Organic Reactions Research Articles

Combination of online hollow fiber liquid phase microextraction with smartphone-based sensing for in situ formaldehyde assay in fabric and wastewater samples.

A miniaturized analytical methodology was introduced based on the combination of a direct and online hollow fiber microextraction method with smartphone color detection. The method was used for the determination of formaldehyde (target analyte) in fabric and wastewater samples. In this regard, two reagents including ammonium acetate buffer and acetylacetone were added to the formaldehyde samples to create a colored compound. The colored compound was extracted from the sample by using the hollow fiber liquid-phase microextraction method, the extracted phase was not taken out of the extraction box and was directly transferred into a specially designed detection cell, and a smartphone was applied forin-situ color sensing and data readout. This combination gathered the advantages of both state-of-the-art microextraction techniques and smartphone sensing. Formaldehyde, as a carcinogenic compound widely used in paint and clothing industries, was selected as a model test. Factors affecting extraction efficiency were investigated and optimized, including the type of organic solvents, reagent concentration, salt, pH, stirring speed, reaction temperature, and extraction time. The linear region of the method under optimal conditions was 40-1500µg L-1 for wastewater samples and 0.3-11.2mg kg-1 for fabrics. The limit of detection and limit of qualification were 13 and 40µg L-1, respectively. The relative standard deviations for concentrations of 100 and 1000µg L-1 were 6% and 4%, respectively. To evaluate the application of the method for real samples, types of fabric and two samples of oil refinery wastewater were selected. The relative recovery in real samples was 84-98%. The results of the analytical parameters of the method show that the developed method can be used as an efficient method to determine formaldehyde in real samples.

Recent Developments of Nanostructured Photocatalysts Based on Semiconducting Chalcogenides for Organic Reactions

Abstract:: The earth-abundant metal chalcogenide is a highly versatile semiconductor with unique electronic and optical properties that seem to outperform the photocatalytic properties of metal oxides and metal nanoparticles. For ages, researchers are reaping the benefits of its photocatalytic properties in numerous reactions. However, the high charge recombination rates, poor compositional stability, and a smaller number of catalytically active sites restrict its application. The development of different kinds of heterojunctions by the combination of metal-chalcogenides with other conducting and semiconducting materials like metal oxides, metal nanoparticles, g-C3N4, single-atom catalysts, and MOF results in superior photocatalytic activity. This review provides insight into the various classes of metal-chalcogenide-based heterostructures and their application in various organic transformations. A brief overview of the synergistic properties arising from the development of such heterostructures helps to understand the surface interactions so that highly stable, efficient, and selective metal-chalcogenide-based heterostructures can be developed for industrially important photocatalytic organic transformations. This review also describes the role of mediators in boosting the stability and catalytic efficiency of the metal chalcogenides. Moreover, a thorough emphasis on the morphological impact of photocatalysts in various reactions will help with the development of metal chalcogenide heterostructures with tunable morphology and bandgap.

Synthesis of 8-Methoxy-1-Tetralone

Several methods have been developed for the synthesis of 8-methoxy-1- tetralone 4. The applications of some named organic reactions can be observed during the synthesis of tetralone 4. Attempts have been made to achieve the direct conversion of 5-methoxy-1-tetralone into the tetralone 4. The method for the ring expansion of tertiary cyclobutanol 30 catalyzed by silver salts has proved useful to obtain the title tetralone 4.

Magnetic Aerogels for Room-Temperature Catalytic Production of Bis(indolyl)methane Derivatives

The potential of aerogels as catalysts for the synthesis of a relevant class of bis-heterocyclic compounds such as bis(indolyl)methanes was investigated. In particular, the studied catalyst was a nanocomposite aerogel based on nanocrystalline nickel ferrite (NiFe2O4) dispersed on amorphous porous silica aerogel obtained by two-step sol–gel synthesis followed by gel drying under supercritical conditions and calcination treatments. It was found that the NiFe2O4/SiO2 aerogel is an active catalyst for the selected reaction, enabling high conversions at room temperature, and it proved to be active for three repeated runs. The catalytic activity can be ascribed to both the textural and acidic features of the silica matrix and of the nanocrystalline ferrite. In addition, ferrite nanocrystals provide functionality for magnetic recovery of the catalyst from the crude mixture, enabling time-effective separation from the reaction environment. Evidence of the retention of species involved in the reaction into the catalyst is also pointed out, likely due to the porosity of the aerogel together with the affinity of some species towards the silica matrix. Our work contributes to the study of aerogels as catalysts for organic reactions by demonstrating their potential as well as limitations for the room-temperature synthesis of bis(indolyl)methanes.

