Synthesis and characterization of Fe3O4@SiO2@(CH2)3NH(CH2)2O2P(OH)2 and its catalytic application in the synthesis of benzo-[h]quinoline-4-carboxylic acids via a cooperative anomeric based oxidation mechanism

Article abstract of DOI:10.1016/j.mcat.2020.110924

In this study, Fe₃O₄@SiO₂@(CH₂)₃NH(CH₂)₂O₂P(OH)₂ as a new and recoverable nanocatalyst with magnetic properties was synthesized. The characterization of the novel nanocatalyst confirmed by thermo gravimetric analysis/ differential thermal analysis (TGA/DTA), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM) equipped by energy dispersive spectroscopy (EDS), elemental mapping analysis, Fourier transform infrared (FT-IR) spectroscopy and vibrating sample magnetometer (VSM). The impact of Fe₃O₄@SiO₂@(CH₂)₃NH(CH₂)₂O₂P(OH)₂ was carefully considered in the synthesis of benzo-[h]quinoline-4-carboxylic acids via a three component reaction of aryl aldehydes, naphtylamine, and pyrovic acid in the absence of solvent. The suggested mechanism proposed an anomeric based oxidation route for final step of the described synthesis. The described catalyst was recycled and reused without any remarkable decrease in the yield and the reaction time after six runs.

Full text of DOI:10.1016/j.mcat.2020.110924

Molecular Catalysis 489 (2020) 110924
Contents lists available at ScienceDirect
Molecular Catalysis
journal homepage: www.elsevier.com/locate/mcat
Synthesis and characterization of Fe O @SiO @(CH ) NH(CH ) O P(OH)
3
4
2
2 3
2 2
2
2
and its catalytic application in the synthesis of benzo-[h]quinoline-4-
carboxylic acids via a cooperative anomeric based oxidation mechanism
Fatemeh Karimi, Meysam Yarie, Mohammad Ali Zolfigol*
Department of Organic Chemistry, Faculty of Chemistry, Bu-Ali Sina University, Hamedan 6517838683, Iran
A R T I C L E I N F O
A B S T R A C T
In this study, Fe
Keywords:
3
O
4
@SiO
2
@(CH
2
)
3
NH(CH
2
)
2
O
2
P(OH)
2
as a new and recoverable nanocatalyst with magnetic
2
-Aminoethyl dihydrogen phosphate
properties was synthesized. The characterization of the novel nanocatalyst confirmed by thermo gravimetric
analysis/ differential thermal analysis (TGA/DTA), transmission electron microscopy (TEM), field emission
scanning electron microscopy (FESEM) equipped by energy dispersive spectroscopy (EDS), elemental mapping
analysis, Fourier transform infrared (FT-IR) spectroscopy and vibrating sample magnetometer (VSM). The im-
Anomeric based oxidation
Synthesis of benzo-[h]quinoline-4-carboxylic
acid
Fe O @SiO @(CH ) NH(CH ) O P(OH)
3 4 2 2 3 2 2 2 2
Multicomponent reactions
Nanomagnetic catalyst
3 4 2 2 3 2 2 2 2
pact of Fe O @SiO @(CH ) NH(CH ) O P(OH) was carefully considered in the synthesis of benzo-[h]quino-
line-4-carboxylic acids via a three component reaction of aryl aldehydes, naphtylamine, and pyrovic acid in the
absence of solvent. The suggested mechanism proposed an anomeric based oxidation route for final step of the
described synthesis. The described catalyst was recycled and reused without any remarkable decrease in the
yield and the reaction time after six runs.
1. Introduction
noteworthy multicomponent reactions are of challenging issue for re-
searchers [25–29].
A paramount important class of the heterocyclic compounds is
Recently, many organochemists are interested to the use of nano-
particles as heterogeneous catalysts, due to the specific structure of
these catalysts which resulted to improve the efficiency, selectivity and
yields of the catalytic processes. Also, the nanoparticles are different
from bulk materials and represent novel electronic, chemical, magnetic
and mechanical properties. But the separation of nano‐particles from
reaction mixtures is often difficult, and needs special filters or ultra-
centrifugation. To conquest to this limitation, the nano-magnetic cata-
lysts as powerful catalytic systems would be utilized. These catalysts
could be comfortably isolated via a magnet which resulted to increase
the reusability in comparison to filtration or centrifugation [30–33].
