首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
The first TfOH-catalyzed three-component Friedel–Crafts alkylation/ketalization sequence of indoles, alcohols and ortho-hydroxychalcones was developed to afford a wide range of 4-indole substituted chromans bearing a ketal motif in 77–99% yields. Notably, only a simple filtration was needed to purify them. By altering methanol to CHCl3, 2,4-bisindole substituted chroman with the same indole substituent at the C2 and C4 positions was afforded. Moreover, 2,4-bisindole substituted chromans with different indole substituents could be obtained by treatment of 4-indole monosubstituted chromans with another indole molecule.

The first TfOH-catalyzed three-component Friedel–Crafts alkylation/ketalization sequence of indoles, alcohols and ortho-hydroxychalcones was developed to afford a wide range of 4-indole substituted chromans bearing a ketal motif in 77–99% yields.  相似文献   

2.
Efforts toward the development of a straightforward greener Gram-scale synthesis of the antibiotic compound 2,4-diacetylphloroglucinol (DAPG) have been developed. This beneficial procedure was accomplished through the Friedel–Crafts acylation of phloroglucinol over inexpensive heterogeneous silica sulphuric acid (SSA) catalyst via ultrasound-assisted (US) synthesis under solvent-free condition. The influences of various parameters such as temperature, catalyst loading, and reaction time on the reaction performance were analysed using a multivariate statistical modelling response surface methodology (RSM). A high yield of DAPG (95%) was achieved at 60 °C after 15–20 min reaction with the presence of 10% (w/w) SSA as the catalyst. Column chromatography-free and a Gram scale-up reaction also exhibited the practical applicability of this newly developed protocol. The SSA catalyst was recovered and recycled up to 10 consecutive runs with no appreciable loss of activity. A plausible mechanism for the Friedel–Crafts acylation of phloroglucinol is proposed. Moreover, an environmental assessment has been carried out over this present method and compared with several established literature using the EATOS software and the Andraos algorithm to assess the consumption of the substrates, solvents, catalysts, and the production of coupled products or by-products. In addition, their energy consumptions were also determined. The data collected showed that the present method is the most promising one, characterised by the highest environmental impact profile against all the other reported methods. The physicochemical properties of the synthesised DAPG were assessed and exhibited reasonable oral bioavailability drug property as determined by Lipinski''s rules.

A greatly improved procedure for the synthesis of antibiotic 2,4-diacetylphloroglucinol has been developed via a newly advanced synthetic method.  相似文献   

3.
Alkoxybenzenes and alkoxynaphthalenes, as nucleophiles, have drawn great attention from organic chemists over the decades. Due to their high ring strain, those particular classes of molecules are often used in synthesis by utilizing their properties to undergo facile Friedel–Crafts alkylations. Different isomeric and low or densely substituted alkoxybenzenes are used for synthesis according to the structure of the target molecule. Isomeric methoxybenzenes, are the most commonly used molecule in this regard. This review aims to comprehensively cover the instances of different alkoxy-benzenes/naphthalenes used as nucleophiles for ring opening.

This concise review reports the ring opening functionalizations of small sized molecular rings with alkoxybenzenes/alkoxynaphthalenes in Friedel–Crafts fashion.  相似文献   

4.
A highly efficient Friedel–Crafts alkylation of indole derivatives with β-(trifluoroacetyl)coumarins using Sc(OTf)3 as a catalyst has been developed, which gives regioselective 1,2-adducts to afford 1-(β-coumarinyl)-1-(β-indolyl)trifluoroethanols. A series of tertiary trifluoroethanols containing different indole and coumarin groups were synthesized in moderate to excellent yields (up to 95%) in the presence of 5 mol% catalyst in a short time (only 2 minutes at least). A mechanism of the reaction, in which the trace amount of water plays the role of proton transfer in catalyzing circulation was proposed and confirmed.