Analysis of undergraduate chemistry students’ responses to substitution reaction mechanisms: a road to mastery

Abstract This study analyzed third-year undergraduate Chemistry major students’ drawings and written explanations of substitution reactions. Seventy (70) students were purposively selected for this study. The main data collection instrument was a diagnostic test and students’ responses were analyzed using deductive coding. The study aimed to unearth students’ conceptual understanding and difficulties on substitution reactions to provide significant insights into improving teaching strategies and learning outcomes. The findings revealed that: 1. Students were more familiar with SN2 reaction mechanisms and could answer questions on SN2 reaction mechanisms better than SN1 reaction mechanisms; 2. Students’ use of ‘chemical vocabulary’ did not translate into an understanding of electron movement and causal mechanistic explanation; 3. About 97 % of the students who gave a correct/partially correct description provided a description of what was happening in the reaction without any further explanation of why the reaction occurred; 4. Students had a slightly better understanding of drawing the correct mechanisms than providing accurate explanations. This study recommends that, in teaching organic reaction mechanisms, instructors should emphasize on electron-pushing formalisms and explain how and why reactions occur to encourage mechanistic thinking in students. Also, students should be given ample practice in organic reaction mechanisms to improve mastery.

Synthesis of Polysubstituted Pyridines via Nitrogen-doped Graphene Catalyzed One-Pot Multicomponent Reaction under Solvent-Free Conditions

Abstract: Polysubstituted pyridine derivatives were producedwith high to excellent yields in the presence of nitrogen-doped graphene (NDG) as a dual acid–based catalyst. NDG efficiently catalyzes the multicomponent reaction between arylaldehydes, diethyl-acetylene dicarboxylates, malononitrile, and ammonium acetate under solvent-free conditions at 80°C to afford the polysubstituted pyridines in short reaction times. The structures of the synthesized pyridines were established by Ft-IR, 1H, and 13C NMR spectroscopic analysis. The advantages of this method include the in-situ oxidation of prepared 1,4-dihydropyridines, one-pot procedure, solventless system, operational simplicity, and no column chromatography. Additionally, neither toxic solvents nor catalysts are needed, and the procedure can be very reliable among the reported methodologies. The yields and reaction times in the presence of four times recycled catalyst are in comparable to the fresh catalyst. background: Graphene quantum dots have attracted considerable attention of chemists because of their unique properties such as: stability, non-toxicity, good water solubility, biocompatibility. In continuation of our interest in using ionic liquids, water or solvent-free systems as green reaction media in organic reactions for the synthesis of important compounds , we wish to report here efficient synthesis of polysubstituted pyridine derivatives in high to excellent yields using Nitrogen-doped graphene as efficient catalyst.

Conventional to “Go Green” Approach in Organic Reaction

In the recent times, the green method of chemical reactions becomes very popular. The scientists are now using the non–hazardous reagents and solvents to design a chemical reaction. The conventional method of most common organic rearrangements e.g Claisen, Fries etc and condensation reactions e.g Aldol, Benzoin, Knoevenegal etc. are designed successfully in greener approach. This article describes green approach of some of these reactions.

Computational and Spectroscopic Studies on the Formation of Halogen-Bonded Complexes Between Tertiary Amines and CBr4 and Application in the Light-mediated Amino Acid Coupling.

In recent years, halogen-bonded complexes (XBCs), in solution, have played a pivotal role in inducing photochemical organic reactions. In this work, we explore the ability of various tertiary amines to act as XB acceptors in the presence of the XB donor CBr4 by computational and spectroscopic studies. DFT studies clearly showcase the formation of XBCs between the studied tertiary amines and CBr4. Simultaneously, computational and experimental UV-Vis studies display intense red shifts that are consistent with charge transfer observed from tertiary amines to CBr4. A detailed NMR study revealed a clear chemical shift of the carbon carrying the bromine atoms upon mixing the XB acceptor with the donor, suggesting that this spectroscopic technique is indeed an experimental tool to identify the generation of XBCs. An application of the ability of such XBCs to activate a carboxylic acid under UVA irradiation or sunlight is presented for amino acid coupling. Among the various tertiary amines studied, the pair DABCO-CBr4 was found to work well for the photochemical amide bond formation. Direct infusion-HRMS studies allowed us to propose a general mechanism for the photochemical amino acid coupling in the presence of a tertiary amine and CBr4, initiated by the photoactivation of an XBC.

