Synthesis of novel benzo[f]chromene compounds catalyzed by ionic liquid

Article abstract of DOI:10.1515/hc-2011-0060

A facile method for the synthesis of benzo[f]chromene derivatives is reported. The procedure involves a novel three-component reaction of 1-naphthol or 2-naphthol, acetophenone derivatives and triethyl orthobenzoate in the presence of silica supported ion

Full text of DOI:10.1515/hc-2011-0060

Heterocycl. Commun., Vol. 18(2), pp. 67–70, 2012 • Copyright © by Walter de Gruyter • Berlin • Boston. DOI 10.1515/hc-2011-0060
Synthesis of novel benzo[f ]chromene compounds
catalyzed by ionic liquid
Hossein Eshghi1, Gholam Hossein Zohuri1,
processes involving acidic ionic liquids on solid supports
have been designed (Du et al., 2006; Gupta et al., 2007; Wang
Reza Sandaroos2 and Saman Damavandi3,*
et al., 2008). The heterogenization of catalysts and reagents can
1Department of Chemistry, Faculty of Science, Ferdowsi
offer important advantages in handling, separation and reuse
University of Mashhad, Mashhad, Iran
procedures. Immobilized acidic ionic liquids have been used as
2Department of Chemistry, Faculty of Science, Birjand
novel solid catalysts for a wide spectrum of reactions (Fischer
University, Birjand, Iran
et al., 1999; Qiao et al., 2006; Sugimura et al., 2007).
3 Department of Chemistry, Sarvestan Branch, Islamic
Chromenes and fused chromenes are biologically active
Azad University, Sarvestan, Iran
compounds and they are used as cosmetics and pigments (Hafez
*Corresponding author
e-mail: Saman_Damavandi@yahoo.com
et al., 1987; Ellis et al., 1997), spasmolytic, diuretic, anticoagu-
lant, antianaphylactic (Triggle, 2003; Poupaert et al., 2005),
antibacterial (Kidwai et al., 2005), anticancer agents (Mohr et
al., 1975), and as potent apoptosis inducers (Gao et al., 2010).
Abstract
Recently, many studies have been devoted to the synthesis of
benzo[f]chromene compounds by developing and modification of
synthetic methods. Claisen rearrangement of alkynyl aryl ethers
from propargylic alcohols and naphthols under acid catalysis to
synthesize 2H-1-benzopyran derivatives has been reported (Xu
et al., 2009). In addition, several catalysts have been utilized for
the synthesis of 2-amino-4H-chromenes such as cetyltrimeth-
ylammonium chloride (Ballini et al., 2000), cetyltrimethylammo-
nium bromide under ultrasound irradiation (Jin et al., 2004), KF/
Al2O3 (Wang et al., 2004), TiCl4 (Sunil et al., 2006), triethylamine
(Shestopalov et al., 2002), basic ionic liquids (Gong et al., 2008),
iodine/K2CO3 (Ren and Cai, 2008), and DABCO (Balalaie et al.,
2008). However, synthesis of 1-ethoxy-3-(4-aryl)-1-phenyl-1-
H-benzo[f]chromene has never been reported up to now. In the
course of our ongoing research for the efficient and convenient
synthesis of a variety of heterocyclic compounds (Damavandi,
2011; Damavandi and Sandaroos, 2011a; Damavandi and
Sandaroos, 2011b), we developed an efficient synthetic proce-
dure for the synthesis of a series of benzo[f]chromenes by one-pot
condensation of 2-naphthol or 1-naphthol, acetophenone deriva-
tives and triethyl orthobenzoate catalyzed by silica supported
A facile method for the synthesis of benzo[f]chromene deriv-
atives is reported. The procedure involves a novel three-com-
ponent reaction of 1-naphthol or 2-naphthol, acetophenone
derivatives and triethyl orthobenzoate in the presence of sil-
ica supported ionic liquid [pmim]HSO4 SiO [silica supported
2
1-methyl-3-(triethoxysilylpropyl)imidazolium hydrogensul-
fate] as an efficient catalyst.
Keywords: benzo[f]chromene; ionic liquid;
one-pot reaction.
Introduction
Currently, one of the major challenges of modern drug dis-
covery is the design of highly efficient chemical reaction
sequences providing a maximum of structural diversity using
a minimum number of synthetic steps to assemble compounds
with interesting properties (Dömling, 2002). Recently, multi-
component reactions (MCRs) have emerged as a highly valu-
able synthetic tool in the realm of modern drug discovery.
The atom economical and convergent character, the simplic-
ity of a one-pot procedure, the possible structural variations,
the accessible complexity of the molecules, as well as the
very large number of accessible compounds are among the
described advantages of MCRs (Trost, 1995).
ionic liquid of [pmim]HSO4 SiO [silica supported 1-methyl-3-
2
(triethoxysilylpropyl)imidazolium hydrogensulfate] (Scheme 1).
