First example of conjugation of quinolizidine alkaloids with ferrocene was presented. The cytotoxic properties of the obtained conjugates against cell lines HEK293, Jurkat, A549, MCF-7 and SH-SY5Y were studied. It was found, that conjugate 17 (having ferrocenyl methylene fragment and phenyl carboxamide moiety) produced a relatively higher cytotoxicity towards cancer Jurkat and SH-SY5Y cells with weak activity against non-cancerous HEK293 cells, suggesting the selectivity of this substance to inhibit certain tumor cells. The effect of leading compound 17 on cell cycle progression of HEK293, Jurkat, A549, MCF-7 and SH-SY5Y lines in a time-dependent fashion was studied. It was shown that hit-compound 17 caused a prominent arrest of MCF-7, Jurkat and A-549 cells in S phase along with a decrease of cells in G1 and a nearly total decline of cells in G2/M; the induction of apoptosis in HEK293 and SH-SY5Y cells was cell-cycle independent. (C) 2020 Elsevier Ltd. All rights reserved.

The new natural 36DCP strain, which is capable of using 4-chlorophenoxyacetic acid (4-CPA) as the sole source of carbon and energy, was characterized. A culture isolated from a soil sample contaminated with chemical waste was identified according to physiological, biochemical, cultural, morphological features and analysis of the 16S rRNA gene sequence as a strain belonging to the Pseudomonas genus. In the batch culture, Pseudomonas sp. 36DCP degraded 45% of 4-CPA from the initial concentration after 5 days of incubation. Based on the identified intermediate metabolites in the culture medium (para-benzoquinone and hydroquinone), it was found that the conversion of 4-CPA in Pseudomonas sp. 36DCP proceeds through the hydroquinone pathway. This degradation pathway of monochlorinated phenoxyacetic acids has not previously been described in bacteria.

The alkylation of methyl 4H-thieno[3,2-b]pyrrole-5-carboxylate with methyl iodide and allyl, propargyl, and benzyl bromides in the presence of sodium hydride in THF afforded the corresponding N-substituted derivatives. Some reactions of the alkylation products were studied.

Electrophilic cyclization initiated by NBS and I 2 of 2,2-dichloro-2-[(1 R ,5 S )- and 2,2-dichloro-2-[(1 S ,5 R )-5-hydroxy-2-cyclopent-2-en-1-yl]- N -[(1 R )-1-phenylethyl]acetamides was investigated. Stable under conditions of chromatography on SiO 2 bicyclic iminoesters, (2 Z ,3a S ,4 S ,6 S ,6a S )-6-bromo-3,3-dichloro- and (2 Z ,3a S ,4 S ,6 S ,6a S )-3,3-dichloro-6-iodo-2-{[(1 R )-1-phenylethyl]imino}hexahydro-2 H -cyclopenta[ b ]furan-4-ols were isolated and characterized, and a possible version was suggested of their step-by-step recyclization transformations. The halocyclization of carboxamides in water-organic mixtures afforded bicyclic epoxylactones (1a R ,2a S ,5a S ,5b S )- and (1a S ,2a R ,5a R ,5b R )-5,5-dichlorohexahydro-4 H -oxireno[3,4]cyclopenta-[1,2- b ]furan-4-ones, whose reductive dechlorination proceeded stepwise with successive removal of Cl atoms and led to the formation of (1a R ,2a S ,5a S ,5b S )- and (1a S ,2a R ,5a R ,5b R )-hexahydro-4 H -oxireno[3,4]cyclopenta-[1,2-b]furan-4-ones.

Depending on the reaction conditions employed, the photooxidation of 4-N,N-dimethylaminophenyl azide led to the formation of 4-N,N-dimethylaminonitrosobenzene and 4-N,N-dimethylaminonitrobenzene or (5Z)-2-(dimethylamino)-5-(hydroxyimino)cyclopenta-1,3-diene-1-carbaldehyde.

Photolysis of 4-vinyloxyphenyl azide in the presence of oxygen in acetonitrile leads to the formation of a fused heterocyclic compound due to the ability of the intermediates of this reaction to undergo a unique domino reaction sequence. The rate constants and activation parameters of some elementary stages of the process are measured by flash photolysis.

