Potassium sorbate as an efficient and green catalyst for Knoevenagel condensation

Potassium sorbate has been utilized as a novel, efficient and green catalyst for the Knoevenagel condensation of aromatic aldehydes with active methylene compounds to afford substituted ole-fins through the conventional stirring or under ultrasound irradiation. Improvements were observed by carrying out the reactions under ultrasound irradiation. The advantages of this procedure are mild reaction conditions, high yields, cleaner reaction profiles and operational simplicity.     

Intensification of heterogeneously catalyzed Suzuki-Miyaura cross-coupling reaction using ultrasound: Understanding effect of operating parameters

Palladium-catalyzed Suzuki-Miyaura cross-coupling reaction is a significant reaction for obtaining industrially important products. The current research work deals with intensification of reaction of 4-bromoanisole and phenylboronic acid catalyzed with 5 wt% Pd/C (5% by weight Pd supported on C available as commercial catalyst) using ultrasound and more importantly, without use of any additional phase transfer catalyst. Heterogeneous catalyst has been selected in the present work so as to harness the benefits of easy separation and the possible limitations of heterogeneous operation are minimized by introducing ultrasonic irradiations. The effect of operating parameters such as ultrasound power, temperature, catalyst loading and molar ratio on the progress of reaction has been investigated. It has been observed that an optimum power, temperature and catalyst loading exist for maximum benefits whereas higher molar ratio was found to be favourable for the progress of the reaction. Also, the use of ultrasound reduced the reaction time from 70 min required in conventional approach to only 35 min under conditions of frequency of 22 kHz, power dissipation of 40 W and catalyst loading as 1.5 mol% (refers to total quantum of catalyst used in the work) in ethanol-water system under ambient conditions. The work also demonstrated successful results at ten times higher volume as compared to the normally used volumes in the case of simple ultrasonic horn. Overall, the work has successfully demonstrated process intensification benefits obtained due to the use of ultrasound for heterogeneously catalyzed Suzuki-Miyaura cross-coupling reaction.     

One-pot synthesis of benzochromeno-pyrazole derivatives

Abstract  

One-pot synthesis of different benzochromeno-pyrazole derivatives has been reported via reaction of aldehydes, 3-methyl-1H-pyrazol-5(4H)-one and α-naphthol/β-naphthol in the presence of sulfamic acid.     

Ionic liquid promoted preparation of 4H-thiopyran and pyrimidine nucleoside-thiopyran hybrids through one-pot multi-component reaction of thioamide

One-pot multi-component reactions of aldehydes, cyanothioacetamide and malononitrile promoted by ionic liquid proved to be an efficient way for the synthesis of thiopyran derivatives. Without any added catalyst, both aromatic and aliphatic aldehydes participated in this reaction smoothly. As an application of this method, a pyrimidine nucleoside-thiopyran chimera with potential biological activities was obtained in high yield from 5-formyl-2’-deoxyuridine. In addition, the ionic liquid used can be easily recovered and effectively reused for at least 5 times. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Efficiency in chemistry: from hydrogen autotransfer to multicomponent catalysis

A hydrogen autotransfer reaction has been applied to the α-alkylation of ketones, with primary alcohols as the electrophilic component, either under homogeneous (using a Ru complex as catalyst) or under heterogeneous (using Ni nanoparticles) conditions. This process is both very efficient (concerning atom economy) and ecologically friendly (water as the only by-product generated). On the other hand, three multicomponent reactions, namely, the Strecker reaction (without any catalyst), the aza-Sakurai process (catalyzed by ferrite), and the addition of in situ generated Zn enolates to chiral sulfinylimines (catalyzed by Cu), have proven to be very efficient in the generation of a diversity of polyfunctionalized molecules.     

Ultrasonic-assisted preparation of nano eggshell powder: A novel catalyst in green and high efficient synthesis of 2-aminochromenes

The nano eggshell powder (NESP) has been prepared by ultrasound irradiation and used as a novel and biodegradable catalyst with high catalytic activity and reusability in green synthesis of 2-aminochromenes via condensation of α- or β-phathol, malononitrile and aromatic aldehydes at 120 °C under solvent-free conditions. The reaction proceeds to completion within 10–35 min in 91–98% yield. Nano eggshell catalyst was characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and X-ray fluorescence, thermal gravimetric, surface area and elemental analyses. In addition, the catalytic activity and chemical structure of nano-sized eggshell were compared with pure CaCO₃.     

