Minor limonoid constituents from Swietenia macrophylla by simultaneous isolation using supercritical fluid chromatography and their biological activities.

This study reports simultaneous isolation of three new limonoids (1-3), six known regio isomers (6, 7, 9-12), and three more known limonoids (4, 5, 8) from Swietenia macrophylla (S. macrophylla) seeds. Structures of these compounds were determined via extensive study of their 1D/2D-NMR and mass spectral data. Known limonoids (4-12) were identified by comparing their physical and spectroscopic data with literature values. A novel environmentally friendly supercritical fluid chromatography (SFC) technique facilitated simultaneous and rapid separation of these compounds. The pharmacological activities of the new limonoids were investigated.

Synthesis of Carbon Dots via Microwave-Assisted Process: Specific Sensing of Fe(III) and Antibacterial Activity.

Carbon dots synthesized from a renewable and sustainable source of biomass have greater attention in the nanomaterial research field. In the present study, we adopted a facile and green synthesis of carbon dots from bio waste of pumpkin seeds using a one-pot microwave-assisted carbonization method. The synthesized carbon dots exhibit excellent photoluminescence properties with a bright blue emission peak at 399 nm and fluorescence quantum yield was about 9.5%. The optical properties and structure of carbon dots were examined using various spectroscopy techniques and the synthesized carbon practical size was about 4.37 nm and possessed good solubility in water. Carbon dots were used for the detection of Ferric ions in the water bodies and the interaction between Fe3+ ions and carbon dots was evaluated by fluorescence spectroscopy techniques. This method is a simple and selective detection of Fe3+ in the aqueous medium. Interestingly carbon dots also show good antibacterial activity at a very low concentration (1 mg/L) for effective control of E. coli 93% and Pseudomonas aeruginosa (81%), within 12 h.

Correction: Efficient amidation of weak amines: synthesis, chiral separation by SFC, and antimicrobial activity of N-(9,10-dioxo-9,10-dihydroanthracen-1-yl)carboxamide.

Correction for 'Efficient amidation of weak amines: synthesis, chiral separation by SFC, and antimicrobial activity of N-(9,10-dioxo-9,10-dihydroanthracen-1-yl) carboxamide' by Kathiravan Asokan et al., Org. Biomol. Chem., 2024, 22, 309-319, https://doi.org/10.1039/D3OB01774E.

Eco-friendly and sustainable process for recovery of sulfate from paper mill mixed salt: Recycling of sulfate for dye fixation process.

Paper mill Electrostatic Precipitator (ESP) ash contains a mixture of alkali metal chloride (34.2 %) and sulfate (84.2 %) which has serious negative effects on the environment and makes it more expensive and constrained to dispose ESP ash. Therefore, handling and recycling ESP ash demands extra thought when disposing of it. Present study, aimed to separate chloride and sulfate from ESP ash using electrochemical membrane technology. Three different concentrations of ESP ash solution such as 200 g L-1, 320 g L-1 and 450 g L-1 were used as the electrolyte. Ti/TiO2-IrO2-RuO2 and titanium (Ti) are used as anode and cathode respectively. Caustic and sulfate solutions were recovered at the respective compartments. The collected sulfate solution was dried by solar light to convert 99 % sulfate salts as confirmed by Energy-dispersive X-ray analysis (EDAX) analysis. Recovered sulfate salt was used for the dye fixing process, in which the colour fixing difference of ΔE value was about 2.10 and the strength of the dye was about 86.72 %. Therefore, the textile industry can repurpose the recovered sulfate salt for the dye fixing process.

Efficient amidation of weak amines: synthesis, chiral separation by SFC, and antimicrobial activity of N-(9,10-dioxo-9,10-dihydroanthracen-1-yl) carboxamide.

