Ferric hydrogensulfate-catalyzed one-pot synthesis of indeno[1,2- b]quinoline-7-ones

Article abstract of DOI:10.1080/15533174.2011.613887

Ferric hydrogensulfate was found to be an efficient catalyst for the three-component synthesis of indeno[1,2-b]quinoline-7-one derivatives through one-pot condensation of 1-naphthylamine or 1-antharacylamine, aromatic aldehydes, and 1,3-indandione. The ca

Full text of DOI:10.1080/15533174.2011.613887

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Ferric Hydrogensulfate-Catalyzed One-Pot Synthesis of
Indeno[1,2-b]quinoline-7-ones
Hossein Eshghi a , Mohammad Ali Nasseri b , Reza Sandaroos b , Hamid Reza Molaei c & Saman
Damavandi c
a Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad, Mashhad,
Iran
b Department of Chemistry, Faculty of Science, University of Birjand, Birjand, Iran
c Department of Chemistry, Sarvestan Branch, Islamic Azad University, Sarvestan, Iran
Available online: 14 Mar 2012
To cite this article: Hossein Eshghi, Mohammad Ali Nasseri, Reza Sandaroos, Hamid Reza Molaei & Saman Damavandi (2012):
Ferric Hydrogensulfate-Catalyzed One-Pot Synthesis of Indeno[1,2-b]quinoline-7-ones, Synthesis and Reactivity in Inorganic,
Metal-Organic, and Nano-Metal Chemistry, 42:4, 573-578
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:573–578, 2012
Copyright ꢀ Taylor & Francis Group, LLC
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ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2011.613887
Ferric Hydrogensulfate-Catalyzed One-Pot Synthesis of
Indeno[1,2-b]quinoline-7-ones
Hossein Eshghi,1 Mohammad Ali Nasseri,2 Reza Sandaroos,2 Hamid Reza
Molaei,3 and Saman Damavandi3
1Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad, Mashhad, Iran
2Department of Chemistry, Faculty of Science, University of Birjand, Birjand, Iran
3Department of Chemistry, Sarvestan Branch, Islamic Azad University, Sarvestan, Iran
Partially hydrogenated quinoline cores are also present in
some important bioactive compounds. For example, the 4-aza-
analogs of Podophyllotoxin, a plant lignan that inhibits mi-
crotubule assembly, revealed to be more potent and less toxic
anticancer agents.[17] A highly selective and operational simple
procedure was reported on the basis of a three-component reac-
tion of arylaldehydes, 2-amino-naphtalene, and either ketones
or β-ketoesters, using 5 mol% of iodine acting as a mild Lewis
acid catalyst.18
In the recent years, a three-component, one-pot synthesis
of indeno[1,2-b]quinoline-7-one derivatives under microwave
irradiation was reported.[19] Ji’s group reported a green multi-
component approach to a new series of these derivatives, con-
sisting of the reaction of either tetronic acid or 1,3-indanedione
with various aldehydes and substituted anilines in water un-
der microwave irradiation conditions.[20] Furthermore, one-pot
synthesis of indeno[1,2-b]quinoline-7-one derivatives by con-
densing 1-naphtylamine, aldehydes, and 1,3-indandione was
reported.[21]
In the recent years, the use of heterogeneous catalysts has
received considerable interest in various disciplines, including
organic synthesis. Synthetic organic routes using heterogeneous
catalysts have an advantage over their homogeneous counter-
parts, as the catalyst can be easily recycled. In view of the
present activity in the area of multicomponent reactions, there
is merit in developing a truly catalytic method for the formation
of indeno[1,2-b]quinoline-7-one derivatives.
To the best of my knowledge, there are no reports for the
use of ferric hydrogensulfate, Fe(HSO4)3, in the synthesis of
indeno[1,2-b]quinoline-7-one derivatives. The catalyst is easy
to prepare, inexpensive, non-toxic, highly reusable, and simul-
taneously has Lewis and Bronsted acidic characters that make
it to act as a bifunctional heterogeneous catalyst.
Ferric hydrogensulfate was found to be an efficient catalyst
for the three-component synthesis of indeno[1,2-b]quinoline-7-one
derivatives through one-pot condensation of 1-naphthylamine or
1-antharacylamine, aromatic aldehydes, and 1,3-indandione. The
catalyst could be recovered conveniently and reused at least four
times without any loss of activity. The efficient method has the
advantages of inexpensiveness of the catalyst, short reaction times,
simplicity, easy workup, and good to excellent yields.
Keywords ferric hydrogensulfate, indenoquinoline, one-pot
INTRODUCTION
Multicomponent reactions[1] involving domino processes,[2]
combining at least three different substrates in a one-pot op-
eration, have emerged as powerful tools and complementary
substrate-directed synthetic alternatives to other well-known
methods.[3–6] Moreover, these transformations combine classical
concerns such as efficiency, selectivity, molecular complexity
and diversity,[7,8] with current preoccupations such as atom- and
step-economy,[9–11] and environmentally benign reactions, thus
approaching quite closely the concept of an ideal synthesis.[12]
In view of the importance of benzoquinoline and its deriva-
tives in various fields of chemistry, biology, and pharmacology,
many efforts have been devoted to their synthesis. Quinoline
derivatives are reported to possess interesting pharmacological
activities such as antiplasmodial, intrinsic, cytotoxic, functional,
antibacterial, antiproliferative, antimalarial, and anticancer ac-
tivities.[13,14] Therefore, various methods such as the Skraup,
Doebner–von Miller, Friedla¨nder, and Combes procedures have
been developed for the synthesis of quinoline derivatives.[15,16]
As a part of the continued research on MCR reac-
tions,[22,23] herein, Fe(HSO4)3-catalyzed one-pot synthesis of
a series of indeno[1,2-b]quinoline-7-ones by condensation of 1-
Received 29 May 2011; accepted 9 August 2011.
Address correspondence to Saman Damavandi, Department of
Chemistry, Islamic Azad University, Sarvestan Branch, Sarvestan, I. naphthylamine or 1-antharacylamine, aromatic aldehydes, and
R. Iran. E-mail: Saman Damavandi@yahoo.com
1,3-indandione is reported (Scheme 1).
573

