Cascade synthesis of fused polycyclic dihydropyridines by Ni–Zn–Fe hydrotalcite (HT) immobilized on silica-coated magnetite as magnetically reusable nanocatalyst

Article abstract of DOI:10.1007/s11164-019-03764-w

Abstract: An efficient ecofriendly approach has been developed for one-pot multicomponent synthesis of fused polycyclic dihydropyridine (DHP) derivatives. Tandem condensation of aromatic aldehydes, 4-hydroxycoumarin, and ammonium acetate was performed usi

Full text of DOI:10.1007/s11164-019-03764-w

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-019-03764-w
Cascade synthesis of fused polycyclic dihydropyridines
by Ni–Zn–Fe hydrotalcite (HT) immobilized on silica‑coated
magnetite as magnetically reusable nanocatalyst
Masumeh Gilanizadeh1 · Behzad Zeynizadeh1
Received: 26 October 2018 / Accepted: 30 January 2019
©
Springer Nature B.V. 2019
Abstract
An efcient ecoꢀriendly approach has been developed ꢀor one-pot multicomponent
synthesis oꢀ ꢀused polycyclic dihydropyridine (DHP) derivatives. Tandem condensa-
tion oꢀ aromatic aldehydes, 4-hydroxycoumarin, and ammonium acetate was per-
ꢀ
ormed using heterogeneous core–shell Fe O @SiO @Ni–Zn–Fe hydrotalcite under
3 4 2
solvent-ꢀree conditions, obtaining the corresponding products in high to excellent
yield. The nanomagnetic layered double hydroxide was characterized using scanning
electron microscopy coupled with energy-dispersive X-ray analysis (SEM–EDX),
powder X-ray diꢁraction analysis, transmission electron microscopy (TEM), and
the Brunauer–Emmett–Teller technique. Moreover, the recoverability oꢀ the green
hydrotalcite was investigated by TEM and SEM analyses. The current research high-
lights the development oꢀ a green method ꢀor synthesis oꢀ DHPs without use oꢀ haz-
ardous solvents under mild conditions.
Graphical abstract
Extended author inꢀormation available on the last page oꢀ the article
Vol.:(012
1
3456789)
3

M. Gilanizadeh, B. Zeynizadeh
Keywords Multicomponent reactions · Green synthesis · Nanocatalyst · Fe O @
3
4
SiO @Ni–Zn–Fe LDH · Polycyclic dihydropyridines
2
Introduction
Catalytic systems have been applied in various organic transꢀormations to improve
product yields and reaction rates [1]. Homogeneous catalysts exhibit better prop-
erties in many reactions; however, the removal oꢀ the catalyst aꢀter completion
oꢀ the reaction causes environmental and economic problems [2]. To overcome
the problems with these types oꢀ reaction, heterogeneous catalysts can be used as
efcient agents in various organic conversions [3–9]. Diꢁerent heterogeneous rea-
gents have been utilized to ꢀacilitate many reactions in organic synthesis [10–17].
Hydrotalcites (HTs) as clay minerals with anionic nature [18, 19] can be syn-
thesized by using economic and simple procedures. However, such preparation
oꢀ HTs using general methods results in powder samples with aggregated surꢀace
area, without sufcient control oꢀ morphology or particle size. The selectivity
and activity oꢀ LDHs can be been improved by combining them with magnetic
nanoparticles (MNPs), enabling easily separation aꢀter completion oꢀ the reaction
[
ꢀ
20–28]. Moreover, hydrotalcites oꢁer various advantages as environmentally
riendly materials, and they are simply used in many ꢂelds [29–34].
In modern processes, multicomponent reactions (MCRs) have been widely
applied as a powerꢀul tool ꢀor synthesis oꢀ organic compounds with attractive bio-
logical and pharmaceutical ꢀeatures [35]. These types oꢀ reaction have the ability
to produce structurally complex molecules in a one-pot synthetic process without
isolation oꢀ intermediates [36]. Thereꢀore, designing new MCRs toward synthe-
sis oꢀ a large variety oꢀ heterocycles such as polycyclic 1,4-dihydropyridine (1,4-
DHP) derivatives under green conditions is essential ꢀor access to such complex
heterocycle scaꢁolds in one pot.
As a major category oꢀ heterocyclic materials with nitrogen atoms and intrigu-
ing molecular structures, 1,4-DHPs exhibit signiꢂcant pharmacological efciency
[
37–40]. These types oꢀ bioactive compound exhibit diverse activities such as
antimicrobial [41], anticancer [42], antitumor [43], antimalarial [44], and antidi-
arrheal eꢁects [45, 46]. Many synthetic procedures have been reported ꢀor prepa-
ration oꢀ ꢀused dihydropyridines [47–58]. However, the reported systems suꢁer
ꢀ
rom some limitations, including use oꢀ expensive catalysts, or hazardous and
toxic solvents, as well as severe reaction conditions. Consequently, development
oꢀ new, environmentally ꢀriendly methods has been considered using efcient
and recoverable catalysts under green conditions ꢀor synthesis oꢀ pharmaceutical
ꢀ
used polycyclic dihydropyridine derivatives.
Following previous research using magnetic LDHs in multicomponent reac-
tions [59], we present herein an efcient approach to produce DHPs by one-pot
condensation oꢀ aromatic aldehydes, 4-hydroxycoumarin, and ammonium acetate
using recyclable nanomagnetic LDH (Scheme 1).
1
3

