A. Yu. Sizov

Reactions of α-fluorine-containing β-functionalized vinyl sulfides with N-nucleophiles

Abstractα-Fluorine-containing β-functionalized vinyl sulfides readily react with N-nucleophiles to form α-fluorine-substituted products. The reactions with phenylhydrazines and amidines of acids are accompanied by cyclization at the functional group. Thermal cyclization of cyanotrifluoromethylketene N,S-acetals proceeds at the trifluoromethyl group to give substituted 3-cyanoquinolin-4-ones.

Reactions of 1,3,3,3-tetrafluoro-2-methoxycarbonylpropenylsulfenyl chloride with aromatic and heterocyclic compounds

Abstract1,3,3,3-Tetrafluoro-2-methoxycarbonylpropenylsulfenyl chloride readily reacts with activated aromatic and heterocyclic compounds to form C-sulfenylation products as Å isomers. In some cases, its reactions with phenolic compounds are accompanied by cyclization giving rise to fused 2-(2,2,2-trifluoro-1-methoxycarbonylethylidene)-1,3-oxathioles.

SYNTHESIS OF POLYFUNCTIONAL ALIPHATIC CARBONYL COMPOUNDS UNDER PHASE-TRANSFER CONDITIONS

We have studied mono- and dialkylation of malonic, acetoacetic, and cyanoacetic esters with esters of haloacetic and Β-halopropionic acids and addition of the CH acids mentioned and their analogs to methyl and ethyl acrylate under phase-transfer catalysis conditions, and also deethoxycarbonylation of the obtained products. We have demonstrated for the first time the possibility of Dieckmann cyclization under phase-transfer catalysis conditions and have developed a simple method for the synthesis of 2,3-di(ethoxycarbonyl)cyclopentanone, a key intermediate in the syntheis of deoxyprostaglandins, by cyclization of triethyl 1,2,4-butanetricarboxylate.

Chlorolysis of β-functionalized alkyl polyfluoroalkenyl sulfides

Chlorolysis of β-functionalized alkyl polyfluoroalkenyl sulfides giving rise to β-functionalized polyfluoroalkenesulfenyl chlorides was examined. β-Cyano-containing sulfenyl chlorides underwent intramolecular cyclization at the nitrile group to form substituted isothiazoles.

Organometallic synthesis in the furazan series. 2. Furazanylethanes

The reactions of Li derivatives of methylfurazans with electrophilic reagents and oxidants were investigated. A series of functionalized furazanylethane derivatives were prepared.

A new method for the synthesis of fluorinated vinyl sulfides and ketene dithioacetals

A new method was developed for the synthesis of fluorine-containing functionally substituted vinyl sulfides and ketene dithioacetals from the corresponding derivatives of α-trifluoromethyl-substituted CH-acids and thiols in the presence of BF3·NEt3.

Organometallic synthesis in the furazan series 1. Functionalization of 3-methyl-4-R-furazans

The possibility of synthesizing functionally substituted furazans by alkylation of lithium derivatives of 3-methyl-4-R-furazans was investigated. It was shown that one or both methyl groups of 3,4-dimethylfurazan could be lithiated and alkylated. A series of previously unknown furazan derivatives was obtained.

Synthesis of substituted thiophenes based on fluorine-containing β-functionalized vinyl sulfides

Derivatives of fluorine-containing 3-(methoxycarbonylmethylthio)acrylic acids readily undergo base-catalyzed cyclization to form 3-hydroxy- and 3-aminothiophenes.

Synthesis of esters of 2-substituted 4-ketopentanoic acids by the alkylation of CH-acids using chloroacetone under phase transfer catalysis conditions

An improved method was developed for the synthesis of ethyl esters of 2-substituted 4- ketopentanoic acids by the alkylation of CH2(X)CO2Et using chloroacetone in the liquid- solid KOH (K2CO3or Na2CO3DMF-PhCH2(Et)3NCl system.

Reactions of 1,3,3,3-tetrafluoro-2-methoxycarbonylpropenesulfenyl chloride with enamines

Abstract1,3,3,3-Tetrafluoro-2-methoxycarbonylpropenesulfenyl chloride readily reacts with enamines (derivatives of β-oxo acids) to give sulfenylation products. The reactions with N-aryl-substituted enamines are accompanied by cyclization to form N-aryl-2-(2,2,2-trifluoro-1-methoxycarbonylethylidene)-2,3-dihydrothiazoles.