


Vol 53, No 11 (2017)
- Year: 2017
- Articles: 30
- URL: https://bakhtiniada.ru/1070-4280/issue/view/13485
Article
Synthesis of polyfluoralkylated 1,3,2-dioxaphospholane and 1,3,2-dioxaphosphorinane oxides
Abstract
Polyfluoroalkyl dichlorophosphates easily react with 1,2- or 1,3-alkanediols in a system pyridine–diethyl ether and afford 2-polyfluoroalkoxy-1,3,2-dioxaphospholane oxides or 2-polyfluoroalkoxy-1,3,2-dioxaphosphorinane oxides. In similar conditions the reaction of methyl dichlorophosphate with 1,2- and 1,3-alkanediols proceeds less effectively.



Investigation of pyramidal inversion of nitrogen atom in carbamate and thiocarbamate ions formed at the reaction of СО2, СOS, CS2 with 2-aminoethanol
Abstract
Dynamic NMR was applied to measuring the value ΔG≠ characterizing the height of the barrier to the pyramidal inversion of the nitrogen atom in carbamate and thiocarbamate anions formed at the reaction of 2-aminoethanol with CO2 and COS. The refinement was introduced in formerly suggested cyclic structures of anions containing an intramolecular hydrogen bond NH···O(S), which contradicted the found large values of the barrier of inversion (ΔG≠ ∼ 70 kJ mol–1). The hydrogen bond in the cyclic anions of carbamates and thiocarbamates is two-electron and three-center. Analogous cyclic structure with a multicenter hydrogen bond does not form in the case of dithiocarbamate anion that is the product of 2-aminoethanol reaction with CS2.



Synthesis of 2-(12-aryldodecanoyl)cyclohexane-1,3-diones
Abstract
Synthesis was developed of 2-(10-undecenoyl)cyclohexane-1,3-diones containing in the side chain keto and hydroxy groups and a phenyl substituent. The synthesis is underlain by a nitrile oxide approach. The scheme included isoxazole synthesis for the protection of the β,β′-tricarbonyl fragment, building up of a heterocycle by 1,3-dipolar cycloaddition of nitrile oxide in situ to the terminal double bond, cycle opening (of isoxazole and isoxazoline), and alkaline hydrolysis.



Synthesis of phenyl analog of retinoic acid methyl ester proceeding from 3-(bromomethyl)but-3-enal diethylacetal
Abstract
Aromatic analog of retinoic acid methyl ester was prepared using a convenient prenylating agent, 3-(bromomethyl)but-3-enal diethylacetal, and Barbier reaction in the key stage of building up the carbon chain of target molecules. A version is offered of the synthesis of methylidene analog of aromatic retinoic acid.



о-Nitroarylidene imines, bifunctional fluorescent chemosensors for lanthanide cations and fluoride anions
Abstract
Condensation of о-nitrobenzaldehydes with anthracen-9-ylmethanamine afforded dialkoxy-substituted azomethines which exhibited a chemosensor activity with respect to lanthanide cations and fluoride, cyanide, and acetate anions. N-[(Anthracen-9-yl)methyl]-1-(4,5-dimethoxy-2-nitrophenyl)methanimine is a highly effective and selective bifunctional sensor for europium(III) cation and fluoride anion.



Formylation of indol-1-yl acetates
Abstract
Preparation procedure was developed for 3-formylindole-5,6-dicarbonitriles underlain by the treatment of 1-acetoxyindole-5,6-dicarbonitriles with Vilsmeier-Haack reagent; a special feature of this reaction consisted in a replacement of the OAc group for hydrogen. A probable mechanism was assumed of the formation of 3-formylindole-5,6-dicarbonitriles.






Synthesis of isoxazole derivatives of 4,5-dihydro-1H-pyrazole
Abstract
Cyclocondensation of pent-1-en-4-yn-3-one with phenylhydrazine and p-tolylhydrazine occurs at the positions 1, 3. Proceeding from the 1-aryl-3-ethynyl-4,5-dihydro-1H-pyrazoles formed in the reaction in yields up to 95% we prepared potentially biologically active isoxazole derivatives of pyrazoline. The structure of 5-[1-(4-methylphenyl)-4,5-dihydro-1H-pyrazol-3-yl]-3-phenyl-1,2-oxazole was studied by X-ray diffraction analysis.



Features of reaction of substituted 4-oxobutanoic acids and 3H-furan-2-ones with 1,3-binucleophiles
Abstract
Differences were found in reactions of 4-alkyl(aryl)-substituted 4-oxobutanoic acids and 3H-furan-2-ones with 1,3-binucleophiles, 2-(aminomethyl)aniline and 2-(aminophenyl)methanol. Depending on initial substrates different fused tricyclic systems are formed.



