Abstract: : 2,3-dihydro-5,6,7,8-tetranitro-1,4-benzodioxine (TNBD), molecular formula =C8H4N4O10 is a completely nitrated in aromatic ring 1,4-benzodioxane derivative. The con-venient method of TNBD synthesis was developed (yield=81 %). The detailed structure of this compound has been investigated by X-ray crystallography. The results of differential thermal analysis (DTA) obtained with twice re-crystallized material showed onset at 247 and isoterm at 288 0C, with further total degradation at 300 0C. The experimental density 1,85 g/cm3 of TNBD was determined by X-ray crystallography. The spectral properties of TNBD (NMR, FT-IR, Ra-man) were explored. The detonation properties of TNBD calculated by EXPLO 5 code was slightly superior in comparison to standard high energy material - tetryl (detonation velocity of TNBD - 7727 m/s; detonation pressure - 278 kbar; tetryl – 7570 m/s and 226.4 kbar at 1.614 g/cm3, or 260 kbar at higher density - 1.71 g/cm3. The obtained preliminary results might suggest TNBD can be a potential thermostable high energy and density material (HEDM).

In spite of unique structural, spectroscopic and redox properties, the synthetic variants of the planar, antiaromatic hexaphyrin (1.0.1.0.1.0) derivatives 2, has been limited due to the low yields and difficulty in access to the starting material. A chemical modification of the meso-substituents could be good alternative overcoming the synthetic barrier. Herein, we report a regio-selective nucleophilic aromatic substitution (SNAr) of meso-pentafluorophenyl group in rosarrin 2 with catechol. The reaction afforded benzodioxane fused rosarrin 3 as single product with high yield. The intrinsic antiaromatic character of the starting rosarrin 2 retained throughout the reactions. Clean, two electron reduction was achieved by treatment of 3 with SnCl2•2H2O affording 26pi-electron aromatic rosarrin 4. The synthesized compounds exhibited noticeable changes in photophysical and redox properties compared with starting rosarrin 2. .

Groundwater contamination by nitrate and organic chemicals (e.g. 1,4-dioxane) is a growing worldwide concern. This work presents a new approach for simultaneously treating nitrate and 1,4-dioxane, which is based on UV sensitization of nitrate and sulfite, and the production of reactive species. Specifically, water contaminated with nitrate and 1,4-dioxane is irradiated by a UV source (< 250 nm) at relatively high doses, to sensitize in-situ nitrate and generate HO•. This leads to the oxidation of 1,4-dioxane (and other organics), and the (undesired) production of nitrite as an intermediate. Subsequently, sulfite is added at an optimized time-point, and its UV sensitization produces hydrated electrons which reacts and reduces nitrite. Our results confirmed the effectivity of the proposed treatment: UV irradiation of nitrate (at > 5 mg N/L) efficiently degraded 1,4-dioxane, while producing nitrite at levels higher than 1 mg N/L (its MCL in drinking water). Adding sulfite to the process after 10 minutes of irradiation reduced the concentration of nitrite, without affecting the degradation rate of 1,4-dioxane. The treated water contained elevated levels of sulfate; albeit at much lower concentration than its MCL. Treating water contaminated with nitrate and organic chemicals (often detected concomitantly) typically requires several (expensive) treatment processes. The proposed approach may present a cost-effective alternative, employing a single system for the treatment of nitrate and organic contaminants

Cancer remains a primary cause of mortality, with over 18.1 million new cases and 9.6 million deaths globally in 2018. Chemotherapy, which utilizes a spectrum of cytotoxic drugs targeting rapidly dividing cancer cells, is a predominant treatment modality. However, the tendency of chemotherapeutics to induce drug resistance and exhibit non-specific cytotoxicity necessitates the development of new anticancer agents with heightened efficacy and minimized toxicity. In recent years, the discovery of safe and effective antibacterial/antiviral agents has also been a hot spot in medicinal chemistry. This paper comprehensively reviews the synthesis, anticancer/ antibacterial/antiviral activity, and structure-activity relationships of natural 1,4-naphthoquinones and their derivatives. It highlights their potential as efficient and low-toxicity anti-tumor and anti-infectious drug candidates.

3,4-Dihydro-2(1H)-pyridones (3,4-DHPo) and their derivatives are privileged structures present in natural products, which has been increased its relevance due to its biological activity in front of a broad range of targets, but especially for its importance as synthetic precursors of a variety of compounds with marked biological activity. Taking into account the large number of contributions published over the years regarding this kind of heterocycle, here we presented a current view of 3,4-dihydro-2(1H)-pyridones (3,4-DHPo), which include general aspects such as those related to nomenclature, synthesis, and biological activity; but also highlighting the importance of DHPo as building blocks of other relevance structures.

