Domino synthesis of quinoxaline derivatives using SBA-Pr-NH2 as a nanoreactor and their spectrophotometric complexation studies with some metals ions

Article abstract of DOI:10.1007/s13738-018-1312-4

Abstract: Amino-functionalized SBA-15 (SBA-Pr-NH₂) with a pore size of 6?nm has been used as a basic nanocatalyst in the domino one-pot synthesis of quinoxaline derivatives via the four-component reaction of ninhydrin, 1,2-aryl-diamines, malono derivatives, and α-methylenecarbonyl compound using microwave irradiation. The solid basic catalyst plays a significant role in catalysis, and enhancing the rate and yield of the reaction, it can be easily handled and removed from the reaction mixture by simple filtration and also reused several times without substantial loss of reactivity. Moreover, the complexation reaction between quinoxaline as a model ligand and some metal ions including Cd²⁺, Co²⁺, Cu²⁺, Fe³⁺, Hg²⁺, Ni²⁺, Pb²⁺, and Zn²⁺ ions was examined spectrophotometrically in DMF solution at 25?°C. The formation constants of the resulting complexes were calculated from the computer fitting of the molar absorbance measurements in different mole ratios. The obtained data indicated that the stability constant of the resulting complexes varied in the following order Pb²⁺>?Hg²⁺>?Cd²⁺>?Ni²⁺>?Cu²⁺>?Fe³⁺>?Zn²⁺>?Co²⁺.

Full text of DOI:10.1007/s13738-018-1312-4

Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-018-1312-4
ORIGINAL PAPER
Domino synthesis of quinoxaline derivatives using SBA‑Pr‑NH2
as a nanoreactor and their spectrophotometric complexation studies
with some metals ions
1
1
1
2
Tahereh Ahmadi · Ghodsi Mohammadi Ziarani · Shahriyar Bahar · Alireza Badiei
Received: 6 September 2017 / Accepted: 21 January 2018
©
Iranian Chemical Society 2018
Abstract
Amino-functionalized SBA-15 (SBA-Pr-NH ) with a pore size of 6 nm has been used as a basic nanocatalyst in the dom-
2
ino one-pot synthesis of quinoxaline derivatives via the four-component reaction of ninhydrin, 1,2-aryl-diamines, malono
derivatives, and α-methylenecarbonyl compound using microwave irradiation. The solid basic catalyst plays a signiꢀcant
role in catalysis, and enhancing the rate and yield of the reaction, it can be easily handled and removed from the reaction
mixture by simple ꢀltration and also reused several times without substantial loss of reactivity. Moreover, the complexa-
2
+
2+
2+
3+
2+
2+
tion reaction between quinoxaline as a model ligand and some metal ions including Cd , Co , Cu , Fe , Hg , Ni ,
2
+
2+
Pb , and Zn ions was examined spectrophotometrically in DMF solution at 25 °C. The formation constants of the
resulting complexes were calculated from the computer ꢀtting of the molar absorbance measurements in diꢁerent mole
ratios. The obtained data indicated that the stability constant of the resulting complexes varied in the following order
2
+
2+
2+
2+
2+
3+
2+
2+
Pb > Hg > Cd > Ni > Cu > Fe > Zn > Co .
Graphical Abstract
Keywords SBA-Pr-NH · Quinoxaline derivatives · Ninhydrin · 1,2-aryl-diamines · Malono derivatives ·
2
α-Methylenecarbonyl compound · Microwave irradiation · Four-component domino reaction · Spectrophotometric
complexation
*
Ghodsi Mohammadi Ziarani
gmziarani@hotmail.com; gmohammadi@alzahra.ac.ir
Extended author information available on the last page of the article
Vol.:(0
1
123456789)
3

Journal of the Iranian Chemical Society
Introduction
in the synthesis of heterocyclic compounds have been pub-
lished [40].
