Acidic ionic liquids catalyzed three-component synthesis of 12-aryl-12H-indeno[1,2-b]naphtho[3,2-e]pyran-5,11,13-trione and 13-aryl-indeno[1,2-b]naphtha[1,2-e]pyran-12(13H)-one derivatives

Article abstract of DOI:10.1016/j.molliq.2012.05.018

Synthesis of 12-aryl-12H-indeno[1,2-b]naphtho[3,2-e]pyran-5,11,13-trione derivatives by the three component reaction of 2-hydroxynaphthalene-1,4-dione, aldehydes, and 2H-indene-1,3-dione under solvent-free conditions at 70 °C in the presence of catalytic amount of acidic ionic liquids such as triethylammonium hydrogensulfate ([Et₃NH][HSO₄]), triethylamine-bonded sulfonic acid ([Et₃N-SO₃H]Cl), 2-pyrrolidonium hydrogensulfate ([Hnhp][HSO₄]), 3-methyl-1-sulfonic acid imidazolium chloride ([Msim]Cl), and 1-methylimidazolium hydrogensulfate ([Hmim][HSO₄]) is described. In addition, 13-aryl-indeno[1,2-b] naphtha[1,2-e]pyran-12(13H)-one derivatives from the reaction of β-naphthol, aldehydes, and 2H-indene-1,3-dione under thermal solvent-free conditions in the presence of mentioned catalysts is reported.

Full text of DOI:10.1016/j.molliq.2012.05.018

Journal of Molecular Liquids 172 (2012) 88–92
Contents lists available at SciVerse ScienceDirect
Journal of Molecular Liquids
journal homepage: www.elsevier.com/locate/molliq
Acidic ionic liquids catalyzed three-component synthesis of 12-aryl-12H-indeno
[1,2-b]naphtho[3,2-e]pyran-5,11,13-trione and 13-aryl-indeno[1,2-b]naphtha[1,2-e]
pyran-12(13H)-one derivatives
⁎
Hamid Reza Shaterian , Majid Mohammadnia, Farzaneh Moradi
Department of Chemistry, Faculty of Sciences, University of Sistan and Baluchestan, PO Box 98135-674, Zahedan, Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
Synthesis of 12-aryl-12H-indeno[1,2-b]naphtho[3,2-e]pyran-5,11,13-trione derivatives by the three component re-
action of 2-hydroxynaphthalene-1,4-dione, aldehydes, and 2H-indene-1,3-dione under solvent-free conditions at
70 °C in the presence of catalytic amount of acidic ionic liquids such as triethylammonium hydrogensulfate
([Et3NH][HSO4]), triethylamine-bonded sulfonic acid ([Et3N–SO3H]Cl), 2-pyrrolidonium hydrogensulfate ([Hnhp]
[HSO4]), 3-methyl-1-sulfonic acid imidazolium chloride ([Msim]Cl), and 1-methylimidazolium hydrogensulfate
([Hmim][HSO4]) is described. In addition, 13-aryl-indeno[1,2-b]naphtha[1,2-e]pyran-12(13H)-one derivatives
from the reaction of β-naphthol, aldehydes, and 2H-indene-1,3-dione under thermal solvent-free conditions in
the presence of mentioned catalysts is reported.
Received 11 March 2012
Received in revised form 24 May 2012
Accepted 24 May 2012
Available online 8 June 2012
Keyword:
Aldehyde
2-Hydroxynaphthalene-1,4-dione
2H-indene-1,3-dione
β-Naphthol
© 2012 Elsevier B.V. All rights reserved.