A series of penta-1,4-dien-3-one containing a H-phosphonate scaffold were designed and synthesized. The structures of all title compounds were determined by 1H-NMR, 13C-NMR, 31P-NMR, and HRMS. Bioassay results showed that several of the title compounds exhibited remarkable antibacterial and antiviral activities. Among these, compounds 3c and 3o exhibited substantial antibacterial activities against Xanthomonas oryzae pv. Oryzae (Xoo) and Xanthomonas axonopodis pv. citri (Xac). In addition, compounds 3c, 3f, and 3r showed remarkable curative activities against tobacco mosaic virus (TMV), with 50% effective concentration (EC50) values of 290.0, 234.0, and 373.6 μg/mL, respectively. These were superior to that of ningnanmycin (386.2 μg/mL). Compound 3r exhibited comparative protective activity against TMV, with an EC50 value of 291.1 μg/mL, which was better than that of ningnanmycin (297.1 μg/mL). Notably, the solubility of all title compounds improved relative to the lead compound curcumin. These results suggest that penta-1,4-dien-3-one containing a H-phosphonate scaffold may be considered as an activator for antibacterial and antiviral agents.

The reaction mechanisms of C-S borylation of aryl sulfides catalyzed by the 1,4-benzoquinone (BQ), were investigated by employing M06-2X-D3/ma-def2SVP method and basis set. In this study, the SMD model was taken to simulate the solvent effect of 1,4-dioxane. Also, TD-DFT calculations of BQ and methyl(p-tolyl)sulfane were performed in SMD solvent model. The computational results indicated that BQ and methyl(p-tolyl)sulfane, serving as a photo-catalyst, would be excited under blue LED of 450 nm, aligning well with experimental observations. Additionally, the role of 3O2 was investigated, revealing that it could be activated to 1O2 from the released energy of 1[BQ+methyl(p-tolyl)sulfane]* or 3[BQ+ methyl(p-tolyl)sulfane]*→BQ+ methyl(p-tolyl)sulfane process. Then 1O2, bis(pinacolato)diboron, and methyl(p-tolyl)sulfane would through a series of reactions to yield the final product P. The Gibbs free energy surface show that path a2-2 is optimal and this path has less steps and lower energy barrier. The electron spin density isosurface graphs were employed to analyze structures and elucidate the single electron distribution. These computational results offer valuable insights into the studied interactions and related processes and shed light on the mechanisms governing C–S borylation from aryl sulfides and b2pin2 catalyzed by BQ and methyl(p-tolyl)sulfane.

A visible-light photoredox functionalization of 3,4-dihydro-1,4-benzoxazin-2-ones through a Friedel-Crafts reaction with indoles using an inexpensive organophotoredox catalyst is described. The reaction uses a dual catalytic system formed by a photocatalyst simple and cheap, 9,10-phenanthrenedione, and a Lewis acid, Zn(OTf)₂. 5W white LEDs are used as visible-light source and oxygen from air as a terminal oxidant, obtaining the corresponding products with good yields. The reaction can be extended to other electron-rich arenes.

A series of novel chiral nonmetallocene pincer-type rare earth metal dialkyl complexes bearing the chiral monoanionic tridentate C2-symmetric 1,3-bis(oxazolinymethylidene)isoindoline (BOXMI) ligand (BOXMI)Ln(CH2SiMe3)2 1-3 (1, Ln = Sc, yield = 57%; 2, Ln = Lu, yield = 55%; 3, Ln = Y, yield = 62%) have been prepared in moderate yields via the acid-base reaction between the BOXMI ligand and rare earth metal tri(trimethylsilylmethyl) complexes. The X-ray diffractions show that both of the complexes 1 and 2 contain one Boxmi ligand and two trimethylsilylmethyl ligands, adopting a distorted-trigonal-bipyramidal configuration. In the presence of cocatalyst such as borate and AlR3, these complexes 1-3 exhibit high activities up to 6.8 × 104 (g of polymer)/(molLn h) and high cis-1,4-selectivities up to 97%) in the polymerization of isoprene in toluene, yielding the cis-1,4-polyisoprenes with high molecular weights (Mn up to 710000 g/mol) and bimodal molecular weight distributions (Mw/Mn = 2.0-4.5).

In this work, an attempt is made to the theoretically substantiate the experimentally known facts of the influence of halogen concentration on the catalytic properties of the neodymium-based Ziegler–Natta system. Based on the structural and thermochemical data obtained using modern methods of quantum chemistry, the process of the 1,3-butadiene cis-1,4-polymerization under the model active centers of the neodymium Ziegler-Natta catalysts with different content of chloride ions was studied. Results are presented that explain the increase in the cis-stereospecificity and activity of the polymerization system with an increase in the content of the chloride ions in the neodymium catalytic system. There were established the reasons for the decrease in the concentration of active centers relative to the introduced Nd(III) with an excess of chloride ions and the occurrence of the anti-syn isomerization as a source of the formation of the trans-1,4-structures in the cis-1,4-polybutadiene.