Results and discussion
Attempts have been made by many research groups to pre-
pare supported catalysts in the area of transition metal cat-
alyst mediated various organic reactions (De et al., 2002;
Rechavi and Lemaire, 2002). In the present study, [pmim]
Recently, ionic liquids have become a powerful alterna-
tive to conventional molecular organic solvents due to their
particular properties, such as undetectable vapor pressure and
the ability to dissolve many organic and inorganic substances
(Wasserscheid and Welton, 2007). In addition, the ionic liq-
uids are readily recycled and tunable to specific chemical
tasks. One type is Brønsted acidic task-specific ionic liquids.
Among these ionic liquids possessing HSO4 as a counteran-
ion finds a broad application in organic synthesis, acting
as both a solvent and a catalyst. Recently, immobilization
HSO4 SiO (Scheme 1) was prepared based on a published
2
report (Chrobok et al., 2009).
Initial experiments were performed with 2-naphthol,
acetophenone and triethyl orthobenzoate as the model sub-
strates. When 2-naphthol (1 mmol) was treated with aceto-
phenone (1 mmol) and triethyl orthobenzoate (1 mmol) in the
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68 H. Eshghi et al.
N
HSO4
NH
2
X
EtO
EtO
OEt
O
Si
OH O
O
OH
OEt
Si Si Si Si
H
O
O
O
O
H
H
O
H
+ 2EtOH + H2O
CH3CN, 65°C
O
H
O
4a-4g
X
1
3
X=H-(4a); Br-(4b); Cl-(4c); NO2-(4d); Me-(4e); OMe-(4f); OH-(4g)
X
N
2
HSO4
EtO
EtO
NH
OEt
O
Si
H
H
H
OH O
O
OH
O
O
H
O
Si Si Si Si
+ 2EtOH
+ H2O
O
O
O
O
O
H
CH3CN, 65°C
X
3
1
4h-4k
X=H-(4h); Cl-(4i); NO2-(4j); Me-(4k)
Scheme 1 Synthesis of benzochromene derivatives 4a–4k.
presence of a catalytic amount of [pmim]HSO4 SiO (0.015
reaction efficiencies were slightly improved by changing the
substituent groups from Br and Cl to the methoxy group. It
can be suggested that the first step, nucleophilic attack of
2-naphthol to the triethyl orthobenzoate might be the rate
determining step.
2
mmol) at 65°C in acetonitrile, the desired 1-ethoxy-1,3-di-
phenyl-1H-benzo[f]chromene (4a) was obtained in 85% yield
(Scheme 1). To investigate the effect of solvent on the cata-
lytic efficiency of [pmim]HSO4 SiO , various solvents were
2
examined for the model reaction (Table 1). Protic solvents
such as ethanol and methanol afforded poor results. Inversely,
application of polar aprotic solvent such as acetonitrile sig-
nificantly improved chemical yields and reaction times.
Moreover, moderate yields were obtained using toluene and
benzene as polar media for the model reaction.
Furthermore, the use of 1-naphthol was also attempted
in the reaction with acetophenone derivatives and triethyl
orthobenzoate under optimized conditions. As shown in
Scheme 1, the corresponding benzo[f]chromene derivatives
4h–j were synthesized successfully in good yields.
We extended the model reaction using different deriva-
tives of acetophenone. It was revealed that the electronic
nature of substituted groups on acetophenone does not affect
the reaction times as well as chemical yields. However,
Conclusion
We report an effective methodology for the synthesis of a
series of novel substituted benzo[f]chromenes by the one-pot
three component reaction of 2-naphthol or 1-naphthol, aceto-
phenone and triethyl orthobenzoate utilizing silica supported
Table 1 Effect of solvents on the catalytic efficiency of [pmim]
HSO4 SiO
.
2
ionic liquid of [pmim]HSO4 SiO
.
2
Entry
Solvent
Time (h)
Isolated yield (%)
1
2
3
4
5
CH3CN
EtOH
MeOH
DMSO
Toluene
6
8
8
6
8
85
64
60
80
72
Experimental
General
All chemicals and ionic liquids were purchased from Merck, Fluka
and Aldrich Chemical Companies. All yields refer to isolated prod-
Reaction conditions: 1.0 equiv. of 2-naphthol, 1.0 equiv. of aceto-
phenone, 1.0 equiv. of triethyl orthobenzoate, 15 mol% of [pmim]
1
ucts. H NMR spectra were recorded on a Bruker 250-MHz spec-
HSO4 SiO , 4 mL of solvent and at 65°C.
trometer in DMSO-d6 as the solvent and TMS as internal standard.
2
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Novel benzo[f]chromene compounds 69
Elemental analysis was performed on a Thermo Finnigan EA1112
elemental analyzer. The catalyst [pmim]HSO4 SiO (extent of labeling
0.25 mmol/g loading) was prepared as reported p2reviously (Chrobok
et al., 2009).
Hz); EIMS: m/z 408 (M+). Anal. Calcd for C28H24O3: C, 82.33; H,
5.92%. Found: C, 81.46; H, 5.83%.