574
H. ESHGHI ET AL.
Ar
O
O
NH2
O
O
Fe(HSO4)3,10 mol%
+
+ ArCHO
DMSO, 90 oC
N
H
Ar
NH2
O
O
Fe(HSO4)3,10 mol%
DMSO, 90 oC
+
+ ArCHO
N
H
SCH. 1.
EXPERIMENTAL
7.35–7.10 (7 H, m, ArH), 5.15 (1 H, s, CH). EIMS m/z:
377 (M+). Anal. Calcd. for C26H16FNO: C, 82.74; H,
4.27; N, 3.71; Found: C, 82.48; H, 4.19; N, 3.74.
(Entry 5): 1H NMR δ 10.10 (1 H, s, NH), 7.83 (1 H, m, ArH),
7.75–7.50 (8 H, m, ArH), 7.35–7.05 (5 H, m, ArH),
5.25 (1 H, s, CH). EIMS m/z: 437 (M+). Anal. Calcd.
for C26H16BrNO: C, 71.25; H, 3.68; N, 3.20; Found: C,
71.17; H, 3.65; N, 3.18.
Materials and Methods
Chemicals were either prepared in our laboratories or pur-
chased from Merck, Fluka, and Aldrich Chemical Companies.
All yields refer to isolated products. IR spectra were recorded on
1
a Shimadzu-IR 470 spectrophotometer. H NMR spectra were
recorded on a Bruker 100-MHz spectrometer (Madison, WI,
USA) in chloroform as the solvent and TMS as internal standard.
Flash column chromatography was performed with 300 and 400
meshes silica gel and analytical thin layer chromatography was
performed on pre-coated silica gel plates (60F-254). Elemental
analyses were performed on Thermo Finnigan EA1112 elemen-
tal analyzer.
(Entry 8): 1H NMR (CDCl3, 100 MHz): δ = 10.70 (1 H, s,
NH), 7.75–7165 (14 H, m, ArH), 5.55 (1 H, s, CH), 2.20
(3 H, S, Me). EIMS m/z: 373 (M+). Anal. Calcd. for
C27H19NO: C, 86.84; H, 5.13; N, 3.75; Found: C, 86.77;
H, 5.19; N, 3.71.
(Entry 10): 1H NMR (CDCl3, 100 MHz): δ = 10.85 (1 H, s, NH),
7.85–7.75 (2 H, m, ArH), 7.70–7.15 (11 H, m, ArH),
5.60 (1 H, s, CH). EIMS m/z: 349 (M+). Anal. Calcd.
for C24H15NO2: C, 82.50; H, 4.33; N, 4.01; Found: C,
82.38; H, 4.29; N, 3.94.
General Procedure for Synthesis of
Indeno[1,2-b]quinoline-7-ones
A mixture of aryl aldehyde (1.0 equiv), 1,3-indandione (1.0
equiv), amine (1.0 equiv), Fe(HSO4)3 (0.1 equiv), and DMSO
(5 mL) was added to a round-bottomed flask. The mixture was
heated at 90◦C condition for the appropriate time indicated by
TLC. Upon completion the ∗∗∗reaction, the heterogeneous cat-
alyst was recovered by simple filtration. The catalyst was rinsed
with a little amount of methanol and dried, to be reused without
loss of activity for further reactions. The residue was poured into
cold acetone. The precipitated products were separated by filtra-
tion and recrystallized in an ethanol-acetonitrile (CH3CN/EtOH:
1/3) solution to give the corresponding indeno[1,2-b]quinoline-
7-ones in good to excellent yields.
(Entry 11): 1H NMR δ 9.95 (1 H, s, NH), 7.85–7.70 (4 H, m,
ArH), 7.70–7.60 (4 H, m, ArH), 7.55–7.05 (9 H, m,
ArH), 5.30 (1 H, s, CH). EIMS m/z: 409 (M+). Anal.
Calcd. for C30H19NO: C, 88.00; H, 4.68; N, 3.42; Found:
C, 88.15; H, 4.71; N, 3.46.
(Entry 15): 1H NMR (CDCl3, 100 MHz): δ = 10.55 (1 H, s,
NH), 7.75 (2 H, d, J = 8.5 Hz, ArH), 7.65–6.90 (14
H, m, ArH), 5.40 (1 H, s, CH). EIMS m/z: 454 (M+).
Anal. Calcd. for C30H18N2O3: C, 79.28; H, 3.99; N,
6.16; Found: C, 79.21; H, 3.90; N, 6.12.
(Entry 16): 1H NMR (CDCl3, 100 MHz): δ = 9.95 (1 H, s,
NH), 7.7–7.25 (16 H, m, ArH), 5.60 (1 H, s, CH), 3.65
(3 H, s, OMe). EIMS m/z: 439 (M+). Anal. Calcd.
for C31H21NO2: C, 84.72; H, 4.82; N, 3.19; Found: C,
84.66; H, 4.77; N, 3.14.
Spectral data of the selected products are the following:
(Entry 3): 1H NMR (CDCl3, 100 MHz): δ = 10.75 (1 H, s, NH),
7.94 (2 H, d, J = 8.5 Hz, ArH), 7.80–7.20 (12 H, m,
ArH), 5.60 (1 H, s, CH). EIMS m/z: 404 (M+). Anal.
Calcd. for C26H16N2O3: C, 77.22; H, 3.99; N, 6.93;
Found: C, 77.13; H, 3.89; N, 6.87.
(Entry 17): 1H NMR (CDCl3, 100 MHz): δ = 9.90 (1 H, s, NH),
7.65–7.30 (11 H, m, ArH), 7.20–6.80 (8 H, m, ArH),
5.45 (1 H, s, CH). EIMS m/z: 427 (M+). Anal. Calcd.
for C31H21NO2: C, 84.29; H, 4.24; N, 3.28; Found: C,
84.15; H, 4.19; N, 3.21.
1
(Entry 4): H NMR (CDCl3, 100 MHz): δ 9.80 (1 H, s, NH),
7.90–7.67 (4 H, m, ArH), 7.55–7.40 (4 H, m, ArH),