An effective and straightforward method for the synthesis of 1-aminoanthracene-9,10-dione carboxamides by coupling a weakly reactive amine, 1-aminoanthracene-9,10-dione, and sterically hindered carboxylic acids was achieved using COMU as the coupling agent. Furthermore, making use of the advantages associated with the super-critical fluid chromatography (SFC) technique, a simplified and straightforward method for the chiral separation of optically active amide derivatives from the impurities associated with the reaction mixture, in a single step, was demonstrated. The antimicrobial activity of selected 1-aminoanthracene-9,10-dione carboxamides was studied. Advanced NMR and other spectral techniques were used for the thorough characterization of all the compounds. This study provides a general and simplified method for coupling a weak amine with a sterically hindered acid using COMU as a coupling agent, and demonstrates the separation of optically pure compounds from reaction related impurities in a single step using SFC, and identification of amide derivatives of 1-aminoanthracene-9,10-dione as potential antimicrobial agents.

Promoting Catalytic C-Selective Sulfonylation of Cyclopropanols against Conventional O-Sulfonylation Using Readily Available Sulfonyl Chlorides.

Against the backdrop of the well-known O-sulfonylation of cyclopropyl alcohols with sulfonyl chlorides, we examined the feasibility of conducting regioselective C-sulfonylation. By emulating an umpolung strategy-guided design, we report for the first time the Cu(II)-catalyzed ß-sulfonylation of cyclopropanols by a mechanism that potentially involves an oxidative addition of a sulfonyl radical to a metal homoenolate. Unlike reported methods, this protocol allows a practical synthetic route to γ-keto sulfone building blocks from cyclopropanols by leveraging commercially available aryl- and alkyl-sulfonyl chlorides, common reagents in organic chemistry laboratories. Using operationally simple open-flask conditions, the preparative scope of starting materials was demonstrated using an array of aryl- and alkyl-substituted sulfonyl chlorides and cyclopropanols (43 examples, up to 96% yield).

Examining the Scope of Deriving ß-Aryl Enones from Enol Silanes as Ketone Equivalents via Pd(II)-Mediated Sequential Dehydrosilylation and Arylation.

Silyl enol ethers were examined as a masked source of saturated ketones to derive ß-aryl enones and their derivatives by dehydrosilylation to generate enones in situ and subsequent oxidative arylation with arylboronic acids as transmetallation coupling partners using relayed Pd(II) catalysis in one pot under base-free conditions. Oxygen was found to be an efficient and green oxidant to enable both dehydrosilylation of enol silanes and arylation. Additionally, arylation conditions can be custom-designed to take advantage of aryl halides as an alternative source of arylating agents. The preparative scope was investigated with 35 examples (up to 95% yield), and mechanistic studies implied a cationic Pd(II)-based catalytic system.

Synthetic Access to α-Oxoketene Aminals by the Nucleophilic Addition of Enol Silane-Derived Palladium(II) Enolates to Carbodiimides.

Synthetically important α-oxoketene aminal intermediates can now be accessed from readily available and inexpensive carbodiimides as starting materials via the nucleophilic addition of palladium enolates derived from enol silane precursors. This operationally simple method features mild reaction conditions, including open air atmosphere, ligand-free metal catalysis, broad substrate scope, and multi-gram scalability. Select synthetic applications that take advantage of the enamine character of α-oxoketene aminals and involve C-nucleophilic additions to electrophilic systems, including an α,ß-unsaturated ester, an azo dicarboxylate, an aralkyl halide, and an aldehyde, are demonstrated.

Electrophilic Hydrazination of Cyclopropanols Using Azodicarboxylates via Copper(II) Catalysis: An Umpolung Strategy to Access ß-Hydrazino Ketone Motifs.