Functionalized quinoxalines are very important heterocycle
compounds, which is a building block of many useful inter-
mediates in organic synthesis and useful dyes [1]. Also they
attracted scientists because of their pharmaceutical proper-
ties including as antibacterial [2], antiviral [3], as kinase
inhibitors [4], and anticancer [5]. Besides clinical drugs and
dye applications, quinoxaline compounds have been known
as the framework in the preparation of organic semiconduc-
tors [6]. Development of many strategies for the preparation
of substituted quinoxalines has been reported [7, 8]. The
most common methods are the condensation of an α,β-aryl-
diamine with a α,β-dicarbonyl compound in reꢂuxing acetic
acid or ethanol [9].
Experimental
Materials and instruments
The chemical materials which were employed in this work
were obtained from Merck Company and used with no puri-
ꢀcation. Melting points were measured by capillary tube
method with an Electrothermal 9200 apparatus. Infrared (IR)
spectra were recorded from KBr disks employing a Fourier-
transform (FT)-IR Bruker Tensor twenty-seven instrument.
1
13
H NMR (250 MHz) and C NMR (62.9 MHz) spectra
Multicomponent reactions (MCRs) have gained signiꢀ-
cant importance as a tool for the synthesis of a wide variety
of useful compounds. Over the past decades, multicompo-
nent reactions have proved to be very powerful and eꢃcient
bond-forming tools in organic chemistry [10, 11] and the
number of used catalysts to promote this reaction is large
such as nanoparticles [12], magnetic nanoparticles [13, 14],
and nanoreactors [15, 16]. Magnetic nanoparticles and nano-
reactors can be also used as carrier [17–19].
were run on a Bruker DPX using tetramethylsilane (TMS)
as internal standard in DMSO. The X-ray powder diꢁrac-
tion (XRD) pattern of the prepared SBA-Pr-NH2 nanoreactor
was collected by a Philips X’pert MPD diꢁractometer using
Cu Kα radiation (λ = 0.15478 nm). Transmission electron
2
microscopy (TEM) was carried out on a Tecnai G F30 at
300 kV. All UV–Vis spectra and absorption measurements
were recorded on a computerized Specord S 600 Analytik
Jena UV–Vis spectrophotometer equipped with a peltier
element with a heating rate of 0.1 °C/min to control the
temperature.
A nanoreactor is a nanoscale environment that a reac-
tion takes place. Due to the nanoscopic conꢀnement eꢁect
of the nanoreactor, the physical properties such as density,
viscosity, and solubility could be varied, and the chemical
properties of reactants and catalysts could be modulated
Synthesis and functionalization of SBA‑15
[
20]. Several types of nanoreactors have been developed
The nanoporous compound SBA-15 was synthesized and
functionalized according to our previous report, and the
modiꢀed SBA-Pr-NH2 was used as a nanoporous solid basic
catalyst in the following reaction [37].
up to now, including carbon nanotubes (CNT) [21, 22],
metal–organic frameworks (MOF) [23], zeolites [24], and
mesoporous silica [25, 26]. Higher reactivity and selectivity
were revealed when reactions were conducted in nanoreac-
tors [27, 28]. Among these nanoreactors, mesoporous silicas,
especially SBA-15, have been widely investigated thanks
to their controllable size, composition, and morphology,
which are highly desirable for catalytic applications. SBA-
General procedure for the synthesis
of spiro[indeno[2,1‑b]quinoxaline derivatives
SBA-Pr-NH2 (0.02 g) was activated into a round-bottomed
