Synthesis and Reactions of Polyhedral Compounds. 27. Development of a Synthetic Route for 2- Spiro-substituted 6-Hydroxy-5,7-dimethyl-1,3-diazaadamantanes

Alternative methods for the synthesis of 2-spiro-substituted 6-hydroxy-5,7-dimethyl-1,3-diazaadamantanes have been developed. These are the reduction of the ketone group to hydroxyl in the corresponding 6-oxo-1,3-diazaadamantanes and the condensation of 9-hydroxy-1,5-dimethyl-3,7-diazabicyclo[3.3.1]nonane (obtained by different routes from 5,7-dimethyl-6-oxo-1,3-diazaadamantane) in reaction with cyclic ketones.     

Selective amination of 1-substituted uracils

Conclusions 1-Substituted uracils were subjected to selective amination at the fourth carbonyl group by reaction with phosphorous acid tris-dimethylamide and phosphoric acid tris-anilide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1198–1200, May, 1970.     

Liquid phase oxidation of transition metals. Part 6. iron and copper complexes containing dimethylsulphoxide,dimethylformamide, and acetonitrile. Anomalous states of ligands

Summary Direct oxidation of iron and copper in a donor-acceptor medium, L + CCl₄, where L is dimethylsulphoxide, dimethylformamide or acetonitrile was employed to obtain complex compounds:cis-[FeCl₂(DMSO)₄]Cl] (3), 2 FeCl₃ · 3 DMSO (5), [FeCl(DMSO)₅][FeCl₄]₂] (6), [FeCl(DMSO)₅][Fe₂Cl₆O] (7),cis-[FeCl₂(DMF)₄][FeCl₄] (8), [Fe(MeCN)₆][FeCl₄]₂ (9) andcis-[CuCl₂(DMF)₂]₂ (10), The structures of complexes (9) and (10) have been established by x-ray diffraction analysis and compared with those of (3), (6), (7) and (8) which are reported elsewhere.The [FeCl(DMSO)₅][Fe₂Cl₆O] complex (7) is formed by oxidation of iron fromcis-[Fe^IIICl₂(DMSO)₄]₂[Fe^IICl₄] (4) in ethanol. One of the 5 DMSO molecules of (7) was found to be disordered; the Mössbauer spectroscopy data suggest that it can move within the cation coordination sphere.Mössbauer spectroscopy and x-ray diffraction analysis indicate electron isomerism in one of the complexes.For papers 4 and 5 of these series see refs. 1 and 2.     

Spectroscopic study of polycrystalline TiO2 doped with vanadium

The structure of coordination sites (V⁴⁺ ions) and their spatial distribution in the polycrystalline titanium dioxide (rutile) lattice were studied by ESR. It was found that at low degrees of doping, at [V⁴⁺] < 0.5 at.%, the vanadium ions are isotropically distributed in the rutile lattice. At [V⁴⁺] > 0.5 at.% a new microphase with the mixed composition {TiO₂—VO²} is formed. The mixed microphase has a noticeably narrower band gap than the initial TiO₂. Comparison of the photocurrent spectra and the plots of the integral photocurrent vs. vanadium content with the structural data obtained using ESR spectroscopy showed that the formation of the {TiO₂—VO²} microphases deteriorates the photoelectrochemical properties of the modified photoelectrodes. Synthetic procedures interfering the formation of such microphases in the doped rutile are discussed.