Aim: Catalytic degradation of azo dye. Background: Azo dyes are toxic agents and pollutants and the degradation of these dyes has an important application in the treatment of textile industry wastes. Catalytic decolorization of fast yellow dye by hexacyanoferrate (III), abbreviated as HCF(III) using polyvinylpyrrolidone abbreviated as PVP stabilized Ir-Ni bimetallic nanocrystals has been evaluated by kinetic spectrophotometric method at 440nm wavelength of the reaction mixture. Methods: The impact of various operational factors such as fast yellow dye abbreviated as [FY], oxidant [HCF(III)] ions, promoter iridium-nickel bimetallic nanoparticles abbreviated as [(Ir-Ni)] BMNPs, and solution pH on the rate of the reaction have been examined. Results: The results represent that the reaction follows first -order kinetics model with respect to [oxidant] at optimum pH 8 and fix temperature 40±0.1◦C. Thermodynamic parameters such as activation energy (Ea), enthalpy (ΔH#), entropy (ΔS#), frequency factor (A), and free energy of activation (ΔF#) have been evaluated by examining the reaction rate at four temperatures i.e. 40⁰C, 45⁰C, 50⁰C, and 55⁰C. On the basis of experimental outcomes, an appropriate mechanism involving complex formation has been proposed. Conclusion: Analytical techniques such as UV-Vis spectroscopy, FTIR, and LCMS of degraded products represent the formation of easier and less harmful compounds.

Abstract: This brief perspective outlines the pivotal role of Machine Learning methods in the green, digital transition of industrial chemistry. The focus on homogenous catalysis highlights the recent methodologies in the development of industrial processes, including the design of new catalysts and the enhancement of sustainable reaction conditions to lower production costs. We report several examples of Machine Learning assisted methodologies through recent Data Science trends on innovation of industrial homogeneous organocatalytic systems. We also stress the current benefits, drawbacks, and limitations towards the mass implementation of these Data Science methodologies.

Abstract:Compounds with three membered rings experience greater strain than those with other ring systems. In general, the synthesis of small ring compounds, particularly three-membered molecules, faces major challenges because of the severe strain in this system. Moreover, microwaveassisted method creates a higher temperature due to the heat and radiation of a reaction mixture more rapidly than conventional methods. This paper reports the successful synthesis of threemembered heterocyclic compounds via microwave-assisted reactions. Microwaves have assisted in making three-membered compounds while inducing high energy to the reaction mixtures. No reviews have reported the synthesis of these types of molecules either by microwave or conventional procedure. In addition, the reaction of a few three-membered ring compounds to other products through the ring rupture method is also included. On this basis of the chemistry (formation and breakage) of three-membered compounds described here, this report can be considered novel, timely, and highly significant. This review may help numerous researchers for further study in this field as the synthesis and cleavage of three-membered ring structures using a microwave is a challenging objective.

Background: Nicotine (NIC) is a lipid-soluble alkaloid found predominantly in tobacco products, including cigarettes, cigars, and oral tobacco products such as snuff and chewing tobacco. Since nicotine substrate is the major constituent of tobacco smoke, it may cause negatively impacted problems for human healthcare, which keeps many users hooked. Method: A spectrophotometric technique has been applied to investigate the kinetics of reductoin hexachloroiridate (IV) as an inert one-equivalent oxidant by carcinogenic nicotine (NIC) in aqueous perchlorate solutions. Results: First-order in [IrCl6]2- and fractional-first-order concerning the nicotine concentration has been revealed. Kinetic evidence for forming a 1:1 intermediate complex between the NIC and [IrCl6]2- before the rate-determining step was confirmed. Conclusion: The ionization constants of nicotine were evaluated from the kinetic data and are 8.57x10-4 and 4.57 x 10-4 moldm-3 at an ionic strength of 0.5 moldm-3 and 30°C and 40°C, respectively. The activation parameters have been deduced from the kinetic results of the temperature dependence of rate constants. A plausible reaction mechanism for the redox reaction is suggested and discussed. Nicotinic acid (Vitamin B3) was formed as an oxidation product of nicotine oxidation.

