Ethylene diamine post-synthesis modification on open metal site Cr-MOF to access efficient bifunctional catalyst for the Hantzsch condensation reaction

Article abstract of DOI:10.1002/aoc.4370

Ethylene diamine functionalized MIL-101(Cr) was established to be an efficient organocatalyst for single-pot synthesis of polyhydroquinolines via four-component condensation reaction between aldehydes, dimedone, β-ketoecters and ammonium acetate in aqueous medium. Ethylene diamine of the parent open metal site MIL-101(Cr) has been carried out through a post-synthetic modification (PSM) technique. Efficient transformation, mild condition, easy product isolation and the potential high recycbility of the organocatalyst are the key feature of this protocol.

Full text of DOI:10.1002/aoc.4370

Received: 8 December 2017
DOI: 10.1002/aoc.4370
Revised: 23 February 2018
Accepted: 2 March 2018
F U L L P A P E R
Ethylene diamine post‐synthesis modification on open
metal site Cr‐MOF to access efficient bifunctional catalyst
for the Hantzsch condensation reaction
Sadegh Rostamnia
| Hassan Alamgholiloo | Maryam Jafari
Organic and Nano Group (ONG),
Ethylene diamine functionalized MIL‐101(Cr) was established to be an effi-
Department of Chemistry, Faculty of
Science, University of Maragheh, PO BOX
55181‐83111, Maragheh, Iran
cient organocatalyst for single‐pot synthesis of polyhydroquinolines via four‐
component condensation reaction between aldehydes, dimedone, β‐ketoecters
and ammonium acetate in aqueous medium. Ethylene diamine of the parent
open metal site MIL‐101(Cr) has been carried out through a post‐synthetic
modification (PSM) technique. Efficient transformation, mild condition, easy
product isolation and the potential high recycbility of the organocatalyst are
the key feature of this protocol.
Correspondence
Sadegh Rostamnia, Organic and Nano
Group (ONG), Department of Chemistry,
Faculty of Science, University of
Maragheh, PO BOX 55181‐83111,
Maragheh, Iran.
Email: rostamnia.sadegh@nims.go.jp;
srostamnia@gmail.com;
KEYWORDS
rostamnia@maragheh.ac.ir
Hantzsch reaction, metal–organic frameworks (MOFs), open metal site MIL‐101(Cr), organocatalyst
1 | INTRODUCTION
to establish a new and facile method for the surface
grafting of porous coordination polymer to catalytic appli-
Post‐synthesis modification (PSM) of metal–organic
framework (MOFs) structures has recently emerged as a
versatile tool to prepare tailored MOFs in chemical
transformation for various applications in gas storage and
separation, sensors/biosensor, drug delivery and heteroge-
neous catalysis.[1–4] Engineering of metal–organic frame-
work structures, to achieve bifunctional MOFs, with
strong Lewis acid sites via grafting of coordinated ligands
makes them excellent candidates as bifunctional heteroge-
neous catalysts.[5,6] Chui et al. reported that the channel
linings of a hybrid inorganic–organic framework can be
chemically functionalized.[7] Kitagawa and co‐worker
have proposed two smart strategies for immobilization of
coordinatively unsaturated sites (CUSs)[8] and introduc-
tion of functional organic sites[9] to decorate channel sur-
faces of bifunctional MOFs for organic synthesis.
Recently, we have reported synthesis of open metal site
OMS‐MOF of OMS‐Cu(BDC) toward the direct grafted of
shift‐base [pyridyl salicylimine (Py‐SI)] on open metal site
MOF and complexation of that with Pd ions and demon-
strated catalytic application of PdII@Cu(BDC)/Py‐SI for
Suzuki cross‐coupling reaction. [10] The challenge was then
cation an attractive goal.
Multicomponent reactions (MCRs) such as
Biginelli,[11,12]
Passerini,[13,14]
Ugi,[15,16]
and
Hantzsch[12,16] play an important role in organic chemis-
try because of their to synthesize small drug‐like mole-
cules.[17] Multicomponent Hantzsch reaction are a very
important class of heterocyclic compound that attracted
much attention because they possess their potential bio-
logical and pharmaceutical activities.[18] The heterocyclic
ring
of
1,4‐Dihydropyridine
(1,4‐DHPs)
and
polyhydroquinolines are among the most widely used
wide range of biological and pharmaceutical activities
such as anticancer, hepatoprotective, antiatherosclerotic,
antitumor, antidiabetic activity, vasodilator and treat-
ment of Alzheimer's disease.[19–21] A number of solid
materials as supports have broadly been investigated for
the synthesis of polyhydroquinolines such as
Mn@PMO‐IL,[22] Ni(II)‐Vanillin‐MCM‐41,[23] Co3O4‐
CNTs,[24] HY‐Zeolite,[25] and Glucosulfonic acid
immobilized on Fe3O4 (GSA@MNPs)[26] have been used
to facilitate these reactions. We have recently reported
on the preparation of SBA‐15/SO3H nanoreactor as a
Appl Organometal Chem. 2018;e4370.
wileyonlinelibrary.com/journal/aoc
Copyright © 2018 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4370

