Sonochemical synthesis,characterization, and effects of temperature,power ultrasound and reaction time on the morphological properties of two new nanostructured mercury(II) coordination supramolecule compounds

Two new mercury(II) coordination supramolecular compounds (CSCs) (1D and 0D), [Hg(L)(I)₂]_n (1) and [Hg₂(L′)₂(SCN)₂]·2H₂O (2) (L = 2-amino-4-methylpyridine and L′ = 2,6-pyridinedicarboxlic acid), have been synthesized under different experimental conditions. Micrometric crystals (bulk) or nano-sized materials have been obtained depending on using the branch tube method or sonochemical irradiation. All materials have been characterized by field emission scanning electron microscope (FESEM), scanning electron microscopy (SEM), powder X-ray diffraction (PXRD) and FT-IR spectroscopy. Single crystal X-ray analyses on compounds 1 and 2 show that Hg²⁺ ions are 4-coordinated and 5-coordinated, respectively. Topological analysis shows that the compound 1 and 2 have 2C1, sql net. The thermal stability of compounds 1 and 2 in bulk and nano-size has been studied by thermal gravimetric (TG), differential thermal analyses (DTA) for 1 and differential scanning calorimetry (DSC) for 2, respectively. Also, by changing counter ions were obtained various structures 1 and 2 (1D and 0D, respectively). The role of different parameters like power of ultrasound irradiation, reaction time and temperature on the growth and morphology of the nano-structures are studied. Results suggest that increasing power ultrasound irradiation and temperature together with reducing reaction time and concentration of initial reagents leads to a decrease in particle size.     

Application of ultrasound technique in the synthesis of methanofullerene derivatives

Methanofullerene derivatives C₆₀(CCl₂) (1a), C₆₀(CBr₂) (1b), C₆₀(CI₂) (1c) and C₁₂₁ (2) were synthesized in 55–84% yields by dehalogenation of the corresponding α-polyhalides via sodium hydroxide, magnesium, respectively, followed by the in situ reaction with fullerene under the irradiation of ultrasound in a non-conventional reaction media, ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM][BF₄]. Only single [6,6]-ring junction cycloaddition isomers of the products were detected in the reaction solutions under our conditions. In contrast, low yields of 6–21% were obtained when the same reactions were operated in tetrahydrofuran. All of the products were purified with HPLC and characterized by ¹³C NMR and FAB-MS.     

Sonochemical synthesis of a novel nanoscale 1D lead(II) [Pb2(L)2(I)4]n coordination Polymer,survey of temperature,reaction time parameters

One new lead(II) coordination supramolecular complex (CSC) (1D), [Pb₂(L)₂(I)₄]_n, L = C₄H₆N₂ (1-methyl imidazole), has been synthesized under different experimental conditions. Micrometric crystals (bulk) or nano-sized materials have been obtained depending on using the branch tube method or sonochemical irradiation. All materials have been characterized by scanning electron microscopy (SEM), powder X-ray diffraction (PXRD) and FT-IR spectroscopy. Single crystal X-ray analyses on complex 1 showed that Pb²⁺ ion is 4-coordinated. Topological analysis shows that the complex 1 is 2,3,5C2 net. Finally, the role of reaction time and temperature on the growth and final morphology of the structures obtained by sonochemical irradiation have been studied.     

Ultrasound irradiation effect on morphology and size of two new potassium coordination supramolecule compounds