The magnetic nanoparticles are used as supporting materials for im-
mobilization of organic and inorganic species [34–43]. In addition, the
nanomagnetic catalysts have a large specific surface area and high
catalytic activity. Thus, these catalysts would be used in the fields of
biocatalysis [44], photocatalysis [45], phase-transfer catalysis and etc.
[46].
quinoline derivatives which they have good candidates for biological
activities. As these series of materials could be applied in the pharma-
cology such as anti-malarial [1], anti-bacterial [2], anti-asthmatic [3],
anti-hypertension [4], anti-inflammatory [5,6], anti-tumor materials
7–11], thus, several researchers have attracted to these compounds.
Among these compounds, quinoline-4-carboxylic acids are quite unique
and applied as active components in industrial utility as antioxidants
[
[
12,13]. Also, the quinoline-4-carboxylic acids could be used as the key
precursors for the preparation of other beneficial quinolone-based
materials [14]. Despite of the above-mentioned properties, a few routes
have been used for the preparation of these compounds [15–24].
Therefore, the synthesis of quinoline-4-carboxylic acids through more
efficient and greener methods is highly desired.
The multicomponent reactions (MCRs) occurred when multiple
compounds, three or more, are one-pot reacted to obtain complicated
molecules displaying features of all inputs. Therefore, these reactions
eliminated the isolation and purification of reaction intermediates, re-
sulting to lower the costs, time, and energy. These reactions due to
application in the synthesis of complex compounds with variety func-
tional groups are being noticeable. Searching for new and synthetically
The anomeric effect as a stereoelectronic phenomenon in chemistry
has been attracted many researchers for generalizing and expanding
this concept [47–49]. Recent investigations show that anomeric effect
can perform a pivotal role for justification of some unusual phenomena
⁎
Corresponding author.
E-mail addresses: zolfi@basu.ac.ir, mzolfigol@yahoo.com (M.A. Zolfigol).
https://doi.org/10.1016/j.mcat.2020.110924
Received 11 February 2020; Received in revised form 22 March 2020; Accepted 23 March 2020
2468-8231/ © 2020 Elsevier B.V. All rights reserved.

F. Karimi, et al.
Molecular Catalysis 489 (2020) 110924
Scheme 1. Deuterium isotope effect at the anomeric position.
2 2
Scheme 3. Selected stereoelectronic interactions and bond lengths in H O and
H O
2 3.
in chemistry. For example, preference of deuterium for equatorial po-
sition in 5, 5‐dimethyl‐1, 3‐dioxane‐2‐d , is related to endocyclic
1
anomeric effect. In equilibrium isotope effects, deuterium generally
prefers the stronger bonds. Due to the anomeric effect, equatorial band
is stronger than axial one (Scheme 1) [50].
Anomeric interactions can also explain more stability anti con-
former of tetrafluorohydrazine than the gauche conformer because of
dihydrogen phosphate (dissolving in 20 mL of deionized water) and it
was added to mixture of 1 g of Fe @SiO @(CH Cl in 50 mL of
ethanol and deionized water. The reaction mixture was stirred for 12 h
at ambient temperature to give final catalyst Fe @SiO @(CH NH
3
O
4
2
2 3
)
3
O
4
2
2 3
)
(
CH
2
)
2
O
2
P(OH)
2
.
participation of the lone pairs of fluorine in homoanomeric n
stabilizing interactions (Scheme 2) [51].
F
→ σ*NF
2.2. General procedure for the Synthesis of benzo-[h]quinoline-4-carboxylic
A prominent example for anomeric effect is occurred in H
related compounds with the longer ‐O ‐ chains. The notable strength-
ening of O‐O bond in H toward H and its non‐planar geometry
2
O
3
and
acid derivatives
n
2
O
3
2 2
O
A mixture of naphtylamine (1 mmol, 0.143 g), aromatic aldehyde
disclose the influence of anomeric interactions and the greater acceptor
ability of O‐O bonds in comparison with O‐H bonds (Scheme 3) [52,53].
