Ionic Liquid in Synthesis: A Phase Transfer Reagent and a Redox Mediating Medium

Ionic liquids (ILs) with chloride anion or bromide anion were attempted as a phase transfer reagent to depolymerize MX₂ (M = Pt, Pd; X = Br, Cl) in chloroform for reaction with 2,2′‐bipyridine (= bpy) to give the (bpy)MX₂ product. Supersonic irradiation of equiv‐molar bpy, PdX₂, and IL in CHCl₃ produced almost quantitative precipitate of (bpy)PdX₂ in a short time at ambient temperature, where IL is either [BEIm]Br or [BMIm]Br. That is, ILs and sono‐techniques assisted greatly on the synthesis of (bpy)PdX₂. For preparation of (bpy)PtX₂, nonetheless, free bpy always remained in mixture even after a long time of supersonic treatment. The system of equiv‐molar bpy, PtBr₂, and IL in CHCl₃, produced yellow (bpy)PtBr₂ and orange (bpy)PtBr₄, both being characterized with ¹H NMR and ¹⁹⁵Pt NMR in d₆‐Me₂SO as well as with single crystal X‐ray diffraction. Overall for PtX₂ reactions with halide anions in highly polar environments attributable to ILs, the redox pathway becomes important in that Pt(II) transforms to Pt(IV) to yield (bpy)PtBr₂ and (bpy)PtBr₄.     

Applications of ultrasound in total synthesis of bioactive natural products: A promising green tool

Total synthesis is frequently compared to climbing as it provides a suitable route to reach a high point from the floor, the complex natural product from simple and commercially available materials. The total synthesis has a privileged position of trust in confirming the hypothetical complex structures of natural products despite sophisticated analytical and spectroscopic instrumentation and techniques that are available presently. Moreover, total synthesis is also useful to prepare rare bioactive natural products in the laboratory as several bioactive secondary metabolites are obtained in small quantities from natural sources. The artistic aspect of the total synthesis of bioactive natural products continues to be praised today as it may provide environmental protection through the concept of green or clean chemistry. The use of ultrasound waves as a non-polluting source of energy is of great interest in the field of sustainable and pharmaceutical chemistry as it differs from conventional energy sources in terms of reaction rates, yields, selectivities, and purity of the products. The present review highlights the application of ultrasound as a green tool in the total synthesis of bioactive natural products as well as this article is also aimed to offer an overview of natural sources, structures, and biological activities of the promising natural products for the first time from 2005 to 2020 elegantly.     

Catalytic performance of Mn3O4 and Co3O4 nanocrystals prepared by sonochemical method in epoxidation of styrene and cyclooctene

A simple sonochemical method was developed to synthesis uniform sphere-like Co₃O₄ and Mn₃O₄ nanocrystals. Epoxidation of styrene and cyclooctene by anhydrous tert-butyl hydroperoxide over the prepared Co₃O₄ and Mn₃O₄ nanocatalysts was investigated. The results of conversion activity were compared with bulk Co₃O₄ and Mn₃O₄. Under optimized reaction conditions, the nanocatalysts showed a superior catalytic performance as compared to the bulk catalysts. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and BET surface area, were used to characterize and investigate the nanocatalysts.     

Sonochemical synthesis of silver, copper and lead selenides

Ag₂Se, CuSe and PbSe were prepared by irradiating the mixtures of AgNO₃, CuI or PbCl₂ with selenium in ethylenediamine (en) with ultrasound at 18 kHz, using a commercial ultrasonic cleaner, respectively. X-ray powder diffraction (XRD) patterns and transmission electron microscope (TEM) images show that the products are orthorhombic Ag₂Se, hexagonal CuSe and cubic PbSe, respectively, and all are well crystallized in nanometers.     

A parametric review of sonochemistry: Control and augmentation of sonochemical activity in aqueous solutions

In this review the phenomenon of ultrasonic cavitation and associated sonochemistry is presented through system parameters. Primary parameters are defined and considered, namely; pressure amplitude, frequency and reactor design; including transducer type, signal type, vessel-transducer ratio, liquid flow, liquid height, liquid temperature and the presence of a reflective plate. Secondary parameters are similarly characterised and involve the use of gas and liquid additives to influence the chemical and physical environments. Each of the parameters are considered in terms of their effect on bubble characteristics and subsequent impact on sonochemical activity. Evidence suggests that via parametric variation, the reaction products and efficiency may be controlled. This is hypothesised to occur through manipulation of the structural stability of the bubble.     

