Synthesis Of Organic Compounds Research Articles

Accelerated synthesis of 1,8-dioxo-octahydroxanthene and 1,8-dioxo-decahydroacridine derivatives using dendritic mesoporous nanosilica functionalized by hexamethylenetetramine: a novel nanocatalyst.

Xanthene and acridine derivatives are interesting organic compounds that are used in different research fields like biomedicine and pharmaceutical science. However, applied catalysts for their synthesis have some limitations such as long reaction times, the need for harsh conditions and low yield. So, discovery of novel catalysts for the synthesis of xanthene and acridine derivatives is highly demanded. To overcome the limitation of previous methods on the efficient synthesis of 1,8-dioxo-octahydroxanthene and 1,8-dioxo-decahydroacridine derivatives, a green heterogeneous organic nano-catalyst (Cu@KCC-1-nPr-HMTA) was synthesized by covalent attachment of hexamethylenetetramine to the cavities and channels of dendritic mesoporous nanosilica (KCC-1). The prepared nano-catalyst was identified using various spectroscopic and microscopic methods including scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), X-ray energy diffraction (EDX), EDX mapping and nitrogen adsorption-desorption analysis (BET-BJH). The prepared green nano-catalyst showed a spherical and dendritic structure with a surface area of 65.699 m2 g-1, average pore size of 40.78 nm and pore volume of 0.66 cm3 g-1. Also, Cu@KCC-1-nPr-HMTA has many chemo-active sites for the condensation reaction and was used as an efficient nano-catalyst towards one-step synthesis of 1,8-dioxo-decahydroacridine and 1,8-dioxo-octahydroxanthene derivatives from the reaction of aromatic aldehydes, dimedone, and ammonium acetate under solvent-free conditions. Short reaction times of 1 to 5 minutes for 1,8-dioxo-decahydroacridine and 30 to 55 minutes for 1,8-dioxo-octahydroxanthene derivatives, high yields and mild reaction conditions are advantages of the proposed synthetic method. It is hoped that the engineered nano-catalyst will be used for the synthesis of other organic compounds in the future.

Clay based heterogeneous catalysts for carbon-nitrogen bond formation: a review.

Clay and modified clay-based catalysts are widely used in organic transformation. Owing to the interlayer ions and good ion exchange capacity of clay, replacement with another ion and incorporation of different nanomaterials can be done. Due to these significant properties of clay, it can be utilized in the synthesis of various organic compounds. Carbon-nitrogen bonded compounds possess diverse applications in different fields. These compounds are prepared using different solid acid heterogeneous catalysts. This review presents a detailed discussion on clay used for the carbon-nitrogen bond formation reaction, such as the Biginelli reaction and A3 and KA2 coupling reactions. Additionally, other C-N bond formation reactions using various clay-based catalysts such as bentonite, montmorillonite, hydrotalcite and halloysite clay with various metals, metal oxides, Kegging type heteropoly acid and various nanomaterial incorporated clay heterogeneous catalysts are discussed.

Batch and continuous flow mechanochemical synthesis of organic compounds including APIs

Mechanochemistry is becoming an enabling technology for the synthesis of organic and inorganic compounds as well as for the synthesis of polymers as it underlines sustainability in a significant manner.

Purification of Rubisco from Leaves.

Rubisco fixes CO2 through the carboxylation of ribulose 1,5-bisphosphate (RuBP) during photosynthesis, enabling the synthesis of organic compounds. The natural diversity of Rubisco properties represents an opportunity to improve its performance and there is considerable research effort focusing on better understanding the properties and regulation of the enzyme. This chapter describes a method for large-scale purification of Rubisco from leaves. After the extraction of Rubisco from plant leaves, the enzyme is separated from other proteins by fractional precipitation with polyethylene glycol followed by ion-exchange chromatography. This method enables the isolation of Rubisco in large quantities for a wide range of biochemical applications.