ꢂask containing a magnetic stirrer at 100 °C for removal
of the adsorbed water. The mixture of ninhydrin (1 mmol,
0.178 g), 1,2-aryl-diamines (1 mmol), and SBA-Pr-NH2 in
5 ml ethanol was heated and stirred at 60 °C to form inde-
noquinoxalineA; then, after about 5 min, malono derivatives
(1 mmol) and α-methylencarbonyl compounds (1 mmol)
were added to the mixture of reaction for the synthesis of
spiro[indeno[2,1-b]quinoxaline derivatives under reꢂux con-
dition using MW irradiation (400 W, 80 °C). Completion
of the reaction was monitored by TLC. After that, obtained
precipitate was cooled to room temperature and extracted
from the solvent. Subsequently, the precipitate was dis-
solved in minimum volume of hot acetone and the unsolv-
able SBA-Pr-NH2 catalyst was removed by ꢀltration. The
residue was puriꢀed by recrystallization from ethanol. The
15 is mesoporous silica, which was synthesized by Zhao and
co-workers, ꢀrstly [29, 30]. This mesoporous silica is hex-
agonal nanoporous silica with high surface area, large pore
size, remarkable thermal stability, and easily handled and
removed from the reaction mixture [31–33]. The surface of
SBA-15 can be modiꢀed by diꢁerent functional groups such
as organic acids and amines [34]. SBA-Pr-NH can act as an
2
eꢃcient heterogenous solid base catalyst in the organic syn-
thesis. In continuation of our researches [35–39], we used
amino-functionalized SBA-15 (SBA-Pr-NH ) as a heteroge-
2
neous nanoreactor in the synthesis of quinoxaline derivatives
through the four-component domino reaction of ninhydrin,
1
,2-aryl-diamines, malononitrile, and α-methylenecarbonyl
compound. In 2015, the advances in the use of ninhydrin
1
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Journal of the Iranian Chemical Society
−
3
−1
new compound was characterized by mass, IR, and NMR
spectroscopy techniques. The melting points of the products
were compared with those reported in the literature.
amount of the 10 mol L solution of diꢁerent metal ions
was added in a stepwise manner using a micro-syringe. Fol-
lowing each addition, the absorbance value of the solution
was measured. The addition of metal ions solution was con-
tinued until the preferred metal ion to ligand mole ratio was
6
1
′‑Amino‑3′‑phenyl‑1′H‑spiro[indeno[1,2‑b]quinoxaline‑1
,4′‑pyrano[2,3‑c]pyrazole]‑5′‑carbonitrile (5 g)
achieved. In the following, the formation constant (k ) of the
f
obtained complexes between quinoxaline and several metal
FT-IR (KBr) υ : 3332, 3309, 3239, 3170, 2200, 1658,
ions at constant temperature (25 °C) was computed by ꢀt-
max
−
1 1
1
6
604, and 1405 cm . H NMR (250 MHz, DMSO-d ) δ :
ting the observed absorbance, A , at various metal ion/
6
H
obs
.26–6.99 (3H, m, Ar–H), 7.29 (s, 2H, NH ), 6.50–8.06
ligand mole ratios to the equation that previously derived
with Shamsipur et al. [41, 42], which expresses the observed
electronic absorbance as a function of the free and com-
plexed metal ions and the formation constant assessment
from a nonlinear least-squares program KINFIT [43].
2
1
3
(
13H, m, Ar–H), 12.84 (s, 1H, NH) ppm. C NMR
62.5 MHz, DMSO-d ) δ : 48.11, 57.93, 97.34, 119.06,
(
6
C
1
1
1
22.01, 126.07, 127.52, 128.28, 128.51, 129.06, 129.30,
29.49, 129.93, 130.66, 133.25, 136.16, 139.31, 141.56,
42.32, 152.35, 153.55, 156.38, 162.36, 165.20 ppm. MS
+
·
(
m/z, %): 440([M ], 26), 414(100), 374(22), 280(78),
2
16(4), 160(22), 66(11).
