Simultaneously application of SBA-15 sulfonic acid nanoreactor and ultrasonic irradiation as a very useful novel combined catalytic system: An ultra-fast, selective, reusable and waste-free green approach

Article abstract of DOI:10.1016/j.molcata.2013.03.017

Sonicated catalytically amount of the SBA-15/SO₃H nanoreactor with organic substrate was found to be an efficient, ultra-fast and waste-free green approach for the synthesis of the indazolophthalazinetriones, polyhydroquinolines and α-aminophos

Full text of DOI:10.1016/j.molcata.2013.03.017

Journal of Molecular Catalysis A: Chemical 374–375 (2013) 85–93
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Journal of Molecular Catalysis A: Chemical
journal homepage: www.elsevier.com/locate/molcata
Simultaneously application of SBA-15 sulfonic acid nanoreactor and ultrasonic
irradiation as a very useful novel combined catalytic system: An ultra-fast,
selective, reusable and waste-free green approach
Sadegh Rostamniaa,∗, Hongchuan Xinb, Xiao Liuc, Kamran Lameia
a Organic and Nano Group (ONG), Department of Chemistry, Faculty of Science, University of Maragheh, P.O. Box 55181-83111, Maragheh, Iran
b Key Laboratory of Biofuels, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, China
c Key Laboratory for Green Chemical Technology of State Education Ministry, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300072, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Sonicated catalytically amount of the SBA-15/SO3H nanoreactor with organic substrate was found to be
an efficient, ultra-fast and waste-free green approach for the synthesis of the indazolophthalazinetri-
ones, polyhydroquinolines and ␣-aminophosphonates as models of organic reactions. The advantages
of present combined method are the use of a low scale catalyst, simple procedure with an easy fil-
terable work-up method, waste-free, green and direct synthetic entry to excellent yield of products in
a high reusability and a short reaction time. SBA-15 nanoreactor anchored covalently bonded PrSO3H
organic groups, to produce organic–inorganic mesochannels, in reaction condition (combined ultra-
sound/nanoreactor system) as catalyst provide a synergistic means of an efficient approach of the
reactants to acidic sites, and suitable mesochannels to drive out the products and water for next recycles.
Received 26 February 2013
Received in revised form 16 March 2013
Accepted 16 March 2013
Available online xxx
Keywords:
Combined catalytic system (US/SBA-15)
Ultrasonic irradiation
SBA-15/SO3H
Green chemistry
© 2013 Elsevier B.V. All rights reserved.
1. Introduction
their potential applications in the field of organic synthesis, green
chemistry and industry [6]. Compared with traditional methods,
The ‘greening’ of global chemical processes has became a major
issue in the chemical industry and biology both in terms of selection
of reactions and for the study of solvent and catalyst effects [1]. The
development of new strategies for recycling catalysts, which mini-
mizes the consumption of auxiliary substances, energy and time
required in achieving separations can result in significant economic
and environmental benefits [2,3]. Green chemistry aims to elimi-
nate pollution by preventing it from happening in the first place and
by using resources for chemical products that are renewable [3].
Functionalized mesoporous silica with their nano-channels has
shown catalytic performance because of their high surface area,
low densities, high thermal and mechanical stability as a result of
small nanoparticle sizes [4]. Incorporating the covalently bonded
Brønsted sulfonic acid functionality into the SBA-15 mesoporous
silicas (SBA-15/SO3H) are of particular interest in organic syn-
thesis, environmental chemistry and industry because of its high
selectivity and high yielding abilities, and also heterogeneity and
reusability capacities based on green chemistry desires [5]. In other
hand, applications of the ultrasound have been demonstrated for
this method is more convenient and easily controlled [6]. A large
number of organic reactions can be carried out in a higher yield,
shorter reaction time or milder conditions under ultrasonic irradi-
ation (Fig. 1).
Compared with ultrasound-promoted reactions or catalyti-
cally applications of zeolite-type porous materials, only a limited
paper has been reported for application of the combined
ultrasound/nanoreactor system. However, many of these used
montmorillonite clays and thin thickness MCM-41 material [7]. For
practical applications, the hydrothermal and solvothermal stability
of the catalyst is very important because most of the acid catalyzed
organic reactions always involve water in high temperature [5].
Hydrothermally stable SBA-15 nanoreactor anchored covalently
bonded sulfonic acid to aim organic–inorganic mesochannels in
reaction condition as catalyst provide a synergistic means of an
efficient approach of the reactants to acidic sites, and suitable
mesochannels to drive out the products and water for next recy-
cles [5]. On the other hand, based on green chemistry desires, the
development of new strategies for recycling catalysts, which mini-
mizes the consumption of auxiliary substances, energy and time
required in achieving separations can result in significant economic
and environmental benefits [8]. In the field of catalytic organic syn-
thesis, many of this process have drawbacks such as low yields of
products without any recycle, long reaction times, harsh reactions
∗
Corresponding author. Tel.: +98 9124338696.
E-mail addresses: srostamnia@gmail.com,
rostamnia@maragheh.ac.ir (S. Rostamnia).
1381-1169/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.molcata.2013.03.017

86
S. Rostamnia et al. / Journal of Molecular Catalysis A: Chemical 374–375 (2013) 85–93
Fig. 1. Proposed reaction pathways.
conditions, tedious work-ups leading to the generation of large
amounts of toxic metal or organic-containing waste, the require-
ment for an inert atmosphere and the use of stoichiometric or
relatively expensive reagents [6–8]. As a result, the challenge in
this field, was developing waste-free and effective green approach.
