Pallado-Catalyzed Cascade Synthesis of 2-Alkoxyquinolines from 1,3-Butadiynamides.

A novel synthesis strategy to access 2-alkoxyquinoline derivatives via a palladium-driven cascade reaction is disclosed. Unlike classic methods based on the alkylation of 2-quinolones with alkyl halides, the present method benefits from the de novo assembly of the quinoline core starting from 1,3-butadiynamides. Palladium-catalyzed reaction cascades with N-(2-iodophenyl)-N-tosyl-1,3-butadiynamides and primary alcohols as external nucleophiles proceed under mild reaction conditions and selectively deliver a variety of differently functionalized 4-alkenyl 2-alkoxyquinolines in a single batch transformation.

Iron Catalyzed Dearomatization of Pyridines into Annelated Azepine Derivatives in a One-Step, Three-Component Reaction.

Commercially available Fe(TTP)Cl catalyzes three-component dearomative formal cycloaddition reactions between pyridines, diazo compounds, and coumalates. Diversely substituted annelated seven-membered N-heterocycles could be generated in less than 10 min in one step at room temperature. The reaction is compatible to gram scale. The extension to benzimidazoles in place of pyridines has been successfully demonstrated. The mechanism of this reaction has been carefully examined by computational studies that corroborate the observed regioselectivities.

Persistent Organic Pollutants and Suspended Particulate Matter in Snow of Eastern Siberia in 2009-2023: Temporal Trends and Effects of Meteorological Factors and Recultivation Activities at Former Industrial Area.

Suspended particulate matter (SPM), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCP) were studied in the snow cover at urban and suburban localities in the Irkutsk region, Eastern Siberia for their temporal variations in 2009-2023, daily deposition fluxes (DDFs), and effects of some meteorological factors, as well as the effects of different technogenic activities in the industrial area of the former organochlorine enterprises of Usol'ekhimprom. SPM loads at both stations were found to be at a low level of pollution. The levels of HCB, α + γ-HCH, and ∑p,p'-DDX were lower than Russian maximum permissible levels (MPLs) in drinking water, groundwater, and surface water for household drinking and cultural purposes. The sums of all organochlorine compounds studied in snow were higher than the MPL in freshwater water bodies for fishery purposes. The levels of the DDFs of HCHs, DDTs, and heptachlorinated PCB decreased, di- and trichlorinated PCB levels increased, and HCB levels changed at a polynomial line during 2009-2023. The change in the relative composition of PCBs was found as a result of recultivation activities at the industrial area of the former organochlorine enterprise of Usol'ekhimprom. The air humidity and temperature are the key meteorological factors affecting the DDFs of PCBs and OCPs.

Media-Driven Pd-Catalyzed Reaction Cascades with 1,3-Diynamides Leading Selectively to Either Indoles or Quinolines.

Divergent Pd-catalyzed reaction cascades with various 1,3-diynamides yielding either 2-amino-3-alkynylindoles or 2-amino-4-alkenylquinolines were established. Omitting or adding TBAF (tetrabutylammonium fluoride) to the reaction of N,N-(2-iodophenyl)(4-toluenesulfonyl)-1,3-diynamides with secondary or primary amines in the presence of KOH in THF and catalytic amounts of Pd(PPh3 )4 completely changed the outcome of the reaction. In the absence of TBAF, 2-amino-3-alkynylindoles were the sole products, while the presence of TBAF switched the product formation to 2-amino-4-alkenylquinolines. Deuterium labeling proceeded selectively at the C3 and C11 positions of the 2-amino-4-alkenylquinoline products and this suggests the unprecedented formation of [4]cumulenimines from 1,3-diynamides as reactive key intermediates.

Complementary Site-Selective Halogenation of Nitrogen-Containing (Hetero)Aromatics with Superacids.

Site-selective functionalization of arenes that is complementary to classical aromatic substitution reactions remains a long-standing quest in organic synthesis. Exploiting the generation of halenium ion through oxidative process and the protonation of the nitrogen containing function in HF/SbF5 , the chlorination and iodination of classically inert Csp2 -H bonds of aromatic amines occurs. Furthermore, the superacid-promoted (poly)protonation of the molecules acts as a protection, favoring the late-stage selective halogenation of natural alkaloids and active pharmaceutical ingredients.

Freshwater seal as a source of direct and indirect increased human exposure to persistent organic pollutants in a background area.

