Silica-bonded propylpiperazine-N-sulfamic acid as recyclable solid acid catalyst for preparation of 2-amino-3-cyano-4-aryl-5,10-dioxo- 5,10-dihydro-4H-benzo[g]chromenes and hydroxy-substituted naphthalene-1,4-dione derivatives

Article abstract of DOI:10.1016/S1872-2067(12)60761-X

An efficient method for the synthesis of 2-amino-3-cyano-4-aryl-5,10-dioxo- 5,10-dihydro-4H-benzo[g]chromenes and hydroxy-substituted naphthalene-1,4-dione derivatives, using silica-bonded propylpiperazine-N-sulfamic acid as a solid acid, green, heterogeneous catalyst, under ambient and solvent-free conditions, is described. A simple procedure, high yields, short reaction time, safety, and reusability of the catalyst are advantages of these protocols.

Full text of DOI:10.1016/S1872-2067(12)60761-X

Chinese Journal of Catalysis 35 (2014) 242–246
ava i l a b l e a t w w w. s c i e n c ed i r e c t . c o m
j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e /c h n j c
Article
Silica‐bonded propylpiperazine‐N‐sulfamic acid as recyclable solid
acid catalyst for preparation of 2‐amino‐3‐cyano‐4‐aryl‐5,10‐dioxo‐
5,10‐dihydro‐4H‐benzo[g]chromenes and hydroxy‐substituted
naphthalene‐1,4‐dione derivatives
Fahime Khorami, Hamid Reza Shaterian*
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:
An efficient method for the synthesis of 2‐amino‐3‐cyano‐4‐aryl‐5,10‐dioxo‐5,10‐dihydro‐4H‐ben‐
zo[g]chromenes and hydroxy‐substituted naphthalene‐1,4‐dione derivatives, using silica‐bonded
propylpiperazine‐N‐sulfamic acid as a solid acid, green, heterogeneous catalyst, under ambient and
solvent‐free conditions, is described. A simple procedure, high yields, short reaction time, safety,
and reusability of the catalyst are advantages of these protocols.
Received 31 August 2013
Accepted 4 November 2013
Published 20 February 2014
© 2014, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.
Published by Elsevier B.V. All rights reserved.
Keywords:
Silica‐bonded propylpiperazine‐N‐
sulfamicacid
Aldehyde
Malononitrile
Amine
Solvent‐free
2‐Hydroxynaphthalene‐1,4‐dione
1. Introduction
devices [8], molecular probes for biochemical research [9], in
traditional textile and polymer fields [10], and as fluorescent
Multicomponent reactions (MCRs) are valuable tools in or‐
ganic and medicinal chemistry [1]. The use of MCRs has be‐
come a major driving force in the development of highly effi‐
cient and sustainable procedures for the assembly of biologi‐
cally active compounds, in both academia and industry [1,2].
2‐Amino‐3‐cyano‐4‐aryl‐5,10‐dioxo‐5,10‐dihydro‐4H‐benzo
[g]chromene derivatives show various biological activity, in‐
cluding anticancer [3], anti‐inflammatory [4], antimalarial [5,6],
and pesticide activity [7]. Hydroxy‐substituted naphtha‐
lene‐1,4‐dione derivatives are fluorescent heterocyclic com‐
pounds. These fluorescent materials are of interest in many
disciplines and are used as emitters in electroluminescence
whitening agents [11].