Many species of wide distributed in natural ecosystems gram-positive Actinomycetes are characterized by original catabolic features that allow members of this taxon to convert aromatic hydrocarbons including their halogenated derivatives. The combination in Rhodococcus cells unique enzyme systems with resistance to adverse environmental conditions opens the opportunities to offer the members of this bacterial genus as one of the most promising group for the development of effective environment remediation in the technosphere. Unfortunately, the experimental data are scarce for most of actinomycetes destructors. We focused our attention on the features of the Rhodococcus genes, determining 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) conversion. The special primers system to the conservative tft A gene regions tft A F: 5 ''CATTCGACGGGAATTGGAA 3'', tft A R: 5 ''-AGGATTGAAGAAATCCTGATA 3'' had been used for PCR analysis [Huong NL, 2007]. The results revealed the similarity of α-subunits 2,4,5-T oxygenase genes, catalyzing the first reaction of 2,4,5-T conversion in R. rubropertinctus 5D and Burkholderia sp. M38-VN3-2W cells. The received data can be applied for the new strains destructors in vitro design.

Ozonolysis of (1 R ,3 R )- p -menth-4-en-3-ol in methylene chloride or methanol in the presence of pyridine afforded a mixture of equimolar amounts of epimeric 1-[(2 R ,4 S ,6 S )- and 1-[(2 S ,4 S ,6 S )-6-hydroxy-4-methyltetrahydro-2 H -pyran-2-yl]-2-methylpropan-1-ones. A probable reaction mechanism is discussed.

Институт органической химии Уфимского научного центра РАН Россия, Республика Башкортостан, 450054 г. Уфа, пр. Октября, 71. Тел./факс: +7 (347) 284 31 05. *Email: tvmark@anrb.ru С использованием системы праймеров к консервативным областям гена tftA Вurkholderia sp. M38-VN3–2W выявлено сходство генов α-субъединиц 2,4,5-Т-оксигеназы, катализирующей первую реакцию конверсии 2,4,5-Т, приводящую к образованию 2,4,5-трихлорфенола, у штам-мов-деструкторов 2,4,5-Т Вurkholderia sp. M38-VN3–2W и Rhodococcus rubropertinctus 5D. Ключевые слова: ПЦР, оксигеназа, актиномицеты, хлорфеноксикислоты.

The cyclization has been studied of N-(2-cyclopent-1-en-1-ylphenyl)benzamides into the corresponding 3,1-benzoxazines by the action of gaseous hydrogen chloride, trifluoroacetic acid, or bromine, and also under conditions of electron impact in the gas phase. A scheme is proposed for the fragmentation of the molecular ions of the products obtained.

Analysis of the electron impact mass spectra, collision-induced dissociation spectra, and high-resolution mass spectrometry data of N-[2-(cyclopent-1-en-1-yl)phenyl]arylamides and isomeric 2-arylspiro[3,1-benzoxazine-4,1'-cyclopentanes] indicated that only a small portion of the molecular ions of the arylamides undergo cyclization to give the corresponding substituted 3,1-benzoxazines prior fragmentation. The donor-acceptor properties of the benzene ring substituents affect the efficiency of cyclization of the molecular ions.

The chromato-mass spectrometric analysis of total alkaloids major components of Thermopsis schischkinii epigeal part from different growing areas was carried out.

It is shown that the photolysis of certain aromatic azides in the presence of oxygen leads to the formation of nitrogen-containing heterocyclic compounds via a domino reaction sequence.

GC/MS analysis was used to study the thermal stability of 2-arylspiro[3,1-benzoxazine-4,1'-cyclo-pentanes] and isomeric N-[2-cyclopent-1-en-1-yl)phenyl]arylamides. Thermal isomerization of the benzoxazines to give arylamides on the chromatographic column was detected. Change in the ratio between peak intensities of the diagnostic [M]+ and [M-C2H5]+ ions allows to determine the ratio between open and cyclic forms. Heating up to 250°C at atmospheric pressure or prolonged storage of the benzoxazines also leads to their isomerization to arylamides in quantitative yield.

The arrangement of N-[2-(cyclopent-1-en-1-yl)phenyl]benzamide to give 2-phenylarylspiro[3,1-benz-oxazine-4,1'-cyclopentane] was carried out in the presence of DCl. Analysis of the electron impact mass spectra of this benzoxazine and its deuterated analogs showed initial formation of a monodeuterated product. The contributions of polydeuterated benzoxazines increase as the reaction progresses.