(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.     

Substituted propanes: V. The vibrational spectra,dipole moments and conformations of 1,2-dichloro-, 1-chloro-2-bromo- and 1,2-dibromopropane

The infrared and Raman spectra of 1,2-dichloro-, 1-chloro-2-bromo- and 1,2-dibromopropane were recorded as liquids, in polar and non-polar solvents and in the crystalline state at low temperatures. The infrared spectrum of a high pressure crystal of 1,2-dibromopropane was recorded at ambient temperature. Dipole measurements were carried out in CCl₄ and C₆H₆solutions.Each of the 1,2-dihalopropanes existed as a mixture of three conformers in the liquid state, the one with the halogens in the anti position was in large abundance. Spectral and dipole measurements revealed a comparatively larger concentration of the two polar gauche conformers in polar solvents. All the compounds crystallized in the anti form. The C-halogen stretching vibrations have been interpreted in detail. Vibrational analyses of the anti conformers have been carried out and a tentative assignment of the majority of the gauche bands has been proposed.     

Reaction of 2-methylene-3-oxoquinuclidine with nucleophilic reagents

The salts and quaternary derivatives of 2-methylene-3-hydroxyquinuclidine readily add nucleophilic reagents because of the high polarity and polarizability of the carbon-carbon double bond, which are due to the overall electron-acceptor effect of the positively charged nitrogen atom and the carbonyl group. The double bond is substantially deactivated in the base, and the addition of nucleophilic reagents is hindered.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1370–1376, October, 1977.     

A study of corrosion on a rotating iron disk electrode

Corrosion of iron in slightly acidified sodium sulphate solutions (mainly pH 4.5) in the open air was studied with a rotating disk electrode method at room temperature.Microscopic observations of corroded iron disk surfaces in the pH 4.5 solution revealed that iron initially corrodes locally with the formation of round pits of 10–30 μm in diameter and of(0.6–1.3) × 10³ in number per apparent square centimetre followed by the U-shaped brown protective wall formation of precipitates (rust) outside the pits. Each protective wall is formed along the lines of flow of the solution adjacent to the iron surface and each pit is located near the upstream end of the wall. Steady state of corrosion sets in when the parts of surface area surrounded by the wall are completely covered with a microscopically non-porous rust film.The amount of iron in the rust film and the total amount of corrosion of iron including that in the film increase parabolically with the increase in the time of immersion. The amount of iron in the film increases in proportion to the total amount of corrosion independently of the speed of rotation of the disk electrode even in the steady state.The fraction of area of iron surface not covered with the film decreases with time and reaches a certain fixed value in the steady state: the value is smaller at higher rotational speed. The corrosion rate is proportional to the uncovered area, as the corrosion is near the steady state. The pH of the bulk solution increases as corrosion progresses.The corrosion rate of iron can be well interpreted by assuming that the rate is controlled by the diffusion of oxygen from the bulk solution to the surface of iron and that the rust film on iron impedes the diffusion of oxygen.     

Koordinationschemie makrocyklischer liganden—I : Kernresonanzspektroskopische untersuchungen über die lösungsstruktur und das komplexierungsverhalten makrocyklischer aminopolyaether

From the highly refined proton-NMR spectra of monocyclic and bicyclic aminopolyethers, signal shifts have been observed which indicate conformation changes in the ligand moiety. Their dependence on solvent, coordinated cation and anion is discussed, and an interpretation of the spectra is put forward on the basis of dynamic symmetry patterns.     

Synthetic studies in the field of the porphyrins. synthesis of a mesoporphyrin and of a diacetyldeuteroporhyrin

A method is proposed for the synthesis of porphyrins based on the cyclization of a tetrapyrrole system with methyl and formyl groups at the ends of the molecule. The synthesis of mesoporphyrin IX and diacetyldeuteroporphyrin IX has been effected.