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1.
Heterocyclic aromatic compounds containing an imine (C Created by potrace 1.16, written by Peter Selinger 2001-2019 N) bond such as benzimidazoles and benzothiazoles are important active pharmaceutical ingredients. The synthesis of 2-aryl-1H-benzimidazoles and 2-arylbenzothiazoles in good to excellent yields was achieved by reacting 2-aminoaromatics with various benzaldehyde derivatives catalysed by the commercial laccases Novoprime and Suberase® at room temperature and in the presence of atmospheric oxygen.

Green chemistry: laccase in acetonitrile and buffer in the presence of O2 can synthesise benzimidazoles and benzothiazoles in good yields.  相似文献   

2.
In this study, perlite nanoparticles were prepared through a simple method and then modified with Lewis acidic ionic liquid (perlite NP@IL/ZrCl4) through a two step procedure. The prepared solid acid catalyst was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX) and thermo gravimetric analysis (TGA). Perlite NP@IL/ZrCl4 was used as a new solid acid, reusable and green heterogeneous nanocatalyst for the one-pot synthesis of xanthene derivatives. Synthesis of xanthenes was performed under solvent free conditions using a catalytic amount (0.005 g, 0.4 mol%) of the prepared catalyst with simple work-up and high to excellent yield of products. The reusability and high efficiency of this catalyst makes this method attractive for large scale environment-friendly operations.

Perlite nanoparticles were prepared, modified with Lewis acidic ionic liquid, and used as a highly efficient catalyst for the eco-friendly, solvent free and high yield synthesis of xanthenes via a multicomponent reaction.  相似文献   

3.
We report a simple and eco-friendly method for producing an amino-polystyrene supported hexaethylene glycol-bridged ionic liquid (APS-HEGBIL) based on the copolymerization of amino-styrene with 1-vinyl imidazolium ionic liquid bearing hexaethylene glycol moieties, and its characterization by several analytical techniques. The resulting APS-HEGBIL catalyst was found to be remarkably efficient at catalyzing the selective nucleophilic hydroxylation of alkyl halides to produce the corresponding alcohols in water, which acted as a solvent and a nucleophilic hydroxide source. The catalyst was easily recycled and maintained its catalytic activity and stability after ten cycles with excellent yields. The main attributes of the catalyst were that it significantly enhanced the nucleophilicity of water during reactions and promoted the rapid conversions of polar and base-sensitive alkyl halide reactants to alcohols in excellent yields. The combination of ionic liquids and polymeric materials afforded quasi-homogeneous catalysts that were recycled by simple filtration and provided environmentally benign means for conducted catalytic procedures.

An amino-polystyrene supported hexaethylene glycol-bridged ionic liquid (APS-HEGBIL) was remarkably efficient at catalyzing the selective nucleophilic hydroxylation of alkyl halides to produce the corresponding alcohols in water.  相似文献   

4.
A new SILP (Supported Ionic Liquid Phase) palladium catalyst was prepared and characterized by 13C and 29Si CP MAS NMR, DTG, FTIR and TEM. The presence of the grafted pyridinium cations on the surface of the support was found to result in the formation of highly dispersed Pd nanoparticles with their diameter in the range of 1–2 nm. The catalyst was proved to be active not only in the aminocarbonylation of some model compounds but also in the synthesis of active pharmaceutical ingredients. Catalyst recycling and palladium leaching studies were carried out for the first time in aminocarbonylations leading to CX-546(1-(1,4-benzodioxan-6-ylcarbonyl)piperidine), Moclobemide, Nikethamide and a precursor of Finasteride. The latter reaction proves that not only aryl iodides but also an iodoalkene can be converted into the products with the help of the heterogeneous catalyst. The results show that the conditions should be always fine-tuned in the reactions of different substrates to achieve optimal results. Palladium loss was also observed to depend considerably on the nature of the reaction partners.

