Formation of dehydrogenated derivatives upon the oxidative dehydrogenation of adamantanes

Russian Chemical Bulletin -     

Photochemical reactions of some mono- and diketo derivatives of adamantane in various solvents

Adamantanes are photoactive in the presence of CCl₄ and CDCl₃. The mechanism of their photolysis, involving the formation of singlet or triplet excited donor-acceptor complexes has been suggested.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1833–1835, September, 1995.This work was partially financially supported by the Russian Foundation for Basic Research (Project No. 93-03-18102).     

Synthesis of 2,2′-(adamantylene-1,3)-diethanoic acids

Via direct oxidative addition of 1,1-dichloroethylene to adamantane or 1,3-dimethyladamantane one obtains diethanoic acids of the adamantane series, which are useful in themselves or for preparation of other functional derivatives. Optimal reaction conditions were found by mathematical modeling.A. V. Topchiev Institute of Petrochemical Synthesis, Volgograd Polytechnic Institute, Russian Academy of Sciences, 117912 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1612–1615, July, 1992.     

Long-lived phosphorescence of arenes in complexes with cyclodextrins 2. Room-temperature phosphorescence of ternary complexes of naphthalene and phenanthrene with β-cyclodextrin and adamantane derivatives in the presence of oxygen

Long-lived room-temperature phosphorescence (RTP) of arene—β-cyclodextrin (β-CD)— cage hydrocarbon complexes in the presence of oxygen was studied. Naphthalene-d₈, phenanthrene, and fluorene were used as arenes and adamantane, 1,3-dimethyladamantane, diamantane, and diadamantyl were used as the cage hydrocarbons (according to PM3 quantum chemical calculations, the use of these compounds might cause the appearance of long-lived RTP). The RTP lifetime of the naphthalene-d8—β-CD—diadamantyl complex is 11.9 s at 20 °C. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2661–2665, December, 2005.     

On the selectivity of the biomimetic oxidation of the saturated hydrocarbon 1,3-dimethyladamantane in a Gif-type system containing a Fe2+ salt, picolinic acid, and pyridine

The effects of the composition of a heterogeneous catalytic system based on Fe₂SO₄ · 7H₂O, picolinic acid (pyridine-2-carboxylic acid), and pyridine and system preparation procedures on the selectivity of oxidation of 1,3-dimethyladamantane (1,3-DMA) with an aqueous 30% hydrogen peroxide solution in an aqueous acetonitrile solvent at room temperature and ambient pressure were studied. The yields of 1,3-DMA oxidation products were increased from fractions of a percent in initial experiments to the tens of percent under new catalytic conditions of final experiments. It was found that three different mechanisms can occur in the test system under various conditions; conceivably, these are radical, ion-molecule, and radical-cation mechanisms. In the first case, a statistical mixture of the products of 1,3-DMA oxidation at tertiary and secondary C-H bonds was formed. In the second and third cases, oxidation occurred only at secondary and tertiary C-H bonds, respectively. Unlike the first two cases, the selectivity of 1,3-DMA oxidation to a tertiary alcohol under conditions of the Gif-type test system corresponds to the selectivity of biological oxidation and, to the best of our knowledge, is the first example of this kind.     

Crystallization of calcium carbonate in magnetic water in the presence of paramagnetic substances

Effect of a paramagnetic substance on the crystallization of calcium carbonate in magnetic water was studied.     

A new bioside of quercetin

Summary A new bioside of quercetin, rumarin, with the composition C₂₆H₂₈O₁₆, characterized as quercetin 3-(-D-galactopyranosyl-6--L-arabinopyranoside), has been isolated from the fruit ofRumex maritimus L.Khimiya Prirodnykh Soedinenii, Vol. 2, No. 2, pp. 85–90, 1966