Green catalyst of cobalt ferrite magnetic nanoparticles using petai peel extract for the synthesis of thiazolidinedione-based chalcone 4H-thiopyran as an antioxidant.

CoFe2O4 magnetic nanoparticles were successfully synthesized using the green synthesis method with petai peel extract (PPE) as the capping and reducing agent. These nanoparticles were characterized using various techniques, including XRD, VSM, FTIR spectroscopy, UV-DRS, FESEM, EDX, TEM, HR-TEM, and SAED. The synthesized nanoparticles possess cubic morphology with an average size of 37.67 nm. CoFe2O4 magnetic nanoparticles were used as a catalyst for the synthesis of organic compounds, namely, chalcones. The synthesized organic compounds were characterized using FTIR, UV-Vis, LC-HRMS, and melting point test. The best result for chalcone synthesis was 62.26% using CoFe2O4 magnetic nanoparticles (5 mol%) in ethanol at reflux condition for 2 h. The nanocatalyst could be used for 5 cycles without any significant loss of yields. The synthesized organic compounds were further examined for their antioxidant activity. The 4H-thiopyran 2-acetyl pyridine variant (product 2) exhibited the highest antioxidant activity with an IC50 value of 90.80 μg mL-1. This was supported by the bond dissociation enthalpy (BDE) values of the C-H groups of benzo[g]thiochromene and pyridine, which were 74.0 kcal mol-1 and 105.1 kcal mol-1, respectively. The objective of this study is to develop a method for synthesizing organic compounds using green catalysts in order to reduce the adverse environmental impact. Furthermore, this research also aims to investigate the antioxidant potential of the thiazolidinedione-based chalcone 4H-thiopyran compounds in order to overcome oxidative stress.

Claisen Rearrangement Toward Cyclic Compound on Different Organic Synthesis Methods: Short Review

The synthesis of functional and complex organic compounds is majorly performed by the Claisen rearrangement method. Claisen rearrangement is one of [3,3] sigmatropic rearrangements, a complex method in the synthesis of organic compounds, where it is mostly used to construct stereoselective compounds. It can be combined with other synthesis methods to synthesize organic compounds giving satisfactory results based on the method used, temperature, time, and yield produced. This review aimed to summarize several recent advances in synthesizing organic compounds through Claisen rearrangement reactions. An understanding of the mechanism and applications of this reaction might improve the ability to synthesize innovative and useful organic compounds in various fields of life sciences.

Design, synthesis and in silico docking techniques of new 1,2,3-triazolylpyrrolidines bearing chalcone derivatives: Discovery of potent antitubercular agents

Compounds with a pyrrolidine scaffold play an important role in organic synthesis and especially in the synthesis of bioactive organic compounds, therefore, the development of new methods for modifying this scaffold is a very interesting framework of this study. We developed a rational approach for the synthesis of 1,2,3-trazolylchalcone substituted pyrrolidines derivatives, which were then examined using a variety of spectroscopic techniques such as 1H NMR, 13C NMR, FT-IR, mass spectroscopy and elemental analysis. Biological profiles showed that compounds 5e, 5h had better antibacterial inhibitory potency against S. aureus, E. coli with zone of inhibition 34 ± 0.1, 33 ± 0.3 mm, whereas 5a, 5e showed potent antifungal activity against C. parapsilosis, A. flavus with dimeter zone of inhibition 26 ± 0.2, and 30 ± 0.2 mm respectively. Among the tested compounds 5b, and 5h were the most potent antitubercular activity against Mycobacterium tuberculosis H37Rv and showing MIC values 5.23 µg/mL, 6.85 µg/mL respectively, which are similar activity that of the standard Streptomycin (MIC = 5.02 µg/mL). The binding mode for compound 5 inside the catalytic pocket of M. tuberculosis cytochrome P450 CYP121A1 and produced a network of hydrophobic and hydrophilic interactions (6GEO). From docking results, 5b demonstrated highly stable binding amino acids SerA:237, ArgA:386, ArgA:286, CysA:345, MetA:62, GlnA:385, AspA:282, PheA:280, LeuA:284, ValA:83, ProA:285, AlaA:337, HisA:343, AsnA:74, and ThrA:65, which are plays a crucial role in ensuring efficient binding of the ligand in a crystal structure of tubercular receptor. Furthermore, the physicochemical and ADME (absorption, distribution, metabolism, and excretion) filtration molecular properties, estimation of toxicity, and bioactivity scores of these scaffolds were evaluated.

