Preparation and characterization of new inorganic–organic hybrid catalyst H3PMo12O40/Hyd-SBA-15 and its application in the domino multi-component reaction

Article abstract of DOI:10.1002/aoc.5201

We present novel inorganic–organic hybrid catalyst to accomplish domino multi-component reaction (MCR) for synthesis of 3-amino-2′-oxospiro[benzo[c]pyrano[3,2-a]phenazine-1,3′-indoline]-2-carbonitrile/carboxylate derivatives. This methodology offers remarkable development by easy production of H₃PMo₁₂O₄₀/Hyd-SBA-15 in regard to solving the problem of using harsh catalysts, also it demonstrates to be impressive and environmentally friendly in term of low reaction times and high yields.

Full text of DOI:10.1002/aoc.5201

Received: 26 March 2019
DOI: 10.1002/aoc.5201
Revised: 5 July 2019
Accepted: 1 August 2019
F U L L P A P E R
Preparation and characterization of new inorganic–organic
hybrid catalyst H3PMo12O40/Hyd‐SBA‐15 and its application
in the domino multi‐component reaction
Javad Safaei‐Ghomi
| Atefeh Bakhtiari
Department of Organic Chemistry,
Faculty of Chemistry, University of
Kashan, Kashan 51167I. R., Iran
We present novel inorganic–organic hybrid catalyst to accomplish domino
multi‐component reaction (MCR) for synthesis of 3‐amino‐2′‐oxospiro[benzo
[c]pyrano[3,2‐a]phenazine‐1,3′‐indoline]‐2‐carbonitrile/carboxylate derivatives.
This methodology offers remarkable development by easy production of
H3PMo12O40/Hyd‐SBA‐15 in regard to solving the problem of using harsh cata-
lysts, also it demonstrates to be impressive and environmentally friendly in
term of low reaction times and high yields.
Correspondence
Javad Safaei‐Ghomi, Department of
Organic Chemistry, Faculty of Chemistry,
University of Kashan, Kashan, 51167, I.R.
Iran.
Email: safaei@kashanu.ac.ir
KEYWORDS
Funding information
diversity‐oriented synthesis, H3PMo12O40, multi‐component reaction, Nanohybrid catalyst, organic–
university of Kashan, Grant/Award Num-
ber: 159196/XXII
inorganic hybrid silica
1 | INTRODUCTION
by using a variety of organic functional groups. There
are a number of methods for the synthesis of hybrids cat-
The considerable attention has been paid to designing
heterogeneous catalysts due to advantages of them such
as easy separation, easy recovery, and high reusability.
The surface support has an influential effect on the
behavior of heterogeneous catalysts. Several solid sup-
ports have been introduced such as polymer resins, silica,
alumina, silica‐coated magnetic particles, and mesopo-
rous molecular sieves. The fully ordered structures of
mesoporous silica lead to generation a framework with
regular porosity, so the ligands could be well immobilized
on them. Because of the advantages of mesoporous silica,
they could be vastly employed in separation, catalysis, gas
storage, drug delivery, and biomolecule. Since the devel-
opment of ordered mesoporous silicas,[1] SBA‐15 mate-
rials with potential application serve in many fields.
SBA‐15 developed by Zhao and Stucky[2] has attracted a
lot of attention due to their interesting textural properties
such as appreciable thermal and hydrothermal stability,
large pore volume, uniform‐sized pores (in the range 4–
30 nm), high special surface area (above 1000 m2/g).[3]
The creation of organic–inorganic hybrid catalysts is the
best methodology to overcome the lack of functionality
alyst. Among them, directing or post‐synthesis methods
are the best strategy which lead to stable attachment
and less leaching.[4] The loading of heteropolyacids
(HPAs) on the surface of SBA‐15 is known to increase
the activity of catalysts.[5] In recent years, many
researchers have studied on providing the manners to
prevent the leaching of active HPAs from the solid sup-
port by modification of silica supports with organic
linkers.[6] HPAs could attach to the supporting materials
via a suitable linker to less leaching from the surface.
The linkers lead to higher stable loading by electrostatic
interactions, hydrogen bonding, and chemical bonding.
The interplay of HPAs with the supporting material is
increased due to the functional groups. Polyoxometalates
are divided into two groups based on their redox abilities,
mono‐oxo (type I) and cisdioxo (type II). The number of
attached terminal oxygen atoms to per each addenda
atom, tungsten or molybdenum, e.g., is the basis of this
classification. Keggins and its derivatives which have
one terminal oxygen atom belong to the type I.[7] The
lowest unoccupied molecular orbital (LUMO), in the type
I octahedral MO6 is a nonbonding metal‐centered orbital.
Appl Organometal Chem. 2019;e5201.
wileyonlinelibrary.com/journal/aoc
© 2019 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.5201

