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Vol 52, No 2 (2016)

Article

Aminopyrimidine derivatives as protein kinases inhibitors. Molecular design, synthesis, and biologic activity

Koroleva E.V., Ignatovich Z.I., Sinyutich Y.V., Gusak K.N.

Abstract

The review compiles the strategies and methods of development of aminopyrimidine derivatives as targeted antitumor pharmaceuticals. The advances in organic and heterocyclic chemistry are considered in the targeted synthesis of aminopyrimidine derivatives whose series contains the most demanded and efficient antitrumor pharmaceuticals. The problems of preparation of compounds with multikinase activity profile and the construction of chimeric molecules are discussed.

Russian Journal of Organic Chemistry. 2016;52(2):139-177
pages 139-177 views

Synthesis of β-(2,2-diethoxyethyl)-substituted (allyl)tributylstannane and its application to asymmetric allylation

Masyuk V.S., Mineeva I.V.

Abstract

Previously unknown tributyl-[(2-methylidene-4,4-diethoxy)butyl]stannane was prepared from diethyl acetal of 3-(bromomethyl)but-3-enal and was brought subsequently into a catalytic asymmetric Keck allylation of butanal in order to obtain optically active homoallylic alcohol. The use of activating additives [B(OBu)3 and CF3COOH] favors the process proceeding with high yields and enantioselectivity. An approach was suggested to the synthesis of С14–С21 fragments of amphidinolide Т applying tributyl[(2-methylidene-4,4-diethoxy)butyl]stannane in the key stage of building up the carbon scaffold.

Russian Journal of Organic Chemistry. 2016;52(2):178-185
pages 178-185 views

Rearrangements in methanolysis of bis(2-bromoalkyl)selenides

Kurkutov E.O., Musalov M.V., Potapov V.A., Larina L.I., Amosova S.V.

Abstract

Addition of selenium dibromide to 1-hexene, 1-octene, and allylic ethers occurs through the formation of intermediate kinetic anti-Markovnikov adducts that further transform into more thermodynamically stable Markovnikov adducts presumably via seleniranium intermediates. The methanolysis of both Markovnikov and anti-Markovnikov adducts leads to the formation of the same products in approximately the same ratio thus showing that the reaction proceeds through seleniranium intermediates.

Russian Journal of Organic Chemistry. 2016;52(2):186-191
pages 186-191 views

Homo and hetero glaser coupling involving acetylene derivatives of trifluoromethanesulfonamide

Shainyan B.A., Ushakova I.V.

Abstract

Glaser homocoupling of N,N-bispropargyltriflamide led to the formation of N,N'-hexa-2,4-diyne-1,6-diylbis(N-prop-2-yne-1-triflamide). Further condensation into a 14-membered heterocycle, 1,8-bis-(triflyl)-1,8-diazacyclotetradeca-3,5,10,12-tetrayne did not occur evidently because of rigid steric requirements to the cyclization. In the Glaser heterocoupling of N-propargyltriflamide with arylacetylenes ArC≡CH (Ar = Ph, p-CNC6H4) the condensation products formed in 20–30% yields.

Russian Journal of Organic Chemistry. 2016;52(2):192-195
pages 192-195 views

Efficient one-stage procedure of Beckmann ketones rearrangement in the presence of hydroxylamine

Kuksenok V.Y., Shtrykova V.V., Filimonov V.D., Sidel’nikova S.P.

Abstract

Ketoximes formed from ketones in the presence of hydroxylamine and silica gel in formic acid undergo in situ the Beckmann rearrangement under mild conditions affording in high yields the corresponding amides. Unsymmetrical aromatic ketones, methyl aryl ketones, and methyl cyclohexyl ketone under these conditions form as a rule amides mixtures.

Russian Journal of Organic Chemistry. 2016;52(2):196-199
pages 196-199 views

Synthesis of chloropolyfluoroarenes from polyfluoroarenethiols and PCl5

Nikul’shin P.V., Maksimov А.M., Platonov V.Е.

