Facile one-pot synthesis of a series of 7-aryl-8H-benzo[h]indeno[1,2-b]quinoline-8-one derivatives catalyzed by cellulose-based magnetic nanocomposite

Article abstract of DOI:10.1002/aoc.3814

A sulfonated magnetic cellulose-based nanocomposite was applied as an efficient, inexpensive and green catalyst for the one-pot three-component synthesis of 7-aryl-8H-benzo[h]indeno[1,2-b]quinoline-8-ones starting from 1,3-indanedione, aromatic aldehydes and 1-naphthylamine under solvent-free conditions in high yields (79–98%) within short reaction times (2–5?min). The nanobiostructure catalyst can be easily separated from the reaction mixture by using an external magnet and reused several times.

Full text of DOI:10.1002/aoc.3814

Received: 23 November 2016
DOI: 10.1002/aoc.3814
Revised: 20 February 2017
Accepted: 4 March 2017
F U L L PA P E R
Facile one‐pot synthesis of a series of 7‐aryl‐8H‐benzo[h]
indeno[1,2‐b]quinoline‐8‐one derivatives catalyzed by cellulose‐
based magnetic nanocomposite
Ali Maleki
| Narges Nooraie Yeganeh
Catalysts and Organic Synthesis Research
Laboratory, Department of Chemistry, Iran
University of Science and Technology,
Tehran 16846‐13114, Iran
A sulfonated magnetic cellulose‐based nanocomposite was applied as an efficient,
inexpensive and green catalyst for the one‐pot three‐component synthesis of
7‐aryl‐8H‐benzo[h]indeno[1,2‐b]quinoline‐8‐ones starting from 1,3‐indanedione,
aromatic aldehydes and 1‐naphthylamine under solvent‐free conditions in high
yields (79–98%) within short reaction times (2–5 min). The nanobiostructure
catalyst can be easily separated from the reaction mixture by using an external
magnet and reused several times.
Correspondence
Ali Maleki, Catalysts and Organic Synthesis
Research Laboratory, Department of
Chemistry, Iran University of Science and
Technology, Tehran 16846‐13114, Iran.
Email: maleki@iust.ac.ir
KEYWORDS
green synthesis; solvent‐free, indeno[1,2‐b]quinoline‐8‐one, magnetic nanoparticles, multicomponent
reaction, nanobiostructure catalyst
1 | INTRODUCTION
simple and direct methods.[16–23] Most of the literature
reports require refluxing systems, organic solvents,
Multicomponent coupling reactions are very important
synthetic tools for building of various complex molecular
structures. These reactions are mainly defined as one‐pot
condensation reactions in which at least three starting
materials are combined to give a product. Atom economy,
operational simplicity, reduction in the number of workup
procedures, easy construction of products in a one‐pot
process from simple molecules, being convergent and
high bond‐forming index are some advantages of these
reactions.[1–4] Due to wide range of biological and
pharmaceutical activities as well as synthetic, chemical
and industrial applications, quinolines have attracted
researcher's attentions. Some of their medicinal properties
include anti‐cancer,[5] anti‐malarial,[6] anti‐inflammatory,[7]
anti‐asthmatic, anti‐pain,[8] anti‐bacterial,[9] anti‐virus,[10]
anti‐fungus,[11] cardiovascular[12] and anti‐hypersensitive
activities.[13] Indenoquinolines are one of the most
important groups of quinoline derivatives that have a wide
range of medicinal activities such as anticancer,[14] anti‐
inflammatory, anti‐tumour[15] and inhibitor of steroid
reductase, etc. Therefore, much effort have been focused
on the synthesis of indenoquinoline skeletons from new,
expensive catalysts, multiple steps and tedious work‐up
procedures.[17] Also, using homogeneous catalysts such
as tribromomelamine (TBM) create many problems such
as difficult separation and impurities contaminations.
Thus, due to importance of indeno[2,1‐b]quinolineones
in bioorganic and pharmaceutical chemistry, design and
development of simple high‐yielding and environmental‐
friendly methods by using new catalysts is of prime
importance.
Nowadays, nanotechnology can help researchers to
reinforce properties of nano‐sized compounds by developing
nanocomposites
materials.
Nanocomposites
against
conventional composites have higher thermal capacity and
recyclablity.[24] Through suitable size and distribution of
magnetic nanoparticles in polymeric materials, nanocompos-
ites can be achieved with special magnetic properties and
applications.[25] Biodegradability, eco‐friendly and relatively
low price of cellulose are some major reasons for its usage
in the composite nanostructures.[24] Therefore, magnetic
nanocomposites based on cellulose can be regarded as a
green and efficient recoverable and biodegradable
nanocatalyst.[26–31]
Appl Organometal Chem. 2017;e3814.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.3814