Progress in Developments of Inorganic Nanocatalysts for Application in Direct Methanol Fuel Cells

Significant progress has been made in the last few years toward synthesizing highly dispersible inorganic catalysts for application in the electrodes of direct methanol fuel cells. In addition, research toward achieving an efficient catalyst supporting matrix has also attracted much attention in recent years. Carbon black- (Vulcan XC-72) supported Platinum and Platinum-Ruthenium catalysts have for long served as the conventional choice as the cathode and the anode catalyst materials, respectively. Oxygen reduction reaction at the cathode and methanol oxidation reaction at the anode occur simultaneously during the operation of a direct methanol fuel cell. However, inefficiencies in these reactions result in a generation of mixed potential. This, in turn, gives rise to reduced cell voltage, increased oxygen stoichiometric ratio, and generation of additional water that is responsible for water flooding in the cathode chamber. In addition, the lack of long-term stability of Pt-Ru anode catalyst, coupled with the tendency of Ru to cross through the polymer electrolyte membrane and eventually get deposited on the cathode, is also a serious drawback. Another source of potential concern is the fact that the natural resource of Pt and the rare earth metal Ru is very limited, and has been predicted to become exhausted very soon. To overcome these problems, new catalyst systems with high methanol tolerance and higher catalytic activity than Pt need to be developed. In addition, the catalyst-supporting matrix is also witnessing a change from traditionally used carbon powder to transition metal carbides and other high-performance materials. This article surveys the recent literature based on the advancements made in the field of highly dispersible inorganic catalysts for application in direct methanol fuel cells, as well as the progress made in the area of catalyst-supporting matrices.     

Cross section and resonance strength measurements of 19F(p, αγ)16O at Ep= 200–800 keV

An excitation function of the ¹⁹F(p, αγ)¹⁶O reaction has been measured over the proton beam energy range E_p= 200–800 keV using a 4 π NaI summing spectrometer. A new resonance was found at E_R= 237 keV and its properties Γ_R, σ_R and ωγ have been extracted. The strengths of all resonances at E_p= 200–800 keV have been also extracted. The importance of the 1⁺ resonance at E_R= 11 keV is discussed and its width has been estimated taking into account interference effects with the strong 1⁺ resonance at E_R= 340 keV. The reaction rates have been calculated over a wide range of temperatures and compared with the rates of the (p, α₀) and (p, α_π) branches of the ¹⁹F(p, α)¹⁶O reaction. Received: 21 June 1999 / Revised version: 30 September 1999     

In situ investigation of the catalytic reaction H2+< ![IGNORE[O2→H2 O with second-harmonic generation

2 +O₂→H₂ O in the pressure range 0.2 Torr≤p_tot≤10 Torr on Pt(111) surface. At a catalyst temperature of T=700 K the equilibrium oxygen coverage θ_o is determined as a function of hydrogen partial pressure α. The experimentally obtained θ_o is modelled in a two step process considering the mass transport in the gas phase as well as the catalytic reaction on the surface. In this pressure range the mass transport in the gas phase changes from molecular flow conditions to laminar flow, inducing a strong modification of the gas phase present at the catalyst through different diffusivities of the reactants as well as through desorbing reaction products from the catalyst. It is shown that these gas phase alterations have to be taken into account for a proper modelling of the surface mechanism. Simulation calculations allow one to identify the sequential hydrogen addition reaction as the main reaction path for water production in this parameter range. Excellent agreement with previous investigations is obtained for the determined activation energies of the water-producing reaction steps equal to E^f _H2O≥0.7 eV. Received: 20 September 1998 / Revised version: 15 December 1998     

Organocatalysis: quantum chemical modeling of nucleophilic addition to α,β‐unsaturated carbonyl compounds

One of the successful transformations within the field of organocatalysis, the organocatalytic asymmetric addition of nitromethane to α,β‐unsaturated aldehydes and ketones, has been studied by quantum chemical modeling. The level of accuracy of the hybrid density functional theory method B3LYP/6‐31G(d) was compared to a high level ab initio benchmark for this reaction. It is concluded that B3LYP/6‐31G(d) performs very well for this reaction type, giving good estimates of critical energies. The reaction between acrolein and nitromethane was studied in detail. The reaction mechanism revealed an intermediate oxazolidin structure, which is currently unknown. Alkyl substitution in various positions on the amine catalyst or α,β‐unsaturated carbonyl compound influences the reactivity in a predictive fashion. The iminium ion, prop‐2‐en‐iminium, is less activated towards nucleophilic attack compared to protonated acrolein. Copyright © 2007 John Wiley & Sons, Ltd.     