Two new potassium coordination supramolecular compounds (2D and 1D), [K(H₃L)(H₂L)(H₂O)]_n·H₂O (1) and [K(H₂L′)(HL′)(H₂O)₂]·H₂O (2), (L = 1,3,5-tricarboxylic acid, L′ = 2,6-pyridinedicarboxylic acid), have been synthesized under different experimental conditions. Micrometric crystals (bulk) or nano-sized materials have been obtained depending on using the branch tube method or sonochemical irradiation. All materials have been characterized by field emission scanning electron microscopy (FE-SEM), scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), FT-IR spectroscopy and elemental analyses. Single crystal X-ray analyses on compounds 1 and 2 show that K⁺ ions are 3- and 7-coordinated, respectively. Additionally, H-bonds incorporate the layers and chains in 1 and 2 into 3D and 2D (along (0,0,1) direction) frameworks. Topological analysis shows that the compound 1 and 2 are 3,6-coordinated kgd and 2,4-coordinated 2,4C4 net. The thermal stability of compounds 1 and 2 in bulk and nano-size has been studied by thermal gravimetric (TG) and differential thermal analyses (DTA) and compared each other. The role of different parameters like temperature, reaction time and ultrasound irradiation power on the growth and morphology of the nano-structures are studied. Results suggest that an increase of temperature, sonication power and reduction of reaction time led to a particle size decrease.     

Ultrasound-assisted one-pot green synthesis of new N- substituted-5-arylidene-thiazolidine-2,4-dione-isoxazoline derivatives using NaCl/Oxone/Na3PO4 in aqueous media

A rapid and green method for the synthesis of novel N-thiazolidine-2,4-dione isoxazoline derivatives 5 from N-allyl-5-arylidenethiazolidine-2,4-diones 3 as dipolarophiles with arylnitrile oxides via 1,3-dipolar cycloaddition reaction. The corresponding N-allyl substituted dipolarophiles were prepared by one-pot method from thiazolidine-2,4-dione with aldehydes using Knoevenagel condensation followed by N-allylation of thiazolidine-2,4-dione in NaOH aqueous solution under sonication. In addition, the isoxazoline derivatives 5 were synthesized by regioselective and chemoselective 1,3-dipolar cycloaddition using inexpensive and mild NaCl/Oxone/Na₃PO₄ as a Cl source, oxidant and/or catalyst under ultrasonic irradiation in EtOH/H₂O (v/v, 2:1) as green solvent. All synthesized products are furnished in good yields in the short reaction time, and then their structures were confirmed by NMR, mass spectrometry and X-ray crystallography analysis.     

Ultrasonic synthesis of two nanostructured cadmium(II) coordination supramolecular polymers: Solvent influence,luminescence and photocatalytic properties

Two nanoparticles of cadmium(II) coordination polymers (CPs) formulated as [Cd(L)(DCTP)]_n (1) and [Cd(L)₂(DCTP)·2H₂O]_n (2) (L = 1,2-bis(2-methylbenzimidazol-1-ylmethyl)benzene, H₂DCTP = 2,5-dichloroterephthalic acid) were prepared by the sonochemical approach in different solvents and characterized by elemental analysis, IR spectra, scanning electron microscopy (SEM), and powder X-ray diffraction. Structural determination reveals that CP 1 displays a 2D four-connected sql net layer, Whilst CP 2 exhibits a 1D “V”-like chain structure. Luminescence properties, thermal behavior, and photocatalytic activities of the nanoparticles of CPs 1 and 2 on the degradation of methylene blue were investigated. The photocatalytic mechanism is carried out by introducing t-butyl alcohol (TBA) as a widely used OH scavenger. Furthermore, the influence of solvents, reaction time, and ultrasound irradiation temperature on the morphology and size of the nanostructure CPs 1 and 2 were investigated. The results indicated that an increase of time and ultrasound irradiation temperature decreased the nanostructured size.     

