An unusual pathway of the oxidation of diethyl ether by bismuth(v) derivatives

Di(tert-butylperoxy)triphenylbismuth and the triphenylbismuth-tert-butyl hydroperoxide system transform diethyl ether into ethoxyacetic aldehyde. The latter undergoes further conversions under these reaction conditions to give the corresponding hydroxyperoxide, ethoxyacetic acid, and bismuth(III) acylates.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 783–784, April, 1995.This work was financially supported by the Competition Center for Fundamental Natural Studies at Saint-Petersburg University (Grant No. 94-9.4-219).     

Cyclocondensation of 3-Amino-1,2,4-triazoles with Esters of Substituted Cinnamic Acids and Aromatic Unsaturated Ketones

We have studied the reactions of 3-amino, 3,5-diamino-, and 3-amino-5-trifluoromethyl-1,2,4-triazole with esters of substituted cinnamic acids and aromatic unsaturated ketones; we have established the directionality of formation of the tetrahydrooxopyrimidine ring. We have carried out hydrolysis and hydrazinolysis of 7-phenyl-4,5,6,7-tetrahydro-1,2,4-triazolo[1,5-a]pyrimidin-5-one. We have conducted an X-ray diffraction study of isopropylidene hydrazide of 3-(5-amino-1,2,4-triazol-1-yl)-3-phenylpropionic acid.     

Fluorine-containing Vinyl Ethers: I. Reactions with Carboxylic Acids

Polyfluoroalkyl vinyl ethers take up aliphatic and aromatic carboxylic acids in the presence of 0.2-5 wt% of trifluoroacetic acid at 55-105°C to give fluorine-containing hemiacetals in 60-100% yields.     

Di(tert-butylperoxy)triphenylbismuth and the triphenylbismuth—tert-butyl hydroperoxide system as efficient oxidants of alcohols

Di(tert-butylperoxy)triphenylbismuth and the triphenylbismuth—tert-butyl hydroperoxide system react with aliphatic alcohols and cyclohexanol to give carbonyl compounds in high yields. The oxidation occurs as the radical dehydrogenation of alcohols; Bi derivatives serve as the sources of free radicals.     

Cleavage of the carbon-carbon bond in α-glycols under the action of bismuth(v) derivatives

Di(tert-butylperoxy)triphenylbismuth and the triphenylbismuth-tert-butyl hydroperoxide system react with 2,3-dimethylbutane-2,3-diol, benzopinacol, butane-2,3-diol, and ethane-1,2-diol with the cleavage of the C−C bond of α-glycol to form carbonyl compounds. Both heterolytic (through formation of cyclic triphenylbismuth glycolate) and homolytic cleavage occur. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1212–1214, June, 1997.