Polyesters based advanced thin films have versatile industrial applications, especially in the filed of textiles, packaging and electronics. Recent advances in polymer science and engineering resulted in development of advanced amorphous and semi-crystalline polyesters with exceptional performance compared to conventional polymeric films. Among these, 1,4-cycloheanedimethanol (CHDM) and cyclic monomer-based polyesters have gained considerable attention attention for their exceptional characteristics and potential applications in smart films. This review article provides a comprehensive overview of the recent advances in the synthesis, characterization, and applications of CHDM and cyclic monomer based advanced polymers for smart film applications. It discussed the structure-property relationship of these innovative polyesters and highlights their unique characteristics including thermal, mechanical, and barrier characteristics. Furthermore, this article also emphases the solution, melt, and solid state polymerization of the polymers. Special emphasis is placed on the influence of the addition of 2nd diol or 2nd diacid on the performance characteristics of synthesized polyesters/copolyesters to explore their versatile industrial applications. Additionally, the impact of stereochemistry of the monomers is also explored to optimized the characterization of polyester, suitable for the industrial applications. Furthermore, this article explores the potential of these advanced polyesters to be considered as a potential materials for smart film applications, especially in the filed of flexible electronics. Finally, the article examines the challenges and future recommendations for the development CHDM and cyclic monomer-based polyesters for smart film applications. It discusses potential avenues for further research, including in-depth studies for the synthesis and characterization of polyesters, development of sustainable and biodegradable alternatives cyclic monomers, alternative green approaches for the synthesis of polymers etc. This review article provides a valuable insights for the researcher from academia and industry working in the field of polymer science and materials engineering.

There is a strong global demand for sulfate- free personal cleansing products. The objective of sulfate-free personal cleansing technology should not be aimed at the absence of “sulfate” wording in the ingredient listing, but on the true benefits to both people and the planet, including but not limited to safety, mildness, and sensory for the people perspective and renewability, low carbon footprint, low water footprint, biodegradability &amp; sustainability for the planet perspective. In addition, some surfactants or their precursors contain 1,4-dioxane as a by-product in their manufacturing, which is a major safety concern. In this paper, several commonly used sulfate-free surfactants are compared based on a variety of desirable criteria from both the people and the planet perspective. There is also an important trend promoting green manufacturing processes using natural, renewable, safe, biodegradable &amp; sustainable feedstocks to mitigate the challenges presented by climate change. It is concluded that the best options for the sulfate-free personal cleansing products of the future are glutamates for skin cleansing and alaninates for hair cleansing.

We hereby describe an efficient method for the preparation of a series of new 1-substituted 1,2,3-triazole-based acetaminophen derivatives through a clean, good-yielding, simple, and expeditious procedure based on the O-propargylation reaction of the acetaminophen (APAP) obtained from expired commercial tablets and the CuBr(PPh3)3-catalyzed Huisgen reaction be-tween O-propargylated APAP and diverse organoazides prepared from commercially available anilines as available starting reagents. An interesting nitric oxide-releasing 1,2,3-triazole hybrid of APAP was also obtained easily using the developed method. The structures of the designed hybrid compounds, which are expected to be pharmacologically active, were fully characterized by FT-IR, 1H- and 13C-NMR and are reported for the first time. According to the in-silico studies performed in this work and literature analysis, these hybrids are interesting models in search of new pharmacological nontoxic agents endowed with anti-inflammatory and anticancer properties.

Bacillus veleznesis RB.EK7 was recently found as a potent rhizobacterial strain for effective management of black pepper root-knot nematodes. This work aimed to produce, purify, and elucidate the chemical structures of antinematode compounds (ANCs). Concerning cost-effectiveness and environmental issues, this study used organic wastes for the bioproduction of ANCs. Among various substrates, shrimp shells powder was the most suitable carbon/nitrogen source to produce ANCs. The fermentation process for enhancement of antinematode activity was investigated. The targeting ANCs were purified from the fermented culture broth, and their structures were elucidated. Two active compounds were thymine (1) and hexahydropyrrolo [1,2-a]pyrazine-1,4-dione (2). Notably, for the first time, these purified compounds showed potential and moderate anti- J2 nematodes and anti-eggs hatching, respectively. The docking study results indicated that the potent antinematode effect of these compounds may be possibly due to the inhibition of the targeting enzyme acetylcholinesterase. The data of this work suggest that organic waste SSP can be potentially reused for the production of thymine and hexahydropyrrolo [1,2-a] pyrazine-1,4-dione with promising use for the management of black pepper nematodes.