Search Results (737)

This paper presents the expected and unexpected, but typically substituent-dependent, ferrocene-catalyzed DDQ-mediated oxidative transformations of a series of 5,8-bis(methylthio)-1-aryl-1,2-dihydropyridazino[4,5-d]pyridazines and 8-(3,5-dimethyl-1H-pyrazol-1-yl)-5-(methylthio)-1-aryl-1,2-dihydropyridazino[4,5-d]pyridazines. Under noncatalytic conditions the reactions were sluggish, mainly producing a substantial amount of undefined tarry materials; nevertheless, the ferrocene-catalyzed reactions of the 5,8-bis(methylthio)-substituted precursors gave the aromatic products the expected aromatic products in low yields. Their formation was accompanied by ring transformations proceeding via aryne-generating fragmentation/Diels–Alder (DA)/N₂-releasing retro Diels–Alder (rDA) sequence to construct arene-fused phthalazines. On the other hand, neither the noncatalytic nor the catalytic reactions of the 8-pyrazolyl-5-methylthio-substituted dihydroaromatics yielded the expected aromatic products. Instead, depending on their substitution pattern, the catalytic reactions of these pyrazolyl-substituted precursors also led to the formation of dearylated arene-fused phthalazines competing with an unprecedented multistep fragmentation sequence terminated by the hydrolysis of cationic intermediates to give 4-(methylthio)pyridazino[4,5-d]pyridazin-1(2H)-one and the corresponding 3,5-dimethyl-1-aryl-1H-pyrazole. When 0.6 equivalents of DDQ were applied in freshly absolutized THF, a representative pyrazolyl-substituted model underwent an oxidative coupling to give a dimer formed by the interaction of the cationic intermediate, and a part of the N-nucleophilic precursor remained intact. A systematic computational study was conducted on these intriguing reactions to support their complex mechanisms proposed on the basis of the structures of the isolated products. Full article

Tocopheramines are a class of antioxidants which are distinguished from tocopherols (vitamin E) by the presence of an amino group instead of the phenolic hydroxyl group. α-Tocopheramine is intensively studied for biomedical applications but also as a stabilizer for synthetic and natural polymers, in particular for cellulose solutions and spinning dopes for cellulosic fibers. This study addresses a fundamental difference in the oxidation chemistry of α-tocopheramine and its tocopherol counterpart: while the formation of the ortho-quinone methide (o-QM) involving C-5a is one of the most fundamental reactions of α-tocopherol, the corresponding ortho-iminoquinone methide (o-IQM) derived from α-tocopheramine has been elusive so far. Synthesis of the transient intermediate succeeded initially via 5a-hydroxy-α-tocopheramine, and its occurrence was confirmed by dimerization to the corresponding spiro-dimer and by trapping with ethyl vinyl ether. Eventually, suitable oxidation conditions were found which allowed for the generation of the o-IQM directly from α-tocopheramine. The underlying oxidation chemistry of α-tocopherol and α-tocopheramine is concisely discussed. Full article

Polycyclic aromatic compounds can often be made by a sequence featuring an initial Diels–Alder [4 + 2] cycloaddition reaction, followed by cheletropic extrusion of carbon monoxide. These reactions normally require heating the diene and dieneophile in petrochemical-derived aromatic hydrocarbon solvents, such as xylenes or diphenyl ether. This article summarizes the results of attempts to use renewable solvents in place of those currently in use to prepare pentaphenylbenzene and 1,2,4-triphenyltriphenylene. Dihydrolevoglucosenone, p-cymene, ethyl lactate, diethyl carbonate, and cyclopentyl methyl ether have all been successfully evaluated as renewable solvent alternatives in Diels–Alder/cheletropic reaction sequences. An analysis of the products from the reactions investigated did not show evidence of oxidative degradation of the diene reactants. Furthermore, norbornadien-7-one intermediates were not isolated from any of the reactions tested. Full article

This study investigated the effect of in situ polymerization on the compressive strength of demolition-derived Scots pine, European beech, and black alder wood. The treatment applied was based on previously confirmed in situ polymerization systems in wood, which are known to lead to polymer formation and composite-like structures. In this study, we assumed similar behavior and focused on a mechanical evaluation of the modified wood. Three different polymer systems were applied to evaluate differences in performance. After modification, the compressive strength levels increased by 60% in beech, 119% in alder, and 150% in pine, with corresponding increases in density and weight percent gain (WPG). The highest relative improvement was observed in the least dense species, pine. The findings suggest that polymer treatment can significantly enhance the mechanical properties, likely due to the incorporation of polymer into the wood matrix; however, this inference is based on indirect physical evidence. Full article

