A highly efficient magnetic solid acid catalyst for synthesis of 2,4,5-trisubstituted imidazoles under ultrasound irradiation

Fe₃O₄ nanoparticles were prepared by chemical coprecipitation method and subsequently coated with 3-aminopropyltriethoxysilane (APTES) via silanization reaction. Grafting of chlorosulfuric acid on the amino-functionalized Fe₃O₄ nanoparticles afforded sulfamic acid-functionalized magnetic nanoparticles (SA-MNPs). SA-MNPs was found to be a mild and effective solid acid catalyst for the efficient, one-pot, three-component synthesis of 2,4,5-trisubstituted imidazoles under ultrasound irradiation. This protocol afforded corresponding imidazoles in shorter reaction durations, and in high yields. This green procedure has many obvious advantages compared to those reported in the previous literatures, including avoiding the use of harmful catalysts, easy and quick isolation of the products, excellent yields, short routine, and simplicity of the methodology.     

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.     

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.     

Re-examination of the magnetic field effects on the thermal reactions of benzyl and pentafluorobenzyl halides with n-butyllithium in hexane

The magnetic field effects reported in 1973 for the thermal reaction of benzyl and pentafluorobenzyl chlorides with n-butyllithium in hexane have been re-examined under various reaction conditions. Using a new reaction apparatus, which has an electromagnet (up to 1.49 T) in a glove box under an argon atmosphere (H₂O and O₂ < 1 ppm), a study has been made on the effects on the yields of asymmetrical products (phenylpentane and pentafluorophenylpentane) and symmetrical ones (diphenylethane and decafluorodiphenylethane) in the absence and presence of external magnetic fields. No appreciable magnetic field effects have been observed with change of sample concentration, reaction temperature, or magnetic field strength, or with various benzyl halides.     

A green protocol for Erlenmeyer–Plöchl reaction by using iron oxide nanoparticles under ultra sonic irradiation

Azlactones have been prepared via Erlenmeyer synthesis from aromatic aldehydes and hippuric acid using Fe₂O₃ nanoparticles under ultrasonic irradiation. Short reaction times, easy and quick isolation of the products, and excellent yields are the main advantages of this procedure.     

Ultrasound promoted rapid and green synthesis of 1,8-dioxo-octahydroxanthenes derivatives using nanosized MCM-41-SO3H as a nanoreactor,nanocatalyst in aqueous media

An efficient and green procedure has been developed for the synthesis of 1,8-dioxo-octahydroxanthenes derivatives. The reaction was carried out in water under ultrasound irradiation, using nanosized MCM-41-SO₃H. In this method, several types of aromatic aldehyde, containing electron-withdrawing groups as well as electron-donating groups, were rapidly converted to the corresponding 1,8-dioxo-octahydroxanthenes in good to excellent yields. This novel synthetic method is especially favored because it provides a synergy of the nanosized MCM-41-SO₃H and ultrasound irradiation which offers the advantages of high yields, short reaction times, simplicity and easy workup compared to the conventional methods reported in the literature.     

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.     

FeCl3-catalysed ultrasonic-assisted,solvent-free synthesis of 4-substituted coumarins. A useful complement to the Pechmann reaction

The catalytic activity of FeCl₃ for the synthesis of a variety of 4-substituted coumarins using high energy techniques has been investigated. The ultrasonic-assisted conditions provide a useful complement to the Pechmann reaction, affording the coumarin derivatives in excellent yields, under solvent-free conditions, in short reaction times using an inexpensive, mild and benign Lewis acid catalyst.     

Pyrolysis of sewage sludge under conditions relevant to applied smouldering combustion

Pyrolysis of sewage sludge under conditions relevant to applied smouldering combustion was carried out in this study to investigate the influences of gas flow rate, oxidative atmosphere, and inert porous medium involvement on the properties of products. The experiments were carried out at 300–600 °C under atmospheres of N₂, 5% O₂/95% N₂, 10% O₂/90% N₂, and 15% O₂/85% N₂, with Darcy flow rates of 1.0 and 3.5 cm/s, respectively, with dried sewage sludge loaded individually or as a mixture with sand. As a result, both the increment of gas flow rate and involvement of sand leaded to lower yields of char and higher yields of bio-oil and gas under N₂ at temperature of ≤500 °C, due to the enhanced efficiency of pyrolysis reaction and gas transportation. However, when temperature increased to 600 °C, the influencing trends on product distributions changed due to the mechanisms of secondary cracking reaction and volatile-char interaction. The involvement of oxygen in fraction of ≤15 vol% at temperatures of 400–500 °C would lead to the intense decreasing yields of char and bio-oil, and increasing yield of the gaseous (dominated by CO₂ and CO), due to the involved oxidation reaction during pyrolysis. Both increment of temperature and oxygen fraction would lead to the delay of ignition and the increase of activation energy of the produced char, except for that of char produced at 400 °C under 5% O₂/95% N₂, whose calculated activation energy was lower and volatile content was higher compared to that of char produced from pyrolysis at 400 °C under N₂. The bio-oil from pyrolysis under N₂ was dominated by aliphatic acids, phenols, steroids, amides, and indoles, etc., and the involvement of partial oxidation would lead to the weakened formation of aromatics, phenols, and S/Cl/F-containing compounds in bio-oil.     