Abstract

Replacement of the thiol group in polyfluoroarenethiols with chlorine was performed by treating with PCl5 as chlorinating agent. By heating in ampules at 200–220°C polyfluoro- and polyfluorochloroarenethiols with PCl5 mono- and dichloropolyfluoroarenes and also 1,2,4-trifluorotrichlorobenzene were synthesized. Dichloropolyfluoroarenes contain chlorine atoms in ortho- and para-positions.

Russian Journal of Organic Chemistry. 2016;52(2):200-205
pages 200-205 views

Synthesis of 1-aryl-3a,8b-dihydroxy-3-(1-hydroxyethylidene)-1,3,3а,8b-tetrahydroindeno[1,2-b]pyrrole-2,4-diones

Yankin A.N., Nosova N.V., Dmitriev M.V., Gein V.L.

Abstract

Reaction of acetoacetic acid N-arylamides with ninhydrin at boiling in ethanol in the presence of iron(III) chloride afforded 1-aryl-3a,8b-dihydroxy-3-(1-hydroxyethylidene)-1,3,3а,8b-tetrahydroindeno[1,2-b]-pyrrole-2,4-diones. The structure of compounds was confirmed by IR, 1Н NMR, and mass spectra and X-ray diffraction (XRD) analysis.

Russian Journal of Organic Chemistry. 2016;52(2):206-208
pages 206-208 views

Synthesis and biologic activity of aryloxyaminopropanoles based on substituted p-tolylalkylamines

Aghekyan A.A., Mkryan G.G., Tsatinyan A.S., Noravyan O.S., Gasparyan G.V.

Abstract

Reaction of 2,2-dimethyl-2-(p-tolyl)ethyl-, 1-p-tolylcyclopenthylmethyl- and 4-(p-tolyl)tetrahydro-2Н-pyran-4-ylmethylamines with phenoxymethyloxiranes substituted in the aromatic ring afforded new aryloxypropanolamines, some of which show moderate adrenoblocking activity.

Russian Journal of Organic Chemistry. 2016;52(2):209-213
pages 209-213 views

6,6'-[piperazine-1,4-diylbis(methylene)]bis[3,5-di(tert-butyl)-1,2- benzoquinone]: Synthesis and properties

Sayapin Y.A., Tupaeva I.O., Tkachev V.V., Shilov G.V.

Abstract

Preparation method is developed for a new 6,6'-[piperazine-1,4-diylbis(methylene)]bis[3,5-di(tert-butyl)- 1,2-benzoquinone], including the stage of 3,5-di(tert-butyl)pyrocatechol aminoalkylation by Mannich reaction followed by oxidation. The molecular structure of one of its hydrolysis products, 4,6-di(tert-butyl)-2,3-dihydroxybenzaldehyde, is established by X-ray diffraction (XRD) analysis.

Russian Journal of Organic Chemistry. 2016;52(2):214-218
pages 214-218 views

Uncommon expansion of piperidine ring into hydroazocine ring in reactions of some piperidine β-acyl derivatives with acetylenecarboxylic acids esters

Malkova A.V., Polyanskii K.B., Soldatenkov A.T., Soldatova S.A., Merkulova N.L., Khrustalev V.N.

Abstract

Cyclohexanone condensation with formaldehyde and methylamine led to the formation of 4ahydroxy-2-methyloctahydrospiro[isoquinoline-4,1'-cyclohexan]-2'-one whose structure was established by means of X-ray diffraction (XRD) analysis. This spiro compound reacted with acetylenecarboxylic acids esters with unexpected conversion of its piperidine ring into a hexahydroazocine cycle. The uncommon expansion reaction of the β-acyl-substituted piperidine ring into a hexahydroazocine cycle is confirmed by the analogous conversion of 4-hydroxy-1-methyl-4-phenylpiperidin-3-yl(phenyl)methanone into azocine derivative at treating with methyl propiolate.

Russian Journal of Organic Chemistry. 2016;52(2):219-222
pages 219-222 views

Synthesis and properties of 1-aroyl-5,5-dialkyl-2,3,5,6-tetrahydropyrrolo[ 2,1-a]isoquinoline-2,3-diones

Mikhailovskii A.G., Yusov A.S., Gashkova O.V.