FERRIC HYDROGENSULFATE INDENOQUINOLINE ONE-POT
575
TABLE 1
Influence of solvent on Fe(HSO4)3-catalyzed reaction of of p-nitrobenzaldehyde, 3-indandione and 1-naphtylamine
NO2
O
NO2
NH2
O
O
Fe(HSO4)3
+
+
DMSO, 90 oC
N
H
Solvent
EtOH
C2H4Cl2
CH3CN
MeOH
DMF
DMSO
Yielda,b
65
72
78
68
70
95
Reusabilityc
94d
93e
92f
91g
90h
88i
aAll the reactions were carried out at 90◦C for 4 h. Reaction conditions: p-nitrobenzaldehyde (1.0 equiv), 1,3-indandione (1.0 equiv), amine
(1.0 equiv), Fe(HSO4)3 (0.1 equiv). bIsolated yields. cReusability of the recovered catalyst in DMSO from run 2[d] to run 7[i].
RESULTS AND DISCUSSION
The present experiments also determined that ferric hydro-
gensulfate is a highly reusable catalyst and after four runs
its catalytic activity is almost the same as that of a fresh
catalyst. The first run, in the presence of ferric hydrogen-
sulfate in DMSO under heating conditions, gave 95% yield
of the corresponding indeno[1,2-b]quinoline-7-one. The sec-
ond run, with the catalyst recovered from the first run, gave
94% of the products. The average chemical yield for four
consecutive runs, using Fe(HSO4)3 recovered from the previ-
ous run, was 91%. The results of all five runs are shown in
Table 2.
The generality of this process was demonstrated by the wide
range of substituted aldehydes as well as 1-antharacylamine
used to synthesize indeno[1,2-b]quinoline-7-one derivatives. In
order to expand the scope of the present method, the replace-
ment of 1-naphtylamine with 1-anthracylamine was examined.
Initially, we explored the role of the catalyst in the synthesis
of indeno[1,2-b]quinoline-7-ones (Table 1). The condensation
of 4-nitrobenzaldehyde, 1-naphthylamine, and 1,3-indanidione
was used as a model reaction. In the absence of the catalyst
no quinoline derivative was observed, even after a prolonged
reaction time. The model reaction was examined in different
solvents under heating conditions. The reaction was examined
using ethanol (EtOH), dichloroethane (C2H4Cl2), acetonitrile
(CH3CN), DMF, and DMSO. As a result of this investigation,
protic solvents such as ethanol and methanol led to the moderate
results. Inversely, application of polar aprotic solvents such as
acetonitrile or dimethyl sulfoxide significantly improved chem-
ical yields (Table 1). This may be due to the high polarity asso-
ciated with DMSO, which may result in the stabilization of the
intermediates coordinated with Fe.
. .
HO
NH2
Ar
HC N
O
O
O
-H2O
ArCHO
+
H
ArCH N
(O4SH)3Fe
..
NH2
Fe(HSO4)3
Ar
O
O
Ar
O
..
HO
H
-H2O
O
CH
Ar
N
H
H
ArCH N
HN
O
O
Fe(HSO4)3
SCH. 2.