Cascade synthesis of fused polycyclic dihydropyridines by…
Scheme 1 One-pot synthesis oꢀ DHPs using nanomagnetic Fe O @SiO @Ni–Zn–Fe LDH
3
4
2
Results and discussion
Synthesis and characterization of catalyst
Ni–Zn–Fe LDH immobilized on silica-layered magnetite was prepared by a three-
step process (Scheme 2). The green magnetic hydrotalcite was characterized by
SEM, EDX, XRD, TEM, and Brunauer–Emmett–Teller (BET) analyses.
Figure 1 shows the size and morphology oꢀ the prepared Fe O @SiO @
3
4
2
Ni–Zn–Fe layered double hydroxide. The SEM images oꢀ the synthesized magnetic
LDH show granules and almost spherical nanoparticles in the nanocomposite sys-
tem. The images show a size distribution ꢀrom 17 to 36 nm, corresponding exactly
to the production oꢀ green mesoporous hydrotalcite.
Figure 2 illustrates the corresponding elements and the EDX spectrum oꢀ the pre-
pared Fe O @SiO @Ni–Zn–Fe LDH. Energy-dispersive X-ray spectroscopy reveals
3
4
2
the presence oꢀ Fe, O, Si, Ni, and Zn elements in the synthesized nanocatalyst.
Figure 3 shows the crystalline structure oꢀ the Fe O @SiO @Ni–Zn–Fe LDH
3
4
2
obtained using X-ray diꢁraction analysis. The XRD pattern illustrates diꢁraction
peaks at 2θ=11.2°, 23.1°, 34.4°, 36.6°, 39.1°, 42.2°, 46.6°, 48.9°, 50.1°, 60.1°, and
6
1.2°, corresponding to (003), (006), (102), (104), (105), (0011), (0012), (109),
(
0013), (110), and (113) reꢃections oꢀ the prepared LDH with hexagonal crystal
structure. The planes are in good agreement with the Inorganic Crystal Structure
Database (ICSD) reꢀerence pattern 00-049-0722 ꢀor iron nickel chloride hydrox-
ide hydrate. The characteristic ꢀeatures oꢀ LDH-like materials are represented by
the symmetric and sharp reꢃections oꢀ (003), (006), (110), and (113) crystal planes
[
62]. The XRD pattern also shows all the diꢁraction peaks oꢀ Fe O at 2θ=30.2°,
3
4
3
5.5°, 43.3°, 53.7°, 57.2°, and 62.9°, related to (220), (311), (400), (422), (511),
Scheme 2 Preparation oꢀ nanomagnetic Fe O @SiO @Ni–Zn–Fe LDH
3
4
2
1
3

