Pyridylethylation of cyclic thioamides and amides. I. Pyridylethylation in the tetrazole and 1, 2, 4-triazole series

1-Aryltetrazoline-5-thiones and 4-aryl-1, 2, 4-triazolyl-3-thiones which are cyclic amides and potential mercapto compounds have been 2-pyridylethylated for the first time. It is shown that in the compounds prepared the 2-pyridylethyl-2 group is on the nitrogen atom of the thioamide group, so that the above compounds react as thiones.     

Composés sulfurés hétérocycliques. CII. Action de l'hydroxylamine sur les dihydro-1,2 benzothiazine-3,1 thiones-4

Hydroxylamine reacts with 1-alkyl-1,2-dihydro-3,1-benzothiazine-4thiones ( 1 ), giving 1-alky1-3-hydroxy-2,3-dihydro-1H-quinazoline-4-thiones ( 2 ). The same reagent, in neutral medium, converts 1-aryl-1,2-dihydro-3,1-benzothiazine-4-thiones ( 3 ) into 1-aryl-4-hydroxyimino-1,4-dihydro-2H-3,1-benzothiazines ( 4 ). In acidic medium, the same starting materials lead to 1-aryl-3-hydroxy-2-3-dihydro-1H-quinazoline-4-thiones ( 5 ). genrally with some quantity of the isomer 4 . Thiones 2 and 5 , as well as oximes 4 , heated at 200°, decomopose, yielding, in varying proportions, 1H-quinazoline-4-thiones ( 6 or 7 ), 1H-quinazoline-4-ones ( 9 ) and 2,3-dihydro-1H-quinazoline-4-thiones ( 11 ). Reacting with methyliodide, 1H-quinazoline-4-thiones ( 7 ) give 4-methylthioquinazolin-1-ium iodidies ( 12 ) which can be hydrolysed into 1H-quinazolin-4-ones ( 9 ). The latter are also obtained by reacting benzonitrile N-oxide with the corresponding thiones. 1-Aryl-1 H-quinazoline-4-thiones ( 7 ) react readily with nitrogen nucleophiles XNH₂ to give 1-aryl-4-imino-1,4-dihydro-quinazolines diversely substituted on the imino group. While thiones 7 are S- methylated by methyl iodide, the corresponding 1-aryl-1H-quinazolin-4-ones (9), with the same reagent, ungergo a N-methylation, yielding 1-aryl-3-methyl-4-oxo-3,4-dihydroquinazolin-l-ium iodides ( 18 ). Structure have been confirmed by uv, ir and nmr spectra.     

Reduction of 4-hydroxy(alkoxy)hexahydropyrimidine-2-thiones and 1,2,3,6-tetrahydropyrimidine-2-thiones by the NaBH4-CF3COOH system. Synthesis of hexahydropyrimidine-2-thiones

A convenient method for the synthesis of hexahydropyrimidine-2-thiones by the reduction of the readily accessible 4-hydroxy(alkoxy)hexahydropyrimidine-2-thiones and 1,2,3,6-tetrahydropyrimidine-2-thiones by the NaBH₄-CF₃COOH system was proposed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1378–1388, October, 1993.     

4- and 5-Hydroxylaminothiazolidine-2-thiones. Reaction with 4-nitrobenzaldehyde

Stable nitrones are formed in the condensation of 5-hydroxylaminothiazolidine-2-thiones with 4-nitrobenzaldehyde. At the same time, nitrones obtained from the isomeric 4-hydroxylaminothiazolidine-2-thiones, as well as 4-hydroxylaminoimidazolidin-2-one, can undergo rearrangement to E- or Z-O-substituted 4-nitrobenzaldoximes, depending on the structure and the reaction conditions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 544–548, April, 1991.     