Self-Thermal Management in Filtered Selenium-Terminated MXene Films for Flexible Safe Batteries.

Li-ion batteries with superior interior thermal management are crucial to prevent thermal runaway and ensure safe, long-lasting operation at high temperatures or during rapid discharging and charging. Typically, such thermal management is achieved by focusing on the separator and electrolyte. Here, the study introduces a Se-terminated MXene free-standing electrode with exceptional electrical conductivity and low infrared emissivity, synergistically combining high-rate capacity with reduced heat radiation for safe, large, and fast Li+ storage. This is achieved through a one-step organic Lewis acid-assisted gas-phase reaction and vacuum filtration. The Se-terminated Nb2Se2C outperformed conventional disordered O/OH/F-terminated materials, enhancing Li+-storage capacity by ≈1.5 times in the fifth cycle (221 mAh·g-1 at 1 A·g-1) and improving mid-infrared adsorption with low thermal radiation. These benefits result from its superior electrical conductivity, excellent structural stability, and high permittivity in the infrared region. Calculations further reveal that increased permittivity and conductivity along the z-direction can reduce heat radiation from electrodes. This work highlights the potential of surface groups-terminated layered material-based free-standing flexible electrodes with self-thermal management ability for safe, fast energy storage.

Integrated Approach of Life Cycle Assessment and Experimental Design in the Study of a Model Organic Reaction: New Perspectives in Renewable Vanillin-Derived Chemicals.

This work is focused on performing a quantitative assessment of the environmental impacts associated with an organic synthesis reaction, optimized using an experimental design approach. A nucleophilic substitution reaction was selected, employing vanillin as the substrate, a phenolic compound widely used in the food industry and of pharmaceutical interest, considering its antioxidant and antitumoral potential. To carry out the reaction, three different solvents have been chosen, namely acetonitrile (ACN), acetone (Ace), and dimethylformamide (DMF). The syntheses were planned with the aid of a multivariate experimental design to estimate the best reaction conditions, which simultaneously allow a high product yield and a reduced environmental impact as computed by Life Cycle Assessment (LCA) methodology. The experimental results highlighted that the reactions carried out in DMF resulted in higher yields with respect to ACN and Ace; these reactions were also the ones with lower environmental impacts. The multilinear regression models allowed us to identify the optimal experimental conditions able to guarantee the highest reaction yields and lowest environmental impacts for the studied reaction. The identified optimal experimental conditions were also validated by experimentally conducting the reaction in those conditions, which indeed led to the highest yield (i.e., 93%) and the lowest environmental impacts among the performed experiments. This work proposes, for the first time, an integrated approach of DoE and LCA applied to an organic reaction with the aim of considering both conventional metrics, such as reaction yield, and unconventional ones, such as environmental impacts, during its lab-scale optimization.

An inexpensive, metal-free and one-pot approach towards N-sulfonyl amidines: Identification of a chorismate mutase inhibitor with activities against S. aureus

The simple yet innovative synthetic approaches for the direct access to the diversity based unique class of compounds of potential biological interest are of considerable interest as that can greatly facilitate the efforts in bioorganic / medicinal chemistry and drug discovery. In our efforts, we have developed a metal-free, inexpensive and one-pot method for the facile and direct synthesis of N-sulfonyl amidines that were designed as inhibitors of chorismate mutase. The methodology involved POCl3-SOCl2 promoted reaction of amide with sulphonamide to afford an array of new and unique class of compounds in good to acceptable yields. The methodology is free from the use of additional organic reaction media and amenable for scale-up. Based on in vitro and in silico studies, 3g has been identified as a first example of chorismate mutase inhibitor with selective and promising activities on a range of S. aureus strains. Indeed, the docking of 3g into AlphaFold predicted structure S. aureus CM I (UniProt ID: A0A380DU97) revealed good interactions with stabilization mostly via π-anion interactions in addition to a halogen (fluorine) bond. Compound 3g is of further pharmacological interest.