Based on above mentioned facts “cooperative anomeric and/or vi-
nylogous anomeric based oxidation” terms represents a new mechan-
istic vision and major driving force for the oxidative aromatization of
some susceptible heterocyclic molecules. Recently, these concepts re-
viewed [54,55].
In pursuance of our research development of the preparation of
biological valuable heterocyclic structures according to anomeric based
oxidation mechanism [54,56–58], via nanomagnetic catalysis, herein a
(
1 mmol), pyrovic acid (1 mmol, 0.088 g) and 10 mg of Fe
3 4
O @
SiO @(CH NH(CH P(OH) were stirred at 80 °C for sufficient
2
2
)
3
2
)
2
O
2
2
time in the absence of solvent (Table 2). After completion of the reac-
tion (as indicated by TLC (n‐hexane 6:4 ethylacetate)), it was diluted
with hot ethylacetate and the catalyst isolated by employing a simple
external magnetic bar. Lastly, the recrystallization of the pure products
was performed from ethylacetate.
2
2
.3. Selected spectral data
novel nanomagnetic catalyst Fe
was prepared by using 2-aminoethyl dihydrogen phosphate (Scheme 4)
58]. Then it was employed for the synthesis of pyridine-4-carboxylic
acids under solvent-free conditions (Scheme 5).
3 4 2 2 3 2 2 2 2
O @SiO @(CH ) NH(CH ) O P(OH)
.3.1. 2-(4-Bromophenyl)benzo[h]quinoline-4-carboxylic acid (1f)
Melting point: 302–304 °C
[
FT-IR (KBr): ν (cm−1): 3062, 1696, 1580, 1253, 828.
1
H NMR (300 MHz, DMSO, δ, ppm): 14.08 (br, 1H, COOH), 9.35 (s,
1
H, ArH), 8.57- 8.51 (m, 2H, ArH), 8.39- 8.36 (m, 2H, ArH), 8.06- 8.01
2
. Experimental
(m, 2H, ArH), 7.81- 7.76 (m, 4H, ArH).
13
C NMR (76 MHz, DMSO, δ, ppm): 168.2, 153.5, 146.7, 138.5,
137.6, 133.6, 132.4, 131.1, 129.6, 129.4, 128.4, 127.9, 124.9, 124.1,
122.7, 122.5, 119.2.
2.1. General procedure for the synthesis of Fe
3
O
4
@SiO
2
@(CH
2
)
3
NH
(CH P(OH)
2
)
2
O
2
2
The synthesis of Fe
Afterwards, a layer of SiO
nanoparticles by reaction with tetraethyl orthosilicate (TEOS) to form
Fe @SiO . After that, Fe @SiO reacted with 3-chloropropyl-
trimethoxysilane in refluxing toluene to produce Fe
SiO @(CH Cl. In the next step, 12 mmol (1.69 g) of 2-Aminoethyl
3
O
4
nanoparticles was reported before [59].
2.3.2. 2-p-Tolylbenzo[h]quinoline-4-carboxylic acid (1 h)
Melting point: 293–295 °C
2
was anchored on the surface of the Fe
3 4
O
FT-IR (KBr): ν (cm−1): 3063, 1697, 1582, 1,255,829.
1
3
O
4
2
3
O
4
2
H NMR (300 MHz, DMSO, δ, ppm): 14.06 (br, 1H, COOH), 9.43-
3
O
4
@
9.40 (m, 1H, ArH), 8.56- 8.53 (m, 2H, ArH), 8.39- 8.36 (m, 2H, ArH),
8.10- 8.03 (m, 2H, ArH), 7.88- 7.80 (m, 2H, ArH), 2.44 (s, 3H, Me).
2
2 3
)
Scheme 2. Efficiency anomeric effect in justification of permanency anti conformer of tetrafluorohydrazine.
2

F. Karimi, et al.
Molecular Catalysis 489 (2020) 110924
3 4 2 2 3 2 2 2
Scheme 4. preparation of Fe O @SiO @(CH ) NH(CH ) O P(OH)2.
