Hydrothiolysis of di(2-thienyl) disulfide

Conclusions The hydrothiolysis of di(2-thienyl) disulfide by hydrogen sulfide at 130–180°C leads to the formation mainly of di(2-thienyl) sulfide. 2-Thiophenethiol is formed as a side-product due to the dissociation of the disulfide at the S-S bond and subsequent reaction of the thiol radicals with hydrogen sulfide. Di(2-thienyl) sulfide also undergoes secondary conversions to 2-thienyl 3-thienyl sulfide and 3-thiophenethiol by the addition of thiol radicals at C-3 of the thiophene ring.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2783–2785, December, 1985.     

Synthesis and nitration of dimethyl-(3-thienyl)sulfonium salts

Conclusions A method was developed for the synthesis of the difficultly accessible methyl (5-nitro-3-thienyl) sulfide, which consisted in the conversion of methyl 3-thienyl sulfide to the sulfonium salt, with subsequent nitration and demethylation.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1161–1163, May, 1973.     

Gas-phase Reaction of 2-Chlorothiophene with Hydrogen Sulfide in the Presence of Alcohols

The effect of methanol and ethanol on the route of the gas-phase reaction of 2-chlorothiophene with hydrogen sulfide, leading to 2-thiophenethiol and to bis(2-thienyl) sulfide, has been investigated. It was found that methanol significantly enhances this reaction and increases its selectivity for the thiol at higher temperatures than without the initiator. The optimal conditions were achieved at 570°C in the presence of 10 mole % of methanol when the conversion of the 2-chlorothiophene in the reaction with hydrogen sulfide reaches 98% and the yield of the thiophenethiol (43%) exceeds that of the bis(2-thienyl)sulfide (31%). In the absence of methanol the 2-thiophenethiol is formed only at 510-540°C in just 17% yield, the basic reaction product being the indicated sulfide (52% yield); the conversion of the 2-chlorothiophene does not exceed 54%.     

Thermal transformations of allyl 2-thienyl sulfide and selenide

In the gas phase at 350–410C allyl 2-thienyl sulfide is converted to thiophene-2-thiol, di(2-thienyl) sulfide, and 2-methylthieno[2,3-b]thiophene. In the presence of acetylene thieno[2,3-b]thiophene is formed in addition to these products. Allyl 2-thienyl selenide is converted quantitatively to 2,3-dihydro-2-methylselenopheno[2,3-b]thiophene during fractional distillation in vacuo. Thiophene, di(2-thienyl) selenide, di(2-thienyl) diselenide, thiophene-2-selenol, and 2-methylselenopheno[2,3-b]thiophene are formed in addition to these compounds in the thermolysis of allyl thienyl selenide in the gas phase. In the presence of acetylene the thermal decomposition of allyl thienyl selenide is accompanied by the formation of selenophene.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1312–1316, October, 1991.     

Thermal hydrothiolysis of di(2-thienyl)sulfide in the gaseous and liquid phase

At 500–600, di(2-thienyl)sulfide is converted to thiophene, thiophene thiols, dithienyls, and dithienothiophenes, and isomerized to 2,3-dithienylsulfide. Hydrogen sulfide accelerates these reactions significantly. In the liquid phase the thermal conversion of di(2-thienyl)sulfide takes place only with the participation of elemental sulfur or in the system sulfur-hydrogen sulfide. Thiophene and diethienothiophenes are not formed in this case, while isomerization occurs to a large degree. The observed thermal conversions of di(2-thienyl)-sulfide are based on the addition of thiyl radicals to the double bonds of the thiophene ring and to the sulfide sulfur atom.Communication 29 of the series High-temperature organic synthesis. For Communication 28 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1614–1619, December, 1986.     

[3,3]-Sigmatropic rearrangement of chloro-substituted allyl thienyl sulfides

The kinetics of the rearrangement of allyl 5-chloro-2-thienyl sulfide and -chloroallyl 2-thienyl sulfide to, respectively, 5-chloro-3-allyl-2-thiophenethiol and 3-(-chloroallyl)-2-thiophenethiol were investigated. It is shown that an acceptor substituent in the allyl group decreases the reactivity of the sulfide significantly, whereas an acceptor in the heterocyclic ring does not have an appreciable effect on it.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 181–183, February, 1982.     

α-Thienyl-substituted thiopyrilium salts

The perchlorates of 2,6-di(2-thiettyl)-4-methylpyrilium and -thiopyrilium, and the isomeric 2,4-di(2-thienyl)-6-methyl derivatives, as well as the perchlorates of 2,4-di(2-thienyl)pyriliurn with tri- and tetramethyl groups in the 5,6 position have been synthesized. Their UV and PMR spectra have been studied. Based on data on Oberhauser's nuclear effect it was concluded that the sulfur atoms of 2(6)-thienyl substituents and the O(S) atoms of heteroaromatic cations are present in the cis position.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 182–188, February, 1994. Original article submitted February 21, 1994.     

Chloromethylation of Bis(2-thienyl) Sulfide

Chloromethylation of bis(2-thienyl) sulfide is accompanied by fast polycondensation of the primary chloromethylation product with the initial sulfide. The reaction gives a new polymer in which the thiophene rings are alternately separated by sulfur atoms and methylene groups. Fusion of the polymer with molecular sulfur gave new sulfur-enriched polymers whose specific electric conductivity is comparable with that of organic semiconductors.     

