H6P2W18O6218H 2O-catalyzed, three-component, one-pot synthesis of indeno[1,2-b]quinoline-7-one derivatives

Article abstract of DOI:10.1080/00397910903249580

In this work, a rapid and efficient one-pot method for the synthesis of indeno[1,2-b]quinoline-7-one derivatives by condensation of 1-naphthylamine, 1,3-indanedione, and different aldehydes in the presence of H₆P ₂W₁₈O

Full text of DOI:10.1080/00397910903249580

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H6P2W18O62·18H2O–Catalyzed, Three-
Component, One-Pot Synthesis
of Indeno[1,2-b]quinoline-7-one
Derivatives
Majid M. Heravi a , Tandis Hosseini a , Fatemeh Derikvand a , Seyed
Yahya S. Beheshtiha a & Fatemeh F. Bamoharram b
a Department of Chemistry , School of Sciences, Azzahra University ,
Vanak, Tehran, Iran
b Department of Chemistry , School of Sciences, Islamic Azad
University , Mashhad Branch, Mashhad, Iran
Published online: 26 Jul 2010.
To cite this article: Majid M. Heravi , Tandis Hosseini , Fatemeh Derikvand , Seyed Yahya S.
Beheshtiha & Fatemeh F. Bamoharram (2010) H6P2W18O62·18H2O–Catalyzed, Three-Component,
One-Pot Synthesis of Indeno[1,2-b]quinoline-7-one Derivatives, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 40:16, 2402-2406,
DOI: 10.1080/00397910903249580
To link to this article: http://dx.doi.org/10.1080/00397910903249580
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Synthetic Communications1, 40: 2402–2406, 2010
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910903249580
H6P2W18O62 ꢀ 18H2O–CATALYZED,
THREE-COMPONENT, ONE-POT SYNTHESIS OF
INDENO[1,2-b]QUINOLINE-7-ONE DERIVATIVES
Majid M. Heravi,1 Tandis Hosseini,1 Fatemeh Derikvand,1
Seyed Yahya S. Beheshtiha,1 and Fatemeh F. Bamoharram2
1Department of Chemistry, School of Sciences, Azzahra University, Vanak,
Tehran, Iran
2Department of Chemistry, School of Sciences, Islamic Azad University,
Mashhad Branch, Mashhad, Iran
In this work, a rapid and efficient one-pot method for the synthesis of indeno[1,2-
b]quinoline-7-one derivatives by condensation of 1-naphthylamine, 1,3-indanedione, and
different aldehydes in the presence of H6P2W18O62 ꢀ 18H2O as a green and reusable catalyst
in refluxing acetic acid is described.
Keywords: H6P2W18O62 ꢀ 18H2O; indeno[1,2-b]quinoline-7-ones; multicomponent reactions; one-pot reactions
INTRODUCTION
Nitrogen-containing heterocyclic compounds often play essential roles as the
scaffolds of biological substances. Quinoline derivatives are reported to possess
interesting pharmacological activities such as antiplasmodial, intrinsic, cytotoxic,
functional, antibacterial, antiproliferative, antimalarial, and anticancer activities[1,2]
as well as farnesyl transferase inhibition.[3] Aryl-substituted quinolines also display
tyrokinase platelet-derived growth factor-receptor tyrosine kinase (PDGF-RTK)-
inhibiting properties.[4] Moreover, the polyquinolines derived from quinolines
undergo hierarchical self-assembly into a variety of nanostructures and mesostruc-
tures with enhanced electronic and photonic roles.[5] Therefore, various methods such
as the Skraup, Doebner–von Miller, Friedla¨nder, and Combes procedures have been
developed for the synthesis of quinoline derivatives.[6,7]
Recently,
a
new three-component, one-pot synthesis of indeno[1,2-
b]quinoline-7-one derivatives under microwave irradiation was reported.[8]
Heteropolyacids (HPAs) and their salts are useful acidic catalysts for diverse reac-
tions that require strong acidity.[9] Wells–Dawson-type HPAs possess superacidity and
remarkable stability, both in solution and in the solid state.[10] Many typical
acid-catalyzed reactions are effective in the presence of an appropriate Wells–
Received May 29, 2009.
Address correspondence to Majid M. Heravi, Department of Chemistry, School of Sciences,
Azzahra University, Vanak, Tehran, Iran. E-mail: mmh1331@yahoo.com
2402