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SAFAEI‐GHOMI AND BAKHTIARI
It should be noted, type I polyoxometalates can act as an
oxidant because of easy reduction and reversibly to form
spiro‐substituted pyranophenazine‐indoline. The intro-
duction of a new synthetic method is required that use
of an efficient and eco‐friendly catalyst. In this research,
a novel inorganic–organic nano‐hybrid material is pre-
sented to advance the synthetic methodology of the above
biological materials. We are interested in the develop-
ment of our research[22] to prepare a more effective cata-
lyst for a variety of MCRs. The catalyst H3PMo12O40/
Hyd‐SBA‐15 was prepared by applying simple and cost
effective materials, also it was characterized as a new
inorganic–organic hybrid catalyst. This new heteroge-
neous, environmentally benign, and highly reusable cata-
lyst represent high catalytic activity to synthesize spiro
[benzo[c]pyrano[3,2‐a]phenazine] derivatives via a dom-
ino, one‐pot, four‐component condensation reaction.
The condensation reaction between 2‐hydroxy‐1,4‐
naphthoquinone (1) (1 mmol), benzene‐1,2‐diamine (2a,
b) (1 mmol), malononitrile (3a,b) (1 mmol) and isatin
(4a‐f) (1 mmol), was carried out in the presence of
H3PMo12O40/Hyd‐SBA‐15 in EtOH at 50 °C (Scheme 1).
mixed‐valence
species.[8]
That's
why,
type
I
Polyoxometalates compounds, especially Keggins, play
an important role in catalytic reactions. Herein, we report
a new catalyst by loading Keggins on the modified surface
of SBA‐15 with hydantoin.
The synthesis of novel polycyclic heterocycles com-
pounds with exciting medicinal and biological properties
is possible by diversity‐oriented synthesis (DOS).[9] The
development of DOS is in progress in organic and medic-
inal chemistry. The aim of DOS is to achieve simulta-
neous, deliberate, and impressive synthesis of
structurally diverse compounds that presence in drug
molecules or natural products.[10] MCRs[11] can be placed
in the class of DOS chemistry due to green characteristics,
high degrees of atom economy, lower costs and environ-
mentally friendly.[12] The term MCR uses also with one‐
pot, domino and cascade processes.[13]
Spirocyclic structures that contain one sp3 carbon atom
common to two rings have many biological properties
such as antibacterial, antibiotic and antifungal activi-
ties.[14] Chemical researchers focused on the synthesis of
functionalized nitrogen‐ and oxygen‐containing organic
compounds that have potential medicinal and biological
activity.[15] The biological properties of organic com-
pounds have been enhanced if at least two heterocyclic
moieties present in a single molecule. Phenazines, pyrans,
and indoles are attracting great attention in academic and
industrial areas so the preparation of compounds incorpo-
rating all of these moieties is very important and signifi-
cant.[16] Each of these moieties has a significant
biological activity to preparation medicinal scaffolds.
The Phenazine moiety has many medicinal properties
such as trypanocidal, antiplatelet, antimalarial, antitu-
mor, fungicidal.[17] Benzophenazines have also been used
as substrates in an industrial application such as pesti-
cides and dyestuffs.[18] The structure of many natural
compounds such as alkaloids and carbohydrates consist
of the heterocyclic pyran ring system.[19] The heterocyclic
indole and indoline have been detected in many natural
and pharmaceuticals products.[20] The use of L‐prolin[21]
and DABCO[16] were reported for the synthesis of a
2 | EXPERIMENTAL SECTION
2.1 | Materials and apparatus
All starting materials and solvents were purchased com-
mercially from Merck and Sigma–Aldrich and were used
1
as received. The H NMR and 13C NMR spectra were
determined on Bruker Avance‐400 MHz spectrometers
with DMSO as a solvent and tetramethylsilane (TMS) as
an internal standard. FT‐IR measurements were carried
out on Magna 550 apparatus by using KBr plates. The ele-
mental analyses (C. H. N) of the samples were recorded
by using a LECO CHNS 923 analyzer. High resolution
mass spectra (HRMS) analyses were carried out using a
Bruker micro‐TOF‐Q‐MS analyzer. The XRD patterns
were evaluated on an X‐ray diffractometer (PHILIPS,
PW 1510, Netherland) with Cu‐Kα radiation
(λ = 0.154056 nm) in the range 2θ = 0–10°. The TGA‐
DTA analyses were performed on a Bahr STA‐503 instru-
ment in air at a heating rate of 10 °C min−1. The N2
adsorption analysis was recorded at −196 °C using an
SCHEME 1 Synthesis of the 3‐amino‐2′‐oxospiro[benzo[c]pyrano[3,2‐a]phenazine‐1,3′‐indoline]‐2‐carbonitrile/carboxylate derivatives in
the presence of H3PMo12O40/Hyd‐SBA‐15.

SAFAEI‐GHOMI AND BAKHTIARI
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automated gas adsorption analyzer (BEL SORP mini II)
and pore‐size distributions were calculated by using BEL
SORP.. The FESEM analysis of nano‐particles was taken
on a Model FE‐SEM. The TEM analysis image was per-
formed on a Philips EM208 transmission electron micro-
scope with an accelerating voltage of 200 kV. The EDX
analysis of the nano‐particles imagined by a Sigma ZEISS,
Oxford Instruments Field Emission. The UV–vis DRS
analysis were obtained by using UV‐1800 240 V.
Pluronic 123 triblock copolymer (EO20–PO70–EO20) was
used as a template. In a general preparation method, the
mixture of 4.0 g pluronic P123 in 2.0 (M) aq. HCl
(120 ml) and distilled water (15 ml) was stirred at room
temperature for 4 hr. Then 8.5 g (40.8 mmol) of
tetraethylorthosilicate (TEOS) was added to the solution
and stirred at 35 °C for 8 hr. Under static conditions in
a Teflon‐lined autoclave, the synthesized gel was heated
for 24 hr at 100 °C. The filtered product was washed by
the deionized water. The calcination was accomplished
to dry and remove the residual organic template materials
at 550 °C for 8 hr.
In a 50 ml round‐bottom flask, 0.2 g of compound A
was solved in 3 ml toluene. The mixture was stirred for
1 hr at room temperature. Then pure siliceous support
SBA‐15 (1.0 g) was added to the above solution. The
resulting mixture was stirred and refluxed for 24 hr. After
which the precipitates were filtered and washed twice
with dry toluene. Homogeneous and unreacted starting
materials were removed by Soxhlet extraction in a tolu-
ene solvent. The solid was dried under reduced pressure
2.2 | Preparation of 3‐(3‐(trimethoxysilyl)p
ropyl)imidazolidine‐2,4‐dione (compound a)
(3‐chloropropyl)triemetoxysilane (7.2 mmol) was added
dropwise on a stirred mixture of hydantoin (6 mmol)
and triethylamine (18 mmol) in CH2Cl2 (20 ml) at 0 °C
over a period of 1 h. The reaction mixture was stirred
and warmed to room temperature. After 3 hr, the
resulting mixture was quenched with NH4Cl solution
(70 ml) and extracted with CH2Cl2 (70 ml × 2). The com-
bined organic extract was washed with 2 N HCl (35 ml × 2)
and brine (50 ml). It was dried over anhydrous sodium
sulfate and concentrated under reduced pressure to afford
overnight to afford Hyd‐SBA‐15. Then 0.5
g of
H3PMo12O40 was solved in the methanol (5 ml) and the
solution was added dropwise on the pure Hyd‐SBA‐15.
The reaction mixture was refluxed for 12 hr. The
resulting mixture was filtered and Soxhlet extraction
was done with methanol for 12 hr. The precipitates were
dried at 100 °C under vacuum to afford pure
H3PMo12O40/Hyd‐SBA‐15. A schematic model of the
preparation of H3PMo12O40/Hyd‐SBA‐15 is presented in
scheme 2.
1
compound A. Figure 1 and 5 represents HNMR and FT‐
IR spectrum of compound A, respectively.
2.3 | Catalyst preparation
The synthesis of SBA‐15 material was carried out based
on the instructions provided by the reported procedure.3a
FIGURE 1 1H NMR of compound A