Abstract

Acylation of 1-methyl-3,3-dialkyl-3,4-dihydroisoquinolines with acid chlorides afforded enaminoketones. Enaminophenylketones from the obtained series were reacted with oxalyl chloride to provide 1-benzoyl-5,5-dialkyl-2,3,5,6- tetrahydropyrrolo[2,1-a]isoquinoline- 2,3-diones. The reaction of the latter with binucleophiles leads to the opening of the pyrrole ring and to the heterocyclization: Under the effect of o-phenyldiamine qinoxaline is formed, 1,2-cyclohexanediamine provides the hexahydro-benzimidazole system, о-aminophenol gives benzoxazole, 3-hydroxy-2-amino-pyridine furnishes oxazolo[4,5-b]pyridine. In the reaction with hydrazine hydrate the acylation occurs with hydrazide formation.

Russian Journal of Organic Chemistry. 2016;52(2):223-227
pages 223-227 views

Reaction of 3-(R-methylidene)-2-ethoxylindolenines with N,N'-binucleophiles

Borovik V.P., Gatilov Y.V., Shkurko O.P.

Abstract

Reactions of 3-isopropylidene- and 3-cyclohexylidene-2-ethoxyindolenine tetrafluoroborates with guanidine afford dihydropyrimido[4,5-b]indole derivatives containing a hydroxy group, unlike analogous reactions of 3-arylmethylidene and 3-(dimethylamino)methylidene tetrafluoroborates.

Russian Journal of Organic Chemistry. 2016;52(2):228-234
pages 228-234 views

One-stage synthesis of condensed pyrimidines by reaction of substituted 3-(pyrimidin-5-yl)propanoic acids with ortho-diamines: Extension of limits

Harutyunyan А.А.

Abstract

By condensation of 2-aryl-substituted pyrimidin-5-ylpropanoic acids with 1,2-ethanediamine and 1,2-benzenediamine in polyphosphoric acid new derivatives of heterocyclic systems were synthesized: imidazo- and benzo[4',5']imidazo[1',2':1,6]pyrido[2,3-d]pyrimidines. Unlike that the reaction of substituted 2-mercaptopyrimidin-5-ylpropanoic acid with 1,2-benzenediamine in polyphosphoric acid in the presence of equimolar amount of ZnCl2 proceeds by a tandem mechanism with the formation of 4-methyl-5,6-dihydrobenzo[4',5']imidazo[1',2':1,6]pyrido[2,3-d]pyrimidine-2-thiol and the corresponding disulfide.

Russian Journal of Organic Chemistry. 2016;52(2):235-239
pages 235-239 views

Synthesis of sulfonamide derivatives of pyrido-[2,1-b]quinazolin-11-one and pyrido[1,2-a]quinazolin-6-one

Shlenev R.M., Filimonov S.I., Tarasov A.V., Danilova A.S., Agat’ev P.A.

Abstract

Methods were developed of indirect introduction of sulfonamide group in the structures of pyrido-[2,1-b]quinazolin-11-one and pyrido[1,2-a]quinazolin-6-one underlain by cyclocondensation of 2-halo-5-(Rsulfamoyl) benzoyl chlorides with derivatives of 2-aminopyridine. The fact of thermal rearrangement of 8-(morpholin-4-ylsulfonyl)pyrido[1,2-a]quinazolin-6-one into isomeric 2-(morpholine-4-ylsulfonyl)pyrido[2,1-b]-quinazolin-11-one was experimentally registered.

Russian Journal of Organic Chemistry. 2016;52(2):240-243
pages 240-243 views

Synthesis and biologic properties of new thiazolylbenzodioxane derivatives

Vartanyan S.O., Avakyan A.S., Sargsyan A.B., Arutyunyan S.A., Noravyan O.S., Tsatinyan A.S.

