Nanoporous crosslinked macrocyclic polyethers based on diethylene glycol divinyl ether and their superbase complexes with KOH

Nanoporous (11–12 nm) crosslinked macrocyclic polyethers with vinyloxy and hydroxyl groups have been synthesized by the free-radical polymerization of diethylene glycol divinyl ether (AIBN, 80°C, i-octane), followed by acidic hydrolysis. It has been shown that the polymers react with KOH to form insoluble superbase complexes and alcoholates capable of catalyzing vinylation of ethylene glycol by acetylene.     

Pyrroles from ketoximes and acetylene. 41. Some reactions of 1-vinyl-2-(2-furyl)- and-(2-thienyl)pyrroles

We have studied the reaction of 1-vinyl-2-(2-furyl)- and -(2-thienyl)pyrroles with trifluoroacetic anhydride, with hydrogen in the presence of catalysts (Raney nickel, palladium black, palladous chloride), with propargyl alcohol in electrophilic conditions [catalysis by perfluorobutyric acid in the system azoisobutyrodinitrile (AIBN)-CCl₄), and with alkane thiols with AIBN initiation. The products are novel substituted hetarylpyrroles.See [1] for Communication 40.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 337–342, March, 1991.     

Synthesis and Liquid Crystal Properties of Aryl Esters of Laterally Substituted 5-Pyrimidinecarboxylic Acids

(p-R-phenyl)-4-methyl-, 4-methoxy-, and 4-hydroxy-5-pyrimidinecarboxylates have been synthesized and their liquid crystal properties examined. Compounds containing methyl and methoxy groups in the lateral position of the molecule are nematic liquid crystals with a mesophase range of 30-50°C, but the 4-hydroxy derivatives are smectic liquid crystals. With variants of the substituents in a series of (p-R-phenyl)-4-substituted 5-pyrimidinecarboxylates the mp of individual representatives were successfully reduced by 50°C in comparison with the 4-unsubstituted analogs and the range of the mesomorphic state was extended to 190°C.     

Synthesis and electrochemical characterization of dipyrroles separated by diphenyleneoxide and diphenylenesulfide spacers via the Trofimov reaction

4,4′-Bis[2-(1-vinylpyrrolyl)]diphenyloxide, 4,4′-bis(2-pyrrolyl)diphenylsulfide, 4-(2-pyrrolyl)-4′-[2-(1-vinylpyrrolyl)]diphenylsulfide and 4,4′-bis[2-(1-vinylpyrrolyl)]diphenylsulfide have been synthesized in a one-pot procedure from oximes of corresponding diacetylphenylenoxide and -sulfide through their reaction with acetylene in the MOH-DMSO systems (M=Li, K) at 80-130 °C under pressure of 10-15 atm, thus illustrating applicability and general character of the reaction of synthesis of diverse dipyrrole-phenylene assemblies and their N-vinyl derivatives. Two of the pipyrroles are promising for creating new conducting polymers with sulfur and oxygen atoms in the conjugation chain and for the study of the influence of the diphenyleneheteroatom moiety on conductivity of final polymer products. For the dipyrroles with the diphenyleneheteroatom moieties and 1,4-phenylene spacer the luminescence characteristics were determined.     

Pyrroles from ketoximes and acetylene. 22. Dihaloethanes in place of acetylene in reactions with cyclohexanone oxime

4,5,6,7-Tetrahydroindole and its 1-vinyl derivative were obtained in overall yields of 30–60% by the reaction of cyclohexanone oxime with 1,2-dichloro- and 1,2-dibromoethane in the MOH-dimethyl sulfoxide (DMSO) superbase system (M = K, Na, Li). Nucleophilic substitution of the halogen in the dihaloethanes by the oximate anion to give the corresponding ethylene glycol bis (imido ether) is a side reaction. The effect of the reaction conditions on the yields of products and the selectivity of the process was examined.See [1] for communication 21.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1202–1204, September, 1982.     

Free-radical addition of alkanethiols to 1-vinylpyrroles

In the presence of 2,2-azobisisobutyronitrile or in the absence of an initiator alkanethiols add to 1-vinylpyrroles exclusively counter to Markovnikov's rule to give 1-(2-alkylthioethyl)pyrroles (in yields up to 94%).Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1636–1639, December, 1977.