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SAFAEI‐GHOMI AND BAKHTIARI
SCHEME 2 Different steps for
synthesis of H3PMo12O40/Hyd‐SBA‐15.
148.72, 159.04, 179.73; HRMS m/z: calcd for C27H15N5O2
[M + H]+:441.1274; found: 441.1258; Anal. Calcd for
C27H15N5O2: C, 73.46; H, 3.42; N, 15.86. Found: C,
73.01; H, 4.48; N, 16.08.
2.4 | General procedure for the
preparation of 3‐amino‐2′‐oxospiro[benzo
[c]pyrano[3,2‐a]phenazine‐1,3′‐indoline]‐2‐
carbonitrile/carboxylate derivatives
The sequence of addition in this reaction was crucial to
avoid the formation of by‐products. The correct sequence
was found by the reaction of 2‐hydroxy‐1,4‐
naphthoquinone (1) and 1,2‐diamine (2a,b) to form the
corresponding quinoxalinone in the presence of 0.03 g
of H3PMo12O40/Hyd‐SBA‐15 in 10 ml EtOH. The mixture
of the reaction was stirred for 5 min at 50 °C. Then,
malone derivatives (3a,b) (1 mmol) and isatin (4a‐f)
(1 mmol) were added to the mixture. The reaction mix-
ture was stirred at 50 °C and monitored by TLC
(EtOAc/n‐hexane 3:7). After completion of the reaction,
the mixture was cooled to room temperature, filtered,
and washed with H2O (10 ml) and EtOH (5 ml) to obtain
the pure product.
2.4.2 | 3‐Amino‐5′‐bromo‐2′‐oxospiro
[benzo[c]pyrano[3,2‐a]phenazine‐1,3′‐
indoline]‐2‐carbonitrile(5b)
IR (KBr, cm−1): 3471, 3255, 3184, 2932, 2858, 2199, 1735,
1
1728, 1669, 1381, 695; H NMR (400 MHz, DMSO‐d6): δ
6.99 (d, 1H, J = 8, ArH), 7.27 (s, 1H, ArH), 7.36 (d, 1H,
J = 8, ArH), 7.61 (s, 2H, NH2), 7.683 (dd, 1H, J = 3.2
and J = 6.2, ArH), 7.86 (dd, 2H, J = 3.3 and J = 6.2,
ArH), 7.983 (t, 1H, J = 7.2, ArH), 8.034 (t, 1H, J = 7.3,
ArH), 8.26 (d, 1H, J = 8.1, ArH), 8.48 (d, 1H,J = 7.8,
ArH), 9.20 (d, 1H, J = 7.8, ArH), 10.979 (s, 1H, NH); 13C
NMR (100 MHz, DMSO‐d6): 49.31, 56.24, 109.99, 111.74,
113.75, 118.07, 123.00, 125.30, 126.17, 127.58, 128.77,
129.93, 130.81, 131.68, 132.24, 132.84, 133.69, 133.98.
138. 31, 139.76, 140.33, 140.93, 141.79, 142.94, 148.44,
149.59, 179.08; HRMS m/z: calcd for C27H14BrN5O2
[M + H]+:519.0336; found: 519.0331; Anal. Calcd for
C27H14BrN5O2: C, 62.43; H, 2.81; N, 13.26%. Found: C,
64.9; H, 2.8; N, 13.01%.
2.4.1 | 3‐Amino‐2′‐oxospiro[benzo[c]
pyrano[3,2‐a]phenazine‐1,3′‐indoline]‐2‐
carbonitrile (5a)
IR (KBr, cm−1): 3460, 3234, 2179, 1721, 1663, 1601, 1382,
1
1301, 1059, 763, 698; H NMR (400 MHz, DMSO‐d6): δ
6.715 (t, 1H, J = 7.6 Hz, ArH), 6.967 (d, 1H, J = 7.2 Hz,
ArH), 7.015 (d, 1H, J = 7.6 Hz, ArH), 7.139 (t, 1H,
J = 7.2 Hz, ArH), 7.536 (s, 2H, NH2), 7.694–7.706 (m,
1H, ArH), 7.87–7.89 (m, 2H, ArH), 7.975(t, 1H, J = 7.2,
ArH), 8.03 (t, 1H, J = 7.3, ArH), 8.490 (d, J = 8 Hz,
ArH), 8.50 (d, 1H, J = 7.6 Hz, ArH), 9.25 (d, 1H,
J = 8.0 Hz, ArH), 10.834 (s, 1H, NH); 13C NMR
(100 MHz, DMSO‐d6): 56.67, 57.76, 109.72, 111.05,
2.4.3 | 3‐Amino‐5′‐fluoro‐2′‐oxospiro
[benzo[c]pyrano[3,2‐a]phenazine‐1,3′‐
indoline]‐2‐carbonitrile (5c)
IR (KBr, cm−1): 3460, 3243, 3170, 2910, 2814, 2124, 1741,
1
1728, 1658, 1378, 749; H NMR (400 MHz, DMSO‐d6): δ
6.99 (d, 2H, J = 7.9, ArH), 7.622 (s, 2H, NH2),7.668(m,
1H, ArH), 7.879 (m, 3H, ArH), 7.973 (t, 1H, J = 7.0,
ArH), 8.02 (t, 1H, J = 7, ArH), 8.24 (d, 1H, J = 8.1,
ArH), 8.48 (d, 1H, J = 7.8, ArH), 9.22 (d, 1H, J = 7.2,
ArH), 10.879 (s, 1H, NH); 13C NMR (100 MHz, DMSO‐
118.20,
118.72,
119.80,
122.73,
122,97,124.04,
125.63,126.70, 128.54, 129.88, 130.64, 131.75, 132.25,
133.08, 136.51, 139.41, 140.49, 141.02, 142.36, 143.13,