As part of our ongoing program [9], we are interested in the
development of efficient and environmentally benign methods
in synthetic organic chemistry. Our aim has been to investigate
designing of the catalyst and energy sources to accomplish the
desired chemical transformations with minimum by-products or
waste generation, as well as to decrease reaction time using ultra-
sound and porous catalysts. Based on our earlier success in the
green application of the ultrasonic in organic synthesis [6f], we
could combine our achievements in nanocatalyst area [9c,i,j], with
ultrasound. Here, we present the results of an extended investiga-
tion on the activity of the sulfonic acid functionalized mesoporous
nanoreactor (SBA-15/SO3H) as an ultra-fast, waste-free, green
approach to synthesis of the heterocycles indazolophthalazinetri-
ones 4, polyhydroquinolines 8 and ␣-aminophosphonate 11 via
multicomponent couplings.
continues irradiation with a maximum power output of 600 W,
was used for the ultrasonic irradiation. Frequencies below 50 kHz
are generally preferred for the heterogeneous systems due to the
more intense mechanical effects. Hence, we selected 19.6 kHz for
sonication. Progress of reactions was monitored by Thin Layer
Chromatography (TLC). 1H and 13C NMR spectra were measured
(CDCl3) with a Bruker DRX-300 AVANCE spectrometer at 300 and
75 MHz, respectively.
2.2. General procedures
Synthesis of SBA-15/SO3H (SI): The synthesis of SBA-15-PrSO3H
has been achieved using three main steps: first step for preparation
of the SBA-15 which known procedure described by Zhao et al.
Second, which is thiol functionalization of the SBA-15 and third
is oxidation of the SBA-15-Pr-SH to SBA-15-Pr-SO3H by hydrogen
peroxide (Fig. 2).
Temperature and solvent volume in ultrasonic method: it is to
be noted here that when substrates and catalyst were added to the
solution and irradiated, during the sonication the reaction temper-
ature raised from its initial value and here the temperature was
not controlled or fixed (maximum fluctuation range 3–10 ◦C). And,
also, volume of solution during reaction progresses was adjusted
by adding solvent using a syringe.
2. Experimental
2.1. Chemicals and apparatus
All reagents were obtained from Merck (Germany) and Fluka
(Switzerland) and were used without further purification. The IR
spectra were determined using a FT-IR Bruker-Vector 22. Melting
points were measured on an Electrothermal 9100 apparatus. A
multi-wave ultrasonic generator (Sonicator 3000; Misonix Inc.,
Farmingdale, NY, USA), equipped with a converter/transducer
and titanium oscillator (horn), 12.5 mm in diameter, operating as
2.3. General procedure for synthesis of
3,3-dimethyl-13-aryl-2,3,4,6,11,13-hexahydro-1H-indazolo[1,2-
b]phthalazine-1,6,11-trione derivatives
4
A mixture of aldehyde (3.3 mmol), dimedone (3 mmol), phthal-
hydrazide (3 mmol), and SBA-15/SO3H (0.07 g, ∼4 mol%) was
Fig. 2. SEM (a) and TEM (b) images of SBA-15/SO3H nanoreactor.

S. Rostamnia et al. / Journal of Molecular Catalysis A: Chemical 374–375 (2013) 85–93
87
heated at 45 ◦C (initial temperature value) for 15–20 min under
irradiation of the ultrasonic in 10 mL EtOH. After completion of
the reaction (TLC) the solvent was removed under reduced pres-
sure, and the residue was added diethyl ether (2 × 15 mL) and
filtered it for remove catalyst. The crude product was recrystal-
lized from ethyl acetate/n-hexane (3:5) to afford the pure product.
Products are known compounds, and their structures were deduced
by comparison of their physical and spectroscopic data with those
previously reported [2–12].
(75 MHz, CDCl3): 28.5, 28.7, 34.7, 38.0, 50.9, 64.3, 115.5, 115.8,
118.21, 127.7, 128.0, 128.9, 129.0, 132.2, 133.6, 134.6, 151.0, 154.4,
156.0, 192.1.
13-(4-chlorophenyl)-3,3-dimethyl-2,3,4,6,11,13-hexahydro-
1H-indazolo[1,2-b]phthalazine-1,6,11-trione
(4i)
1H
NMR
(300.13 MHz, CDCl3): 1.20 (6 H, s), 2.33 (2 H, s), 3.20 and 3.40 (2
2
H, ABq, JHH 19.2 Hz), 6.41(1 H, s), 7.29–7.38 (4 H, m), 7.84–7.87
(2 H, m), 8.24–8.37 (2 H, m). 13C NMR (75 MHz, CDCl3): 28.4, 28.7,
34.6, 38.0, 50.6, 64.3, 118.0, 127.7, 128.0, 128.2, 128.5, 128.9, 129.7,
133.6, 134.5, 134.6, 134.9, 151.1, 154.3, 155.9, 192.1.
3,3-dimethyl-13-phenyl-2,3,4,6,11,13-hexahydro-1H-
indazolo[1,2-b]phthalazine-1,6,11-trione
(4a):
1H
NMR
(300.13 MHz, CDCl3): 1.22 (6 H, s), 2.34 (2 H, s), 3.21–3.45 (2
2
H, ABq, JHH 18.9 Hz), 6.45 (1 H, s), 7.27–7.43 (4 H, m), 7.83–7.86
2.4. General procedure for synthesis of alkyl 4-(aryl)-2,7,7-
trimethyl-5-oxo-1,4,5,6,7,8-hexahydro-3-quinolinecarboxylate
derivatives 8
(2 H, m), 8.25–8.37 (2 H, m). 13C NMR (75 MHz, CDCl3): 28.5, 28.7,
34.7, 38.0, 50.9, 64.9, 118.6, 127.1, 127.7, 127.9. 128.7, 28.9, 129.0,
133.5, 134.5, 136.4, 150.8, 154.3, 156.0, 192.1.
13-(2-chlorophenyl)-3,3-dimethyl-2,3,4,6,11,13-hexahydro-
To a solution of EtOH (10 mL) was added ␤-diketon (3 mmol),
aldehyde (3.3 mmol), dimedone (3 mmol), ammonium acetate
(4 mmol) and SBA-15/SO3H (0.07 g, ∼4 mol%). The mixture was
sonicated at room temperature (initial temperature value) for
appropriate time and reaction progress monitored by TLC. After
completion of the reaction, catalyst was filtrate by centrifuge and
then the product recrystallized in ethanol. The products are known
and were identified by their physical and spectral data.
Methyl 2,7,7-trimethyl-5-oxo 4-phenyl -1,4,5,6,7,8-hexahydro-
3-quinolinecarboxylate (8a) 1H NMR (300.13 MHz, CDCl3): 0.94 (s,
3 H), 1.09 (s, 3 H), 2.11–2.40 (m, 8 H), 3.62 (s, 3 H), 5.08 (s, 1 H),
7.08–7.31 (m, 5 H).