Sonochemical synthesis and structural characterization of a new nanostructured Co(II) supramolecular coordination polymer with Lewis base sites as a new catalyst for Knoevenagel condensation

A new Co(II) mixed-ligand coordination supramolecular polymer with composition [Co₂(ppda)(4-bpdh)₂(NO₃)₂]_n (1) (where, ppda = p-phenylenediacrylic acid, 4-bpdh = 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene) was synthesized using solvothermal, mechanochemical and sonochemical methods. Compound 1 and the new nanostructure have been characterized by single-crystal X-ray, infrared spectroscopy (IR), powder X-ray diffraction (PXRD) analysis and scanning electron microscopy (SEM). The thermal stability of compound 1 was also studied by thermal gravimetric analysis (TGA). The surface area of these compounds was determined by BET. The single-crystal X-ray data shows a new interesting two-dimensional coordination polymer (CP). In addition, the effect of various sonication concentrations of initial reagents, power of ultrasound irradiation and also the time on the size and morphology of nano-structured coordination polymer 1 were evaluated. Moreover, it has been demonstrated that the nanostructure of the CP1 can be used as a catalyst in Knoevenagel condensation reaction.     

Ultrasound-assisted fabrication of a new nano-rods 3D copper(II)-organic coordination supramolecular compound

High-energy ultrasound irradiation has been used for the synthesis of a new copper(II) coordination supramolecular compound, [Cu₂(μ-O₂CCH₃)₂(μ-OOCCH₃)(phen)₂](BF₄) (1), (“phen” is 1,10-phenanthroline) with nano-rods morphology. The new nano-structure was characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), FT-IR spectroscopy and elemental analyses. Compound 1 was structurally characterized by single crystal X-ray diffraction. The utilization of high intensity ultrasound has found as a facile, environmentally friendly, and versatile synthetic tool for the supramolecular coordination compounds.     

Ultrasound and microwave assisted synthesis of dihydroxyacetophenone derivatives with or without 1,2-diazine skeleton

A thorough study concerning O-alkylation and α-bromination of dihydroxyacetophenone (DA) and N-alkylation of 1,2-diazine, under ultrasound (US) and microwave (MW) irradiation as well as under conventional thermal heating (TH) is presented. Under US and MW irradiation the yields are higher, the amount of used solvent decreases substantially, the reaction time decreases considerable (from hours or days to minutes) and the consumed energy decreases, consequently the O-alkylation, α-bromination and N-alkylation methods could be considered environmentally friendly. A selective and efficient way to either bis-O-alkylation or mono-O-alkylation of DA has been found, the relative position of the two hydroxyl groups on the phenyl moiety being compulsory. A selective and efficient way for α-bromination in heterogeneous catalysis of DA derivatives under US irradiation is presented. The N-alkylation reaction of DA under US and MW irradiation proved to be the most convenient setup procedure for these types of reactions. Overall, the use of US proved to be more efficient than MW or TH.     

Ultrasound mediation for one-pot multi-component synthesis of amidoalkyl naphthols using new magnetic nanoparticles modified by ionic liquids

The ionic liquid 1-methyl-3-(3-trimethoxysilylpropyl) imidazolium acetate was immobilized on the Fe₃O₄ nanoparticles (MNPs-IL-OAc) and used as an efficient new heterogeneous nanocatalyst for the one-pot multi-component synthesis of 1-amidoalkyl-2-naphthols under ultrasound irradiation. The advantages of present combined method are the use of a low scale catalyst, easier work-up procedure, waste-free, green and efficient synthetic entry to excellent yield of products in a high reusability and a short reaction time.     

A f acile,regioselective synthesis of novel 3-( N-phenylc arbox amide)pyr azolo[1,5- a]pyrimidine an alogs in the presence of KHSO$$_{}$$ in aqueous medi a assisted by ultr asound and their antib acteri al activities

An environmentally benign, simple, efficient, and convenient route is described for the synthesis of novel pyrazolo[1,5-a]pyrimidine derivatives under ultrasound irradiation. Condensation of aminopyrazole 5 with formylated active proton compounds (6, 8, E–G, 12, and 15) furnished pyrazolopyrimidine (7, 9, 10, 13, and 16) in high-to-excellent yields. In comparison with conventional methods, ultrasound irradiation offers several advantages, such as shorter reaction time, higher yields, milder conditions, and environmental friendliness. The reaction is clean with excellent yields and reduces the use of solvents. X-ray crystallographic study of compound 7c confirmed the regioselectivity of the reaction. The antibacterial profile of the newly synthesized compounds was evaluated by cup and saucer method.     