The scope of an umpolung approach to expand synthetic access to bifunctional γ-keto hydrazine intermediates via electrophilic amination of ß-homoenolates derived from cyclopropanol precursors that took advantage of azodicarboxylates or azodicarboxamides as electron-deficient nitrogen sources was examined. This new synthetic procedure avails commercially available or readily accessible starting materials along with a ligand-free Cu(II) salt as an inexpensive catalyst. Using this operationally simple reaction, which proceeds under mild conditions (open-flask and ambient temperature) and is suitable for multigram scale, preparative applications were established with a range of aryl- and alkyl-substituted cyclopropanols and azodicarboxylate/azodicarboxamide substrates (26 examples, 74-95% yields). Further, the obtained products have been shown to provide convenient synthetic access to γ-hydroxy hydrazide, γ-amino hydrazide, and heterocyclic derivatives.

Orchestrating a ß-Hydride Elimination Pathway in Palladium(II)-Catalyzed Arylation/Alkenylation of Cyclopropanols Using Organoboron Reagents.

The scope of chemoselective ß-hydride elimination in the context of arylation/alkenylation of homoenolates from cyclopropanol precursors using organoboronic reagents as transmetalation coupling partners was examined. The reaction optimization paradigm revealed a simple ligand-free Pd(II) catalytic system to be most efficient under open air conditions. The preparative scope, which was investigated with 48 examples, supported the applicability of this reaction to a wide range of substrates tolerating a variety of functional groups while delivering ß-substituted enone and dienone derivatives in 62-95% yields.

The Ligand Free Palladium(II)-Catalyzed Regioselective 1,2-Addition of Enol Silanes to Quinones to Access 4-Hydroxy-4-(2-oxo-2-arylethyl)cyclohexadien-1-ones and Synthetic Applications.

In contrast to the conventional 1,4-addition process, regioselective 1,2-addition of silyl enol ethers to quinones can now be achieved via a palladium(II) enolate pathway that provides access to 4-hydroxy-4-(2-oxo-2-arylethyl)cyclohexa-2,5-dien-1-one derivatives. This quinone alkylation protocol proceeds under mild reaction conditions at ambient temperature under open air and does not require either an external ligand for the palladium or the use of a base. Additionally, the cyclohexadienone products have been exploited as synthetic precursors for the construction of fused heteroaryl systems.

BF3·OEt2-TFAA Mediated Tetra-Functionalization of Amino Acids - Synthesis of Di- and Tri-Substituted 2-Trifluoromethyl Oxazoles in One Pot.

A highly efficient, TFAA-BF3·OEt2 mediated multicomponent coupling of amino acid, TFAA, and aromatics provides a broad library of 2-trifluoromethyl equipped 2,5-disubstituted/2,4,5-trisubstituted oxazoles or N-(trifluoroacetyl)-ß-aminoalkyl ketones. This amino acid tetra-functionalization approach involves amidation (C-N), anhydride (C-O), Friedel-Crafts acylation (C-C), and Robinson-Gabriel annulation (C-O) followed by dehydrative aromatization. This reaction takes place under operationally simple, mild, and metal-free conditions using readily available amino acids and aromatic compounds.

Utility of Organoboron Reagents in Arylation of Cyclopropanols via Chelated Pd(II) Catalysis: Chemoselective Access to ß-Aryl Ketones.

Organoborane reagents were investigated as coupling partners to cyclopropanol-derived ß-ketone enolates in the presence of a chelated Pd(II) catalyst. Efficient coupling of a range of electronically and sterically diverse cyclopropanols and aryl/alkenyl boronic derivatives (39 examples, 65-94% yield) could be achieved with the generation of synthetically important ß-aryl ketone intermediates in a chemoselective fashion. This reactivity paradigm, which broadens the scope of aryl donor partners to homoenolates, allows open-flask conditions, water as a cosolvent, and preparation of halogen-bearing ß-aryl ketones that are distinct from previous methods. This chelated Pd(II) catalysis appears to be different from the Pd(0) pathway, as evident from deuterium scrambling studies that could reveal differentiating protonolysis of an α-keto carbopalladium complex in the terminal step.

The silver catalyzed direct C-H functionalization of quinones with dialkyl amides.