Microbiological transformations of 9-amino-1,2,3,4,5,6,7,8-octahydroacridine

Chemistry Faculty, M. V. Lomonosov Moscow State University, Moscow 199899. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 712–713, May, 1994. Original article submitted April 25, 1994     

Synthesis of certain dipyridylacetylenes using palladium-catalyzed cross-coupling of ethynyl-and halopyridines

A series of dipyridylacetylenes were obtained by reacting ethynypyridines with chloro- and bromopyridines during catalysis with phosphino complexes of palladium in the presence of copper iodide and a base.M. V. Lomonosov Moscow State University, Moscow 119899. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, 1378–1383, October 1994. Original article submitted November 22, 1994.     

Rearrangement of allyl thienyl sulfides to allylthiophenethiols

It is shown that the rearrangement of allyl 2-thienyl and allyl 3-thienyl sulfides in various solvents at 89–136°C gives the corresponding allylthiophenethiols, which can subsequently undergo transallylation with the starting sulfide and cyclization to thienodihydrothiopyrans and methyldihydrothienothiophenes. The energy of activation of the rearrangement of both isomeric sulfides is 19 kcal/mole. The pK_a values of thiophenyl and some thiols of the thiophene series were determined, and it was established that the acidities of the allylthiophenethiols do not have a decisive effect on their ability to undergo cyclization.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 186–189, February, 1978.     

Synthesis of 5,7-dihydro-6h-indolo[2,3-c]quinolin6-ones

A new synthesis of derivatives of 5, 7-dihydro-6H-indolo[2,3-clquinolin-6-one was accomplished by the reaction of 1-methyl-3-formyloxindole with phenylhydrazines.K. A. Timiryazev Moscow Agricultural Academy, Moscow 127550. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 495–498, April, 1994 Original article submitted January 10, 1994.     

Advanced in the synthesis of heterocyclic compounds from aliphatic nitro derivatives. A review

The literature on the synthesis of heterocyclic compounds from aliphatic nitro derivatives in the past decade has been summarized.Moscow State Textile Academy, 117918, Moscow. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1299–1336, October, 1994. Original article submitted October 6, 1994.     

Synthesis, structure, and some reactions of 1,2-bis(2-alkylthio-3-thienyl)perfluorocyclopentene

The synthesis of 1,2-bis(2-ethylthio-3-thienyl)perfluorocyclopentene is described. Metallation with n-BuLi and subsequent treatment with DMF or CO₂ gave the corresponding 5,5-diformyl and dicarboxy derivatives. The structure of 1,2-bis(2-ethylthio-3-thienyl)perfluorocyclopentene was studied by x-ray structural analysis. It was established that the unit cell contains two crystallographically independent molecules with geometrical and conformational parameters close to one another. The thiophene rings were inclined at an angle of 60° to the plane of the perfluorocyclopentene fragment, the thioalkyl groups were disposed antiparallel to it.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 927–933, July, 1998.     

Synthesis and steric structure of 1,3(1,5)-dimethyl-2-phenyl-and -2,4-diphenyl-4-piperidols

1,3(1,5)-dimethyl-2-phenyl- and -2,4-diphenyl-4 piperidols were respectively obtained with the reaction of 1,3-and 1,5-dimethyl-2 phenyl-4-piperidoraes with sodium borohydride and phenyllithium. The steric isomers of the compounds obtained were separated and identified by spectral methods.Moscow State Academy of Precision Chemical Technology, Moscow 117571. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 941–945, July, 1994. Original submitted July 11, 1994.     

Effect of the substituent in the thiophene ring on the [3,3]-sigmatropic rearrangement of allyl thienyl sulfides

The thio Claisen rearrangement of a number of 5-substituted allyl 2-thienyl sulfides was studied. On the basis of kinetic data it is shown that substituents that decrease the aromatic character of the transition state decrease the reactivity of the sulfide.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1195–1197, September, 1982.     

Reactions of aromatic and heteroaromatic compounds bearing electron-acceptor substituents

The specificity of the nitration and bromination of dimethyl(2-thienyl)sulfonium salts was studied. It was found that, in contrast to methyl 2-thienyl sulfide, which reacts to form 3- and 5-substituted derivatives, the sulfonium salts give a mixture of 4- and 5-substituted products. Total suppression of the activity of the position under the influence of the sulfonium grouping is not observed.See [1] for communication VIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 310–314, March, 1972.     

Cyclization reactions of 2-(2-chloro-4-nitrophenylsulfonyl)-1-(2-thienyl)ethanone

A new sulfonyl group-containing heterocyclic compound 2-(2-chloro-4-nitrophenylsulfonyl)-1-(2-thienyl)ethanone 2 was prepared from the corresponding sulfide 2-(2-chloro-4-nitrophenylthio)-1-(2-thienyl)ethanone 1 . Two different cyclization reactions of the compound 2 were discussed. In contrast to the tandem alkylation-cyclization process [1], another cyclic procedure was described. In the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene as a base and dimethylformamide as a solvent, compound 2 was treated with ethyl acrylate or methyl methacrylate at 50–55° to give the 1,4-benzoxathiin 4,4-dioxide 5 or 6 respectively via a tandem Michael conjugate addition-cyclization process.     

Microbiological synthesis of 4-hydroxy-5-isopropyl-5-methoxy-2-oxo-2,5-dihydrofuran

M. V. Lomonosov Moscow State University, Moscow 119899, and Chemistry Section, Leipzig University, 7062 Leipzig, Germany. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 711–712, May, 1994.     

Synthesis of 2-mercaptothieno[3,2-d]- and 2-mercaptobenzo[4, 5]thieno[2,3-d]thiazoles

2-Mercaptothieno[3,2-d]- and 2-mercaptobenzo[4, 5]thieno[2,3-d]thiazoles were synthesized by reduction of bis(3,3′-nitro-2,2′-thienyl) and bis(2,2′-nitrobenzo[b]thien-3,3′-yl) disulfides, respectively, with sodium hydrosulfite or sodium sulfide in the presence of carbon disulfide.