Reaction of hydroxy derivatives of piperidines and pyridines with acetylene under pressure

Methods for the synthesis of vinyl ethers of N-(-hydroxyethyl)-piperidine, 3-hydroxy-N-methylpiperidine, 2-(-hydroxyethyl)pyridine, and 2-(hydroxypyridine) based on the addition of the corresponding derivatives to acetylene have been developed. Their hydrogenation forms the corresponding ethyl ethers.     

Reaction of trimethyliodosilane with monosubstituted acetylene derivatives

Conclusions The reaction of phenylacetylene and 1-hexyne with Me₃SiI in the presence of Mg at 170–180° gave the corresponding trimethyl(organylethynyl)silanes in 80–95% yield.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, p. 897, April, 1981.     

Reaction of 3-mercaptoindole and its ethyl derivatives with acetylene

1-Vinyl-3-vinylthioindole, 1-vinyl-3-ethylthioindole, and 1-ethyl-3-vinylthioindole, respectively, were obtained by the reaction of 3-mercaptoindole, 3-ethylthioindole, and 1-ethyl-3-mercaptoindole with acetylene. 3-Mercaptoindole reacts with acetylene in aqueous media to give 3-vinylthioindole. The structures of the vinyl derivatives of 3-mercaptoindole obtained were proved by means of IR and PMR spectroscopy and the results of elementary analysis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 352–354, March, 1979.     

Acetylene derivatives Communication 174. Condensation of aldehydes and ketones with acetylene under pressure. II

Summary A further study was made of a new method of synthesizing secondary and tertiary acetylenic alcohols by the condensation of aldehydes and ketones with acetylene under pressure in presence of potassium hydroxide powder.     

Reaction of pyridines with epichlorohydrin

The reaction of pyridines with epichlorohydrin can occur by three routes depending upon the conditions used. Two of these lead to stable 1-cycloimmonium-2-chloro-2-propanol and 1,3-biscycloimmonium-2-propanol salts whereas the third gives unstable colored compounds.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 507–510, April, 1990.     

Reaction of azolones with acetylene

Conclusions The reaction of 4,5-diphenylimidazol-2-, benzimidazol-2-, and indazol-3-ones with acetylene gave their N- and O-mono- and N,N- and N,O-divinyl derivatives.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1882–1885, August, 1988.     

Reaction patterns of cyclopentadienylcobalt(I) carbonyl and acetylene derivatives

Studies have been made of photochemical and thermal reaction sequences through which bisubstituted acetylenes are transformed in (C₅H₅)Co-carbonyl reaction systems into cyclobutadiene and cyclopentadienone complexes and hexasubstituted benzenes. A primary intermediate observed by its IR spectrum in low-temperature photochemical reactions of (C₅H₅)Co(CO)₂ with diphenyl alkynes RCCR is the mixed mononuclear species (C₅H₅)Co(CO)(RCCR). At room temperature this species is converted by excess alkyne into the cyclopentadienone complex (C₅H₅)Co(R₄C₄CO). We have isolated from these reactions systems an important intermediate the mixed binuclear compound(C₅H₅)₂Co₂(μ-CO)(RCCR). In the presence of excess alkyne this compound is thermally converted either to the cyclobutadiene or to the cyclopentadienone complex of (C₅H₅)Co, depending on the partial pressure of CO in the reaction system. The mixed binuclear compound forms a catalyst for the cyclotrimerization of excess 2-butyne. The fluxional binuclear metallocycle (C₅H₅)₂Co₂[(CH₃)₄C₄], which is formed by sodium amalgam reduction of (C₅H₅)Co(CO)I₂ in the presence of 2-butyne, is a true catalyst for alkyne cyclotrimerization.     

Reaction of indazole and alkylpyrazoles with acetylene

The reaction of indazole and pyrazole and its alkyl-substituted derivatives with acetylene was studied. It was established that indazole and 3(5)-methylpyrazole form a mixture of vinyl isomers corresponding to their tautomeric forms under vinylation conditions. The ratios of the isomers of vinylindazoles in the reaction mixtures depend on the nature of the catalyst. The indazole isomers were separated by gas-liquid chromatography, and the 3(5)-methylpyrazole isomers were separated by vacuum fractionation. 1-Di(1-pyrazolyl)ethanes, the structure of which was confirmed by their PMR spectra, are also formed in the vinylation of pyrazoles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1247–1251, September, 1976.     

Reaction of tellurium tetrachloride with acetylene

Russian Chemical Bulletin -     

Reaction of diselenium dichloride with acetylene

Russian Journal of Organic Chemistry -     

Reaction of 2-aminobenzimidazole with acetylene

The reaction of 2-aminobenzimidazole (1) with acetylene under pressure proceeds with the formation of vinyl monomers, corresponding to amine and imine forms, 1-vinyl-2-amino- and 1,3-divinyl-2-iminobenzimidazoles, depending on the reaction conditions. 1,3-Divinyl-2-benzimidazolone was also isolated in aqueous dioxane in addition to the monovinyl derivative of1. Cyclization of the divinyl derivative of1 with acetylene proceeds to give 9-vinyl-1,2-dimethylimidazo[1,2-a]-benzimidazole.Irkutsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, 664033 Irkutsk. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 749–751, March, 1992.     

Reaction of chlorine fluosulfate with acetylene

Conclusions The reaction of chlorine fluosulfate with acetylene leads mainly to the formation of 1,1-bis(fluorosulfonyloxy)-2,2-dichloroethane.Translated from Izvestiya Akademii Nauk SSSR Seriya Khimicheskaya, No. 10, pp. 2374–2376, October, 1981.     

Acetylene derivatives. Communication 177. Condensation of aromatic and aliphatic-aromatic ketones with acetylene under pressure. Part III.

Summary In presence of potassium hydroxide powder, aliphatic-aromatic and aromatic ketones of the aceto- and benzo-phenone types condense smoothly with acetylene at a pressure of 5–10 atm with formation of the corresponding tertiary acetylenic alcohols in yields of more than 90%. When the 2-aryl-3-butyn-2-ols so obtained are selectively hydrogenated over a palladium catalyst, 2-aryl-3-buten-2-ols are obtained in almost quantitative yield, and dehydration of these gives 2-aryl-1,3-butadienes, which are extremely reactive in polymerization (dimerization) reactions and in the diene condensation.     

Reaction of tetrachloroethylene with methanol under pressure

Conclusions A method was developed for the preparation of trichloroallyl alcohol from methanol and tetrachloroethylene in a titanium apparatus under a pressure of 100–120 atm in the presence of CC1₄ (335°), CH₃COC₂H₅ (365°) or (CH₃)₃COOC (CH₃)₃ (185°), in a yield of 35–55% when based on starting TCE and 85–90% when based on reacted TCE, with a reactor output of up to 1000 g/h liter.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2868–2870, December, 1974.