卷 55, 编号 7 (2019)

The review systematizes and generalizes modern approaches to the synthesis of ethers using metal complex catalysts.

4,5-Dibenzoyl-1H-pyrrole-2,3-diones and 4-benzoyl-5-phenyl-1H-pyrrole-2,3-diones reacted with 3-arylamino-1H-inden-1-ones at a molar ratio of 1:2 to give substituted spiro[diindeno[1,2-b:2′,1′-e]pyridine-11,3′-pyrroles]. The molecular and crystal structures of 4′,5′-dibenzoyl-1′-(4-methoxyphenyl)-5-phenyl-5H-spiro[diindeno[1,2-b:2′,1′-e]pyridine-11,3′-pyrrole]-2′,10,12(1′H)-trione were determined by X-ray analysis.

Mixed-ligand double-decker lutetium, erbium, dysprosium, gadolinium, and europium complexes with tetra-tert-butyltetrabenzoporphyrin and phthalocyanine have been synthesized, and their structure was confirmed by IR, ¹H NMR, and mass spectra. Relations have been found between the electronic absorption and luminescence spectra of the complexes and radius of the central metal ion.

The condensation of 7-amino-1-benzyl-3-tert-butyl-4-oxo-1,4-dihydropyrazolo[5,1-c][1,2,4]triazine-8-carbonitrile with formic acid afforded 1-benzyl-3-tert-butylpyrimido[4′,5′:3,4]pyrazolo[5,1-c][1,2,4]-triazine-4,10(1H,9H)-dione which was also synthesized by alkylation of 3-tert-butylpyrimido[4′,5′: 3,4]pyrazolo[5,1-c][1,2,4]triazine-4,10(1H,9H)-dione with benzyl chloride. The reactions of 1-benzyl- and 1-butyl-3-tert-butylpyrimido[4′,5′: 3,4]pyrazolo[5,1-c][1,2,4]triazine-4,10(1H,9H)-diones with butyl bromide and benzyl chloride, respectively, under harsh conditions gave substitution products at the N⁹ atom, the corresponding 1-benzyl-9-butyl and 9-benzyl-1-butyl derivatives. The alkylation of 3-tert-butyl pyrimido[4′,5′: 3,4]-pyrazolo[5,1-c][1,2,4]triazine-4,10(1H,9H)-dithione and its 8-methyl derivative in alkaline medium led to the formation of alkyl derivatives at the sulfur atom in the 10-position.

3,3′-(Ethane-1,2-diyl)-, 3,3′-(butane-1,4-diyl)-, 3,3′-hexane-1,6-diyl-, and 3,3′-[azanediylbis(ethane-2,1-diyl)]bis(2-methylquinazolin-4(3H)-ones) were synthesized by reactions of 2-methyl-4H-3,1-benzoxazin-4-one with ethane-1,2-diamine, butane-1,4-diamine, hexane-1,6-diamine, and N-(2-aminoethyl)ethane-1,2-di-amine, respectively, and their condensation with aromatic and heterocyclic aldehydes in acetic anhydride under reflux afforded the corresponding bis[2-[(E)-2-arylethenyl]quinazolin-4(3H)-ones].

5-(Arylmethylidene)pyrimidine-2,4,6(1H,3H,5H)-triones reacted with substituted benzaldehyde oximes in the presence of N-bromosuccinimide and triethylamine to give 1,4-diaryl-2-oxa-3,7,9-triazaspiro-[4.5]dec-3-ene-6,8,10-triones and 3,4-diaryl-1,2,5-oxadiazole N-oxides.

Mono-, di-, and trichlorobiphenyls showed different reactivities toward alkali in 2-aminoethanol under reflux: 3-chlorobiphenyl remained unchanged, 2,4,5- and 2,4′,5-trichlorobiphenyls were completely converted to hydroxy derivatives, whereas 3,4-dichlorobiphenyl and a mixture of 2,4′-, 3,4′-, and 4,4′-dichlorobiphenyls gave rise to chlorobiphenyls in addition to hydroxybiphenyls.

The condensation of malononitrile with unsymmetrical dienones of the cyclohexane series under basic conditions selectively afforded substituted tetrahydroquinolinecarbonitriles. The reaction of 2,6-bis-(3-nitrophenylmethylidene)cyclohexan-1-one with malononitrile under similar conditions led to the formation of substituted tetrahydrochromenecarbonitrile. Factors determining the reaction direction and selectivity were discussed. The structure of the newly synthesized compounds was confirmed by IR and ¹H NMR spectra.

