Том 54, № 10 (2018)

A series of 1-alkyl-5-amino-1H-1,2,4-triazoles were synthesized starting from 3,5-dibromo-1H- 1,2,4-triazole by alkylation and subsequent nucleophilic substitution of the 5-bromine atom by azido group, reduction of the latter to amino group, and hydrodebromination.

A mechanism has been proposed for the reaction of 1,3-dichloropropene with ethane-1,2-dithiol in the system hydrazine hydrate–potassium hydroxide on the basis of DFT quantum chemical calculations [B3LYP/6-311++G(d,p)]. The proposed mechanism involves several consecutive steps, in particular nucleophilic substitution of chlorine at the sp³-hybridized carbon atom by sulfur, prototropic allylic rearrangement of the monosubstitution product with double bond migration toward the sulfur atom, dithiolane ring closure via nucleophilic attack of the second thiolate group on the carbon atom in the γ-position with respect to the second chlorine atom, and prototropic allylic rearrangement of 2-vinyl-1,3-dithiolane to more stable 2-ethylidene-1,3-dithiolane.

A short synthetic route to bicyclo[6.2.1]undec-9-ene-2,6-dione has been developed on the basis of retro-aldol reaction of 7-hydroxytricyclo[6.2.1.0^2,7]undec-9-en-3-one obtained from the Diels–Alder adducts of 3-tosylcyclohex-2-en-1-one with cyclopentadiene.

Amines of the adamantane series reacted with carbon disulfide and di-tert-butyl dicarbonate in the presence of triethylamine and a catalytic amount of 4-(dimethylamino)pyridine to give homologs of 1-isothiocyanatoadamantane in 80–86% yields. Adamantan-2-amine, 1-(adamantan-1-yl)ethanamine, and adamantan- 1-ylmethanamine turned out to be more reactive than adamantan-1-amine; in the latter case, the reaction time was twice as long.

A series of new monomers have been synthesized on the basis of O- and N-acryloyl derivatives of polyfluorinated chalcones via acylation of 4-hydroxypiperidin-1-yl and piperazin-1-yl substituents introduced in succession into different positions of the perfluorinated benzene rings. Polyfluorinated chalcone containing an epoxy group and acrylamide fragments has been obtained according to an original procedure.

Conjugates of allocolchicine and a cetirizine analog have been synthesized as potential anti-inflammatory and anti-allergic drugs.

The condensation of methyl (ethyl) phenylcarbamates with ninhydrin in concentrated sulfuric acid gave dialkyl [1,3-dioxoindan-2,2-diyldi(4,1-phenylene)]biscarbamates. Treatment of the latter with hydrazine hydrate resulted in the transformation of the indandione fragment into phthalazinone. Ninhydrin reacted with methyl (hydroxyphenyl)carbamates in glacial acetic acid to produce dihydroxy derivative of oxotrihydroindeno[ 1,2-b][1]benzofuran possessing a carbamate group. Tandem reaction of ninhydrin with methyl (acetylphenyl) carbamates on heating in boiling glacial acetic acid, followed by addition of hydrazine hydrate in acetonitrile, afforded methyl (5-oxo-5H-indeno[1,2-c]pyridazin-3-yl)phenylcarbamates.

The major product of intramolecular [3 + 2]-cycloaddition of münchnones generated by heating syn- and anti-atropisomers of N-acetyl-N-[2-(cyclopent-2-en-1-yl)-6-methyl-, 2,4-dimethyl-, 2,5-dimethylphenyl)- and N-acetyl-N-[2-(cyclohex-2-en-1-yl)-6-methylphenyl]glycines with acetic anhydride was that formed from the anti isomer. Isomeric glycine derivatives having no methyl group in the ortho position of the aromatic ring gave rise to (1S*,3aR*,4S*,7S*,13S*)-1-methyl- and (1S*,3aR*,4S*,7S*,13S*)-3a-acetyl-1-methyl-4,5,6,7- tetrahydro-1,4,7-epimethanetriyl[1,3]oxazolo[3,4-a][1]benzazocin-3(3aH)-one as the major product. Treatment of 1,11-dimethyl- and 1,9,11-trimethyl-4,5,6,7-tetrahydro-1,4,7-epimethanetriyl[1,3]oxazolo[3,4-a][1]benzazocin- 3(3aH)-ones with methylamine in methanol on heating in a sealed ampule afforded epimethanetriylimidazobenzazocinones, whereas acid-stable compound with a methanocyclopenta[c]quinoline skeleton was formed under similar conditions from the 1,8,11-trimethyl analog.

The synthesis of acyclic precursors to epothilone D analogs has been explored. Optimal conditions have been found for enolization of (1R)-1-(1,3-dithiolan-2-yl)-1-(methoxymethoxy)-2,2-dimethylpentan-3-one and its aldol condensation with C⁶‒C²¹ and C⁶‒C⁹ aldehydes.

Apart from the expected [2 + 2]-cycloaddition product, the reaction of N-chloro-N-(2-methoxy-2-oxoethyl)-β-alanine methyl ester with dichloroacetyl chloride in the presence of ethyl(diisopropyl)amine gave minor N-(1,2-dichloro-2-oxoethyl)-β-alanine methyl ester and (3E)-1,1,1-trichloro-4-(diisopropylamino)- but-3-en-2-one.

The reaction of malononitrile with acetylacetone in alkaline medium afforded a mixture of 2-amino-4,6-dimethylbenzene-1,3-dicarbonitrile and 4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carbonitrile, whereas only the latter was formed in alcoholic medium in the absence of a catalyst. The alkylation of 4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carbonitrile with allyl bromide gave a mixture of N- and O-allyl derivatives.

3-Aroylpyrrolo[1,2-c][4,1]benzoxazepine-1,2,4-triones reacted with 2-aminobenzenethiol to give 3′-aroyl-4′-hydroxy-1′-[2-(hydroxymethyl)phenyl]-2H,4H-spiro[1,4-benzothiazine-2,2′-pyrrole]- 2,5′(1′H)-diones.

New (S)-homocysteine derivatives containing a meta-carborane fragment were synthesized. m-Carboranyl-(S)-homocysteine sulfoxide was obtained as a mixture of diastereoisomers. The reduction of the side-chain carboxy group of N-tert-butoxycarbonyl-(S)-aspartic acid α-tert-butyl ester with sodium tetrahydridoborate was not accompanied by racemization.

Reference to the funding source is missing in the article:

This study was performed in the framework of the project (no. 10.735.2014/K) and base parts (no. 10.7608.2017/8.9) of state assignment of the Ministry of Education and Science of the Russian Federation in the sphere of research activity.