SYNTHESIS OF INDENO[1,2-b]QUINOLINE-7-ONES
2403
Scheme 1. Synthesis of indeno[1,2-b]quinoline-7-one derivatives in the presence of H6P2W18O62 ꢀ 18H2O.
Dawson-type HPA catalyst.[11–13] To the best of our knowledge, there are no examples
of the use of solid acid catalysts in the synthesis of indeno[1,2-b]quinoline-7-one deriva-
tives. In continuation of our work on catalytic properties of HPAs and synthesis of het-
erocyclic compounds with biological activities,[14–19] here we report the catalytic activity
of H6P2W18O62 ꢀ 18H2O as a Wells–Dawson-type HPA in the one-pot synthesis of
indeno[1,2-b]quinoline-7-one derivatives by condensing 1-naphtylamine, aldehydes,
and 1,3-indandione in refluxing acetic acid (Scheme 1).
RESULTS AND DISCUSSION
To optimize the reaction conditions, condensation of 4-chlorobenzaldehyde,
1-naphthylamine, and 1,3-indanidione was used as a model reaction. The model
reaction was examined in different solvents under heating conditions. Then the reac-
tion was repeated in acetic acid, the solvent of choice, in different temperatures.
As shown in Table 1, the best results were obtained in refluxing acetic acid.
The scope and generality of this method are illustrated with respect to various
aromatic aldehydes, and the results are summarized in Table 2. A variety of functio-
nalized indeno[2,1-b]quinoline-8-one can be prepared from structurally diverse alde-
hydes. The reaction tolerated both electron-withdrawing and electron-donating
groups (Table 2).
To test the recyclability of H6P2W18O62 ꢀ 18H2O, after completion of the model
reaction, the mixture was poured into ice water, and precipitated products were
separated by filtration and washed with water to separate the catalyst. The catalyst
was recycled by evaporation of water and acetic acid from combined residues under
reduced pressure. The obtained catalyst was washed with diethyl ether, dried, and
reused for the next reaction with only a modest loss in activity (Table 3).
Table 1. Optimization of the reaction conditions in the synthesis model reaction
Entry
Solvent
Temperature (ꢁC)
Time (h)
Yield (%)a
1
2
3
4
5
6
7
8
9
—
AcOH
H2O
120
Reflux
Reflux
Reflux
Reflux
27
12
5
0
97
40
50
50
0
12
12
12
12
12
12
5
DMF
EtOH
AcOH
AcOH
AcOH
AcOH
60
80
70
83
90
100
aYields refer to the isolated pure products.