A natural mutant kumquat fruit with abnormal oil glands shows lower volatile production, better fruit flavor and higher resistance to postharvest disease

Oil glands of citrus peel are known sites for synthesis and deposition of volatile organic compounds (VOCs). However, it is unclear how oil glands and VOCs affect fruit flavor and postharvest disease resistance in vivo. Here, we report characterization of a natural mutant ‘Huapi’ (HP) kumquat (Fortunella crassifolia Swingle) compared with its wild progenitor ‘Rongan’ (RA). HP fruit decreased in both size and number of oil glands from the onset of fruit development when compared to RA. The total VOCs concentration and the number of individual VOCs in mature HP fruit were lower than that in RA. Limonene, α-pinene and β-myrcene concentrations showed the greatest reduction (30-, 21- and 20-fold). Sensory evaluation showed that flavor of HP fruit was more acceptable to consumers compared to that of RA. Sweeter, less acidic features of HP fruit were likely due to higher soluble sugars content and lower organic acid content, respectively. Changes in HP fruit VOCs likely contribute to its less pungent and better aroma features. HP fruit displayed stronger resistance to the fungal pathogens Penicillium italicum and Geotrichum candidum compared to RA in in vivo inoculation experiments. Transcriptomic analysis and qPCR validation indicated that FcERF096, FcCHI, FcCXE, FcPi21L1, FcPi21L2, FcPIP and FcXYLL potentially involve in enhanced disease resistance of HP fruit. Taken together, these results reveal the potential of oil glands and terpenes in affecting fruit sensory attributes and postharvest disease resistance in planta in kumquat, providing new insights into the technologies improving these important traits in citrus.

MCM‐41@CPTMS as an Efficient and High‐Performance Catalyst for One‐Pot Construction of Indeno[1,2‐b]quinolin‐8‐one Derivatives**

AbstractIn this work, MCM‐41@CPTMS nanoparticles were readily prepared and evaluated as acidic nanosilica spheres for the synthesis of indeno[1,2‐b]quinolinone derivatives through one‐pot three‐component reaction of 1‐naphthylamine, aromatic aldehydes and 1,3‐indandione. A high surface area, a hexagonal array of uniform mesoporous, high thermal stability, recyclability, nontoxicity and the easy separation of the nanocatalyst, make this nanocatalyst very useful for the synthesis of organic compounds. Mesoporous silica nanoparticles (MSN) was prepared easily and affirmed to be effective and prepared the products with excellent yields under reflux conditions. The structure of obtained nanoparticles was characterized by FE‐SEM, TEM, EDX, FT‐IR, XRD, TGA and BET. This synthetic protocol provides several benefits such as excellent yields in short reaction times (83–97 %),saving costs, reusability of the catalyst (five runs), and low catalyst loading.

Recent Advances in Asymmetric Catalysis Using p-Block Elements.

The development of new methods for enantioselective reactions that generate stereogenic centres within molecules are a cornerstone of organic synthesis. Typically, metal catalysts bearing chiral ligands as well as chiral organocatalysts have been employed for the enantioselective synthesis of organic compounds. In this review, we highlight the recent advances in main group catalysis for enantioselective reactions using the p-block elements (boron, aluminium, phosphorus, bismuth) as a complementary and sustainable approach to generate chiral molecules. Several of these catalysts benefit in terms of high abundance, low toxicity, high selectivity, and excellent reactivity. This minireview summarises the utilisation of chiral p-block element catalysts for asymmetric reactions to generate value-added compounds.