Sonochemical syntheses and characterization of nano-sized lead(II) coordination polymer with ligand 1H-1,2,4-triazole-3-carboxylate

Nanoparticles of a two-dimensional coordination polymer, {[Pb(L)(μ_1,1-NCS)(H₂O)]}_n (1), (L⁻ = 1H-1,2,4-triazole-3-carboxylate), have been synthesized by a sonochemical process and characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. The thermal stability of compound 1 both its bulk and nano-size has been studied by thermal gravimetric (TG) and differential thermal (DTA) analyses and compared each other. Concentration of initial reagents effects and the role of power ultrasound irradiation on size and morphology of nano-structured compound 1, have been studied. Calcination of the single crystals and nano-sized compound 1 at 400 °C under air atmosphere yields mixture of PbS and Pb₂(SO₄)O nanoparticles. Results show that the size and morphology of the PbS and Pb₂(SO₄)O nanoparticles are dependent upon the particles size of compound 1. A decrease in the particles size of compound 1 leads to a decrease in the particles size of the PbS and Pb₂(SO₄)O.     

A simplified green chemistry approaches to synthesis of 2-substituted 1,2,3-triazoles and 4-amino-5-cyanopyrazole derivatives conventional heating versus microwave and ultrasound as ecofriendly energy sources

Cyanoacetamides 3 were prepared via reacting ethyl cyanoacetate with benzylamine. Yields and reaction times needed for reaction completion at room temperature, by microwaves (μω) heating and under ultrasound (US) irradiations are compared. The formed cyanoacetamides were coupled with aromatic diazonium salts and the formed arylhydrazones were used as precursors to title triazoles and pyrazoles via reacting the former with hydroxylamine and chloroacetonitrile. Yields of products formed via conventional heating are compared with those of μω and US irradiation.     

A facile synthesis of deuteroporphyrins derivatives under ultrasound irradiation

A facile, efficient and general method for preparing deuteroporphyrin derivatives by using concentrated H₂SO₄ and alcohol under ultrasound irradiation has been developed. A series of new deuteroporphyrin derivatives bearing different propionic ester groups have been synthesized in good yields starting from readily accessible deuterohemin. The characterization of these compounds confirms the synthetic methodology. Compared with conventional methods, the main advantages of the present procedure are shorter reaction time and higher yields.     

Sonochemical preparation of pure t-LaVO4 nanoparticles with the aid of tris(acetylacetonato)lanthanum hydrate as a novel precursor

Herein a simple and fast method is introduced for the synthesis of lanthanum orthovanadate (LaVO₄) nanoparticles under ultrasound irradiation. The effect of tris(acetylacetonato)lanthanum hydrate ([La(acac)₃·3H₂O]) and La(OAc)₃ as two different precursors on the morphology and phase purity of LaVO₄ was investigated. To optimum the particle size of the products, sonication time and the kind of surfactants have been changed. The as-synthesized products were characterized by XRD, FT-IR, SEM, TEM, and EDS. Based on the obtained results, it was found that the size and shape of the sonochemically formed LaVO₄ nanoparticles were dramatically dependent on the sonication time, type of surfactant and lanthanum precursor. According to the XRD results, it was observed that pure tetragonal phase lanthanum orthovanadate (t-LaVO₄) could be obtained only by using [La(acac)₃·3H₂O] as precursor under ultrasound irradiation for 30 min. On the other hand, monoclinic phase lanthanum orthovanadate (m-LaVO₄) with poor crystallinity has been produced by vigorous stirring at room temperature without sonication.     

