V-N-C catalysts anchored to mesoporous Al-SBA-15 with tailorable pore sizes for the synthesis of spirooxindole dihydroquinazolinones derivatives

Article abstract of DOI:10.1002/aoc.5150

Heterogeneous nanoscale catalyst was successfully synthesized via anchoring of V-bis(2-aminobenzamide) complex on the Al-SBA-15. This modified mesoporous was identified by several characterization techniques, such as X-ray diffraction, field emission-scanning electron microscopy, Fourier transform-infrared, Brunauer–Emmett–Teller and transmission electron microscopy. V-Bis(2-aminobenzamide)@Al-SBA-15 was found to be an efficient heterogeneous catalyst for the rapid and desirable synthesis of various spirooxindole dihydroquinazolinones derivatives. In addition, the heterogeneous nanocatalyst was chemically stabilized in organic and aqueous solutions as well as can be expeditiously reused for at least seven cycles without a significant loss in catalytic activity.

Full text of DOI:10.1002/aoc.5150

Received: 17 January 2019
DOI: 10.1002/aoc.5150
Revised: 9 July 2019
Accepted: 11 July 2019
F U L L P A P E R
V‐N‐C catalysts anchored to mesoporous Al‐SBA‐15 with
tailorable pore sizes for the synthesis of spirooxindole
dihydroquinazolinones derivatives
Javad Safaei‐Ghomi
| Raheleh Teymuri
Department of Organic Chemistry,
Faculty of Chemistry, University of
Heterogeneous nanoscale catalyst was successfully synthesized via anchoring
of V‐bis(2‐aminobenzamide) complex on the Al‐SBA‐15. This modified meso-
porous was identified by several characterization techniques, such as X‐ray dif-
fraction, field emission‐scanning electron microscopy, Fourier transform‐
infrared, Brunauer–Emmett–Teller and transmission electron microscopy. V‐
Bis(2‐aminobenzamide)@Al‐SBA‐15 was found to be an efficient heteroge-
neous catalyst for the rapid and desirable synthesis of various spirooxindole
dihydroquinazolinones derivatives. In addition, the heterogeneous
nanocatalyst was chemically stabilized in organic and aqueous solutions as
well as can be expeditiously reused for at least seven cycles without a signifi-
cant loss in catalytic activity.
Kashan, KashanP.O. Box 87317‐51167, I.
R., Iran
Correspondence
Javad Safaei‐Ghomi, Department of
Organic Chemistry, Faculty of Chemistry,
University of Kashan, Kashan, P.O. Box
87317‐51167, I. R. Iran.
Email: safaei@kashanu.ac.ir
Funding information
University of Kashan
KEYWORDS
aluminosilicate, dihydroquinazolinones, modified mesoporous, three‐component condensation
1 | INTRODUCTION
high catalytic activity and short reaction times for the
preparation of spirooxindole dihydroquinazolinone is still
In recent years, spirooxindole and their derivatives have
attracted momentous attention due to its unequalled core
structure and great biological activities, such as antican-
cer, anticonvulsant, fungicidal and herbicidal (Figure 1).
favored.
Ordered mesoporous silicas such as those of M41S,
SBA‐n and MSU‐X families discovered in the early 1990s
have been regarded as a promising class of materials for
catalysis and separation.[11,12] These materials serve as
an exceptional choice for such applications. Moreover,
they offer high specific surface areas, large and defined
pore sizes, defined surface acidity, and excellent mechani-
cal and thermal stability.[13–16] In this regard, the substitu-
ents such as aluminum, titanium and zirconium can be
incorporated into the silica framework to obtain materials
for applications such as catalysis and ion exchange.
Among the metal‐substituted mesoporous materials,
aluminum‐incorporated mesoporous materials have great
potential in moderating acid‐catalyzed reactions for large
molecules.[17,18] Moreover, the addition of heteroatoms
such as aluminum (with lower than silicon valence) intro-
duces the negative charges in the silica walls that are
[1–5]
Spirooxindole dihydroquinazolinone is one of this
class of compounds that combines two pharmacophores
into one molecule, so our attention was attracted to find
more potent pharmaceutical active molecules.[6] To date,
many attempts have been devoted to disclose desirable
protocols for the synthesis of spirooxindoles. In this
line, the utilities of many catalysts, including KAl
(SO4)2·12H2O (alum),[7] 1‐methylimidazolium hydrogen
sulfate,[8] ethylenediamine diacetate[9] and nano
CeO2,[10] have been evidenced, whereas some of these
experimental procedures have obvious negative aspects,
such as long reaction times, low yields and harsh reaction
conditions. Accordingly, to avoid these limitations, the
exploration of an efficient, easily available catalyst with
Appl Organometal Chem. 2019;e5150.
wileyonlinelibrary.com/journal/aoc
© 2019 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.5150