SILP catalyst with grafted pyridinium ions was used for either mono- or double carbonylation depending on the reaction conditions. Good recyclability and low palladium loss were observed during the synthesis of pharmaceutically active compounds.  相似文献   

5.
Cu(NO3)2 supported on natural phosphate, Cu(ii)/NP, was prepared by co-precipitation and applied as a heterogeneous catalyst for synthesizing xanthenes (2–3 h, 85–97%) through Knoevenagel–Michael cascade reaction of aromatic aldehydes with 1,3-cyclic diketones in ethanol under refluxing conditions. It was further used for regioselective synthesis of 1,4-disubstituted-1,2,3-triazoles (1–25 min, 95–99%) via a three-component reaction between organic halides, aromatic alkynes and sodium azide in methanol at room temperature. The proposed catalyst, Cu(ii)/NP, was characterized using X-ray fluorescence, X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, Brunauer–Emmett–Teller, Barrett–Joyner–Halenda and inductively coupled plasma analyses. Compared to other reports in literature, the reactions took place through a simple co-precipitation, having short reaction time (<3 hours), high reaction yield (>85%), and high recyclability of catalyst (>5 times) without significant decrease in the inherent property and selectivity of catalyst. The proposed protocols provided significant economic and environmental advantages.

Cu(NO3)2 supported on natural phosphate, Cu(ii)/NP, was prepared by co-precipitation and characterized. The Cu(ii)/NP catalyzed the synthesis of xanthenes and triazoles. The proposed protocols provided significant economic and environmental advantages.  相似文献   

6.
1,1′-(6-(Propyl amino)-1,3,5-triazine-2,4-diyl)bis(pyridinium) hydrogen sulfate immobillized on halloysite nanotubes [(PATDBP)(HSO4)2@HNT] as a solid acid nanocatalyst was successfully synthesized and characterized by various analysis techniques such as FT-IR, TGA, SEM/EDX, elemental mapping, TEM and elemental analysis. This catalyst was found to be highly efficient for the convenient synthesis of naphthopyranopyrimidine derivatives through a one-pot three-component reaction of β-naphthol, aldehydes and N,N-dimethylbarbituric acid in excellent yields under solvent-free conditions. Furthermore, the catalyst could be recovered and reused five times without any notable loss of its activity.

A novel method for synthesis of naphthopyranopyrimidines, using [(PATDBP)(HSO4)2@HNT] as a green and reusable catalyst is reported.  相似文献   

7.
A facile strategy for the synthesis of acidic ionic liquid based UiO-67 type MOFs was developed in this study. Brønsted acids (H2SO4, CF3SO3H and hifpOSO3H (hexafluoroisopropyl sulfuric acid)) were introduced into UiO-67–bpy (bpy = 2,2′-bipyridine-5,5′-dicarboxylic acid) frameworks by reacting with bipyridyl nitrogen to introduce the properties of an acidic ionic liquid into the frameworks. The prepared catalysts, denoted as UiO-67–HSO4, UiO-67–CF3SO3 and UiO-67–hifpOSO3, were characterized by XRD, SEM, FT-IR, EA, TGA and N2 adsorption–desorption studies. The relatively high surface area was still maintained and acidic active groups were uniformly dispersed in the frameworks. The catalytic performance of UiO-67–HSO4, UiO-67–CF3SO3 and UiO-67–hifpOSO3 was evaluated by the esterification of acetic acid with isooctyl alcohol. The prepared catalysts showed good catalytic activities in the esterification, of which UiO-67–CF3SO3 gave the maximum isooctyl alcohol conversion of 98.6% under optimized conditions. The catalyst could be reused five times without a significant decrease in the conversion of isooctyl alcohol, and almost no active species were leached, indicating the excellent stability and reusability of the catalyst. Our study provides one effective way to synthesize heterogeneous acidic ionic liquid catalysts consisting of isolated, well defined acidic groups that will probably attract interest in acid catalyst chemistry.