Prolylproline has been synthesized by both classical peptide synthesis method utilizing tert-butoxycarbonyl or trifluoroacetyl protection of the NH group and carbodiimide-promoted peptide bond formation and by opening of the dioxopiperazine ring in octahydrodipyrrolo[1,2-a:1′,2′-d]pyrazine-5,10-dione obtained by thermolysis of proline methyl ester.

3-Acylpyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones reacted with thiocarbonohydrazide to give mixtures of 4-amino-6-(acylmethyl)-3-sulfanylidene-3,4-dihydro-1,2,4-triazin-5(2H)-ones and 6-substituted 1,4-benzoxazine-2,3-diones which can be separated by fractional crystallization directly from the reaction mixture. The reaction is likely to involve a sequence of nucleophilic transformations with intermediate formation of spiro[pyrrole-2,6′-[1,2,4]triazines] which undergo cleavage of the C²-N¹ bond in the pyrrole ring. The structure of the products was determined by X-ray analysis, and intermediate products were identified by UPLC/MS. 1,2,4-Triazine derivatives can also be synthesized independently from alkyl 2,4-dioxobutanoates or 2-oxobutanedioic acid and thiocarbonohydrazide. The known procedure for the synthesis of 4-amino-1,2,4-triazines from 4-aryl-2,4-dioxobutanoic acids and thiocarbonohydrazide was improved to meet the “green chemistry” principles. Two new methods for the synthesis of substituted 4-amino-1,2,4-triazines were developed. The obtained compounds attract interest for medicinal chemistry, pharmacology, and fine organic synthesis.

Two series of substituted pyridyl 4-chlorobenzoates have been synthesized by microwave-assisted condensation of the corresponding 2-oxo-1,2-dihydropyridine-3-carbonitriles with 4-chlorobenzoyl chloride under solvent-free conditions. Alternatively, some compounds have also been prepared by conventional heating in methylene chloride in the presence of triethylamine. The structure of the synthesized compounds has been confirmed by spectral data (FTIR, 1D and 2D NMR). The new pyridyl benzoates were evaluated for antibacterial activity against gram-negative and gram-positive bacteria. The activity of 3-cyano-5-[(4-hydroxyphenyl)diazenyl]-4-methyl-6-phenylpyridin-2-yl 4-chlorobenzoate against gram-positive bacteria (Bacillus subtilis and Staphylococcus aureus) was comparable to that of amikacin used as standard antibiotic.

Ten N(N′)-arylbenzamidines were synthesized in 60–77% yield by one-pot microwave-assisted reaction of the corresponding N-arylbenzamides with aniline or ammonia in the presence of copper(II) oxide powder. The synthesized compounds were evaluated in vitro for inhibitory activity against several enzymes, namely acetylcholinesterase, butyrylcholinesterase, lipoxygenase, α-glucosidase, urease, and reverse transcriptase. Some compounds showed very good acetylcholinesterase and butyrylcholinesterase inhibitory activity. N′-(1,3-Benzothiazol-2-yl)- and N′-(1,3,4-thiadiazol-2-yl)benzamidines were the most active α-glucosidase inhibitors with IC₅₀ values of 134.2 and 244.57 µM, respectively. N′-(1,3-Benzothiazol-2-yl)benzamidine also inhibited urease. Most of the obtained compounds showed inhibitory activity against reverse transcriptase (anti-HIV activity), presumably due to intermolecular hydrogen bonding, good solubility, and hydrophilicity.

A series of propargyl and allyl carbamates were prepared directly from propargyl and allyl alcohols and phenyl or cyclohexyl isocyanate or indirectly by generating the isocyanates in situ from the corresponding Cbz-protected amines. The obtained carbamates underwent intramolecular nucleophilic cyclization in presence of cesium hydroxide monohydrate as a base catalyst under conventional and ultrasonic irradiation conditions to give the corresponding substituted 4-(benzylidene)methylidene-2-oxazolidinones in good to excellent yields. The use of ultrasonic irradiation provided remarkably improved yield of the cyclization products and significant shortening of the reaction time. In some cases the reaction was highly stereoselective, and (Z)-4-benzylideneoxazolidinones were formed as a single stereoisomer. A series of biological tests were performed to evaluate the inhibitory potential of all synthesized compounds against some protein kinases.