New facilities of Biginelli reaction. Synthesis of methyl 6-aryl-5-benzoyl-4-methoxy-2-oxohexahydropyrimidine-4-carboxylates
Abstract
Three-component reaction of methyl benzoylpyruvate, aromatic aldehyde, and urea in methanol in the presence of sodium bisulfate stops at the stage of the formation of nondehydrated product with a methylated tertiary hydroxy group and results in methyl 6-aryl-5-benzoyl-4-methoxy-2-oxohexahydropyrimidine-4-carboxylates.



Conformational analysis of 2-isopropyl-5-methyl-5-methoxymethyl-1,3,2-dioxaborinane
Abstract
Study of conformational transformations of 2-isopropyl-5-methyl-5-methoxymethyl-1,3,2-dioxaborinane using DFT approximation PBE/3ζ and the second order perturbation theory method RI-MP2/λ2 revealed beside the interconversion route sofa–sofa through a transition state corresponding to 2,5-twist form a number of local minima due to internal rotation of isopropyl and methoxymethyl substituents in sofa conformers. Over 88% of the molecules of the studied compound are present in a sofa form with the equatorially oriented CH2OCH3 group.



Synthesis of (2R,4R)-2-alkyl-3-(2-mercaptobenzoyl)thiazolidine-4-carboxylic acids
Abstract
Basing on natural amino acid L-cysteine, commercially available aliphatic aldehydes, 2-acetylsulfanylbenzoyl chloride and 2,2′-disulfandiyldibenzoyl dichloride a synthesis was developed of (2R,4R)-2-alkyl-3-(2-mercaptobenzoyl)thiazolidine-4-carboxylic acids, potential antihypertensive compounds, inhibitors of angiotensin transforming enzyme.






Uncommon reaction of 2-bromomethyl-1,3-thiaselenole with pyridine and its derivatives
Abstract
Regioselective reaction of 2-bromomethyl-1,3-thiaselenole with pyridine and its derivatives is followed by rearrangement with ring expansion and the formation of a bond between a nitrogen atom and a carbon in the position 2. A set of derivatives of 2,3-dihydro-1,4-thiaselenine was obtained, substituted in the position 2 by a pyridinium residue functionalized by pharmacophoric groups.



N-acylimino-substituted 2-oxa-7-azaspiro[4.4]nona-3,6,8-trienes in the synthesis of 3-(1H-1,2,4-triazol-3-yl)-3H-pyrrole-4-carbonitriles
Abstract
Reaction with phenylhydrazine of 3Н-pyrroles spirobound to a furan ring, N-acylimino-substituted 2-oxa-7-azaspiro[4.4]nona-3,6,8-trienes, occurs with a diasteroselective formation of previously unknown derivatives of 1,2,4-triazole: 5-amino-3-(5-alkyl-1-phenyl-1H-1,2,4-triazol-3-yl)-2-morpholin-4-yl-3H-pyrrole-4-carbonitriles.



One-pot synthesis of 1,2,3-triazole derivatives of maleopimaric and dihydroquinopimaric acids
Abstract
Effective one-pot synthesis of 1,2,3-triazole derivatives of maleopimaric and dihydroquinopimaric acids consists in the reaction of diterpene propargyl esters with organic azides generated in situ in the presence of СuI catalyst.



Pd-catalyzed synthesis of 2-alkynyl derivatives of 19β,28-epoxy-18α-olean-1-en-3-one
Abstract
Basing on Sonogashira reaction of 2-iodo-19β,28-epoxy-18α-olean-1-en-3-one with alkynes an effective approach was developed to the synthesis of 2-alkynyl derivatives of 19β,28-epoxy-18α-olean-1-en-3-one. Initial 2-iodo-19β,28-epoxy-18α-olean-1-en-3-one was obtained by isomerization of the accessible betulin into allobetulin in the presence of Amberlyst 15, oxidation of allobetulin to 19β,28-epoxy-18α-olean-1-en-3-one under the action of 2-iodoxybenzoic acid, and iodination of the obtained enone in the presence of DMAP.



Synthesis and anti-influenza activity of 2-cyanoethoxy and 2-(1H-tetrazol-5-yl)ethoxy derivatives of dammarane-type triterpenoids
Abstract
A series of 3-(2-1Н-tetrazol-5-ylethoxy- and 2-1Н-tetrazol-5-ylethoxyimino) derivatives of dammarane triterpenoids was synthesized by azidation of 3-(2-cyanoethoxy- and 2-cyanoethoxyimino)-dammaranes. The anti-influenza activity of the prepared tetrazolyldammaranes and intermediate compounds against influenza virus А H1N1 was tested. A considerable antiviral activity was observed for 20(S)-3-(2-1Н-tetrazol-5-ylethoxyimino)-25,26,27-trinor-20,24-olidedammarane (SI 26).



