Adamantanol nitrates in nucleophilic substitution reactions

Conclusions Functional derivatives of alkyladamantanes may be obtained in good yields from the corresponding alkyladamantanol nitrates.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2144–2146, September, 1985.     

Synthesis of alkoxycarbonylaminoadamantanes and acetylamino-adamantanes in nitric acid

Conclusions The reaction of adamantanes with nitric acid and urethanes or acetamide gave 1-alkoxycarbonylaminoadamantane and 1-acetylaminoadamantane derivatives, respectively.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 878–880, April, 1988.     

Methylation of adamantane

Russian Chemical Bulletin -     

Catalytic Activity of Tetraarylporphyrins in the Oxidation Reactions of Saturated Hydrocarbons

The oxidation of cyclic hydrocarbons by potassium peroxymonosulfate catalyzed by the iron and manganese complexes of tetra-(4-N-butylpyridinium)porphyrin, tetraphenylporphyrin, and mixed porphyrins containing phenyl and butylpyridyl substituents was studied in an aqueous acetonitrile medium. The test catalysts were dissolved in the reaction medium or adsorbed on layered aluminosilicates. It was found that the immobilization of metal complexes on layered aluminosilicates, as well as the bromination of porphyrins, decreased the activity of catalysts in a number of cases, although it improved their stability. The addition of pyridine in an equimolar amount with respect to metal complexes to the reaction mixture increased the activity of dissolved manganese complexes. An increase in the number of butylpyridyl meso-substituents in a porphyrin molecule improved the catalytic activity of a metal complex.     

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

Based on an analysis of the ratio between the final products of the oxidation of 1,3-dimethyladamantane (1,3-DMA) with hydrogen peroxide under new catalytic conditions, an EPR-spectroscopic study of the 1,3-DMA radical cation under model radiation-chemical conditions, and the results of PM3 quantum-chemical calculations, a new mechanism was proposed for the biomimetic oxidation of the saturated hydrocarbon. This mechanism involves the intermediate formation of the 1,3-DMA radical cation, in which a tertiary C-H bond is selectively activated. Next, oxene (oxygen atom) is inserted into this C-H bond to form a tertiary alcohol. It was found that a comparison of the composition of final products in the oxidation of saturated hydrocarbons under conditions of a real chemical experiment with the structure and reactivity of their radical cations under model radiation-chemical conditions can be a methodologically new general technique for the analysis and prediction of the reactivity of saturated hydrocarbons under oxidative conditions.