A literature survey showed that 2‐amino‐3‐cyano‐4‐aryl‐
5,10‐dioxo‐5,10‐dihydro‐4H‐benzo [g] chromenes have been
prepared in the presence of DBU[CH3COO], [Pyrr][CH3COO],
[Pyrr][HCOO], [Pip][CH3COO], [Pip][HCOO], [Hmim][HCOO],
and 3‐HPAA [12], Et3N and CH3CN [13], HOAc/dimethylfor‐
mamide [14], [bmim]OH [15], triethylbenzylammonium chlo‐
ride [16], DBU [17], Et3N and EtOH [18], 2‐hydroxy‐
ethylammonium formate and 2‐hydroxyethylammonium ace‐
tate [19], and cetyltrimethylammonium bromide [20] as cata‐
lysts from three‐component condensation reactions of aro‐
matic aldehydes, malononitrile, and 2‐hydroxynaphthalene‐
* Corresponding author. Tel: +98‐541‐2447010; Fax: +98‐541‐2431067; E‐mail: hrshaterian@chem.usb.ac.ir
DOI: 10.1016/S1872‐2067(12)60761‐X | http://www.sciencedirect.com/science/journal/18722067 | Chin. J. Catal., Vol. 35, No. 2, February 2014

Fahime Khorami et al. / Chinese Journal of Catalysis 35 (2014) 242–246
1,4‐dione. Also, hydroxy‐substituted naphthalene‐1,4‐dione
solvent‐free and ambient conditions
derivatives have been synthesized in the presence of
DBU[CH3COO], [Pyrr][CH3COO], [Pyrr][HCOO], [Pip][CH3COO],
[Pip][HCOO], [Hmim][HCOO], and 3‐HPAA [12], InCl3 [21], and
nano copper(II) oxide [22] as catalysts in the three‐component
condensation reactions of aromatic aldehydes, aromatic
amines, and 2‐hydroxynaphthalene‐1,4‐dione.
In a continuation of our studies on the use of solid acid cat‐
alysts in organic transformations [23–27], we report an effi‐
cient method for the synthesis of 2‐amino‐3‐cyano‐4‐aryl‐5,10‐
A mixture of an aldehyde (10 mmol), malononitrile (10
mmol), 2‐hydroxynaphthalene‐1,4‐dione (10 mmol), and
SBPPSA (0.05 g; 0.25 g equals 0.31 mmol of H+ [28]) as a solid
acid catalyst was stirred under ambient and solvent‐free condi‐
tions for a specific time. Completion of the reaction was moni‐
tored using TLC. Ethanol (5 mL) was then added, the reaction
mixture was filtered, and the remaining solid was washed with
warm ethanol (3 × 5 mL) to separate the catalyst. The filtrate
solution containing the crude product was evaporated and
recrystallized from ethanol. The recovered catalyst was dried
and reused in subsequent runs. All of the desired product(s)
were characterized by comparison of their physical data with
those of known compounds.
Selected spectra for a known product are given below.
2‐Amino‐3‐cyano‐4‐(2,4‐dichlorophenyl)‐5,10‐dioxo‐5,10‐dihy
dro‐4H‐benzo[g]chromene (Table 2, entry 13): orange powder;
m.p. = 288 °C; IR (KBr, cm−1): νmax 3467, 3341, 3168, 2201,
1664, 1631, 1591, 1364, 1247, 1200; 1H NMR (300 MHz,
DMSO‐d6): δ 4.74 (1H, s, CH), 8.08–7.48 (9 H, m, Ar and NH2);
13C NMR (75 MHz, DMSO‐d6): δ 37.1, 56.9, 110.3, 119.2, 119.5,
121.1,126.2 (2C), 126.5, 129.3, 131.2, 131.3, 133.1, 136.6 (2C),
136.9,149.5, 158.1, 177.2, 183.6.
dioxo‐5,10‐dihydro‐4H‐benzo[g]chromenes,
using
silica‐
bonded propylpiperazine‐N‐sulfamic acid (SBPPSA) [28–31] as
the catalyst, by three‐component condensation reactions of
aromatic aldehydes, malononitrile, and 2‐hydroxynaphthalene‐
1,4‐dione under ambient and solvent‐free conditions (Scheme
1).
We also used this environmentally friendly SBPPSA in the
condensation reactions of aromatic aldehydes, aromatic
amines, and 2‐hydroxynaphthalene‐1,4‐dione in the prepara‐
tion of hydroxy‐substituted naphthalene‐1,4‐dione derivatives
under ambient and solvent‐free conditions (Scheme 2).