Background: Baylis-Hillman reaction requires cheap starting materials, easy reaction protocol, and possibility to create the chiral center in the reaction product has increased the synthetic efficacy of this reaction which also suffers from high catalyst loading, low reaction rate, and poor yield. Objective: The extensive use of various functional or non-functional ionic liquids (ILs) with organocatalyst acts not only as reaction medium but also as a support to anchor the catalysts to increase the reaction rate of various organic transformations. Methods: In this manuscript, we have demonstrated the synthesis of quinuclidine-supported trimethylamine-based functionalized ionic liquid as a catalyst for the Baylis-Hillman reaction. Results: We obtained the Baylis-Hillman adducts in good, isolated yield along with low catalyst loading, short reaction time, wide substrate scope, easy product, and catalyst recycling. N- ((E,3S,4R)-5-benzylidene-tetrahydro-4-hydroxy-6-oxo-2H-pyran-3-yl) palmitamide was also successfully synthesized using CATALYST-3 promoted Baylis-Hillman reaction. Conclusion: We successfully isolated the 25 types of Baylis-Hillman adducts using three different quinuclidine-supported ammonium-based ionic liquids such as Et3AmQ][BF4] (CATALYST-1), [Et3AmQ][PF6] (CATALYST-2), and [TMAAmEQ][NTf2](CATALYST-3) as new and efficient catalysts. Generally, all the reactions demonstrated higher activity and gave good to high yield in competition with various previously reported homogenous and heterogeneous catalytic systems. Easy catalyst and product recovery followed by 6 times of catalysts recycling were the added advantages of the prosed catalytic system. Tedious and highly active N-((E,3S,4R)-5-benzylidene-tetrahydro- 4-hydroxy-6-oxo-2H-pyran-3-yl) palmitamide derivative was also synthesized using CATALYST- 3 followed by Baylis-Hillman reaction.

: Organocatalysis was established to be a wide-applicable approach from its inception and rediscovery in the year 2000, where proline was used as a catalyst in aldol condensation and soon after the successful emergence of iminium catalysed reactions in organic synthesis. Development of new potential catalytic systems is always an important as well as an uphill task for scientists and researchers. The fundamental organic synthesis majorly deals with metal based catalysts, whereas there is a constant surge of developing metal free reaction condition to make the reactions environmental friendly. For the synthesis of complex organic molecules, reduction and oxidation reactions are always needed and there are plenty of catalysts available for these reactions. Organocatalysts are also developed and applied for these two elementary reactions. This review focuses on some of the latest developments and applications of organocatalysts in oxidation and reduction reactions in fundamental organic synthesis.

Aims: In search of a ligand-free, recyclable, selective, and stable catalytic system, we engineered both Pd/GO and Pd/rGO composites and tested them as catalysts for Heck and Suzuki reactions in [bmim] NTf2 ionic liquid medium. Background: Various reports and reviews have been published on exploring the application of ionic liquids as a reaction medium for different organic transformations. Recently, graphene-supported Pt nanoparticles have immobilized with the 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene bis(trifluoromethylsulfonyl) imide ionic liquid [MTBD][bmsi] and further tested to study the oxygen reduction reaction. Surprisingly, [MTBD][bmsi] immobilized system was found highly active towards electrocatalytic reaction. Objective: In various reports, palladium nanoparticles were immobilized with graphene oxide (GO) or with reduced graphene oxide (rGO), and these two types of graphene were further tested as a catalyst for different coupling reactions such as Suzuki-Miyaura, Heck, and Suzuki reaction. Both Pd/- GO and Pd/rGO were found attractive concerning catalyst specific property, i.e., high surface area, and because of that, graphene immobilized palladium was found to be similar to other commercially available palladium catalysts (e.g., Pd on charcoal), but collectively, both hybrid materials (Pd/- GO and Pd/rGO) possess various drawbacks, like high catalyst loading, catalyst leaching (via agglomeration of Pd metals into the clusters) during the recycling test (especially in case of Pd/GO), limited substrate scope, and the requirement of polar solvents, etc. Methods: All the chemicals were purchased from Sigma Aldrich, Acros, or Fluka. NMR spectra were recorded on a standard Bruker 300WB spectrometer with an Avance console at 300 and 75 MHz for 1H and 13C NMR, respectively. Pd/O and Pd/rGO were synthesized as per the reported procedure. The residue was purified by flash chromatography (FC) with hexane/ethyl acetate. The detailed 1H and 13C NMR of each Heck and Suzuki reaction product were found similar to the reported analytical data. 1-butyl-3-methylimidazolium bis (trifluoromethyl sulfonyl) imide ([bmim]NTf2) was synthesized as per the reported procedure. Results and Conclusion: We have successfully developed a highly efficient ligand-free method for Heck and Suzuki reaction, using Pd/rGO catalysts in an ionic liquid medium which afforded the coupling products with excellent yield. One of the major advantages of the proposed protocol is that the catalyst system can be easily re-usable without the loss of catalytic activity, thereby multiplying catalyst turnover. Another advantage is that the reaction proceeds without phosphine ligands, which are expensive, toxic, and contaminants of the product. The green nature of ionic liquid and the simplicity of its operation make the present Heck and Suzuki reactions more attractive.

