Showing papers by "G. I. Nikishin published in 1975"
TL;DR: In the absence of Cu(II) ions, these radicals in the mentioned solutions cleave H atoms from organic substrates and are converted to heptane, dimerize to the normal and branched tetradecanes, and are oxidized by Ag(I) to secondary heptanols.
Abstract: 1.
The 1- and 3-heptyl radicals were generated by reacting the octanoic and 2-ethyl-hexanoic acids with the oxidation systems Na2S2O8-AgNO3 and Na2S2O8-AgNO3-CuSO4 in aqueous or aqueous acetonitrile solution.
2.
In the absence of Cu(II) ions, these radicals in the mentioned solutions cleave H atoms from organic substrates and are converted to heptane, dimerize to the normal and branched tetradecanes, and are oxidized by Ag(II) to secondary heptanols. In addition, in aqueous solutions the 1-heptyl radicals are oxidized by the silver ions to 1-heptane.
3.
In aqueous solutions that contain CuSO4, the 1- and 3-heptyl radicals are converted to heptenes and the corresponding heptanols. Heptane and n-heptyl octanoate are also formed from the 1-heptyl radicals in aqueous acetonitrile solutions.
4.
The S2O 8 2− ions oxidize primary alkyl radicals to the corresponding primary alcohols. This reaction fails to occur in the presence of AgNO3.
3 citations
TL;DR: The reaction of peroxydicarboxylic acids (CH3OOC(CH2)nCOO)2 with Fe(II) sulfate leads to the selective generation of ω-carbomethoxyalkyl radicals CH 3OOC-(CH 2)n, n=2-5, 7, 8, 10 as mentioned in this paper.
Abstract: 1.
The reaction of the esters of peroxydicarboxylic acids (CH3OOC(CH2)nCOO)2 with Fe(II) sulfate leads to the selective generation of ω-carbomethoxyalkyl radicals CH3OOC-(CH2)n, n=2-5, 7, 8, 10.
2.
These radicals predominantly recombine under the influence of Fe(II) sulfate, while Cu(II) sulfate oxidizes them to the esters of the corresponding ω-unsaturated carboxylic acids, and Cu(II) chloride converts them to the esters of (ω-chlorocarboxylic acids.
1 citations
TL;DR: In contrast to the 3-carboxypropyl radical, which is oxidized by the system Na2S2O8-AgNO3-CuSO4 toγ-butyrolactone, the 1-alkyl-3-CARBOXYpropyl radicals are oxidized predominantly to the δ-α,β-butenolide.
Abstract: In contrast to the 3-carboxypropyl radical, which is oxidized by the system Na2S2O8-AgNO3-CuSO4 toγ-butyrolactone, the 1-alkyl-3-carboxypropyl radicals are oxidized predominantly to theγ-alkyl-Δα,β-butenolide.
TL;DR: In this paper, the reaction of lead tetraacetate with dicarboxylic acids of general formula RCH2CH(COOH) (R=Alk, n=1, 2, 3 or 10) in the presence of pyridine led to their selective oxidation decarboxylation and the generation of carboxyalkyl radicals.
Abstract: 1.
The reaction of lead tetraacetate with dicarboxylic acids of general formula RCH2CH(COOH)(CH2)n-COOH (R=Alk, n=1, 2, 3 or 10) in the presence of pyridine led to their selective oxidation decarboxylation and the generation of carboxyalkyl radicals RCH2ĊH(CH2)COOH. In a similar manner, the 1-(carbomethoxymethyl)nonyl and 2-carbomethoxycyclohexyl radicals were obtained from the monomethyl esters of the 2-octylsuccinic and cyclohexane-1,2-dicarboxylic acids.
2.
The main products when the radicals are oxidized with the Pb(IV) and Cu(II) carboxylates are alkenoic acids and their esters, γ- and δ-laetones (in the oxidation of the carboxylalkyl radicals with n = 2 and 3), and esters of acetoxy-substituted monocarboxylic acids (when oxidation is with Pb(IV) carboxylates).
3.
The carboxy and carbomethoxy groups in the 2- and 3-carboxy- and 2-carbomethoxyalkyl radicals direct the oxidativeΒ-deprotonation of these radicals under the influence of copper ions predominantly toward the formation of alkenoic acids or of their esters, where the double bond is further away from the functional group.