Results and discussion
Assessment of mole ratio and formation constants
of quinoxaline complexes
In this method, a rapid and highly eꢃcient strategy for the
synthesis of spiro [indeno[1,2-b] quinoxaline derivatives
5
a–h through four-component domino condensation reaction
In order to calculate the stoichiometry of the resulting com-
plexes of quinoxaline as a model, ligand with some metal
ions, spectrophotometric titration was used. For this pur-
of ninhydrin 1,1,2-aryl-diamines 2a–b, malono derivatives
3a–b, and α-methylencarbonyl compounds 4a–g in the pres-
ence of SBA-Pr-NH under MW irradiation in ethanol was
2
−5
−1
pose, 2.5 mL of quinoxaline solution (5.0 × 10 mol L ) in
DMF was located in the spectrophotometer cuvette and the
absorbance of solution was measured. Afterward, a suitable
studied (Scheme 1). In order to assess the impact of solvent
on the reaction, its progress in diꢁerent conditions such as
reꢂux in EtOH and solvent-free systems in the presence of
Scheme 1 Synthesis of quinoxaline derivatives 5 using SBA-Pr-NH2
1
3

Journal of the Iranian Chemical Society
SBA-Pr-NH was compared and reported in Table 1. The
by SBA-Pr-NH followed by Knoevenagel condensation of
2
2
reaction times and yields of the products under various con-
ditions (i.e., reꢂux, 140 °C, and MW irradiation), in the pres-
ence of solvent and under a solvent-free system, were com-
pared, and the best result was obtained after 15 min under
MW irradiation in EtOH as solvent (entry 5). We also tested
the reaction with various catalysts, and the results showed
indenoquinoxaline A with malononitrile 3 aꢁorded inter-
mediate B, which subsequently underwent Michael addition
with α-methylene carbonyl compound 4 to form intermedi-
ate C. In the next step, the oxygen of the enolate attacks to
the nitrile group in intermediate C and the desired products
were obtained after a cyclization.
that SBA-Pr-NH plays a signiꢀcant role in this reaction and
There are only few reports for spiro[indeno[1,2-b]
quinoxaline-11,4′-pyrano-5′-carbonitriles synthesis through
the mentioned four-component domino reaction in the lit-
erature. As shown in Table 3, the products were synthesized
with excellent yields and short reaction times when com-
pared with other existing methods.
2
enhances the rate and yield of the reaction. With the opti-
mized reaction conditions, we explored the generality of this
method using diꢁerent 1,2-aryl-diamine, malono derivatives
and α-methylencarbonyl compounds. Consequently, accord-
ing to the current synthetic requirements, this multicompo-
nent procedure under MW irradiation in EtOH and in the
optimum quantity of SBA-Pr-NH (0.02 g) is preferable due
Spectrophotometric studies
2
to the shorter reaction time and high yields of the products.
2
+
2+
The new products were characterized by melting point, IR,
The absorption spectra of quinoxaline and its Cd , Co ,
1
13
2+
3+
2+
2+
2+
2+
H NMR, C NMR spectra, and MS spectral analysis. Melt-
Cu , Fe , Hg , Ni , Pb , and Zn complexes in DMF
solution are shown in Fig. 1. As can be seen, the spectral
changes (increase in the absorbance in the 350 nm) are the
result of the complex formation between quinoxaline and
metal cations. The stoichiometry of the obtained complexes
with diꢁerent metal ions was measured by the mole ratio
method, and the resultant plots of the absorbance change
versus the metal ion/quinoxaline mole ratio at 350 nm
ing points of known products were compared with reported
values in the literature (Table 2).
The suggested reaction mechanism and signiꢀcant role of
SBA-Pr-NH as solid basic catalyst in accelerating reaction
2
rate are depicted in Scheme 2. First, through a nucleophilic
addition of 1,2-aryl-diamine moiety to ninhydrin 1, indeno-
quinoxaline A was achieved. Deprotonation of malononitrile
Table 1 Optimization of
a
Entry
Catalyst
Reaction condition
Temperature Time (min)
Yield (%)
a
reaction condition for the
(
°C)
synthesis of quinoxaline 5e
1
2
3
4
5
6
AcONH4
EtOH, Reꢂux
EtOH, Reꢂux
EtOH, MW
EtOH, Rele 3ꢂux
EtOH, MW
80
80
80
80
80
80
12 h
8 h
20
7 h
15
80
SBA-Pr-SO3H
SBA-Pr-SO3H
SBA-Pr-NH2
SBA-Pr-NH2
Trace
Trace
85
94
94
SBA-Pr-NH2/SBA- EtOH, MW
15
Pr-SO3H
7
8
SBA-Pr-NH2
SBA-Pr-NH2
Neat
Neat
170
120
60
4 h
80
50
a
Ninhydrin (1 mmol), o-phenylendiamine (1 mmol), malononitrile (1 mmol), 3-methyl-5-pyrazolone
(
1 mmol), and catalyst
Table 2 Synthesis of
Entry
R
X
Carbonyl
Product
Yield (%)
M.p. (°C)
M.p. (Lit.)
quinoxaline derivatives in the
compound
presence of SBA-Pr-NH
2
1
2
3
4
5
6
7
8
H
H
H
H
H
Me
H
CN
CO2Et
CN
CN
CN
CN
CN
CN
4a
4b
4c
4d
4e
4e
4f
5a
5b
5c
5d
5e
5f
90
88
93
92
94
89
98
95
298 dec.