Influence of physical and water quality parameters on residual chlorine decay in water distribution network

Chlorine is the most common disinfectant in drinking water distribution practice. World Health Organization recommends 0.2–5.0 mg/l of residual chlorine in drinking water. This paper analyzed influence of physical and water quality parameters on chlorine decay in drinking water distribution. Principal component analysis, directed tree and regression were used to investigate influence of these parameters on chlorine from water treatment plant to water consumption points. Results show that initial chlorine, electrical conductivity and distance explain 62 % of chlorine decay with estimated error of 0.045 mg/l. The decision-tree feature importance scores of initial chlorine and electrical conductivity were 0.47 and 0.23 respectively. The combined feature importance scores of physical parameters of distance (0.09), pipe diameter (0.06), flow velocity (0.03), pressure (0.02) and travel time (0.046) were less than that for initial chlorine concentration (0.47) alone. These results show that conventional chlorination at water treatment plants removes largely fast inorganic reactants leaving traces of slow organic reactants as the dominant secondary contaminants in water distribution system. The key policy recommendation is to use water quality parameters more than physical parameters in order to enable water utility managers maintain residual chlorine within safe public health standards.

Synthesis and density functional theory study of functionalized Oxazolidine-2-ones using a novel MnFe2O4@SiO2-SiO3H magnetic nanocatalyst

This study introduces MnFe2O4@SiO2-SiO3H as a novel magnetic catalyst and thoroughly investigates its structure, catalytic activity, and reusability. The synthesis of the magnetic catalyst was meticulously characterized using an array of analytical techniques. Utilizing MnFe2O4@SiO2-SiO3H, the synthesis of functionalized oxazolidine-2-ones were performed, versatile compounds widely employed in chiral auxiliaries, protecting groups, and medicinal chemistry. Remarkably, the two-step process from chalcones demonstrated one of the shortest reported pathways, highlighting the efficiency of our novel nanocatalyst. To elucidate the stability and reactivity of the synthesized products, we employed Density Functional Theory (DFT) calculations, including molecular electrostatic potential (MEP) mapping and reactivity indices such as electronegativity, electrophilic index, softness, and hardness, as well as frontier molecular orbitals (HOMO-LUMO). Furthermore, our investigations extended to the recycling capabilities of the nanocatalyst. Through a comprehensive evaluation of at least five reaction cycles, MnFe2O4@SiO2-SiO3H showcased a remarkable retention of activity (97–92 %), reaffirming its reusability and long-term potential. Our research presents MnFe2O4@SiO2-SiO3H as a highly effective and recoverable nanomagnetic catalyst for organic reactions, with demonstrated applications in synthesizing functionalized oxazolidine-2-ones. As such, our findings offer a promising alternative to traditional methods, presenting new opportunities in catalysis and materials science.

Solid-state mechanochemical Clemmensen reduction

Mechanochemical synthesis has emerged as a sustainable alternative to traditional organic reactions, offering several advantages, including reduced solvent usage, lower reaction time, lower energy consumption, and enhanced reaction efficiency. In this study, we explored the application of mechanochemistry to Clemmensen reduction, a classic method for converting aldehydes and ketones into alkanes. By employing ball milling as a mechanical activation, we demonstrate the feasibility and efficacy of mechanochemical Clemmensen reduction in various substrates. Our results indicate that this approach offers comparable or improved yields and functional group compatibility compared to conventional methods while minimizing environmental impact. The reaction optimization strategies and scope of substrates are discussed, highlighting the potential of mechanochemical synthesis for sustainable organic transformations.

Direct de/carboxylation of cannabidiolic acid (CBDA) and cannabidiol (CBD) from hemp plant material under supercritical CO2

Many organic reactions rely on CO2 sources to generate important structural units and valuable chemicals. In this study, we compared the effects of cannabidiol (CBD) and cannabidiolic acid (CBDA) on the supercritical CO2 (scCO2)-induced de/carboxylation reaction. The results showed that CBD was directly carboxylated in the ortho-position to form CBDA with up to 62% conversion. Meanwhile, CBDA decarboxylation occurred on hemp plant material via varying composition. Mechanistic studies revealed that CBD carboxylation was influenced not only by the physical properties of scCO2, but also by the vegetable matrix.

Electrochemical oxidation of concentrated benzyl alcohol to high-purity benzaldehyde via superwetting organic-solid-water interfaces.