Sonochemical synthesis and characterization of nano-sized lead(II) 3D coordination polymer: Precursor for the synthesis of lead(II) oxybromide nanoparticles

Nanoparticles of a three-dimensional coordination polymer, [Pb(L)(μ₂-Br)(H₂O)]_n (1), (L^? = 1H-1,2,4-triazole-3-carboxylate), have been synthesized by an ultrasonic method and characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. The thermal stability of compound 1 both its bulk and nano-size has been studied by thermal gravimetric (TG) and differential thermal (DTA) analyses and compared each other. Concentration of initial reagents effects and the role of power ultrasound irradiation on size and morphology of nano-structured compound 1, have been studied. Calcination of the compound 1 at 500 °C under air atmosphere yields Pb₃O₂Br₂ nanoparticles.     

Catalytic-oxidative/adsorptive denitrogenation of model hydrocarbon fuels under ultrasonic field using magnetic reduced graphene oxide-based phosphomolybdic acid (PMo-Fe3O4/rGO)

In this work, the effect of ultrasound irradiation on the catalytic oxidative/adsorptive denitrogenation (COADN) of model hydrocarbon fuels (composed of pyrrole or indole as an organonitrogen compounds dissolved in n-nonane) has been investigated using magnetic reduced graphene oxide supported with phosphomolybdic acid (PMo-Fe₃O₄/rGO) as a heterogeneous catalyst/adsorbent and hydrogen peroxide as an oxidant. The synthesized PMo-Fe₃O₄/rGO nanocomposite was characterized by XRD, FE-SEM, VSM and BET surface area analysis methods. Moreover, different experimental variables including catalyst dose, initial pyrrole/indole concentration, H₂O₂ to pyrrole/indole molar ratio, ultrasound power and sonication time have been studied on the COADN process. The regeneration/recyclability of PMo-Fe₃O₄/rGO catalyst was also examined. Experimental results revealed that, the ultrasound treatment significantly improved the adsorption process of organonitrogen compounds from model fuels (q_e increased by 50.3% for pyrrole and 18% for indole). Furthermore, high ultrasound-aided catalytic oxidative denitrogenation efficiency (85.6% for pyrrole and 90% for indole) has been attained under optimal conditions (ultrasonic power = 200 W, sonication time = 240 min, catalyst dose = 2 g/L, and H₂O₂:pyrrole/indole molar ratio = 5). The recyclability of catalyst displayed that the prepared catalyst can be reused five times without any significant reduction in its performance.     

An efficient synthesis of quinolines derivatives promoted by a room temperature ionic liquid at ambient conditions under ultrasound irradiation via the tandem addition/annulation reaction of o-aminoaryl ketones with α-methylene ketones

The condensation reaction involving an o-aminoaryl ketones with α-methylene ketones via the tandem addition/annulation reaction by the ionic liquid of [Hbim][BF₄] (IL) as a solvent with methanol as co-solvent at room temperature under ultrasound irradiation afforded the corresponding quinolines derivatives in excellent yields. The use of ionic liquid and ultrasound, which promoted this protocol under room temperature without the requirement of any added catalyst. Quinoline derivatives are important and have a potential use as special biological drug in medicine.     

An expeditious synthetic approach towards the synthesis of Bis-Schiff bases (aldazines) using ultrasound

Aldazines (Bis-Schiff bases) 1–24 were synthesized using aromatic aldehydes (heterocyclic and benzaldehydes) and hydrazine hydrate under reflux using conventional heating and/or via ultrasound irradiation using BiCl₃ as catalyst. Ultrasonication conditions with cat. BiCl₃ proved to be an effective, environmentally friendly synthetic procedure. This methodology is robust in the presence of electron donating and electron withdrawing groups affording desired products with high yields (>95%) in just a couple of minutes vs. hours using conventional heating.     

Solvent free synthesis of 1,3-diaryl-2-propenones catalyzed by commercial acid-clays under ultrasound irradiation

This paper presents a novel solvent free method of synthesis of trans-chalcones. The method was based on ultrasound irradiation of the reagents (aryl methyl ketones and aryl aldehydes) in presence of commercial acid-montmorillonites as catalysts. The trans-chalcones were synthesized in high yields (85–95%) and excellent selectivity in a short reaction time.