A Friedel–Crafts alkylation of indoles with β-(trifluoroacetyl)coumarins catalyzed by Sc(OTf)3 to afford 1-(β-coumarinyl)-1-(β-indolyl)trifluoroethanols in a short time and high yield was developed.  相似文献   

5.
It is still a great challenge to develop new materials for the highly efficient entrapment of organic dyes from aqueous solution. Herein, a novel triptycene-based hyper-crosslinked porous polymer (TPP–PP) was designed and synthesized by a simple Friedel–Crafts reaction. The obtained polymer TPP–PP has a high surface area, abundant pore structure and stable thermal performance. Due to the above characteristics, TPP–PP has good adsorption performance for anionic methyl orange solution (MO) and cationic methyl blue solution (MB). Under the optimal experiment conditions, the TPP–PP showed an excellent adsorption capacity for MO (220.82 mg g−1) and MB (159.80 mg g−1), respectively. The adsorption kinetics fitted the pseudo-second-order model. The adsorption of MO by TPP–PP reaches equilibrium within 180 minutes, and the adsorption of MB reaches equilibrium within 150 minutes. The adsorption behavior was not only spontaneous but also endothermic in reality. At the same time, TPP–PP also has good reusability. After 5 cycles of experiments, the removal rate of MO and MB by TPP–PP can still reach more than 80%. Thus, the Friedel–Crafts reaction crosslinked method might be a promising approach for the synthesis of novel material for the highly efficient extraction of dye wastewater.

A novel triptycene-based hyper-crosslinked porous polymer was developed for the highly efficient entrapment of organic dyes from aqueous solution.  相似文献   

6.
To develop an efficient solid acid catalysts for the Friedel–Crafts alkylation reaction, especially for involving bulky molecules, the direct synthesis of hierarchical nanocrystalline β zeolites were achieved by using amphiphilic organosilane ([(CH3O)3SiC3H6N(CH3)2C18H37]Cl, TPOAC) as collaborative structure-directing agent (SDA). The growth evolution of β crystals and the influence of TPOAC/SiO2 molar ratio on the mesoporous structure, crystal size, and acidic properties of β zeolites were investigated and discussed in detail. The characterization results reveal that intracrystalline mesopores and intercrystalline mesopores/macropores via the stacking of β nanocrystals were generated over the hierarchical β zeolites. Moreover, most of the strong acid sites were well remained compared with the conventional microporous β zeolite. Consequently, the hierarchical nanocrystalline β zeolite synthesized under the optimized synthesis conditions shows improved specific catalytic activity of acid sites (turnover number, TON) in alkylation of benzene with benzyl alcohol, which can be attributed to the integrated balance of considerable mesoporosity, accessibility of the acid sites, and well-remained strong acid sites in the hierarchical β zeolite.

Hierarchical β zeolite with enhanced transport and specific catalytic activity of acid sites in Friedel–Crafts alkylation was achieved by using amphiphilic organosilane surfactant as mesopores-directing agent and crystal growth inhibitor.  相似文献   

7.
A simple and effective template-free method to prepare hierarchical porous carbons (HPCs) has been developed by using low-cost coal-tar pitch as a starting material, anhydrous aluminum chloride as the Friedel–Crafts catalyst, and oxalyl chloride as the cross-linking agent. By a simple controllable Friedel–Crafts reaction, diketone-functionalized coal-tar pitch as the hierarchical porous coal-tar pitch precursor was obtained via a one-step carbonization to provide a well-developed micro–mesoporous network. Nitrogen adsorption and desorption measurements showed that the surface area, pore volume, pore size and pore size distributions of the resulting carbon materials was dependent on the usage of the cross-linking agent. The as-fabricated HPCs have a large Brunauer–Emmett–Teller specific surface area of 1394.6 m2 g−1 and exhibit an excellent electrochemical performance with the highest specific capacitance of 317 F g−1 at a current density of 1 A g−1 in a three-electrode system. A symmetric supercapacitor was fabricated from HPC-DK-1.0 in a two-electrode system, which exhibits a high specific capacitance of 276 F g−1 at a current density of 0.25 A g−1, a high rate capability and an excellent cycling stability with a capacitance retention of 92.9% after 10 000 cycles. The one-step carbonization method that produced HPCs for electrical double-layer capacitors represents a new approach for high-performance energy storage.

