Vol 59, No 1 (2023)

The review demonstrates new areas of application of ninhydrin as a universal reagent in organic synthesis for the construction of a wide range of polycyclic compounds with benzofuran, pyrroline, pyrrole, imidazole, pyrimidine, propellanic and other fragments.

When perfluorinated 1-methyl- and 1-ethylbenzocyclobutenes, 2-methyl- and 2-ethylbenzocyclobutenones react with 20% oleum at 150°C, 3-perfluoroalkyl-4,5,6,7-tetrafluorophthalides and perfluoro-3hydroxy-3-alkylphthalides are formed in approximately equal proportions. Along with them, perfluoro-2hydroxy-2-methylbenzocyclobutenone was obtained in the reaction of perfluoro-2-methylbenzocyclobutenone with oleum at 100°C. Under the action of oleum, perfluoro-2-phenylbenzocyclobutenone forms perfluoro-2-benzoylbenzoic acid, and polyfluorobenzocyclobutene-1,2-diols form their cyclic sulfates.

The recyclization reaction of tetraoxathiaspiroalkanes and tetraoxathiocanes with primary amines ( o , p -fluoroanilines, m , p -chloroanilines, o -toluidine, o , p -anisidines, ammonium chloride) to obtain cycloazadiperoxides under the action of samarium nitrate crystal hydrate as a catalyst was studied. The possibility of recycling N -( tert -butyl)hexaoxaazadispirocycloalkanes with arylamines to the corresponding azatriperoxides was shown. It was found that the rate of the recyclization reaction depends on the nature of the central heteroatom in the heterocycle (S > N > O).

A previously unknown sulfur-containing alcohol, 1-(benzylsulfanyl)octane-2-ol, was synthesized in 65% yield. Further, on the basis of the obtained alcohol, formaldehyde, and aliphatic (diethyl-, dibutyl-, dipropyl-, dipentyl-, dihexylamine) or heterocyclic (piperidine, morpholine, hexamethyleneimine) amines, new representatives of 2-aminomethoxy derivatives of 1-(benzylsulfanyl)octane-2-ol were obtained by Mannich condensation. The yield of target products was 68-75%. The physicochemical data of the synthesized compounds were determined. The composition and structure of the obtained compounds were confirmed by elemental analysis, IR, ¹H NMR spectroscopy, and mass spectrometry. The resulting products are colorless liquids with a characteristic odor, insoluble in water, and readily soluble in organic solvents. The synthesized compounds were tested for antimicrobial activity against pathogenic and conditionally pathogenic microorganisms. The antimicrobial activity of the substances was studied by the method of serial dilutions. The results obtained showed that the tested compounds exhibit more pronounced antimicrobial activity than alcohol, carbolic acid (phenol), rivanol, nitrofungin, furacillin and chloramine used in practice. The synthesized compounds have also been tested as antimicrobial additives to oils, and it has been found that they effectively suppress the vital activity of microorganisms.

Ethyl ester of 12-chlorosulfodehydroabietic acid, when reacted with the methyl esters of glycine, methionine, leucine, glutamic acid, tyrosine, proline, histidine, for the first time yielded the corresponding sulfonamides, the ester group (-COOMe) of which was selectively transferred to the hydrazide (-COONHNH₂) without affecting the ethyl group bounded with the dehydroabietic acid fragment. In the case of glutamic acid, the corresponding dihydrazides were obtained. The reaction of 12-chlorosulfodehydroabietic acid ethyl ester with cystine dimethyl ester led to the selective formation of bis-sulfonamide, while carrying out the same reaction in an acetone-contained solution was accompanied by the cleavage of the disulfide bond of the cystine fragment to give thioketal. The obtained bis-sulfonamide and thioketal were oxidized with chlorine dioxide to afford in both cases sulfochloride.

The synthesis of the title compound from l-threonine with the participation of β-metallyl chloride amide in the N -alkylation step is described.