2. Experimental
All reagents were purchased from Merck or Aldrich and
used without further purification. SBPPSA was prepared by the
reaction of 3‐piperazine‐N‐propylsilica with chlorosulfonic acid
in chloroform, according to the method reported in the litera‐
ture [28]. All yields refer to isolated products after purification.
Nuclear magnetic resonance (NMR) spectra were recorded
using a Bruker Advance DPX 300 MHz instrument. The spectra
were measured in DMSO‐d6 relative to tetramethylsilane. In‐
frared (IR) spectra were recorded using a JASCO FTIR 460 Plus
spectrophotometer. Melting points were determined in open
capillaries using a BUCHI 510 melting point apparatus. Thin‐
layer chromatography (TLC) was performed on silica‐gel Poly
Gram SIL G/UV 254 plates.
2.2. Synthesis of hydroxy‐substituted naphthalene‐1,4‐dione
derivatives under ambient and solvent‐free conditions
A mixture of an aldehyde (10 mmol), aniline (10 mmol),
2‐hydroxynaphthalene‐1,4‐dione (10 mmol), and SBPPSA (0.05
g; 0.25 g equals 0.31 mmol of H+ [28]) as a solid acid catalyst
was stirred under ambient and solvent‐free conditions for a
specific time. Completion of the reaction was monitored using
TLC. Ethanol (5 mL) was added, the reaction mixture was fil‐
tered, and the remaining solid was washed with warm ethanol
(3 × 5 mL) to separate the catalyst. The filtrate solution con‐
taining the crude product was evaporated and recrystallized
from ethanol. The recovered catalyst was dried and reused in
subsequent runs. All of the desired product(s) were character‐
ized by comparison of their physical data with those of known
compounds.
2.1. General procedure for synthesis of 2‐amino‐3‐cyano‐4‐
aryl‐5,10‐dioxo‐5,10‐dihydro‐4H‐benzo[g]chromenes under
CHO
O
O
Selected spectra for a known product are given below.
2‐Hydroxy‐3‐[phenyl(phenylamino)methyl]naphthalene‐1,4‐di
one (Table 3, entry 1): orange powder; m.p. = 145–146 °C; IR
O
NH2
CN
OH
CN
CN
SBPPSA (Catalyst)
Solvent-free
Room temparature
X
1
(KBr, cm−1): νmax 3434, 3321, 1660, 1636; H NMR (300 MHz,
O
O
DMSO‐d6): δ 5.98 (1H, s, CH), 7.25–8.07 (15H, m, Ar and NH),
9.26 (1H, s, OH); 13C NMR (75 MHz, DMSO‐d6): δ 37.3, 113.4,
123.9, 125.9, 125.9, 126.4, 128.5, 129.6, 130.3, 132.6, 133.1,
133.5, 135.0, 138.1, 146.0, 156.8, 157.6, 181.8, 184.0.
O
O
X
Si
N
SiO2
O
N
SO3H
SBPPSA
Scheme 1. Synthesis of 2‐amino‐3‐cyano‐4‐aryl‐5,10‐dioxo‐5,10‐
dihydro‐4H‐benzo[g]chromene derivatives.
3. Results and discussion
X
O
CHO
X
NH2
Y
O
Y
First, the reaction conditions were optimized using the reac‐
tion of 4‐methoxybenzaldehyde, malononitrile, and 2‐hy‐
droxynaphthalene‐1,4‐dione in the presence of SBPPSA as a
catalyst under ambient and solvent‐free conditions as a model.
The reaction was carried out with different amounts of SBPPSA
OH
SBPPSA (Catalyst)
N
H
Solvent-free
Room temparature
OH
O
O
Scheme 2. Synthesis of hydroxy‐substituted naphthalene‐1,4‐dione
derivatives.