The hierarchical porous carbons have an excellent cycling stability with a capacitance retention of 92.9% after 10 000 cycles.  相似文献   

8.
Methylation of acetoin with dimethyl carbonate was performed in a sustainable one-step process, with improved process mass intensity (PMI) and atom economy compared to previously published methods. The resulting product, 3-methoxybutan-2-one (MO) was successfully evaluated as a bio-based solvent, while both Kamlet–Taft solvatochromic parameters and Hansen solubility parameters demonstrate its potential viability in the substitution of chlorinated solvents. MO exhibited a low peroxide forming potential and a negative Ames mutagenicity test and was successfully used as a solvent in a Friedel–Crafts acylation (79% yield compared to 77% in dichloromethane) and for N-alkylations. MO is a renewable oxygenated solvent, with the potential ability to substitute carcinogenic halogenated solvents in some applications.

Methylation of acetoin with dimethyl carbonate was performed in a sustainable one-step process, with improved process mass intensity (PMI) and atom economy. 3-Methoxybutan-2-one is a sustainable bio-based alternative to chlorinated solvents.  相似文献   

9.
Berberine hydrochloride (BH), an important alkaloid, can be captured from water and released in organic solution circularly by a charged porous polymer (TPB–HCP), which is hypercross-linked using the cost-effective Friedel–Crafts reaction using sodium tetraphenylborate as the monomer. With high BET surface area, hierarchical porous structure and charged characteristics, TPB–HCP displays excellent adsorption capacity for BH owing to the synergistic effects of size matching and electrostatic interaction.

A charged porous polymer displays excellent adsorption capacity for berberine hydrochloride from the synergistic effects of size matching and electrostatic interaction.  相似文献   

10.
In this study, acrylic acid (AA) and sulfonated hydroxypropyl chitosan (SHPCS) were covalently grafted on the PSf membrane surface to improve its hemocompatibility. First, the modified AA-PSf membrane was obtained through the Friedel–Craft reaction between acrylic acid and the PSf membrane surface. Then, the modified SHPCS-AA-PSf membrane was prepared by grafting SHPCS onto the AA-PSf membrane surface via the dehydration acylation of the carboxyl group of the AA-PSf membrane with the amino group of SHPCS. ATR-FTIR and XPS measurements confirmed that the –COOH group and SHPCS were successfully grafted onto the surface of the PSf membrane. The modified PSf membranes showed suppressed platelet adhesion and lower protein adsorption (161 μg cm−2) compared with the pristine PSf membrane (341 μg cm−2). Hemocompatibility testing showed that modified membrane materials had a prolonged clotting time, plasma recalcification time (PRT), activated partial thromboplastin time (APTT), thrombin time (TT), and prothrombin time (PT). All of these results indicated that the surface modification of the PSf membrane with acrylic acid and SHPCS had good hemocompatibility and anticoagulant property.

In this study, acrylic acid (AA) and sulfonated hydroxypropyl chitosan (SHPCS) were covalently grafted on the PSf membrane surface to improve its hemocompatibility.  相似文献   

11.
Given their excellent reusability and environmental friendliness, solid acid catalysts have drawn considerable attention in acid-catalyzed reactions. However, the rational design and synthesis of solid acid catalysts with abundant Brønsted acid sites remains a challenge. In this paper, KIT-6, Zr-KIT-6, Mo-KIT-6, and ZrMo-KIT-6 solid acid catalysts are designed and synthesized. The textural properties, chemical bonds, and acidic properties of these catalysts are explored. Theoretical calculations are conducted to explore the formation mechanism of Brønsted acid sites. The theoretical trend of acidity is consistent with the experimental result of acidity and further demonstrates that the synergistic effect of Zr and Mo species improves the formation of Brønsted acid sites. The as-obtained ZrMo-KIT-6 solid acid catalysts are employed in Friedel–Crafts benzylation reaction, and the outstanding catalytic performance of the ZrMo-KIT-6 catalyst indicates that it is an excellent Brønsted solid acid catalyst.