Cycloadditionen von Heterocumulenen an CN-Bindungssysteme. 3. Mitteilung. Bildung von Dihydro-1,3,5-oxadiazin- und Perhydro-s-triazinthionen bei der Reaktion von Iminodithiocarbonaten und Azomethinen mit Aroylisothiocyanaten

The iminodithiocarbonates 5a–5g and the N-(p-methoxybenzylidene)amines 6a–61 undergo 4 + 2-cycloaddition with the aroyl isothiocyanates 4a–4f to yield the expected dihydro-1,3,5-oxadiazine-4-thiones 7, 8 and 14 . The addition of the aroyl isothiocyanates 4a–4f to the azomethines 11a–11c and 15a–15f , however, furnishes both the 4 + 2-cycloaddition products 12 and 16 and the perhydro-s-triazine-2-thiones 13a–13j . The mechanism of formation is discussed.     

Nucleophilic substitution at the C(4) atom in series of functionally 4-substituted hexahydropyrimidine-2-thiones. Synthesis of 4-alkylthiohexahydropyrimidine-2-thiones

Nucleophilic substitution at the C₍₄₎ atom in 4-hydroxy(alkoxy)hexahydropyrimidine-2-thiones under the influence of alkanethiols in acidic, neutral, and basic media, as a result of which 4-alkylthiohexahydropyrimidine-2-thiones are formed, was studied. Hydrolysis and alcoholysis of the latter lead to the corresponding 4-hydroxy- or 4-alkoxyhexahydropyrimidine-2-thiones. The three-dimensional structures of the 4-alkylthiopyrimidines obtained were established by PMR spectroscopy, and it was shown that the stereoisomers with an axially oriented alkylthio group are thermodynamically more stable.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 234–240, February, 1988.     

Une nouvelle reaction de transposition: acces facile a des thiopyranne thiones a partir de (dimethylamino-2 vinyl)-5 alkylthio-3 dithiole-1,2 yliums

Reduction by potassium borohydride of 5-(2-dimethylaminovinyl) 3-alkylthio 1,2-dithiole yliums yields, 4-alkylthio 2H-thiopyranne 2-thiones, or 2-alkylthio 4H-thiopyranne 4-thiones (depending on the alkyl group); these react with secondary amines to yield 4-amino 2H-thiopyranne 2-thiones.     

The Action of Carbon Disulfide and Sulfur on Enamines,Ketimines, and CH Acids

The reaction of sulfur, carbon disulfide, and enamines at room temperature leads mainly or exclusively to 3H-1,2-dithiole-3-thiones; these are occasionally accompanied by 2H-1,3-dithiole-2-thiones, which can also be prepared by a modified procedure. Many enamines react with sulfur at room temperature to form thioamides. At about 50°C, enamines of acetophenone give 2-benzylidene-4-phenyl-2H-1,3-dithiol. The action of isothiocyanates and sulfur on enamines leads to the formation of thiazolidine-2-thiones. 2H-Thiopyran-2-thiones can be prepaAred from enamines or dienamines with carbon disulfide at room temperature. The reaction of ketimines (Schiff bases) with carbon disulfide and sulfur yields 3H-1,2-dithiole-3-thiones or isothiazoline-5-thiones. The reaction of alkynes with sulfur and carbon disulfide leads to 2H-1,3-dithiole-2-thiones. Nitriles containing active methylene groups react with carbon disulfide and sulfur to form 5-amino-3H-1,2-dithiole-3-thiones. When isothiocyanates are used instead of CS₂, the reaction leads to δ⁴-4-amino-thiazoline-2-thiones.     

Additionsreaktionen von 2-Thiazolin-5-thionen mit Acetylenen Vorläufige Mitteilung

Addition Reactions of 2-Thiazolin-5-thiones with Acetylenes The reaction of the 2-thiazolin-5-thiones 1 and 5 , respectively, with acetylen carboxylates yields mainly 1, 4-dithiafulvenes of type 3. In the presence of the acetylenic compounds, the 1, 4-dithiafulvenes undergo an isomerization to give the corresponding 2, 3-dihydrothiophene-2-thiones 4.     

