Showing papers by "G. I. Nikishin published in 1986"
9 citations
1 citations
TL;DR: The principal difference in the oxidative reactions of aliphatic thioamides and their oxygen analogs in a Na2S2O8-CuCl2 system is determined by the tendency of the S atom of the thiocarbonyl group to add radicals formed in the oxidation process.
Abstract: 1.
Oxidative cyclization of N-unsubstituted aliphatic thioamides in the Na2S2O8-CuCl2 system leads to 3,5-dialkyl-1,2,4-thiadiazoles in a yield of 50–60%.
2.
N-Monoalkyl- and N,N-dialkyl-substituted thioamides quantitatively convert in this system into the corresponding O-amides.
3.
The principal difference in the oxidative reactions of aliphatic thioamides and their oxygen analogs in a Na2S2O8-CuCl2 system is determined by the tendency of the S atom of the. thiocarbonyl group to add radicals formed in the oxidation process.
1 citations
TL;DR: One-step outlying oxidative chlorination of alkanesulfonamides by the action of the Na/sub 2/S/Sub 2/O/sub 8/-CuCl/sub2/ system via intermediate sulfonamidyl radicals gives 3- and 4-chloroalkanesulfamides as discussed by the authors.
Abstract: One-step outlying oxidative chlorination of alkanesulfonamides by the action of the Na/sub 2/S/sub 2/O/sub 8/-CuCl/sub 2/ system via intermediate sulfonamidyl radicals gives 3- and 4-chloroalkanesulfonamides. Rearrangements of sulfonamidyl radicals with H atom migration from the sulfonyl segment predominates over rearrangement with H atom migration from the amide segment.
TL;DR: In this paper, the reaction of 2-, 3-, and 4-methylcyclohexanols with the Pb(OAc)4,LiCl oxidizing system was confirmed by EPR with the use of a spin trap.
Abstract: 1.
In the reaction of 2-, 3-, and 4-methylcyclohexanols with the Pb(OAc)4,-LiCl oxidizing system, methylcyclohexylalkoxyl radicals are generated, and their formation was confirmed by EPR with the use of a spin trap.
2.
The 2- and 4-methylcyclohexylalkoxyl radicals are regioselectively rearranged into 1-methyl- and 3-methyl-5-formylamyl radicals, and the 3-methylcyclohexylalkoxyl radical decomposes in two directions, yielding 2-methyl- and 4-methyl-5-forraylarayl radicals. In the Pb(OAc)4-LiCl system, these radicals are quantitatively oxidized into chloroalkanals.
3.
The trans-2 and cis-3-methylcyclohexanols exhibit higher reactivity with respect to the Pb(OAc)4-LiCl system than cis-2 and trans-3-methylcyclohexanols. The reactivity of both isomers of 4-methylcyclohexanol is the same.
TL;DR: In this article, cyclopentanone and cyclohexanone cyanhydrins are converted to 5- and 6-cyanoalkanoic acids, while cycloheptanone is converted to 4-cyanocycloheptonone.
Abstract: 1.
Oxidative rearrangement of cycloalkanone cyanhydrins is most efficiently initiated by Ce(IV) ammonium nitrate and the S2O82−/Ag(I) and S2O82−/Ce(III) oxidant systems. Here the cyclopentanone and cyclohexanone cyanhydrins are converted to 5- and 6-cyanoalkanoic acids, while cycloheptanone cyanhydrin is converted to 4-cyanocycloheptanone.
2.
Rearrangement of cycloheptanone cyanhydrin to 4-cyanocycloheptanone also proceeds efficiently by the action of peroxydisulfate ion in the absence of silver and cerium ions.