Unimolecular gas-phase reactions of the methyl acetoacetate radical cation. Oxygen atom permutation via ion-molecule complexes

The reactions of metastable decomposing methyl acetoacetate (a mixture of keto a ad enol tautomers) are reported and discussed. The unimolecular fragmentations of the tautomers are different. The metastable decomposing radical cation of the keto form displays four specific ions: [M –CO]⁺˙, [M – CH₂O]⁺˙, [M – CH₂CO]⁺˙ and m/z 43. The results derived from D-, ¹³C- and ¹⁸O-labelled precursors together with thermochemical data have been used to study the mechanisms. Experimental results indicate that an unexpected isomerization occurs before dissociation. It formally corresponds to oxygen atom permutation of the two carbonyl groups without participation of the carbon atoms. This remarkable process is interpreted in terms of a mechanism involving ion-molecule complexes.     

Préparation et structure des germanates métalliques. I

Résumé L'auteur reprend et complète la méthode de dosage microgravimétrique du germanium à l'état de germanimolybdate de tétraphénylarsonium (F _Ge=0,02137). Dans une deuxième partie, il décrit une méthode de préparation des heptagermanates alcalins et de métagermanates de métaux bivalents à partir des solutions d'oxyde GeO₂ et d'acétates métalliques. Les courbes de thermolyse et les spectres d'absorption infrarouge sont présentés. Aucun orthogermanate ne précipite des solutions aqueuses.

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Summary The author resumes and completes the method for the microgravimetric determination of germanium as the germanium molybdate of tetraphenylarsonium (F _Ge=0.02137). In a second part he describes a method for preparing some heptagermanates of divalent metals from solutions of the oxide GeO₂ and metal acetates. The thermolysis curves and the infrared absorption curves are given. No orthogermanate precipitates from aqueous solutions.

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Zusammenfassung Der Verfasser berichtet über die mikrogravimetrische Bestimmung des Germaniums als Tetraphenylarsonium-Germanium-Molybdat (F _Ge=0,02137). Im zweiten Teil der Arbeit wird die Herstellung von Alkaliheptagermanat sowie von Metagermanaten bivalenter Metalle aus Germaniumoxidlösungen und Metallacetaten beschrieben. Die Thermolysekurven und IR-Absorptionsspektren werden vorgelegt. Aus wäßrigen Lösungen fällt kein Orthogermanat aus.

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Mémoire en l'honneur du professeurA. A. Benedetti-Pichler.     

Molar excess heat capacities and volumes for mixtures of alkanoates with cyclohexane at 25°C

Molar excess volumes V ^E at 25°C have been determined by vibrating-tube densimetry, as a function of mole fraction x for different series of an alkanoate (H _2m+1 C _m COOC _n H _2n+1 )+cyclohexane. Three types of alkanoates were investigated, i.e., methanoates (m=0, with n=3 and 4), ethanoates (m=1, with n=2, 3, and 4) and propanoates (m=2, with n=1, 2, and 3). In addition, a Picker flow calorimeter was used to obtain molar excess heat capacities C _p ^E at constant pressure at the same temperature. V ^E is positive for all systems and rather symmetric, with V ^E (x=0.5) amounting to almost identical values in a series of mixtures containing an alkanoate isomer of same formula (say C₄H₈O₂, C₅H₁₀O₂, or C₆H₁₂O₂). The composition dependence of C _p ^E is rather unusual in that two more or less marked minima are observed for most of the mixtures, especially when the alkanoate is a methanoate or an ethanoate. These results are discussed in terms of possible changes in conformation of both the ester and cyclohexane.     

An overview of laboratory performance studies conducted by the IAEA for marine pollution studies of metals and organic contaminants

Aspects of the International Atomic Energy Agency (IAEA) Analytical Quality Control Services (AQCS) for marine environmental studies are discussed, focusing on recent laboratory performance studies (LPS) and the production of reference materials for trace metals and organic compounds in various marine matrices. The IAEA has organized seventeen global interlaboratory studies for a range of organic contaminants. Of note has been the inclusion of numerous polychlorinated biphenyl congeners (PCBs) and some sterols of anthropogenic origin. Concurrently, there have been eleven worldwide intercomparison exercises for trace metals in the marine environment, most of which included methylmercury. Although such interlaboratory studies can help improve performance in individual laboratories and regional laboratory networks, the results reveal that problems remain in the determination of some metals and many organic contaminants.     

