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Vol 53, No 11 (2017)

Article

Synthesis of polyfluoralkylated 1,3,2-dioxaphospholane and 1,3,2-dioxaphosphorinane oxides

Gusarova N.K., Verkhoturova S.I., Arbuzova S.N., Kazantseva T.I., Albanov A.I., Nalibaeva A.M., Bishimbaeva G.K.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1623-1629
pages 1623-1629 views

Investigation of pyramidal inversion of nitrogen atom in carbamate and thiocarbamate ions formed at the reaction of СО2, СOS, CS2 with 2-aminoethanol

Talsi V.P., Evdokimov S.N.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1630-1636
pages 1630-1636 views

Synthesis of 2-(12-aryldodecanoyl)cyclohexane-1,3-diones

Vasilyeva N.G.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1637-1641
pages 1637-1641 views

Synthesis of phenyl analog of retinoic acid methyl ester proceeding from 3-(bromomethyl)but-3-enal diethylacetal

Masyuk V.S., Mineeva I.V.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1642-1650
pages 1642-1650 views

о-Nitroarylidene imines, bifunctional fluorescent chemosensors for lanthanide cations and fluoride anions

Tolpygin I.E., Tikhomirova K.S., Revinskii Y.V., Bren Z.V., Dubonosov A.D., Bren V.A.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1651-1654
pages 1651-1654 views

Formylation of indol-1-yl acetates

Chirkova Z.V., Chernov F.A., Filimonov S.I., Abramov I.G., Plakhtinskii V.V., Danilova A.S.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1655-1659
pages 1655-1659 views

Synthesis of 4-halo-3-(phenylamino)furo[3,4-c]pyridin-1(3H)-ones

Fedoseev S.V., Belikov M.Y., Ershov O.V., Tafeenko V.A.

Abstract

A method was developed for the synthesis of 4-halo-3-(phenylamino)-furo[3,4-c]pyridin-1(3H)-ones by the reaction of 4-halo-3-hydroxyfuro[3,4-c]pyridin-1(3H)-ones with aniline at room temperature.

Russian Journal of Organic Chemistry. 2017;53(11):1660-1663
pages 1660-1663 views

Synthesis of isoxazole derivatives of 4,5-dihydro-1H-pyrazole

Golovanov A.A., Odin I.S., Vologzhanina A.V., Voronova E.D., Anoshina O.S., Bekin V.V.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1664-1668
pages 1664-1668 views

Features of reaction of substituted 4-oxobutanoic acids and 3H-furan-2-ones with 1,3-binucleophiles

Grinev V.S., Amalchieva O.A., Egorova A.Y.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1669-1674
pages 1669-1674 views

New facilities of Biginelli reaction. Synthesis of methyl 6-aryl-5-benzoyl-4-methoxy-2-oxohexahydropyrimidine-4-carboxylates

Gein V.L., Gorgopina E.V., Zamaraeva T.M., Dmitriev M.V.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1675-1677
pages 1675-1677 views

Conformational analysis of 2-isopropyl-5-methyl-5-methoxymethyl-1,3,2-dioxaborinane

Valiakhmetova O.Y., Kuznetsov V.V.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1678-1681
pages 1678-1681 views

Synthesis of (2R,4R)-2-alkyl-3-(2-mercaptobenzoyl)thiazolidine-4-carboxylic acids

Ershov А.Y., Lagoda I.V., Nasledov D.G., Vasil’eva M.Y., Kuleshova L.Y., Pavlova L.V., Yakimanskii A.V.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1682-1686
pages 1682-1686 views

Synthesis of a chiral block for С1–С5 fragment of epothilones

Valeev R.F., Sunagatullina G.R., Miftakhov M.S.

Abstract

Synthesis was developed of a new chiral block for epothilone analogs from R-(‒)-pantolactone.

Russian Journal of Organic Chemistry. 2017;53(11):1687-1690
pages 1687-1690 views

Uncommon reaction of 2-bromomethyl-1,3-thiaselenole with pyridine and its derivatives

Amosova S.V., Penzik M.V., Rykunova Y.I., Potapov V.A., Albanov A.I.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1691-1695
pages 1691-1695 views

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

Belikov M.Y., Belikova I.V., Ershov O.V., Fedoseev S.V., Tafeenko V.A.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1696-1700
pages 1696-1700 views

One-pot synthesis of 1,2,3-triazole derivatives of maleopimaric and dihydroquinopimaric acids

Tret’yakova E.V., Salimova E.V., Shakurova E.R., Parfenova L.V., Odinokov V.N.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1701-1704
pages 1701-1704 views

Pd-catalyzed synthesis of 2-alkynyl derivatives of 19β,28-epoxy-18α-olean-1-en-3-one

Shakhmaev R.N., Sunagatullina A.S., Abdullina E.A., Zorin V.V.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1705-1709
pages 1705-1709 views

Synthesis and anti-influenza activity of 2-cyanoethoxy and 2-(1H-tetrazol-5-yl)ethoxy derivatives of dammarane-type triterpenoids

Zorina A.D., Kaledina A.S., Motsepuro I.A., Anokhina V.V., Marchenko S.A., Selivanov S.I., Zarubaev V.V., Trifonov R.E.