Synergistic effect of Zr and Mo species in the formation of Brønsted acid sites is investigated by experimental and theoretical study.  相似文献   

12.
Over the years, Friedel–Crafts (FC) reactions have been acknowledged as the most useful and powerful synthetic tools for the construction of a special kind of carbon–carbon bond involving an aromatic moiety. Its stoichiometric and, more recently, its catalytic procedures have extensively been studied. This reaction in recent years has frequently been used as a key step (steps) in the total synthesis of natural products and targeted complex bioactive molecules. In this review, we try to underscore the applications of intermolecular and intramolecular FC reactions in the total syntheses of natural products and complex molecules, exhibiting diverse biological properties.

In this review, we try to underscore the applications of intermolecular and intramolecular FC reactions in the total syntheses of natural products and complex molecules, exhibiting diverse biological properties.  相似文献   

13.
A nanocomposite coating comprising mercapto functional hybrid silica sol–gel coating and functionalized graphene nanoplates nanocomposite coatings with advanced anticorrosive properties was prepared by a sol–gel method. In this study, graphene oxide (GO) nanoplates were silanized using 3-aminopropyltriethoxysilane (APTES) to obtain functional graphene nanoplates (f-GNs). The f-GNs were characterized by FTIR, XRD, XPS, TEM, AFM and TGA techniques. The functionalized graphene nanoplates were chemically bonded to a sol–gel matrix and showed good dispersion in the sol. Then, silica hybrid sol–gel nanocomposites with raw GO and different amounts of f-GNs were applied on the copper surface. Uniform, defect-free and adherent sol–gel films were obtained. Various corresponding methods were used to investigate the nanocomposite coating''s properties. The corrosion resistance of copper significantly improved after being coated with mercapto functional hybrid silica sol–gel. The addition of f-GNs to the mercapto functional silica sol–gel coatings further improved the corrosion resistance due to a synergistic effect. Moreover, with an increase in the amount of f-GNs in the nanocomposite coating, the nanocomposite showed improved corrosion resistance. The nanocomposite containing 0.1 wt% f-GNs can efficiently protect the copper substrate from corrosion. This improvement was primarily attributed to the homogeneous dispersion of the f-GNs in the silica gel matrix and their effective barrier against corrosive molecules and ions. However, adding raw GO or excess f-GNs to the silica hybrid sol–gel coating had a negative effect on the corrosion resistance.

An anticorrosion coating on copper consisting of mercapto functional hybrid silica sol–gel and f-GNs nanoplates with a synergistic effect was prepared.  相似文献   

14.
In this study, a series of polystyrene-divinylbenzene resins with precise physical structure regulation and chemical modification were successfully synthesized. The regulation of Friedel–Crafts reaction conditions resulted in several physical resins with various BET surface areas and pore structures, while the adsorption of 1,3-propanediol revealed that the molecular size and other physical properties exhibited a moderate contribution to the adsorption of hydrophilic compounds. The adsorption processes between 1,3-propanediol and nitrogen, oxygen and boron functional group modified resins were further explored, and boronic acid modified resins named PS-3NB and PS-SBT exhibited higher adsorption capacities than commercial resin CHA-111. The adsorption capacity of PS-3NB and PS-SBT reached 17.54 mg g−1 and 17.23 mg g−1, respectively, which were 37% and 35% higher than that of commercial resin CHA-111. Furthermore, the adsorption mechanism demonstrated that the content of boronic acid, solution pH and adsorbate hydrophobicity were the primary adsorption driving forces. Herein, we provided a method to modify polystyrene-divinylbenzene materials with boronic acid to selectively adsorb hydrophilic polyols via the specific affinity between boronic acid and diol molecule.

Chemically modified materials efficiently captured 1,3-propanediol via the specific affinity between boronic acid and diol.  相似文献   