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SAFAEI‐GHOMI AND TEYMURI
FIGURE 1 Reported biologically active
spirooxindole‐based molecules
compensated by protons, and generates an acidity in these
systems, improving the surface properties of the final
product.[19] Based on these distinctive attributes, a large
number of research groups have pursued new and creative
approaches toward incorporating multiple functional
groups onto heterogeneous catalysts, which can catalyze
multistep reaction cascades in one system or work in a
cooperative manner to alter the characteristics of a single
reaction.[20–29]
diffractometer (PHILIPS, PW 1510, the Netherlands)
using Cu‐Kα radiation (λ = 0.154056 nm) in the range
2θ = 0–10°. Field emission‐scanning electron microscopy
(FE‐SEM) of nanoparticles was taken on a Model FE‐
SEM. Transmission electron microscopy (TEM) images
were performed on a Philips EM208 TEM with an accel-
erating voltage of 200 kV. The N2 adsorption/desorption
analysis
[Brunauer–Emmett–Teller
(BET)]
was
performed at 120°C using an automated gas adsorption
analyzer (BEL SORP mini II). X‐ray photoelectron spec-
troscopy (XPS) spectra were recorded using a ESCA Sys-
tem 100 spectrometer (VSW Scientific Instruments, UK).
In the current work, the use of material with surface
functional
groups
shows
improved
selectivity
catalyst. Consequently, we synthesize the novel hybrid
V‐bis(2‐aminobenzamide)@Al‐SBA‐15 (V‐N‐C@Al‐SBA‐
15) by chloro‐functionalized with employing 3‐
chloropropyltriethylsilane (CPTES) and anchored bis(2‐
aminobenzamide) on it. The synthesizing process was
pursued by grafting of V (IV) to catch the desired prod-
uct. Also the activity of the catalyst has been scrutinized
by synthesizing spirooxindole dihydroquinazolinone
derivatives (Scheme 1).
2.2 | Preparation of Al‐SBA‐15
Al‐SBA‐15 was synthesized following published proce-
dures.[30,31] In a classic procedure, 2 g of pluronic P123
was dissolved in 75 ml hydrochloric acid solution at
pH 1.5. The solution was stirred at 40°C for 6 hr. A sec-
ond solution was made by adding 3.2 ml of TEOS
(tetraethylorthosilicate) and 5 ml of hydrochloric acid
solution at pH 1.5 to 0.22 g of aluminum isopropoxide.
This suspension was vigorously stirred in a closed flask
for 1.5 hr, during which it became clear. The TEOS solu-
tion was quickly added to the surfactant solution and
stirred for 20 hr at 40°C. The resulting clear suspension
was transferred to a Teflon‐lined stainless‐steel autoclave
and heated to 100°C for 20 hr. The recovered white solid
was filtrated and washed three times with demineralized
water and twice times with ethanol. The sample was
dried overnight at 100°C. The template was removed by
calcination for 10 hr at 550°C with a heating ramp of
1°C/min. The sample is designated as Al‐SBA‐15.
2 | EXPERIMENTAL
2.1 | Materials and apparatus
All organic materials were purchased commercially from
Sigma–Aldrich and Merck, and were used without fur-
ther purification. Melting points of products were deter-
mined by Electro thermal 9200. All infrared (IR) spectra
were recorded by means of Fourier transform (FT)‐IR
Magna spectrometer 550 Nicolet using KBr plates. NMR
spectra were attained in DMSO‐d6 as a solvent, and are
reported as parts per million (ppm) downfield from
TMS as an internal standard. The NMR spectra were
obtained on a Bruker Avance‐400 MHz spectrometer.
The elemental analyses (C, H, N) were obtained from a
Carlo ERBA Model EA 1108 analyzer. The X‐ray diffrac-
tion (XRD) patterns were recorded on an X‐ray
2.3 | Preparation of CPTES@Al‐SBA‐15
Cl‐functionalized Al‐SBA‐15 was prepared according to
the literature.[32] Typically, to a suspension of Al‐SBA‐15
SCHEME 1 V‐N‐C@Al‐SBA‐15
catalyzed synthesis of spiro[indoline‐3,2′‐
quinazoline]‐2,4′(3′H)‐dione derivatives