Synthesis and Photoreaction of 5-Aikenyloxypsoralen Derivatives

Abstract— In order to investigate the intramolecular "quenching" of the photoexcitation of some 5-alkenyloxypsoralen derivatives, we have prepared model compounds in which a psoralen moiety was linked at position 5 to a terminal double bond via a polymethylenic chain of various length (n = 2-9). The isolation and characterization of photocycloadducts obtained for each compound after irradiation at 365 nm in a polar solvent was performed. The results on the photoreactivity of this series of compounds show that the 3,4-pyrone double bond of 5-alkoxypsoralens is the most reactive. Four kinds of intramolecular photocycloadducts between the 3,4-pyrone double bond and the chain unsaturation were obtained according to the length of the linking chain: cis-syn, trans-syn, cis-anti and trans-anti. Their structures were established by a combination of ¹H and ¹³C NMR and fully assigned by ^lH NOE (nuclear Overhauser effect) and ¹H-¹³C HMQC (heteronuclear multiquantum correlation) spectroscopies. No traces of 4',5' adducts were detected.     

Modifications de la position C-8 de purines nucleosides par action de reactifs electrophiles sur leurs derives silyles et lithies

The alkylation of 8-lithiopurine trimethylsilyl nucleosides at carbon 8 can be carried out conveniently by reaction with various electrophilic reagents.     

Competitive Complexation of Lanthanide Cations by Xylitol and Nitrate Anion in Aqueous Solution: A Microcalorimetric Investigation

The apparent equilibrium constants and enthalpies of complexation of Nd³⁺, Sm³⁺, Eu³⁺, and Gd³⁺ by xylitol in aqueous solutions containing NaNO₃ at an ionic strength of 2.0 mol-kg^–1 have been determined by microcalorimetry at 25°C. Since nitrate anion weakly complexes the lanthanide cations, these values are analyzed in terms of competition between xylitol and NO ₃ ^- The method leads to the apparent equilibrium constants and enthalpies of complexation of the lanthanide cations by NO ₃ ^- at this particular ionic strength. Despite the difficulties encountered in characterizing rather weak associations, the results are, whenever comparison is possible, in good agreement with those obtained by direct microcalorimetry. The advantage of this competition method is that it can be used when the enthalpic effects are too weak and insufficiently concentration dependent for direct microcalorimetric determination. In the present case, it allows us to thermodynamically characterize the formation of SmNO ₃ ²⁺ and EuNO ₃ ²⁺ , processes we have not been able to study directly.     

Ecdysteroid glycosides: identification, chromatographic properties, and biological significance

Ecdysteroid glycosides are found in both animals and plants. The chromatographic behavior of these molecules is characteristic, as they appear much more polar than their corresponding free aglycones when analyzed by normal-phase high-performance liquid chromatography (HPLC), whereas the presence of glycosidic moieties has a very limited (if any) impact on polarity when using reversed-phase HPLC. Biological activity is greatly reduced because the presence of this bulky substituent probably impairs the interaction with ecdysteroid receptor(s). 2-Deoxy-20-hydroxyecdysone 22-O-beta-D-glucopyranoside, which has been isolated from the dried aerial parts of Silene nutans (Caryophyllaceae), is used as a model compound to describe the rationale of ecdysteroid glycoside purification and identification.     

Oxygen-17 nuclear magnetic resonance: The effects of remote unsaturation on 17o-chemical shifts in polycyclic ethers

Natural-abundance ¹⁷O-NMR spectra of 7-oxanorbornane exo-3-oxatricyclo [3.2.1.0^2.4]octane and their unsaturated derivatives (endo cyclic and exocyclic double bonds) have been measured. Linear correlation laws were observed for $\text{δ}{}_{\mathrm{o}}\text{δ}{}_{\mathrm{c}}$ of these ethers/corresponding hydrocarbons. The “cyclization shifts” for δ_o in ethers were not correlated by the “cyclization shifts” for δ_c of the corresponding hydrocarbons.