Aims: A green route for the oxidation of alcohols to corresponding carbonyl compounds in room temperature ionic liquid ([CEMIM]BH4) was developed by using hydrogen peroxide as the oxygen source. In aqueous solution at room temperature, 0.2 mol% of ([CEMIM]BH4) showed excellent catalytic properties for selective oxidation of aromatic and aliphatic alcohols Background: One of the vital reactions in organic synthesis is the oxidation of alcohols to carbonyl compounds. In particular, the conversion of primary alcohols to aldehydes has received a variety of applications as they are used as intermediates in fine chemicals mostly for the perfume industry. Objective: In the present work, we have reported an effective green route for the selective oxidation of alcohols to the carbonyl compounds using peroxide in an ionic liquid 1-carboxyethyl-3-methyl-imidazolium tetrahydroborate ([CEMIM]BH4) Methods:: A mixture of alcohol (2 mmol), ([CEMIM]BH4) (0.2 mol%), H2O2 (2 mmol) were stirred thoroughly with the help of a magnetic stirrer for 10 min at ambient temperature Results: The catalytic activity of ([CEMIM]BH4) is very effective, which reflects its good solvating nature during the oxidation. Conclusion: In conclusion, the series of experiments described represents a useful method for the oxidation of primary and secondary alcohols to carbonyl compounds at room temperature. The catalyst can be easily prepared and is therefore extremely cost-effective. The rapid reaction times for the substrates mean a large number of materials may be screened in parallel over a short period of time.

Background: Transfer hydrogenation methods that employ non-H2 hydrogen sources have evolved as an attractive alternative for conventional hydrogenation approaches. Objective: In this study, we aimed at developing optimized conditions to induce the selective transfer hydrogenation reduction of aromatic alkynes catalyzed by PdCl2(PPh3)2 and using formic acid as the hydride source. Methods: The effect of various reaction parameters, such as the nature and amount of the catalyst, the H-donor/base couple, reaction time and temperature, and the nature of the solvent on the outcome of the alkyne reduction were investigated. Results: The reduction of the alkyne can be chemoselectively controlled by adjusting the reaction conditions. Among the tested catalysts, PdCl2(PPh3)2 was the most suitable, with 2% of the catalyst being the optimal amount. While the reduction was successful in different solvents of different polarities, THF was selected as the solvent of choice. The reduction of diphenylacetylene yielded the alkene both at 50°C and 80°C. When testing the optimized conditions on the reduction of 4- phenyl-3-butyne-2-one, quantitative partial reduction to the corresponding α,β-unsaturated ketone was obtained at 50°C, while the saturated ketone was produced as the major product at 80°C. Conclusion: The chemoselective reduction of aromatic alkynes was performed successfully with complete conversion using 2% PdCl2(PPh3)2 as a catalyst, formic acid/NEt3 as the H-donor/base couple, THF as the solvent, at 50°C and 80°C.