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ROSTAMNIA ET AL.
highly efficient solid acidic catalyst for the synthesis of
polyhydroquinolines.[27] We then developed catalytic
applications of magnetic nanoparticles γ‐Fe2O3 for syn-
thesis of polyhydroquinolines via domino Knovenagel‐
Michael‐cyclization coupling reactions.[28] Although
interesting results have been achieved for the MCR
condensation reaction, the development of new synthesis
method and synthesis nanoreactor as an efficient
recyclable solid catalyst for this purpose remains an
attractive goal and the development of the mild and
environmentally friendly method for polyhydroquinoline
skeleton remains highly desirable for organic synthesis.
Herein we have demonstrated MIL‐101(Cr) as an
efficient open metal site of coordination framework
[OMS‐MIL‐101(Cr)] toward the direct grafting ethylene
diamine with PSM technique in an oven/vacuum. The
bifunctional organocatalyst shows excellent catalytic
activity in short reaction time and can be recycled up to
forth catalytic cycles without apparent loss of activity
(Figure 1).
Electrothermal 9100 apparatus. The 1H and 13CNMR
spectra were measured (CDCl3) with a Bruker AVANCE
300 spectrometers at 300.13 and 75.46 MHz, respectively.
2.2 | Synthesis and activation of open
metal site Cr‐MOF [OMS‐MIL‐101(Cr)]
MOFs of MIL‐101(Cr) was synthesis under hydrothermal
conditions according to the literature reported method[29]
with some minor modification. In a typical preparation,
equimolar quantities of Cr(NO3)2.9H2O (6 mmol, 2.4 g)
and terephthalic acid (H2BDC: 6 mmol, 0.978 g) and
1.2 ml of 5 M hydrofluoric acid (HF) (6 mmol) in 30 ml
H2O were dissolved by sonicate and the it was stirred
for 1 h. This solution was placed in a Teflon‐lined
autoclave and put it in an oven at 220 °C for 8 h (rate
of furnace 1 °C/min). Then after the reaction, the Teflon‐
lined autoclave cooled slowly at a rate of 1 °C/min to
room temperature. The green precipitated solid was col-
lected, and washed with H2O and DMF. To remove
unreacted H2BDC and purified by double treatment with
DMF at 70 °C for 3 h and then triple treatment with hot
ethanol for 2 h. The MIL‐101(Cr) was activated under
oven/vacuum at 423 K for 12 h to obtain open metal site
MOF structure as named OMS‐MIL‐101(Cr). The OMS‐
MIL‐101(Cr) was then characterized using a variety of
different techniques.
2 | EXPERIMENTAL
2.1 | Chemicals and apparatus
All the chemicals were obtained commercially from
Sigma‐Aldrich, Merck (Germany) and Fluka (Switzer-
land), they were used without further purification.
Fourier transform infrared (FT‐IR) spectra were obtained
using a Shimadazu IR‐640 spectrometer, absorbencies are
reported in cm−1. Homogeneous stirring was done by
ultrasonic (Ultrasonic Homogenizer‐model APU500
Advanced Equipment Engineering Company‐Adeeco,
Iran). Melting points were compiled based on an
2.3 | Synthesis of ED/MIL‐101(Cr)
For synthesis of ED/MIL‐101(Cr), 1 g of synthesized
dehydrated Cr‐MOF of OMS‐MIL‐101(Cr) was stirred in
30 ml of dry toluene at the 90 °C for 60 min. Then 0.3 g
of pure ethylene diamine (ED) ≥99% in 15 ml ultra‐dry
FIGURE 1 Schematic synthetic process of ED‐MIL‐101(Cr)

