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. 2017 Jun 16;7(6):149.
doi: 10.3390/nano7060149.

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

Pedro Leo  1 , Gisela Orcajo  2 , David Briones  3 , Guillermo Calleja  4 , Manuel Sánchez-Sánchez  5 , Fernando Martínez  6
Affiliations

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

Pedro Leo et al. Nanomaterials (Basel). .

Abstract

The activity and recyclability of Cu-MOF-74 as a 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 having 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. The catalytic advantages of using nanostructured Cu-MOF-74 catalyst were also proven.

Keywords: 4-formyldiphenyl ether; 4-nitrobenzaldehyde; MOF; O-arylation reaction; catalyst; ligand-free; phenol; recyclable Cu-MOF-74.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Catalyst characterization of Cu-MOF-74: (a) PXRD patterns; (b) SEM images; (c) nitrogen adsorption–desorption isotherms at −196 °C with an inset showing the micropore size distribution curve as generated by NL-DFT method, and (d) TGA under inert atmosphere.
Figure 2
Figure 2
Kinetics of 4-nitrobenzaldehyde (NB) conversion catalyzed by Cu-MOF-74 at different temperatures
Figure 3
Figure 3
NB conversion in the absence of catalyst (blank), in the presence of Cu-MOF-74 catalyst for 120 min and in the presence of Cu-MOF-74 for 5 min and subsequent removal.
Figure 4
Figure 4
NB conversion vs. reaction time given by Cu-MOF-74 catalyst at different NB/Ph ratios.
Figure 5
Figure 5
NB conversion vs. reaction time given by different concentration of Cu-MOF-74.
Figure 6
Figure 6
NB conversion vs. reaction time given by Cu-MOF-74 catalysts in different solvents.
Figure 7
Figure 7
NB conversion vs. reaction time given by Cu-MOF-74 catalysts in the absence of base and in the presence of different bases.
Figure 8
Figure 8
NB conversion vs. reaction time given by Cu-MOF-74 catalysts at different K2CO3 concentrations.
Figure 9
Figure 9
NB conversion vs. reaction time using different substituted-phenols.
Figure 10
Figure 10
NB conversion vs. reaction time using different nitroarenes.
Figure 11
Figure 11
NB conversion vs. reaction time given by different homogeneous and heterogeneous Cu-based catalysts.
Figure 12
Figure 12
(a) PXRD patterns; (b) nitrogen adsorption–desorption isotherms at −196 °C of nano sized- and micron sized-Cu-MOF-74.
Figure 13
Figure 13
NB conversion vs. reaction time given by nano- and micron-sized Cu-based catalysts.
Figure 14
Figure 14
Catalytic activity of Cu-MOF-74 catalyst after several reaction cycles.
Figure 15
Figure 15
XRD patterns of Cu-MOF-74 catalyst after several reaction cycles.
Scheme 1
Scheme 1
C–O cross-coupling reaction of phenol with 4-nitrobenzaldehyde.
See this image and copyright information in PMC

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