Beiträge zur chemie der Pyrrolpigmente, 10. Mitt.: Elektronenspektrometrische Untersuchungen über die Struktur von Quadratsäurederivaten

The structure of squaric acid derivatives was investigated on the basis of the PPP—SCF—LCAO—MO—CI method utilizing the π-electron densities and bond orders. The parameters used in the calculations were modified to fit the experimental data for representative compounds. The data were obtained by X-ray photoelectron spectrometry and electron absorption spectroscopy (including the polarization of the bands as determined by liquid crystal induced circular dichroism measurements).     

N-Monobromamide: Darstellung durch Bromierung mit „Dibromisocyanursäure”, Eigenschaften

By reaction of primary carboxamides with “dibromoisocyanuric acid” (DBI) N-monobromoamides can be readily obtained as well as the N,N-dibromoamides described in an earlier paper¹. Reactions, some of them new, and properties of these compounds are described and compared with those of the N,N-dibromoamides. Like other compounds bearing the NHBr group^{2, 3} the N-monobromocarboxamides disproportionate at room temperature according to: 2 RCONHBr ? ? RCONH₂+RCONBr₂. For CH₃CONHBr the equilibrium constant was found to beK=0.02. In aqueous solution they behave as weak acids. The dissociation constants of eight compounds [R=?CH₃, ?C₂H₅, ?CH₂Cl, ?CHCl₂, ?CCl₃, ?CF₃, ?C(CH₃)₃ and ?C₆H₅] were measured: they differ from those of the corresponding carboxylic acids by about three powers of ten.     

Ein biologischer Vergleich zwischen Benzol und Pyridin in kondensierten Ringsystemen

The synthesis of imidazo[4,5-b]pyridines and of [1,2,4]-triazolo[1,5-a]pyridines is described, and their biological activity in relation to the standard antiviral substance, 2-(α-hydroxybenzyl)benzimidazol, is discussed.     

Über Dialkylidensulfamide

Aldehydes and ketones containing no α-hydrogen atoms yield the corresponding dialkylidene sulfamides both by reacting with sulfamide in presence of a proton acid or of SOCl₂ and by reacting with bis(trichlorphosphazo)-sulfone. The dialkylidene sulfamides of ketones also were obtained by treating ketone imines with sulfamide. Chloral did not react with sulfamide in this way but yielded 3,7-bis-(trichloromethyl)-perhydro-1,5,2,4,6,8-dithiatetrazocine-1,1,5,5-tetroxide.     

Über 1-Alkyl-bzw. 1-Aryl-dihydro-6-methyl-2(1H)-pyrimidinthione

The title compounds7 are formed in a general reaction by heating β-isothiocyanoketones3 with primary amines in inert solvents, or by thermal elimination of water from tetrahydro-6-hydroxy-6-methyl-2(1H)-pyrimidinethiones5, also in inert solvents. The 1-alkyl compounds can also be prepared under similar conditions from α,β-unsaturated ketones by reaction with alkylammonium rhodanides. The NMR-spectra show that the 1-substituted dihydro-6-methyl-2(1H)-pyrimidinethiones are in tautomeric equilibrium with the tetrahydro-6-methylene-2(1H)-pyrimidinethiones13. The reactivity of 1-alkyl and 1-aryldihydro-6-methyl-2(1H)-pyrimidinethiones is similar to that of dihydro-4,4,6-trimethyl-2(1H)-pyrimidinethione7 j, although their ring stability is certainly less.     

Zur Thermochemie der Zinnhalogenide

The enthalpy change of the reaction at 298 K between Br₂ (l) and Sn(c) in CS₂ as solvent giving SnBr₄ (s) has been determined by calorimetry to be (?374, 2±1.4) kJ·mol^?1, [(?89.45±0.33) kcal·mol^?1]. By the same method the heat of solution of SnBr₄ (c) in CS₂ has been found to be (11.9±0.3) kJ·mol^?1, [(2.84±0.08) kcal·mol^?1]. Combining these results, a value of (?386.1±1.5) kJ·mol^?1, [(?92.3±0.4) kcal·mol^?1] is derived for the standard heat of formation of SnBr₄ (c). Substituting this figure in the thermochemical cycle hitherto used for calculating the heat of formation of SnBr₄ (c) gives ?124.3 kcal·mol^?1 for the standard heat of formation of SnCl₄ (l), which is in reasonable agreement with a recent determination of this quantity⁸.     

Das Schwingungsspektrum von Magnesium-orthovanadat

The infrared and laser-Raman spectra of crystalline Mg₃(VO₄)₂ are reported and a factor group analysis for the full lattice is presented to support the discussion. The 1,000 to 600 cm^?1 region of the spectrum is essentially related to internal (stretching) modes of the greatly distorted VO₄ tetrahedra, whereas the bands in the low frequency region must be assigned to complex vibrations originating in the interaction of the bending vibrations of the tetrahedral groups with the external modes.     

Einige Probleme im Zusammenhang mit der direkten Bestimmung der spezifischen Wärmen mittels Differential Scanning-Kalorimetrie

The relation between sample mass andDSC-amplitude was investigated under various experimental conditions for vitreous quartz, both as discs and powders. Contrary to other authors³ proportionality has been found up to the highest masses (75 mg) used. A statistical analysis of the data indicates that the accuracy of directC _p-measurements byDSC can be increased by determining the blank value by extrapolation of the amplitudes for several masses to zero mass instead of using the usual procedure, which involves a run with the empty pans. The overall error ofC _p due to instrument errors is estimated not to exceed 2%.     

Die Stabilität der Kobalt(II)- und Kupfer(II)-Komplexe mit α-, β- und γ-Aminobutyrat

Stability constants of cobalt(II) and copper(II) complexes with α-, β-, and γ-aminobutyrate as well as the protonation constants of these ligands have been determined by potentiometric titration. ΔG ^? values, computed from the stability constants, increase in the orderAABA. The increase in ΔG ^? AABA→BABA amounts approx. 15 per cent. The same difference was observed for α- and β-alaninato complexes with various transition metal ions.     

Beiträge zur Chemie der Pyrrolpigmente, 9. Mitt.: Bildung,Struktur und Konfiguration vonZ- undE-Arylmethyliden-3,4-dimethyl-3-pyrrolin-2-onen

The condensation of 3.4-dimethyl-3-pyrrolin-2-one with p-methyl-, p-chloro-benzaldehyde and ferrocenealdehyde yields theZ-andE-isomers of the corresponding condensates. Due to kinetic control theZ-isomers are obtained almost exclusively in this reaction. TheE-isomers of the two firstmentioned products can be produced by photochemical isomerization. The structures (tautomeric forms) and configurations of the isomers were established by the Lanthanide-induced-shift-technique and by evaluating the Nuclear-Overhauser-Effect.