ROSTAMNIA ET AL.
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toluene was added drop‐wise to the mixture at same tem-
perature. After 12 h, the solid product was separated
through filtration, washed with CH2Cl2 and dried at
373 K overnight in vacuum.
post‐synthetic modification strategy was employed for
the rapid and facile introduction of primary alkyl amino
group.[34] Saikia et al. synthesized MIL‐101(Cr)‐SO3H
using
a post‐synthetic modification approach and
employed as a heterogeneous catalyst for one‐pot three
component reactions.[35] Herein, in our current method,
MIL‐101(Cr) was prepared by using chrome nitrate and
terephthalic acid in solvothermal conditions, which it
was then activated at 423 K under vacuum to obtain
OMS‐MIL‐101(Cr). Then, the OMS‐MOFs reacted with
ethylene diamine in ultra‐dried toluene to coordination
ethylene diamine to unsaturated Cr‐cluster site of acti-
vated MIL‐100(Cr) (Scheme 1).
The powder XRD patterns (PXRD) of MIL‐101(Cr)
and ED/MIL‐101(Cr) are presented in Figure 2. The
XRD patterns of our synthesized MIL‐101(Cr) matched
well with those reported in the literature confirming the
formation of MIL‐101(Cr)[36] The pattern of the ethylene
diamine grafted MOF materials exhibits a very similar
profile with the pattern of the as‐synthesized MIL‐
101(Cr) and is composed of main diffraction peaks of
the MOF, confirming the structures of MIL‐101 (Cr)
retained intact with no apparent loss of crystallinity, but
with some slight decreases of peak intensities with the
increase of ethylene diamine contents, due to the partial
filling by the grafting guest molecules.
2.4 | General procedure for the synthesis
of polyhydroquinolines
A mixture of aldehyde (1 mmol), dimedone (1 mmol),
β‐ketoecters (1.2 mmol) and ammonium acetate
(1.5 mmol) in 3 ml hot ethanol for the certain period of
time in presence of ED/MIL‐101(Cr) (0.5 g, 4 mol%).
The progress of reaction was monitored by TLC. After
completion of the reaction, the product was extracted
from reaction mixture with acetone by several times,
then evaporated solvent and the residue was purified by
column chromatography and the product. All products
and characterized by comparison of their physical and
1H and 13C spectra with those of already reported (see
Supporting Information).
3 | RESULT AND DISCUSSION
Mesoporous Open metal site MOFs (OMS‐MOFs) of
MIL‐101(Cr) with Cr3O+7 clusters and terephthalic acid
(1,4‐H2BDC) as a linker, a three‐dimensional chromium
(III) terephthalate MOF, is outstanding due to its high
thermal and chemical stability and its large BET and
Langmuir surface area.[29,30] This structure has two types
zeotypic MTN network with free diameters of ca. 29 and
34 Å accessible through two microporous windows of
ca. 12 and 16 Å.[31,32] Also OMS‐MIL‐101(Cr) with
unsaturated cluster of Cr3O+7 are ideal platform for
post‐synthetic modification (PSM) reactions,[33] and
therefore is an interesting candidate for catalytic aims.
Wang and co‐worker have recently reported a simple
Figure 3 shows the FT‐IR spectra of the bare
MIL‐101(Cr) compound compared with the sample after
ethylene diamine (ED) grafting. As for MIL‐101(Cr),
strong peaks at 1395 cm−1 symmetric and 1620 cm−1
asymmetric vibration are corresponding to carboxylate
presence in the structured of MOF. The ν(NH) and
ν(CH) stretching regions demonstrated the presence of
ED in framework. It's worth noting that the observed
aliphatic C‐H stretching vibrations (2800–2950 cm−1
)
are shifted to larger values and appears a new peak at
3150 cm−1 (shows frequencies of the N‐H group of the
SCHEME 1 Schematic illustration for the preparation of ED/MIL‐101(Cr)