SAFAEI‐GHOMI AND BAKHTIARI
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d6): 50.08, 57.03, 109.64, 111.89, 113.88, 118.35, 123.09,
125.30, 126.08, 127.01, 128.52, 130.52, 130.73, 131.48,
132.00, 132.99, 133.73, 138.20, 139.94, 140.69, 140.93,
141.93, 142.92, 148.15, 160.28, 179.17; HRMS m/z: calcd
for C27H14FN5O2 [M + H]+:459.1180; found: 459.1168;
Anal. Calcd for C27H14FN5O2: C, 70.58; H, 3.07; N,
15.24%. Found: C, 70.94; H, 3.2; N, 15.45%.
2.4.6 | 3‐Amino‐5′‐methyl‐2′‐oxospiro
[benzo[c]pyrano[3,2‐a]phenazine‐1,3′‐
indoline]‐2‐carbonitrile (5f)
IR (KBr, cm−1): 3489, 3348, 3298, 3151, 2150, 1715, 1660,
1
1580, 1342, 1298, 1049, 657; H NMR (400 MHz, DMSO‐
d6): δ 2.02 (s, 3H, CH3), 6.99(s, 1H, ArH), 7.01 (d, 1H,
J = 8, ArH), 7.336 (d, 1H, J = 8, ArH), 7.616 (s, 2H,
NH2), 7.683 (m, 1H, ArH), 7.911 (m, 3H, ArH), 7.983 (t,
1H, J = 7.0, ArH), 8.03, (t, 1H, J = 7, ArH), 8.488 (d,
1H, J = 7.8, ArH), 9.22 (d, 1H, J = 7.8, ArH), 10.97 (s,
1H, NH); 13C NMR (100 MHz, DMSO‐d6): 21.81, 50.04,
58.46, 109.72, 111.38, 118,69, 123.31, 124.92, 125.75,
126.55, 128.75, 129.83, 130.63, 131.18, 131.46, 131.71,
131.98, 136.59, 140.14, 140.68, 141.21, 141.50, 141.2,
141.78, 148.28, 160.20, 179.49; HRMS m/z: calcd for
C28H17N5O2 [M + H]+:455.1437; found: 455.1432; Anal.
Calcd for C28H17N5O2: C, 73.91; H, 3.62; N, 15.17%.
Found: C, 70.81; H, 3.49; N, 15.26%.
2.4.4 | 3‐Amino‐5′‐chloro‐2′‐oxospiro
[benzo[c]pyrano[3,2‐a]phenazine‐1,3′‐
indoline]‐2‐carbonitrile(5d)
IR (KBr, cm−1): 3359, 3179, 3048, 2943, 2881, 2179, 1718,
1
1690, 1651, 1469, 1383, 1059, 763; H NMR (400 MHz,
DMSO‐d6): δ 7.036 (d, 1H, J = 8.0 Hz, ArH), 7.163 (s,
1H, ArH), 7.197 (dd, 1H, J = 8.0 Hz, J = 2.0 Hz, ArH),
7.62 (s, 2H, NH2), 7.68 (m, 1H, ArH), 7. 89 (m, 2H,
ArH), 7.988 (t, 1H, J = 7.0, ArH), 8.039 (t, 1H, J = 7,
ArH), 8.014 (d, 1H, J = 8, ArH), 8.49 (d, 1H, J = 8.0 Hz,
ArH), 9.25 (d, 1H, J = 7.6 Hz, ArH), 10.98 (s, 1H, NH);
13C NMR (100 MHz, DMSO‐d6): 47.15, 58.31, 109.02,
111.30, 118.17, 123.14, 124.28, 125.81, 126.19, 126.58,
128.49, 128.90, 129.65, 130.02, 130.40, 130.79, 131.92,
132.29, 138.03, 139.57, 140.34, 140.71, 141.47, 142.23,
148.36, 159.81, 161.31; HRMS m/z: calcd for
C27H14ClN5O2 [M + H]+:475.0899; found: 475.0867; Anal.
Calcd for C27H14ClN5O2: C, 68.21; H, 3.17; N, 14.72.
Found: C, 68.11; H, 2.89; N, 14.68.
2.4.7 | 3‐Amino‐12‐methyl‐2′‐oxospiro
[benzo[c]pyrano[3,2‐a]phenazine‐1,3′‐
indoline]‐2‐carbonitrile(5 g)
Isomers ratio: 62:38; IR (KBr, cm−1): 3469, 3381, 3239,
2929, 2869, 2178, 1719, 1670, 1371, 1059, 773, 711; H
1
NMR (400 MHz, DMSO‐d6): δ 2.576 (s, 1.34H, CH3),
2.605 (s, 2.38H, CH3), 6.71–6.75 (t, 1H, ArH), 6.96 (d,
1H, J = 7.8 Hz, ArH), 7.009 (dd, 1H, J = 8 Hz,
J = 8.0 Hz, ArH), 7.052 (m, 1H, ArH), 7.524 (s, 2H,
NH2), 7.582 (d, 0.75H, J = 8.2 Hz, ArH), 7.718 (dd,
1.44H, ArH), 7.98 (dd, 0.74H, J = 7.2 Hz, J = unknown
ArH), 8.01 (m, 1.56H, ArH), 8.14 (d, 1.07H, J = 8.2 Hz,
ArH), 8.48 (d, 1H, J = 8.0 Hz, ArH), 9.212 (dd, 1H,
ArH), 10.786 (s, 0.20H, NH), 10.80 (s, 0.50H, NH); 13C
NMR (100 MHz, DMSO‐d6): 22.07, 47.39, 109.79, 110.79,
122.07, 122.81, 123.81, 125.09, 125.33, 125.84, 126.84,
127.84, 128.10, 128.84, 129.10, 130.08, 130.83, 131.10,
133.85, 136.11, 139.10, 140.12, 140.85, 141.37, 141.86,
147.89, 160.41; HRMS m/z: calcd for C28H17N5O2
[M + H]+:455.1437; found: 455.1437; Anal. Calcd for
C28H17N5O2: C, 73.34; H, 3.61; N, 15.83%. Found: C,
70.45; H, 3.49; N, 15.52%.
2.4.5 | 3‐Amino‐5’‐Nitro‐2′‐oxospiro[benzo
[c]pyrano[3,2‐a]phenazine‐1,3′‐indoline]‐2‐
carbonitrile (5e)
IR (KBr, cm−1): 3340, 3160, 3033, 2912, 2854, 2162, 1682,
1
1673, 1642, 1423, 1400, 1106, 763; H NMR (400 MHz,
DMSO‐d6):
δ 7.188 (s, 1H, ArH), 7.253 (d, 1H,
J = 8.0 Hz, ArH), 7.652 (m, 1H, ArH), 7.75 (s, 2H, NH2),
7.68 (m, 1H, ArH), 7.882 (m, 2H, ArH), 7.99 (t, 1H,
ArH), 8.048 (t, 1H, ArH), 8.178 (dd, 1H, J = 7.6 Hz,
J = 2.2 Hz, ArH), 8.244 (m, 1H, ArH), 8.502 (d, 1H,
J = 8.0 Hz, ArH), 9.232 (d, 1H, J = 7.8 Hz, ArH), 11.615
(s, 1H, NH); 13C NMR (100 MHz, DMSO‐d6): δ 49.92,
56.35, 109.28, 109.89, 118.08, 120.05, 122.97, 125.108,
125.83, 126.37, 128.061, 129.402, 129.571, 130.084,
130.645, 130.769, 130.947, 131.163, 137.151, 139.912,
140.46, 141.36, 142.953, 148.619, 149.961, 160.324; HRMS
m/z: calcd for C27H14N6O4 [M + H]+:486.1143; found:
486.1129; Anal. Calcd for C27H14N6O4: C, 66.66; H, 2.9;
N, 17.27%. Found: C, 67.01; H, 2.99; N, 17.85%.
2.4.8 | 3‐Amino‐5’‐Nitro‐11‐methyl‐2′‐
oxospiro[benzo[c]pyrano[3,2‐a] phenazine‐
1,3′‐indoline]‐2‐carbonitrile (5 h)
Isomers ratio: 60:40; IR (KBr, cm−1): 3452, 3373, 3225,
2932, 2876, 2184, 1725, 1656, 1345, 1020, 750, 711; H
NMR (400 MHz, DMSO‐d6): δ 2.537 (s, 1.38H, CH3),
2.56 (s, 2.72H, CH3), 7.24 (t, 1H, ArH), 7.427 (s, 1H,
1