Ionic liquid
Catalyst
1. Introduction
and 14-aryl-14H-dibenzo[a,j]xanthenes [12], 2-pyrrolidonium hydro-
gensulfate [13] can catalyzed synthesis of benzoxanthene derivatives
Ionic liquids (ILs), because of their low volatility, nonflammability, ca-
pability to dissolve various organic and inorganic compounds, and po-
tentially recyclable properties, have attracted considerable attention as
environmentally friendly reaction media in the green organic
synthesis [1–5]. ILs could effectively drive the development of green
and chemical industries. As is known to all, discovering a new ionic liquid
is relatively easy, but determining its usefulness as a solvent and catalyst
requires a much more substantial investment [1–9]. With the fast devel-
opment of green chemistry and our tireless efforts, herein, we applied
some acidic ionic liquids such as triethylammonium hydrogensulfate
([Et3NH][HSO4]), triethylamine-bonded sulfonic acid ([Et3N–SO3H]Cl),
2-pyrrolidonium hydrogensulfate ([Hnhp][HSO4]), 3-methyl-1-sulfonic
acid imidazolium chloride ([Msim]Cl), and 1-methylimidazolium
hydrogensulfate ([Hmim][HSO4]) as catalysts (Scheme 1) in the synthe-
sis of 12-aryl-12H-indeno[1,2-b]naphtho[3,2-e]pyran-5,11,13-trione and
[13], 3-methyl-1-sulfonic acid imidazolium chloride [14] was used in
preparation of 1-amidoalkyl-2-naphthols [15], benzimidazoles [16],
and 1-methylimidazolium hydrogensulfate [17] was applied in the syn-
thesis of 3,4-dihydropyrimidin-2-(1H)-ones [18] and 1,1-diacetates [17].
2. Experimental
All reagents were purchased from Merck and Aldrich and used
without further purification. The acidic ionic liquids such as
triethylammonium hydrogensulfate [10], triethylamine-bonded sulfon-
ic acid [12], 2-pyrrolidonium hydrogensulfate [13], 3-methyl-1-sulfonic
acid imidazolium chloride [14], and 1-methylimidazolium hydro-
gensulfate [17] were prepared according to literature [10,12–14,17].
All yields refer to isolated products after purification. The NMR spectra
were recorded on a Bruker Avance DPX 300 MHz instrument. The spec-
tra were measured in DMSO-d6 relative to TMS (0.00 ppm). IR spectra
were recorded on a JASCO FT-IR 460 plus spectrophotometer. TLC was
performed on silica-gel Poly Gram SIL G/UV 254 plates.
13-aryl-indeno[1,2-b]naphtha[1,2-e]pyran-12(13H)-one
derivatives
(Scheme 2).
Triethylammonium hydrogensulfate [10] was used in the iodination
of alcohols [11], triethylamine-bonded sulfonic acid [12] was applied in
the preparation of β-acetamido ketones, 1,8-dioxo-octahydroxanthenes
2.1. Synthesis of 12-aryl-12H-indeno[1,2-b]naphtho[3,2-e]pyran-5,11,
13-trione under solvent-free conditions
The mixture of the aldehydes (10 mmol), 2H-indene-1,3-dione
⁎
Corresponding author. Tel.: +98 541 2446565; fax: +98 541 2431067.
E-mail address: hrshaterian@chem.usb.ac.ir (H.R. Shaterian).
(11 mmol), 2-hydroxynaphthalene-1,4-dione (10 mmol) and ionic
0167-7322/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.molliq.2012.05.018

H.R. Shaterian et al. / Journal of Molecular Liquids 172 (2012) 88–92
89
12-(4-Nitrophenyl)-12H-indeno[1,2-b]naphtho[3,2-e]pyran-5,11,13-
trione (Table 2, entry 4): Yellow powder, mp >330 °C.; IR (KBr):
ν
max =3076, 1664, 1636, 1590 cm−1.; 1H NMR (300 MHz, DMSO-
d6): δ=6.06 (s, 1H, CH), 7.46–7.68 (m, 6H, ArH), 7.79–7.96 (m,
4H, ArH), 8.06 (d, J=8.8 Hz, 1H, ArH), 8.12 (d, J=7.6 Hz, 1H, ArH)
ppm.
2.2. General procedure for the synthesis of 13-aryl-indeno[1,2-b]naphtha
[1,2-e]pyran-12(13H)-one derivatives under solvent-free conditions
The mixture of β-naphthol (10 mmol), benzaldehydes (10 mmol)
and 2H-indene-1,3-dione (10 mmol) and ionic liquids containing
[Et3NH][HSO4] (14 mol%), [Et3N–SO3H]Cl (16 mol%), [Hnhp][HSO4]
(15 mol%), [Msim]Cl (17 mol%), and [Hmim][HSO4] (16 mol%) as
acidic catalysts was stirred at 70 °C for the specific time. The reaction
mixture changed from liquid phase to soft-solid phase during the
reaction. After completion of the reaction, it was cooled to room tem-
perature. Then, 5 mL of water was added to the mixture and heated
again. The ionic liquid was dissolved in water, and filtered for
separation of the crude product. The separated product was washed
twice with water (2×5 mL). The solid product was purified by column
chromatography on silica gel using CH2Cl2 as eluent. All of the desired
product(s) were characterized by comparison of their physical data
with those of known compounds. For recycling the catalysts, after
washing solid products with water completely, the water containing
ionic liquid (IL is soluble in water) was evaporated under reduced pres-
sure and ionic liquid was recovered and reused.