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MALEKI AND YEGANEH
Recently, sulfonic acid‐functionalized cellulose‐coated
spectra were taken by Bruker DRX‐500 and 300 Avance
spectrometers. The magnetic property was measured at room
temperature on a vibrating sample magnetometer (VSM) of
Meghnatis Daghigh Kavir Co., Iran. Scanning electron
micrograph (SEM) images and energy‐dispersive X‐ray
spectroscopy (EDX) spectra sequentially were obtained with
Seron AIS 2100 and Numerix DXP‐X10P, respectively.
Fe3O4 nanoparticles (Fe3O4@cellulose‐SO3H, MCSA) has
been introduced in our laboratory.[4] Herein, in continuation
of our previous works on catalysis,[32–37] MCSA as a non‐
toxic
and
environmentally‐friendly
heterogeneous
nanocatalyst was used in the synthesis of 7‐aryl‐8H‐benzo[h]
indeno[1,2‐b]quinoline‐8‐one derivatives via a one‐pot multi-
component reaction of 1,3‐indanedione, aromatic aldehydes
and 1‐naphthylamine under solvent‐free conditions at
40 °C (Scheme 1). To the best of our knowledge, this is
the first report on the application of the present composite
nanostructures in the synthesis of indenoquinoline deriva-
tives. Furthermore, this work includes several advantages
such as green reaction media, easy work‐up procedures,
high surface area, activity and recyclability of the
nanocatalyst. MCSA could be separated easily from the
reaction mixture by using an external magnet and can be
reused several times.
2.2 | Preparation of MCSA nanocatalyst
The nanocomposite was prepared according to our previous
report,[4] as follows: first, NaOH, urea and water were
combined at a ratio of 7:12:81 and decrease temperature of
solution to −12 °C. Then, 2.0 g of cellulose was added to
the solution. Next, an aqueous solution of 0.3 g of FeCl2.4H2O
and 0.8 g of FeCl3.6H2O in 100 mL of water was added
dropwise to the solution to form Fe3O4@cellulose microcrys-
tals. After that, 5.0 g of the microcrystals were added to 20 mL
of chloroform and stirred vigorously. Then, chlorosulfonic
acid (1.0 g) was added dropwise at 0 °C during 2 h. When
addition was completed, the mixture was stirred for 2 h and
brown powder washed with methanol and dried at room
temperature to yield the MCSA nanocatalyst.
2 | EXPERIMENTAL
2.1 | General
All the solvents, chemicals were taken from Merck, Sigma
and Aldrich. Melting points of the products were measured
using Electrothermal 9100 apparatus. UV lamp with a wave-
length of 254 nm was used in thin layer chromatography
(TLC) reaction. TLC performed by a silica gel and alumi-
num plate with thickness of 0.2 mm. Fourier transform
infrared spectroscopy (FT‐IR) spectra were taken by
Shimadzu spectrometer by KBr discs. 1H and 13C NMR
SCHEME
1
MCSA‐catalyzed synthesis of 7‐aryl‐8H‐benzo[h]
indeno[1,2‐b]quinoline‐8‐ones 4a–m
FIGURE 1 SEM images of MCSA

