卷 60, 编号 5 (2024)

BODIPY derivatives (4,4-difluoro-4-boron-3a,4a-diaza-S-indacene) due to their high molar extinction coefficients and fluorescence quantum yields and photochemical stability have gained popularity as optical sensors in the field of bioimaging and detection of various analytes. BODIPY molecules differ in substituents not only at the meso-carbon atom, but also at the boron atom. The review article provides information on various approaches to the synthesis of BODIPY derivatives and methods for obtaining “classical” BODIPY, in which the boron atom has 2 fluorine atoms as substituents (F₂-BODIPY). The advantages and limitations of synthesis methods are considered, the use of reagents and the frequency of their use are analyzed. Based on literature data, reaction mechanisms for the synthesis of BODIPY derivatives are proposed, attention is paid to the reasons affecting the yield of BODIPY derivatives, including low stability of reagents, the formation of by-products, and the influence of water.

The synthesis was carried out and the transformations of 1-aryladamantanes in fuming nitric acid were studied. The reactions include nitroxylation of saturated cage and nitration of the aromatic moiety and lead to 3-(dinitroaryl)-1-adamantylnitrates. A number of new polyfunctional compounds have been synthesized based on reactions of substituted 3-(dinitroaryl)-1-adamantyl nitrates with nucleophiles in concentrated sulfuric acid. Due to the multifunctionality, the obtained compounds can be used as starting materials in the synthesis of substances with a wide spectrum of biological activity and materials with a complex of valuable properties.

The interaction of chloromethyl(ethyl)allyl ether with carbonyl compounds, with the participation of zinc ground into small shavings, catalytic amounts of HgCl₂ in ethyl acetate, leads to chloromethyl(ethyl)allyl monoethers of α-glycols in moderate yield (68.2%).

New 5'-methylamino-2´-nitro-m-terphenyls were obtained by rearrangement of quaternary nitropyridinium salts under the action of aqueous alcoholic alkali and aqueous methylamine. 4-Aryl-2-methyl-5-nitro-6-phenyl-1,4-dihydropyridines of Hantzsch obtained by cyclocondensation of nitrochalcones with various enamines were used as starting compounds. By oxidation of 1,4-dihydropyridines with sodium nitrite in acetic acid, 4-aryl-2-methyl-5-nitro-6-phenylpyridines were synthesized. Dimethyl sulfate and fluorosulfonic acid methyl ester were used for alkylation nitropyridines.

N-substituted 3,5-dimethyl-4-nitroso-1H-pyrazoles was oxidized and reduced. The resulting 4-aminopyrazole was acylated, diazotized with further azo coupling or amino group replacement by iodine. Aminopyrazole was also condensed with 4-nitrobenzaldehyde. The first condensation of nitrosopyrazole with 2,4-dinitrotoluene was shown. As a result, new functionalised pyrazole derivatives were isolated. The structure of novel pyrazoles was confirmed by IR, ¹H, ¹³C NMR spectroscopy, gas chromatography-mass spectrometry, and elemental analysis. The obtained compounds are promising for further research in medicine and pharmaceutical chemistry.

The possibility of using new 7-methylazolo[1,5-a]pyrimidine-6-carbonitriles for the construction of heterocyclic systems annulated at the pyrimidine ring has been demonstrated. Cascade cyclizations are carried out by intermediate preparation of dimethylaminovinyl derivatives. The peculiarity of using ammonia or aliphatic amines as N1 synthons in cascade reactions, depending on the process conditions used, is shown.

A method for the synthesis of 2-amino-3-(3,4-dihydroxyphenyl)propanoic acid, a racemic form of the antiparkinsonian drug levodopa and a biosynthetic precursor of melanins, has been developed. This amino acid is obtained in three steps with total yield of 59%, which exceeds previously published data. At the first step, the condensation of 3,4-dimethoxybenzaldehyde with benzoylglycine produced azlactone with 83% yield, followed by hydrolysis and reduction by Raney alloy in an alkaline solution, carried out in one step gave 3-(3,4-dimethoxyphenyl)-2-benzoylamineopropanoic acid with 90% yield. Further removal of the protective groups with hydrobromic acid followed by treatment with an aqueous ammonia solution resulted in 2-amino-3-(3,4-dihydroxyphenyl)propanoic acid with 80% yield. The structure of all compounds obtained was confirmed by NMR and IR spectroscopy and elemental analysis. The X-ray diffraction analysis data of (Z)-2-benzamido-3-(3,4-dimethoxyphenyl)acrylic acid - an intermediate in the synthesis of DOPA has been provided for the first time in this paper.