Acidic ionic liquid groups were introduced into the frameworks successfully and the resulting materials showed excellent activity.  相似文献   

8.
A series of imidazolinium-based porous poly(ionic liquid)s (PILs) with different anions prepared by free-radical copolymerization of an arene-bridged tris-vinylimidazolium salt and divinylbenzene (DVB) were constructed. The as-prepared PILs were characterized by BET, SEM, TEM, TGA and Elemental Analysis (EA), and the results showed that they had plentiful ionic sites, and abundant and stable mesopores. In particular, the density of ionic sites and pore structure of PILs could be controlled by adjusting the content of DVB. Moreover, the PILs were used as efficient heterogeneous catalysts for the decarboxylation of cyclic carbonates to epoxides for the first time. Results showed that the catalytic activity of PILs was positively correlated with the nucleophilicity of the anions in PILs, and PDVB-[PhTVIM]Cl-1 with a chloride anion-enriched skeleton displayed the best catalytic performance. Without any solvent or cocatalyst, PDVB-[PhTVIM]Cl-1 achieved a TOF value of 108.1 h−1 and the yield of butylene oxide of 89.6%, which was even better than the homogeneous IL-based catalysts (TOF value: 8.7 h−1) that had been previously reported. Meanwhile, PDVB-[PhTVIM]Cl-1 also exhibited excellent recyclability and substrate compatibility.

The tris-imidazolium-based porous poly(ionic liquid)s with plentiful ionic sites prepared by free-radical polymerization exhibited superior catalytic performance toward the heterogeneous conversion of butylene carbonate to butylene oxide.  相似文献   

9.
A nano-sized Fe3O4-supported Lewis acid ionic liquid catalyst for the synthesis of polyhydroquinolines and propargylamines under ultrasound irradiation has been developed. LAIL@MNP was synthesized from imidazolium chlorozincate(ii) ionic liquid grafted onto the surface of Fe3O4 nanoparticles and evaluated by FT-IR, TGA, SEM, Raman, TEM, ICP-OES, and EDS. The multicomponent synthesis of polyhydroquinolines and propargylamines proceeded smoothly to afford the desired products in high yields. LAIL@MNP can be separated easily from the reaction mixture and reused for several runs without a significant degradation in catalytic activity.

A nano-sized Fe3O4-supported Lewis acid ionic liquid catalyst for the synthesis of polyhydroquinolines and propargylamines under ultrasound irradiation has been developed.  相似文献   

10.
Significant efforts have been devoted to developing immobilized chiral catalysts with high activity, selectivity, and stability. In this present study, a new heterogeneous proline catalyst system was prepared based on strong noncovalent interactions between polymer ionic liquid (PIL) and l-proline. First, pyridine PILs, which can complex with l-proline monomers through noncovalent interactions, were synthesized using reversible addition–fragmentation chain transfer (RAFT) polymerization. The polymer network-supported chiral catalysts were obtained following further free radical polymerization. Different structures were formed in response to different ratios of PIL and chiral monomer, as well as different PIL anions, in the reactions. The new formed layer structures and synergic effects of PIL resulted in heterogeneous catalysts with high catalytic activity and enantioselectivity, thus endowing them with better catalytic performance for the one-pot synthesis of heterocyclic compounds compared to homogeneous catalytic systems. These catalytic systems were able to be reused and recycled five times with no discernible loss in catalytic activity and enantioselectivity. l-Proline was efficiently loaded onto the polymer network simply based on supramolecular interactions, providing a novel method of synthesizing high performance supported catalysts for organic reactions.

Significant efforts have been devoted to developing immobilized chiral catalysts with high activity, selectivity, and stability.  相似文献   

11.
Basic imidazolium-based ionic liquids not only possess the extraordinary physicochemical properties of ionic liquids, but also have excellent basicity and surfactivity. 1-Propyl-3-alkylimidazole hydroxide ionic liquids ([PRIm][OH]) were synthesized and their catalytic and surfactant behavior were studied in this work. [PRIm][OH] owned excellent surfactivity, and their alkyl chains and ion pairs benefit hydrophobicity and hydrophilicity respectively. The surfactivity of [PRIm][OH] increased with increasing alkyl chain length. [PRIm][OH] showed better catalytic performance than NaOH in the condensation of 2-aminobenzonitrile with cyclohexanone in aqueous medium, and the catalytic performance was well coincident with their surfactant behavior. [PRIm][OH] could decrease the interfacial tension of solvent effectively and form micelles in water. The formed micelles could solubilise more reactants into water and effectively increase the chance of contact between reactants and catalytic active sites. The catalyst dosage obviously affected catalytic performance. The catalytic system is a promising recyclable system.

