Showing papers by "G. I. Nikishin published in 1974"
11 citations
TL;DR: In this paper, 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.
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.
3 citations
TL;DR: In this article, a method was developed for the preparation of trichloroallyl alcohol from methanol and tetrachloroethylene in a titanium apparatus under a pressure of 100-120 atm in the presence of CC14 (335°), CH3COC2H5 (365°), or (CH3)3COOC (CH 3)3 (185°), in a yield of 35-55% when starting TCE and 85-90% when reacted TCE, with a reactor output of up to 1000 g/h liter.
Abstract: A method was developed for the preparation of trichloroallyl alcohol from methanol and tetrachloroethylene in a titanium apparatus under a pressure of 100–120 atm in the presence of CC14 (335°), CH3COC2H5 (365°) or (CH3)3COOC (CH3)3 (185°), in a yield of 35–55% when based on starting TCE and 85–90% when based on reacted TCE, with a reactor output of up to 1000 g/h liter.
TL;DR: The relation between the yield of the products and the ratio of the reactants was determined in this article, where the relation between yield and ratio of reactants in the products was determined for unsaturated dicarboxylic acids.
Abstract: 1
The 1,2,4-butane- and 1,2,5-pentanetricarboxylic acids were obtained via the addition of theβ-carboxyethyl andγ-carboxypropyl radicals to maleic acid
2
Some g10 and C14 unsaturated dicarboxylic acids were synthesized by the addition ofβ-carboxyethyl radicals to butadiene The relation between the yield of the products and the ratio of the reactants was determined
TL;DR: In this paper, the 3-carboxypropyl 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 also the effect of added copper ions on these transformations.
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.
TL;DR: The ROOC (CH2)2 CH2 radicals were generated by the decarboxylation of glutaric acid and its monoesters (methyl, ethyl, isopropyl, and benzyl) under the influence of Na2S2O8, in the presence of AgNO3, where R = H, CH3, C2H5, i-C3H7 or C6H5CH2 as mentioned in this paper.
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.
TL;DR: The decomposition of peroxydiglutaric acid in aqueous solution under the influence of FeSO4 proceeds by the one-electron transfer mechanism, and makes it possible to selectively generate 3-carboxypropyl radicals as discussed by the authors.
Abstract: 1.
The decomposition of peroxydiglutaric acid in aqueous solution under the influence of FeSO4 proceeds by the one-electron transfer mechanism, and makes it possible to selectively generate 3-carboxypropyl radicals.
2.
The 3-carboxypropyl radicals that are formed in this system are converted into products by three directions: they are cyclized toγ-butyrolactone, dimerized to suberic acid, and they cleave hydrogen to give butyric acid.
3.
Water cannot serve as a hydrogen donor for the 3-carboxypropyl radicals; organic compounds function as the substrate here.
TL;DR: In this article, the free-radical addition of the esters of pyruvic, cyanoacetic, acetoacetic and alkylmalonic acids to 1-alkenes was performed under the influence of the Mn(OAc)3-Cu(OAC)2 system.
Abstract: Unsaturated adducts with aγ,δ-position of the multiple bond were obtained by the free-radical addition of the esters of pyruvic, cyanoacetic, acetoacetic, malonic, and alkylmalonic acids to 1-alkenes, which was accomplished under the influence of the Mn(OAc)3-Cu(OAc)2 system.
TL;DR: In this article, the 1-ethyl-3-aeetoxypropyl and 1-methyl-4-acetoxybutyl radicals were respectively generated by the oxidative decarboxylation of the 2-ethyl, 3-pentenyl and 4-hexenyl acids under the influence of lead tetraacetate, and a study was made of their oxidation by the acetate, trifluoroacetate and fluoborate of divalent copper.
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.