Fe3O4@GlcA@Cu-MOF: A Magnetic Metal-Organic Framework as a Recoverable Catalyst for the Hydration of Nitriles and Reduction of Isothiocyanates, Isocyanates, and Isocyanides

Article abstract of DOI:10.1021/acscombsci.0c00178

A novel magnetic metal-organic framework (Fe3O4@GlcA@Cu-MOF) has been prepared and characterized by spectroscopic, microscopic, and magnetic techniques. This magnetically separable catalyst exhibited high catalytic activity for nitrile hydration and the ability to reduce isothiocyanates, isocyanates, and isocyanides with excellent activity and selectivity without any additional reducing agent.

Full text of DOI:10.1021/acscombsci.0c00178

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Research Article
Fe3O4@GlcA@Cu-MOF: A Magnetic Metal−Organic Framework as a
Recoverable Catalyst for the Hydration of Nitriles and Reduction of
Isothiocyanates, Isocyanates, and Isocyanides
Arash Ghorbani-Choghamarani* and Zahra Taherinia*
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ABSTRACT: A novel magnetic metal−organic framework (Fe3O4@GlcA@Cu-MOF) has
been prepared and characterized by spectroscopic, microscopic, and magnetic techniques.
This magnetically separable catalyst exhibited high catalytic activity for nitrile hydration and
the ability to reduce isothiocyanates, isocyanates, and isocyanides with excellent activity and
selectivity without any additional reducing agent.
KEYWORDS: nitrile hydration, reduction of isothiocyanates, isocyanates, isocyanides, gluconic acid, 4-phenylurazole
on oxoamides in the presence of thionating agents including the
INTRODUCTION
■
Lawesson reagent,23 phosphorus pentasulfide,24 or elemental
sulfur25 (Scheme 2B), partial reduction of isothiocyanates with
reducing agents (Scheme 2C),26 and Schwartz reagent (Scheme
2,D).27 Although useful, some of these methods suffer from one
or more of the following drawbacks: the use of toxic reagents,
unpleasant smelling, unstable reagents, harsh reaction con-
ditions, tedious workup, and difficulty in separation and
recovery of the catalyst.
Nitriles are relatively stable functional group that transformed by
transition metal catalysis in organic syntheses.1−6 The
conversion of nitriles into amides by conventional acid7/base8
reagents or catalysts (Scheme 1A,B) is a useful transformations
in organic chemistry. It usually requires harsh reaction
conditions and remains impractical for many purposes due to
issues of low yield and selectivity, since classical methods are
frequently unable to control the overhydrolysis of the primary
amide product. The use of transition metal complexes as
catalysts under neutral and mild conditions has allowed
researchers to overcome these traditional barriers (Scheme
1C).9 Moreover, the reaction of isocyanates with LiAlH4,10 and
Schwartz reagent has been considered for the synthesis of the N-
formylamide derivative (Scheme 1D).11 Nonetheless, some of
these methods have drawbacks such as reduction termination at
the formamides stage and poor tolerance of certain functional
groups.
Thioamides and their derivatives are useful synthons in
organic synthesis,12 such as in regio- and stereoselective
heterocyclization reactions.13 Moreover, they can be used as
flotation14 and vulcanization agents,15 as additives to lubricating
oils and greases16 and as interesting ligands in coordination
chemistry.17 Thioamides are often prepared via the reaction of
isothiocyanates with aromatic compounds catalyzed by Lewis
acids18 (Scheme 2A), thioacylation of amines with thiofor-
mates,19 dimethyl thioformamide,20 or carbon mono21 or
disulfide22 (Scheme 2B), formal oxygen−sulfur replacement
N-methylated amines have emerged as essential bioactive
compounds in drug discovery,28 and are often prepared by
reductive amination formaldehyde as a carbon source together
with a reducing agent29 (Scheme 3A), or with methylating
agents such as methyl halides, methyl triflate, dimethylsulfate, or
diazomethane overmethylation is a common problem.30−33 In
this respect, green sources of “methyl equivalents” have recently
been investigated, allowing the use of carbon dioxide,34 dimethyl
carbonate,35 MeOH,36 and formic acid37 in N-methylation
reactions (Scheme 3B). Moreover, these compound may be
achieved from carboxylic acids via utilization of acyl azides as
amine surrogate and methanol as carbon source (Scheme 3C),38
Received: September 7, 2020
Revised: October 18, 2020
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Scheme 1. Previous Methodology for the Synthesis of Amides
Scheme 2. Previous methodology for the preparation of thioamides
from methylamine and functionalized aryl electrophiles under
transition-metal catalysis (Scheme 3D).39 Lastly, the reaction of
aromatic nitroso compounds with methylboronic acid promoted
by triethylphosphite (Scheme 3E)40 and the catalytic reduction
of isonitriles with hydrogen (Scheme 3F)41 have also been
reported.