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SAFAEI‐GHOMI AND BAKHTIARI
ArH), 7.544 (d, 1H, J = 8.1 Hz, ArH), 7.724 (s, 2H, NH2),
7.864–7.887 (m, 1H, ArH), 8.03–8.066 (m, 1.8H, ArH),
7.58 (dd, 1H, J = 8.8 Hz, ArH), 7.72 (d, 1.44H,
J = 8.8 Hz, ArH), 8.134 (dd, 1H, J = 8 Hz, J = 4 ArH),
8.172 (m, 0.9, ArH), 8.189 (m, 0.8H, ArH), 8.493(d, 1H,
J = 7.8 Hz, ArH), 9.20 (d, 1H, J = 8.0 Hz, ArH), 11.548
(s, 0.44H, NH), 11.586 (s, 0.94H, NH); 13C NMR
(100 MHz, DMSO‐d6): δ 21.89, 22.02, 49.87, 56.26,
109.32, 109.84, 109.90, 118.01, 119.97, 122.97, 123.00,
125.01, 125.1, 125.68, 125.84, 126.32, 126.37, 126.41,
127.61, 127.78, 129.04, 129.2, 130.12, 130.18, 130.85,
130.93, 133.351, 133.811, 137.164, 139.21, 139.23, 139.78,
139.81, 140.053, 140.422, 140.632, 141.26, 142.906,
148.12, 148.459, 149.92, 160.29, 180.07, 180.12; HRMS
m/z: calcd for C28H16N6O4 [M + H]+:500.1206; found:
500.1202; Anal. Calcd for C28H16N6O4: C, 67.19; H, 3.22;
N, 16.79. Found: C, 67.25; H, 3.44; N, 16.61.
2H, NH2), 7.892 (m, 2H, ArH), 7.96 (t, 1H, J = 7.3,
ArH), 8.03 (t, 1H, J = 7.1, ArH),, 8.22, (t, 1H, J = 4.3,
ArH), 8.60 (d, 1H, J = 7.9, ArH), 9.22 (d, 1H, J = 7.7,
ArH), 10.649 (s, 1H, NH); 13C NMR (100 MHz, DMSO‐
d6): 13.52, 49.25, 59.29, 76.43, 108.44, 113.28, 121.08,
123,34, 125.93, 127.79, 128.16, 129.99, 130.77, 131.12,
131.54, 137.45, 139.33, 139.71, 141.18, 141.58, 145.65,
146.04, 160.92, 168.73, 181.02; HRMS m/z: calcd for
C29H20N4O4 [M + H]+:488.1506; found: 488.1502; Anal.
Calcd for C29H20N4O4: C, 71.29; H, 4.23; N, 11.32. Found:
C, 71.38; H, 4.15; N, 11.41.
2.4.11 | Ethyl‐3‐amino‐5′‐bromo‐2′‐
oxospiro[benzo[c]pyrano[3,2‐a]phenazine‐
1,3′‐indoline]‐2‐carboxylate(5 k)
IR (KBr, cm−1): 3464, 3369, 3249, 3114, 2977, 2943, 1707,
1648, 1614, 1570, 1476, 1376, 1126, 1098, 764, 544 cm−1
;
1H NMR (400 MHz, DMSO‐d6): δ 0.95 (t, 3H, CH3,
J = 7.2 Hz), 3.85–3.9 (m, 2H, OCH2), 6.99 (d, 1H,
J = 8.4 Hz, ArH), 7.277 (s, 1H, ArH), 7.336 (d, 1H,
J = 8.0 Hz, ArH), 7.193(s, 2H, NH2), 7.53 (d, 1H,
J = 8.0 Hz, ArH), 7.86–8.06 8.24 (m, 1H, ArH), 8.60 (d,
1H, J = 8.0 Hz, ArH), 9.23 (d, 1H, J = 7.6 Hz, ArH),
9.30 (s, 1H, ArH), 10.79 (s, 1H, NH); 13C NMR
(100 MHz, DMSO‐d6): 16.06, 50.23, 54.33, 76.76, 110.10,
112.28, 112.89, 118.77, 123.78, 125.64, 126.30, 128.78,
129.70, 130.33, 130.63, 131.24, 131.55, 131.89, 132.81,
139.95, 140.29, 140.59, 141.21, 141.53, 145.59, 147.77,
160.54, 168.29, 181.37; HRMS m/z: calcd for
C29H19BrN4O4 [M + H]+:566.0656; found: 566.0642; Anal.
Calcd for C29H19BrN4O4: C, 61.11; H, 3.13; N, 10.07.
Found: C, 61.24; H, 3.26; N, 10.13.
2.4.9 | Ethyl‐3‐amino‐11‐methyl‐2′‐
oxospiro[benzo[c]pyrano[3,2‐a]phenazine‐
1,3′‐indoline]‐2‐carboxylate(5i)
Isomers ratio: 60:40; IR (KBr, cm−1): 3465, 3380, 3242,
3121, 2976, 2911, 1704, 1650, 1610, 1372, 1348, 1105, 758;
1H NMR (400 MHz, DMSO‐d6): δ 0.92 (t, 3H, CH3,
J = 7.2 Hz), 3.80–3.88 (m, 2H, OCH2), 6.58–6.627 (m, 1H,
ArH), 6.86 (dd, 1H, J = 7.8 Hz, J = 2 Hz, ArH), 6.93 (d,
1H, J = 7.6 Hz, ArH), 7.05 (dd, 1H, J = 7.8 Hz, J = 2 Hz,
ArH), 7.17,7.174 (m, 2H, NH2, ArH), 7.66 (dd, 1H,
J = 7.8 Hz, J = 2 Hz, ArH), 7.89 (m, 2H, ArH), 8.036 (d,
1H, J = 8 Hz, ArH), 8.151 (d, 1H, J = 8.1 Hz, ArH), 9.217
(d, 1H, J = 8.0 Hz, ArH), 11.417(s, 0.38H, NH); 11.458 (s,
0.9H, NH); 13C NMR (100 MHz, DMSO‐d6): 13.22, 21.84,
22.14, 44.47, 49.60, 59.55, 76.75, 108.40, 108.73, 113.20,
120.77, 123.19, 123.48, 124.70, 125.00, 125.61, 125.91,
126.80, 127.12, 127.71, 128.01, 128.61, 129.19, 129.54,
129.81, 130.41, 130.72, 131.03, 131.34, 133.12, 133.44,
133.75, 137.65, 137.97, 138.57, 139.16, 140,69, 141.89,
142.51, 145.50, 146.40, 159.52, 160.64, 181.48, 182.64.
HRMS m/z: calcd for C30H22N4O4 [M + H]+:500.4606;
found: 500.4602; Anal. Calcd for C30H22N4O4: C, 71.89;
H, 4.82; N, 11.01. Found: C, 71.42; H, 4.52; N, 11.13.
3 | RESULTS AND DISCUSSION
3.1 | Structural analysis of H3PMo12O40/
Hyd‐SBA‐15
Small angle X‐ray diffraction patterns of SBA‐15 and
H3PMo12O40/Hyd‐SBA‐15 are shown in Figure 2. The pat-
terns for both of them show an intense peak at 2θ about
1° which locates to diffraction peak (1 0 0) and references
to meso‐structure with a remarkable degree of long‐range
ordering. Two secondary weak peaks corresponding to (1
1 0) and (2 0 0) reflections are appeared due to 2D‐hexag-
onal planes of the mesoporous.[23] The XRD pattern of
H3PMo12O40/Hyd‐SBA‐15 indicates a striking effect by
loading HPA. The width and intensity of diffraction peak
(1 0 0) become broader and weaker respectively, also it
shifts to lower 2θ values. Partly block of the pores by
HPA decreased the long‐range order of SBA‐15. It can
2.4.10 | Ethyl‐3‐amino‐2′‐oxospiro[benzo
[c]pyrano[3,2‐a]phenazine‐1,3′‐indoline]‐2‐
carboxylate (5j)
IR (KBr, cm−1): 3485, 3383, 3265, 2977, 2911, 1716, 1687,
1
1627, 1378, 1309, 1111, 758; H NMR (400 MHz, DMSO‐
d6): δ 0.94 (t, J = 7.0, CH3), 3.86 (q, 2H, CH2), 6.588 (t,
1H, J = 7.8, ArH), 6.853 (d, 1H, J = 7.8, ArH), 6.916 (d,
1H, J = 7.6, ArH), 7.02 (t, 1H, J = 7.5, ArH), 7.193 (s,