290 dec.
282 dec.
276 dec.
270–272
262–264
275–277
241–243
297 dec. [44]
289 dec. [44]
280 dec. [44]
278 dec. [44]
263–266 [45]
258–262 [45]
New
5g
5h
H
4g
241–244 [45]
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Journal of the Iranian Chemical Society
Scheme 2 Proposed mechanism for the synthesis of quinoxaline derivatives 5
Table 3 Comparison of
Entry
Catalyst
Na CO
Solvent
Condition
Time (h)
Yield (%)
References
diꢁerent conditions in the
synthesis of compound 5 h
3
1
2
4
EtOH
EtOH
EtOH
EtOH
70 °C
Reꢂux
Reꢂux
MW
17
12
10
15 min
85
93
93
95
[45]
[46]
[44]
This work
2
3
NH OAc
4
InCl3
SBA-Pr-NH2
Fig. 1 UV–Vis spectra of qui-
−
5
noxaline (5 × 10 M) and its
2+
2+
2+
3+
2+
Cd , Co , Cu , Fe , Hg
,
2+
2+
2+
Ni , Pb , and Zn complexes
in DMF solution
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3

Journal of the Iranian Chemical Society
Fig. 2 Mole ratio plots of
n+
absorbance as [M ]/[L] at
3
50 nm
Table 4 log k values for
f
Metal ion log k ± SD
f
various metal ions complexes
with quinoxaline
2+
−3
−4
−4
−4
−4
−4
−4
−4
Pb
3.87 ± 1.55 × 10
3.72 ± 2.16 × 10
3.03 ± 1.23 × 10
3.02 ± 1.02 × 10
3.00 ± 7.77 × 10
3.00 ± 5.13 × 10
2.99 ± 7.35 × 10
2.99 ± 6.99 × 10
2
+
Hg
Cd
Ni
Cu
Fe
Zn
Co
2
+
2
+
2
+
3
+
2
+
2
+
2
+
the stabilities of the complexes vary in the accordance
Fig. 3 Computer ꢀtting of absorbance versus [Pb ]/[L] mole ratio
2
+
2+
2+
2+
2+
3+
2+
2+
plot in DMF at 25 °C, (×) experimental point, (O) calculated point,
Pb > Hg > Cd > Ni > Cu > Fe > Zn > Co .
(
=) experimental and calculated points are the same within the reso-
lution of the plot
Synthesis and functionalization of SBA‑15
are shown in Fig. 2. The stability constants of the formed
complexes between diꢁerent metal ions and quinoxaline
were obtained using measurement of the variation in the
absorbance amount of the solutions in which diꢁerent con-
centrations of metal ions were added to constant quantity
SBA-15 was aꢁorded via triblock copolymer pluronic P126
as a commercially available structure-directing agent [29]. A
pathway for the synthesis of SBA-Pr-NH is shown in Fig. 4,
2
and post-grafting technique was used for the modiꢀcation of
SBA-15 surface with the APTES ((3-aminopropyl)triethox-
ysilane) in reꢂuxing toluene for 24 h [37].
−
5
−1
(
5 × 10 mol L ) of quinoxaline solution.