Recent Advances in Asymmetric Catalysis Using p‐Block Elements

AbstractThe development of new methods for enantioselective reactions that generate stereogenic centres within molecules are a cornerstone of organic synthesis. Typically, metal catalysts bearing chiral ligands as well as chiral organocatalysts have been employed for the enantioselective synthesis of organic compounds. In this review, we highlight the recent advances in main group catalysis for enantioselective reactions using the p‐block elements (boron, aluminium, phosphorus, bismuth) as a complementary and sustainable approach to generate chiral molecules. Several of these catalysts benefit in terms of high abundance, low toxicity, high selectivity, and excellent reactivity. This minireview summarises the utilisation of chiral p‐block element catalysts for asymmetric reactions to generate value‐added compounds.

Chemical components as a potential resource for synthesis of organic compounds and anti-inflammatory activity of essential bark oil of Illicium verum

In this work, the essential bark oil (EBO) of Illicium verum cultivated at Cao Bang in Vietnam obtained by hydro-distillation was investigated for its chemical composition by gas chromatography-mass spectrometry (GC-MS). Trans-anethole (78.6%), estragole (13.7%), linalool (2.1%) and eucalyptol (2.0%) were determined to be the main components among 14 identified compounds, which accounted for 96.4% of the total EBO. Anti-inflammatory activity of EBO was evaluated by inhibition of nitric oxide (NO) production in lipopolysaccharide (LPS)-stimulated RAW 264.7 cells. EBO exhibited an interesting inhibitory effect on NO production in LPS-stimulated RAW246.7 cells with an inhibitory value at 93.87 μg/mL. From the starting material, trans-anethole isolated from EBO, there are two new amine-derivatives that were synthesized. The structure elucidation of these analogues of trans-anethole was carried out by 1D (1H NMR and 13C NMR) and IR spectral analysis.

Ultrasonic Assisted Three Component Synthesis of 3-Cyano-pyridine-2(1H)-ones

The requirements of sustainability and the green chemistry principles have prompted organic chemistry researchers to come up with novel methods for the synthesis of organic compounds that require minimum energy consumption and pose lesser environment harm. Ultrasonication of reaction mixtures is one such methodology. High frequency sound waves are known to emit energy that is utilized in product generation. Attempts were made to synthesize 2-pyridone derivatives using ultrasonication assisted method of synthesizing 3-cyano-pyridine-2(1H)-one starting from a three component one pot reaction. The reaction between cyanoacetamide, aromatic ketones and substituted aromatic aldehydes in the presence of NaOH as base yielded 4,6-diaryl-2-oxo-1,2-dihydropyridine-3-carbonitrile derivatives as a result of one-pot multicomponent reaction. The synthesized 4,6-diaryl-2-oxo-1,2-dihydropyridine-3-carbonitrile derivatives were characterized by 1H NMR, 13C NMR, HRMS and FTIR spectra. Ultrasonication has been found to significantly reduce reaction time, enhance reaction rate and yield compared to conventional heating methods.

Toward effective electrocatalytic C–N coupling for the synthesis of organic nitrogenous compounds using CO2 and biomass as carbon sources

AbstractThermochemical conversion of fossil resources into fuels, chemicals, and materials has rapidly increased atmospheric CO2 levels, hindering global efforts toward achieving carbon neutrality. With the increasing push for sustainability, utilizing electrochemical technology to transform CO2 or biomass into value‐added chemicals and to close the carbon cycle with sustainable energy sources represents a promising strategy. Expanding the scope of electrosynthesis technology is a prerequisite for the electrification of chemical manufacturing. To this end, constructing the C─N bond is considered a priority. However, a systematic review of electrocatalytic processes toward building C─N bonds using CO2 and biomass as carbon sources is not available. Accordingly, this review highlights the research progress in the electrosynthesis of organic nitrogen compounds from CO2 and biomass by C─N coupling reactions in view of catalytic materials, focusing on the enlightenment of traditional catalysis on C─N coupling and the understanding of the basis of electrochemical C─N coupling. The possibility of C─N bond in electrocatalysis is also examined from the standpoints of activation of substrates, coupling site, mechanism, and inhibition of hydrogen evolution reaction (HER). Finally, the challenges and prospects of electrocatalytic C─N coupling reactions with improved efficiency and selectivity for future development are discussed.

