Showing papers by "G. I. Nikishin published in 1982"
TL;DR: In this paper, LiCl was introduced to the acacH + 1-hexene + Mn(OAc)3 + AcOH system, which led to the formation of CH3COCHClCOCH3, which can be oxidatively added to 1hexene to give 3-acetyl-3,5-dichloro-2-nonanone.
Abstract: The reaction between acetylacetone (acacH) and 1-hexene in the presence of Mn(III) acetate in excess of acetic and trifluoroacetic acids leads to the preferential formation of substituted dihydrofuran. The introduction of LiCl to the acacH + 1-hexene + Mn(OAc)3 + AcOH system changes the course of the reaction and leads to the formation of CH3COCHClCOCH3, which can be oxidatively added to 1-hexene to give 3-acetyl-3,5-dichloro-2-nonanone.
3 citations
TL;DR: In this paper, it was shown that the principal path followed in the oxidative addition of acetone to aromatic compounds (ArH) under the action of Mn(III) acetate in AcOH solution to be the formation of a [CH2=C(CH3)-OMnIII·ArH] complex, which breaks down with rupture of the MnIII-O bond and subsequent addition of the acetonyl radical to the coordinated ArH (limiting step); this is, in turn, followed by rapid one-electron oxidation of the intermediate adduct radical
Abstract: Kinetic data indicate that the principal path followed in the oxidative addition of acetone to aromatic compounds (ArH) under the action of Mn(III) acetate in AcOH solution to be the formation of a [CH2=C(CH3)-OMnIII·ArH] complex, which breaks down with rupture of the MnIII-O bond and subsequent addition of the acetonyl radical to the coordinated ArH (limiting step); this is, in turn, followed by rapid one-electron oxidation of the intermediate adduct radical by the Mn(III) ion, and formation of the final product.
1 citations
TL;DR: In this paper, the Hoffmann type rearrangement in a Na2S2O8-NaCl-NaOH system was used to convert the alkanoic acid amides into amines containing one carbon atom less than the initial amides.
Abstract: 1.
Unsubstituted alkanoic acid amides R(CH2)4CONH2 (R=H or alkyl) convert in Na2S2O8-CuCl2 and Na2S2O8-NaCl oxidation systems via intermediate amidyl radicals R(CH2)4C(O)NH intoγ- and δ-lactones with a considerable predominance ofγ-lactones.
2.
Monoalkyl amides of alkanoic acids are lactonized to an inappreciable extent by the action of the S2O82−-Cl− system; N,N-diethyl valeramide undergoes oxidative dealkylation into N-alkyl valeramide.
3.
As the result of an oxidative, Hoffmann type rearrangement in a Na2S2O8-NaCl-NaOH system, unsubstituted alkanoic acid amides convert into amines containing one carbon atom less than the initial amides.
1 citations
1 citations
TL;DR: In this article, a method has been developed for generating free radicals by introducing salts containing complex-forming anions into a system consisting of Cu(II) aquo ions and a hydroperoxide.
Abstract: 1.
A method has been developed for generating free radicals by introducing salts containing complex-forming anions into a system consisting of Cu(II) aquo ions and a hydroperoxide. The radical nature of the reaction has been confirmed by the inhibitor method.
2.
Data have been obtained indicating the formation of hydroxyl radicals in the decomposition of hydroperoxides under the influence of Cu(II) complexes.
3.
Mixed complexes of Cu(II) with hydroperoxides in an aqueous medium are ionic in character, as indicated by results obtained in potentiometric measurements.
TL;DR: In this paper, the K3Fe(CN)6-NaOH system on heptylamine also leads to its N-cyanation with the formation of N-heptylurea, which is readily hydrolyzed under the reaction conditions.
Abstract: 1.
By the action of the K3Fe(CN)6-NaOH system, primary alkylamines RCH2NH2 are oxidized into alkanoic acid nitriles RCN. The action of the K3Fe(CN)6-NaOH system on heptylamine also leads to its N-cyanation with the formation of N-heptylurea, which is readily hydrolyzed under the reaction conditions.
2.
By the action of the K3Fe(CN)6-NaOH system, primary sec-alkylamines R,R'CHNH2 convert into alkylhydrazones of alkanones RR'C=N-NHCHRR' as the result of oxidative dimerization.
TL;DR: As a result of a radical reaction between tetrachloroethylene and aliphatic alcohols in liquid phase, not only products of the substitution of hydrogen at theα-C atom of the alcohol for the trichlorovinyl group, but also isomers with a trichlo-vinyl group at other C atoms, preferably in theω-1 position, are formed as discussed by the authors.
Abstract: As the result of a radical reaction between tetrachloroethylene and aliphatic alcohols in liquid phase, not only products of the substitution of hydrogen at theα-C atom of the alcohol for the trichlorovinyl group, but also isomers with a trichlorovinyl group at other C atoms, preferably in theω-1 position, are formed.