1H-indazolo[1,2-b]phthalazine-1,6,11-trione
(4b)
1H
NMR
(300.13 MHz, CDCl3): 1.21 (6 H, s), 2.32 (2 H, s), 3.20–3.44 (2
2
H, ABq, JHH 20.3 Hz), 6.68 (1 H, s), 7.21–7.33 (4 H, m), 7.84–7.87
(2 H, m), 8.24–8.39 (2 H, m). 13C NMR (75 MHz, CDCl3): 28.4, 28.8,
34.8, 38.0, 50.9, 64.1, 127.2, 127.7, 128.1, 128.7, 129.0, 129.8, 130.5,
133.0, 133.6, 134.5, 151.8, 154.2, 156.2, 192.1.
13-(2-bromophenyl)-3,3-dimethyl-2,3,4,6,11,13-hexahydro-
1H-indazolo[1,2-b]phthalazine 1,6,11-trione (4c) 1H NMR
(300.13 MHz, CDCl3): 1.22 (6 H, s), 2.32 (2 H, s), 3.21–3.43 (2
2
H, ABq, JHH 18.9 Hz), 6.71 (1 H, s), 7.12–7.54 (4 H, m), 7.84–7.87
(2 H, m), 8.24–8.38 (2 H, m). 13C NMR (75 MHz, CDCl3): 28.6, 28.7,
34.6, 38.0, 50.9, 65.7, 126.9, 127.7, 127.8, 128.0, 128.7, 129.1, 130.1,
133.6, 133.9, 134.5, 151.9, 154.3, 156.2, 192.0.
Methyl 4-(2-chlorophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-
hexahydro-3-quinolinecarboxylate (8b) IR (KBr vmax/cm−1): 3289,
3,3-dimethyl-13-(2-nitrophenyl)-2,3,4,6,11,13-hexahydro-
2951, 1707, 1654, 1608, 1490, 1222, 1080, 1034, 827, 773, 540. 1
H
1H-indazolo[1,2-b]phthalazine-1,6,11-trione (4d) 1H NMR
NMR (300.13 MHz, CDCl3): 0.91 (s, 3 H), 1.07 (s, 3 H), 2.04–2.36 (m,
7 H), 3.57 (s, 3 H), 5.38 (s, 1 H), 6.81 (s, 1 H), 7.00–7.34 (m, 4 H).
13C NMR (75 MHz, CDCl3): 19.19, 27.15, 29.37, 32.54, 35.61, 40.96,
50.62, 50.83, 105.17, 111.37, 126.42, 127.26, 129.61, 131.64, 131.64,
133.10, 143.87, 144.33, 148.92, 167.91, 195.51.
Methyl 4-(2-methylphenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-
hexahydro-3-quinolinecarboxylate (8c) IR (KBr vmax/cm−1) 3282,
3189, 3071, 2956, 1693, 1644, 1484. 1H NMR (300.13 MHz, CDCl3):
0.95 (s, 3 H), 1.09 (s, 3 H), 2.11–2.44 (m, 8 H), 3.62 (s, 3 H), 5.03 (s,
1 H), 5.90 (s, 1 H), 7.00–7.19 (m, 4 H). 13C NMR (75 MHz, CDCl3):
27.21, 29.37, 35.79, 41.23, 51.03, 127.66, 128.73.
Methyl 4-(4-chlorophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-
hexahydro-3-quinolinecarboxylate (8d) IR (KBr vmax/cm−1): 3288,
2958, 1645, 1610, 1391, 1218, 1074, 1012, 840, 775, 538. 1H NMR
(300.13 MHz, CDCl3): 0.92 (s, 3 H), 1.08 (s, 3 H), 2.10–2.32 (m, 4 H),
2.39 (s, 3 H), 3.61 (s, 3 H, OCH3), 5.04 (s, 1 H), 6.2 (s, 1 H), 7.15–7.27
(m, 4 H). 13C NMR (75 MHz, CDCl3): 19.45, 27.06, 28.09, 28.24, 29.42,
32.71, 35.95, 41.05, 50.63, 51.08, 105.40, 111.90, 128.10, 129.24,
131.64, 143.98, 145.36, 148.23, 167.67, 195.57.
2
(300.13 MHz, CDCl3): 1.18 (6 H, s), 2.26–2.38 (2 H, ABq, JHH
2
19.2 Hz), 3.21–3.47 (2 H, ABq, JHH 20.3 Hz), 7.32–7.57 (4 H, m),
7.82–7.93 (2 H, m), 8.22–8.37 (2 H, m). 13C NMR (75 MHz, CDCl3):
28.5, 28.6, 34.6, 38.0, 50.7, 60.5, 116.8, 125.1, 127.7, 128.1, 128.6,
129.0, 129.5, 130.7, 133.1, 133.8, 134.7, 149.2, 152.0, 154.4, 156.0,
191.9.
3,3-dimethyl-13-(3-nitrophenyl)-2,3,4,6,11,13-hexahydro-
1H-indazolo[1,2-b]phthalazine-1,6,11-trione
(4e)
1H
NMR
(300.13 MHz, CDCl3): 1.23 (6 H, s), 2.35 (2 H, s), 3.24–3.47 (2
H, ABq, 2JHH 19.2 Hz), 6.52 (1 H, s), 7.53–7.59 (1 H, m), 7.87–7.91 (3
H, m), 8.15–8.18 (2 H, m), 8.24–8.40 (2 H, m). 13C NMR (75 MHz,
CDCl3): 28.4, 28.7, 34.8, 38.0, 50.8, 64.2, 117.2, 121.5, 123.7, 127.7,
128.3, 128.6, 128.9, 129.7, 133.9, 134.3, 134.8, 138.6, 148.5, 151.8,
154.7, 155.9, 192.1.