Synthesis of Hypervalent Iodine Diazo Compounds and Their Application in Organic Synthesis.

Diazomethyl-substituted iodine(III) compounds with electron-withdrawing groups (EWG) connected to diazo methyl center were a type of donor-acceptor diazo compounds with potential reaction abilities similar to ordinary diazo compounds. Although several diazomethyl-substituted iodine(III) compounds were synthesized and used in the nucleophilic substitution reactions as early as 1994, the synthesis and application of new iodine(III) diazo compounds have only been reported to a certain extent in recent years. In the presence of rhodium catalyst, photocatalyst, or nucleophiles, diazomethyl-substituted iodine(III) compounds can be converted into rhodium-carbenes, diazomethyl radicals, ester radicals or nucleophilic intermediates, which can be used as key intermediates for the formation of chemical bonds. The aim of this review is to give an overview of diazomethyl-substituted iodine(III) compounds in organic synthesis.

Secondary-Electrospray Ionization Mass Spectrometry-Based Online Analyses of Mouse Volatilome Uncover Gut Microbiome-Dictated Metabolic Changes in the Host.

The symbiotic relationship between the gut microbial population is capable of regulating numerous aspects of host physiology, including metabolism. Bacteria can modulate the metabolic processes of the host by feeding on nutritional components within the lumen and releasing bioactive components into circulation. Endogenous volatile organic compound (VOC) synthesis is dependent on the availability of precursors found in mammalian metabolism. Herein, we report that microbial-mediated metabolic influences can alter the host volatilome and the prominent volatile changes can be uncovered by a novel volatile analysis technique named secondary electrospray ionization mass spectrometry. Mice were subjected to an antibiotic cocktail to deplete the microbiome and then inoculated with either single strain bacteria or fecal matter transplantation (FMT) to replete the microbial population in the gut. VOC sampling was achieved by using an advanced secondary electrospray ionization (SESI) source that directly mounted onto a Thermo Q-Exactive high-resolution mass spectrometer (HRMS). A principal component analysis summarizing the volatile profiles of the mice revealed independent clustering of each strain of the FMT-inoculated groups, suggesting unique volatile profiles. The Mummichog algorithm uncovered phenylalanine metabolism as a significantly altered metabolic profile in the volatilome of the microbiome-repleted mice. Our results indicated that the systemic metabolic changes incurred by the host are translated to unique volatile profiles correlated to the diversity of the microbial population colonized within the host. It is thus possible to take advantage of SESI-HRMS-based platforms for noninvasive screening of VOCs to determine the contribution of various microbial colonization within human gut that may impact host health.

New Methyl Methacrylate Derived Adsorbents - Synthesis, Characterization and Adsorptive Removal of Toxic Organic Compounds.

