O-Alkylation of furan and thiophene ketoximes in conditions of interphase catalysis in a liquid/solid system

Alkylation of 2 furanyl- and 2-thienylalkyl ketoximes with alkyl, allyl, and propargyl halides in the two phase catalytic system sol. K₂CO₃/C₆H₆/18-crown-6 at room temperature causes the formation of mixtures of E- and Z-isomers of the corresponding O-ethers with yields of 32–74%. Partial E/Z-isomerization takes place during the reaction.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 18–23, January, 1994.     

Catalytic Hydrosilylation of Furan, Thiophene, and Pyridine Aldimines

The addition of hydrosilanes (HSiEt₃, HSiMe₂Ph, H₂SiPh₂) to the CH=N bond of heterocyclic azomethines has been studied in the presence of monovalent complexes of rhodium and palladium. The effect on the reaction of the CF₃ group of the aldimines, which were obtained from O-, S-, and N-heteroaromatic aldehydes and 2-trifluoromethylaniline, has been clarified, as were other regularities of the processes being studied. A series of corresponding furans, thiophenes, and pyridine amines has been synthesized.     

Synthesis and Structure of Some N-[3-(Het)aryl-2-propenylidene]trifluoromethylanilines

The reactions of 4-nitrocinnamaldehyde with trifluoromethylanilines in the presence of molecular sieves were studied, and a series of new aromatic and heterocyclic aldimines were synthesized. The molecular and crystal structure of some of them were determined by X-ray crystallographic analysis.     

Different specificities in the bromination of 6-(2-furyl)imidazo[2,1-b]thiazole and its derivatives with 1 mole of bromine

The action of 1 mole of bromine on 6-(2′-furyl)imidazo[2,1-b]thiazole, its 2-methyl-, 3-methyl-, and 2,3-dimethyl-substituted derivatives, and their hydrobromides in chloroform and glacial acetic acid was studied. The bromination of bases containing a methyl group in the 3 position leads primarily to the 5′-derivatives with respect to the furan ring in chloroform, whereas in the remaining cases 5-bromo derivatives with respect to the imidazothiazole system are formed. Compounds of the latter type are formed by the action of bromine in glacial acetic acid or of sodium hypobromite in alkaline media on the bases. The hydrobromides are brominated in both acetic acid and chloroform, regardless of the substituents in the thiazole ring, primarily in the 5′ position of the furan ring. The structures of the bromination products were proved by means of alternative syntheses, thin-layer chromatography, and the PMR spectra.     

Hydrogenation of ethyl esters of 4-phenyl-and (2-furyl)-substituted 2,4-dioxobutyric acids at palladium black

The hydrogenation of ethyl 4-R-2,4-dioxobutyrates (R = phenyl, 2-furyl) at 5% Pt/Al₂O₃ catalyst, modified with cinchonidine, and at palladium black was investigated. The former had low activity under the conditions we tested. The main products during the hydrogenation of these compounds at palladium black are ethyl 4-R-2-hydroxy-4-oxobutyrates. The yield of the phenyl derivative amounts to 68.5%, while the yield of the corresponding 2-furyl derivative amounts to 97%. In the last case ethyl 2-hydroxy-4-oxo-4-(2-tetrahydrofuryl)butyrate was detected as impurity. The optimum conditions for the formation of ethyl 2-hydroxy-4-phenylbutyrate (yield 88.2%) were determined. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 655–659, May, 2006.     

Synthesis and Cytotoxic Activity of 4-Substituted 3-Cyano-6,6-dimethyl-5,6-dihydro-2-pyranones

The respective 4-(arylvinyl)lactones and compounds of the Michael adduct type were synthesized by the condensation of substituted benzaldehydes with 3-cyano-4,6,6-trimethyl-5,6-dihydro-2-pyranone in the presence of catalytic amounts of sodium hydroxide. It was shown by the semiempirical AM1 method that the indicated products can be formed through one and the same intermediate compound. Some of the synthesized phenylvinyl-5,6-dihydro-2-pyranones have a cytotoxic effect, and this corresponds to the prognosis of the OREX expert system.     

Alkylation of n-methylpyrrole with tert-butanol in the presence of amberlyst 15 ion exchanger

The 2- and 3-tert-butylderivatives of 1-methylpyrrole, hitherto unknown, have been obtained by a single-stage method. The process is characterized by a low positional selectivity with asomewhat predonminating -substitution. The results have been compared with data, obtained by the quantum-chemical calculation of the molecules of pyrrole, N-methylpyrrole, and also of their -complexes with protons, introduced in the - and -position of the rings.Latvian Institute of Organic Synthesis, Riga LV-1006.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 163–167, February, 1995. Original article submitted January 17, 1995.     

Pmr spectra and stereochemistry of chiral 2-aryl- and 2-hetaryloxazolidines-1,3

PMR spectra of 2-aryl- and 2-hetaryloxazolidines-1,3 are studied. A PMR criterion is revealed according to which the absolute configuration of the C₍₂₎ atom of the oxazolidine ring can be assigned.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 678–680, May, 1992.     

Novel radial oligothienyl silanes

A series of thiophene-based homologues with a silicon core surrounded by mono-, bi-, terthiophene, and their derivatives with alkylsilyl linkages has been prepared using hydrosilylation and Stille coupling methods.     

The role of palladium catalyst and base in stereoselective transformations of (E)-2-chlorovinylsulfides

Stereoselective transformations of 2-chlorovinylsulfides in the presence of soluble (t-BuOK) or insoluble (solid KOH or Cs₂CO₃/18-crown-6) base and palladium catalyst (dppb)Pd(OAc)₂ have been studied. Depending on the substrate or catalytic system, the reaction leads to the formation of (E)-1,2-bis[aryl(or arylmethyl)thio]ethenes and/or (E)-1,4-bis[aryl(or arylmethyl)thio]-1-buten-3-ynes in yields of up to 93%.