2404
M. M. HERAVI ET AL.
Table 2. Synthesis of indeno[1,2-b]quinoline-7-one derivatives in the presence of a catalytic
amount of H6P2W18O62 ꢀ 18H2O
Mp (ꢁC)
Entry
Ar
C6H5
4-F-C6H4
Time (h)
Yield (%)a
Obtained
Reported[8]
1
2
3
4
5
6
7
5
95
97
96
95
92
93
96
315–317
341–343
323–325
317–318
354–356
358–360
337–339
>300
>300
>300
>300
>300
>300
>300
4.5
4
4-Cl-C6H4
4-MeO-C6H4
4-NO2-C6H4
3-NO2-C6H4
4-Br-C6H4
4.3
4.45
4.45
3.45
aYields refer to the isolated pure products.
Table 3. Reusability of catalyst in the model reaction
Entry
Run
Time (h)
Yield (%)a
1
2
3
1
2
3
5
5
5
95
90
87
aYields are related to isolated pure products.
In summary, we report here a high-yielding one-pot synthesis of indeno[2,1-b]
quinoline-8-one derivatives from readily available 1-naphtylamine, aldehydes, and
1,3-indandione under simple and convenient conditions. The conditions are mild,
and a wide range of functional groups can be tolerated. Using H6P2W18O62 ꢀ 18H2O
O as catalyst offers advantages including simplicity of operation, easy workup, excel-
lent yields of products, and the recyclability of the catalyst.
EXPERIMENTAL
Melting points are uncorrected. NMR spectra were recorded on a Bruker ARX
300 (300-MHz) instrument. Infrared (IR) spectra were recorded from KBr disks on
the Fourier transform (FT)–IR Bruker Tensor 27. Elemental analysis was done on a
2400 series Perkin-Elmer analyzer. The reactions were monitored by thin-layer chro-
matography (TLC). All solvents and reagents were purchased from Aldrich and
Merck with high-grade quality and were used without any purification. All of the
products were known; their physical and spectroscopic data were compared with
those of authentic samples and found to be identical.[8]
General Procedure: Synthesis of Indeno[1,2-b]quinoline-7-ones
A two-necked, round-bottomed flask equipped with a mechanical stirrer and
reflux condenser was charged with aldehyde (1 mmol), 1,3-indandione (1 mmol),
1-naphtylamine (0.1 mmol), acetic acid (5 mL), and H6P2W18O62 ꢀ 18H2O

SYNTHESIS OF INDENO[1,2-b]QUINOLINE-7-ONES
2405
(0.01 mmol). The reaction mixture was stirred for the time indicated as required to
complete the reaction under the heating conditions (Table 2). Upon completion of
the reaction, monitored by TLC, the mixture was poured into ice water. The preci-
pitated products were separated by filtration, washed with water to separate the cata-
lyst, and recrystallized in a dimethylformamide–ethanol (DMF-EtOH) solution.
Recycling of the Catalyst
The catalyst was recycled by evaporation of water and acetic acid from com-
bined aqueous phases under reduced pressure. The obtained catalyst was washed
with diethyl ether, dried, and reused for the next reaction with only a modest loss
in activity. The catalyst was recovered and reused two times in the model reaction,
and the results are summarized in Table 3.
ACKNOWLEDGMENT
The authors are thankful to the Azzahra Research Council for partial financial
support.
REFERENCES
1. Wang, X.-S.; Zhang, M.-M.; Jiang, H.; Yao, C.-S.; Tu, Sþ.-J. Three-component green
synthesis of N-arylquinoline derivatives in ionic liquid [Bmim ][BFꢀ4 ]: Reactions of arylal-
dehyde, 3-arylamino-5,5-dimethylcyclohex-2-enone, and active methylene compounds.
Tetrahedron 2007, 63, 4439.
2. Tu, S. J.; Jiang, B.; Jia, R. H.; Zhang, J. Y.; Zhang, Y.; Yao, C. S.; Shi, F. An efficient
one-pot, three-component synthesis of indeno[1,2-b]quinoline-9,11(6H,10H)-dione,
acridine-1,8(2H,5H)-dione, and quinoline-3-carbonitrile derivatives from enaminones.
J. Org. Biomol. Chem. 2006, 4, 3664.
3. Yadav, J. S.; Reddy, B. V. S.; Premalatha, K. Bi(OTf)3-catalysed Friedla¨nder
hetero-annulation: A rapid synthesis of 2,3,4-trisubstituted quinolines. Synlett 2004,
6, 963.
4. Maguire, M. P.; Sheets, K. R.; McVety, K.; Spada, A. P.; Zilberstein, A. A new series of
PDGF receptor tyrosine kinase inhibitors: 3-Substituted quinoline derivatives. J. Med.
Chem. 1994, 37, 2129.
5. Jenekhe, S. A.; Lu, L.; Alam, M. M. New conjugated polymers with donor–acceptor
architectures: Synthesis and photophysics of carbazole-quinoline and phenothiazine-
quinoline copolymers and oligomers exhibiting large intramolecular charge transfer.
Macromolecules 2001, 34, 7315.
6. Jiang, B.; Si, Y.-C. Zn(II)-mediated alkynylation–cyclization of o-trifluoroacetyl anilines:
One-pot synthesis of 4-trifluoromethyl-substituted quinoline derivatives. J. Org. Chem.
2002, 67, 9449.
7. Theoclitou, M.-E.; Robinson, L. A. Novel facile synthesis of 2,2,4 substituted 1,2-
dihydroquinolines via a modified Skraup reaction. Tetrahedron Lett. 2002, 43, 3907.
8. Tu, S.; Zhang, Y.; Zhang, J.; Jiang, B.; Jia, R.; Zhang, J.; Ji, S. A simple procedure for the
synthesis of 4-aza-podophyllotoxin derivatives in water under microwave irradiation
conditions. Synlett 2006, 17, 2785–2790.
9. Mizuno, N.; Misono, M. Heterogeneous catalysis. Chem. Rev. 1998, 98, 199.