This study aimed to synthesize polymeric adsorbents by suspension polymerization using methyl methacrylate (MMA) with different crosslinking monomers. Divinylbenzene (DVB) and aliphatic monomers: ethylene glycol dimethacrylate (EGDMA) or N,N'-methylenebisacrylamide (NN) containing additional amide groups were used. The possibility of using the prepared copolymers (MMA-NN, MMA-EGDMA, MMA-DVB) as adsorbents for the removal of toxic compounds such as dyes (C.I. Acid Red 18 (AR18), C.I. Acid Green 16 (AG16), C.I. Acid Violet 1 (AV1), C.I. Basic Yellow 2 (BY2), C.I. Basic Blue 3 (BB3) and C.I. Basic Red 46 (BR46)) and phenol (PhOH) from dye baths and effluents was evaluated. Preferential adsorption of basic-type dyes compared to acid-type dyes or phenol was observed by the polymers. Adsorbent based on MMA-EGDMA exhibited the highest capacity for investigated dyes and phenol. The pseudo-second order kinetic model as well as the intraparticle diffusion model can find application in predicting sorption kinetics. Based on the equilibrium sorption data fitted to the Langmuir, Freundlich, Temkin and Dubinin-Radushkevich model, uptake of BB3, AV1 and PhOH is rather physisorption than chemisorption. The regeneration yield of MMA-EGDMA does not exceed 60 % using 1 M HCl, 1 M NaCl, and 1 M NaOH in 50 %v/v methanol.

AI-driven robotic chemist for autonomous synthesis of organic molecules.

The automation of organic compound synthesis is pivotal for expediting the development of such compounds. In addition, enhancing development efficiency can be achieved by incorporating autonomous functions alongside automation. To achieve this, we developed an autonomous synthesis robot that harnesses the power of artificial intelligence (AI) and robotic technology to establish optimal synthetic recipes. Given a target molecule, our AI initially plans synthetic pathways and defines reaction conditions. It then iteratively refines these plans using feedback from the experimental robot, gradually optimizing the recipe. The system performance was validated by successfully determining synthetic recipes for three organic compounds, yielding that conversion rates that outperform existing references. Notably, this autonomous system is designed around batch reactors, making it accessible and valuable to chemists in standard laboratory settings, thereby streamlining research endeavors.

Circularly Polarized Light Responsive Materials: Design Strategies and Applications.

Circularly polarized light (CPL) with the end of optical vector traveling along circumferential trajectory, shows left- and right-handedness, which transmits chiral information to materials via complicated CPL-matter interactions. Materials with circular dichroism respond to CPL illumination selectively with differential outputs that can be used to design novel photodetectors. Racemic or achiral compounds under CPL go through photodestruction, photoresolution and asymmetric synthesis pathways to generate enantiomeric bias and optical activity. By this strategy, helical polymers and chiral inorganic plasmonic nanostructures are synthesized directly, and their intramolecular folding and subsequent self-assembly are photo-modulable as well. In the aggregated state of self-assembly and liquid crystal phase, helical sense of the dynamic molecular packing is sensitive to enantiomeric bias brought by CPL, enabling the chiral amplification to supramolecular scale. In this review, we aim to systematically summarize and discuss the application-guided design strategies of CPL-responsive materials. Asymmetric synthesis, resolution and property-modulation of small organic compounds, polymers, inorganic nanoparticles, supramolecular assemblies and liquid crystals are highlighted based on the important developments during the last decades. Besides, applications of light-matter interactions including CPL detection and biomedical applications are also referred. This article is protected by copyright. All rights reserved.

The molecular structure of 4-substituted pyridine N-oxides–boron trifluoride triel bonded complexes: Peculiarities and regularities

Pyridine N-oxides are widely used in medicine, organic synthesis and design of functional coordination compounds and supramolecular systems. However, at present, issues related to the complex formation and stereochemistry of pyridine N-oxide molecular complexes as well as the nature of the complexing bond and the substituent effect remain relevant. In this paper the substituent effect on geometric, electronic, thermodynamic and spectral properties was established by quantum chemical calculations (DFT/M062-X/aug-cc-pvTZ) for the series of 4-substituted pyridine N-oxides with boron trifluoride as model complexes. Theoretical insights into the nature of OB triel bond was considered in terms of QTAIM and NBO analysis. A conformational analysis has been performed to resolve the contradictions in the literature data concerning the stereochemistry of such complexes. The calculated structural parameters, as well as complex formation energy, binding energy, thermodynamic characteristics, vibrational frequencies and chemical shifts reveal high correlation with the empirical Hammett substituent constants.