Showing papers by "G. I. Nikishin published in 1988"
TL;DR: In this paper, the kinetics and mechanism of intramolecular hydroacylation catalyzed by complexes Co2(μ-N2)(PPh3)6 (III) and (PPh 3)2Co(dppe) (IV) (dppe-1,2-bis(di-phenylphosphino)ethane) were studied.
32 citations
TL;DR: The formation of cycloalkoxy, α-hydroxycycloalkyl, and ω-formylalkyl radicals in the oxidation of secondary cyclic alcohols by Pb(OAc)4 was recorded by an EPR method in the presence of spin traps as discussed by the authors.
Abstract: 1.
The formation of cycloalkoxy, α-hydroxycycloalkyl, and ω-formylalkyl radicals in the oxidation of secondary cycloalkanols by Pb(OAc)4 was recorded by an EPR method in the presence of spin traps.
2.
In the presence of the Pb(OAc)4-Cu(II) system, the ability of secondary cyclic alcohols to undergo oxidative decyclization with the formation of ω-alkenals decreases in the series cyclopentanol > cycloheptanol > cyclohexanol > cyclooctanol.
6 citations
TL;DR: The selective electrochemical bromoalkoxylation of olefins has been achieved using a membrane-free (diaphragmless) cell to give bromomethane in 60-95% yields, under conditions of cathodic conversion of dibromides formed via competing side reactions back to olefin precursors.
Abstract: 1.
The selective electrochemical bromoalkoxylation of olefins has been achieved using a membrane-free (diaphragmless) cell to give bromoethers in 60–95% yields, under conditions of cathodic conversion of dibromides formed via competing side reactions back to the olefin precursors.
2.
Bromide ion has been found to catalyze the electrochemical addition of methanol to allylbenzene, resulting in the formation of ethers in 75% yield.
2 citations
TL;DR: The results of the reaction depends to a significant degree on the temperature and the nature of the cation in the catalyst carrier as mentioned in this paper, and each of the enumerated esters can be obtained with the yield of 50-80%.
Abstract: 1.
The throughgoing electrochemical oxidation of esters of malonic acid in the presence of catalyst carriers — salts of hydriodic acid — in methanol and ethanol leads to esters of ethylenetetracarboxylic acid and the products of the addition to it of alcohols and dialkyl malonates, namely 1-alkoxyethane-1,1,2,2-tetracarboxylic and propane-1,1,2,2,3,3-hexacarboxylic esters.
2.
The results of the reaction depends to a significant degree on the temperature and the nature of the cation in the catalyst carrier. Under optimal conditions, each of the enumerated esters can be obtained with the yield of 50–80%.
2 citations
TL;DR: The Na2S2O8-alkali metal chloride system in water in the presence of sulfuric acid gives 1,1-dialkoxy-2-chloroalkanes as discussed by the authors.
Abstract: The oxidation of primary aliphatic alcohols by the Na2S2O8-alkali metal chloride system in water in the presence of sulfuric acid gives 1,1-dialkoxy-2-chloroalkanes.
1 citations
TL;DR: In this paper, it was shown that dialkyl sulfones with systems containing sodium peroxydisulfate results in remote functionalization, the site of which is dependent on the length of the alkyl chain, in agreement with polar control of this reaction by the electronacceptor sulfonyl group.
Abstract: 1.
Oxidation of dialkyl sulfones with systems containing sodium peroxydisulfate results in remote functionalization, the site of which is dependent on the length of the alkyl chain, in agreement with polar control of this reaction by the electron-acceptor sulfonyl group.
2.
Butyl alkyl sulfones are selectively oxidized by Na2S2O8 to 3-oxobutyl alkyl sulfones, and oxidative chlorination in the system Na2S2O8-CuCl2 gives 3- and 4-chlorobutyl alkyl sulfones, the γ-chlorination products predominating.
1 citations
1 citations
TL;DR: Secondary cyclic alcohols with C5-C8 ring size are oxidized by the lead tetraacetate-metal chloride or bromide system in three directions as mentioned in this paper.
Abstract: Secondary cyclic alcohols with C5-C8 ring size are oxidized by the lead tetraacetate-metal chloride or bromide system in three directions: with ring cleavage and the formation of ω-haloalkanals and without ring cleavage with the formation of the corresponding ketones and also, for C7-C8, 1,4-epoxycycloalkanes.
TL;DR: In this paper, a mechanism has been proposed for the electrochemical oxidation of esters of ethane-1,1,2,2-tetracarboxylic acid, including the formation of the α-anion of the ester on a cathode, generation of a molecular halogen on the anode and their chemical transformations in solutions.
Abstract: 1.
Electrochemical oxidation of esters of ethane-1,1,2,2-tetracarboxylic acid in the presence of hydrohalic acid salts in acetonitrile leads to esters of ethylenetetracarboxylic acid; in alcohols not only an oxidative dehydrogenation takes place, but also esters of 1-alkoxyethane-1,1,2,2-tetracarboxylic acid are formed.
2.
When the reaction is carried out in methanol, the yield of the ester of ethylenetetracarboxylic acid and the ester of 1-methoxyethane-1,1,2,2-tetracarboxylic acid depends on the temperature, type of carrier-catalyst, and under the optimal conditions, each of the esters can be obtained in a yield of up to 80%.
3.
A mechanism has been proposed for the electrochemical oxidation of esters of ethane-1,1,2,2-tetracarboxylic acid, including the formation of the α-anion of the ester on a cathode, generation of a molecular halogen on the anode and their chemical transformations in solutions.
TL;DR: The reaction of trichloroallyl alcohol with sodium thiolates in DMF gave previously unreported 3,3-dialkyl- and 3, 3-diarylthio-2-chloro-2propen-1-ols in good yields.
Abstract: 1.
The reaction of trichloroallyl alcohol with sodium thiolates in DMF gave previously unreported 3,3-dialkyl- and 3,3-diarylthio-2-chloro-2-propen-1-ols in good yields.
2.
The analogous reaction with 1,1,2,3-tetrachloro-1-propene gave the products of the consecutive replacement of the allylic and two vinylic chlorine atoms by SR groups.
TL;DR: In this article, it was shown on the basis of quantum-chemical analysis by the LCAO-MO SCF method in the INDO approximation that the complexation of acyloxyl radicals with copper(II) salts and also their combination with chlorine atoms are factors which lead to the stabilization of these radicals and to the possibility of the realization of reactions with retention of the carboxy function.
Abstract: 1.
It was shown on the basis of quantum-chemical analysis by the LCAO-MO SCF method in the INDO approximation that the complexation of acyloxyl radicals with copper(II) salts and also their combination with chlorine atoms are factors which lead to the stabilization of these radicals and to the possibility of the realization of reactions with retention of the carboxy1 function.
2.
In the radical-cation RC(O)OH+ generated during the one-electron oxidation of carboxylic acids RCOOH the unpaired electron is concentrated mainly at the carbonyl oxygen atom, while in the acyloxyl radical RC(O)O it is delocalized at both oxygen atoms.