13-(3-bromophenyl)-3,3-dimethyl-2,3,4,6,11,13-hexahydro-
1H-indazolo[1,2-b]phthalazine-1,6,11-trione
(4f)
1H
NMR
(300.13 MHz, CDCl3): 1.21 (6 H, s), 2.34 (2 H, s), 3.20–3.44 (2
H, ABq, 2JHH 19.2 Hz), 6.39 (1 H, s), 7.19–7.24 (1 H, m), 7.40–7.48 (3
H, m), 7.85–7.88 (2 H, m), 8.25–8.38 (2 H, m). 13C NMR (75 MHz,
CDCl3): 28.5, 28.6, 34.7, 38.0, 50.9, 64.2, 117.9, 122.8, 126.3, 127.8,
128.1, 128.9, 129.0, 129.8, 130.2, 131.9, 133.7, 134.7, 138.7, 151.2,
154.4, 156.0, 192.0.
Methyl
1,4,5,6,7,8-hexahydro-3-quinolinecarboxylate
max/cm−1): 3274, 2960, 1705, 1648, 1608, 1494. 1H NMR
4-(4-methoxyphenyl)-2,7,7-trimethyl-5-oxo-
(8e) IR (KBr
v
(300.13 MHz, CDCl3): 0.94 (s, 3 H), 1.08 (s, 3 H), 2.10–2.38 (m, 7
H), 3.62 (s, 3 H), 3.74 (s, 3 H), 5.01 (s, 1 H), 5.95 (s, 1 H), 6.74 (d,
J = 8.7 Hz, 2 H), 7.21 (d, J = 8.7 Hz, 2 H). 13C NMR (75 MHz, CDCl3):
19.52, 27.16, 29.41, 35.40, 41.22, 50.68, 51.02, 55.10, 113.36,
128.75.
Ethyl 4-(2-methylphenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-
hexahydro-3-quinolinecarboxylate (8f) IR (KBr vmax/cm−1): 3245,
3078, 2958, 1701, 1600. 1H NMR (300.13 MHz, CDCl3): 0.95 (s, 3
H), 1.07 (s, 3 H), 1.22 (t, J = 6.9 Hz, 3 H), 2.13–2.34 (m, 10 H), 4.06
(q, J = 6.9 Hz, 2 H), 5.02 (s, 1 H), 6.30 (s, 1 H), 7.00–7.27 (m, 4 H).
13C NMR (75 MHz, CDCl3): 14.20, 19.31, 21.04, 27.21, 29.34, 32.74,
36.11, 41.05, 50.27, 59.85, 106.84, 112.01, 127.87, 128.63, 135.46,
143.08, 143.94, 167.38, 195.38.
3,3-dimethyl-13-(4-nitrophenyl)-2,3,4,6,11,13-hexahydro-
1H-indazolo[1,2-b]phthalazine-1,6,11-trione
(4g)
1H
NMR
(300.13 MHz, CDCl3): 1.18 (6 H, s), 2.33 (2H, s), 3.22–3.44 (2
H, ABq, 2JHH 18.9 Hz), 6.50 (1 H, s),7.60 (2 H, m), 7.86–7.89 (2 H, m),
8.17–8.25 (3 H, m), 8.35–8.39 (1 H, m). 13C NMR (75 MHz, CDCl3):
28.4, 28.7, 34.7, 38.0, 50.8, 64.8, 117.3, 124.0, 127.8, 128.1, 128.2,
128.6, 128.9, 133.9, 134.8, 143.4, 147.8, 151.7, 154.5, 155.9, 192.0.
13-(4-fluorophenyl)-3,3-dimethyl-2,3,4,6,11,13-hexahydro-
1H-indazolo[1,2-b]phthalazine-1,6,11-trione (4h) 1H NMR
(300.13 MHz, CDCl3): 1.21 (6 H, s), 2.34 (2 H, s), 3.20–3.44 (2
2
3
H, ABq, JHH 19.2 Hz), 6.43 (1 H, s), 7.02 (2 H, t, JHH 5.4 Hz),
7.38–7.43 (2 H, m), 7.84–7.87 (2 H, m), 8.25–8.37 (2 H, m). 13C NMR

88
S. Rostamnia et al. / Journal of Molecular Catalysis A: Chemical 374–375 (2013) 85–93
3
2
3JHP = 10.5, 3 H), 3.78 (d, JHP = 10.5, 3 H), 4.80 (d, JHP = 24.3, 1 H),
Ethyl
4-(2-chlorophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-
hexahydro-3-quinolinecarboxylate (8g) IR (KBr vmax/cm−1): 3292,
3072, 2957, 1700, 1650, 1621, 1486, 758. 1H NMR (300.13 MHz,
CDCl3): 0.89 (s, 3 H), 1.07 (s, 3 H), 1.17 (t, J = 6.9 Hz, 3 H), 1.65–2.35
(m, 7 H), 4.04 (q, J = 6.9 Hz, 2 H), 5.38 (s, 1 H), 6.11 (s, 1 H), 7.00–7.41
(m, 4 H). 13C NMR (75 MHz, CDCl3): 14.19, 19.35, 27.22, 29.32,
32.53, 35.97, 41.13, 50.57, 59.83, 105.33, 111.18, 126.24, 127.27,
129.67, 132.09, 133.20, 143.56, 148.68, 167.43, 195.35.
6.02 (br, 1 NH), 6.54–7.38 (m, 8H).
Dimethyl(p-tolylamino)(2-methoxyphenyl)methylphosphonate
(11f) 1H NMR (300.13 MHz, CDCl3): 2.18 (m, 3 H), 3.45 (d,
3
3JHP = 10.5, 3 H), 3.82 (d, JHP = 10.5, 3 H), 3.93 (s, 3 H), 4.06 (br, 1
NH), 5.43 (d, 2JHP = 24.0, 1 H), 6.54–7.49 (m, 8 H).