3 4 2 2 3 2 2 2 2
Scheme 5. Preparation of benzo-[h]quinoline-4-carboxylic acids using catalytic amount of Fe O @SiO @(CH ) NH(CH ) O P(OH) .
3 4 2 2 3 3 4 2 3 4
Fig. 1. The comparative FT-IR spectra of novel catalyst, Fe O @SiO @(CH ) Cl, Fe O @SiO and Fe O .
1
3
C NMR (76 MHz, DMSO, δ, ppm): 168.4, 154.8, 146.7, 140.1,
2.3.3. 2-(3, 4-Dimethoxyphenyl)benzo[h]quinoline-4-carboxylic acid (1k)
Melting point: 215–217 °C
1
1
38.5, 135.8, 133.6, 131.3, 130.2, 129.3, 128.9, 128.4, 127.9, 127.5,
24.9, 122.8, 122.1, 119.1, 21.4.
FT-IR (KBr): ν (cm−1): 3069, 1693, 1583, 1510, 1421, 1265, 1173,
8
29.
1
H NMR (300 MHz, DMSO, δ, ppm): 14.11 (br, 1H, COOH), 9.42-
3

F. Karimi, et al.
Molecular Catalysis 489 (2020) 110924
3 4 2 2 3 2 2 2 2
Fig. 2. EDS analysis of Fe O @SiO @(CH ) NH(CH ) O P(OH) .
Fig. 3. Elemental mapping analysis of Fe
3
O
4
@SiO
2
@(CH
2
)
3
NH(CH
2
)
2
O
2
P(OH)
2
.
9
7
3
.39 (m, 1H, ArH), 8.55- 8.48 (m, 2H, ArH), 8.10- 8.02 (m, 4H, ArH),
2.3.4. 2-(3-Ethoxy-4-hydroxyphenyl)benzo[h]quinoline-4-carboxylic acid
(1 l)
.86- 7.82 (m, 2H, ArH), 7.21- 7.18 (m, 1H, ArH), 4.00 (s, 3H, OMe),
.90 (s, 3H, OMe).
Melting point: 229–231 °C
1
3
FT-IR (KBr): ν (cm−1): 3386, 1701, 1582, 1264.
C NMR (76 MHz, DMSO, δ, ppm): 168.5, 154.7, 151.1, 149.7,
1
1
1
46.6, 138.9, 133.7, 131.3, 131.2, 129.3, 128.6, 128.4, 127.9, 124.9,
22.9, 121.8, 120.7, 118.8, 112.4, 110.8, 56.2, 56.1.
H NMR (300 MHz, DMSO, δ, ppm): 14.05 (br, 1H, COOH), 9.51 (s,
1H, ArH), 9.40- 9.37 (m, 1H, ArH), 8.51- 8.48 (m, 2H, ArH), 8.06- 8.00
(
7
m, 3H, ArH), 7.94- 7.92 (m, 1H, ArH), 7.83- 7.82 (m, 2H, ArH) 7.05-
.02 (m, 1H, ArH), 4.27 (q, 2H, J = 6 Hz, OCH ), 1.46 (t, 3H, J = 6 Hz,
2
4

F. Karimi, et al.
Molecular Catalysis 489 (2020) 110924
3 4 2 2 3 2 2 2 2
Fig. 4. SEM images of Fe O @SiO @(CH ) NH(CH ) O P(OH) .
3 4 2 2 3 2 2 2 2
Fig. 5. TEM images of Fe O @SiO @(CH ) NH(CH ) O P(OH) .
ArH).
1
3
C NMR (76 MHz, DMSO) δ: 168.2, 150.9, 146.5, 144.8, 138.8,
1
1
33.7, 130.7, 130.4, 129.4, 129.3, 128.7, 128.4, 127.9, 127.7, 124.7,
22.9, 122.1, 118.1.