DMA and other dialkylamides were successfully used as synthons for the C-H functionalization of quinones. This novel amidoalkylation reaction works with a variety of substituted quinones and dialkyl/alkyl amides, such as DMF, NMP and NMA, and the corresponding products were obtained in moderate to good yields. The amidoalkylation of quinones is demonstrated for the first time. A suitable mechanism and the synthetic utility of these compounds are demonstrated. The molecular docking of compound 5 with an Alzheimer's disease (AD) associated AChE target site was studied.

Oxidative radical coupling of hydroquinones and thiols using chromic acid: one-pot synthesis of quinonyl alkyl/aryl thioethers.

An efficient, simple and practical protocol for one-pot sequential oxidative radical C-H/S-H cross-coupling of thiols with hydroquinones (HQs) and oxidation leading to the formation of quinonyl alkyl/aryl thioethers using H2CrO4 was developed. This cross-coupling of thiyl and aryl radicals offers mono thioethers in good to moderate yield and works well with a wide variety of thiols. Similarly, this method works well for coupling of 2-amino thiophenol and HQs to form phenothiazine-3-ones 5a-c. C-S bond formation via thioether synthesis was observed using a chromium reagent for the first time. Theoretical studies on the pharmacokinetic properties of compounds 5a-c revealed that due to drug-like properties, compound 5b strongly binds with Alzheimer's disease (AD) associated AChE target sites.

Reducing-agent-free facile preparation of Rh-nanoparticles uniformly anchored on onion-like fullerene for catalytic applications.

Herein we report a very simple 'mix and heat' synthesis of a very fine Rh-nanoparticle loaded carbon fullerene-C60 nanocatalyst (Rh(0)NPs/Fullerene-C60) for the very first time. The preparation method used no reducing agent and capping agent to control the morphology of the nanocatalyst. Transmission electron microscopy (TEM) results confirmed the uniform decoration of small Rh-nanoparticles on the surface of fullerene-C60. The Rh-content in Rh(0)NPs/Fullerene-C60 was found to be 2.89 wt%. The crystalline properties of Rh(0)NPs/Fullerene-C60 were studied by X-ray diffraction (XRD). The metallic state of Rh-nanoparticles in Rh(0)NPs/Fullerene-C60 was confirmed by X-ray photoemission spectroscopy (XPS). Raman results depicted good interaction between Rh-nanoparticles and fullerene-C60. To our delight, the present Rh(0)NPs/Fullerene-C60 showed excellent catalytic activity in the reduction of 4-nitrophenol with NaBH4 in water. Very high k app, k' and TOF values of 82.14 × 10-3 min-1, 4107 × 10-3 min-1 and 138 min-1, respectively, were calculated for the Rh(0)NPs/Fullerene-C60 catalyzed reduction of 4-nitrophenol. To the best of our knowledge, this is the most efficient fullerene-based nanocatalyst for the rapid reduction of 4-nitrophenol reported to date. Moreover, the catalytic activity of Rh(0)NPs/Fullerene-C60 was also tested towards Suzuki cross-coupling reactions. Reusability of the Rh(0)NPs/Fullerene-C60 was also tested.

Copper-catalyzed oxidative amination of methanol to access quinazolines.

A novel method for the copper-catalyzed oxidative amination of 2'-aminoarylketones with methanol as a C1 carbon source and ammonium acetate as an amine source to construct quinazolines was established in a one-pot manner. The reaction conditions are straightforward and highly atom economic to deliver the corresponding quinazolines in high yields with wide functional group tolerance. Importantly, the present method is applicable on a multigram scale and its synthetic utility is demonstrated by synthesizing quazodine, a muscle-relaxing drug in high yields.

Evaluation of pheromone-based kit: A noninvasive approach of estrus detection in buffalo.