Scheme 1. The structure of acidic Brønsted ionic liquids: [Et3NH][HSO4], [Et3N–SO3H]
Cl, [Hnhp][HSO4], [Msim]Cl, [Hmim][HSO4].
liquids containing [Et3NH][HSO4] (15 mol%), [Et3N–SO3H]Cl (16 mol%),
[Hnhp][HSO4] (14 mol%), [Msim]Cl (17 mol%), and [Hmim][HSO4]
(15 mol%) as acidic catalysts was stirred at 70 °C for the specific time.
The reaction mixture changed from liquid phase to soft-solid phase
during the reaction. After completion of the reaction, it was cooled to
room temperature. Then, 5 mL of water was added to the mixture and
heated again. The ionic liquid was dissolved in water, and filtered for
separation of the crude product. The separated product was washed
twice with water (2×5 mL). The solid product was purified by column
chromatography on silica gel using CH2Cl2 as eluent. All of the desired
product(s) were characterized by comparison of their physical data
with those of known compounds. For recycling the catalysts, after
washing solid products with water completely, the water containing
ionic liquid (IL is soluble in water) was evaporated under reduced pres-
sure and ionic liquid was recovered and reused.
Selected spectra for two known products are given below:
13-(4-Methylphenyl)-indeno[1,2-b]naphtho[1,2-e]pyran-12(13H)-
one (Table 4, entry 6):
Yellow solid, mp 194 °C.; IR (KBr): νmax=2950, 1649, 1597, 1372,
1228, 1185 cm−1.; 1H NMR (300 MHz, CDCl3): δ=2.24 (s, 3H),
5.61 (s, 1H), 7.02 (d, J=8.0 Hz, 2H, ArH), 7.21 (d, J=8.0 Hz, 2H,
ArH), 7.43–7.28 (m, 6H, ArH), 7.50 (d, J=9.2 Hz, 1H, ArH ), 7.88–
7.82 (m, 3H, ArH) ppm.
Selected spectra for two known products are given below:
12-Phenyl-12H-indeno[1,2-b]naphtho[3,2-e]pyran-5,11,13-trione
(Table 2, entry 1): yellow powder, mp 312–313 °C.; IR (KBr):
ν
13-(4-Chlorophenyl)-indeno[1,2-b]naphtho[1,2-e]pyran-
12(13H)-one (Table 4, entry 2): Yellow solid, mp 227 °C.; IR (KBr):
ν
max =3032, 1667, 1635, 1660 cm−1.; 1H NMR (300 MHz, DMSO-
max =2952, 1649, 1594, 1375, 1225, 1189 cm−1.; 1H NMR
d6): δ=5.49 (s, 1H, CH), 7.16–7.54 (m, 6H, ArH), 7.64–7.92 (m, 4H,
ArH), 7.99 (d, J=8.4 Hz, 1H, ArH), 8.12 (d, J=7.6 Hz, 1H, ArH), 8.17
(d, J=7.6 Hz, 1H, ArH) ppm.
(300 MHz, CDCl3): δ=5.63 (s, 1H), 7.18 (d, J=8.4 Hz, 2H, ArH),
7.45–7.25 (m, 8H, ArH), 7.51 (d, J=8.8 Hz, 1H, ArH), 7.75 (t, J=
9.2 Hz, 1H, ArH), 7.88–7.84 (m, 2H, ArH) ppm.
Scheme 2. Synthesis of 12-aryl-12H-indeno[1,2-b]naphtho[3,2-e]pyran-5,11,13-trione and 13-aryl-indeno[1,2-b]naphtha[1,2-e]pyran-12(13H)-one derivatives.