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.     

The systematics of (n, α) reaction cross-sections at 14.5 MeV neutron energy

A comprehensive review of the experimental data for 14.5 MeV neutron induced reaction crosssections for (n, α) reaction has been made for the isotopes having Z up to 82. Two different parameter groups have been considered by the classification of nuclei into odd-mass and even-even nuclei. The empirical formulae with two parameters for the evaluation of (n, α) reaction cross-sections are discussed in the present study. The odd-even effects have been observed as the cross-sections of odd-mass nuclei are higher as compared to their neighboring even-even nuclei. The shell effects have also been established at magic nucleon numbers for these reaction cross-sections.     

One-pot three-component Mannich-type reactions using Sulfamic acid catalyst under ultrasound irradiation

Sulfamic acid (NH₂SO₃H, SA) was used as an efficient, inexpensive, non-toxic and recyclable green catalyst for the ultrasound-assisted one-pot Mannich reaction of aldehydes with ketones and amines. This ultrasound protocol has advantages of high yield, mild condition, no environmental pollution, and simple work-up procedures. Most importantly, β-aminocarbonyl compounds with ortho-substituted aromatic amines are obtained in acceptable to good yields by this methodology for the first time.     

Efficient synthesis and free-radical scavenging capacity of new 2,4-substituted tetrahydroquinolines prepared via BiCl<Subscript>3</Subscript>-catalyzed three-component Povarov reaction,using <Emphasis Type="Italic">N</Emphasis>-vinylamides

Efficient synthesis of new structurally different 2-(het)aryl-4-amidyl-substituted tetrahydroquinolines 8–29 is reported. The synthesis based on BiCl₃-catalyzed three-component Povarov reaction between anilines, (het)aryl aldehydes and enamides offers a fast, safe, and cheap way for efficient tetrahydroquinoline libraries construction. Using N-vinylamides (N-vinylpyrrolidin-2-one and N-vinylacetamide) in this reaction, it was possible to obtain two series of different cis tetrahydroquinolines with antioxidant properties. Among 14 tested compounds, 7 tetrahydroquinolines revealed a prominent anti-radical capacity, equal or higher than that of the commercial antioxidants. Being the most active molecule, the N-[2-(α-furanyl)-6-methoxy-1,2,3,4-tetrahydroquinolin-4-yl] acetamide 21 was ca. 2.2-fold more potent than the well-known antioxidant, vitamin E (α-tocopherol).     

An IR study of 2-chlorovinyldichloroarsine transformations in aqueous media

The interaction of 2-chlorovinyldichloroarsine (α-lewisite) (I) with usual and deuterated water was studied by IR spectroscopy (7000-350 cm⁻¹). A comparison of the corresponding IR spectra with the spectra of I and the supposed products of its destruction (2-chlorovinylarsonous acid (II), 2-chlorovinylarsine oxide (III), and 2-chlorovinylarsonic acid (IV)) obtained for the first time showed that, under the selected experimental conditions (room temperature, 30-fold molar excess of water, time of contact between the reagents up to an hour), complete destruction of α-lewisite did not occur. After an experiment, the reaction mixture consisted of an aqueous phase and a heavier fraction containing a liquid insoluble in water with an admixture of solid particles. The basic aqueous fraction element was acid II, the primary product of the hydrolysis of the toxin, with an admixture of α-lewisite. The heavy fraction was a mixture of unreacted α-lewisite and the secondary product of the hydrolysis of the toxin, oxide III.     

Fe(ClO4)3· 6H2O: a mild and efficient catalyst for one-pot three component synthesis of β-acetamido carbonyl compounds under solvent-free conditions

A one-pot multi-component reaction for the synthesis of β-acetamido carbonyl compounds is reported. The reaction uses a variety of aldehydes, acetophenone derivatives or methyl acetoacetate, acetonitrile, and acetyl chloride in the presence of ferric perchlorate, a mild, efficient and inexpensive catalyst effective under solvent free conditions.     

A chemical placebo: NaCl as an effective, cheapest, non-acidic and greener catalyst for Biginelli-type 3,4-dihydropyrimidin-2(1H)-ones (-thiones) synthesis

Despite prior reports of several really effective catalytic and non-catalytic approaches towards Biginelli’s 3,4-dihydropyrimidin-2(1H)-ones, an overwhelming number of new catalysts for the Biginelli reaction have been recently published. Most of the catalysts are somewhat exotic, expensive, harmful and even uneffective in the absence of acidic additives. Herein we reduce the “yet-another-one-catalyst” idea to absurdity by proposing NaCl promotes the reaction that actually requires no catalyst, neither rare nor expensive.     