SAFAEI‐GHOMI AND BAKHTIARI
7 of 14
by N2 adsorption analysis and BJH pore size distributions
(Figure 3A‐C). All of them show type IV isotherm with an
H1 hysteresis loop which are in agreement with typical
meso‐structure. The steep adsorption step is indicated in
the relative pressure 0.4 to 0.8 P/Po which corresponds
to the capillary condensation of nitrogen in uniform
pores. Based on these results, the ordered mesoporous
structure of SBA‐15 with narrow pore sizes distributions
well remains and it is also confirmed by the BJH analysis.
The BET surface area (758 m2/g), average pore diameter
(9.4 nm) and total pore volume (0.7378 cm3/g) of SBA‐
15 were detected (Table 1). The textural parameters of
the Hyd‐SBA‐15 and H3PMo12O40/Hyd‐SBA‐15 are
changed by the cooperation of organic linker and HPA.
It should be noted that functionalization of SBA‐15 not
only diminished the sharpness but also shifted the inflec-
tions to lower P/Po ranges, due to pore blocking effect.3b
The sharpness of the pore‐filling step is related to the uni-
formity of the mesoporous size distribution. The reduc-
tion of sharpness of the functionalized SBA‐15 shows
less uniformity of the mesoporous size distribution. The
data of the surface area, average pore width, and total
pore volume are presented in Table 1. The results
FIGURE 2 The XRD pattern of SBA‐15 and H3PMo12O40/Hyd‐
SBA‐15
be inferred from the above results that the framework of
mesoporous material is preserved despite functionalizing.
Also, HPA is well dispersed on the hyd‐SBA‐15 support
(Supporting information).
The surface and structure properties of pure SBA‐15,
Hyd‐SBA‐15 and H3PMo12O40/Hyd‐SBA‐15 are evaluated
FIGURE 3 Nitrogen adsorption–desorption isotherms and volume plots of A) SBA‐15, B) Hyd‐SBA‐15 and C) H3PMo12O40/Hyd‐SBA‐15

8 of 14
SAFAEI‐GHOMI AND BAKHTIARI
TABLE 1 Structural and Textural Parameters of SBA‐15, Hyd‐
SBA‐15, H3PMo12O40/Hyd‐SBA‐15
S BETa
[m2 g−1
Dp
VP
b
c
Sampel
]
[nm]
[cm3 g−1
]
SBA‐15
758.68
182.29
143.53
9.40
8.06
7.05
0.7378
0.3922
0.3156
Hyd‐SBA‐15
H3PMo12O40/Hyd‐SBA‐15
aS BET = surface area.
bDp = average pore width.
cVp = total pore volume.
indicated obviously that HPA is placed mainly inside the
channels of the modified Hyd‐SBA‐15 materials.
The morphology of SBA‐15 and H3PMo12O40/Hyd‐
SBA‐15 are studied by FESEM (Figure 4 A, B). The
FESEM images show that both of them have a structural
integrity
morphology.
The
microstructure
of
H3PMo12O40/Hyd‐SBA‐15 is evaluated by TEM. The
TEM result demonstrates the hexagonal arrangement of
pores channels has been uniformly distributed through-
out the specimen without agglomeration of H3PMo12O40
(Figure 4C). The obtained results are in agreement with
the results of N2 adsorption analysis and XRD.
FT‐IR spectra of Compound A, Hyd‐SBA‐15, and
H3PMo12O40/Hyd‐SBA‐15 are shown in Figure 5 to evalu-
ate the structural characterization. The FT‐IR spectrum
for compound A shows three highlight bonds at 1777,
1708, 3266. The peaks at 1777, 1708 are assigned to car-
bonyl groups of hydantoin and the peak at 3266 is
assigned to NH group. In the spectrum of hyd‐SBA‐15,
the peaks of absorption bands associated with the forma-
tion of a condensed silica network appear around 1077,
801, 455 cm−1. The peak at 1077 cm−1 can be attributed
to the asymmetry stretching vibration peak of Si–O–Si
groups. The immobilization of HPA over Hyd‐SBA‐15
leads to revealing the absorption peak at 839 and
942 cm−1 which are assigned to the asymmetry stretching
FIGURE 5 FT‐IR spectra of compound A, Hyd‐SBA‐15 and
H3PMo12O40/Hyd‐SBA‐15
vibration peak of (Mo_O_Mo), (Mo_O) respectively. The
absorbing peak associated with (P_O) overlaps with asym-
metry stretching vibration peak of Si–O–Si groups.[24]
Based on these results the loading of HPA over hyd‐
SBA‐15 is confirmed. H3PMo12O40 is absolutely dispersed
on the pores of SBA‐15 support and the immobilization is
occurred by strong chemical interaction.
The elemental composition of H3PMo12O40/Hyd‐SBA‐
15 is shown by EDX spectrum (Figure 6). Elemental anal-
ysis results confirm the composition of this sample. The
amount of carbon, nitrogen, oxygen, silicon, phosphorus
and molybdenum in H3PMo12O40/Hyd‐SBA‐15 are deter-
mined as 15.31, 8.75, 47.87, 21.36, 0.57, 6.13 (wt %),
respectively. EDX mapping analysis discovers the uni-
form dispersion of HPA and organic linker over SBA‐15
in H3PMo12O40/Hyd‐SBA‐15.
FIGURE 4 SEM images of A) pure SBA‐15 and B) H3PMo12O40/Hyd‐SBA‐15, and C) TEM image of H3PMo12O40/Hyd‐SBA‐15