3. Result and discussion
3
.1. Characterization of Fe
3
O
4
@SiO
2
@(CH
2
)
3
NH(CH
2
)
2
O
2
P(OH)
2
The structure of Fe
3
O
4
@SiO @(CH
2
2
)
3
NH(CH
2
)
2
O
2
P(OH)
2
catalyst
Fig. 6. VSM hysteresis curve of a) Fe
3
O
4
, c) Fe
3
O
4
@SiO
2
@(CH
2
)
3
Cl and desired
with phosphate spacer was fully characterized using FT-IR spectro-
scopy, TGA/DTA, FESEM, EDS, elemental mapping analysis, TEM and
VSM.
catalyst d) Fe
3
O
4
@SiO
2
2
@(CH )
3
NH(CH
2
)
2
O
2
P(OH) .
2
3 4 2 2 3 2 2 2 2
The FT‐IR spectrum of Fe O @SiO @(CH ) NH(CH ) O P(OH) has
been compared with Fe O , Fe O @SiO and Fe O @SiO @(CH ) Cl
3 4 3 4 2 3 4 2 2 3
Me)1.
3
C NMR (76 MHz, DMSO) δ: 168.5, 155.0, 149.6, 147.7, 146.5,
38.4, 133.6, 131.2, 129.9, 129.2, 128.4, 127.8, 124.9, 122.8, 121.6,
21.1, 118.7, 116.5, 112.7, 64.6, 15.3.
(
Fig. 1). In FT‐IR spectrum of Fe
the broad peak at about 2900- 3500 cm
Also, the observed band at about 1200 cm
functional groups.
3
O
4
@SiO
2
@(CH
2
)
3
NH(CH
2
)
2
O
2
2
P(OH) ,
1
1
−
1
is attributed to OH groups.
−1
is related to of P]O
2.3.5. 2-(Thiophen-2-yl)benzo[h]quinoline-4-carboxylic acid (1p)
The EDS analysis of Fe
3
O
4
@SiO
2
@(CH
2
)
3
NH(CH P(OH) in
2
)
2
O
2
2
Melting point: 278–280 °C
Fig. 2, exert the elemental composition of the new nanomagnetic cat-
alyst to be Fe, Si, P, O, N and C. Also, these observations verified by
achieved data from the elemental mapping analysis as indicated in
Fig. 3.
FT-IR (KBr): ν (cm−1): 3065, 1702, 1584, 1254, 827.
1
H NMR (300 MHz, DMSO, δ, ppm): 14.11 (br, 1H, COOH), 9.29-
9
8
.26 (m, 1H, ArH), 8.53- 8.48 (m, 2H, ArH), 8.18- 8.15 (m, 1H, ArH),
.10- 8.02 (m, 2H, ArH), 7.87- 7.79 (m, 3H, ArH), 7.32- 7.28 (m, 1H,
3 4 2 2 3
The size and morphological features of Fe O @SiO @(CH ) NH
5

F. Karimi, et al.
Molecular Catalysis 489 (2020) 110924
3 4 2 2 3 2 2 2 2
Fig. 7. TGA/DTG analysis curves of Fe O @SiO @(CH ) NH(CH ) O P(OH) .
Table 1
Optimizing reaction parameters for preparation of benzo-[h]quinoline-4-carboxylic acid.
Entry
1
Solvent
Temperature (˚C)
Load of catalyst (mg)
Time (min)
Yield (%)b
–
–
–
–
–
–
–
–
70
80
90
80
80
80
80
80
80
80
Reflux
Reflux
Reflux
10
10
10
15
5
40
30
35
40
45
90
60
60
120
90
120
120
120
71
89
88
75
80
61
70
70
61
90
77
83
45
c
2
3
4
5
6
–
d
7
10
10
10
10
10
10
10
e
8
9
H₂O
C₂H₅OH
EtOAc
10
11
12
13
CH
2 2
Cl
n-Hexane
a
Reaction conditions: 4-Methylbenzaldehyde (1 mmol, 0.120 g), pyruvic acid (1 mmol, 0.088 g) and 1-naphthylamine (1 mmol, 0.143 g). bIsolated yields. cData for
d
e
the model reaction under air, nitrogen and argon atmosphere are similar. Reaction performed using Fe
Fe @SiO @(CH Cl nanoparticles as a catalyst.