Synthesis of new N-polysubstituted oxaazaisowurtzitanes by acid-catalyzed condensation of sulfonamides with glyoxal
Abstract
By application of acid-catalyzed condensation of propane-2-, benzene- and methanesulfonamides with glyoxal a series of new derivatives of oxaazaisowurtzitanes were obtained, in particular, new heterocyclic systems: 2,4,6,8,12-pentaoxa-10-aza- and 2,4,8,12-tetraoxa-6,10-diazatetracyclo[5.5.0.03,11.05,9]-dodecanes.



Synthesis, structure, spectral properties, and electrochemistry of bis(crown ether) containing 1,3-distyrylbenzenes
Abstract
The reaction of tetraethyl [1,3-phenylenedi(methylene)]bis(phosphonate) with formyl derivatives of benzocrown-ethers or formyl derivatives of o-dimethoxybenzene lead to high yield formation of the respectful bis(crown ether) containing 1,3-distyrylbenzenes or tetramethoxy-substituted 1,3-distyrenebenzenes. NMR spectra and quantum-chemical calculations showed the prevalence of unsymmetrical syn/anti,(syn,anti),syn/anti-conformations in 1,3-distyrylbenzenes. 1,3-Distyrylbenzenes absorb in shorter wavelength spectral region and have a weaker fluorescence than 1,4-distyrylbenzenes. The difficulty in the electrochemical reduction of 1,3-distyrylbenzenes comparing with 1,4-distyrylbenzenes is due to a less effective conjugation system in the metaderivatives.



Short Communications









Aminium salts obtained from diethyl [(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadienylidene)methyl]phosphonate
Abstract
In reaction of diethyl [(3,5-di-tert-butyl-4-oxocyclohexa-2,5-diеn-1-ylidene)methyl]phosphonate with N1,N1-dimethylethane-1,2-diamine aminophosphonate was obtained that was transformed into aminium salts by reactions with halogen derivatives of hydrocarbons.



Products of reaction of 1-phenyltricyclo[4.1.0.02,7]heptane with N-iodosuccinimide in aqueous THF
Abstract
Iodohydroxylation of 1-phenyltricyclo[4.1.0.02,7]heptane in aqueous THF at 20°C with N-iodosuccinimide proceeds at the central bicyclobutane bond C1–C7 and results in the formation of two-component mixture of diastereomeric 7-iodo-6-phenyl-6-norpinanols in the ratio 1 : 1.8 in favor of the product of the anti-addition. Treating of iodonorpinanols with trimethylamine in aqueous THF affords 1-benzoylcyclohex-1-ene as a result of 1,4-dehydroiodination accompanied with the Grob fragmentation of the carbon scaffold.



N-(2,2,2-trichloroethylidene)- and N-(2,2-dichloro-2-phenylethylidene)-4-methoxybenzenesulfonamides from 4-methoxy-N,N-dichlorobenzenesulfonamide, trichloroethylene, and phenylacethylene
Abstract
Reaction of 4-methoxy-N,N-dichlorobenzenesulfonamide with trichloroethylene and phenylacetylene underlies an effective method developed for the synthesis of highly reactive 4-methoxy-N-(2,2,2-trichloroethylidene)- and 4-methoxy-N-(2,2-dichloro)-2-phenylethylidene)benzenesulfonamides, valuable reagents for the preparation of new difficultly accessible derivatives of the sulfonamide series.



Synthesis and radical scavenging activity of dimethylaminomethyl derivatives of 2-isobornyl-6(4)-(1-phenylethyl)phenol and 2-isobornyl-6(4)-(1-phenylpropyl)phenol
Abstract
Dimethylaminomethyl derivatives of 2-isobornyl-6(4)-(1-phenylethyl)phenol, 2-isobornyl-6(4)-(1-phenylpropyl)phenol were synthesized and their radical scavenging activity was evaluated by a test with 2,2-diphenyl-1-picrylhydrazyl.



Three-component synthesis of 2-halo-6-methoxy-5,6-dihydropyridine-3,4,4(1H)-tricarbonitriles
Abstract
One-stage preparation method of 2-halo-6-methoxy-5,6-dihydropyridine-3,4,4(1H)-tricarbonitriles was developed, consisting in the reaction of 3,3-dialkyl-4-oxoalcane-1,1,2,2-tetracarbonitriles with hydrohalic acids in methanol.



Product of uncommon reaction of 1,1,1-trifluoro-4-phenylbut-3-yn-2-one with diphenyldiazomethane
Abstract
1,1,1-Trifluoro-4-phenylbut-3-yn-2-one reacts with diphenyldiazomethane at 20°С in ethyl ether to afford 4-(trifluoromethyl)-1,1,6,6-tetraphenyl-4,6-dihydro-1H-benz[5,6]oxepino[4,5-c]pyrazole. The process involves a stage of [3+2]-cycloaddition of the reagents, and the arising 3H-pyrazole subsequently enters in an uncommon [3+6]-cycloaddition with 1 more molecule of diphenyldiazomethane. Further the formed diadduct of the initial acetylene suffers a 1,5-hydride shift and undergoes fragmentation with a loss of a nitrogen molecule thus converting into the final product.