Simultaneous sonication assistance for the synthesis of tetrahydropyridines and its efficient catalyst ZrP2O7 nanoparticles

In this research, a general synthetic method for the synthesis of tetrahydropyridines were developed using ZrP₂O₇ nanoparticles under ultrasonic irradiations. Firstly by a simple and green process, nano zirconium pyrophosphate was prepared via sonication. Subsequently, this nanoparticle was used as an efficient catalyst for the synthesis of highly functionalized tetrahydropyridines via five-component reaction of aromatic aldehyde, amine and ethyl acetoacetate in ethanol under ultrasound irradiation. The present approach offers several advantages such as high yields, environmentally benign, simple work-up, excellent yield of products, short reaction times as well as recoverability and reusability of the catalyst.     

Predicting experimental yields as an index to rank synthesis routes II: application to the Curtius rearrangement

Synthesis yields of organic reactions are one of the most important factors in ranking synthesis routes created by synthesis route design systems such as Transform‐Oriented Synthesis Planning and Knowledge base‐Oriented Synthesis Planning. If it is possible to predict the yields of synthesis reactions before starting experiments, one can easily determine an order of synthesis routes for experimental works. In the present study, the reaction profiles of the Curtius rearrangement with different substituents were calculated to generate an equation predicting experimental yields of this reaction. Reactions followed by the formation of isocyanates were also analyzed to consider the relationship between reaction times and experimental yields. A partial least squares (PLS) regression was used to correlate the experimental yields with the calculated activation energies, E_a(calc), together with experimental conditions such as dielectric constants of solvents, reaction times, and reaction temperatures as explanatory variables. Although the PLS regression using all the data gave very poor results, we succeeded in making a model equation with R² = 0.887 using a modified data set. However, there is a conflict between the predictability and the interpretability on the reaction time. This discrepancy mainly comes from unnecessarily long reaction times in the experiments for azides with calculated E_a values of less than 33 kcal mol^–1. To construct a good model equation for the experimental yields of the Curtius reaction, we have to use data sets obtained from within 90 min of the reaction for the PLS regression. Copyright © 2011 John Wiley & Sons, Ltd.     

An efficient synthesis of 2-substituted benzothiazoles in the presence of FeCl3/Montmorillonite K-10 under ultrasound irradiation

2-Substituted benzothiazoles have been synthesized via one-pot reaction from aromatic aldehydes and o-aminothiophenol in the presence of FeCl₃/Montmorillonite K-10 in absolute methanol at 25–30 °C under ultrasound irradiation. The remarkable advantages are an inexpensive and easily available reagent, a simple procedure, mild conditions, short reaction times and moderate to good yields.     

Expanding cyclitol structural diversity by biocatalysis and metalocatalysis. A click chemistry approach

The palladium catalyzed cross-coupling reaction of phenyltrifluoroborate with a chemoenzymatically derived bromoazidoconduritol, combined with 1,3-dipolar cycloaddition, with a variety of alkynes is described. Fourteen new compounds were synthesized in moderate to good yields. The click chemistry reaction can be effected by using sodium ascorbate and CuSO₄ · 5H₂O as catalyst in toluene–H₂O at room temperature.     

Ultrasound-assisted synthesis of aromatic 1,2-diketones from oximinoketones under neutral conditions in aqueous media

We report a convenient, neutral, and facile methodology for the synthesis of aromatic 1,2-diketones from the corresponding oximinoketones in the presence of I₂/SDS/water system under ultrasound-assisted conditions. Furthermore, a series of compounds were synthesized and characterized by melting point, IR, NMR, MS, and elemental analysis. Utilization of easy reaction conditions, very high to excellent yields, and short reaction times makes this manipulation potentially very useful.     