Intramolecular rearrangement of substituted l,2,3,6-tetrahydropyrimidine-2-thiones

The intramolecular rearrangement of substituted 1,2,3,6-tetrahydropyrimidine-2-thiones to the isomeric 2-alkyl(aryl)amino-4H-1,3-thiazines was studied. The rearrangement proceeds in acid media to form the intermediate 4-hydroxyhexahydropyrimidine-2-thiones and their tautomeric 3-oxoalkylthioureas and is accompanied by ring cleavages of the tetrahydropyrimidine-2-thiones.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1690–1694, December, 1970.     

Conversion of 4- and 5-hydroxyaminothiazolidine-2-thiones under the action of alkalis

5-Hydroxyaminothiazolidine-2-thiones are oxidized in an alkaline medium to 5-hydroxyiminothiazolidine-2-thiones or undergo recyclization to derivatives of imidazolidine-2-thiones, depending on their structure. 4-Hydroxyaminothiazolidine-2-thiones break down under analogous conditions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1143–1145, August, 1989.     

4-Thiazoline-2-thiones. IV. Preparation from amino acids

4-Thiazoline-2-thiones derived from amino acids have been obtained by an improved procedure. Depending on substitution, the type of intermediate product isolated may be a 4-hydroxythiazolidine-2-thione or a dithiocarbamate.     

Reactions of 1,3-thiazine-2,6-dithiones. Part 5. Novel synthesis of 3,5-dicyano-4-thiopyridones via 2-cyanomethyldihydro-1,3-thiazine-6-thiones

A novel synthesis of a series of 2,6-disubstituted 3,5-dicyano-4-thiopyridones 4 by the decomposition of 2,4-disubstituted 5-cyano-2-cyanomethyldihydro-1,3-thiazine-6-thiones 2 , which are synthesized from 4-substituted 5-cyano-1,3-thiazine-2,6-dithiones and enaminonitriles, is described.     

Synthesis,structure, and reactivity of l,2,3,6-tetrahydropyrimidine-2-thiones

Dehydration of 4-hydroxyhexahydropyrimidine-2-thiones formed 1,2,3,6-tetrahydropyrimidine-2-thiones containing no substituent at the C₍₄₎ carbon atom. It is shown that the synthesized compounds, in contrast to their 4-alkyl-substituted analogs, react easily with various nucleophilic reactants (alcohols, butylmercaptan, benzenesulfinic acid, hydrazoic acid, p-toluidine) to form the corresponding 4-functionally substituted hexahydropyrimidine-2-thiones.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1259–1270, September, 1993.     

Heterocyclic compounds from 3,3-dimercapto-1-aryl-2-propen-1-ones. Note 3. Condensation with N-methyl-o-phenylenediamine and N-benzyl-o-phenylenediamine

Two seven-membered ring compounds and three five-membered ring compounds were obtained by reaction in hot xylene of 3,3-dimercapto-l-phenyl-2-propen-1-one (1) with N-alkyl-o-phenylenediamines (2) . Compounds isolated were the 4-phenyl-5-alkyl-1,5-dihydro-2H-1,5-benzodiazepine-2-thiones (3) the 1-alkyl-4-phenyl-1,3-dihydro-2H-1,5-benzodiazepine-2-thiones (4) , the 1-alkyl-2-phenacylbenzimidazoles (5) , the 1-alkyl-2-phenylbenzimidazoles (6) and the 1-alkyl-2-methylbenzimidazoles (7) . The structures of these compounds were elucidated from their chemical reactivity and their nmr and ir spectra.     