Fahime Khorami et al. / Chinese Journal of Catalysis 35 (2014) 242–246
Table 1
matic aldehydes, malononitrile, and 2‐hydroxynaphthalene‐
1,4‐dione for the preparation of 2‐amino‐3‐cyano‐4‐aryl‐5,10‐
dioxo‐5,10‐dihydro‐4H‐benzo[g]chromene derivatives were
investigated under the optimized conditions (Table 2). The
reaction time and yields of the corresponding products were
unaffected by the presence of electron‐donating groups and
electron‐withdrawing groups on the benzaldehydes. We also
examined aliphatic aldehydes such as n‐heptanal instead of
benzaldehydes in the reaction. All the starting materials were
intact and none of the desired products or byproducts were
formed after 24 h (Table 2, entry 16).
Optimization of amount of SBPPSA as catalyst in three‐component
synthesis of 2‐amino‐3‐cyano‐4‐(4‐methoxyphenyl)‐5,10‐dioxo‐5,10‐
dihydro‐4H‐benzo[g]chromene from the reaction of 2‐hydroxynaph‐
thalene‐1,4‐dione, malononitrile, and 4‐methoxybenzaldehyde under
solvent‐free and ambient conditions.
Entry
Catalyst (g)
0.02
Time (min)
Yield a (%)
1
2
3
4
40
25
15
9
72
90
90
91
0.05
0.10
0.20
a Yields refer to pure isolated product.
(0.02, 0.05, 0.1, 0.2 g; Table 1). As the data in Table 1 show, 0.05
g of SBPPSA afforded 2‐amino‐3‐cyano‐4‐(4‐methoxyphenyl)‐
5,10‐dioxo‐5,10‐dihydro‐4H‐benzo[g]chromene in 90% yield
in 25 min.
The proposed mechanism for the preparation of 2‐amino‐
3‐cyano‐4‐phenyl‐5,10‐dioxo‐5,10‐dihydro‐4H‐benzo[g]chrom
ene from benzaldehyde, malononitrile, and 2‐hydroxynaph‐
thalene‐1,4‐dione, using SBPPSA as a catalyst, is shown in
Scheme 3. According to a literature report [13], 2‐benzyli‐
Next, the three‐component condensation reactions of aro‐
Table 2
Three‐component synthesis of 2‐amino‐3‐cyano‐4‐aryl‐5,10‐dioxo‐5,10‐dihydro‐4H‐benzo[g]chromene derivatives from reaction of 2‐hy‐
droxynaphthalene‐1,4‐dione, malononitrile, and aldehydes in the presence of SBPPSA as catalyst under solvent‐free and ambient conditions.
Time
(min)
21
Yielda Melting point (Reported)
Time
(min)
24
Yielda Melting point (Reported)
Entry
1
Aldehyde
Entry
9
Aldehyde
(%)
91
(°C)
(%)
89
(°C)
NO
2
260–263 (260–261 [12])
247–250 (247–249 [13])
H
H
O
O
O N
2
Cl
2
3
4
20
27
26
93
89
90
250–251 (249–252 [13]) 10
241–242 (242–244 [13]) 11
249–251 (248–250) [12] 12
23
25
27
89
90
87
232–234 (233–234 [12])
246–248 (247–248 [13])
272 (272–273 [12])
H
H
H
O
O
O
MeO
Me
H
O
H
OMe
OMe
MeO
Cl
H
O
O
Br
Cl
5
6
19
20
92
90
251–253 (252–253 [12]) 13
260–261 (259–260 [13]) 14
19
18
88
85
288 (286–288 [13])
H
H
O
O
H
Br
OMe
290–292 (291–292 [12])
MeO
OMe
O
H
2
O
Cl
NO
H
7
8
22
23
88
92
235–237 (237 [12])
15
21
86
—
241–243 (243 [12])
—
H
O
O
HO
253–255 (257–258 [13]) 16
n‐Heptanal
24 h
H
O
a Yields refer to the isolated pure products. The desired known pure products were characterized by a comparison of their physical data (m.p., IR, 1H
and 13C NMR) with those of the known compounds.