MALEKI AND YEGANEH
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2.3 | General procedure for the synthesis of
7‐aryl‐8H‐benzo[h]indeno[1,2‐b]quinoline‐
8‐one derivatives 4a–m
3.2 | Catalytic application of MCSA in the
synthesis of desired 7‐aryl‐8H‐benzo[h]
indeno[1,2‐b]quinoline‐8‐one derivatives
A
mixture of an aromatic aldehyde
1
(1 mmol),
To optimize the reaction conditions, a pilot reaction for the
synthesis of 7‐(4‐methyl phenyl)‐8H–benzo[h]indeno[1,2‐b]
quinoline‐8‐one (4d) was carried out. The effects of the
amount of the nanocatalyst, solvents and the reaction temper-
ature were studied on the pilot reaction (Tables 1 and 2).
First, we studied the effect of different amounts of MCSA
nanocomposites. 0.03 g of MCSA represented the highest
yields (98%) under solvent‐free conditions at 40 °C after
5 min (Table 1, entry 9). As can be seen in Table 1, we have
also investigated various components of the catalyst as the
1,3‐indanedione 2 (1 mmol), 1‐naphthylamine 3 (1 mmol)
and MCSA (0.03 g) was heated under solvent‐free conditions
in an oil bath at 40 °C for an appropriate time. After comple-
tion of the reaction (monitored by TLC), the reaction mixture
was dissolved in ethyl acetate and the catalyst easily sepa-
rated by an external magnet. Then, the pure products
obtained by recrystallization from EtOH.
2.4 | Spectral data of 7‐(4‐cyano phenyl)‐
8H–benzo[h]indeno[1,2‐b]quinoline‐8‐one 4a
TABLE 2 Optimizing of the solvent and temperature in the presence
of 0.03 g of MCSA
Yellow solid: mp 240 °C. FT‐IR (KBr) (υmax, cm−1): 3043,
2227, 1716, 1687, 1606, 3415. 1H NMR (500 MHz, CDCl3)
(δ, ppm): 6.99–8.45 (13H, Ar‐H), 9.47 (d, J = 7.8 Hz, 1H,
Ar‐H). 13C NMR (125 MHz, CDCl3) (δ, ppm): 113.3,
119.0, 122.0, 123.6, 124.4, 124.7, 126.2, 128.0, 128.2,
128.8, 130.0, 130.9, 131.9, 132.0, 132.4, 132.6, 134.1,
134.9, 135.9, 144.1, 145.2, 149.9, 162.1, 191.0.
Entry
Solvent
Temperature (°C)
Yielda (%)
1
2
3
4
5
6
Solvent‐free
Ethanol
40
40
40
25
70
80
98
29
96
73
98
95
Water
Solvent‐free
Solvent‐free
Solvent‐free
3 | RESULTS AND DISCUSSION
aIsolated yields after 90 min.
3.1 | Characterization of the prepared MCSA
nanocatalyst
The nanocomposite was prepared and characterized accord-
ing to our previous report.[4] The structure, morphology and
elemental analysis of MCSA nanocatalyst were confirmed
by FT‐IR spectra, SEM images (Figure 1) and EDX pattern
analysis (carbon, oxygen, sulfur and iron elements were
seen), respectively.
TABLE 3 Synthesis of 7‐aryl‐8H‐benzo[h]indeno[1,2‐b]
quinoline‐8‐ones 4a–m by using MCSA
Mp (°C)
Yielda
(%)
Entry
R
Product
Found
Reported
1
4‐Cn
H
4a
4b
4c
4d
4e
4f
98
96
98
98b
96
90
79
91
97
95
96
96
91
240–241
200–203
245–246
240‐242
225–226
230–233
320–322
284–285
240–242
230–233
240–241
228–230
212–215
‐
2
202–204[17]
259–261[16]
256‐260[16]
218–220[17]
233–235[17]
328–329[16]
289–291[16]
231–235[16]
222–224[17]
236–238[17]
230–233[17]
220–222[17]
TABLE 1 Optimizing of the model reaction conditions under
solvent‐free conditions at 40 °C
3
4‐cl
4
4‐me
4‐Br
4‐MeO
3‐oh
2‐cl
Catalyst
amount (mg) (min)
Time Yielda
5
Entry
Catalyst
(%)
6
1
2
3
4
5
6
7
8
9
‐
‐
90
90
90
90
90
90
90
90
5
10
87
91
98
95
68
53
77
98
7
4g
4h
4i
Fe3O4@cellulose‐OSO3H
Fe3O4@cellulose‐OSO3H
Fe3O4@cellulose‐OSO3H
Fe3O4@cellulose‐OSO3H
Nano‐ Fe3O4
10
20
30
40
30
30
30
30
8
9
4‐F
10
11
12
13
3‐NO2
3‐Br
3‐cl
4j
4k
4l
Cellulose
2,4‐di‐cl
4m
Fe3O4@cellulose
aIsolated yields after 5 min.
bYields of the five subsequent runs by using the same recovered catalyst were 95,
93, 89, 87, and 82%, respectively.
Fe3O4@cellulose‐OSO3H
aIsolated yields.