[PRIm][OH] showed excellent catalytic properties in synthesis of quinazolinone in aqueous medium, owing to its excellent surfactivity and basicity.  相似文献   

12.
One-pot green synthesis of propargylamines using ZnCl2 loaded TiO2 nanomaterial under solvent-free conditions has been effectively accomplished. The aromatic aldehydes, amines, and phenylacetylene were reacted at 100 °C in the presence of the resultant catalyst to form propargylamines. The nanocrystalline TiO2 was initially synthesized by a sol–gel method from titanium(iv) isopropoxide (TTIP) and further subjected to ZnCl2 loading by a wet impregnation method. X-ray diffraction (XRD) patterns revealed the formation of crystalline anatase phase TiO2. Field emission scanning electron microscopy (FESEM) showed the formation of agglomerated spheroid shaped particles having a size in the range of 25–45 nm. Transmission electron microscopy (TEM) validates cubical faceted and nanospheroid-like morphological features with clear faceted edges for the pure TiO2 sample. Surface loading of ZnCl2 on spheroid TiO2 nanoparticles is evident in the case of the ZnCl2 loaded TiO2 sample. X-ray photoelectron spectroscopy (XPS) confirmed the presence of Ti4+ and Zn2+ species in the ZnCl2 loaded TiO2 catalyst. Energy-dispersive X-ray (EDS) spectroscopy also confirmed the existence of Ti, O, Zn and Cl elements in the nanostructured catalyst. 15% ZnCl2 loaded TiO2 afforded the highest 97% yield for 3-(1-morpholino-3-phenylprop-2-ynyl)phenol, 2-(1-morpholino-3-phenylprop-2-ynyl)phenol and 4-(1,3-diphenylprop-2-ynyl)morpholine under solvent-free and aerobic conditions. The proposed nanostructure-based heterogeneous catalytic reaction protocol is sustainable, environment-friendly and offers economic viability in terms of recyclability of the catalyst.

A one-pot green synthesis of propargylamines using nanostructured ZnCl2–TiO2 under solvent-free conditions has been effectively accomplished. The proposed reaction protocol is sustainable, environment-friendly and offers economic viability.  相似文献   

13.
A CuO NP decorated reduced graphene oxide (CuO NPs/rGO) composite was synthesized and characterized using various analytical techniques viz. XRD, TEM, SEM, UV-Vis, FT-IR, EDX, XPS and CV. The activity of the catalyst was probed for the Petasis-Borono–Mannich (PBM) reaction of boronic acids, salicylaldehydes, and amines under microwave irradiation (MW). The CuO NPs/rGO composite works as a catalyst as well as a susceptor and augments the overall ability of the reaction mixture to absorb MW. The synergistic effect of MW and CuO NPs/rGO resulted in an excellent outcome of the reaction as indicated by the high TOF value (3.64 × 10−3 mol g−1 min−1). The catalytic activity of the CuO NPs/rGO composite was about 12-fold higher under MW compared to the conventional method. The catalyst was recovered by simple filtration and recycled 8 times without significant loss in activity. This atom-economical protocol includes a much milder procedure, and a catalyst benign in nature, does not involve any tedious work-up for purification, and avoids hazardous reagents/byproducts and the target molecules were obtained in good to excellent yields.

