V. I. Gostevskaya

Divinyl Sulfide as Synthetic Equivalent of Ethenethiolate and 3-Butenethiolate Anions in Nucleophilic Substitution in Halopyridines and Haloalkanes

The use of divinyl sulfide as synthetic equivalent of ethenethiolate and 3-butenethiolate anions makes it possible to obtain vinylthio(halo)- and 3-butenylthio(halo)pyridines from halopyridines. 2,6-Bromo(chloro)pyridines react with a mixture of ethenethiolate and 3-butenethiolate ions more readily than does 3,5-dibromopyridine. The reaction yields mainly products of halogen replacement by vinylthio group. The formation of 3-butenethiolate ion in the reaction of divinyl sulfide with sodium in liquid ammonia is governed by the order of mixing of the reactants. Possible ways of generation of 3-butenethiolate ion in the reaction with 1-bromobutane are discussed.

2,3,5,6-Tetra(vinylthio)difluorobenzene in reactions with difunctional nucleophiles

Reaction of 2,3,5,6-tetra(vinylthio)difluorobenzene with ethylene glycol affords 1,4-bis[2,3,5,6-tetra(vinylthio)-4-fluorophenoxy-1-ethyloxy-]-2,3,5,6-tetra(vinylthio)benzene, with diethylene glycol arises 2,3,5,6-tetra(vinylthio)-4-(4-hydroxyethoxyethyloxy)-1-fluorobenzene, with 1,5-diaminopentane forms 1,5-bis[2,3,5,6-tetra(vinylthio)-4-fluoroanilino]pentane; in reactions with 2-aminoethanethiol and 2-mercaptoethanol occurs substitution of two fluorine atoms by RS groups.

Synthesis of polyfunctionally substituted benzothiazines based on vinylthionahlobenzenes and 2-mercaptoethylamine

Regioselective nucleophilic substitution of the fluorine atoms in positions 2 and 5 of the benzene ring takes place in the reaction of 3,6-bis(vinylthio)-1,2,4,5-tetrafluoro- and 3-vinylthio-6-chloro-1,2,4,5-tetrafluorobenzenes with 2-mercaptoethylamine in isopropyl alcohol-water-dimethylformamide mixture at 40–45°C in the presence of KOH. The products of disubstitution obtained are converted into 1,4-benzothiazines on heating to 100°C in dimethylformamide in the presence of K2CO3 as a result of intramolecular substitution.

Fluorobenzo-1,4-thiazine oxides from bis-(vinylsulfinyl)-and bis(vinylsulfonyl)-fluorobenzenes and 2-aminoethanol

It has been established that 1, 2, 4, 5-tetrafluoro-3, 6-bis (vinylsulfinyl)- and 1, 2, 4, 5-tetrafluoro-3, 6bis(vinylsulfonyl)benzenes react with 2-aminoethanol by nucleophilic addition at the activated double bond with replacement of fluorine atoms on the benzene ring by the amino group of 2-aminoethanol to give 4, 9-bis(2 hydroxyethyl)-5,10-difluoro-1, 2, 3, 4, 6, 7, 8, 9-octahydrobenzo[1, 2-b; 5, 4-b]di-1, 4-thiazine 1,6-dioxide and 1, 1, 6, 6-tetraoxide respectively.

Reactions of 1,2,4,5-Tetrafluoro-3,6-bis(vinylsulfonyl)benzene with Nucleophilic Reagents Containing a Mercapto Group

Addition of 2-aminoethanethiol and 2-mercaptoethanol at both vinylsulfonyl groups of 1,2,4,5-tetrafluoro-3,6-bis(vinylsulfonyl)benzene occurs through the thiol group of the reagent and yields the corresponding 3,6-bis[2-(2-aminoethylthio)ethylsulfonyl] and 3,6-bis[2-(2-hydroxyethylthio)ethylsulfonyl] derivatives. The reaction of the title compound with 1,2-ethanedithiol leads to formation of only polymeric addition products.

New heterocyclic system based on vinylsulfonylfluorobenzene and X-ray structural study of this compound

Oxidation of 1,2,4,5-tetrafluoro-3,6-bus (vinylthio)benzene (1) affords 1,2,4,5-tetra fluoro3,6-bis(vinylsulfonyl)benzene (2) in 65 % yield. The reaction of compound 2 with allylamine gives a new heterocyclic compound, 5,6-difluorobenzo-[a,d]-bis(3,3′-dihydro-l,l′-sulfonylallyl-4,4′-perhydroazine) (3). This compound is the product of nucleophilic addition at the vinylsulfonyl group and intramolecular replacement of fluorine atoms of the benzene ring. The structure of compound 3 has been established by X-ray structural study.

Conformation of S-vinyl-N,N-diethyldithiocarbamate and C-H...S intramolecular interaction between atoms of olefinic hydrogen and sulfur of thiocarbonyl group according to1H and13C NMR data

According to1H and13C NMR data, in S-vinyl-N,N-diethyldithiocarbamate, which exists primarily in the s-trans conformation with a syn-position of the thiocarbonyl and vinyl groups, a specific interaction C-H...S apparently takes place between the α-hydrogen atoms of the vinyl group and the thiono sulfur.

Preparative synthesis of divinyl ditelluride

The only known method for the production of divinyl ditelluride (I) with a 67% yield is based on the reaction of the intermediate CH/sub 2/=CHTeMgBr with water during oxidation by air. The authors have proposed a preparative method for the synthesis of the ditelluride (I) with a yield of 70% by the reaction of divinyl telluride with metallic sodium in liquid ammonia, followed by treatment with water in air. The formation of the ditelluride (I) evidently results from oxidation of the vinyltelluride anions, formed under the conditions of the decomposition of divinyltelluride, by atmospheric oxygen.

Synthesis of Hexakis(vinylthio)benzene

Exhaustive nucleophilic replacement of fluorine atoms in hexafluorobenzene by vinylthio groups was accomplished by the action of sodium ethenethiolate in dimethylformamide-liquid ammonia at -5 to 0°C.

Stereo specificity of the direct13C-1H spin-spin coupling constants of the vinylthio group in alkyl vinyl sulfides

The direct13C-1H coupling constants in the vinylthio group are stereospecific and depend on the conformation of the vinyl sulfide.