15.
In the present work, leucoemeraldine-based hybrid porous polyanilines (LHPPs) have been synthesized by the Friedel–Crafts reaction of leucoemeraldine and octavinylsilsesquioxane (OVS) for Cr(vi) removal. The resulting LHPPs were characterized by Fourier transform infrared spectroscopy, powder X-ray diffraction, thermogravimetric analysis, scanning electron microscopy and N2 adsorption–desorption. The findings indiated that the LHPPs were amorphous, with apparent surface areas (SBET) in the range of 147 to 388 m2 g−1 and total volumes in the range of 0.13 to 0.44 cm3 g−1. Cr(vi) removal experiments displayed that the LHPPs exhibited highly efficient Cr(vi) removal performance. The maximum Cr(vi) removal capacity of LHPP-1 was 990.1 mg g−1 at 308 K and pH 1, which is higher than those of other reported polyaniline-based adsorbents. The adsorption process was a spontaneous, endothermic and chemical adsorption process. The adsorption behavior agreed well with Langmuir models and pseudo second-order equations. X-ray photoelectron spectroscopy and Fourier transformed infrared (FTIR) spectroscopy analysis revealed that the highly efficient Cr(vi) removal performance can be mainly attributed to the existence of numerous amine and imine groups on the surface of the LHPPs; these can function as adsorption active sites for Cr(vi) removal through electrostatic adsorption and reduction to Cr(iii) under acidic conditions. Moreover, the LHPPs exhibited excellent adsorption selectivity for Cr(vi) despite the presence of other metal ions (K+, Cu2+, Mn2+) and anions (NO3, SO42−). Therefore, the LHPPs have potential applications for Cr(vi) removal in industrial wastewater.

In the present work, leucoemeraldine-based hybrid porous polyanilines (LHPPs) have been synthesized by the Friedel–Crafts reaction of leucoemeraldine and octavinylsilsesquioxane (OVS) for Cr(vi) removal.  相似文献   

16.
Herein, we explore a new carbon source for preparation of carbon quantum dots (CQDs) with controllable composition using a porous organic polymer (POP) derived porous carbon via a nitric acid oxidation method. The POP used for the preparation of CQDs was synthesized by mechanochemical Friedel–Crafts alkylation under solvent free conditions. Using the as-prepared CQDs, we develop a simple and effective electrochemiluminescence (ECL) detection method for dopamine (DA) using a CQD/chitosan–graphene composite modified glassy carbon electrode (GCE). Both the electrochemical and ECL behaviors were studied in detail with ammonium persulfate as a coreactant. The complementary structure and synergistic function of the composite give the ECL sensor special properties. Apart from the high stability, it also presents good repeatability and high sensitivity to DA with a wide linear range from 0.06 to 1.6 μM. And a satisfactory detection limit of 0.028 μM (S/N = 3) was achieved for the prepared sensor. Furthermore, the ECL also shows high selectivity toward DA with an excellent interference resistance ability at a high concentration ratio of 100 (Cinterference : CDA = 100). In addition, the ECL sensor was successfully applied for effective detection and quantitative analysis of the actual dopamine in human body fluids for disease diagnosis and pathological studies.

CQDs were obtained from a POP derived porous carbon via nitric acid oxidation. CQDs/CG composite film with special properties were fabricated and used for ECL detection of DA in human body fluids.  相似文献   

17.
ZrO2–WO3 mixed oxide plays an essential role in the chemical and petroleum industries. So far, very little work has paid attention to the activation of the low activity of ZrO2–WO3 catalysts. In this work, poorly reactive ZrO2–WO3 was prepared as a model catalyst by a sol–gel method and it was accompanied by post-hydrothermal treatment with various solutions. The catalytic results in the Friedel–Crafts reaction of anisole and benzyl alcohol showed that the post-hydrothermal treatment with ethylenediamine or ammonium hydroxide solutions dramatically improved the activity of ZrO2–WO3, while the hydrothermal treatments with water or ammonia chloride solution resulted in poorer activity and selectivity. The former treatments were found to induce a huge transformation of the ZrO2 crystal from monoclinic to tetragonal as well as a significant increase in acidic WOx clusters that anchored onto ZrO2. The generation of the WOx clusters was responsible for the activation of ZrO2–WO3.