In view of the silent nature of estrus in buffalo, a noninvasive assay kit has long been felt necessary for easy and effective estrus detection. This study was designed to detect estrus in buffalo using a kit formulated in our laboratory based on pheromone compound. Group I: Urine samples collected at estrus phase and group II: randomly collected urine samples were subjected to the test using the kit. No colour developed (i.e., positive reaction) in estrus urine after adding the kit solution. By contrast, pale and/or dark pink colour developed (i.e., negative reaction) in urine from the proestrus and diestrus buffaloes, respectively. Field evaluation of the kit in groups I and II revealed that 60.87% and 71.43% of urine samples were correctly identified as estrus and nonestrus (i.e., proestrus and diestrus), respectively. Therefore, the first of its kind estrus detection kit formulated based on urinary pheromone can as well be used as a simple device to detect estrus in buffalo.

Discovery of 6,7-dihydro-3H-pyrano[4,3-c]isoxazol-3-ones as a new class of pathogen specific anti-leptospiral agents.

A simple and efficient method for the synthesis of a series of 6,7-dihydro-3H-pyrano[4,3-c]isoxazol-3-one derivatives starting from 5-carboalkoxy-2,3-dihydropyranone (5-CDHPs) has been developed. Pyranoisoxazolones 10a-j, dihydronaphthopyran-4-one (DHNPs) class of natural product 12b and 12c and its analogues 12a and 13a-c were preliminarily screened against pathogenic leptospiral serovar Autumnalis strain N2 at various concentrations. Six pyranoisoxazolones, 10b, 10d, 10f, 10g, 10i and 10j which displayed very good anti-leptospiral activity was taken for secondary screening against twelve strains of pathogenic and one non-pathogenic leptospiral serovars. While all the compounds displayed significant anti-leptospiral activity against the pathogenic serovars at MIC of 62.5-500 µg/mL. Compounds 10d, 10g and 10j did not show any significant effect on non-pathogenic serovar. Inhibition of leptospires at a significant level by pyranoisoxazolone 10g was confirmed using RT-qPCR assay. In vivo treatment of BALB/c mice with compound 10g revealed that, it has 95% survivability against the pathogenic strain Canicola and also showed inhibition of renal colonization of leptospires. Compound 10g was found to show cytotoxicity against THP-1 cells only at higher concentration (≥75 µg/mL). Effective binding of compound 10g with leptospiral outer membrane protein LipL32 observed via in silico molecular docking provided a suitable explanation for pathogen specificity of compound 10g. Antibiotics acting against leptospirosis in human are very few. The results obtained from in vitro, in vivo and in silico study reveals that 6,7-dihydro-3H-pyrano[4,3-c]isoxazol-3-ones class of compounds are lead molecules for further development as pathogen specific anti-leptospiral agents.

Natural product-inspired rational design, synthesis and biological evaluation of 2,3-dihydropyrano[2,3-f]chromen-4(8H)-one based hybrids as potential mitochondrial apoptosis inducers.

Synthesis of novel pyranochromanone amide hybrids, by combining pyranochromanone pharmacophore and privileged scaffolds such as 2-amino-1,3,4-thiadiaole/2-aminothiazole/aminopyridine/aminonaphthalene and anti-cancer evaluation of a series led us to discover a series of new chemical entities (NCEs) showing broad spectrum of anti-cancer activity against three different human cancer cell lines (MCF-7, A549 and HeLa), at IC50 values ranging from 14.3 to 97.8 µM. Among them, some compounds such as 15b, 15d, 20a and 20b displayed excellent activity against breast cancer cell line MCF-7. Detailed biological studies such as AO/EB dual staining, Hoechst 33342 staining, FACS analysis of mitochondrial membrane potential (Δψm) using JC-1 dye and DNA fragmentation confirmed the apoptosis induced by the hybrids. Gene expression studies by Real time RT-PCR has shown that these compounds are efficient regulator of anti-apoptotic gene Bcl-2. Western blot analysis also revealed that these compounds persuade apoptosis through intrinsic pathway by up-regulating the pro-apoptotic protein Bax and down-regulating the anti-apoptotic protein Bcl-2. Molecular docking studies reveal that compounds 15b and 20b binds efficiently with Bcl-2 promoter G-quadruplex.