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ROSTAMNIA ET AL.
FIGURE 2 PXRD patterns of the MIL‐101(Cr) and ED/MIL‐101(Cr)
FIGURE 3 FT‐IR spectrum of MIL‐101(Cr) (brown) and ED/MIL‐101(Cr) (blue)
ED ligand), as observed when the ED is coordinated to an
open metal site of Cr‐MOF.[31,37] Also, according to the
hydroxyl group (appear 3578 cm−1) the OH group show
in the ED/MIL‐101(Cr).
Scanning electron microscopy (SEM) and energy dis-
persive X‐ray spectroscopy (EDX) were also used to charac-
terize the morphology and composition of the MIL‐101(Cr)
and ED/MIL‐101(Cr) materials. Figure (4a and b) shows a
FESEM micrograph of the as‐synthesized MIL‐101(Cr) and
modified MIL‐101(Cr) with ED demonstrating a typical
octahedral shape and a particle size ranging from 2 to
3μm. After modification with ED, ED‐MIL‐101 shows a
similar particle size. However, it can be clearly seen that
the surfaces of the ED/MIL‐101 tend to be rougher and
octahedral shape becomes fuzzy. This can be due to the
reason that morphology of crystals suffer from a slight

ROSTAMNIA ET AL.
5 of 9
damage during the modifying process. SEM–EDX analysis
were performed for the synthesized ED/MIL‐101 material.
Based on this analysis, Cr, C, O and N atoms exist in the
structure of ED/MIL‐101(Cr) which N atoms existence
exhibit the successful grafting of ED to MOF (Figure 4c).
According to CHNS analysis of the ED‐MOF, the wt% of
N was 0.82%.
Figure (5a and b) shows a transmission electron
microscopy (TEM) micrograph of the as‐synthesized
MIL‐101(Cr) and modified MIL‐101(Cr) with ED demon-
strating a typical octahedral morphology, although the
particles are not uniform in size. Moreover, in the TEM
images of an individual octahedral shows the clear and
regular framework. The SEM and TEM micrograph of
the ED/MIL‐101(Cr) confirms stability of structure and
even morphology after post‐modifications ED grafting
reaction.
FIGURE 5 TEM images of MIL‐101(Cr) (a) and ED/MIL‐
101(Cr) (b)
We have explored the catalytic activity of the
synthesized ED/MIL‐101(Cr) in a MCRs condensation
between aromatic aldehydes, dimedone, β‐ketoecters
and ammonium acetate. The effect of different factors
on the mentioned condensation reaction has been moni-
tored by taking the condensation between benzaldehyde,
dimedone, methyl acetoacate and ammonium acetate as a
model reaction (Table 1). To optimize the reaction condi-
tions, when the reaction was carried out in the absence of
MOF no product was formed. For bare MIL‐101(Cr),
moderate yield of desired products was proud and in the
case of ED/MIL‐101(Cr) using a good yield of product
was formed, which confirming the bifunctional ability
of Lewis acidic of Cr and organocatalytic behavior of free
‐EtNH2 moiety on the framework structure to perform
the MCRs condensation. The best yield and selectivity
were obtained when the reaction was carried out in the
presence of 4 mol% of catalyst in hot ethanol (Table 1,
entry 3). This may be due to the increase in the number
of active sites on the ED/MIL‐101(Cr) with increase in
FIGURE 4 FESEM images of MIL‐101(Cr) (a), ED/MIL‐101(Cr)
(b) and corresponding EDX spectra (c)