The high pH value of the post-hydrothermal treatment induces the generation of acidic WOx cluster active sites.  相似文献   

18.
Removal of soluble organic and inorganic contaminants from wastewater to produce clean water has received much attention recently. However, the simultaneous enhancement of water permeability and removal efficiency is still a challenge for filtration membranes. Here, we present a new kind of nanocomposite paper (CSH/CNF) consisting of calcium silicate hydrate (CSH) nanosheets and cellulose nanofibers (CNFs), and demonstrate the rapid water filtration and highly efficient contaminant (e.g., dyes, proteins, and metal ions) adsorption properties. The CNFs can serve as the bridging material to connect the CSH nanosheets to form a porous network structure and vital channels in the CSH/CNF paper for rapid water transportation. The weight ratio of CSH nanosheets in the paper is up to 75–85%. The weight ratio of CSH nanosheets has a significant effect on the water permeability and removal efficiency. The water permeability of the CSH/CNF paper with 82.5 wt% CSH nanosheets reaches as high as 312.7 L m−2 h−1 bar−1, which is about 14.7 times that of the CSH/CNF paper with 75 wt% CSH nanosheets. Because of the high specific surface area and abundant adsorption sites of CSH nanosheets, the CSH/CNF paper with 82.5 wt% CSH nanosheets exhibits high adsorption capacities and removal efficiencies for methyl blue (242.6 mg g−1, 97.3%), bovine serum albumin (289.2 mg g−1, 98.5%) and Pb2+ ions (366.2 mg g−1, 98.2%). The CSH/CNF nanocomposite paper holds great potential for application in environmental wastewater purification.

A nanocomposite paper with high water permeability and removal efficiency was prepared for the removal of organic and inorganic contaminants by filtration.  相似文献   

19.
In this study, bio-responsive polymeric MoS2 nanocomposites were prepared for use as a drug carrier for cancer therapy. Herein, we report the synthesis and demonstrate the self-assembly of pluronic F127 (PF127) on a cystamine–glutathione–MoS2 (CYS–GSH–MoS2) system, which can be used for GSH-triggered drug release under biological reducing conditions. The reduction-sensitive disulfide bond containing CYS was incorporated between the amphiphilic copolymer PF127 and GSH–MoS2 to achieve feasible drug release. Percent drug loading capacity and encapsulation efficiency were 51.3% and 56%, respectively. In addition, when the MoS2–GSH–CYS–PF127 nanocomposite was incubated in a GSH environment, the morphology of the nanocomposite tended to change, ultimately leading to drug release. The drug-loaded PF127–CYS–GSH–MoS2 polymeric nanocomposites efficiently released 52% of their drug content after 72 h of incubation in a GSH reduction environment. The HeLa cells treated with DOX loaded MoS2–GSH–CYS–PF127 showed 38% toxicity at drug concentration of 40 μg, which indicated that the successfully released of drug from carrier and caused the cell death. Further, fluorescence microscopy images of HeLa cells revealed the potential behavior of the MoS2–GSH–CYS–PF12 nanocomposite during the 2- and 4 h incubation periods; the nanocomposite was only found in the cytoplasm of HeLa cells. Interestingly, after 6 h of incubation, the drug was slowly released from the nanocomposite and could enter the nucleus as confirmed by fluorescence imaging of HeLa cells. Altogether, our synthesized PF127-coated MoS2 nanocomposite could be effectively adopted in the near future as a GSH-sensitive drug carrier.

In this study, bio-responsive polymeric MoS2 nanocomposites were prepared for use as a drug carrier for cancer therapy.  相似文献   

20.
The excessive use of antibiotics has led to various environmental problems; the control and separation of these antibiotics are important in environmental science. Herein, a novel mesoporous nanocomposite, Fe3O4@SiO2@mSiO2-CD, has been synthesized for the removal of antibiotic compounds from aqueous media. The well-designed nanocomposite is composed of β-cyclodextrin functionalized surfaces, ordered mesoporous silica shells with large radially oriented mesopores, and nonporous silica-coated magnetic cores (Fe3O4). The synergistic action of both the mesoporous structure and the accessible cavity of β-cyclodextrin ensures the good adsorption of doxycycline. Furthermore, the Fe3O4@SiO2@mSiO2-CD nanocomposite can be collected, separated and easily recycled from aqueous solution using an external magnet.

The controllable synthesis of a core–shell structured mesoporous organic–inorganic hybrid nanocomposite, Fe3O4@SiO2@mSiO2-CD, which demonstrates good adsorption of doxycycline.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号