SAFAEI‐GHOMI AND TEYMURI
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(5 g) in dry toluene (100 ml), (3‐chloropropyl)
trimethoxysilane (5 ml) was added. The mixture was sub-
sequently refluxed at 110°C for 24 hr under inert (N2)
atmosphere. Upon completion, the obtained white partic-
ipate was filtered, washed several times with toluene, and
dried at 90°C overnight.
at 90°C overnight to dry and furnish the functionalized
Al‐SBA‐15.
2.6 | Preparation of V‐bis(2‐
aminobenzamide)@Al‐SBA‐15
One gram of bis(2‐aminobenzamide)@Al‐SBA‐15 was
suspended in 50 ml absolute ethanol, then 0.2 g of VCl3
was added and refluxed for 12 hr to anchor VCl3. Upon
stirring and heating to 65°C, the color of the turbid reac-
tion mixture changed to greenish gray after 12 hr, and
solid V‐bis(2‐aminobenzamide)@Al‐SBA‐15 (V‐N‐C
@Al‐SBA‐15) resulted. It was washed repeatedly with
ethanol and dried under vacuum.
All of the steps for the functionalization of the modi-
fied surface of mesoporous Al‐SBA‐15 with chloro‐N,N′‐
(propane‐1,3‐diyl)bis(2‐aminobenzamide) vanadium (IV)
complex have been shown in Scheme 2.
2.4 | Preparation of bis(2‐
aminobenzamide)
The bis(2‐aminobenzamide) compound was synthesized
by gradually adding 0.575 mg of 1,3–diaminopropane
(6.125 mmol) in 10 ml DI water to 2.0 mg of isatoic anhy-
dride (12.25 mmol) with continuous stirring. Efferves-
cence was observed while warming the reaction mixture
on a water bath, which ceased after 1 hr. Microcrystalline
solid product was created on allowing the mixture to
stand overnight. The desired product was purified and
recrystallized from ethanol/water mixture.[33] The struc-
ture of the ligand was confirmed using 1H‐NMR and
shown in Figure 2.
2.7 | General procedure for the
preparation of spiro[indoline‐3,2′‐
quinazoline]‐2,4′(3′H)‐dione under mild
reaction
2.5 | Preparation of bis(2‐
Regularly, isatoic anhydride (1.0 mmol), aniline
(1.1 mmol), isatin (1 mmol) and V‐bis(2‐
aminobenzamide)@Al‐SBA‐15 as catalyst were mixed in
H2O/EtOH =1:1 (10 ml). Aniline and isatoic anhydride
were refluxed in the presence of catalyst for 10 min,
followed by the addition of isatin for the desired times.
As soon as the reaction was completed (monitored by
thin‐layer chromatography), the modified mesoporous
catalyst was separated by filtration. At that instant,
10 ml ice water was added and the precipitated product
aminobenzamide)@Al‐SBA‐15
The Al‐SBA‐15 with chloropropyl linkers (1 g) were
suspended in absolute ethanol (60 ml) in a 250‐ml
round‐bottom flask by sonication to form a uniform dis-
persion. Then 0.312
g (1 mmol) of the bis(2‐
aminobenzamide) ligand was added to the solution and
the reaction mixture was refluxed for 18 hr. To remove
unreacted substrate, the precipitated solid was washed
repeatedly with toluene. Then it was put at a hot‐air oven
FIGURE 2 1H‐NMR of bis(2‐aminobenzamide) in DMSO