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ROSTAMNIA ET AL.
TABLE 1 Optimization of the reaction condition in Hantzsch coupling reactiona
Entry
mol%
Solvent
Time (h)
Temp. (°C)
Yield (%)[b]
1
‐
2
4
4
4
4
4
4
4
4
4
EtOH
EtOH
EtOH
EtOH
MeOH
H2O
2
80
80
80
80
80
80
80
80
80
25
100
<5
55
2
2
3
2
>98
92
4
1.5
2
5
90
6
2
85
7
CH3CN
DMF
2
80
8
2
75
9
Toluene
EtOH
EtOH
2
70
10
11
2
90
2
98
aReaction condition: dimedone (1 mmol), benzaldehyde (1 mmol), methyl acetoacetate (1.2 mmol), NH4OAc (1.5 mmol) in 3 ml of solvents.
bIsolated yield.
MOF‐catalyst dosage. In the next step, the effect of polar
and nonpolar solvent such as H2O, MeOH, CH3CN, DMF
and toluene on the reaction progress was also monitored
(Table 1, entry 3, 5–9). The influence of the temperature
on the Hantzsch condensation reaction has been
invested. The results show that at room temperature the
reaction cannot proceed even running the reaction for
24 h, while with increase in the temperature (Table 1,
entry 10, 11) the amount of desired product increases
with a maximum yield. Therefore, taking all these
aspects, we have chosen 80 °C as the optimum tempera-
ture in reaction.
After examination of various conditions on the
reaction progress, we explored the general applicability
of the ED‐MOF organocatalyst with aryl aldehydes
containing electron withdrawing or donating substituents
and variety of β‐ketoecters, and results are presented in
Table 2. It has been observed that ED/MIL‐101(Cr) is very
active in all kind aryl aldehydes and β‐ketoecters. As
shown in Table 2, all the derivatives electron
withdrawing or donating were in good to excellent yields.
Overall ED/MIL‐101(Cr) has been established to be
highly flexible organocatalyst for the single‐pot four‐
component Hantzsch condensation reaction.
washed it with ethyl acetate for several times and then
dried in an oven/vacuum at 100 °C for 6 h. As shown in
Figure 6, this catalyst could be recycled over five runs
without any significant loss of its catalytic activity.
A comparison of the efficiency and catalytic perfor-
mance of ED/MIL‐101(Cr) with several previous methods
for single‐pot synthesis of polyhydroquinolines is pre-
sented in Table 3. It turned out that organocatalyst ED/
MIL‐101(Cr) gave better results than the results than
the other homogeneous and heterogeneous catalysts
listed in Table 3 in terms of reaction rate and yield. The
advantages of our method are short reaction time, high
selectivity and mild conditions and good to excellent
yields (Table 3).
The plausible mechanism for this reaction is shown in
(Scheme 2). First dimedone is converted to an enamine
using ED/MIL‐101(Cr) and reacted to activated aryl alde-
hyde to give intermediate I. On the other hand, the active
β‐ketoesters by the ED/MIL‐101(Cr) as an organocatalyst
affords enamine form. Afterword, the intermediate I and
mentioned enamine react with each other give intermedi-
ate II. Intermediate II is converted to III by addition of
ammonia, and intermediate
II affords final
polyhydroquinoline by intermolecular nucleophilic cycli-
zation process.[38,39] The organocatalyst ED/MIL‐101(Cr)
as an organocatalyst, play a major role here by pre‐associ-
ating with the carbonyl group and amine‐based
organocatalytic capability, consequently accelerates the
additional steps.
The recyclability and recovery of the ED/MIL‐
101(Cr) bifunctional organocatalyst was also monitored
by taking the condensation reaction for model reaction.
After completion of the reaction, the catalyst was recov-
ered from the reaction mixture through filtration,