2406
M. M. HERAVI ET AL.
10. Briand, L. E.; Baronetti, G. T.; Thomas, H. The state of the art on Wells–Dawson
heteropoly compounds: A review of their properties and applications. J. Appl. Catal. A:
Gen. 2003, 256, 37.
11. Romanelli, G. P.; Baronetti, G.; Thomas, H. J.; Autino, J. C. Efficient method for tetra-
hydropyranylation=depyranylation of phenols and alcohols using a solid acid catalyst
with Wells–Dawson structure. Tetrahedron Lett. 2002, 43, 7589.
12. Romanelli, G. P.; Thomas, H. J.; Baronetti, G. T.; Autino, J. C. Solvent-free catalytic
preparation of 1,1-diacetates from aldehydes using
a
Wells–Dawson acid
(H6P2W18O62 ꢀ 24H2O). Tetrahedron Lett. 2003, 44, 1301.
13. Baronetti, G.; Briand, L.; Sedran, U.; Thomas, H. Heteropolyacid-based catalysis.
Dawson acid for MTBE synthesis in gas phase. Appl. Catal. A: Gen. 1998, 172, 265.
14. Heravi, M. M.; Khorasani, M.; Derikvand, F.; Oskooie, H. A.; Bamoharram, F. F.
Highly efficient synthesis of coumarin derivatives in the presence of H14[NaP5W30O110
as a green and reusable catalyst. Catal. Commun. 2007, 8, 1886.
]
15. Heravi, M. M.; Ranjbar, L.; Derikvand, F.; Bamoharram, F. F. H6P2W18O62: An efficient
and reusable catalyst for one-pot synthesis of b-acetamido ketone and esters. Catal.
Commun. 2007, 8, 289.
16. Heravi, M. M.; Ranjbar, L.; Derikvand, F.; Bamoharram, F. F. A modified and
green Dakin–West reaction: An efficient and convenient method for a one-pot synthesis
of b-acetamido carbonyl compounds. J. Mol. Catal. A: Chem. 2007, 271, 28.
17. Heravi, M. M.; Derikvand, F.; Hasanpour, S.; Bakhtiari, K.; Bamoharram, F. F.;
Oskooie, H. A. Oxidative aromatization of Hantzsch 1,4-dihydropyridines in the presence
of mixed-addenda vanadomolybdophosphate heteropolyacid, H6PMO9V3O40. Bioorg.
Med. Chem. Lett. 2007, 17, 3305.
18. Heravi, M. M.; Ranjbar, L.; Derikvand, F.; Alimadadi, B.; Oskooie, H. A. A three-
component, one-pot procedure for the synthesis of [1,2,4]triazolo=benzimidazolo-
quinazolinone derivatives in the presence of H6P2W18O62 ꢀ 18H2O as a green and reusable
catalyst. Mol. Divers. 2008, 12, 181.
19. Heravi, M. M.; Ranjbar, L.; Derikvand, F.; Alimadadi, B. Three-component, one-pot
synthesis of 4,6-diarylpyrimidin-2(1H)-ones under solvent-free conditions in the presence
of sulfamic acid as a green and reusable catalyst. Mol. Divers. 2008, 12, 191.