Stark- and Zeeman-effect of resonance lines of Ba I

Laserspectroscopic investigations were performed on a collimated atomic beam of barium (natural isotope abundance). The metastable ground levels (³D_1,2,3 and ¹D₂) of the investigated lines were populated by a discharge burning in barium vapour directly in front of the oven hole. We could investigate 14 spectral lines between 580 and 690 nm. The tensor polarizabilities of the upper and the lower level as well as the differences in the scalar polarizabilities could be determined. Spectra in magnetic fields up to 0.03 Tesla showed no deviation from the pattern resulting from a simple Russell-Sounders coupling.     

Lewis acid catalyzed addition of 2,2,2-trifluorodiazoethane to unactivated aldehydes

Condensations of 2,2,2-trifluorodiazoethane with pentanal, cyclohexancarboxaldehyde and benzaldehyde have been performed in presence of antimony pentachloride or boron trifiuoride. These reactions lead mainly to homologated aldehydes or ketones α substituted by a trifluoromethyl group.     

Synthesis and chemical transformations of perfluoroalkylimidoyl iodides

The addition of perfluoroalkyliodes CF₃(CF₂)_nl (n= 3, 5, 7) to isocyanides 2 produces perfluoroalkylimidoyl iodides 3 under thermal conditions when the isocyanide nitrogen substituent is n-butyl or cyclohexyl, but fails when it is t-butyl or 2,6-dimethylphenyl. The same reaction can be induced at room temperature by the addition of decimolar quantity of copper powder. This type of metal-catalyzed condensation is general for all perfluoroalkyliodides and isocyanides studied. The perfluoroalkylimidoyl-iodides 3 have been transformed into a variety of perfluorocarboxylic acid derivatives (amides, amidines. imidates, imidoylfluorides) and perfluoroalkylamines.     

Functional derivatives of thiophene. I. Synthesis and 1H-NMR spectra in the 2-aminothiophene series

The preparation of 2-amino-5-nitrothiophene, 2-formamido-5-nitrothiophene, 2-acetamido-5-nitrothiophene and 2-t-butyloxycarbonylamino-5-nitrothiophene are described. Abnormal values of the coupling constants J_3.4 had been observed in the ¹H-nmr spectra of compounds obtained.     

The structure of the ion pairs of the carbanion of indene with alkali metal cations

NMR spectra have been measured of the Li⁺, Na⁺ and K⁺ ion pairs of the indenyl carbanion in 1,2-dimethoxyethane and tetrahydrofuran as a function of temperature. The changes of the chemical shifts are explained in terms of the detailed structure of the ion pairs. The results in both solvents strongly suggest that in indenyl-Li⁺ the counterion is predominantly located over the six-membered ring. In THF the preferred position of the cations Na⁺ and K⁺ in the contact ion pairs seems to be the five-membered ring.     

Lösungsmitteleinfluß auf das Redoxverhalten von Bistriphenylphosphinquecksilber(II)-perchlorat

The influence of solvents on the redox behaviour of bistriphenylphosphinomercury perchlorate has been investigated by polarographic, voltammetric and potentiometric methods. The electrode process was found to be reversible in acetonitrile, propylene carbonate, N,N-dimethylformamide and dimethyl sulfoxide. An irreversible process was observed in nitromethane employing the dropping mercury electrode as well as in N,N-dimethylthioformamide and N-methyl-2-thiopyrrolidinone employing the rotating platinum electrode. Half wave potentials and diffusion coefficients have been measured. A linear relationship between theE _1/2 and the donor number (DN) of the solvent has been found for the reversible electrode reactions. Ligand replacement occurs in N,N-dimethylthioformamide and N-methyl-2-thiopyrrolidinone.

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Condensation du complexe hexafluoroacetone - fluorure de potassium sur les cetones alpha - halogenees

During its condensation with α-halo ketones, the hexafluoro- acetone-potassium fluoride complex behaves as a weak nucleophile and a strong base. Nucleophilic substitution produces α-perfluoroalkoxy ketones. Abstraction of a proton α to the carbonyl function leads to the formation of ether-ketones substituted by the group C(CF₃)₂. In some cases, hydrogen halide elimination can occur.