3 4
O nanoparticles as a catalyst. Reaction performed using
3
O
4
2
2 3
)
(
CH
2
)
2
O
2
P(OH)
2
was investigated by FESEM images. As distinguished
3.2. Application of Fe
3 4 2 2 3 2 2 2 2
O @SiO @(CH ) NH(CH ) O P(OH) in the
in Fig. 4, the particle size of the catalyst is lower than 30 nm.
Also, Fig. 5 represents TEM micrographs of the novel catalyst. The
obtained TEM images depict that the particles of novel catalyst have
spherical morphology and nano sizes.
synthesis of benzo-[h]quinoline-4-carboxylic acids
As the characterization of the synthesized nanocatalyst completed,
the catalytic performance of Fe @SiO @(CH NH(CH P(OH)
2
3
O
4
2
2
)
3
2
)
2
O
2
The magnetic properties of Fe
OH) was also studied using VSM analysis and compared to that of a)
Fe and c) Fe @SiO @(CH Cl as intermediates in the synthetic
3
O
4
@SiO
2
@(CH
2
)
3
NH(CH
2
)
2
O
2
P
was surveyed for the synthesis benzo-[h]quinoline-4-carboxylic acid
derivatives (Scheme 2). For determine the optimized reaction para-
meters including various temperatures, catalyst loads and solvents, the
reaction between 4-methyl benzaldehyde, naphtylamine and pyrovic
acid was selected as a test reaction. According to the above mentioned
results, 80 °C using 10 mg of the novel catalyst in the absence of solvent
was chosen as the optimal reaction parameters (Table 1, entry 2). In
(
2
3
O
4
3
O
4
2
2 3
)
pathways. According to the obtained results (Fig. 6), during different
stages of synthesis, by coating successive layers, the saturation mag-
−1
−1
netization decreases from 66.23 emu g
3 4
for Fe O to 46.11 emu g
for final desired catalyst.
Fig. 7 declare the obtained TGA and DTA analysis curves of novel
catalyst. These curves show high thermal stability for Fe
SiO @(CH NH(CH P(OH) and confirms its proficiency at uti-
lizable elevated temperatures.
2
addition, the reaction was tried under N and argon atmosphere and in
3
O
4
@
the optimized conditions in order to demonstrate the last step of the
proposed mechanism of reaction. The obtained data in all atmospheres
are alike (Table 1, entry 2).
2
2
)
3
2
)
2
O
2
2
6

F. Karimi, et al.
Molecular Catalysis 489 (2020) 110924
Table 2
3
O
4
@SiO
2
@(CH
2 3 2 2 2 2
) NH(CH ) O P(OH)
a.
Synthesis of desired molecules 1a-p using Fe
Entry
1
Aldehyde
Product
Structure
Time (min)
35
Yield (%)b
87
Melting point (°C), [found] [Lit]·
294-296 [282-284] [56]
1a
2
3
4
5
1b
1c
1d
1e
20
30
25
35
89
87
85
82
309-311 [Dec. 250] [56]
283-285 [215-218] [56]
309-311 [299-302] [56]
305-307 [290-293] [56]
6
7
1f
35
35
84
81
302-304 [New]
1g
278-280 [ < 300] [56]
8
9
1 h
30
89
293-295 [282-284] [11]
1i
1j
35
30
25
83
86
80
272-274 [279-280] [8]
218- 220 [287-288] [56]
215- 217 [New]
1
0
1
1
1k
1
1
2
3
1 l
35
35
80
85
229-231 [New]
1m
317-319 [312-315] [56]
(
continued on next page)
7

F. Karimi, et al.
Molecular Catalysis 489 (2020) 110924
Table 2 (continued)
Entry
Aldehyde
Product
Structure
Time (min)
30
Yield (%)b
85
Melting point (°C), [found] [Lit]·
300-302 [300-302] [56]
1
4
1n
1
1
5
6
1o
1p
30
20
86
84
230-232 [234-238] [56]
278-280 [New]
a
Reaction conditions: Arylaldehyde (1 mmol), pyrovic acid (1 mmol, 0.088 g) and 1-naphthylamine (1 mmol, 0.143 g), optimal reaction conditions.
