Showing papers by "G. I. Nikishin published in 1984"
TL;DR: In this paper, the Mn(OAc)3-LiCl system was used for the addition of chloromalonic esters to 1-hexene, 1-hexyne, norbornene, acrylonitrile, and methyl acrylate.
Abstract: The oxidative addition of chloromalonic ester to 1-hexene, 1-hexyne, norbornene, acrylonitrile, and methyl acrylate has been carried out under the influence of the Mn(OAc)3-LiCl system. It yields functionally substituted 1,3-dichlorides that are used for the synthesis of substituted 1,1-diethoxycarbonylcyclopropanes.
7 citations
TL;DR: In this paper, the authors carried out the oxidative addition of acetylacetone, ethyl acetoacetate, diethyl malonate to ethylene, 1hexene, and cyclohexene using Mn(III) acetate in the presence of LiCl, leading to the predominant formation of either mono- or dichloroadducts depending on the structure of the carbonyl compound and the olefin.
Abstract: 1.
We carried out the oxidative addition of acetylacetone, ethyl acetoacetate, diethyl malonate to ethylene, 1-hexene, and cyclohexene using Mn(III) acetate in the presence of LiCl, leading to the predominant formation of either mono- or dichloroadducts depending on the structure of the carbonyl compound and the olefin.
2.
1,1-Difunctional cyclopropanes were obtained from the chloro derivatives synthesized.
7 citations
TL;DR: In this paper, the action of catalytic amounts of copper ions in the presence of MX salts (M=K and Na, X=Cl, Br, I, SCN) leads to the decomposition of the hydroperoxides of C5-C7 cycloalkanones with the formation of ω-chloro-,ω-bromo-, ωiodo-, and ω -thiocyanoalkanoic acids
Abstract: The action of catalytic amounts of copper ions in the presence of MX salts (M=K and Na, X=Cl, Br, I, SCN) leads to the decomposition of the hydroperoxides of C5-C7 cycloalkanones with the formation of ω-chloro-,ω-bromo-, ω-iodo-, and ω-thiocyanoalkanoic acids
4 citations
TL;DR: The use of variable valency metals for the initiation of homolytic and ion-radical reactions has been studied in the literature as mentioned in this paper, and metal complexes have been used as oxidants of the reactants and the radicals formed from them.
Abstract: Investigations into the liquid phase reactions of functional aliphatic and alicyclic compounds which are initiated by peroxides and UV radiation constitute an important stage along the route of the conversion of free radical chemistry into a powerful instrument of contemporary organic synthesis. The progress made in recent years in the development of this route has been determined by the use of compounds containing variable valency metals for the initiation of homolytic and ion-radical reactions. Such compounds act as oxidants of the reactants and the radicals formed from them. 0ne-electron oxidants, ions, and metal complexes have significantly extended the range of homolytic reactions; they enable one to generate those radicals which cannot be prepared by other methods, and to convert alkyl groups into functional compounds readily.
3 citations
TL;DR: In this article, the reaction of the butyraldehyde with 1-heptene in acetic acid by the action of Mn(III) acetate (in an inert atmosphere) supports the previously proposed mechanism for the catalytic alkylation of aldehydes by olefins.
Abstract: The kinetics of the reaction of the butyraldehyde with 1-heptene in acetic acid by the action of Mn(III) acetate (in an inert atmosphere) supports the previously proposed mechanism for the catalytic alkylation of aldehydes by olefins. In accord with this mechanism, the selectivity in the formation of α-alkyl-substituted aldehydes is attributed to the reaction proceeding in the coordination sphere of the metal.
2 citations
1 citations
TL;DR: The LTA-Cu(OAc)2-mediated oxidation of tertiary cyclic alcohols produces cycloalkoxy radicals as mentioned in this paper, which undergo Β-fragmentation along two pathways: a) with ring opening to generate oxoalkyl radicals RCO(CH2)n-1CH2, which are oxidized quantitatively to Ω-unsaturated ketones, and b) with elimination of alkyl radicals (R.) and the formation of cycloencogenones.
Abstract: 1.
The LTA-Cu(OAc)2-mediated oxidation of tertiary cyclic alcohols produces cycloalkoxy radicals
(R=alkyl; n=4–5), which undergo Β-fragmentation along two pathways: a) with ring opening to generate oxoalkyl radicals RCO(CH2)n-1CH2, which are oxidized quantitatively to Ω-unsaturated ketones, and b) with elimination of alkyl radicals (R.) and the formation of cycloalkanones. This reaction forms the basis for the synthesis of Ω-unsaturated ketones.
2.
The relative rates for the two pathways of Β-decomposition depend upon the structure of the alkyl substituent. The frequency of Β-fragmentation via ring cleavage increases as the stability of the departing radical (R.) decreases:
$$\dot CH_3< RCH_2 \dot CH_2< CH_3 \dot CH_2< (CH_3 )_2 \dot CH< (CH_3 )_3 \dot C< C_6 H_5 CH_2$$
.
3.
The oxidation of 1-alkylcyclohexanols in which the alkyl groups exceed four carbon atoms results in the formation of alkoxy radicals which undergo oxidative cyclization and are converted into 2-alkyl-5-pentamethylenetetrahydrofurans.