CuO NPs/rGO composite was synthesized and characterized by various analytical techniques an used as a recyclable catalyst for Petasis-borono–Mannich reaction under microwave irradiation.  相似文献   

14.
We used a novel hybrid catalyst in chemo-, regio-, and diastereoselective multi-component reactions (MCR) for the synthesis of the 2-aza analogue of pyrrolizidine and spirooxindole-2-azapyrrolizidine derivatives. The nanocatalyst, W(iv)/NNBIA–SBA-15 [where NNBIA = N,N′-(ethane-1,2-diyl)bis(2-aminobenzamide)] was synthesized by covalent grafting on chloro-functionalized SBA-15. The synthesis process was followed by the anchoring of WCl6 to catch the desired catalyst. The quality of the catalyst was assessed using different analytical techniques such as X-ray diffraction spectroscopy (XRD), Fourier-transform infrared spectroscopy (FT-IR), N2 adsorption analysis, transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDX), ammonia Temperature Programmed Desorption (TPD), X-Ray photoelectron spectroscopy (XPS) and thermogravimetric, differential thermal analysis (TGA-DTA). The catalyst, W(iv)/NNBIA–SBA-15, with high catalytic performance is a good candidate for the diastereoselective synthesis of 2-azapyrrolizidine alkaloid scaffolds. The catalyst could be recovered for reuse without noticeable loss of activity.

We used a novel hybrid catalyst in chemo-, regio-, and diastereoselective multi-component reactions (MCR).  相似文献   

15.
An efficient and environmentally sustainable domino protocol has been presented for the synthesis of structurally diverse spiroannulated pyrimidophenazines involving a four component reaction of 2-hydroxynaphthalene-1,4-dione, benzene-1,2-diamine, cyclic ketones and amino derivatives in the presence of erbium doped TiO2 nanoparticles as a recyclable and reusable heterogeneous acid catalyst. The present synthetic protocol features mild reaction conditions with operational simplicity, excellent yield with high purity, short reaction time and high atom economy with the use of a recoverable and reusable environmentally sustainable heterogeneous catalyst.

An efficient and environmentally sustainable domino protocol has been presented for the synthesis of structurally diverse spiroannulated pyrimidophenazines using erbium doped TiO2 nanoparticles as a recyclable and reusable heterogeneous acid catalyst.  相似文献   

16.
Nano-γ-Al2O3/SbCl5 as a new Lewis acid nano catalyst was synthesized and characterized by FTIR, XRD, FESEM, TEM, EDS, BET and TGA techniques. Nano-γ-Al2O3/SbCl5 has been employed for synthesis of 2-substituted perimidines via reaction of naphthalene-1,8-diamine with various aldehydes at room temperature under solvent-free conditions. This protocol proffers several benefits including high yields, easy workup, short reaction times and simple reaction conditions.

Nano-γ-Al2O3/SbCl5 as a new Lewis acid nano catalyst was synthesized and characterized by FTIR, XRD, FESEM, TEM, EDS, BET and TGA techniques.  相似文献   

17.
Using a simple method of impregnation and then calcination, diatomite supported binary transition metal sulfates (Fe and Zr, designated as Fe2(SO4)3&Zr(SO4)2@diatomite) were prepared and used as a catalyst in the preparation of renewable biofuels. The synthesised Fe2(SO4)3&Zr(SO4)2@diatomite catalyst (Fe2(SO4)3 : Zr(SO4)2 : diatomite = 1 : 2 : 6, mass ratio) was thoroughly characterised using transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, microbeam X-ray fluorescence (μ-XRF) spectroscopy and thermogravimetric analysis (TG). The results demonstrated that the sulfate was successfully loaded onto the diatomite with a uniform distribution. The N2 adsorption/desorption analysis indicated that the catalyst''s specific surface area was 1.54 m2 g−1. The catalyst exhibited outstanding performance in the preparation of renewable biofuel (biodiesel) from waste fatty acids and the optimal parameters were methanol-to-oil 1.25 : 1, reaction temperature 70 °C, catalyst concentration 10 wt%, reaction time 4 h. The conversion was found to reach 98.90% under optimal parameters, which is better than that of Fe2(SO4)3·xH2O, Zr(SO4)2·4H2O, Fe2(SO4)3@diatomite and Zr(SO4)2@diatomite. Moreover, the catalyst can be recycled by simple filtration and reused for three cycles after regeneration without noticeable reduction in catalytic activity.