Dimethyl(N,N-diethylamino)(3-nitrophenyl)methylphosphonate
(11g) 1H NMR (300.13 MHz, CDCl3): 0.95 (t, J = 7.2 Hz, 6 H), 2.21 (m,
2 H), 2.88 (m, 2 H), 3.37 (d, 3JHP = 9.3 Hz, 3 H), 3.77 (d, 3JHP = 9.3 Hz,
3 H), 4.12 (d, 2JHP = 24.9 Hz, 1 H), 7.17–7.38 (m, 5 H).
Ethyl
4-(4-chlorophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-
hexahydro-3-quinolinecarboxylate (8h) IR (KBr vmax/cm−1): 3243,
3076, 2958, 1706, 1647, 1604, 1488, 844. 1H NMR (300.13 MHz,
CDCl3): 0.92 (s, 3 H), 1.08 (s, 3 H), 1.17 (t, J = 6.9 Hz, 3 H), 2.10–2.38
(m, 7 H), 4.06 (q, J = 6.9 Hz, 2 H), 5.02 (s, 1 H), 6.25 (s, 1 H), 7.15–7.27
(m, 4 H). 13C NMR (75 MHz, CDCl3): 14.19, 19.38, 27.08, 27.76,
29.41, 32.69, 36.22, 41.00, 50.64, 59.90, 105.70, 111.77, 128.00,
129.44, 131.57, 143.79, 145.60, 148.51, 167.26, 195.60.
Dimethyl
(2-methoxyphenyl)(pyrrolidin-1-
yl)methylphosphonate (11h) 1H NMR (300.13 MHz, CDCl3):
3
1.69 (m, 4 H), 2.16 (m, 2 H), 2.64 (m, 2 H), 3.46 (d, JHP = 6.3 Hz, 3
H), 3.77 (d, 3JHP = 6.3 Hz, 3 H), 3.85 (s, 3 H), 4.66 (d, 2JHP = 18.0 Hz, 1
H), 6.89–7.75 (m, 4 H).
Dimethyl 1-(phenylamino)cyclohexylphosphonate (11i) 1H
NMR (300.13 MHz, CDCl3): 1.13–2.13 (m, 10 H), 3.45 (br, 1 NH),
3.55 (d, 3JHP = 10.5 Hz, 6 H), 6.66–7.06 (m, 5 H).
Ethyl
2,7,7-trimethyl-4-(4-nitrophenyl)-5-oxo-1,4,5,6,7,8-
hexahydro-3-quinolinecarboxylate (8i) IR (KBr vmax/cm−1): 3275,
3200, 3075, 2964, 1704, 1604, 1518, 1378. 1H NMR (300.13 MHz,
CDCl3): 0.92 (s, 3 H), 1.10 (s, 3 H), 1.18 (t, J = 6.9 Hz, 3 H), 2.10–2.43
(m, 7 H), 4.05 (q, J = 6.9 Hz, 2 H), 5.16 (s, 1 H), 5.85 (s, 1 H), 7.47–8.10
(m, 4 H). 13C NMR (75 MHz, CDCl3): 14.17, 19.50, 27.06, 29.35,
32.74, 37.17, 41.10, 50.51, 60.08, 105.05, 111.19, 123.33, 128.95,
144.27, 146.24, 148.60, 154.26, 166.78, 195.26.
3. Results and discussion
Based on chemical and biological interests of indazolophtha-
lazinetrione [10], for the synthesis of 4, efficacy of different catalysts
was studied. As expected, in which adduct of dimedone and
aldehydes was treated with phthalhydrazide under the reaction
conditions (Scheme 1), led to the products indazolophthalazinetri-
ones 4, arylmethylene bis(3 hydroxy-2-cyclohexene-1-one) 5 and
heptahydroxanthenes 6 [11]. For our study, dimedone, benz-
aldehyde and phthalhydrazide were chosen as the benchmark
substrates in the model reaction.
In model reaction, to obtain the desired product (4a), we tested
the reaction using different catalysts. As shown in Table 1, the use
of catalysts such as morpholine (entry 1), piperidine (entry 2), and
iron oxide magnetic nanoparticles (entries 5–6) led to no desired
product being obtained. Performing the reaction in the presence of
sulfonic acid porous nanoreactor SBA-15 resulted in the production
of 4a in 45% yield with a trace amount of the side products 5a and
6a (entry 4) in compared of alternative core-shell structure (entry
7).
Next, due to the fact that the pore size of the nanoreactor may
play an important role in the synthesis of 4a, and based on our pre-
vious experience about ultrasonic effects in organic process and
also in order to determine the evaluate the ultrasonic efficiency,
in next step as comparative study efficacy of porous nanoreactor
such as MCM-41/SO3H and SBA-15/SO3H catalyst was investigated
via ultrasonic assisted (US), and high speed stirrer (HSS, 1500 rpm)
method. The MCM-41/SO3H with ∼1.1 nm and SBA-15/SO3H with
∼5 nm pore size were chosen and investigated for the model reac-
tion (SI). The synthesis of 4a was carried out in MeCN during
ultrasonic irradiation (US) and high speed stirrer (HSS). When the
model reaction was run using SBA-15/SO3H under sonicated condi-
tion, the product 4a was obtained 87% yield at 60 ◦C during 0.25 h.
The reaction rates and yields were enhanced by ultrasound (Fig. 3).
The model reaction was screened in different solvents using
6% mol of SBA-15/SO3H (Table 2). When the reaction was run under
sonicated condition in EtOH, the product was obtained in 96% yield
at 65 ◦C in 25 min.
Ethyl 4-(4-methoxyphenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-
hexahydro-3-quinolinecarboxylate (8j) IR (KBr vmax/cm−1): 3300,
3078, 2950, 1648, 1610, 1032. 1H NMR (300.13 MHz, CDCl3): 0.94
(s, 3 H), 1.07 (s, 3 H), 1.21 (t, J = 7.2 Hz, 3 H,), 2.13–2.29 (m, 4 H),
2.36 (s, 3 H), 3.74 (s, 3 H), 4.07 (q, J = 7.2 Hz, 2 H), 5.00 (s, 1 H),
6.14 (s, 1 H), 6.72–6.75 (m, 2 H), 7.20–7.27 (m, 2 H). 13C NMR
(75 MHz, CDCl3): 14.22, 19.38, 27.17, 29.40, 32.72, 35.70, 41.07,
50.52, 55.10, 59.81, 112.26, 113.24, 129.00, 139.50, 143.02, 148.51,
157.80, 167.50, 195.53.