The aim of the study is to investigate POP levels in environmental media (air, snow, soil and sediment), certain food items in the Olkhon district (Irkutsk Region, Russia) and Lake Baikal seal (nerpa) fat and meat in order to define the main pathways of elevated human exposure to POPs in the area. POP levels in soil and air samples and in almost all of the food items from the Olkhon district were comparable to levels in background areas of the Lake Baikal region. Only certain chicken eggs, large fish and blubber of nerpa pups exceeded maximum permissible levels of ΣDDTs and ΣHCHs. The combination of elevated levels of POPs in the Baikal nerpa with the use of Baikal nerpa fat (traditional nutritional habits, feed additives, as well as medicine for humans and domestic animals) results in two pathways for POPs to enter the human body: from seals it enters the human body directly, and indirectly from seals to poultry and livestock and then to the human body. Several scenarios of human exposure to POPs including the incidental ingestion of soil, inhalation of air, and ingestion of food were considered. The largest part of POPs enters the human organism through chicken eggs followed by fish and cow's milk in the scenario without the consumption of nerpa meat and blubber. The high consumption rate of fish as well as the consumption of the fat of nerpa pups or melted fat of nerpa increases the daily intake of POPs 1.3-11 times. The indexes of non-cancer risk and total cancer risk were assessed for residents of the Olkhon district and compared with indexes of risk for the average population of Irkutsk Region. Limiting the use of nerpa fat and meat as food and feed supplement reduces the potential human health risk.

PCBs and OCPs in human milk in Eastern Siberia, Russia: Levels, temporal trends and infant exposure assessment.

The aim of our study is to investigate the spatial distribution of polychlorinated biphenyls (PCBs), hexachlorobenzene (HCB), dichlorodiphenyltrichloroethane (p,p'-DDT) and its metabolites, α- and γ-isomers of hexachlorocyclohexane (HCH) in 155 samples of human milk (HM) from Eastern Siberia (six towns and seven villages in Irkutsk Region, one village of the Republic of Buryatia and one town in Zabaikal'sk Region, Russia), and to examine the dietary and social factors influencing the human exposure to the organochlorines. The median and range of the concentration of six indicator PCBs in HM in 14 localities in Eastern Siberia (114 (19-655) ng g-1 lipids respectively) are similar to levels in the majority of European countries. However, in one village, Onguren, the median and range of levels of six indicator PCBs (1390 (300-3725) ng g-1 lipids) were comparable to levels measured in highly contaminated populations. The Lake Baikal seals are highly exposed to persistent organic pollutants (POPs) and could be a potential source of PCB and DDT exposure in the Onguren cohort via the consumption of the Lake Baikal seal tissue. The location of food production in areas exposed to the emissions of local POP sources can also significantly influence POP levels in HM samples from industrialized areas. Estimated daily intakes (EDI) of HCH and HCB for infants are considerably lower or close to acceptable daily intake (ADI). The EDI of total DDTs and total PCBs are higher than ADI.

Access to pyridyl-substituted 1,3,5-triazines from 4H-pyrido[1,3]oxazin-4-ones via a cyclocondensation process.

Pyridyl-substituted 1,3,5-triazines were synthesized in good to excellent yields via an unprecedented one-step cyclocondensation of 4H-pyrido[1,3]oxazin-4-ones with amidines at room temperature or under microwave irradiations. The broad applicability was demonstrated by 33 examples with a variety of amidines and three different 4H-pyrido[1,3]oxazin-4-one chemical series. In addition, a one-pot process from 4H-pyrido[1,3]oxazin-4-one precursors (imide sodium salts) was developed and led to the desired triazines compounds, thus allowing a one-step economy in their global synthetic preparation. This approach provides rapid access to pyridyl (or pyridone)-substituted 1,3,5-triazines with high potential in various fields of application.

Polychlorinated biphenyls in surface soil in urban and background areas of Mongolia.

Polychlorinated biphenyls (PCBs) were measured in soil in some industrial towns (Ulaanbaatar, Suhbaatar, Erdenet, Darhan, Tsetserleg, Hovd, Ulaangom, Altay, Bayanhongor, Arvayheer, Saynshand, Choybalsan) and in background and rural areas of Mongolia. The average sum of all investigated PCB congeners in soil of Mongolia comes to 7.4 ng/g dry weight (DW) and varies from 0.53 ng/g DW till 114 ng/g DW. PCB levels in soil from towns are significantly higher than those in soil from background and rural areas. The PCB homological composition in soil sampled in highly-PCB-polluted sites is similar to the PCB homological pattern in Sovol and Aroclor 1254. Significant correlation between soil organic carbon and low chlorinated PCB both for towns and background sites was found. Significant differences in PCB means in soil in different natural zones were found.