M. Gilanizadeh, B. Zeynizadeh
Fig. 1 SEM images oꢀ nanomagnetic LDH
and (440) crystal planes, in agreement with the standard magnetite structure in Joint
Committee on Powder Diꢁraction Standards (JCPDS) card no. 65-3107 [63, 64].
Furthermore, using the Debye–Scherrer equation (D=kλ/βcosθ), the mean crystal-
line size oꢀ Fe O @SiO @Ni–Zn–Fe LDH was calculated to be about 24.17 nm. In
3
4
2
this equation, β represents the ꢀull-width at halꢀ-maximum intensity (FWHM), being
0
.32° (0.006 rad) at θ=5.786°.
Figure 4 presents TEM images oꢀ the prepared Fe O @SiO @Ni–Zn–Fe LDH,
3
4
2
revealing dark nanoparticle cores surrounded by the LDH shell.
Figure 5 displays the nitrogen adsorption–desorption isotherm oꢀ the
green Fe O @SiO @Ni–Zn–Fe LDH. The surꢀace area and pore size distri-
3
4
2
bution oꢀ the synthesized nanocatalyst were investigated using the BET and
1
3

Cascade synthesis of fused polycyclic dihydropyridines by…
Element Weight percent Atom percent
(
%)
(%)
65.83
11.29
10.14
9.35
O
Si
Fe
Ni
Zn
38.91
11.71
20.91
20.28
8.19
3.39
Fig. 2 Elemental composition and EDX spectrum oꢀ nanomagnetic LDH
Fig. 3 XRD pattern oꢀ nanomagnetic LDH
Barrett–Joyner–Halenda (BJH) methods. The calculated BET speciꢂc surꢀace
2
−1
3
−1
area (S ) and pore volume (V ) were 90.716 m g and 0.3187 cm g , respec-
BET
p
tively. The activity and selectivity oꢀ the nanocatalyst are increased due to its high
surꢀace-to-volume ratio. The average pore size oꢀ the green LDH was determined
1
3

M. Gilanizadeh, B. Zeynizadeh
Fig. 4 TEM images oꢀ nanomagnetic LDH
Fig. 5 Nitrogen adsorption–des-
orption isotherm oꢀ nanomag-
netic LDH
Adsorption / desorption isotherm
3
2
1
00
00
00
0
0
0.5
p/p0
1
ADS
DES
1
3

Cascade synthesis of fused polycyclic dihydropyridines by…
to be 14.054 nm using the Barrett–Joyner–Halenda (BJH) method, corresponding
to the size range oꢀ mesoporous materials.
Synthesis of fused polycyclic dihydropyridines
Polycyclic dihydropyridine derivatives have great pharmaceutical properties and
exhibit a wide variety oꢀ biological activities. In the present research, an efcient
green method was developed to prepare DHPs in accordance with the importance
oꢀ this category oꢀ compounds. Domino condensation oꢀ benzaldehyde (0.5 mmol),
4
-hydroxycoumarin (1 mmol), and ammonium acetate (3 mmol) was selected as
model reaction. At the beginning oꢀ the research, the model reaction was heated
without catalyst; aꢀter 2 h, only trace amount oꢀ product was ꢀormed. In the next
step, the eꢁect oꢀ Fe O @SiO @Ni–Zn–Fe LDH on the model reaction was stud-
3
4
2
ied; the desired product ꢀormed quickly when using the magnetic nanocatalyst. The
eꢁects oꢀ diverse temperatures, solvents, and amounts oꢀ catalyst were evaluated
to optimize the conditions. The eꢁect oꢀ temperature was also investigated using
the model reaction at gradually increasing temperatures ꢀrom room temperature to
1
10 °C. The results indicated that increase oꢀ the reaction temperature enhanced the
perꢀormance oꢀ the reaction, with the maximum yield being obtained in the range oꢀ
00–110 °C (Fig. 6). The eꢁect oꢀ diꢁerent solvents on the model reaction was then
studied. The ꢂndings conꢂrmed that the best result was obtained without solvent
Fig. 7). Also, the eꢁect oꢀ the amount oꢀ catalyst on the model reaction was studied
1
(
to determine the exact concentration oꢀ catalyst (Fig. 8). The amount oꢀ catalyst was
increased ꢀrom 0 to 50 mg, with continuous growth in yield being observed. How-
ever, increasing the catalyst content to 60 mg did not show any ꢀurther improvement
in the perꢀormance oꢀ the reaction. Thereꢀore, 50 mg oꢀ catalyst was determined to
be optimum amount with the best activity. The results showed that use oꢀ 50 mg
oꢀ Fe O @SiO @Ni–Zn–Fe LDH was sufcient to achieve condensation between
3
4
2
4
-hydroxycoumarin (1 mmol), benzaldehyde (0.5 mmol), and ammonium acetate
3 mmol) under solvent-ꢀree conditions (100–110 °C) within 10 min (Table 1, entry
).
(
1
Fig. 6 Eꢁect oꢀ temperature on
Temperature (°C)
Yield (%)
model reaction
1
20
00
1
05
1
100
8
5
8
0
80
6
5
6
0
4
5
50
2
5
30
4
0
1
0
2
0
0
1
2
3
4
5
1
3