Herein we described, a versatile catalyst based on a metal−
organic framework (MOF) to accomplish each of these
transformations (Scheme 4), in which 4-phenylurazole based
copper metal organic framework as a hydrogen donor was used
as hydride source. This methodology offers more benign
reaction conditions and the use of more convenient and
environmentally friendly reagents, as well as efficient catalyst
recovery and recycling.
Metal−organic frameworks (MOFs) are a class of porous
materials comprised of metal ions or clusters coordinated to
organic ligands.42 Because of their high porosities and tunable
structural properties, they have many applications in cataly-
sis,41,43−45 gas storage,46 sensors,47 biomedicines,48 etc. When
the MOF is bound to a magnetic component,49 a multifunc-
tional material can result in which magnetic separability coexists
with the functional porous catalyst. Based on our previous study
of magnetic nanoparticles,50 we prepared gluconic acid (GlcA)-
coated magnetic microspheres with surface modification by
copper-based MOFs, designated as Fe3O4@GlcA @Cu-MOF
(Scheme 5). We found this material to be an effective
heterogeneous catalyst for the hydration of nitriles and the
reduction of isothiocyanates, isocyanates, and isocyanides
without any added reducing agent through transfer hydro-
genation with sustainable 4-phenylurazole based copper metal
organic frameworkas a hydrogen donor. Excellent chemo-
selectivity in the presence of sensitive functionalities such as
nitro and carbonyl groups was observed. Moreover, the
nanocatalyst was easily recovered by an external magnetic field
and reused at least four times with minimal deterioration in
catalytic activity.
CHARACTERIZATION OF FE3O4@GLCA @CU-MOF
■
The nanocatalyst material was characterized by FTIR, XRD,
BET, TEM, FE-SEM, EDX, TGA, DSC, EDS elemental
mapping, ICP, CHNSO analysis, and VSM. Successful coupling
of gluconic acid to the surface of Fe3O4 nanoparticles, and the
binding of the Cu MOF to that surface were verified most easily
by FTIR analysis (Supporting Information (SI)).
Magnetic properties of the Fe3O4@GlcA nanoparticles and
the final Fe3O4@GlcA @Cu-MOF catalyst were evaluated by
VSM (Figure 1), showing a significant decrease in saturation
magnetization intensity of Fe3O4@GlcA@Cu-MOF (37 emu
B
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Scheme 3. Previous Procedures for the Synthesis of N-Methylated Amines
Scheme 4. General Context of Present Work
g−1) relative to that of the precursor Fe3O4@GlcA (57 emu g
−1). However, both particles retained enough magnetization to
be easily separated from reaction mixtures by applying an
external magnet (Figure 1).
ICP analysis showed the copper content in Cu-MOF and
Fe3O4@GlcA@Cu-MOF to be 0. 050 mmol g−1 and 0.045
mmol g−1, respectively, and elemental (C, H, N, S, O) analysis
confirmed the expectation of complexation with a 1:1 molar
ratio of the metal to ligand (Table 1).