1 citations
TL;DR: In this paper, a simple method for separating reaction products has been developed to distinguish reaction products in a sodium peroxydisulfate-sodium cyanide system, and the introduction of sodium hydroxide to the oxidizing system favors the increase in the yield of alkylureas and 2-(Alkylamino)alkanonitriles.
Abstract: 1.
In a sodium peroxydisulfate-sodium cyanide system, the aminyl radicals RCH2CH2NH generated from n-alky1amines undergo N-cyanation to form alkylureas, and are oxidized to aldimines, predecessors of N-alkyl alkanamides and 2,5,6-trialkyl-1,3-diox-4-enes.
2.
The introduction of sodium hydroxide to the oxidizing system favors the increase in the yield of alkylureas and alkyl cyanamides to 70%. 2-(Alkylamino)alkanonitriles are also formed. A simple method for separating the reaction products has been developed.
3.
In the oxidation of sec-alkylamine, cyclohexylamine, oxidative deprotonation predominates over the N-cyanation reaction.
1 citations
TL;DR: The use of peroxydisulfate instead of the peroxysulfate-monovalent silver system as the oxidant favors the oxidative rearrangement of alkanal cyanohydrins into cyanoalkanoic acids due to a decrease in the competitive transformation into alkanoic acid.
Abstract: 1.
Alkanal cyanohydrins (R(CH2)4CH(OH)CN (R=H, alkyl) are transformed into 4- and 5-cyanoalkanoic and alkanolc acids: RCH2CH(CN)CH2CH2COOH, RCH(CN)CH2CH2CH2COOH, and R(CH2)4·COOH, under the effect of peroxydisulfate ions on heating (60–80°C).
2.
The use of peroxydisulfate instead of the peroxydisulfate-monovalent silver system as the oxidant favors the oxidative rearrangement of the alkanal cyanohydrins into cyanoalkanoic acids due to a decrease in the competitive transformation into alkanoic acids, and also permits obtaining cyanoalkanoic and alkanoic acids with a higher total yield.
3.
The formation of the cyanohydrin cation-radical and its isomerization with 1,5- and 1,6-migration of the hydrogen atom are the most probable initial stages of the reaction of peroxydisulfates with alkanal cyanohydrins.
1 citations
TL;DR: The biuret complexes of Cu(II) and Cu(III) are efficient catalysts for the decomposition of organic hydroperoxides and H2O2 in water at room temperature as discussed by the authors.
Abstract: 1.
The biuret complexes of Cu(II) when treated with 2-methyltetrahydro-2-furyl peroxide in water are converted to diamagnetic Cu(III) compounds.
2.
The biuret complexes of Cu(II) and Cu(III) are efficient catalysts for the decomposition of organic hydroperoxides and H2O2 in water at room temperature.
TL;DR: The mechanism of the reaction, consisting of homolytic decomposition of two molecules of peroxide in the coordination sphere of Co(III), was proposed based on the study of the kinetics of decomposition in α-hydroxethyl peracetate catalyzed by cobalt acetate in a solution of acetaldehyde as discussed by the authors.
Abstract: 1.
The mechanism of the reaction, consisting of homolytic decomposition of two molecules of peroxide in the coordination sphere of Co(III), was proposed based on the study of the kinetics of decomposition of α-hydroxethylperacetate catalyzed by cobalt acetate in a solution of acetaldehyde.
2.
In the thermal decomposition of α-hydroxyethylperacetate, a homolytic reaction of decomposition of the peroxide with liberation of CH4, and CO2 takes place in addition to the monomolecular heterolytic reaction of formation of acetic acid.
TL;DR: In this article, the Na2S2O8-CuCl2 oxidizing system was used to convert O-methylpentanehydroxamic acid to a mixture of γ- and δ-valerolactones, with a significant preponderance of β-lactone.
Abstract: 1.
N,O-unsubstituted alkanehydroxamic acids R(CH2)4CONHOH (where R=H or Me) are convered in the Na2S2O8-CuCl2 oxidizing system to γ-lactones and 3-chloroalkanoic acids, respectively, by way of N-hydroxyamidyl radicals R(CH2)4CONHO and amidoxyl radicals R(CH2)4C(O)NHO.
2.
In the Na2S2O8-CuCl2 oxidizing system O-methylpentanehydroxamic acid is converted to a mixture of γ- and δ-valerolactones, with a significant preponderance of γ-lactone.
TL;DR: As a result of the reaction of cyclopentanol and cyclohexanol with the Pb(OAc)4-LiCl and Pb[OAc]4-Cu(OAC)2 systems, ω-formylalkyl radicals CH2(CH2)n+1CHO (n=2, 3) are formed, which are oxidized by these systems into ωchloroalkanals and ωalkenals, respectively as discussed by the authors.
Abstract: As the result of the reaction of cyclopentanol and cyclohexanol with the Pb(OAc)4-LiCl and Pb(OAc)4-Cu(OAc)2 systems, ω-formylalkyl radicals CH2(CH2)n+1CHO (n=2, 3) are formed, which are oxidized by these systems into ω-chloroalkanals and ω-alkenals, respectively.