90
H.R. Shaterian et al. / Journal of Molecular Liquids 172 (2012) 88–92
Table 1
Optimization conditions for preparation 12-(4-chlorophenyl)-12H-indeno[1,2-b]naphtho[3,2-e]pyran-5,11,13-trione from 4-chlorobenzaldehyde, 2-hydroxynaphthalene-1,4-dione, and
2H-indene-1,3-dione in the presence of different amount of ionic liquids, A: triethylammonium hydrogensulfate, B: triethylamine-bonded sulfonic acid, C: 2-pyrrolidonium
hydrogensulfate, D: 3-methyl-1-sulfonic acid imidazolium chloride, and E: 1-methylimidazolium hydrogensulfate, as catalyst under varieties temperature.
Entry
Catalyst (mol%)
Temperature
(°C)
Time (min)
Yield (%)a
A
A
B
C
D
E
A
B
C
D
E
B
C
D
E
1
2
3
4
5
6
7
20
35
20
30
10
15
20
21
32
18
31
10
16
20
20
30
19
30
8
20
34
20
30
10
17
23
18
32
19
31
10
15
19
25
25
50
50
70
70
70
30
30
22
15
13
12
12
28
30
20
12
10
9
28
30
24
10
8
35
38
30
15
11
10
10
30
32
26
15
10
9
44
56
60
70
81
94
95
40
55
58
69
80
93
94
49
60
62
70
82
93
94
49
60
62
70
81
92
93
40
54
60
72
81
91
92
14
20
7
7
9
9
a
Yields refer to pure isolated products.
3. Results and discussions
synthesize the corresponding products in high to excellent yields
using the five acidic ionic liquids as catalysts (Table 2). Then, we exam-
ined aliphatic aldehyde such as heptanal instead of benzaldehyde in the
reaction. The all starting materials in the reaction almost were intact,
only trace product was formed without any side products after 24 h
(Table 2, Entry 12).
We also investigated the recycling of the ionic liquids under solvent-
free conditions using the model reaction of 4-chlorobenzaldehyde,
2-hydroxynaphthalene-1,4-dione, and 2H-indene-1,3-dione in the
presence of [Et3NH][HSO4] (15 mol%),[Et3N–SO3H]Cl (16 mol%),
[Hnhp][HSO4] (14 mol%), [Msim]Cl (17 mol%), and [Hmim][HSO4]
(15 mol%) (Table 2, Entry 2). After completion of the reaction, water
was added and the precipitated mixture was filtered off for separation
of crude products. After washing the solid products with water
completely, the water containing ionic liquid (IL is soluble in water)
was evaporated under reduced pressure and ionic liquid was recovered
and reused (Fig. 1). The recovered catalysts were reused four runs with-
out any loss of its activities.
In order to show the accessibility of the present work in comparison
with only one reported results in the literature, we summarized some
of the results for the preparation of 12-(4-chlorophenyl)-12H-indeno
[1,2-b]naphtho[3,2-e]pyran-5,11,13-trione in Table 3. The results
show that acidic ionic liquids such as [Et3NH][HSO4] (15 mol%),[Et3N–
SO3H]Cl (16 mol%), [Hnhp][HSO4] (14 mol%), [Msim]Cl (17 mol%),
and [Hmim][HSO4] (15 mol%) under solvent-free conditions relative
to poly(4-vinylpyridinium) hydrogensulfate (P(4-VPH)HSO4) (20 mg)
at 100 °C [19], are the most efficient catalysts with respect to the reac-
tion time and exhibits broad applicability in terms of yields. If we com-
pare the catalytic activity of the acidic ionic liquids together in the
present work (Table 3), we will observe that the 2-pyrrolidonium
hydrogensulfate, ([Hnhp][HSO4]), show much higher activities and
To study the effect of catalyst loading and temperature on the three
component condensation reactions for the synthesis of 12-(4-
chlorophenyl)-12H-indeno[1,2-b]naphtho[3,2-e]pyran-5,11,13-trione,
the solvent-free reaction of 4-chlorobenzaldehyde, 2H-indene-1,3-
dione, 2-hydroxynaphthalene-1,4-dione in the presence of the ionic liq-
uid, triethylammonium hydrogensulfate ([Et3NH][HSO4]), as catalyst
was selected as a model (Table 1). The reaction was carried out with dif-
ferent amount of triethylammonium hydrogensulfate as catalyst (10,
15, 20, 30, 35, mol%) and varieties temperature (25, 50, 70 °C)
(Table 1). As it was shown from Table 1, 15 mol% of [Et3NH][HSO4] as
catalyst at 70 °C afforded the corresponding product in 12 min with
94% of yield. In continuation of our study, optimization conditions of
ionic liquids, [Et3N–SO3H]Cl, [Hnhp][HSO4], [Msim]Cl, and [Hmim]
[HSO4], as catalysts in the model were investigated. According to
Table 1 and its general optimization procedure, 16 mol% of [Et3N–
SO3H]Cl, 15 mol% of [Hnhp][HSO4], 17 mol% of [Msim]Cl, and 16 mol%
of [Hmim][HSO4] as catalysts under solvent-free conditions at 70 °C
was chosen (Table 1). In addition, we used concentrated H2SO4 (98%)
as catalyst in the selected model. Thus, H2SO4 (7 mol%) was used
instead of acidic ionic liquids at room temperature and in an ice bath.