Synthesis of 3-oxoisothiazolo[5,4-b] pyridines

3-Oxoisothiazolo[5,4-b]pyridines were synthesized for the first time by the reaction of 3-cyanopyridine-2-thiones or bis(3-cyanopyridyl) disulfides with concentrated sulfuric acid. It is demonstrated that 3-carbamoylpyridine-2-thiones are formed as intermediates. The 3-oxoisothiazolopyridines were converted to 3-bromoisothiazolopyridines and pyridine-2-thiones. The bromination of pyridine-2-thione was studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 508–512, April, 1982.     

Synthesis and properties of azoles and their derivatives. 36. Synthesis of 2-amino-1,3,4-oxadiazoles, 2-amino-1,3,4-thiadiazoles,and 1,2,4-triazoline-3-thiones containing indolyl radicals

On the heterocyclization of 1-(indol-3-ylcarbonyl)thiosemicarbazides, depending on the conditions of performing the reaction, either 1,2,4-triazoline-3-thiones, 2-amino-1,3,4-thiadiazoles, or 2-amino-1,3,4-oxadiazoles containing an indolyl residue in position 5 are obtained. 1,2,4-Triazoline-3-thiones and 2-amino-1,3, 4-thiadazoles have also been synthesized by the reaction of the hydrochloride of ethyl indol-3-carboximidate with thiosemicarbazides.For communication 35, see [1].Translated from Khimiya Geterotsilicheskikh Soedinenii, No. 9, pp. 1271–1276, September, 1984.     

1,4-Dithiafulvene aus der Umsetzung von 4,4-disubstituierten 1,3-Thiazol-5(4H)-thionen mit Acetylenderivaten

1,4-Dithiafulvenes, Products of the Reaction of 4,4-Disubstituted 1,3-Thiazol-5(4H)-thiones and Acetylenic Compounds On heating in toluene, 4,4-disubstituted 1,3-thiazol-5(4H)-thiones 1 and acetylenecarboxylates or acetylenecarbonitriles 2 undergo a cyclosubstitution reaction to yield 2-methylidene-1,3-dithiol derivatives 3 (1,4-dithiafulvenes) and a nitrile. Further heating of 3a and 3b in the presence of excess 2a leads to the isomeric 2,3-dihydrothiophene-2-thiones 4a and 4b , respectively. The benzodithiafulvene 14 has been formed in a similar reaction from 1a and in situ generate benzyne.     

Synthesis of heterocycles. Part VI. Synthesis and antimicrobial activity of some 4-amino-5-aryl-1,2,4-triazole-3-thiones and their derivatives

4-Amino-5-aryi-1,2,4-triazole-3-thiones I react with acid chlorides to yield 4-acylamino-5-aryl-1,2,4-triazole-3-thiones II. Compounds I also react with methylene iodide, chloroacetonitrile and methyl bromoacetate to give bis-(4-amino-5-aryl-1,2,4-triazol-3-ylthio)methanes III, 4-amino-5-aryl-3-cyanomethylthio-1,2,4-triazoles IV and 4-amino-5-aryl-3-carbomethoxymethylthio-1,2,4-triazoles V, respectively. Compounds V react with hydrazine hydrate to give the corresponding acid hydrazides VI which in turn condenses with acid chlorides and aldehydes to afford respectively 1-[(4-amino-5-aryl-1,2,4-triazol-3-ylthio)acetyl]-2-aroylhydrazines VII and aryl methylene (4-amino-5-aryl-1,2,4-triazol-3-ylthio)acethydrazones VIII. The antimicrobial activities of the above compounds were screened against different strains of bacteria and fungi.     

Synthesis of imidazoline-2-thiones and imidazolidine-2-thiones

1-Aryl (or alkyl)-4,5-( -glucopyrano)imidazolidine-2-thiones are obtained by condensation of 2-amino-2-deoxy- -glucose with aryl (or alkyl) isothiocyanates. 1-Aryl-4- -arabinotetrahydroxybutylimidazoline-2-thiones are prepared by reaction of N-arylamino-1-deoxy- -fructoses with potassium thiocyanate. A comparative structure study of both types of compound is reported.