Synthetic approaches to 5,7- and 5,8-dimethoxyquinoline. Sonochemical dehalogenation of substituted 2,4-dichloroquinolines. Use of the 2D COLOC spectrum for the NMR assignment of 5,8-dimethoxyquinoline

Summary Sonochemical dehalogenation of 2,4-dichloroquinoline is very facile. However, with 5,7-dimethoxy-2,4-dichloroquinoline the reaction proceeds stepwise to provide the title dimethoxyquinolines which cannot be prepared via theSkraup reaction. The¹³C NMR chemical shift assignments for 5,8-dimethoxyquinoline are presented. These were made by utilising the coupling connectivities from the bridgehead carbons in the 2D COLOC spectrum.

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Synthese von 5,7- und 5,8-Dimethoxychinolin. Sonochemische Dehalogenierung von substituierten 2,4-Dichlorochinolinen. NMR-Spektroskopische Zuordnung von 5,8-Dimethoxychinolin mittels eines COLOC-Experiments

Zusammenfassung 2,4-Dichlorchinoline können sonochemisch leicht dehalogeniert werden. Mit 5,7-Dimethoxy-2,4-dichlorchinolin verläuft die Reaktion in mehreren Schritten zu den Titelverbindungen, die mittelsSkraup-Reaktion nicht hergestellt werden können. Das¹³C-NMR-Spektrum von 5,8-Dimethoxychinolin wurde, ausgehend von den Brückenkopfkohlenstoffatomen, mit Hilfe eines COLOC-Experiments zugeordnet.

     

Bulk polymerized polystyrene in the presence of multiwalled carbon nanotubes

The in situ bulk polymerization method was applied to synthesize composites of multiwalled carbon nanotubes (MWNTs) and polystyrene (PS) under ultrasonication to open π-bonds in the MWNTs. Morphology of the composite products was studied by both scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Thermal properties and molecular weight of the PS synthesized in the presence of the MWNTs were examined by thermogravimetric analysis (TGA) and gel permeation chromatography (GPC), respectively. The MWNTs were observed to play an important role as initiator consumers during the polymerization reaction. Electrical conductivity of a film-type sample of the PS/MWNT nanocomposite was found to increase with increased amount of MWNTs added, following the percolation theory.     

频率对双频超声辐照声化学产额增强效应的影响

本文采用电学法研究了２８ｋＨｚ分别与０．８７ＭＨｚ、１ＭＨｚ、１．７ＭＨｚ组成的双频超声辐照的声化学效应。结果表明，双频辐照增强声化学产额具有明显的频率效率。     

Sonically modified hierarchical FAU-type zeolites as active catalysts for the production of furan from furfural

In this study, the sonochemical-assisted desilication method was applied as a special and innovative way of preparing hierarchical zeolites. The physicochemical properties of the hierarchical zeolites prepared using the sonochemical route were compared with those prepared using the conventional desilication method. Commercial zeolite with FAU-type structure was desilicated with a sodium and tetrabutylammonium hydroxide aqueous solution (NaOH/TBAOH) for 30 min. The ultrasound treatment process was performed using a QSonica Q700 sonicator (Church Hill Rd, Newtown, CT, USA) equipped with a ½″ diameter horn. The average power of sonication was 60 W, and the frequency was 20 kHz. During the sonication procedure, the alkaline solution with the catalyst precursor and sonicator probe were placed in an ice bath to keep them at room temperature. The prepared catalyst samples were examined by ICP-OES, XRD, SEM, NMR, and nitrogen sorption techniques. The acidic properties of the prepared hierarchical zeolite samples were assessed by means of IR spectroscopy with ammonia and carbon monoxide sorption as probe molecules. All catalysts were studied in the decarbonylation of furfural into furan.Independently of the application of ultrasonic irradiation, desilication of zeolites with an NaOH/TBAOH mixture extracts comparable amounts of silicon, resulting in comparable crystallinity and acidity. On the other hand, the samples prepared in the presence of ultrasounds revealed higher both mesoporosity and enhanced catalytic properties in the reaction of decarbonylation of furfural into furan in comparison with their counterparts prepared using the conventional method.     

Ultrasound Promoted 1, 3-Dipolar Cycloaddition Reactions of Nitrile Oxides with α, β-Unsaturated Acetals

The 1,3-dipolar cycloaddition reactions of nitrile oxides and α,β-unsaturated 1,3-dioxolanes were effectively accelerated by ultrasound irradiation to give the A²-isoxazolines with yields and regioselectivities surpassing those of the corresponding thermal reactions.