Copper-based MOF-74 material as effective acid catalyst in Friedel–Crafts acylation of anisole

Calleja, Guillermo; Sanz, R.; Orcajo, Gisela; Briones, David; Leo, Pedro; Martı́nez, Fernando

doi:10.1016/j.cattod.2013.11.062

Cited by 114 publications

(78 citation statements)

References 44 publications

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“…However, recent reports by Sanz et al 12 and our own synthetic procedure reported herein show that CPO-27-Cu can be successfully synthesised. However, recent reports by Sanz et al 12 and our own synthetic procedure reported herein show that CPO-27-Cu can be successfully synthesised.…”

Section: Introductionmentioning

confidence: 65%

Intriguing differences in hydrogen adsorption in CPO-27 materials induced by metal substitution

et al. 2015

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An extraordinarily interesting series of metal-organic framework compounds are the isostructural microporous coordination polymers [M 2 (dhtp)] (CPO-27-M, M-MOF-74 or M 2 (dobdc)) in which a high concentration of coordinatively unsaturated metal sites results in high initial heats of adsorption for a variety of adsorbents. We present here a comparative study of hydrogen gas adsorption experiments on CPO-27-Cu and -Mn, which show significant differences in their hydrogen uptake behaviours which can be attributed to the difference in interaction between hydrogen and the respective metal cation incorporated in the framework structure. Inelastic neutron scattering and neutron diffraction experiments were carried out to gain additional insight into the adsorption processes leading to the difference in hydrogen uptake behaviour by the two compounds. On the basis of the experimental results the hydrogen uptake properties of CPO-27-Cu and -Mn are compared, and finally related to the properties of the other members of the CPO-27 series. It is found that CPO-27-Cu demonstrates the lowest isosteric heat of adsorption for H 2 of all the CPO-27-M materials reported to date, where M ¼ Ni, Co, Mg, Zn, Mn, and Fe, whereas CPO-27-Mn demonstrates the second lowest. While all the previously reported CPO-27 materials show two steps in the adsorption isotherm and two distinct values corresponding to the first and second adsorption sites in the heats of adsorption, these are not observed for CPO-27-Cu. Consequently, the open metal site and the second adsorption site are energetically equivalent, and there is no preference for the hydrogen gas at the open metal centre.Fig. 2 Reference isotherm showing two step hydrogen adsorption for CPO-27-Ni, in a semi-logarithmic plot. 18 J. Mater. Chem. A This journal is

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Section: Introductionmentioning

confidence: 65%

Intriguing differences in hydrogen adsorption in CPO-27 materials induced by metal substitution

et al. 2015

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“…In the case of the acylation of anisole, URJC-1 material was studied and compared with other catalysts typically used for this reaction, like Cu-based MOF material (HKUST-1) and some conventional microporous zeolitic materials (Beta and ZSM-5), using the same operation conditions of previous works [12,30]. Figure 9 shows the catalytic performance in terms of anisole conversion and p-methoxyacetophenone (p-MAP) yield as the final product for all materials, including a blank experiment with no catalyst.…”

Section: Catalytic Activity Of Urjc-1 Materialsmentioning

confidence: 99%

“…Both reactions were carried out in a round bottom flask placed in a silicone bath under nitrogen atmosphere. For Friedel-Crafts acylation, anisole (10 mmol), acetyl chloride (10 mmol) catalyst (25 mg), and nitrobenzene solvent (10 mL) were charged at room temperature and heated up to 120˝C [12]. In the case of Knoevenagel condensation, malononitrile (5.1 mmol) and catalyst (48 mg) were added to DMF (10 mL) at room temperature, and then heated up to 80˝C.…”

Section: Catalytic Testsmentioning

confidence: 99%

“…In the last years, copper-based MOF materials with unsaturated metal centers as Lewis acid sites have been studied in several catalytic reactions, like O-arylation of phenols with nitroarenes [11] and Friedel-Crafts acylation [12,13]. Knoevenagel condensation between carbonyl (C=O) and activated methylene groups has also been explored as a feasible catalytic application of MOF materials [14].…”

Section: Introductionmentioning

confidence: 99%

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New URJC-1 Material with Remarkable Stability and Acid-Base Catalytic Properties

et al. 2016

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Abstract:Emerging new metal-organic structures with tunable physicochemical properties is an exciting research field for diverse applications. In this work, a novel metal-organic framework Cu(HIT)(DMF) 0.5 , named URJC-1, with a three-dimensional non-interpenetrated utp topological network, has been synthesized. This material exhibits a microporous structure with unsaturated copper centers and imidazole-tetrazole linkages that provide accessible Lewis acid/base sites. These features make URJC-1 an exceptional candidate for catalytic application in acid and base reactions of interest in fine chemistry. The URJC-1 material also displays a noteworthy thermal and chemical stability in different organic solvents of different polarity and boiling water. Its catalytic activity was evaluated in acid-catalyzed Friedel-Crafts acylation of anisole with acetyl chloride and base-catalyzed Knoevenagel condensation of benzaldehyde with malononitrile. In both cases, URJC-1 material showed very good performance, better than other metal organic frameworks and conventional catalysts. In addition, a remarkable structural stability was proven after several consecutive reaction cycles.

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“…This Cu-MOF-74 material was previously tested in the acylation of anisole with phenol, exhibiting a remarkable catalytic activity and structural stability [23]. The influence of different reaction variables such as temperature, type of solvent, catalyst concentration and type and concentration of base in the absence of assisting ligands was evaluated, in order to determine the best operation conditions for the synthesis of diaryl ethers.…”

Section: Introductionmentioning

confidence: 99%

Recyclable Cu-MOF-74 Catalyst for Ligand-Free O-Arylation Reaction of 4-Nitrobenzaldehyde and Phenol

Leo¹,

Orcajo²,

Briones³

et al. 2017

Preprint

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Abstract:The activity and cyclability of Cu-MOF-74 as catalyst was studied for the ligand-free C-O cross-coupling reaction of 4-nitrobenzaldehyde (NB) with phenol (Ph) to form 4-formyldiphenyl ether (FDE). Cu-MOF-74 is characterized by unsaturated copper sites in a highly porous metal-organic framework. The influence of solvent, reaction temperature, NB/Ph ratio, catalyst concentration and basic agent (type and concentration) were evaluated. High conversions were achieved at 120°C, 5 mol% of catalyst, NB/Ph ratio of 1:2, DMF as solvent and 1 equivalent of K2CO3 base. The activity of Cu-MOF-74 material was higher than other ligand-free copper catalytic systems tested in this study. This catalyst was easily separated and reused in five successive runs, achieving a remarkable performance without significant porous framework degradation. The leaching of copper species in the reaction medium was negligible. The O-arylation between NB and Ph took place only in the presence of Cu-MOF-74 material, being negligible without the solid catalyst.

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Copper-based MOF-74 material as effective acid catalyst in Friedel–Crafts acylation of anisole

Cited by 114 publications

References 44 publications

Intriguing differences in hydrogen adsorption in CPO-27 materials induced by metal substitution

Intriguing differences in hydrogen adsorption in CPO-27 materials induced by metal substitution

New URJC-1 Material with Remarkable Stability and Acid-Base Catalytic Properties

Recyclable Cu-MOF-74 Catalyst for Ligand-Free O-Arylation Reaction of 4-Nitrobenzaldehyde and Phenol

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