Showing papers by "Yu. N. Ogibin published in 1974"

Peroxydisulfate-initiated reactions of 1-heptene with acetic and propionic acids

Abstract: 1. A study was made of the sodium peroxydisulfate-initiated reaction of 1-heptene with acetic and propionic acids at 90–105°, as well as the effect of potassium hydroxide on this reaction. 2. We were the first to discover that an olefin can be oxidized by a peroxydisulfate. The composition and character of the oxidation products are in agreement with the mechanism of a one-electron oxidation of the olefin and the formation of the cation-radical\(R--CH--\mathop {CH_2 }\limits^ + \) as the primary reaction product. 3. Potassium hydroxide substantially suppresses the oxidation of the olefin by the peroxydisulfate and facilitates the homolytic alkylation of acids by the olefin.

Oxidative cyclization of ω-carboxyalkyl radicals

Abstract: 1. The 3-carboxypropyl and 4-carboxybutyl radicals were generated by the respective decarboxylation of glutaric and adipic acids at 60°C in aqueous solution under the influence of Na2S2O8 in the presence of a catalytic amount of AgNO3, and their transformations under the decarboxylation conditions were studied, and also the effect of added copper ions on these transformations. 2. The system Na2S2O8-AgNO3-CuSO4 causes an efficient oxidative cyclization of the studiedω-carboxyalkyl radicals, in which connection the 3-carboxypropyl radicals are selectively converted toγ-butyrolactone, while the 4-carboxybutyl radicals are converted to δ-valerolactone to the extent of 90%. 3. Oxidative cyclization also occurs in the absence of copper ions, but its contribution to the sum of the transformations of the 3-carboxypropyl radicals does not exceed 50%, and not over 30% in the case of the 4-carboxybutyl radicals.

Generation and reactions of 3-carboxy- and 3-carbalkoxypropyl radicals

Abstract: 1. The oxidative decarboxylation of glutaric acid and its monoesters (methyl, ethyl, isopropyl, and benzyl) under the influence of Na2S2O8, in the presence of AgNO3, led to the generation of the ROOC (CH2)2 CH2 radicals, where R = H, CH3, C2H5, i-C3H7 or C6H5CH2. 2. The principal transformation products of these radicals are butyric acid and alkyl butyrates, and also γ-butyrolactone. The yield of the lactone relative to butyric acid and its ester increases as follows in the R series: H > i-C3H7 > C2H5 > CH3 ∼ C6H5CH2.

Oxidation of acetoxyalkyl radicals by divalent copper salts

Abstract: 1. The 1-ethyl-3-aeetoxypropyl and 1-ethyl-4-acetoxybutyl radicals were respectively generated by the oxidative decarboxylation of the 2-ethyl-3-acetoxybutanoic and 2-ethyl-4-acetoxypentanoic acids under the influence of lead tetraacetate, and a study was made of their oxidation by the acetate, trifluoroacetate, fluoborate, sulfate, chloride and perchlorate of divalent copper. 2. Most of the copper salts oxidize the 1-ethyl-3-acetoxypropyl and 1-ethyl-4-acetoxybutyl radicals exclusively to the 2- and 3-pentenyl and the 3- and 4-hexenyl acetates, with the predominant formation of the isomers where the acetoxy group is furthest away from the double bond. Ligands that are coordinated with the copper are practically without effect on the ratio of the formed isomeric alkenyl acetates.