SAFAEI‐GHOMI AND BAKHTIARI
9 of 14
strong absorption band around 280–400 nm for
H3PMo12O40/Hyd‐SBA‐15 is assigned to the ligand to
metal charge‐transfer transitions (LMCT), due to the pro-
motion of an electron from the ligand‐centered the
highest occupied molecular orbital (HOMO) to the
molybdenum centered LUMO.[26] Two absorption bands
are selected at 250 and 342 which are assigned to vibra-
tions of terminal Mo = Ot and bridging bonds Mo_Oe
respectively.[24] The band gap energy of the prepared cat-
alyst was decreased because of HPAs doped on the sur-
face of SBA‐15 by coordinating to the hydantoin linker,
which can extend into the visible light region.[27]
3.2 | Comparison of the efficiency of
H3PMo12O40/Hyd‐SBA‐15 with some
reported catalysts
FIGURE 6 EDX spectrum of H3PMo12O40/Hyd‐SBA‐15
Thermal behavior of H3PMo12O40/Hyd‐SBA‐15 is
shown in Figure 7. The TGA profile exhibits two steps
of weight loss. A weak endotherm and concomitant small
weight loss related to the desorption of physisorbed water
is revealed in the temperature range of 200 °C. A second,
larger weight loss occurred with an endothermic peak in
DTA curve is revealed between 300–400 °C. It can be
related to the combustion of hydantoin linker. A second
weak exothermic peak overlapping with a broad endo-
thermic DTA peak is revealed in a wide temperature
range of 600–700 °C. It corresponds mainly to the thermal
decomposition of the HPA. The results of thermal analy-
sis express that the thermal decomposition completes at
a temperature of 823 °C.
The best method for characterization and identifica-
tion of metal ion frameworks is UV–vis DRS analysis.
The spectra of calcined SBA‐15 and H3PMo12O40/Hyd‐
SBA‐15 are measured in the range of 200–800 nm and
presented in Figure 8 to get further information about
the oxidation state and the coordination environment of
molybdenum. An absorbance band at 216 nm is revealed
for siliceous materials as reported elsewhere.[25] The
The reaction between 2‐hydroxynaphthalene‐1,4‐dione
(1) and benzene‐1,2‐diamine (2a) malononitrile (3a)
(1 mmol) and isatin (4a) (1 mmol) was selected as a
model reaction. The efficiency of H3PMo12O40/Hyd‐SBA‐
15 was compared with the reported catalysts in terms of
the amount of the catalyst, the yield of product, reaction
time, and temperature (Table 2, entries 1–2, 4). New het-
erogeneous nano‐hybrid catalyst, H3PMo12O40/Hyd‐SBA‐
15, showed higher performance than two previously
reported conventional organo‐catalysts. A very low
amount of the catalyst was loaded in this methodology.
However, the reaction was catalyzed by DABCO in a
short time, it was carried out at high temperature and
required toxic and expensive solvents and also high
amount of the catalyst.
3.3 | Optimize the condition of the
reaction
We investigated the effect of solid supporting materials on
the catalytic activity of H3PMo12O40 and the results
showed the time of reaction was increased and the yield
of product was decreased in the absence of solid
supporting materials (Table 2, entries 4, 6). In the presence
of 0.06 g of H3PMo12O40, the desired product was created
after 25 min with %71 yield whereas, the loading of
0.03 g of H3PMo12O40/Hyd‐SBA‐15 yielded excellent prod-
uct yield (98%) after a short reaction time (5 min). We per-
formed a screening of catalyst amount to reduce the
catalyst loading (Entries 4, 7–11). The optimum amount
of catalyst is 0.03 g and no benefit observed by adding the
amount of catalyst. In order to evaluate the effects of tem-
perature on the product yield, the reaction was carried out
in the presence of 0.03 g of H3PMo12O40/Hyd‐SBA‐15 at
various temperatures. The best results were obtained at
FIGURE 7 TGA and DTA curves of H3PMo12O40/Hyd‐SBA‐15

10 of 14
SAFAEI‐GHOMI AND BAKHTIARI
FIGURE 8 UV–vis DRS spectra of the samples Hyd‐SBA‐15 and H3PMo12O40/Hyd‐SBA‐15
TABLE 2 Optimization of reaction conditionsa
Entry
Catalyst
Amount of catalyst
Temperature
Solvent
Time (min)
Yieldb (%)
1
DABCO
10 mol%
30 mol %
0.03 g
0.03 g
0.03 g
0.06 g
0.04 g
0.02 g
0.01 g
0.005 g
0.03 g
0.03 g
0.03 g
0.03 g
0.03 g
0.03 g
reflux
reflux
reflux
50 °C
r.t.
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
CH3CN
CHCl3
DMSO
AcOH
toluene
water
15
98
2
L‐proline
246
20
94
3
H3PMo12O40/Hyd‐SBA‐15
H3PMo12O40/Hyd‐SBA‐15
H3PMo12O40/Hyd‐SBA‐15
H3PMo12O40
70
4
10
98
5
60
≥10
71
6
50 °C
50 °C
50 °C
50 °C
50 °C
50 °C
50 °C
50 °C
50 °C
50 °C
50 °C
25
7
H3PMo12O40/Hyd‐SBA‐15
H3PMo12O40/Hyd‐SBA‐15
H3PMo12O40/Hyd‐SBA‐15
H3PMo12O40/Hyd‐SBA‐15
H3PMo12O40/Hyd‐SBA‐15
H3PMo12O40/Hyd‐SBA‐15
H3PMo12O40/Hyd‐SBA‐15
H3PMo12O40/Hyd‐SBA‐15
H3PMo12O40/Hyd‐SBA‐15
H3PMo12O40/Hyd‐SBA‐15
10
98
8
10
94
9
10
92
10
11
12
13
14
15
16
10
83
60
30
240
240
240
240
30
≥15
≥15
≥15
≥15
76
aReactions conditions: 2‐hydroxy‐1,4‐naphthoquinone (1) (1 mmol), benzene‐1,2‐diamine (2a) (1 mmol), malononitrile (3a) (1 mmol) and isatin (4a) (1 mmol).
bIsolated yield.

