Synthesis of 5-mercapto-1,2-dithiole-3-thiones and their transformation into 5-chloro-1,2-dithiol-3-ones

A number of 4-dialkylamino-5-mercapto-1,2-dithiole-3-thiones were synthesized by reactions of alkyl(diisopropyl)amines with S₂Cl₂. Their reactions with S₂Cl₂—DABCO unexpectedly gave 5-chloro-4-dialkylamino-1,2-dithiol-3-ones. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 143–147, January, 2006.     

Synthesis of 5-Formyl and 5-Acyl-1,2-dithiole-3-ones

The preparation of new 5-formyl-, 5-acetyl- and 5-propionyl-1,2-dithiole-3-ones by oxidation of the corresponding 1,2-dithiole-3-thiones with mercuric acetate is described.     

A convenient route to 4-mercapto-1,2-dithiole-3-thiones from terminal alkynes

4-Mercapto-1,2-dithiole-3-thiones are easily prepared by deprotonation of terminal alkynes followed by sequential treatment with carbon disulfide, sulfur and acid; addition of alkylating agents at the last stage gives 4-alkylthio-1,2-dithiole-3-thiones instead.     

Differentiation and electron ionization-induced isomerization of 4,5-Bis(alkylthio)-1,3-dithiole-2-thiones and 1,2-dithiole-3-thiones

The electron impact ionization mass spectra of 4,5-bis(alkylthio)-1,3-dithiole-2-thiones and their 1,2-dithiole-3-thione isomers were studied by accurate mass measurements and linked scans. The relative abundance of ions formed following the extrusion of S₂, CS or CS₂ allows an unambiguous isomer differentiation. Isomerization of molecular ions was studied by means of metastable ion analysis and collision-induced dissociation. The order of reactivity was analogous to that observed in isomerization under photochemical conditions.     

Studies of the reaction of 1,2-dithiole-3-thiones with nucleophiles

Substituted 1,2-dithiole-3-thiones react with nucleophiles (alkoxides, thiolates) to give various reaction products depending on the nucleophiles and on the substituents on the 1,2-dithiole-3-thione ring. The mechanistic aspects of these reactions are discussed.     

Electroorganic synthesis. Reductive alkylation of functionalized 1,2-dithiole-3-thiones

Two-electron reduction of some substituted 1,2-dithiole-3-thiones 1 followed by alkylation of the dianionic intermediates leads through electrosynthesis to mixture of Z and E isomers of the corresponding substituted alkyl-(3-thioalkyl)-2-propenedithioates 2, 3 in satisfactory yield. The structure of those products was established by ¹³C and ¹H nmr and mass spectroscopy. The isomers ratios were determined by nmr spectroscopy.     

Convenient one-pot syntheses of 1,2-dithiole-3-thiones and 3-imino-1,2-dithioles from terminal alkynes

The reaction of acetylide anions with carbon disulfide or phenyl isothiocyanate followed by addition of sulfur in the presence of a protonating agent such as a primary amine or alcohol affords 1,2-dithiole-3-thiones or 3-imino-1,2-dithioles in good to excellent yields.     

Selective synthesis of bis[1,2]dithiolo[1,4]thiazines from 4-isopropylamino-5-chloro-1,2-dithiole-3-ones

Reaction of 4-isopropylamino-5-chloro-1,2-dithiole-3-ones 3 and S₂Cl₂ in acetonitrile gave selectively 3-oxo-bis[1,2]dithiolo[1,4]thiazine-5-thiones 1 by the addition of triethylamine and bis[1,2]dithiolo[1,4]thiazine-3,5-diones 5 under the action of formic acid. 3,5-Diones 5 were also obtained by intramolecular cyclization of N,N-bis(5-chloro-3-oxo[1,2]dithiol-4-yl)amines 6 with S₂Cl₂ in the presence of Et₃N.     

Synthesis of 1,3-dithiin dithioortho esters from the reaction of Fischer carbenes and 3H-1,2-dithiole-3-thiones

[reaction: see text] Tricyclic 4-ethyl-5-thioxo-3H,5H-bis[1,2]dithiolo[3,4-d][4,3-b]pyrrol-3-one and monocyclic 3H-1,2-dithiole-3-thione derivatives reacted with Fischer carbene complexes, giving 1,3-dithiin dithioortho esters through insertion of the carbenic carbon into the S-S bond next to the thiocarbonyl function of the substrate.     