For assessment of the stability constants of the result-
Analysis of the catalyst surface was performed by totally
diꢁerent ways including thermogravimetric analysis (TGA),
Brunauer–Emmett–Teller (BET) analysis, X-ray diꢁrac-
tion (XRD), and elemental analysis (CHN). These analyses
proved that the 3-aminopropyl groups were successfully
immobilized into the pores [37].
ant complexes from absorbance amount versus [M]/[L]
mole ratio, a nonlinear least-squares curve fitting pro-
gram KINFIT was applied. A model computer ꢀtting of
2
+
the absorbance–mole ratio data for the Pb ion is illus-
trated in Fig. 3. The logk values for all metal ions com-
f
plexes which evaluated from the computer ꢀtting of the
related absorbance–mole ratio data at 25 °C are shown
in Table 4. The obtained data revealed that, at 25 °C,
In this work, SBA-Pr-NH was used as a nanoporous cata-
2
lyst in the synthesis of 5. Figure 5 shows the SEM and TEM
images of SBA-Pr-NH . The SEM image shows uniform
2
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Journal of the Iranian Chemical Society
As depicted in Fig. 6, the XRD patterns of SBA-15
showed the intensity of the strongest reꢂection peaks at
0
.8°–0.9° with two other relatively intense of less reꢂec-
tions at higher degrees, which might be indexed to the 100,
1
10, and 200 planes, respectively. NH -SBA-15 was also
2
described by a similar pattern, informing the successful
grafting of APTES into the channels of the mesostructure
without changing the structural integrity of SBA-15 [47].
As shown in Fig. 7, the prepared SBA-15-NH has the
2
amine groups within its pores. As the pore size of the cata-
lyst is about 6 nm, which was proved by BET analysis, the
starting materials enter into the pores and react together in
contact with the basic groups to give the product. Therefore,
SBA-15-NH is a solid basic catalyst, which can act as a
2
nontoxic, available, and reusable nanoreactor.
At the end of reaction, the reusability of the catalyst was
determined for the preparation of compounds 5e. As shown
in Fig. 8, the catalyst can be recovered and reused four times
without signiꢀcant loss of activity. The yields for the four
runs were 91, 88, 86, and 83%, respectively.
Fig. 4 Preparation of SBA-Pr-NH2
Conclusion
In the present work, SBA-Pr-NH organocatalyst was pre-
particles about 1 μm which have the same morphology as
SBA-15. It can be illustrated that the morphology of the
solid was remained and no changes occurred during the sur-
face modiꢀcations. Furthermore, TEM image shows parallel
2
pared and well characterized. The prepared SBA-Pr-NH
2
nanoparticles play a signiꢀcant role in the domino four-
component reaction of ninhydrin, 1,2-aryl-diamines, malono
compounds, and α-methylenecarbonyl for the synthesis of
spiro[indeno[2,1-b]quinoxaline derivatives. The key advan-
tages of this study include high yields, short reaction times,
channels in the SBA-Pr-NH , which resembled the conꢀgu-
2
ration of the pores in SBA-15.
Fig. 5 SEM and TEM images of
SBA-15-NH2
TE
SE
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Journal of the Iranian Chemical Society
1
00
80
60
40
20
0
1
2
3
4
Cycle
Fig. 8 Reusability of SBA-Pr-NH in the synthesis of compound 5e
2
Fig. 6 Low-angle XRD patterns of SBA-15 and SBA-Pr-NH2
Fig. 7 SBA-15-NH acts as a nanoreactor
2
easy workup, available catalyst, reusable catalyst, and
puriꢀcation of compounds using a crystallization method
Acknowledgements We gratefully acknowledge the ꢀnancial support
from the Research Council of Alzahra University and the University of
Tehran. This work was supported by the Iran National Science Founda-
tion (INSF) under Contract 95005360.
(
non-chromatographic). In the following, the complexa-
tion study of the quinoxaline with some metal ions indi-
cated that the prepared compound has a good selectivity
2
+
for the complexation of the Pb ions. The obtained logk
f
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Aꢀliations
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Tahereh Ahmadi · Ghodsi Mohammadi Ziarani · Shahriyar Bahar · Alireza Badiei
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Department of Chemistry, Alzahra University, Vanak
Square, Tehran, P.O. Box 1993893973, Iran
School of Chemistry, College of Science, University
of Tehran, Tehran 14155-6455, Iran
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