O
N
O
O
O
N
O
NH
O
NH
2
O
H
CHO
O
CN
CN
N
4
O
SBPPSA
SBPPSA
Tautomerism
H
N
N
N
O
O
O
SBPPSA
6
2
3
7
5
1
Scheme 3. Suggested mechanism for formation of 2‐amino‐3‐cyano‐4‐phenyl‐5,10‐dioxo‐5,10‐dihydro‐4H‐benzo[g]chromene.

Fahime Khorami et al. / Chinese Journal of Catalysis 35 (2014) 242–246
100
80
60
40
20
0
Table 3
Three‐component synthesis of hydroxy‐substituted naphthalene‐1,4‐
dione derivatives from reaction of 2‐hydroxynaphthalene‐1,4‐dione,
anilines, and aldehydes in the presence of SBPPSA as catalyst (Scheme
2) under solvent‐free and ambient conditions.
Time Yield a Melting point (Reported)
Entry
1
Aldehyde
Y
(min) (%)
(°C)
H
8
91 145–146 (144–146 [12])
H
O
HO
F
2
3
4
5
6
4‐Me
4‐Me
H
11
91 150–152 (151–152 [12])
1
2
3
4
H
Run number
O
Fig. 1. Recycling of SBPPSA catalyst under ambient and solvent‐free
conditions for the reaction of benzaldehyde, malononitrile, and 2‐hy‐
droxynaphthalene‐1,4‐dione as a model.
9
9
90 142–145 (143–144 [21])
87 145–147 (145–148 [21])
89 184–186 (189–190 [12])
91 145–149 (144–147) [21]
H
O
O2N
HO
MeO
denemalononitrile, which contains an electron‐poor C=C dou‐
ble bond, is formed by Knoevenagel addition of malononitrile
to the benzaldehyde in the presence of an acid catalyst. The
acid‐activated 2‐benzylidenemalononitrile is then attacked by
2‐hydroxynaphthalene‐1,4‐dione (4), which leads to interme‐
diate 5. Tautomerization and cyclization by nucleophilic attack
of the OH group on the activated cyano (CN) moiety gives in‐
termediate 6. Subsequent tautomerization produces the de‐
sired product.
The possibility of recycling the catalyst was examined using
the reaction of benzaldehyde, malononitrile, and 2‐hy‐
droxynaphthalene‐1,4‐dione for the preparation of 2‐amino‐
3‐cyano‐4‐phenyl‐5,10‐dioxo‐5,10‐dihydro‐4H‐benzo[g]chrom
ene, under the optimized conditions (Table 2, entry 1). After
completion of the reaction, warm ethanol (5 mL) was added,
the reaction mixture was filtered, and the remaining solid was
washed with warm ethanol (3 × 5 mL) to separate the catalyst.
The recycled catalyst was used for the next reaction. The recy‐
cled catalyst could be reused at least four times without any
appreciable loss of catalytic activity (Fig. 1).
H
H
H
O
H
8
O
4‐Me
10
O
7
8
4‐F
7
88
89
152–153 (151 [12])
152 (151–152 [12])
H
O
Cl
4‐Me
12
H
O
O N
2
9
4‐F
4‐Me
4‐F
9
11
88
91
—
151 (149–152 [21])
145–147 (146 [12])
—
H
O
Cl
Cl
10
H
O
11 n‐Heptanal
480
a Yields refer to the isolated pure products. The desired known pure
products were characterized by a comparison of their physical data
(m.p., IR, 1H and 13C NMR) with those of the known compounds.
The three‐component condensation of aromatic aldehydes,
anilines, and 2‐hydroxynaphthalene‐1,4‐dione over 0.05 g of
SBPPSA catalyst, under ambient and solvent‐free conditions,
for the preparation of hydroxy‐substituted naphthalene‐1,4‐
diones was then investigated. A wide range of substituted and
structurally diverse aldehydes and anilines was used, and the
corresponding products were obtained in high to excellent
yields (Table 3). n‐Heptanal, an aliphatic aldehyde, produced
only traces of the desired compounds and almost all of the
starting materials were intact (Table 3, entry 11).
lene‐1,4‐dione, using SBPPSA as a catalyst, is shown in Scheme
4. According to a literature report [21], an imine is formed by
condensation of benzaldehyde and aniline. 2‐Hydroxynaph‐
thalene‐1,4‐dione is then added to the activated imine in the
presence of an acid catalyst. Tautomerization converts inter‐
mediate 11 to the desired product.