576
H. ESHGHI ET AL.
TABLE 2
Results of indenoquinoline sunthesisa
Entry
Product
Time (h) Yieldb (%). Entry
Product
Time (h) Yield (%) Reported
1
2
3
3.45
3.5
3
92
90
95
6
7
8
3
91
92
90
3.45
3.45
4
3.5
94
9
4
90
5
3.5
90
10
4
87
(Continued on next page)

FERRIC HYDROGENSULFATE INDENOQUINOLINE ONE-POT
577
TABLE 2
Results of indenoquinoline sunthesisa (Continued)
Entry
Product
Time (h) Yieldb (%). Entry
Product
Time (h) Yield (%) Reported
11
12
3.5
4.5
85
84
15
15
3.5
92
82
4.45
13
4
90
16
4.45
86
14
3.45
90
17
4.5
90
aReaction condition: DMSO as the solvent, aldehyde (1.0 equiv), 1,3-indandione (1.0 equiv), amine (1.0 equiv), Fe(HSO4)3 (0.1 equiv) at
90◦C,. bIsolated yields.
The reaction of various aldehyde, 1-anthracylamine, and 1,3- sation of aldehyde and aromatic amine obtained Schiff base.
indanidione were carried under the similar conditions. As shown The addition of Schiff base to 1,3-indanone then afforded the
in Table 2 this protocol could be applied not only to aro- intermediate product B, which upon intermolecular cyclization
matic aldehydes with either electron-withdrawing or electron- and dehydration resulted in the corresponding product.
donating groups, but also to heterocyclic aldehydes (entries 10,
To support the accuracy of the proposed mechanism the re-
15). Upon the addition of reactants into the flask, a yellow action of Schiff base C and 1,3-indanone was carried out under
solid formed immediately, which could be identified by spectral similar conditions. The expected product was obtained in al-
study. The intermediate was a Schiff base obtained from the most similar chemical yield by one-pot reaction (Scheme 3). In
condensation of aldehyde and amine. Accordingly, the probable addition, to more concise postulate the mechanism, the inter-
mechanism was depicted in Scheme 2. As shown, the conden- mediate D was separately prepared, isolated, and reacted with