The repair efficiency of various self-healing materials often depends on the ability of the prepolymer and curing agent to form mixtures. This paper presents a synthesis and study of the properties of modified self-healing polyurethanes using the Diels–Alder reaction (DA reaction), obtained from a maleimide-terminated preform and a series of furan–urethane curing agents. The most commonly used isocyanates (4,4′-methylene diphenyl diisocyanate (MDI), 2,4-tolylene diisocyanate (TDI), and hexamethylene diisocyanate (HDI)) and furan derivatives (furfurylamine, difurfurylamine, and furfuryl alcohol) were used as initial reagents for the synthesis of curing agents. For comparative analysis, polyurethanes were also obtained using the well-known “traditional” approach—from furan-terminated prepolymers based on mono- and difurfurylamine, as well as furfuryl alcohol and the often-used bismaleimide curing agent 1,10-(methylenedi-1,4-phenylene)bismaleimide (BMI). The structure and composition of all polymers were studied using spectroscopic methods. Molecular mass was determined using gel permeation chromatography (GPC). Thermal properties were studied using TGA, DSC, and TMA methods. The mechanical and self-healing properties of the materials were investigated via a uniaxial tensile test. Visual assessment of the completeness of damage restoration after the self-healing cycle was carried out using a scanning electron microscope. It was shown that the proposed modified approach helps obtain more durable polyurethanes with a high degree of self-healing of mechanical properties after damage. Full article

Wood is a green and renewable bio-based building material, but its hygroscopicity affects its dimensional stability, limiting its use in construction. Chemical modification can improve its properties, yet its effectiveness depends on wood permeability and traditional modifiers. This study first used a deep eutectic solvent (DES) to boost the permeability of North American alder wood. Then, methyl trimethoxysilane was impregnated under supercritical carbon dioxide (SCI), pressure (PI), vacuum (VI), and atmospheric pressure (AI) conditions. DES treatment damaged the cell structure, increasing wood permeability. Silane was deposited and polymerized in the cell lumen, chemically bonding with cell-wall components, filling walls and pits, and thickening walls. The VI group had the highest absolute density (0.59 g/cm³, +36.6%) and the lowest moisture absorption (4.4%, −33.3%). The AI group had the highest ASE (25%). The PI group showed the highest surface hardness (RL, 2592 N) and a water contact angle of 131.9°, much higher than natural wood. Overall, the VI group had the best performance. Silane reacts with cellulose, hemicellulose, and lignin in wood via hydrolysis and hydroxyl bonding, forming stable bonds that enhance the treated wood’s hydrophobicity, dimensional stability, and surface hardness. Full article

In the chemistry of bio-based furans, the Diels–Alder reaction plays an important role as a renewable route for the synthesis of fuels, fine chemicals, and monomers. Nonetheless, the unfavorable kinetic and thermodynamic parameters inherent to the Diels–Alder reaction involving furans as dienes often lead to the reversibility of cycloaddition, resulting in decreased equilibrium conversion and diastereoselectivity. In this study, we present a new strategy for overcoming the problem of reversibility in chemical reactions. We demonstrate that conducting the reaction under solvent-free conditions can facilitate the transition from a molten state formed by the initial reactants to a solid phase containing the reaction product along with an excess of the initial substrate. According to our results, such a liquid-to-solid transition of the reaction mixture can lead to exceptionally high conversion and diastereoselectivity in the furan–maleimide Diels–Alder reaction, particularly for challenging electron-poor furanic substrates. Our approach enables the reversible furan–maleimide Diels–Alder reaction to be performed in a cleaner and more environmentally friendly manner, free from the complexities associated with the use of solvents and the need for purification from side products. Full article

The Białowieża Forest is home to both primary forests under strict protection and commercial forests, which provides an opportunity to compare them in terms of the number of individuals, number of species, and composition of different animal assemblages. The main goal of our study was to compare spider assemblages inhabiting herbaceous vegetation in these two types of forest stands. Spiders were sampled using a sweep net in an oak–lime–hornbeam forest, an ash–alder forest, and an alder carr. More spiders were found in unmanaged stands compared to managed stands, but a significant difference was found only in the alder carr. Total species richness did not significantly vary between managed and unmanaged stands in all forest types. In the oak–lime–hornbeam forest, more species per sample were found in commercial stands compared to primeval stands, while the result was the opposite for the alder carr. Our research did not show a clear negative impact of forest management on plant-dwelling spiders. The impact of forest management was evident in the case of the riparian forest, where the managed stand was characterized by low canopy cover as a result of logging carried out years ago, which is likely to have resulted in differences in family composition. Full article