A new catalyst: diatomite supported binary transition metal sulfates (Fe2(SO4)3 and Zr(SO4)2) was prepared. It exhibited excellent catalytic activity in the synthesis of biodiesel from waste fatty acids (conversion close to 100%).  相似文献   

18.
Development of heterogeneous catalysts for the cycloaddition of CO2 with epoxides to produce cyclic carbonates is a hot issue in the field of chemical fixation of carbon dioxide. It is fairly promising as production of by-products is quite low. In this study, the [Zn3(BTC)2]/n-Bu4NBr catalytic system was investigated for the solventless cycloaddition of carbon dioxide with epoxides and had an excellent synergetic effect in promoting the reaction. The reaction parameters were moderate i.e. (130 °C and 13 bar CO2 pressure) and were selected by a study of the catalytic system. Under the optimal reaction conditions, the yield of cyclic carbonate reached 99%. A decrease in the yield of cyclic carbonate was not apparent after [Zn3(BTC)2] was reused three times, indicating that [Zn3(BTC)2] was stable. At the same time, the catalytic activity of the catalyst for other epoxides was also verified. The acidic and alkaline nature of the [Zn3(BTC)2] catalyst did not change obviously after recycling the catalyst three times. In this study it is also verified that the [Zn3(BTC)2] catalytic cycloaddition reaction was closely related to the Lewis acid/base distribution. In addition, a plausible mechanism for the synergistic effect of the catalyst (Lewis acid and base properties) and the co-catalyst was suggested.

[Zn3(BTC)2], a heterogeneous catalyst, can efficiently catalyze the cycloaddition reaction. Under relatively moderate and solvent-free conditions, the yield of cyclic carbonate reached 99%.  相似文献   

19.
We hereby report the synthesis, characterization and catalytic applications in the epoxidation of alkenes by a vanadyl porphyrin having bulky bromo substituents at the β-positions viz. vanandyltetrabromotetraphenylporphyrin (1). The synthesized porphyrin was characterized by various spectroscopic techniques like UV-visible, FT-IR, EPR, MALDI-TOF mass spectrometry and single crystal X-ray analysis. Porphyrin 1 has a nonplanar structure as indicated by its X-ray structure, DFT and electrochemical studies. 1 was analyzed for its catalytic application in the epoxidation of various alkenes. The catalytic reactions were carried out in CH3CN/H2O mixture in 3 : 1 (v/v) ratio. 1 displayed good efficiency in terms of mild reaction conditions, lower reaction temperature and minimal catalyst amount consumption. 1 exhibited excellent selectivity, high conversion efficiency and huge TOF (7600–9800 h−1) in a significantly low reaction time of 0.5 h. Catalyst 1 was regenerated at the end of various catalytic cycles making it reusable and industrially important.

We have synthesized β-tetrabromo-meso-tetraphenylporphyrinatooxidovanadium(iv) (VOTPPBr4) which possesses high thermal stability and nonplanar macrocyclic core. Further, it was utilized for selective epoxidation of olefins in good yields with very high TOF numbers.  相似文献   

20.
In this study, simple and effective methods were used for the preparation of an ionic liquid that immobilized magnetite nanoparticles. Fe3O4 nanoparticles were prepared via a chemical co-precipitation method. Then, a SiO2 shell was coated on the magnetic core via the Stober method. Finally, CPTES (chloropropyltriethoxysilane) and morpholine were coated on the SiO2 shell. Morpholine sulfate, an acidic ionic liquid, was successfully bound to magnetite nanoparticles (Mag@Morph-AIL) and this was used as an efficient catalyst for the preparation of 3,4-dihydropyrimidinones. Compared to previous works, the easy separation of the nanocatalyst using an external magnet and the recyclability, non-toxicity, versatility, and high stability of the catalyst, combined with low reaction times and excellent yields, make the present protocol very useful for the synthesis of the title products. The synthesized products and catalyst were confirmed via1H-NMR, 13C-NMR, FT-IR, scanning electron microscope, X-ray diffraction, and elemental analysis.

In this study, morpholine sulfate acidic ionic liquid bonded on magnetite nanoparticles (Mag@Morph-AIL) has been used as a catalyst for the preparation of 3,4-dihydropyrimidinones.  相似文献   

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