Organic electrosynthesis in aqueous media is presently hampered by the poor solubility of many organic reactants and thus low purity of liquid products in electrolytes. Using the electrooxidation of benzyl alcohol (BA) as a model reaction, we present a "sandwich-type" organic-solid-water (OSW) system, consisting of BA organic phase, KOH aqueous electrolyte, and porous anodes with Janus-like superwettability. The system allows independent diffusion of BA molecules from the organic phase to electrocatalytic active sites, enabling efficient electrooxidation of high-concentration BA to benzaldehyde (97% Faradaic efficiency at ~180 mA cm-2) with substantially reduced ohmic loss compared to conventional solid-liquid systems. The confined organic-water boundary within the electrode channels suppresses the interdiffusion of molecules and ions into the counterphase, thus preventing the hydration and overoxidation of benzaldehyde during long-term electrocatalysis. As a result, the direct production of high-purity benzaldehyde (91.7%) is achieved in a flow cell, showcasing the effectiveness of electrocatalysis over OSW interfaces for the one-step synthesis of high-purity organic compounds.

Efficient Radical-Mediated Intermolecular α-Alkylation Reactions of Carbonyl Compounds with Nonactivated Alkenes.

Alkylation reactions are fundamental carbon-carbon bond-forming reactions in synthetic organic chemistry. Among them, intermolecular α-alkylation reactions of carbonyl compounds with alkenes are important because they are more atom-economical than the equivalent processes using alkyl halides. However, intermolecular reactions with nonactivated alkenes such as 1-hexene, which can allow the use of a wide range of valuable substrates, have been considered to be very challenging for a long time. In this review, radical-mediated intermolecular α-alkylation reactions of carbonyl compounds with nonactivated alkenes are discussed. The examples are grouped into three types of reactions: peroxide-mediated reactions, metal-oxidant-mediated reactions, and photoactivated reactions. Photoredox-catalyzed alkylation reactions under visible-light irradiation are discussed as a particularly promising recent hot topic. This review provides brief history and new prospects on the α-alkylation process with nonactivated alkenes using α-carbonyl radical species.

Preparation of Magnetic Nano-Catalyst Containing Schiff Base Unit and Its Application in the Chemical Fixation of CO2 into Cyclic Carbonates

The development of a catalyst for the conversion of CO2 and epoxides to the corresponding cyclic carbonates is still a very attractive topic. Magnetic nano-catalysts are widely used in various organic reactions due to their magnetic separation and recycling properties. Here, a magnetic nano-catalyst containing a Schiff base unit was designed, synthesized and used as a heterogeneous catalyst to catalyze CO2 and epoxides to form cyclic carbonates without solvents and co-catalysts. The catalyst was characterized using Fourier transform infrared (FTIR), X-ray diffraction (XRD), thermogravimetric (TG), VSM, SEM, TEM and BET. The results show that the magnetic nano-catalyst containing the Schiff base unit has a high activity in the solvent-free cycloaddition reaction of CO2 with epoxide under mild conditions, and is easily separated from the reaction mixture driven by external magnetic force. The recovered catalyst maintains a high performance after five cycles.

ChatGPT Convincingly Explains Organic Chemistry Reaction Mechanisms Slightly Inaccurately with High Levels of Explanation Sophistication

ChatGPT Convincingly Explains Organic Chemistry Reaction Mechanisms Slightly Inaccurately with High Levels of Explanation Sophistication

Silica Nanoparticles Functionalized with an Ionic Liquid: A Green and Efficient Heterogeneous Catalyst for a Cascade Reaction

AbstractA new strategy for a catalytic C−C bond forming cascade reaction comprising acetal hydrolysis and Knoevenagel condensation is presented here. The heterogeneous nanocatalyst is prepared by immobilizing an ionic liquid on the surface of highly monodisperse silica nanoparticles. This work is the first example of showing that there is no need to use bifunctional acid‐base catalysts for a cascade reaction including the hydrolysis of benzaldehyde dimethyl acetal to benzaldehyde and the subsequent Knoevenagel condensation of the resulting benzaldehyde with malononitrile. It is shown here that these reactions can proceed smoothly with a mono‐functional heterogeneous catalyst that contains a neutral ionic liquid. It has been proposed that such a neutral ionic liquid can “switch on” to an acidic catalyst in conjunction with water. The selected ionic liquid has potentially biodegradability characteristics, which is an important issue to achieve a sustainable catalyst. The simple procedure for preparing both the ionic liquid and the monodisperse silica nanoparticles provides opportunities for a large‐scale synthesis of the catalyst. This work introduces a breakthrough in the design and synthesis of heterogeneous catalysts for acid/base catalyzed cascade organic reactions.