Isolated yields.
b
3 4 2 2 3 2 2 2 2
Fig. 8. The reusing test of Fe O @SiO @(CH ) NH(CH ) O P(OH) .
After assessment of the best reaction parameters, for evaluate the
applicability and versatility of the presented protocol for the prepara-
tion of target products, a good domaine of aryl aldehydes were reacted
naphtyl amine to aromatic aldehyde leads to the formation of imine
intermediate A, which it has followed by Mannich reaction with
pyruvic acid to produce compound B. After that, molecule B is con-
verted to C by a ring‐closing reaction. We believed that, the final step of
the reaction might be progressed through a cooperative anomeric
supporting. For demonstration of this idea, the optimized conditions
were performed in the absence of any molecular oxygen under argon
and nitrogen atmosphere. The results in air, nitrogen and argon atmo-
sphere are alike (Table 1, entry 2). By considering the above mentioned
evidence, in the intermediate C, electron donation from the nitrogen
lone pairs into the antibonding of C–H (σ*C–H), make breaking C–H
with naphtylamine and pyrovic acid in the presence of Fe
3 4
O @
SiO @(CH NH(CH P(OH) as a heterogeneous recoverable cata-
2
2
)
3
2
)
2
O
2
2
lyst under the optimal conditions. As declared in Table 2, all target
molecules were furnished in brief times with appropriate yields.
3
.3. Recycling test of Fe
3
O
4
@SiO
2
@(CH
2
)
3
NH(CH
2
)
2
O
2
P(OH)
2
Since that the possibility of recycling Fe
3
O
4
@SiO
2 2 3
@(CH ) NH
2
bond via reaction with a proton from catalyst and releasing H . Re-
(
CH P(OH) is a beneficial feature of any catalyst, the model re-
2
)
2
O
2
2
cently, we have been propounded the term of “anomeric based oxida-
tion” (ABO) for this event. The expansion of catalytic “cooperative
anomeric based oxidation” for susceptible molecules is our main re-
action between 4‐methylbenzaldehyde, 1-naphtylamine and pyrovic
acid was examined for six runs under the optimized reaction. At the end
of each run, addition of hot ethylacetate to the mixture, caused dis-
search interest [54,55]. Finally, in the presence of Fe
3 4
O @
solving the products and isolation of Fe
3 4 2 2 3
O @SiO @(CH ) NH
SiO @(CH NH(CH P(OH) , hydrogen molecule releasing from
2
2
)
3
2
)
2
O
2
2
(
CH P(OH) utilizing an external magnet. Then, it washed with
2
)
2
O
2
2
intermediate C results to production of intermediate D and finally
target molecule 1a.
ethylacetate, dried and reused for the subsequent run. As showed in
Fig. 8, the separated catalyst, conserved it's catalytic performance at
least for six consecutive runs.
A proposed mechanistic pathway construction of molecule 1a via
anomeric based oxidation mechanism is portrayed in Scheme 6. In the
4. Conclusions
presence of Fe
3
O
4
@SiO
2
@(CH
2
)
3
NH(CH
2
)
2
O
2
P(OH)
2
, the reaction of
In summary, the design and preparation of a new nanomagnetic
8

F. Karimi, et al.
Molecular Catalysis 489 (2020) 110924
Scheme 6. A proposed mechanism for construction of molecule 1a via cooperative anomeric based oxidation.
catalyst bearing phosphate linkers was presented. Structural verifica-
tion was investigated using various methods like TEM, VSM, TG, FT‐IR
spectroscopy, FESEM, EDS and elemental mapping. The impact of
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.mcat.2020.110924.
3 4 2 2 3 2 2 2 2
Fe O @SiO @(CH ) NH(CH ) O P(OH) was carefully considered in
the synthesis of benzo-[h]quinoline-4-carboxylic acids via a three
component reaction of aryl aldehydes, naphtylamine, and pyrovic acid
in the absence of solvent. The major merits of this investigation are the
environmental friendly and temperate reaction conditions, smooth se-
paration and purification of protocols, short reaction times, high yields
of products, and simple separation and reusability of the catalyst. In the
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