Chlorination and oxidation of 4-fluoro-5-tetrafluoroethyl-1,2-dithiole-3-thione

Chlorination of 4-fluoro-5-(1,1,2,2-tetrafluoroethyl)-1,2-dithiole-3-thione with an equimolar amount of chlorine or sulfuryl chloride gives 3-chlorosulfanyl-4-fluoro-5-(1,1,2,2-tetrafluoroethyl)-1,2-dithiolium chloride. The reaction of the title compound with excess chlorinating agent leads to 3,3,4,5-tetrachloro-4-fluoro-5-(1,1,2,2-tetrafluoroethyl)-1,2-dithiolane. By oxidation and oxidative imination of 4-fluoro-5-(1,1,2,2-tetrafluoroethyl)-1,2-dithiole-3-thione, the corresponding S-oxide and sulfimide were obtained, respectively.     

Synthesis of 5-alkyl(aryl)sulfanyl-4-chloro-3-trichloromethyl-1,2-thiazoles and 5-Alkyl(aryl)sulfanyl-4-chloro-1,2-thiazole-3-carboxylic acids

Butane-, phenylmethane-, and benzenethiols reacted with 4,5-dichloro-3-trichloromethyl-1,2-thiazole in the presence of sodium ethoxide to give the corresponding 5-alkyl(aryl)sulfanyl-4-chloro-3-trichloromethyl-1,2-thiazoles. The reaction of 4,5-dichloro-1,2-thiazole-3-carboxylic acid with the same thiols under similar conditions resulted in the formation of sodium 4,5-dichloro-1,2-thiazole-3-carboxylate, while in the presence of pyridine 5-alkyl(aryl)sulfanyl-4-chloro-1,2-thiazole-3-carboxylic acids were obtained.     

Reactions of 4-chloro-7-dialkylamino- and 3-alkyl-4-chloro-7-dialkylaminocoumarins with primary and secondary alkylamines

Reaction of series of 4-chloro-7-dialkylaminocoumarins and 3-alkyl-4-chloro-7-dialkylaminocoumarins with primary and secondary amines, namely tert-butylamine, benzylamine, cyclohexylamine, monoethanolamine, diethylamine, piperidine, and morpholine, has yielded novel substituted 4,7-diaminocoumarins. The PMR spectra of these newly synthesized compounds are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 836–841, June, 1990.     

Synthesis of 4-ethoxycarbonylmethyl-, 4-N-phenylcarbamoylmethyl-, and 4-carboxymethyl-1,3-dithiole-2-thiones and the corresponding 1,3-dithiolium salts

A method for the preparation of 4-ethoxycarbonylmethyl-, 4-N-phenylcarbamoylmethyl-, and 4-carboxymethyl-1,3-dithiole-2-thiones and the corresponding 1,3-dithiolium salts from -bromoacetoacetic ester, -bromoacetoacetanilide, and sodium tertbutyltrithiocarbonate was developed. The compounds were characterized by their IR and PMR spectra.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 180–183, February, 1984.     

Reactivity of 3H-1,2,4-dithiazole-3-thiones and 3H-1,2-dithiole-3-thiones as sulfurizing agents for oligonucleotide synthesis

The reactivity of 5-amino-3H-1,2,4-dithiazole-3-thiones substituted at their amino group and 5-amino-3H-1,2-dithiole-3-thiones substituted at their amino group and C4 toward compounds containing P(III) atoms has been studied. N,N-Disubstituted-N′-(3-thioxo-3H-1,2,4-dithiazol-5-yl)methanimidamides were selected as novel efficient sulfur transfer reagents suitable for DNA and RNA synthesis.     

Studies of the reaction of substituted 1,2-dithiole-3-thiones and -3-ones with sodium cyanide in acetonitrile

The reactions of substituted 1,2-dithiole-3-thiones and -3-ones with sodium cyanide, in acetonitrile, afford convenient routes to indolizine, pyrrolo[1,2-a]pyrazine and 4H-1,3-thiazin-4-one species.