The proposed mechanism for the preparation of 2‐hydroxy‐
3‐[phenyl(phenylamino)methyl]naphthalene‐1,4‐dione from
the reaction of benzaldehyde, aniline, and 2‐hydroxynaphtha‐
Catalyst recycling was studied using a similar procedure to
that described above, using the reaction of benzaldehyde, ani‐
line, and 2‐hydroxynaphthalene‐1,4‐dione as a model. The re‐
O
O
O
O
O
H
H
CHO
NH2
O
NH
NH
OH
H
C
-H2O
O
Tautomerism
N
O
SBPPSA
10
8
9
11
12
Scheme 4. Suggested mechanism for formation of 2‐hydroxy‐3‐[phenyl(phenylamino)methyl]naphthalene‐1,4‐dione.

Fahime Khorami et al. / Chinese Journal of Catalysis 35 (2014) 242–246
100
80
60
40
20
0
[6] de Andrade‐Neto V F, Goulart M O F, da Silva Filho J F, da Silva M J,
Pinto M d C F R, Pinto A V, Zalis M G, Carvalho L H, Krettli A U.
Bioorg Med Chem Lett, 2004, 14: 1145
[7] Pérez‐Sacua E, Estérez‐Braun A, Ravelo Á G, Yapu D G, Turba A G.
Chem Biodivers, 2005, 2: 264
[8] Shestopalov A M, Emelianova Yu M, Nesterov V N. Russ Chem Bull,
2003, 52: 1164
[9] Hunger K. Industrial Dyes. Weinheim: WILEY‐VCH Verlag, 2003
[10] Aldakov D, Anzenbacher P Jr. Chem Commun, 2003: 1394
[11] Gold H. In: Venkataraman H Ed. The Chemistry of Synthetic Dyes.
New York: Academic Press, 1971
1
2
3
4
Run number
[12] Shaterian H R, Mohammadnia M. J Mol Liq, 2013, 177: 353
[13] Shaabani A, Ghadari R, Ghasemi S, Pedarpour M, Rezayan A H,
Sarvary A, Ng S W. J Comb Chem, 2009, 11: 956
Fig. 2. Recycling of SBPPSA catalyst under ambient and solvent‐free
conditions for the reaction of benzaldehyde, aniline, and 2‐hy‐
droxynaphthalene‐1,4‐dione as a model.
[14] Wang X H, Zhang X H, Tu S J, Shi F, Zou X, Yan S, Han Z G, Hao W J,
Cao X D , Wua S S. J Heterocyclic Chem, 2009, 46: 832
[15] Yu Y, Guo H Y, Li X J. J Heterocyclic Chem, 2011, 48: 1264
[16] Yao C S, Yu C X, Li T J, Tu S J. Chin J Chem, 2009, 27: 1989
[17] Khurana J M, Nand B, Saluja P. Tetrahedron, 2010, 66: 5637
[18] Khodeir M, El‐Taweel F, Elagamey A. Pharmazie, 1992, 47: 486
[19] Shaterian H R, Kangani M. Sci Iran, 2013, 20: 571
[20] Khurana J M, Magoo D, Chaudhary A. Synth Commun, 2012, 42:
3211
[21] Dabiri M, Tisseh Z N, Bazgir A. Dyes Pigment, 2011, 89: 63
[22] Shaterian H R, Moradi F. Res Chem Intermediate, DOI: 10.1007/
s11164‐013‐1191‐3
[23] Shaterian H R, Khorami F, Doostmohammadi R, Amirzadeh A,
Ghashang M. Phosphorus Sulfur Silicon, 2009, 184: 2227
[24] Shaterian H R, Doostmohammadi R, Khorami F, Ghashang M.
