrogen molecule appears to be assisted by a Br?nsted-base (i.e., alkoxide), the latter being bound to the substrate ketone or the catalyst ligand, respectively, by a bridging Lewis-acidic alkali ion.     

Biogenic substances in sediments and fossils

Most sedimentary rocks contain small concentrations of finely divided organic material. With the aid of modern analytical methods, samples of such rocks can be examined in detail, and conclusions can be drawn concerning the origin of the organic substances. Intact or modified biogenic compounds such as paraffins, isoprenoids, alcohols, ketones, carboxylic acids, steroids, triterpenes, and porphyrins have been isolated from the soluble fractions of the organic material of many sediments and from identified fossils of various geological ages. Even Precambrian rocks contain biogenic substances, so that life forms must have existed more than three billion years ago. The main component of the organic material is “kerogen”, the complicated polymeric structure of which has not yet been established.     

Abtrennung durch Diasolyse mit Hilfe gequollener Silicongummimembranen

Zusammenfassung Ein Gerät zur Diasolyse (Flüssig-flüssig Extraktion mit phasentrennender Membran) wird beschrieben, bei dem ein Silicongummischlauch als Membranmaterial dient. Der Einfluß einer Reihe von Parametern wurde untersucht (Pumpgeschwindigkeit, Schlauchlänge, Temperatur, pH, Volumen der wäßrigen Phase, Konzentration der zu bestimmenden Substanz, Quell- und Lösungsmittel, Fremdsubstanzen, kontinuierliche und diskontinuierliche Ausführung). Als Testsubstanzen wurden Barbiturate verwendet. Die Methode eignet sich zur Trennung von lipophilen und lipophoben Stoffen sowie zur Spurenanreicherung.

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Separation by diasolysis by means of swollen silicone rubber membranes

An apparatus for diasolysis (liquid-liquid extraction with phase separation by membranes) is described, which employs silicone rubber tubes as membrane material. The effect of various parameters has been investigated (pumping rate, tube length, temperature, pH, volume of aqueous phase, concentration of substance to be determined, swelling agent, solvent, foreign substances, continuous and discontinuous mode of operation). Barbiturates served as testing substances. The method is suitable for the separation of lipophilic from lipophobic substances and also for the enrichment of traces.

     

Eine Bemerkung zum Satz von Ivory

In 1809 J. IVORY found a distance relation between any two confocal ellipsoids in Euclidean space E³. After that, the theorem of IVORY has been formulated for any two nondegenerate confocal quadrics of the same type. In this paper we succeed in completing these results and in formulating and proving them uniformly for any two quadrics of the same type belonging to a general system of confocal quadrics.

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Herrn Prof. Dr. Oswald Giering zum 60. Geburtstag gewidmet     

‘Lone pair’ Electronic Structure,Conformation and Oxidation Behaviour of Diaziridines

Photoelectron spectroscopic investigations indicate that (i) monocyclic diaziridines prefer a trans-conformation of the nitrogen-lone pairs, and (ii) the interaction between these is comparable to that exhibited by open-chain analogues, i.e. alkyl-substituted hydrazines. The chemical experience concerning the particular case of ? NH? NH? →? N?N? oxidation of diaziridines can therefore not be accounted for by a prevailing unfavorable ‘lone pair’ interaction. Thermochemical as well as entropy arguments may serve as an explanation. A rather unsatisfactory agreement between predictions from various theoretical procedures and experimental results for the ionization potentials of ‘lone pair’ MO electrons is noted.     

Zur hochspannungselektrophoretischen Trennung anorganischer Ionen unter besonderer Berücksichtigung der Platmmetalle

Zusammenfassung Die hochspannungselektrophoretische Wanderung der Halogenokomplexe der Platinmetalle und einer Reihe weiterer anorganischer Ionen wird mit Nitrilotriessigsäure und Äthylendiamintetraessigsäure als Elektrolyt in Abhängigkeit von verschiedenen Versuchsparametern (Elektrolytkonzentration,ph-Wert und Substanzmenge) untersucht. Die Wanderungsgeschwindigkeiten der verschiedenen Metallionen bzw.-komplexe zeigen charakteristische Abstufungen, die sich mit den für die hochspannungselektrophoretische Wanderung gültigen Gesetzmäßigkeiten erklären lassen. Beispielsweise beobachtet man eine Abnahme der Beweglichkeit bei Ersatz von Chlorid- durch Bromidionen (Masseneinfluß), Auswirkungen der vomph bzw. der Elektrolytkonzentration abhängigen unterschiedlichen Komplexierungen zwei- und dreiwertiger Ionen, Einflüsse der auf Hydrolyse zurückgehenden Änderungen der Ligandenzusammensetzung sowie Unterschiede der Wanderungsgeschwindigkeiten als Folge der Komplexierung mit NTE oder AeDTE.Durch die unter bestimmten Bedingungen erreichbare Abstufung der Beweglichkeiten können verschiedene Gemische, unter anderem auch die Chlorokomplexe der meisten Platinmetalle in der Reihenfolge Ir > Os Pt > Rh Pd > Ru (> Rh), getrennt werden. NTE ist dabei für Trennungen besser als AeDTE geeignet.

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The high tension electrophoretic separation of inorganic ions with special reference to the platinum metals. I

Summary The high tension electrophoretic migration of the halogeno complexes of the platinum metals and several other inorganic ions was investigated with nitrilotriacetic acid and ethylenediaminetetraacetic acid as electrolytes in relation to the various experimental parameters (electrolyte concentration,ph-value, and amount of substance). The migration velocities of the various metal ions or complexes exhibit characteristic gradations that may be explained on the basis of the regularities that are valid for the high tension electrophoretic migration. Instances are: a decrease was observed in the mobility when chloride was replaced by bromide ions (mass effect), influence of different complexing of di- and trivalent ions that are related to changes in theph or electrolyte concentration, or influences of the changes due to hydrolysis in the composition of the ligands or alterations in the migration rates resulting from complexing with nitrolotriacetic acid or EDTA.The gradation of the mobility obtained under certain conditions are employed as the basis of a procedure for separating various mixtures, including also the chloro complexes of most of the platinum metals in the succession Ir > Os Pt > Rh Pd > Ru (> Rh). It has been found that NTE is better for separations than EDTA.

     

The small momentum transfer k L o C→K S 0 C regeneration at high energies

Results of the first elastic K _S ^o regeneration experiment on carbon, using magnetic spark chamber spectrometer, are presented in the beam momentum interval 10p50 GeV/c. The d ifferentia cross section d/dt is reconstructed in the range 0·0025–t0·02 (GeV/c)² and its slopeB is found to be momentum independent with an average valueB=(65±11) (GeV/c)^–2. The results are in agreement with the calculations using the coherent production model.     

Synthesis of s-triazolocycloalkyl-, s-triazolobenzocycloalkyl-, and s-triazolocycloalkylhydrothiadiazines

The reaction of cyclic-α-haloketones with 5-subslituted-4-amino-4H-1,2,4-triazole-3-lhiols gave s-triãzolocycloalkylhydrothiadiazines and s-triazolobenzocycloalkylthiadiazines. Reduetion of the 5,5a-imine bond of the s-triazoloeycloalkylthiadiazines gave s-triazolocycloalkylhydrothia-diazines.