Specific Features of Alkylation of Organic Hydroperoxides with Chlorinated Hydrocarbons in Superbasic Media

Alkylation of organic hydroperoxides with chlorinated hydrocarbons in superbasic media (dipolar nonhydroxyl solvent-strong ionic base) was performed.     

Oxidation of dimethyl sulfoxide with hydrogen peroxide in the presence of potassium hydroxide

Kinetic relationships in oxidation of DMSO to dimethyl sulfone with hydrogen peroxide in the presence of potassium hydroxide were studied. Kinetic parameters of the process were calculated. It was established that the reaction proceeded through the intermediate formation of potassium hydroperoxide.     

Alkylation of alkali metal salts of hydroperoxides with haloalkanes in dipolar nonhydroxyl solvents

The possibility of alkylation with chloroalkanes of cumyl hydroperoxide sodium salt hexahydrate in dopolar nonhydroxyl solvents with high donor numbers was examined. The kinetic featutes of the process in hexamethylphosphoric triamide were studied.     

Kinetic Features of Decomposition of Benzoyl Peroxide in Superbasic Media

Kinetics of decomposition of benzoyl peroxide in superbasic media comprising mixtures of a dipolar aprotic solvent and a strong ionic base is studied. The process occurs in two steps through formation of intermediate perbenzoate anion. The contribution of ionic reactions is controlled by the polarity and dielectric constant of the solvent. The decomposition products are molecular oxygen and an alkali metal benzoate or perbenzoate. These products can be alkylated with butyl bromide in superbasic media.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 5, 2005, pp. 803–808.Original Russian Text Copyright © 2005 by Lyavinets.     

General relations in heterogeneous alkylation of sodium carbonate in dimethyl sulfoxide

The kinetics of alkylation of sodium carbonate with 1-bromobutane in dimethyl sulfoxide were studied. The reaction was revealed to tend to autoinhibition. The mechanism of autoinhibition was established, ways of avoiding it were proposed, and the role of solvent in this process was described. Carbonate ion was found to react as ion pair with specifically solvated sodium cation.     

Synthesis of nitrogen-containing heterocycles on the basis of 3-(4-acetylphenyl)-1-methylquinolin-2(1<Emphasis Type="Italic">H</Emphasis>)-one

The Meerwein reaction of 1-methylquinolin-2(1H)-one with 4-acetylbenzenediazonium chloride gave 3-(4-acetylphenyl)-1-methylquinolin-2(1H)-one which was brominated to 3-[4-(2-bromoacetyl)phenyl]-1-methylquinolin-2(1H)-one. The latter reacted with pyridine, 4-methylpyridine, quinoline, benzo[f]quinoline, and triphenylphosphine to afford the corresponding quaternary salts, and its reactions with thioacetamide, thiourea, 2-aminopyridine, and 2-aminopyrimidine led to the corresponding thiazole, imidazo[1,2-a]pyridine, and imidazo[1,2-a]pyrimidine derivatives containing a 2-oxoquinoline fragment. 3-(4-{2-[2-(Arylmethylidene)-hydrazinyl]-1,3-thiazol-4-yl}phenyl)-1-methylquinolin-2(1H)-ones were obtained by condensation of 3-[4-(2-bromoacetyl)phenyl]-1-methylquinolin-2(1H)-one with thiosemicarbazide and aromatic aldehydes.     

Effect of base nature on the oxidation of dimethyl sulfoxide with hydrogen peroxide in superbasic media

Kinetic relationships of the dimethyl sulfoxide oxidation to dimethyl sulfone with hydrogen peroxide in the presence of an alkali (MOH) or sodium tert-butoxide were investigated. Kinetic parameters of the process were calculated. The process was found to proceed through the intermediate formation of the alkaline salts MeOOH. The effect of the base nature on the stage of salt formation and oxidation was revealed.     

Kinetics and Mechanism of Oxidation of Dimethyl Sulfoxide with Benzoyl Peroxide in Superbasic Media

Oxidation of dimethyl sulfoxide with benzoyl peroxide in some dipolar aprotic solvents and superbasic media was studied. The kinetic parameters were correlated with the main physicochemical characteristics of solvents. The oxidation rate grows with increasing donor number and polarizability of the solvent. A two-step scheme of dimethyl sulfoxide oxidation with benzoyl peroxide in superbasic media was suggested, involving preliminary cleavage of the peroxide to perbenzoate with the base. In the reaction, sodium tert-butylate is preferable over sodium hydroxide.