SAFAEI‐GHOMI AND BAKHTIARI
11 of 14
1
50 °C (Entry 4). At temperatures, both higher and lower
(Entries 3, 5), the product was synthesized in lower iso-
lated yields than the above temperature condition. The
effect of various solvents such as CH3CN, CHCl3, DMSO,
AcOH, EtOH, water and toluene were evaluated on the
domino MCR. In the presence of polar solvents such as
H2O and EtOH, the product was created in excellent yield,
but the use of water provided a gummy solid which
required a difficult separation step. The best results were
obtained in EtOH in reasonable reaction time and high
yield, thus we kept this as an optimal solvent for the subse-
quent reaction. (Entries 4, 11–16).
The substrate scope of this MCR was studied by opti-
mized reaction conditions. Various malone derivatives
including malononitrile and ethyl cyanoacetate gave the
desired products in good yield. Malononitrile showed
more activity compared to ethyl cyanoacetate. Further-
more, the results of the scope of the reaction showed that
the reaction went well with a broad range of isatin deriv-
atives. In the presence of monosubstituted benzene‐1,2‐
diamine, two isomers were yielded. The signal peak of
NH for major isomer was revealed at δ 10.82 (0.56 H,
NH indole) and for minor isomer was located at δ 10.78
(0.2 H, NH indole). The experimental results in Table 3
indicate that all of the reactions could be catalyzed by
H3PMo12O40/Hyd‐SBA‐15. The structures of these
compounds were characterized by IR, H and 13C NMR
spectroscopy, HRMS and elemental analyses.
3.4 | Plausible mechanism
A mechanism for a plausible catalytic cycle for this domino
MCR over H3PMo12O40/Hyd‐SBA‐15 is outlined in
scheme 3. Phenazine derivatives (A) are formed via initial
condensation of 2‐hydroxynaphthalene‐1,4‐dione 1 and
1,2‐diamine derivatives.17b, 28 Coordination of the carbonyl
groups of 2‐hydroxy‐1,4‐naphthoquinone to a molybde-
num sites at the surface ofH3PMo12O40/Hyd‐SBA‐15 would
increase the activity. In the presence of monosubstituted
benzene‐1,2‐diamine, major and minor isomers of the cor-
responding products are generated. On the other side, the
electrophilicity of malono derivatives increased by coordi-
nation with the H3PMo12O40/Hyd‐SBA‐15. The nitrile was
coordinated to a molybdenum site which followed by a
mechanism involving a proton abstraction, and a stable
hydrido (enolato)‐complex (B) was afforded.[29] Then inter-
mediate B undergoes in situ knoevenagel condensations
with carbonyl group derivatives to produce the cyano
olefins (C).[30] Intermediate C is in close proximity to
intermediate A at the surface of H3PMo12O40/Hyd‐SBA‐15
that resulted in the Michael addition to generating
TABLE 3 Synthesis of 3‐amino‐2′‐oxospiro[benzo[c]pyrano[3,2‐a]phenazine‐1,3′‐ indoline]‐2‐carbonitrile/carboxylate using H3PMo12O40/
Hyd‐SBA‐15 via scheme 1a
Melting point
c
d
Time
(min)
Yield
(%)
e
Entry
Nameb
R1
R2
R3
Observed
Reported
1
5a
5b
5c
5d
5e
5f
H
H
CN
10
10
10
10
10
10
10
12
12
12
12
98
95
95
96
96
94
96
95
91
91
90
314
334
298
345
315
300
311
301
272
270
310
317[16]
338[16]
> 250[21]
343[16]
‐‐
> 250[21]
315[16]
‐‐
2
H
Br
F
CN
3
H
CN
4
H
Cl
CN
5
H
NO2
Me
H
CN
6
H
CN
7
5 g
5 h
5i
Me
Me
Me
H
CN
8
NO2
H
CN
9
CO2Et
CO2Et
CO2Et
274[16]
268[16]
307[16]
10
11
5j
H
5 k
H
Br
aReactions conditions; 2‐hydroxy‐1,4‐naphthoquinone (1 mmol), benzene‐1,2‐diamine (1 mmol), malone derivatives (1 mmol) and isatin derivatives (1 mmol),
H3PMo12O40/Hyd‐SBA‐15 (0.03 g), 50 °C, EtOH.
bAll products were characterized from their spectroscopic data FT‐IR, 1H NMR, 13C NMR, HRMS and C. H. N analysis.
cTotal time of the first and second steps.
dIsolated yield.
eReferences of reported compounds.

12 of 14
SAFAEI‐GHOMI AND BAKHTIARI
SCHEME 3 Proposed reaction mechanism for the formation of 3‐amino‐2′‐oxospiro[benzo[c]pyrano[3,2‐a]phenazine‐1,3′‐ indoline]‐2‐
carbonitrile/carboxylate derivatives catalyzed by H3PMo12O40/Hyd‐SBA‐15 under optimize condition.
intermediate D. The amino groups distributed on the
surface of H3PMO12O40/HYD‐SBA‐15 deprotonated
hydroxy group of intermediate D to yield the nucleophile.
On the other hand, coordination of nitril group of interme-
diate D to a molybdenum site of the H3PMO12O40/HYD‐
SBA‐15 would activate the electrophile which is then
cyclized to afford the products 5a‐l.[16,21,31]The amino
groups distributed on the surface of H3PMo12O40/Hyd‐
SBA‐15 provide a nucleophilic mechanism. Molybdenum
sites at the surface of H3PMo12O40/Hyd‐SBA‐15 increased
the electrophilicity of reactants, which simplifies the
reaction. The high surface area of the SBA‐15 is very
important for the high turn‐over frequency of the reaction.
This method represents high privilege including, simple
procedures, reusability, cost efficiency and high yields.
FIGURE 9 Recyclability study of H3PMo12O40/Hyd‐SBA‐15 for
the reaction of 2‐hydroxy‐1,4‐naphthoquinone (1) (1 mmol),
benzene‐1,2‐diamine (2a) (1 mmol), malononitrile (3a) (1 mmol)
and isatin (4a) (1 mmol), H3PMo12O40/Hyd‐SBA‐15 (0.03 g) under
optimize condition
3.5 | Reusability of H3PMo12O40/Hyd‐SBA‐
15
reused for the new reaction under similar conditions to
The model reaction was also employed to exam the reus-
ability of H3PMo12O40/Hyd‐SBA‐15. The results demon-
strate the catalyst can be used for five cycles under
optimized conditions. Figure 9 shows the catalytic activity
of H3PMo12O40/Hyd‐SBA‐15 did not decrease dramati-
cally. After accomplishment of the reaction, the catalyst
was separated by filtering and it was washed with hot
EtOH (3 × 10 ml) and water (2 × 5 ml), respectively to
remove the residual product. The nano‐catalyst was
achieve the corresponding product with excellent yield.
3.6 | Hot filtration test for H3PMo12O40/
Hyd‐SBA‐15
We did hot filtration test to confirm that the HPA was
attached to functionalized SBA‐15 by covalent binding.
This test was accomplished on the model reaction in the

SAFAEI‐GHOMI AND BAKHTIARI
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presence of H3PMo12O40/Hyd‐SBA‐15 at 50 °C for 3 min.
At the end of this time, 50% of the product was achieved.
Under hot condition, the catalyst was filtered, and the
reaction will continue for another 2 min under the same
condition. No improvement was revealed in product
yield. These experimental results are evidence of hetero-
geneity as well as leach‐resistant characteristics of HPA
from the SBA‐15 support during the course of the
reaction.
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In conclusion, we have suggested a manner to design a
new inorganic–organic nano‐hybrid material by new
organic linker and molybdenum kegging HPA. The effi-
ciency of catalyst has been tested to synthesize 3‐amino‐
2′‐oxospiro[benzo[c]pyrano[3,2‐a]phenazine‐1,3′‐
indoline]‐2‐carbonitrile/carboxylate derivatives that have
many biological properties. This methodology is based
on the principle of green chemistry. We synthesize a wide
range of corresponding products in excellent yields with
low catalyst loading in the absence of any hazardous
organic solvents. The benefits of this catalyst are easy
reusability and high recyclability. Observed results ensure
us that the method has an important contribution to
develop synthesis of 3‐amino‐2′‐oxospiro[benzo[c]pyrano
[3,2‐a]phenazine‐1,3′‐indoline]‐2‐ carbonitrile/carboxyl-
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ACKNOWLEDGMENTS
The authors are grateful to university of Kashan for
supporting this work by Grant NO: 159196/XXII.
ORCID
[15] V. A. Chebanov, E. A. Muravyova, S. M. Desenko, V. I.
Musatov, I. V. Knyazeva, S. V. Shishkina, O. V. Shishkin, C.
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Javad Safaei‐Ghomi
https://orcid.org/0000-0002-9837-
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How to cite this article: Safaei‐Ghomi J,
Bakhtiari A. Preparation and characterization of
new inorganic–organic hybrid catalyst
H3PMo12O40/Hyd‐SBA‐15 and its application in the
domino multi‐component reaction. Appl
Organometal Chem. 2019;e5201. https://doi.org/
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