Selection of a cyclic nonapeptide inhibitor to α-chymotrypsin using a phage display peptide library

A cyclic nonapeptide library displayed on filamentous bacteriophages was selected 6 times against α-chymotrypsin (EC 3.4.21.1) at three different pH conditions (6.5, 7.0, and 7.5). Phage peptide clones from the sixth selection, at all three pH conditions, interacted more strongly with α-chymotrypsin than the original library and a wild-type phage did. DNA sequencing of the selected phage peptide clones showed that different cyclic nonapeptide sequences had been selected at the different pH conditions. The oxidized form of the synthetic peptide, Cys-Cys-Phe-Ser-Trp-Arg-Cys-Arg-Cys, selected at pH 7.5, could completely inhibit the enzymatic activity of α-chymotrypsin. The structurally related enzymes trypsin (bovine) and elastase (porcine) were only marginally inhibited by the same peptide under the same conditions. The inhibition constant for α-chymotrypsin was estimated to be 10^-6 M. Phage clones expressing this peptide had a lower affinity for phenylmethylsulfonylfluoride-modified α-chymotrypsin than for natural α-chymotrypsin as determined by an enzyme immunosorbent assay. This peptide phage clone was also competitively prevented from binding to α-chymotrypsin by the corresponding synthetic oxidized peptide. Collectively, the results suggest that the oxidized form of the selected peptide Cys-Cys-Phe-Ser-Trp-Arg-Cys-Arg-Cys interacts with the active site of α-chymotrypsin and acts as a specific inhibitor to the enzyme. To our knowledge, the selected sequence Cys-Cys-Phe-Ser-Trp-Arg-Cys-Arg-Cys has not been found in nature. This revised version was published online in August 2006 with corrections to the Cover Date.     

Investigation of <Emphasis Type="Italic">γ</Emphasis>-ray fold distributions in N ≤ 82 Gd,Eu and Sm nuclei: Observation of a double-humped fold distribution

Cross-sections and γ-ray fold distributions have been measured for the ⁹⁷Mo+⁵¹V, ¹⁰⁰Mo+⁴⁸Ti and ¹¹⁴Cd+³⁶S reactions at energies of 238, 215 and 182 MeV of the ⁵¹V, ⁴⁸Ti and ³⁶S projectiles, respectively. For the ⁹⁷Mo(⁵¹V, α2n ¹⁴²Eu reaction channel a double-humped fold distribution has been observed. This fold distribution can only be understand if an incomplete-fusion reaction mechanism associated with the α-particle emission is assumed. The ⁹⁷Mo(⁵¹V, α n ¹⁴³Eu reaction channel represents an incomplete-fusion reaction channel as well and its single-humped fold distribution can be described on the same footing as that of the α2n channel. The fold distributions associated with xn and pxn channels can be explained assuming complete-fusion reactions. For the calculations in terms of an incomplete-fusion reaction mechanism a narrow angular momentum window, ranging from ≈ 68 to 82ℏ has been assumed for the ⁹⁷Mo(⁵¹V, αn and α2n reaction channels. The complete-fusion reaction mechanism is considered to be negligible in this angular-momentum range.     

In situ surface dynamics in heterogeneous catalysis

During the former half of the last century the mechanism of heterogeneous catalysis had been studied, keeping the catalyst in a black box, and on the basis of the information outside of the black box, it was discussed just from mere conjectures. The author initiated a method to study directly the behavior of the working catalyst surface, looking into the inside of the black box by measuring adsorption on the working catalyst surface. In the same period many varieties of recent physical tools to study the solid surfaces have been developed and were applied to study the in situ dynamics of working catalyst surface. However, even if some chemisorbed species were observed on the working catalyst surface, it does not follow that they are reaction intermediates. A new dynamic approach to identify the dynamic behavior of each of the chemisorbed species under the reaction conditions, had been proposed by the author by use of “isotope jump method”, in which labeled species are replaced during the course of reaction to study the behavior of each of the adsorbed species under the reaction conditions. By using such new techniques we could not only identify the reaction path and the rate-determining step, but also new phenomena which are called “adsorption assisted processes” were discovered, It is, accordingly, hoped that by means of new nanotechnologies recently developed to study the behavior of single molecules on solid surfaces the nature of heterogeneous catalysis should make a remarkable advances on the basis of this in situ dynamic methods. In this review article emphasis has been put in the fundamental methods of dynamic approaches.