Palaeoecological investigations connected with extensive pre-bog, stone walls, and field systems at Kilmore, Dingle peninsula, Ireland, are presented. The main pollen profile, KLM I, spans the last 4000 years. When the record opened, pine (Pinus sylvestris) was already a minor tree, oak (probably Quercus petraea) was the main tall-canopy tree, and birch and alder were dominant locally. Substantial farming is recorded between ca. 1530 and 600 BCE (Bronze Age) when the stone walls were likely constructed. From ca. 560 CE onwards, intensive farming was conducted for much of the time. A largely treeless landscape emerged in the late twelfth century CE. Fine-spatial reconstructions of landscape and vegetation dynamics, including the timing of blanket bog initiation, are made. Post-glacial change in the western Dingle peninsula, based on published Holocene lake profiles and drawing on the new information presented here, is discussed. Reported are (a) fossil spores of the filmy ferns Hymenophyllum tunbrigense, H. wilsonii, and Trichomanes speciosum; (b) the first fossil pollen record for Arbutus unedo (strawberry tree) in the Dingle peninsula (540 CE); and (c) the first published records for Fagopyrum fossil pollen in Ireland, indicating that buckwheat was grown at Kilmore in the late eighteenth/early nineteenth centuries. Full article

Chemical control is key to minimizing agricultural losses, driving the search for more efficient and selective herbicides. This study reports the synthesis of epoxyoxirenes, their phytotoxic evaluation, and an in silico analysis to identify the protein target of the most active compound in plants. Compounds 2–19 were tested on Lactuca sativa spp., Allium cepa spp., Cucumis sativus spp., Triticum aestivum, and Bidens pilosa. The synthetic route began with anhydride 1, obtained via a Diels–Alder reaction between maleic anhydride and furan (91% yield). Anhydride 1 was converted into amides 2–7 through reactions with aromatic amines (>92% yields), followed by cyclization to imides 8–13 (60–83% yields), and subsequent epoxidation to afford epoxides 14–19 (62–98% yields). All the compounds interfered with seedling development, with compounds 2–7 showing the greatest phytotoxicity to B. pilosa at concentrations of 500 μM and 1000 μM. An in silico analysis suggested plant tubulin as a potential protein target for the most active compounds. These findings highlight epoxyoxirenes as promising scaffolds for novel herbicide development and support further investigation into their mechanism of action. Full article

Accelerating the recovery of compacted soils caused by logging machinery using bioengineering techniques is a key goal of Sustainable Forest Management. This research was conducted on an abandoned skid trail with a uniform 15% slope and a history of heavy traffic, located in the Nav forest compartment of northern Iran. The main objectives were to assess (a) soil physical properties 35 years after skidding by a tracked bulldozer, (b) the impact of natural alder regeneration on soil recovery, and (c) the contribution of alder fine-root development to the restoration of compacted soils in beech stands. Soil physical properties and fine root biomass were analyzed across three depth classes (0–10 cm, 10–20 cm, 20–30 cm) and five locations (left wheel track (LT), between wheel tracks (BT), right wheel track (RT)) all with alder trees, and additionally control points inside the trail without alder trees (CPWA), as well as outside control points with alder trees (CPA). Sampling points near alder trees (RT, LT, BT) were compared to CPWA and CPA. CPA had the lowest soil bulk density, followed by LT, BT, RT, and CPWA. Bulk density was highest (1.35 ± 0.07 g cm⁻³) at the 0–10 cm depth and lowest (1.08 ± 0.4 g cm⁻³) at 20–30 cm. The fine root biomass at 0–10 cm depth (0.23 ± 0.21 g dm⁻³) was significantly higher than at deeper levels. Skid trail sampling points showed higher fine root biomass than CPWA but lower than CPA, by several orders of magnitude. Alder tree growth significantly reduced soil bulk density, aiding soil recovery in the study area. However, achieving optimal conditions will require additional time. Full article