2.5. General procedure for synthesis of dialkyl
anilino(aryl)methylphosphonate derivatives 11
A mixture of aldehyde (5 mmol), amine (5 mmol), dimethyl
phosphite (6 mmol) and SBA-15 (0.06 g, ∼2 mol%) in EtOH (6.5 mL)
was irradiated by ultrasound at room temperature (initial temper-
ature value) for the required reaction time. The progress of the
reaction was monitored by TLC. After completion of the reaction,
the catalyst was removed by simple filtration and the reaction mix-
ture was quenched with water (10 mL) and extracted with EtOAc
(3 × 10 mL). Evaporation of the solvent followed by purification on
silica gel afforded pure ␣-aminophosphonates. All products were
known and characterized by comparison of their physical and spec-
tra data with those of already reported.
Dimethyl (4-chlorophenyl)(phenylamino)methylphosphonate
(11a) 1H NMR (300.13 MHz, CDCl3): 3.55 (d, 3JHP = 10.8, 3 H), 3.77 (d,
3JHP = 10.8, 3 H), 4.52 (br, 1 NH), 4.79 (d, 2JHP = 24.3, 1 H), 6.59–7.44
(m, 9 H).
Dimethyl phenyl(phenylamino)methylphosphonate (11b) 1H
3
NMR (300.13 MHz, CDCl3): 3.47 (d, JHP = 10.5, 3 H), 3.78 (d,
3JHP = 10.5, 3 H), 4.84 (d, 2JHP = 24.3, 1 H), 5.02 (br, 1 NH), 6.51–7.51
(m, 10 H).
Dimethyl (3-nitrophenyl)(phenylamino)methylphosphonate
3
(11c) 1H NMR (300.13 MHz, CDCl3): 3.64 (d, JHP = 10.8 Hz, 3 H),
3
2
3.83 (d, JHP = 10.4, 3H), 5.00 (d, JHP = 25.1, 1 H), 5.25 (br, 1 NH),
6.62–8.41 (m, 9 H).
Next, the model reaction was carried out using different
amounts of SBA-15/SO3H as the catalyst (Fig. 4). A very high yield
of 2H-indazolo[2,1-b]phthalazine-trione (96%) was obtained with
4 mol% of the catalyst. A further increase in the amount of catalyst
(4–8 mol%) did not have any significant effect on the product yield
or reaction time.
Dimethyl (p-tolylamino)(2-chlorophenyl)methylphosphonate
(11d) 1H NMR (300.13 MHz, CDCl3): 2.16 (m, 3 H), 3.43 (d, 3JHP = 9.9,
3
2
3 H), 3.83 (d, JHP = 9.9, 3 H), 4.85 (br, 1 NH), 5.39 (d, JHP = 24.9, 1
H), 6.49–7.56 (m, 8 H).
Dimethyl (p-tolylamino)(4-nitrophenyl)methylphosphonate
To the best of our knowledge, when the reaction was per-
formed in DMSO, DMF and H2O with 6 mol% of SBA-15/SO3H under
(11e) 1H NMR (300.13 MHz, CDCl3): 2.24 (m, 3 H), 3.50 (d,

S. Rostamnia et al. / Journal of Molecular Catalysis A: Chemical 374–375 (2013) 85–93
89
O
O
+
Ar
O
OH
Ar
H
- H2O
O
O
O
O
O
Ar
O
O
OH
2
1
(I)
Ar
N
N
O
HO
+
+
O
O
O
Ar
4
5
NH
NH
6
3
Scheme 1. Expected products from the reaction of dimedone, aldehyde and phthalhydrazide.
Table 1
Different catalyst in the three-component coupling of dimedone, benzaldehyde, and phthalhydrazide.a
O
O
O
Ph
O
O
Ph
O
OH
O
N
N
NH
NH
+
+
+
+
O
Ph
H
O
OH
O
HO
Ph
O
O
4a
6a
5a
.
Entry
Catalyst
Temp (◦C)
Time (h)
Yield%b
4a
5a
6a
1
2
3
4
5
6
7
O(CH2CH2)2NH
(CH2)5NH
Reflux
Reflux
r.t.
Reflux
Reflux
Reflux
Reflux
2
2
7
44
40
24
Td
25
27
Td
10
Td
45
Td
Td
28
SBA-15/SO3H
SBA-15/SO3H
nano-Fe3O4
ꢀ-Fe2O3
1.5
1.25
2.5
2.5
1.25
Td
Td
75
80
17
Td
20
ꢀ-Fe2O3@SiO2/SO3Hc
a
b
c
Reaction conditions: dimedone (3 mmol), benzaldehyde (3.3 mmol), phthalhydrazide (3 mmol), catalyst (6 mol%) and MeCN (15 mL).
Isolated yield.
See Ref. [9j].
Trace yield based on TLC analysis.
d
ultrasonic condition, although dimedone and benzaldehyde were
almost consumed soon, but 4a was formed with mixture of 5a, 6a
and adduct I. When model reaction for synthesis of 4a was carried
out in ethanol by ultrasonic irradiation and high speed stirrer over
6 mol% catalyst, to our surprise in comparative study, the ultrasonic
assisted method were completed during 15 min without any waste
and side products (Table 2). The conversion for US method was
100% with 96% isolated yield while at the same reaction time, in
HSS method conversion and yield was 63% and 45%, respectively.
To demonstrate the diversity of this combined ultrasonic and
SBA-15/SO3H catalytic system and to expand the scope of the
process, the optimized conditions were applied to a series of
2H-indazolo[2,1-b]phthalazine-triones 4 via a three-component
condensation of an aldehydes, dimedone and phthalhydrazide. The
obtained results are summarized in Table 3.
The possibility of recycling the SBA-15/SO3H was also stud-
ied under sonicated condition. For practical applications of the
SBA/SO3H based on sonicated heterogeneous systems, the lifetime
of the catalyst and its recovery are important factors. We therefore
devised a set of experiments to recover and reutilize the SBA/SO3H
catalyst in the model coupling process. It can be seen that, the sup-
ported catalyst was highly reusable under the investigated reaction
conditions, preserving almost unaltered its initial catalytic activity
after seven uses. As comparison, SiO2/OSO3H and HClO4/SiO2 as the
Table 2
Study of the solvent and temperature on the model reaction.a
Solventb
Temp (◦C)b
Time (h)
Yield%c 4a
HSS
US
DMF e
H2O e
MeOH
EtOH
r.t
r.t
r.t
r.t
60
60
60
0.25
0.25
0.25
0.25
0.25
0.25
0.25
<10d
25
18
13
45
35
40
20
20
96
92
30
EtOH
CH3CN
40
15
DMSOe
a
Reaction scale: 3 mmol.