M. Gilanizadeh, B. Zeynizadeh
Fig. 7 Eꢁect oꢀ solvent on
Yield (%)
80
Time (min)
100
model reaction
1
00
80
80
6
0
60
60
5
0
4
0
30
3
0
3
0
3
0
3
0
2
0
0
10
1
00
100
100
8
6
4
2
0
0
0
0
0
7
0
80
5
0
60
1
0
0
10
20
30
40
50
60
70
Catalyst amount (mg)
Fig. 8 Eꢁect oꢀ amount oꢀ catalyst on model reaction
To investigate the scope and generality oꢀ the green Fe O @SiO @Ni–Zn–Fe
3
4
2
LDH, the multicomponent condensation was ꢀurther studied in the reaction oꢀ struc-
turally diverse aromatic aldehydes, 4-hydroxycoumarin, and ammonium acetate to
produce corresponding polycyclic dihydropyridine derivatives under the optimized
conditions. The summarized results in Table 1 show that all the condensations
were carried out successꢀully within 10–40 min to aꢁord the products in yield oꢀ
7
5–88 %. The results in this table also show that the products are similar to those
reported in literature in terms oꢀ their spectral and physical data.
Although the precise mechanism oꢀ this synthetic method is not clear, we propose
the ꢀollowing plausible mechanistic pathway ꢀor ꢀormation oꢀ ꢀused polycyclic dihy-
dropyridines by multicomponent condensation oꢀ aromatic aldehydes, ammonium
acetate, and 4-hydroxycoumarin (Scheme 3). First, all the substrates are activated
by active sites oꢀ the nanocatalyst. Second, aromatic aldehyde is attacked by acti-
vated methylene group to ꢀorm C–C bond, then dehydration oꢀ intermediate 1 occurs
instantly to obtain the arylidene derivative. On the other hand, an additional mol-
ecule oꢀ 4-hydroxycoumarin reacts with ammonium acetate as a source oꢀ ammonia
1
3

Cascade synthesis of fused polycyclic dihydropyridines by…
Table 1 One-pot synthesis oꢀ ꢀused polycyclic dihydropyridines using nanomagnetic Fe O @SiO @Ni–
3
4
2
Zn–Fe LDHa
Time Yield
Mp (°C)
Entry
Substrate
Product
(%)b
(
min)
Found
Reported [Ref.]
209 [58]
O
O
O
O
CHO
1
2
O
O
O
O
10
85
208-210
N
H
CHO
Cl
Cl
13
15
85
87
275-277
274-276
275-278 [57]
275-276 [56]
N
H
Cl
CHO
O
O
3
Cl
O
O
N
H
Cl
CHO
Cl
O
O
O
O
Cl
4
5
10
20
88
87
221-223
257-259
-
Cl
O
O
O
O
N
H
Me
CHO
O
258 [56]
Me
O
N
H
NO2
CHO
O
O
6
7
8
18
10
15
81
88
75
240-242
217-219
203-205
242-244 [56]
216-218 [37]
-
O
2
N
O
N
H
NO2
O
CHO
O
O
NO2
N
H
Cl
NO2
O
CHO
O
Cl
O
O
NO2
N
H
H
N
O
O
O
O
CHO
O
O
O
O
9
40
75
>300
-
OHC
N
H
1
3

M. Gilanizadeh, B. Zeynizadeh
Table 1 (continued)
a
All reactions carried out with 4-hydroxycoumarin (1 mmol), aromatic aldehyde (0.5 mmol), ammonium
acetate (3 mmol), and Fe O @SiO @Ni–Zn–Fe LDH (50 mg) under solvent-ꢀree conditions in oil bath
3
4
2
(
100–110 °C)
b
Yields reꢀer to isolated pure products
Scheme 3 Plausible mechanism ꢀor synthesis oꢀ ꢀused polycyclic dihydropyridines using nano-Fe O @
3
4
SiO @Ni–Zn–Fe LDH
2
1
3