ROSTAMNIA ET AL.
7 of 9
TABLE 2 Synthesis of various polyhydroquinolines in the presence of ED/MIL‐101(Cr)a
Product
Ar
OR
Time (h)
Yield (%)
a
b
c
d
e
f
Ph‐
CH3O‐
2
98
95
90
89
93
90
94
90
86
4‐Cl‐C6H5‐
2‐Cl‐C6H5‐
2‐Me‐C6H5‐
4‐MeO‐C6H5‐
2‐Me‐C6H5‐
2‐Cl‐C6H5‐
4‐Cl‐C6H5‐
4‐O2N‐C6H5‐
CH3O‐
2
CH3O‐
2
CH3O‐
2
CH3O‐
2.5
2.5
2
CH3CH2O‐
CH3CH2O‐
CH3CH2O‐
CH3CH2O‐
g
h
i
2
2
aReaction condition: dimedone (1 mmol), benzaldehyde (1 mmol), methyl acetoacetate (1.2 mmol), NH4OAc (1.5 mmol) in 3 mL of ethanol for 2–2.5 h at 80 °C.
FIGURE 6 Recyclability and 5th SEM of
ED/MIL‐101(Cr) in model Hantzsch
reaction
TABLE 3 Comparison on the efficiency of ED/MIL‐101(Cr) for the Hantzsch reaction
Entry
Catalyst
Reaction condition
Time (h)
Yield (%)
Ref.
[38]
1
Bi(NO3)3.5H2O
Al2(SO4)3
EtOH/80 °C
EtOH/reflux
C10F18/60 °C
EtOH/r.t.
4
92
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[12]
[48]
2
4
92
3
Hf(Npf)4
3
95
4
Sc(OTf)3
4
93
5
Yb(OTf)3
EtOH/r.t.
5
90
6
Pd nanoparticle
Gd(OTf)3
THF/reflux
EtOH/r.t.
4
89
7
5
89
8
p‐Toluene sulfonic acid
Ce(IV) ammonium nitrate
Na‐HSO4‐SiO2
IRMOF‐3
EtOH/r.t
2
93
9
EtOH/r.t
2
94
10
11
12
13
CH3CN/r.t.
S.F/70 °C
5–6
8
75–90
85
PPh3
EtOH/reflux
EtOH/80 °C
2–5
2
72–96
98
ED/MIL‐101(Cr)
This work

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ROSTAMNIA ET AL.
SCHEME 2 Plausible mechanism for ED‐MIL‐101(Cr) catalysis of Hantzsch reaction
[8] S. Kitagawa, S.‐i. Noro, T. Nakamura, Chem. Commun. 2006,
7, 701.
4 | CONCLUSIONS
[9] S. Hasegawa, S. Horike, R. Matsuda, S. Furukawa, K.
Mochizuki, Y. Kinoshita, S. Kitagawa, J. Am. Chem. Soc.
2007, 129, 2607.
In this work, ethylene diamine functionalized
MIL‐101(Cr) have been synthesized by adopting a post‐
synthesis modification technique using ethylene diamine
(ED) as ligand reagent. The synthesized ED/MIL‐101(Cr)
exhibits a high surface area and thermal stability and
thus can be effectively employed as a organocatalyst for
single‐pot four‐component condensation reaction
between aryl aldehydes, dimedone, β‐ketoecters and
ammonium acetate in aqueous medium to synthesize
polyhydroquinolines. The proposed catalyst could be sep-
arated from the reaction mixture by common filtration,
and could be reused next run a without a significant loss
of catalytic activity.
[10] S. Rostamnia, H. Alamgholiloo, X. Liu, J. Colloid Interface Sci.
2016, 469, 310.
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ORCID
Sadegh Rostamnia http://orcid.org/0000-0001-6310-8754
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