Phosphorus Sulfur Silicon, 2010, 185: 171
covered catalyst was reused for at least four runs without any
loss of activity (Fig. 2).
4. Conclusions
We have developed a green and simple protocol for the
synthesis of 2‐amino‐3‐cyano‐4‐aryl‐5,10‐dioxo‐5,10‐dihy‐
dro‐4H‐benzo[g]chromenes and hydroxy‐substituted naphtha‐
lene‐1,4‐dione derivatives via three‐component condensation
reactions using SBPPSA as a solid acid catalyst under ambient
and solvent‐free conditions. This procedure is a promising
strategy and has several advantages such as clean reactions,
easy workup, and eco‐friendliness. It is expected that the pre‐
sent methodology will find application in organic synthesis.
[25] Shaterian H R, Khorami F, Amirzadeh A, Ghashang M. Phosphorus
Sulfur Silicon, 2008, 183: 2865
[26] Shaterian H R, Amirzadeh A, Khorami F, Ghashang M. Synth Com‐
mun, 2008, 38: 2983
References
[27] Shaterian H R, Khorami F, Amirzadeh A, Ghashang M. Chin J Chem,
2009, 27: 815
[1] Zhu J, Bienaymé H. Multicomponent Reactions. Weinheim:
WILEY‐VCH Verlag, 2005
[28] Niknam K, Deris A, Naeimi F, Majleci F. Tetrahedron Lett, 2011, 52:
4642
[29] Ghashang M, Mansoor S S, Aswin K. Res Chem Intermediate, DOI:
10.1007/s11164‐013‐1419‐2
[30] Rahi T, Baghernejad M, Niknam K. Chin Chem Lett, 2012, 23:
1103
[31] Niknam K, Tayebi S. Iran J Catal, 2012, 2(2): 69
[2] Lakontseva E, Krasavin M. Tetrahedron Lett, 2010, 51: 4095
[3] Chrobok A, Baj S W, Pudło A. Appl Catal A, 2009, 366: 22
[4] Ough M, Lewis A, Bey E A, Gao J M, Ritchie J M, Bornmann W,
Boothman D A, Oberley L W, Cullen J J. Cancer Biol Ther, 2005, 4:
95
[5] Moon D O, Choi Y H, Kim N D, Park Y M, Kim G Y. Int Im‐
munopharmacol, 2007, 7: 506
Graphical Abstract
Chin. J. Catal., 2014, 35: 242–246 doi: 10.1016/S1872‐2067(12)60761‐X
Preparation of 2-amino-3-cyano-4-aryl-5,10-dioxo-5,10-dihydro-4H-benzo[g]chromenes
Silica‐bonded propylpiperazine‐N‐sulfamic acid as recyclable
solid acid catalyst for preparation of 2‐amino‐3‐cyano‐4‐aryl‐
5,10‐dioxo‐5,10‐dihydro‐4H‐benzo[g]chromenes and hy‐
droxy‐substituted naphthalene‐1,4‐dione derivatives
O
CHO
O
OH
O
NH2
CN
CN
CN
SBPPSA (Catalyst)
Solvent-free
Room temparature
X
O
O
Fahime Khorami, Hamid Reza Shaterian*
University of Sistan and Baluchestan, Iran
O
Si
N
O
SiO2
O
X
N
SBPPSA
SO3H
X
Preparation of hydroxyl naphthalene-1,4-dione derivatives
An efficient method for the synthesis of 2‐amino‐3‐cyano‐4‐aryl‐5,10‐
dioxo‐5,10‐dihydro‐4H‐benzo[g]chromenes and hydroxy‐substituted
naphthalene‐1,4‐dione derivatives, using silica‐bonded propylpipera‐
zine‐N‐sulfamic acid (SBPPSA) as a solid acid, green, heterogeneous
catalyst, under ambient and solvent‐free conditions, is described.
O
O
O
CHO
NH2
Y
OH
SBPPSA (Catalyst)
N
H
Solvent-free
Room temparature
OH
X
Y
O