Cascade synthesis of fused polycyclic dihydropyridines by…
to produce β-aminobenzopyran-2-one 2. Subsequently, the two intermediates 1 and
2
react via Michael-type addition. Finally, the ꢀused polycyclic dihydropyridine
derivative is obtained aꢀter dehydration oꢀ the product.
Recycling of Fe O @SiO @Ni–Zn–Fe LDH
3
4
2
The economical attractiveness oꢀ this approach is the ability to recover the green
nanomagnetic Fe O @SiO @Ni–Zn–Fe LDH at the end oꢀ the reaction. The reus-
3
4
2
ability oꢀ LDH was thus investigated in the condensation oꢀ benzaldehyde, ammo-
nium acetate, and 4-hydroxycoumarin at the optimized conditions. Aꢀter reaction
completion, hot ethanol was added to the mixture, and the catalyst was separated
magnetically, washed with diethyl ether, and dried ꢀor reuse in the next run. The
results indicated that the nanocatalyst could be recovered several times without sig-
niꢂcant loss oꢀ activity (Fig. 9).
Further studies on the recycled nanocatalyst were perꢀormed by SEM (Fig. 10)
and TEM (Fig. 11) analyses. The images revealed that the structure oꢀ the recovered
catalyst was not altered but remained intact.
Experimental
Chemicals and materials were purchased ꢀrom Merck and Fluka Companies. The
FT-IR spectrum was obtained using a Thermo-Nicolet-Nexus 670 spectrophotom-
1
eter. H nuclear magnetic resonance (NMR) spectra were measured on a Bruker
Avance spectrometer (300 MHz). Reaction progress was determined using thin-
layer chromatography (TLC). The morphology oꢀ the nanoparticles was observed
by ꢂeld-emission scanning electron microscopy (FESEM, TESCAN). X-ray diꢁrac-
tion (XRD) patterns were obtained using a PANalytical X’PertPRO diꢁractometer
with Cu K radiation in the scan range between 5° and 80°. Transmission electron
α
microscopy (TEM) images were captured on a Zeiss EM10C microscope at accel-
erating voltage oꢀ 100 kV in each case. Nitrogen adsorption–desorption isotherms
were measured using a BELsorp-mini (BEL, Japan). The speciꢂc surꢀace area, pore
volume, and pore size distribution were obtained using the Brunauer–Emmett–Teller
(
BET) and Barrett–Joyner–Halenda (BJH) methods.
Fig. 9 Catalyst reusability in the
100
model reaction
8
0
6
0
8
5
85
83
83
81
80
4
0
2
0
0
1
2
3
4
5
6
1
3

M. Gilanizadeh, B. Zeynizadeh
Fig. 10 SEM image oꢀ nano-
magnetic LDH aꢀter second
recovery
Fig. 11 TEM images oꢀ nanomagnetic LDH aꢀter second recovery
Synthesis of magnetite (Fe O ) MNPs
3
4
3
+
2+
Nanomagnetite was prepared by chemical coprecipitation oꢀ Fe and Fe chlo-
ride salts [60]. Generally, FeCl ·6H O (5.838 g, 0.0216 mol) and FeCl ·4H O
3
2
2
2
(
2.147 g, 0.0108 mol) were added to H O (100 mL). The reaction content was
2
mixed magnetically in N atmosphere at 85 °C. Aꢀter stirring ꢀor about 10 min,
2
1
0 mL aqueous ammonia (25 wt%) was added, and black precipitate ꢀormed
immediately. The mixture was kept at 85 °C under stirring ꢀor 30 min in N
2
atmosphere, then the resulting mixture was placed at ambient temperature. The
obtained Fe O was cooled down, separated, and washed three times using
3
4
0
.02 M NaCl solution and distilled water.
1
3