4-(1-Ethoxy-1-phenyl-1H-benzo[f]chromen-3-yl)phenol
1
(4g) After 5 h the yield was 84%; mp 253–255°C; H NMR: δ
9.45 (1 H, s), 7.60–7.45 (2 H, m), 7.35–7.20 (10 H, m), 7.15–7.05
(3 H, m), 5.65 (1 H, s), 3.52 (2 H, q, J=7 Hz), 1.10 (3 H, t, J=7 Hz,
CH3); EIMS: m/z 394 (M+). Anal. Calcd for C27H22O3: C, 82.21; H,
5.62%. Found: C, 81.43; H, 5.54%.
General procedure for the synthesis of benzo[f]-
chromene derivatives 4a–g
A mixture of 2-naphthol (1 mmol), an acetophenone (1 mmol),
triethyl orthobenzoate (1.1 mmol) and ionic liquid catalyst (0.15
mmol) in CH3CN (4 mmol) was stirred at 65°C for the period of
time indicated below. The reaction was monitored by TLC and, after
completion of the reaction, the catalyst was recovered by filtration
and washed with dichloromethane. The residue was concentrated
under reduced pressure and the crude product was crystallized from
ethanol/H2O (3:1).
1-Ethoxy-1,3-diphenyl-1H-benzo[f]chromene (4h) After 7 h
the yield was 87%; mp 208–210°C; 1H NMR: δ 7.90 (1H, d, J=8 Hz),
7.74–7.40 (4 H, m), 7.35–7.05 (11 H, m), 5.65 (1 H, s), 3.55 (2 H, q,
J=7 Hz,), 1.21 (3 H, t, J=7 Hz); EIMS: m/z 378 (M+). Anal. Calcd for
C27H22O2: C, 85.69; H, 5.86%. Found: C, 84.02; H, 5.76%.
3-(4-Chlorophenyl)-1-ethoxy-1-phenyl-1H-benzo[f]chromene
(4i) After 4 h the yield was 91%; mp 214–215°C; H NMR: δ
7.85 (1 H, d, J=7 Hz), 7.70–7.45 (6 H, m), 7.35–7.14 (8 H, m), 5.57
(1 H, s), 3.52 (2 H, q, J=7 Hz), 1.20 (3 H, t, J=7 Hz); EIMS: m/z 412
(M+). Anal. Calcd for C27H21ClO2: C, 78.54; H, 5.13%. Found: C,
77.24; H, 5.03%.
1
General procedure for the synthesis of benzo[f]-
chromene derivatives 4h–k
The procedure described above was conducted in the presence of
1-naphthol under otherwise identical conditions. Products 4h–k were
crystallized from ethanol/water (3:1).
1-Ethoxy-3-(4-nitrophenyl)-1-phenyl-1H-benzo[f]chromene
(4j) After 5 h the yield was 92%; mp 221–223°C; 1H NMR: δ 7.95
(2 H, m), 7.65–7.35 (5 H, m), 7.35–7.10 (8 H, m), 5.70 (1 H, s), 3.60
(2 H, q, J=7 Hz), 1.18 (3 H, t, J=7 Hz); EIMS: m/z 423 (M+). Anal.
Calcd for C27H21NO4: C, 76.58; H, 5.00; N, 3.31%. Found: C, 74.83;
H, 5.06; N, 3.22%.
1-Ethoxy-1,3-diphenyl-1H-benzo[f]chromene (4a) After 6 h
the yield was 85%; mp 211–213°C; 1H NMR: δ 7.60–7.40 (6 H, m),
7.35–7.05 (10 H, m), 5.72 (1 H, s), 3.62 (2 H, q, J=7 Hz), 1.25 (3 H, t,
J=7 Hz); EI-MS: m/z 378 (M+). Anal. Calcd for C27H22O2: C, 85.69;
H, 5.86%. Found: C, 84.18; H, 5.73%.
3-(4-Bromophenyl)-1-ethoxy-1-phenyl-1H-benzo[f]chromene
(4b) After 7 h the yield was 85%; mp 217–219°C; H NMR: δ
7.65–7.45 (5 H, m, ArH), 7.35–7.08 (10 H, m, ArH), 5.65 (1 H, s,
CH), 3.57 (2 H, q, J=7 Hz), 1.22 (3 H, t, J=7 Hz); EIMS: m/z 456
(M+). Anal. Calcd for C27H21BrO2: C, 70.90; H, 4.63%. Found: C,
68.73; H, 4.52%.
1-Ethoxy-1-phenyl-3-p-tolyl-1H-benzo[f]chromene (4k) After
5 h the yield was 88%; mp 217–219°C; 1H NMR: δ 7.85–7.40
(3 H, m), 7.35–7.20 (7 H, m), 7.15–7.05 (5 H, m), 5.63 (1 H, s), 3.48
(2 H, q, J=7 Hz), 2.24 (3 H, s), 1.19 (3 H, t, J=7 Hz); EIMS: m/z
392 (M+). Anal. Calcd for C28H24O2: C, 85.68; H, 6.16%. Found: C,
85.17; H, 6.26%.
1
3-(4-Chlorophenyl)-1-ethoxy-1-phenyl-1H-benzo[f]chromene
1
(4c) After 7 h the yield was 88%; mp 233–235°C; H NMR: δ
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Received September 17, 2011; accepted December 2, 2011;
previously published online March 2, 2012
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