We observed that all of starting materials were decomposed in the
exothermic reaction accompanied by the release of heat. These results
confirm that reusable acidic ionic liquids act better than non recyclable
H2SO4.
Next, three-component condensation reaction of aromatic alde-
hydes, 2-hydroxynaphthalene-1,4-dione, and 2H-indene-1,3-dione,
under optimized conditions for preparation of 12-aryl-12H-indeno
[1,2-b]naphtho[3,2-e]pyran-5,11,13-trione was investigated (Table 2).
The wide ranges of substituted and structurally diverse aldehydes
Table 2
Three component synthesis of 12-aryl-12H-indeno[1,2-b]naphtho[3,2-e]pyran-5,11,13-trione derivatives from the reaction of 2-hydroxynaphthalene-1,4-dione, 2H-indene-1,3-
dione, and aldehydes in the presence of A: [Et3NH][HSO4] (15 mol%), B: [Et3N-SO3H]Cl (16 mol%), C: [Hnhp][HSO4] (14 mol%), D: [Msim]Cl (17 mol%), and E: [Hmim][HSO4]
(15 mol%) as catalysts.
Entry
Aldehydes
Time (min)
A
Yield (%)a
A
Melting point m.p
(°C)/lit. m.p (°C) [ref]
B
C
D
E
B
C
D
E
1
2
3
4
5
6
7
8
C6H5
12
12
13
12
12
12
13
12
12
12
24 h
10
10
10
9
9
9
10
10
9
9
–
8
8
9
7
7
7
8
8
7
7
–
10
10
11
10
10
10
11
10
10
10
–
9
9
10
9
9
9
10
9
9
9
91
92
90
94
92
93
90
90
91
92
91
93
91
91
91
91
91
90
–
92
91
90
93
91
92
90
90
90
90
–
90
91
90
92
91
91
90
91
92
91
–
89
90
89
91
90
91
91
89
90
89
–
313/(311–314) [19]
>330/(>330) [19]
317/(314–316) [19]
>330 /(>330) [19]
317/(316–318) [19]
304/(302–305) [19]
310/(309–311) [19]
291/(290–292) [19]
>330 /(>330) [19]
>330/(>330) [19]
–
4-BrC6H4
4-MeC6H4
4-ClC6H4
2-ClC6H4
3,4-Cl2C6H3
4-MeOC6H4
4-FC6H4
4-NO2C6H4
3-NO2C6H4
n-Heptanal
9
10
12
91
90
Trace
–
a
Yields refer to the isolated pure products. The desired known pure products were characterized by comparison of their physical data (melting points, IR, 1H NMR) with those of
known compounds.

H.R. Shaterian et al. / Journal of Molecular Liquids 172 (2012) 88–92
91
[Et3NH][HSO4]
[Et3N–SO3H]Cl
[Hnhp][HSO4]
[Msim]Cl
[Hmim][HSO4]
100
90
80
70
60
50
40
30
20
10
0
92 92
92
91
91
91
90
90
90
90
89
89 89
88
88
88
87
86 86
87
1
2
3
4
Reaction cycles
Fig. 1. Investigation the recycling of the ionic liquids in the synthesis of 12-(4-chlorophenyl)-12H-indeno[1,2-b]naphtho[3,2-e]pyran-5,11,13-trione.
better results than [Et3NH][HSO4], [Et3N–SO3H]Cl, [Msim]Cl, and
[Hmim][HSO4].