Binary decay of light nuclear systems

A review of the characteristic features found in fully energy-damped, binary decay yields from light heavy-ion reactions with 20≤A_target+A_projectile≤80 is presented. The different aspects of these yields that have been used to support models of compound-nucleus (CN) fission and deep-inelastic dinucleus orbiting are highlighted. Cross-section calculations based on the statistical phase space at different stages of the reaction are presented and compared to the experimental results. Although the statistical models are found to reproduce most of the observed experimental behaviors, an additional reaction component corresponding to a heavy-ion resonance or orbiting mechanism is also evident in certain systems. The system dependence of this second component is discussed. The extent to which the binary yields in very light systems (A_CN≤32) can be viewed as resulting from a fusion–fission mechanism is explored. A number of unresolved questions, such as whether the different observed behaviors reflect characteristically different reaction times, are discussed.     

A simple approach to the synthesis of highly functionalized 3-alkylidene-2,3-dihydro-1<Emphasis Type="Italic">H</Emphasis>-pyrrole-2-ol derivatives and related pyrroles

The reaction of various primary amines with acetylenic esters at ambient temperature in THF/H₂O (50:50) produced related enaminones. Subsequently reaction of these in situ prepared enaminones with dibenzoylacetylene leads to 3-alkylidene-2,3-dihydro-1H-pyrrol-2-ol derivatives in good yields. The reaction of these products with various alcohols in the presence of a catalytic amount of HCl produced highly functionalized pyrroles in nearly quantitative yields.     

Sulfonated reduced graphene oxide as a highly efficient catalyst for direct amidation of carboxylic acids with amines using ultrasonic irradiation

Sulfonated reduced graphene oxide nanosheets (rGO-SO₃H) were prepared by grafting sulfonic acid-containing aryl radicals onto chemically reduced graphene oxide (rGO) under sonochemical conditions. rGO-SO₃H catalyst was characterized by Fourier-transform infrared (FT-IR) spectroscopy, Raman spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and X-ray photoelectron spectroscopy (XPS). rGO-SO₃H catalyst was successfully applied as a reusable solid acid catalyst for the direct amidation of carboxylic acids with amines into the corresponding amides under ultrasonic irradiation. The direct sonochemical amidation of carboxylic acid takes place under mild conditions affording in good to high yields (56–95%) the corresponding amides in short reaction times.     

The NO + CO reaction on Pt(100)

The interaction of NO with CO and with H₂ on Pt(100) was studied by temperature programmed desorption (TPD), isothermal desorption mass spectrometry, and low energy electron diffraction (LEED), TPD of NO and CO coadsorbed at 120 K yields almost complete reaction with both N₂ and CO₂ products desorbing as sharp, simultaneous peaks at ≈ 410 K. with full widths at half maximum as narrow as 3 K. Isothermal desorption mass spectrometry yields N₂ and CO₂ rates that exhibit a maximum with time. Both experiments indicate that the reaction mechanism is autocatalytic. Annealing NO-CO adlayers formed at 120 K to temperatures above 300 K causes the subsequent N₂ and CO₂ TPD peaks to broaden.'TPD of NO coadsorbed with H₂ yields sharp N₂ and H₂O product peaks that closely resemble the N₂ and CO₂ peaks observed in the NO + CO reaction. LEED experiments during TPD and isothermal desorption showed that the (1 × 1) → hex substrate phase transformation sometimes accompanies desorption of N₂ and CO₂. The TPD and isothermal desorption results can be fit by two simple models: chemical autocatalysis, in which an intermediate chemical species participates in a “chain propagation” reaction, and structural autocatalysis, which involves the formation of a reactive intermediate structure involving Pt atom displacements.     

感应耦合非热等离子体催化转化二氧化碳

射频感应耦合等离子体能够在室温条件下选择活化并分解二氧化碳,本文通过调控等离子体放电条件(气体流量、放电频率等)获得了较高的一氧化碳产率. 研究发现网状金属催化剂在二氧化碳等离子体中能促进氧原子的复合反应,从而有效抑制其与目标产物一氧化碳的逆反应,提升反应整体效率. 本文为实时转化过剩的可再生电能(来自太阳能、风能、潮汐能等)为高附加值一氧化碳中的化学能提供了一个可行的方案.     

A facile one-pot ultrasound assisted for an efficient synthesis of 1H-spiro[furo[3,4-b]pyridine-4,3′-indoline]-3-carbonitriles

A convenient one-pot protocol was developed for the synthesis of 1H-spiro[furo[3,4-b]pyridine-4,3′-indoline]-3-carbonitrile derivatives. This reaction was carried out through a three component condensation reaction of isatins, malononitrile, and anilinolactones in the presence of a catalytic amount of Et₃N as an inexpensive and available basic catalyst in THF under ultrasound irradiation. The products were obtained in high yields and short reaction times. The main advantage of this synthetic method is that the obtained products in ultrasonic irradiations are different from classical heating.