The size and morphology of the Fe3O4@GlcA @Cu-MOF
NPs were studied by transmission electron microscopy (TEM)
and field emission scanning electron microscopy (SEM)
(representative images in Figure 2). It was found that the
Fe3O4@GlcA NPs core was well-encapsulated by Cu-MOF NPs,
C
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Scheme 5. Schematic Synthesis of Fe3O4@GlcA @Cu-MOF
giving irregular Fe3O4@GlcA @Cu-MOF NPs of about 50−500
nm in diameter.
To determine the spatial distribution of elements in the
Fe3O4@GlcA @Cu-MOF, elemental mapping was performed
(Figure S3) in which the O, C, Fe, and Cu are uniformly
distributed in the nanocatalyst (Figure S3).
The TGA thermograms of Fe3O4@GlcA @Cu-MOF NPs
were shown in SI Figure S4. The thermogram curve exhibited
three different regions (SI Figure S4): (1) Mass loss (1.7%)
region between 25 and 150 °C indicating the loss of moisture;
(2) the region between 160 and 380 °C with a slow mass loss of
6.53% is related to loss of the organic spacer groups (gluconic
acid) on the surface of Fe3O4; (3) The third region starts
between 400 and 580 °C in which the structure of Cu-MOF NPs
collapses.
Figure 1. Magnetization curve of Fe3O4@GlcA (A), Fe3O4@GlcA @
Cu-MOF (b).
The differential scanning calorimetry of Fe3O4@GlcA @Cu-
MOF NPs is shown in SI Figure S4. Besides, Fe3O4@GlcA @
Cu-MOF NPs show an exothermic peak located in the range of
120−370 °C and indicating the existence of crystallization in the
bulk material. The second exothermic peak is at the range of
380−520 °C that could be due to crystallization for Fe3O4.
The porous properties of Fe3O4@GlcA @Cu-MOF NPs were
investigated by measuring the nitrogen adsorption isotherm, as
Table 1. Elemental Analysis for Cu-MOF
elemental analysis (mmol·g−1
)
C
N
H
O
Cu
0.020
0.008
0.017
0.005
0.050
D
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Table 3. Results of Conversion of Nitriles to Amides Using
Fe3O4@GlcA @Cu-MOF
Figure 2. (a,b)TEM images of Fe3O4@GlcA @Cu-MOF. (c) SEM
images of Fe3O4@GlcA @Cu-MOF.
Table 2. Optimization of Reaction Conditions for the
Synthesis of Amide
a
b
entry
solvent
temp. (°C)
cat (mg)
yield (%)
1
2
3
4
5
6
7
DMSO:H2O (2:0.1)
DMF
PEG
100
100
100
100
100
100
80
100
100
100
50
50
50
50
50
40
50
-
90
33
-
27
47
76
53
N.R
N.R
38
H2O
DMSO: H2O (2:0.3)
DMSO
DMSO
DMSO
DMSO
c
8
d
9
50
50
e
10
DMSO
a
Reaction conditions: benzonitrile (1 mmol), and Catalyst(mg).
b
c
d
Isolated yield. In the absence of any catalyst. In the absence of
e
Fe3O4@GlcA. In the absence of Cu-MOF. Time 12 h.
shown in SI Figure S5. The Brunauer−Emmett−Teller surface
area (SBET) and pore volume of Fe3O4@GlcA @Cu-MOF NPs
were determined to be 33.77 m2 g−1 and 7.29 cm3 g−1,
respectively based on the N2 adsorption−desorption measure-
ment. The BJH pore size calculations using the adsorption
branch of the nitrogen isotherm indicates a micropore peak at
about 3.55 nm (SI Figure S6).
a
Reaction conditions: Substrate (1 mmol), and Catalyst (50 mg).
Isolated yield. Catalyst(65 mg). Time(10−15 h).
b
c
E
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Scheme 6. Proposed Mechanism for Reduction of Isocyanates
chlorophenyl)methanethioamide, N-phenylformamide, and N-
methylcyclohexanamine. After completion of the reactions, the
catalyst was recovered by applying an external magnet and
washed several times with ethyl acetate and used in the next run.