Solvent: 5 mL.
Isolated yield.
Less than 10%.
Contain 5a and adduct I.
b
c
Fig. 3. Comprative study of the model reaction over porous nanoreactors: (a) US
conditions: equal –SO3H loaded (blue), equel surface area (red) and equel wieght
(green) conditions. (b) HSS (violet) conditions. (For interpretation of the references
to color in this figure legend, the reader is referred to the web version of the article.)
d
e

90
S. Rostamnia et al. / Journal of Molecular Catalysis A: Chemical 374–375 (2013) 85–93
Table 3
One-pot a three-component synthesis of 2H-indazolo[2,1-b]phthalazine-triones 4.a
O
O
O
O
O
O
N
N
NH
NH
6
+
5
+
+
+
Ph
H
O
OH
Ph
4
1
2
3
.
Entry
Ar
Time (min)
Conv%b
Yield%c
4
5
6
1
2
3
4
5
6
7
8
9
C6H5
15
20
20
20
18
18
15
15
15
100
100
100
100
100
100
100
100
100
96 (4a)
93 (4b)
92 (4c)
93 (4d)
94 (4e)
95 (4f)
96 (4g)
93 (4h)
95 (4i)
Nd
Nd
Nd
Nd
Nd
Nd
Nd
Nd
Nd
Nd
Te
2-Cl-C6H4
2-Br-C6H4
2-NO2-C6H4
3-NO2-C6H4
3-Br-C6H4
4-NO2-C6H4
4-F-C6H4
Te
Te
Nd
Nd
Nd
Te
4-Cl-C6H4
Nd
a
b
c
Reaction scale: 3 mmol.
Conversion calculated based on consume of dimedone (TLC).
Isolated yield.
No detected of the this product based on TLC analysis.
Trace yield based on TLC analysis.
d
e
With these results in hand we decided to explore the scope of
this method (ultrasonic/nanoreactor combined system). The cat-
alytic activity of combined ultrasonic/nanoreactor system in the
four-component synthesis of polyhydroquinolines [12], by the con-
densation of dimedone, aldehyde, ␤-dicarbonyl compound and
ammonium acetate was also studied, in which adduct of dime-
done and aldehyde was treated with 1,3-dicarbonyls in presence
of the ammonium acetate under the reaction conditions, led to the
products polyhydroquinolines 8, and the molecules of 9, 10 or 5, 6
(Scheme 2).
Polyhydroquinolines are among the most fundamental and
important bioactive systems in the various fields of organic chem-
istry [12]. Sonicated SBA-15 sulfonic acid have been considered
candidates for the catalytically partner in the solid acid cat-
alyzed four-component preparation of polyhydroquinolines 8.
Four-component reaction of dimedone, benzaldehyde, methyl ace-
toacetate, and ammonium acetate was carried out using SBA-15
sulfonic acid as the catalyst, under ultrasonic irradiation and
HSS method (Fig. 6). Methyl 4-(phenyl)-2,7,7-trimethyl-5-oxo-
1,4,5,6,7,8-hexahydro-3 quinolinecarboxylate 8a with 92% yield
was obtained over 4 mol% of the SBA-15/SO3H under sonicated con-
ditions at room temperature. The expanded and obtained results
are summarized in Table 4. It may be emphasized that in this green
waste-free combined catalytically system not a trace of the byprod-
ucts 5, 6 or 9, 10 was observed in this reaction by TLC analysis.
Fig. 4. Catalyst amounts study of SBA-15/SO3H in combine ultrasound/nanoreactor
system (blue for HSS) and (red for US). (For interpretation of the references to color
in this figure legend, the reader is referred to the web version of the article.)
most relevant solid-acid catalysts have been investigated in same
condition (Fig. 5).
These results clearly point out the efficiency of the proposed
combined methodology (ultrasonic/nanoreactor) in both activity
and recyclability of the high surface area mesoporous porous cata-
lyst.
Fig. 5. Recyclability study on the synthesis of 4a and XRD patterns of SBA-15/SO3H: (a) newly prepared; (b) used 7 times.

S. Rostamnia et al. / Journal of Molecular Catalysis A: Chemical 374–375 (2013) 85–93
91
O
Ar
O
Ar
O
Ar
O
E
E
E
O
O
NH4OAc
+
5
+
6
+
+
+
Ar
H
N
H
OH
N
H
N
H
E
8
10
9
E = ester
Scheme 2. Synthesis of the polyhydroquinolines 8 and possible products.
Table 4
A clean one-pot synthesis of polyhydroquinolines 8.a
O
O
Ar
O
O
SBA-15/SO3H
(4 mol%)
E
+
6
9
+
+
5
10
+
+
+
+
NH4OAc
Ar
H
EtOH, r.t.
OH
N
H
E
.
Entry
Ar
E
Time (min)
Conv%b
Yield%c
5
6
8
9
10
1
2
3
4
5
6
7
8
9
C6H5
2-Cl-C6H4
CO2Me
CO2Me
CO2Me
CO2Me
CO2Me
CO2Et
CO2Et
CO2Et
CO2Et
CO2Et
25
25
25
15
20
25
25
15
15
20
100
100
100
100
100
100
100
100
100
100
Te
Nd
Nd
Nd
Nd
Nd
Nd
Nd
Nd
Nd
Nd
92 (8a)
91 (8b)
90 (8c)
95 (8d)
92 (8e)
90 (8f)
91 (8g)
96 (8h)
95 (8i)
94 (8j)
∼4
∼5
∼5
Te
Nd
Nd
Nd
Nd
∼5
Nd
Nd
Nd
Nd
∼4
Nd
Te
2-Me-C6H4
4-Cl-C6H4
4-MeO-C6H4
2-Me-C6H4
2-Cl-C6H4
4-Cl-C6H4
4-NO2-C6H4
4-MeO-C6H4
Nd
Nd
Te
Te
∼5
∼5
Nd
Te
Te
Nd
Nd
Nd
10
Te
a
Reaction scale: 3 mmol.