[HSO4] (9, 15, 18, 20, 21, 30, 32 mol%), [Msim]Cl (11, 17, 20, 21, 23, 31,
34 mol%), and [Hmim][HSO4] (10, 16, 18, 19, 20, 30, 32 mol%), and varie-
ties temperature (25, 50, 70 °C) under solvent-free conditions. The best
results were obtained when the amount of catalysts were chosen as
[Et3NH][HSO4] (14 mol%), [Et3N–SO3H]Cl (16 mol%), [Hnhp][HSO4]
(15 mol%), [Msim]Cl (17 mol%), and [Hmim][HSO4] (16 mol%) at 70 °C
for both of them. Then, three-component condensation reaction of aro-
matic aldehydes, β-naphthol, and 2H-indene-1,3-dione under optimized
conditions for preparation of 13-aryl-indeno[1,2-b]naphtha[1,2-e]pyran-
12(13H)-one derivatives was investigated (Table 4). A wide range of
substituted and structurally diverse aldehydes were used and the
corresponding products were synthesized in high to excellent yields,
which demonstrated that this method tolerates both electron-
withdrawing and electron-donating constituents (Table 4). Then, we ex-
amined aliphatic aldehyde such as n-heptanal instead of benzaldehyde
in the reaction. The all starting materials in the reaction almost were in-
tact, only trace product was formed without any side products after 24 h
(Table 4, Entry 10).
We also applied [Et3NH][HSO4], [Et3N–SO3H]Cl, [Hnhp][HSO4],
[Msim]Cl, and [Hmim][HSO4] in condensation reaction of β-naphthol, al-
dehydes, and 2H-indene-1,3-dione under solvent-free conditions for
preparation of 13-aryl-indeno[1,2-b]naphtha[1,2-e]pyran-12(13H)-one
derivatives under (Scheme 1). As, we described optimization procedure,
the reaction of 4-chlorobenzaldehyde, β-naphthol, 2H-indene-1,3-dione
was selected as model. The reaction was carried out in the presence dif-
ferent amount of catalysts, [Et3NH][HSO4] (9, 14, 20, 21, 22, 28,
35 mol%), [Et3N–SO3H]Cl (11, 16, 19, 20, 22, 30, 32 mol%), [Hnhp]
Table 3
Comparison the results of [Et3NH][HSO4], [Et3N-SO3H]Cl, [Hnhp][HSO4], [Msim]Cl, and
[Hmim][HSO4] with P(4-VPH)HSO4 in the synthesis 12-(4-chlorophenyl)-12H-indeno
[1,2-b]naphtho[3,2-e]pyran-5,11,13-trione.
Entry Catalyst (mol%)
Conditions
Time
Yield (%)a [ref]
The recycling of the ionic liquids was studied such as above proce-
dure in selected model. The recovered catalysts were reused four runs
without any loss of its activities (Fig. 2).
1
2
P(4-VPH)HSO4 (20 mg)
Solvent-free, 100 °C 90 min 92 [19]
[Et3NH][HSO4] (15 mol%) Solvent-free, 70 °C 12 min 94
(present work)
93
In order to show the accessibility of the present work in compari-
son with only one reported results in the literature such as silica
chloride [20], we summarized some of the results for the preparation of
13-(4-chlorophenyl)-indeno[1,2-b]naphtho[1,2-e]pyran-12(13H)-one in
Table 5. The results show that acidic ionic liquids such as [Et3NH][HSO4]
(14 mol%), [Et3N–SO3H]Cl (16 mol%), [Hnhp][HSO4] (15 mol%), [Msim]
Cl (17 mol%), and [Hmim][HSO4] (16 mol% are the most efficient catalysts
with respect to the reaction time and yields of the products. As it was
shown from Table 5, [Hnhp][HSO4] show much higher activities and
3
4
5
6
[Et3N-SO3H]Cl (16 mol%) Solvent-free, 70 °C
[Hnhp][HSO4] (14 mol%) Solvent-free, 70 °C
9 min
7 min
(present work)
93
(present work)
[Msim]Cl (17 mol%)
Solvent-free, 70 °C
10 min 92
(present work)
91
(present work)
[Hmim][HSO4] (15 mol%) Solvent-free, 70 °C
9 min
a
Yields refer to isolated pure products and based on the reaction of
4-chlorobenzaldehyde, 2-hydroxynaphthalene-1,4-dione, and 2H-indene-1,3-dione.