Abstract

Reaction of 4-(1,4-benzodioxan-2-yl)thiazol-2-amine with acid chlorides afforded N-substituted amides which further were reduced into the corresponding amines. A new method was developed of preparation of 2-acetyl-1,4-benzodioxane, the initial compound in the synthesis of thiazolylbenzodioxane and numerous derivatives of this series. The adreno- and sympatholytic as well as antihypoxic effect of the obtained biheterocyclic 1,4-benzodioxane derivatives were investigated.

Russian Journal of Organic Chemistry. 2016;52(2):244-248
pages 244-248 views

Chemical transformations of betulonic aldehyde

Semenenko A.N., Babak N.L., Eremina A.M., Gella I.M., Shishkina S.V., Musatov V.I., Lipson V.V.

Abstract

Chemical transformations of 3-oxolup-20(29)-en-28-al in oxidation, reduction, reductive amination, aldol crotonic condensation, cyclopropanation, Grignard, and Wittig reactions were investigated. The structure of reaction products was established by X-ray diffraction (XRD) analysis.

Russian Journal of Organic Chemistry. 2016;52(2):249-260
pages 249-260 views

Synthesis and properties of 2,3,9,10,16,17,23,24-octakis(3-phenoxyphenoxy)phthalocyanine and its complexes with erbium of diverse structures

Koptyaev A.I., Ageeva E.S., Galanin N.E., Shaposhnikov G.P.

Abstract

Reaction of 4,5-dichlorophthalonitrile with 3-phenoxyphenol led to the formation of 4,5-bis(3-phenoxyphenoxy)phthalonitrile. It has underlain the synthesis of 2,3,9,10,16,17,23,24-octakis(3-phenoxy-phenoxy) phthalocyanine and its single and double deck sandwich complexes with erbium. As show the electron absorption spectra the complexes are dissociated in dichloromethane at concentrations below 1 × 10–5 mol L–1.

Russian Journal of Organic Chemistry. 2016;52(2):261-267
pages 261-267 views

Parquet compounds on the basis of eight- and twelve-membered structure blocks: Quantum-chemical study

Gribanova T.N., Minyaev R.M., Minkin V.I.

Abstract

Annelated structures of cyclooctatetraene and cyclododecahexene and their expanded lowmolecular derivatives were studied using DFT B3LYP method with 6-311G(d,p), 6-311(df,p), 6-311+G(3df) basis sets. Monomer systems including planar antiaromatic cycles are stable in the singlet state, whereas the corresponding triplet states are significantly destabilized. The stability of nonstandard planar forms with antiaromatic cycles is provided by steric factors and the effects of π-electron interaction between the central and peripheral fragments.

Russian Journal of Organic Chemistry. 2016;52(2):268-282
pages 268-282 views

Short Communications

Synthesis of bis(tetrahydrofuran-2-ylmethyl) sulfide and sulfoxide

Potapov V.A., Ishigeev R.S., Musalov M.V., Musalova M.V., Amosova S.V.
Russian Journal of Organic Chemistry. 2016;52(2):283-284
pages 283-284 views

Reactions of 2-perfluoroacylcycloalkanones with benzoylhydrazine

Petrov A.A., Pakal’nis V.V., Zerova I.V., Yakimovich S.I.
Russian Journal of Organic Chemistry. 2016;52(2):285-288
pages 285-288 views

Synthesis of 5-(hetarylmethylidene)pyrimidine-2,4,6(1H,3H,5H)-triones

Yurtaeva E.A., Tyrkov A.G.
Russian Journal of Organic Chemistry. 2016;52(2):289-291
pages 289-291 views

Synthesis of 2-aryl-2-(trifluoromethyl)-2,5-dihydro-1,3-thiazoles

Bentya A.V., Mel’nichenko N.V., Vovk M.V.
Russian Journal of Organic Chemistry. 2016;52(2):292-293
pages 292-293 views

7-tert-butyl[1,2,4]triazino[4',3':1,5]pyrazolo[3,4-d][1,2,3]triazine-4,8(3Н,9Н)-dione in nucleophilic substitution reactions

Mironovich L.M., Shcherbinin D.V.
Russian Journal of Organic Chemistry. 2016;52(2):294-297
pages 294-297 views