The regioselectivity and the molecular mechanism of the Diels–Alder reactions between N-(2,2,2-trichloroethylidene)carboxamides and dicyclohexylcarbodiimide were explored based on the ωB97xd/6-311G(d) (PCM) calculations. It was found that the reaction course is determined by polar local interactions. It is interesting that the most favored reaction channel is realized not via classical single-step Diels–Alder mechanism, but according to the stepwise scheme with the intervention of the zwitterionic intermediate. The details of the electron density redistribution along the reaction coordinate were explained using the ELF technique. Full article

Perylenediimides are an interesting group of compounds that are finding more and more applications. However, the synthetic route of obtaining and modifying them is usually very complicated, costly, and time-consuming. Therefore, the conducted research aimed to develop new, greener, electrochemical methods of obtaining unknown perylenediimides (containing 2-ethylhexyl at the nitrogen atom). For the products obtained in this way, optical and electrochemical studies were conducted and compared with DFT results (i.e., energy gaps and HOMO and LUMO levels). Asa result of optical studies, different emission wavelengths of two isomers originating from the same excitation wavelength were observed. Electrochemical studies also confirmed significant differences in properties between the obtained isomers. Spectroelectrochemical measurements were also performed; they revealed the electrochromic properties of the obtained isomers in the visible and near-infrared range. Considering all the properties (optical and (spectro)electrochemical), the obtained compounds have a high potential for use in optoelectronic devices. Moreover, unprecedented pi-expansion of cis-DBPDI via 1,2-bis(p-bromophenyl)acetylene Diels–Alder cycloaddition into the bay region was also realized successfully. Summing up, electrosynthesis and further pi-expansion via cycloaddition offer a sea of opportunities for obtaining nanographenes. Full article

The grey-headed woodpecker (Picus canus) (GHW) is one of the least-studied European woodpeckers, listed in Annex I of the Birds Directive. We examined the key environmental characteristics that determine the possibility of GHW occurrence in vast forests in northeast Poland. Woodpeckers were inventoried in spring on 54 study plots (4 km²) covering 20% of the forest area. Active territories were detected and mapped using the playback experiment of territorial voices and drumming. The generalized linear model GLM, random forest RF, and Boosting were used for modeling. GLM was used to indicate the most critical factors affecting the abundance of GHW. The number of territories in a single study plot ranged from 0 to 3; the most frequent were areas without woodpeckers. The probability of the nesting of the GHW was increasing at plots with watercourses, a bigger share of mixed forest area, and a proportion of stands over 120 years old. The calculation for all 400 quadrats allowed us to estimate the population size at approximately 180–200 breeding pairs. The overall density of GHW in the study area was assessed at 0.13/km², while at the optimal quadrats, it increased to about 0.75/km². Preference for watercourses was linked to alders growing along water banks. Near the water, there are often small meadows where the GHW can prey on ants. In turn, old-growth forests above 120 years old increased the probability of the presence of the GHW. There are more dead and dying trees in older forests, which are the ones the GHW chooses to excavate cavities. To effectively protect the habitats of the GHW, it is necessary to maintain a larger area of stands over 120 years old, mainly on wet sites. Full article

Soil erosion and surface runoff on forest road slopes are major environmental concerns, especially in harvested areas, making effective mitigation strategies essential for sustainable forest management. The study compared the effectiveness of three selected woody species on forest road slopes as a possible mitigating action for runoff and soil erosion in harvested sites. Plots measuring 2 m × 3 m were set up with three species—alder (Alnus glutinosa (L.) Gaertn.), medlar (Mespilus germanica L.) and hawthorn (Crataegus monogyna Jacq.)—on the slopes of forest roads. Within each plot, root abundance, root density, canopy percentage, canopy height, herbaceous cover percentage, and selected soil characteristics were measured and analyzed. Root frequency and Root Area Ratio (the ratio between the area occupied by roots in a unit area of soil) measurements were conducted by excavating 50 × 50 cm soil profiles at a 10-cm distance from the base of each plant in the four cardinal directions. The highest root abundance and RAR values were found in hawthorn, followed by alder and medlar in both cases. The same order of magnitude was evidenced in runoff (255.42 mL m⁻² in hawthorn followed by 176.81 mL m⁻² in alder and 67.36 mL m⁻² in medlar) and the reverse order in terms of soil erosion (8.23 g m⁻² in hawthorn compared to 22.5 g m⁻² in alder and 50.24 g m⁻² in medlar). The results of the study confirm that using plant species with dense and deep roots, especially hawthorn, significantly reduces runoff and erosion, offering a nature-based solution for sustainable forest road management. These results highlight the need for further research under diverse ecological and soil conditions to optimize species selection and improve erosion mitigation strategies. Full article