Table 4
Three component synthesis of 13-aryl-indeno[1,2-b]naphtha[1,2-e]pyran-12(13H)-one derivatives from the reaction of β-naphthol, 2H-indene-1,3-dione, and aldehydes in the
presence of A: [Et3NH][HSO4] (14 mol%), B: [Et3N-SO3H]Cl (16 mol%), C: [Hnhp][HSO4] (15 mol%), D: [Msim]Cl (17 mol%), and E: [Hmim][HSO4] (16 mol%) as catalysts.
Entry
Aldehydes
Time (min)
A
Yield (%)a
A
Melting point m.p
(°C)/lit. m.p (°C)
[ref]
B
C
D
E
B
C
D
E
1
2
3
4
5
6
7
8
9
10
C6H5
4-ClC6H4
10
10
10
11
12
12
12
12
10
24 h
10
9
9
9
8
8
9
10
11
11
10
9
9
9
9
10
11
10
10
9
10
10
10
11
12
11
9
89
93
91
91
92
90
91
90
90
93
92
91
91
91
90
91
91
–
92
92
91
91
91
91
91
91
91
–
90
92
92
92
90
90
91
90
90
–
91
91
92
92
92
92
89
91
89
–
201/(202–03) [20]
227/(225–226) [20]
254/(252–253) [20]
242/(240–241) [20]
241/(240–241) [20]
194/(192–193) [20]
227/(225–226) [20]
209/(208–209) [20]
246/(245–246) [20]
–
2,4-Cl2C6H3
3-NO2C6H4
2-ClC6H4
4-MeC6H4
4-MeOC6H4
4-FC6H4
9
10
10
10
11
10
–
10
10
–
3,4-Cl2C6H3
n-Heptanal
11
–
90
Trace
–
a
Yields refer to the isolated pure products. The desired known pure products were characterized by comparison of their physical data (melting points, IR, 1H NMR) with those of
known compounds.

92
H.R. Shaterian et al. / Journal of Molecular Liquids 172 (2012) 88–92
[Et3NH][HSO4]
[Et3N–SO3H]Cl
[Hnhp][HSO4]
91 91
89 89 89
[Msim]Cl
[Hmim][HSO4]
100
90
80
70
60
50
40
30
20
10
0
93
92
92 92
91
91
90
90
89
88
88
87
87
86 86
1
2
3
4
Reaction cycles
Fig. 2. The recycling of the ionic liquids in the preparation of 13-(4-chlorophenyl)-indeno[1,2-b]naphtho[1,2-e]pyran-12(13H)-one.
Table 5
Acknowledgments
Comparison the results of [Et3NH][HSO4], [Et3N-SO3H]Cl, [Hnhp][HSO4], [Msim]Cl, and
[Hmim][HSO4] with SiO2-Cl in the synthesis 13-(4-chlorophenyl)-indeno[1,2-b]naph-
tho[1,2-e]pyran-12(13H)-one.
We are thankful to the University of Sistan and Baluchestan Re-
search Council for the partial support of this research.
Entry Catalyst (mol%)
Conditions
Time
Yield (%)a [ref]
References
1
2
SiO2–Cl (150 mg)
Solvent-free, 110 °C 1 h
90 [20]
[Et3NH][HSO4] (14 mol%) Solvent-free, 70 °C
[Et3N–SO3H]Cl (16 mol%) Solvent-free, 70 °C
[Hnhp][HSO4] (15 mol%) Solvent-free, 70 °C
12 min 93
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(present work)
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3
4
5
6
9 min
7 min
(present work)
[Msim]Cl (17 mol%)
Solvent-free, 70 °C
10 min 92
(present work)
91
(present work)
[Hmim][HSO4] (16 mol%) Solvent-free, 70 °C
9 min
a
Yields refer to isolated pure products and based on the reaction of
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4. Conclusion
We have shown that acidic ionic liquids, which can be prepared
from commercially available and inexpensive starting materials, cata-
lyzed efficiently synthesis of 12-aryl-12H-indeno[1,2-b]naphtho[3,2-e]
pyran-5,11,13-triones and 13-aryl-indeno[1,2-b]naphtha[1,2-e]pyran-
12(13H)-one derivatives. The simplicity of the procedure, eco-
friendly, non-volatile, easy handling, safety and reusability of catalyst
are the advantages of these methods. These methods not only afford
the products in excellent yields but also avoid the problems associated
with catalyst cost, and pollution.
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