The results showed that the catalyst can be efficiently recycled
and reused for four consecutive cycles without any significant
loss of its catalytic activity in the synthesis of benzamide, N-(4-
chlorophenyl)methanethioamide, N-phenylformamide, and N-
methylcyclohexanamine; recovered catalyst gave the desired
products with yields of (90, 90, 89, and 88%), (95, 95, 94, 92%),
(92, 91, 91, 90%), (65, 64, 63, 62%), respectively.
Moreover, in order to show the structural stability of the
catalyst after recyling, the recovered catalyst was characterized
by FT-IR technique. The FT-IR spectrum of the recovered
Fe3O4@GlcA@Cu-MOF indicate that this catalyst can be
recycled without any change in its structure (SI Figure S7).
CATALYTIC ACTIVITY OF MAGNETIC
METAL−ORGANIC FRAMEWORK FE3O4@GLCA
@CU-MOF
■
The catalytic property of magnetic metal−organic framework
Fe3O4@GlcA @Cu-MOF NPs was investigated for nitrile
hydration and isothiocyanates, isocyanates, and isocyanides
reduction.
We studied the effect of some specific parameters; including,
the amount of the catalyst, nature of the solvents, and the
temperature (Table 2). Initially, we have screened various
solvents in which DMSO: H2O (2:0.1) was found to be the best
solvent providing an excellent yield (Table 2), while the reaction
in solvents, such as PEG, was not effective. The effect of
temperature was also investigated, and the highest yield was
obtained at 100 °C.
However, the reaction did not proceed in the absence of the
catalyst (Table 2, entry 8). We also evaluated the effect of the
amount of catalyst on the product yield that 50 mg of the catalyst
was found to be the optimal amount for the reaction. Afterward,
the reaction scope was explored with a series of nitriles. The
results are indicated in Table 3 in which we observed that the
reactions provided good to excellent yield of the corresponding
products (58−96%).
CONCLUSIONS
■
In conclusion, we report a novel mesoporous material Fe3O4@
GlcA@Cu-MOF nanoparticle as it is successfully employed to
reduce nitriles, isocyanate, isothiocyanates, and isocyanides. This
study described an atom-efficient, versatile, excellent chemo-
selectivity, and economical method for the preparation of amines
without additional hydrogen sources. Besides, the recovered
nanocatalysts were applied for at least four times. Refs 54, 55, 56,
57, 58, 59, 60, 61, 62, 63, 64, and 65.
A plausible mechanism for the reduction of isocyanates shown
in Scheme 6 based on previous reports.51−53
The possibility of metal leaching from the catalyst was studied
using a hot filtration test. When the reaction preceded to nearly
50% completion, the catalyst was separated from the reaction
mixture and the filtrate was monitored for continued activity.
The results show that after removal of the catalyst particles, the
reaction did not proceed even after 5 h.
ASSOCIATED CONTENT
■
sı
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acscombsci.0c00178.
The reusability of the mesoporous catalyst has been
investigated for the synthesis of benzamide, N-(4-
Experimental and spectroscopical details (PDF)
F
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AUTHOR INFORMATION
■
Corresponding Authors
Arash Ghorbani-Choghamarani − Department of Organic
Chemistry, Faculty of Chemistry, Bu-Ali Sina University,
Hamedan 6517838683, Iran; orcid.org/0000-0002-7212-
1317; Phone: +988138282807; Email: a.ghorbani@
basu.ac.ir, arashghch58@yahoo.com; Fax: +988138380709
Zahra Taherinia − Department of Chemistry, Ilam University,
69315516 Ilam, Iran; Department of Organic Chemistry,
Faculty of Chemistry, Bu-Ali Sina University, Hamedan
6517838683, Iran; Phone: +98 841 2227022;
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Email: zahra.taheriniya@yahoo.com; Fax: +98 841 2227022
Complete contact information is available at:
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank Ilam University, Bu-Ali Sina University, and Iran
National Science Foundation (INSF) for financial support of
this research project.
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