Conversion calculated based on consume of dimedone (TLC).
Isolated yield.
No detected of the this product based on TLC analysis.
Trace yield based on TLC analysis.
b
c
d
e
In addition to the total overall catalytic activity, recyclability
The catalytic activity of the simultaneously application
of SBA-15/SO3H nanoreactor and ultrasonic irradiation as
combined catalytic system for three-component synthesis of ␣-
aminophosphonates was studied. The reaction was set under the
above optimized conditions at room temperature in EtOH medium
(Table 5).
The possibility of recycling the catalyst was then examined. As a
model reaction (11a), p-chlorobenzaldehyde, aniline and dimethyl
phosphite were sonicated in the presence of 2 mol% SBA-15/SO3H.
In this case, after completion of the reactions, the catalyst was fil-
tered and reused at least 7 times without any significant decrease
in catalytic activity (Fig. 7).
The synthesis of 11a with high-scale (20 mmol) amount of
reactant was carried out in 25 mL EtOH (Fig. 8). When the p-
chlorobenzaldehyde and aniline coupled with dimethylphosphite
is obviously a critical feature of supported catalysts. As compar-
ison with catalytic efficiency of SBA-15/SO3H, SiO2/OSO3H and
HClO4/SiO2 as the most relevant solid acid have been also investi-
gated in the reaction condition. Employing SBA-15/SO3H in which
the ultrasonic was used, we found that the material displayed min-
imal loss of activity after 6 runs (Fig. 6).
It is noteworthy that ␣-aminophosphonate derivatives manifest
a number of important and therapeutically useful biologicalactivi-
ties [13]. ␣-aminophosphonates have received significant attention
in organic synthesis, and various methods have been developed for
their synthesis [14]. Here, we explored the effectiveness of com-
bined ultrasound/nanoreactor catalytically system as an ultra-fast,
waste-free and highly reusable method for the generation of ␣-
aminophosphonates 11 via a three-component coupling (Table 5).
a
Fig. 6. Recyclability study on the synthesis of 8a.
Fig. 7. Recyclability study on the synthesis of 11a.

92
S. Rostamnia et al. / Journal of Molecular Catalysis A: Chemical 374–375 (2013) 85–93
Table 5
A ultra-fast waste-free synthesis of ␣-aminophosphonates 11.a
R
NH
O
R'
O
O
P
SBA-15-SO3H
P
RNH2
CHO
5-7 min, r.t.
ultrasonic
O
H
OMe
OMe
11
R'
.
Entry
Amine
Ar(Rꢀ)CHO
Time (min)
Yield%b 11
1
2
3
4
5
6
7
8
9
PhNH2
PhNH2
PhNH2
4-Me-C6H4NH2
4-Me-C6H4NH2
4-Me-C6H4NH2
Et2NH
4-Cl-C6H4
C6H5
5
5
5
5
4
5
4
5
7
94 (a)
95 (b)
95 (c)
94 (d)
95 (e)
94 (f)
93 (g)
94 (h)
91 (i)
3-NO2-C6H4
2-Cl-C6H4
4-NO2-C6H4
2-MeO-C6H4
3-NO2-C6H4
2-MeO-C6H4
(CH2)5NH
(CH2)4NH
PhNH2
a
Reaction scale: 5 mmol.
Isolated yield method.
b
Fig. 8. Progress of reaction in large-scale: (a) beginning of reaction; (b) reaction as
it progresses; (c) end of reaction.
Fig. 9. Possible explanation for SBA-15/SO3H and ultrasonic irradiation catalysis.
in optimized conditions, a 91% yield was obtained, which showed
efficiency of this green method in high-scale amount of substrates.
In a comparative study, the reactivity of dimethyl phosphite in
presence of the mixture of aldehydes, ketones with aniline may
show the chemoselectivity in our method. To show the chemoselec-
tivity, dimethyl phosphite was treated with the mixture of aniline,
benzaldehyde and cyclohexyl ketone. Analysis of the mixture after
10 min shows that only benzaldehyde reacted with aniline to cor-
responds 11b (Scheme 3).
Although we have not established the mechanism of the simul-
taneously application of SBA-15/SO3H and ultrasonic irradiation
in an experimental manner, a possible explanation is proposed in
Fig. 9. In this condition the irradiations of ultrasonic in presence of
the SBA-15/SO3H provide a synergistic means to input the reactants
and also drive out the products for next recycles.
4. Conclusion
Simultaneously application of the ultrasonic and nanoreactor
as combined catalytic system in preparation of the some biologi-
cally interesting organic molecules via multicomponent reaction.
In fact, we have developed a green synthetic method for ultra-
fast and waste-free preparation of the indazolophthalazinetrione,
polyhydroquinolines, and ␣-aminophosphonate molecules using
SO3H-functionalized SBA-15 porous nanoreactor in presence of
an ultrasound. Undoubtedly, as part of the continuing explo-
ration of ultrasonic/nanoreactor for the green organic synthesis,
these reaction methods have great prospects of applications in
organic syntheses, pharmacy and industrial processes that which
this report opens an important field to the use of green strategy
in organic process. At the outset of our studies, there was few
literature precedent for the direct application of nanoreactor in
combination with ultrasound.
NHPh
O
Acknowledgements
O
P
O
NH2
CHO
The author gratefully acknowledges financial support from the
Iran National Science Foundation (INSF).
O
SBA-15/SO3H
(90%)
(trace)
NHPh
P
O
(MeO)2POH
ultrasonic
Appendix A. Supplementary data
(5 mmol)
(5 mmol) (5 mmol)
O
O
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/j.molcata.
2013.03.017.
Scheme 3. Chemoselective addition of phosphite to different carbonyl.

S. Rostamnia et al. / Journal of Molecular Catalysis A: Chemical 374–375 (2013) 85–93
93
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