578
H. ESHGHI ET AL.
Me
O
O
O
H
N
HC
H2N
+
O
N
H
Ferric hydrogensulfate/DMSO
Me
Me
Me
Isolated intermediate[C]
NH2
O
H
O
O
O
O
CH
Ar
+
Ferric hydrogensulfate/DMSO
N
O
H
Me
Isolated intermediate [D]
SCH. 3.
1-anthracylamine. The indenoquinoline product was obtained
in similar yield by one-pot reaction (Scheme 3). According to
these experiments, the suggested mechanism in Scheme 2 was
approved.
4. Ramon, D. J.; Yus, M. Angew. Chem. Int. Ed. 2005, 44, 1602.
5. Guillena, G.; Ramon, D. J.; Yus, M. Tetrahedron: Asym. 2007, 18, 693.
6. Padwa, A.; Bur, S. K. Tetrahedron. 2007, 63, 5341.
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B.; Orru, R. V. A. Chem. Eur. J. 2006, 12, 7178.
The catalyst is capable of binding with the nitrogen atom of
the Schiff base to ease the knoevenagel reaction to prepare the
intermediate A. Also it can be coordinated with carbonyl oxygen
increasing the reactivity of the carbonyl compound. Addition-
ally, the catalyst facilitates the formation of the intermediate B,
which after dehydration gives the indenoquinoline product.
8. Nielsen, T. E.; Schreiber, S. L. Angew. Chem. Int. Ed. 2008, 47, 48.
9. Trost, B. M. Acc. Chem. Res. 2002, 35, 695.
10. Wender, P. A.; Baryza, J. L.; Brenner, S. E.; Clarke, M. O.; Gamber, C. G.;
Horan, J. C.; Jessop, T. C.; Kan, C.; Pattabiraman, K.; Williams, T. J. Pure
Appl. Chem. 2003, 75, 143.
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Am. Chem. Soc. 2005, 127, 2836.
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2007, 63, 4439.
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CONCLUSION
We have shown that ferric hydrogensulfate is an excellent cat-
alyst for the one-pot three-component synthesis of indeno[1,2-
15. Jiang, B.; Si, Y. C. J. Org. Chem. 2002, 67, 9449.
b]quinoline-7-ones. This simple methodology represents an 16. Theoclitou, M. E.; Robinson, L. A. Tetrahedron Lett. 2002, 43, 3907.
17. Duque, M. D. M. S.; Allais, C.; Isambert, N.; Constantieux, T.; Rodriguez,
J. Top. Heterocycl. Chem. 2010, 23, 227.
18. Wang, X. S.; Li, Q.; Wu, J. R.; Li, Y. L.; Yao, C. S.; Tu, S. J. Synthesis
alternative to existing procedures. This is the first report of
Fe(HSO4)3 catalyzed synthesis of indeno[1,2-b]quinoline-7-
ones from 1-antharacylamine, aromatic aldehydes, and 1,3-
indandione and thus, this new methodology opens an important
alternative by the use of Fe(HSO4)3.
2008, 1902.
19. Tu, S.; Zhang, Y.; Zhang, J.; Jiang, B.; Jia, R.; Zhang, J.; Ji, S. Synlett. 2006,
17, 2785.
20. Tu, S. J.; Zhang, Y.; Zhang, J. Y.; Jiang, B.; Jia, R. H.; Zhang, J. P.; Ji, S. J.
Synlett. 2006, 2785.
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Nano-Met. Chem. 2011, 41, 1.
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2-aryl-1 H -phenanthro[9,10-d] imidazoles. Heterocycl. Commun. 2011,
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