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MALEKI AND YEGANEH
catalyst in the pilot reaction. Then, different solvents and
varies temperature were investigated. It was found that
solvent‐free conditions and heating at 40 °C were yielded
the best results (Table 2, entry 1). After optimizing the
reaction conditions, to investigate scope and limitation of
the present approach, various 7‐aryl‐8H‐benzo[h]
indeno[1,2‐b]quinoline‐8‐one derivatives were synthesized
by using MCSA nanocomposite and the products were
obtained in high yields within short reaction times (less than
5 min) (Table 3).
an activated aldehyde carbonyl group and 1,3‐indanedione
in the presence of MCSA nanocatalyst. Then, an intermedi-
ate was formed from 1‐naphthylamine and 1,4‐
dihydroquinoline during ring formation by removing an
H2O molecule. In the final step, MCSA‐promoted the oxida-
tion of 1,4‐dihydroindenoquinolines to the target product
indenoquinolines[38–43] (Scheme 2).
3.3 | Recyclability study on MCSA
nanocatalyst
The suggested possible mechanism for the formation of
7‐aryl‐8H‐benzo[h]indeno[1,2‐b]quinoline‐8‐one derivatives
(4a–m) is shown in Scheme 2. In the first step, a
Knoevenagel condensation reaction was occurred between
One of the advantages of heterogeneous catalysts is their easy
separation from the reaction mixture and ability for reusing in
SCHEME 2 The proposed mechanism for the synthesis of 7‐aryl‐8H‐benzo[h]indeno[1,2‐b]quinoline‐8‐ones

MALEKI AND YEGANEH
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heterogeneous catalysts. In this regard, recyclability and
reuse of MCSA were evaluated in models reaction. MCSA
was recycled and used in model reaction at least for five
times without any significant decrease in efficiency
(Table 3, entry 4).
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were described by using a green magnetic nanobiostructure
catalyst. This method offers several advantages such as high
yields, avoiding use of organic solvents, short reaction times,
green recyclable organometallic nanostructure catalyst and
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ACKNOWLEDGEMENTS
The authors gratefully acknowledge the partial support from
the Research Council of the Iran University of Science and
Technology.
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[26] A. Maleki, M. Aghaei, R. Paydar, J. Iran. Chem. Soc. 2017, 14,
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How to cite this article: Maleki A, Nooraie Yeganeh
N. Facile one‐pot synthesis of a series of 7‐aryl‐8H‐
benzo[h]indeno[1,2‐b]quinoline‐8‐one derivatives
catalyzed by cellulose‐based magnetic nanocomposite.
Appl Organometal Chem. 2017;e3814. https://doi.org/
10.1002/aoc.3814
[43] M. Kiafar, M. A. Zolfigol, M. Yari, A. Taherpour, RSC Adv. 2016,
6, 102280.
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