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).

Russian Journal of Organic Chemistry. 2017;53(11):1710-1716
pages 1710-1716 views

Synthesis of new N-polysubstituted oxaazaisowurtzitanes by acid-catalyzed condensation of sulfonamides with glyoxal

Paromov A.E., Sysolyatin S.V.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1717-1725
pages 1717-1725 views

Synthesis, structure, spectral properties, and electrochemistry of bis(crown ether) containing 1,3-distyrylbenzenes

Nuriev V.N., Fedorov O.V., Moiseeva A.A., Freidzon A.Y., Kurchavov N.A., Vedernikov A.I., Medved’ko A.V., Pod’yacheva E.S., Vatsadze S.Z., Gromov S.P.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1726-1737
pages 1726-1737 views

Short Communications

Relativistic effects of chlorine in 15N NMR chemical shifts of chlorine-containing amines

Samul’tsev D.O., Rusakov Y.Y., Krivdin L.B.

Abstract

Quantum-chemical calculations by DFT method demonstrated that the accounting is necessary of the shielding by chlorine of nitrogen atom in practical calculations and interpretation of chemical shifts in 15N NMR spectra.

Russian Journal of Organic Chemistry. 2017;53(11):1738-1739
pages 1738-1739 views

Synthesis of glycidyl propargyl ether

Tarasova O.A., Nedolya N.A., Trofimov B.A.

Abstract

Glycidyl propargyl ether was prepared in 80% yield from propargyl alcohol and epichlorohydrin in a superbasic suspension NaOH–DMSO.

Russian Journal of Organic Chemistry. 2017;53(11):1740-1741
pages 1740-1741 views

Epoxidation of unsaturated carbonyl compounds

Talybov G.M.

Abstract

Epoxidation of unsaturated carbonyl compounds by reaction with chloromethyl propargyl(allyl) ether in the presence of an alcoholate occurs exclusively at the carbonyl groups to form vinyl epoxides.

Russian Journal of Organic Chemistry. 2017;53(11):1742-1745
pages 1742-1745 views

Aminium salts obtained from diethyl [(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadienylidene)methyl]phosphonate

Azmukhanova R.R., Gibadullina E.M., Pazilova N.B., Pudovik M.A., Burilov A.R.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1746-1748
pages 1746-1748 views

Products of reaction of 1-phenyltricyclo[4.1.0.02,7]heptane with N-iodosuccinimide in aqueous THF

Vasin V.A., Romanova E.V., Razin V.V.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1749-1752
pages 1749-1752 views

N-(2,2,2-trichloroethylidene)- and N-(2,2-dichloro-2-phenylethylidene)-4-methoxybenzenesulfonamides from 4-methoxy-N,N-dichlorobenzenesulfonamide, trichloroethylene, and phenylacethylene

Aizina Y.A., Rozentsveig I.B., Popov A.V., Levkovskaya G.G.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1753-1755
pages 1753-1755 views

Synthesis and radical scavenging activity of dimethylaminomethyl derivatives of 2-isobornyl-6(4)-(1-phenylethyl)phenol and 2-isobornyl-6(4)-(1-phenylpropyl)phenol

Buravlev E.V., Shchukina O.V., Shevchenko O.G., Chukicheva I.Y., Kutchin A.V.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1756-1759
pages 1756-1759 views

Three-component synthesis of 2-halo-6-methoxy-5,6-dihydropyridine-3,4,4(1H)-tricarbonitriles

Lipin K.V., Ershov O.V.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1760-1762
pages 1760-1762 views

Product of uncommon reaction of 1,1,1-trifluoro-4-phenylbut-3-yn-2-one with diphenyldiazomethane

Vasin V.A., Bezrukova E.V., Razin V.V., Somov N.V.

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.

Russian Journal of Organic Chemistry. 2017;53(11):1763-1765
pages 1763-1765 views

Synthesis and structure of N-(4,6-dimethylpyrimidin-2-yl)-2-(5-phenyl-2H-tetrazol-2-yl)acetohydrazide and 1-(4,6-dimethylpyrimidin-2-yl)-3-[(5-phenyl-2H-tetrazol-2-yl)methyl]-1H-pyrazol-5-ol

Nesterova O.M., Zarubina O.S., Tolstyakov V.V., Danagulyan G.G., Trifonov R.E., Smirnov S.N., Slepukhin P.A., Ignatenko N.K., Ostrovskii V.A.

Abstract

New tetrazolyl derivatives of pyrimidine were synthesized containing various linker groups. The structure of these compounds was established by NMR spectroscopy and X-ray diffraction analysis.

Russian Journal of Organic Chemistry. 2017;53(11):1766-1768
pages 1766-1768 views