Cascade synthesis of fused polycyclic dihydropyridines by…
Preparation of silica‑layered magnetite (Fe O @SiO ) MNPs
3
4
2
Fe O @SiO was synthesized using a previously reported method [61]. Distilled
3
4
2
water (20 mL) was poured into 1.5 g magnetite, and 2-propanol (200 mL) was
added. Next, the mixture was homogenized using ultrasound ꢀor about 30 min, then
5
.36 g polyethylene glycol (PEG), 20 mL H O, 10 mL NH OH (28 wt%), and 2 mL
2 4
tetraethylorthosilicate (TEOS) were added to the suspension. The mixture was kept
at ambient temperature under stirring ꢀor 28 h. The prepared Fe O @SiO was mag-
3
4
2
netically separated and washed with water and ethanol.
Preparation of Ni–Zn–Fe LDH immobilized on silica‑layered magnetite (Fe O @
3
4
SiO @Ni–Zn–Fe LDH)
2
Fe O @SiO @Ni–Zn–Fe LDH was prepared as ꢀollows: 0.25 g Fe O @SiO ,
3
4
2
3
4
2
1
.060 g Na CO (0.01 mol), and 0.160 g NaOH (0.004 mol) were added to
2 3
H O (30 mL) (solution A). Solution B was prepared ꢀrom 1.352 g FeCl ·6H O
2
3
2
(
0.005 mol), 2.617 g Ni(NO ) ·6H O (0.009 mol), and 1.785 g Zn(NO ) ·6H O
3 2 2 3 2 2
(
0.006 mol) in H O (30 mL). Solution A and B were exposed to ultrasound ꢀor
2
3
0 min. The solutions were then added simultaneously to distilled water (30 mL)
under electromagnetic stirring, and the pH value was adjusted to 10 by addition oꢀ
‏
HCl and NaOH solutions. Aꢀter addition, the slurry was ꢂercely stirred at ambient
temperature (30 min), then the suspension was leꢀt ꢀor 20 h at 80 °C. Finally, the
resulting mixture was ꢂltrated and the precipitate was dried (150 °C) to obtain nano-
magnetic Fe O @SiO @Ni–Zn–Fe LDH.
3
4
2
General procedure for multicomponent condensation of benzaldehyde, ammonium
acetate, and 4‑hydroxycoumarin using Fe O @SiO @Ni–Zn–Fe LDH
3
4
2
In a test tube equipped with a magnetic stirrer, a mixture oꢀ benzaldehyde (0.053 g,
.5 mmol), NH OAc (0.231 g, 3 mmol), and 4-hydroxycoumarin (0.162 g, 1 mmol)
0
4
was prepared. Magnetic Fe O @SiO @Ni–Zn–Fe LDH (50 mg) was added, and the
3
4
2
resulting mixture was stirred at 100–110 °C ꢀor 10 min under solvent-ꢀree condi-
tions. Reaction progress was monitored by TLC (n-hexane:EtOAc at 4:2 as eluent).
On reaction completion, hot ethanol (5 mL) was poured into the mixture, and the
nanocatalyst was separated magnetically. The precipitate was collected aꢀter evapo-
ration oꢀ solvent, and the pure product was obtained by recrystallization ꢀrom etha-
nol (entry 1, Table 1, 85 %).
Conclusions
An extremely efcient method ꢀor tandem synthesis oꢀ ꢀused polycyclic dihydropyri-
dine derivatives via multicomponent condensation oꢀ aromatic aldehydes, ammo-
nium acetate, and 4-hydroxycoumarin using nano-Ni–Zn–Fe LDH immobilized on
silica-layered magnetite (Fe O @SiO @Ni–Zn–Fe LDH) was developed. All reac-
3
4
2
tions were perꢀormed under solvent-ꢀree condition within 10–40 min. The prepared
1
3

M. Gilanizadeh, B. Zeynizadeh
nanomagnetic LDH was characterized using SEM, EDX, XRD, TEM, and BET
analyses. The attractive ꢀeatures oꢀ the current protocol include short reaction time,
absence oꢀ hazardous solvents, high catalytic efciency, and the ability to recover
the green nanomagnetic LDH.
Acknowledgements The authors grateꢀully appreciate ꢂnancial support oꢀ this work by the Research
Council oꢀ Urmia University.
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Aꢀliations
Masumeh Gilanizadeh1 · Behzad Zeynizadeh1
*
Masumeh Gilanizadeh
masumehgilanizadeh@gmail.com
1
Faculty oꢀ Chemistry, Urmia University, Urmia 5756151818, Iran
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