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SAFAEI‐GHOMI AND TEYMURI
SCHEME 2 Grafting route for
mesoporous Al‐SBA‐15 functionalization
was filtered. At the end of the process, the residue was
recrystallized from ethanol to obtain the crude product.
(1H, s), 7.33–7.30 (2H, m), 7.04 (1H, d, J = 6.8 Hz), 6.90
(1H, d, J = 7.6 Hz), 6.76 (1H, t, J = 7.2 Hz), 6.67 (1H, d,
J = 6.8 Hz), 6.60 (1H, d, J = 7.6 Hz). 13C‐NMR
(100 MHz, DMSO‐d6): δ (ppm) 171.2, 166.3, 145.9, 143.7,
133.2, 132.5, 129.4, 126.1, 124.2, 117.1, 116.4, 115.1,
110.2, 99.1. Anal. calcd for C15H10N4O4: C, 58.07; H,
3.24; N, 18.06; found: C, 57.96; H, 3.12; N, 17.92%.
2.8 | Representative spectral data of
spiro[indoline‐3,2′‐quinazoline]‐2,4′(3′H)‐
dione
2.8.1 | 1′H‐Spiro[indoline‐3,2′‐
quinazoline]‐2,4′(3′H)‐dione (4a)
2.8.3 | 3′‐Benzyl‐1′H‐spiro[indoline‐3,2′‐
quinazoline]‐2,4′(3′H)‐dione (4c)
m.p. 262–264°C. FT‐IR (KBr) cm−1: 3374, 3328, 3248,
1744, 1617, 1484, 1360, 1189, 748, 694. 1H‐NMR
(400 MHz, DMSO‐d6): δ (ppm) 10.55 (1H, s), 7.72 (1H,
s), 7.65 (1H, d, J = 7.2 Hz), 7.63 (1H, d, J = 8 Hz), 7.29
(2H, d, J = 7.6 Hz), 7.22–7.15 (2H, m), 7.00–6.98 (1H, d,
J = 7.2 Hz), 6.72 (1H, t, J = 7.6 Hz), 6.66 (1H, d,
J = 7.6 Hz), 6.57 (1H, t, J = 8.4 Hz). 13C‐NMR
(100 MHz, DMSO‐d6): δ (ppm) 172.8, 169.2, 148.2, 142.3,
141.8, 134.2, 131.5, 128.2, 127.9, 125.7, 118.6, 117.2,
115.8, 114.6, 100.3. Anal. calcd for C15H11N3O2: C,
67.92; H, 4.17; N, 15.84; % found: C, 67.62; H, 4.02; N,
15.93%.
m.p. 212–214°C. FT‐IR (KBr) cm−1: 3332, 1729, 1623,
1487, 1350, 1190, 750, 694.1H‐NMR (400 MHz,
DMSO‐d6): δ 10.32 (1H, s), 7.68 (1H, d, J = 7.6 Hz), 7.43
(1H, s), 7.32–7.21 (3H, m), 7.13 (3H, m), 6.88 (3H, m),
6.79 (1H, d, J = 8 Hz), 6.73 (1H, t, J = 7.6 Hz), 6.63
(1H, d, J = 8 Hz), 4.45 (1H, d, J = 15.6 Hz), 4.12 (1H, d,
J = 15.2 Hz). 13C‐NMR (100 MHz, DMSO‐d6): δ (ppm)
171.3, 162.9, 143.7, 142.6, 138.1, 136.3, 131.3, 130.8,
129.3, 129.1, 128.6, 128.1, 122.8, 119.3, 118.6, 118.3,
115.2, 104.2, 46.3. Anal. calcd for C22H17N3O2: C, 74.35;
H, 4.82; N, 11.82; found: C, 74.61; H, 4.80; N, 12.03%.
2.8.2 | 5‐Chloro‐1′H‐spiro[indoline‐3,2′‐
quinazoline]‐2,4′(3′H)‐dione (4b)
2.8.4 | 3′‐Benzyl‐5‐nitro‐1′H‐
spiro[indoline‐3,2′‐quinazoline]‐2,4′(3′H)‐
dione (4d)
m.p. 253–255°C. FT‐IR (KBr) cm−1: 3435, 3278, 1738,
1
1639, 1613, 1511, 1480, 1359, 1190, 813, 753. H‐NMR
m.p. 289–291°C. FT‐IR (KBr) cm−1: 3334.13, 1727.85,
1624.61, 1488.14, 1351.01, 1191.32, 752.14, 694.56. 1H‐
(400 MHz, DMSO‐d6): δ 10.54 (1H, s), 7.75 (1H, s), 7.65

SAFAEI‐GHOMI AND TEYMURI
5 of 13
NMR (400 MHz, DMSO‐d6): δ 10.53 (1H, s), 7.71 (1H, d,
J = 7.6 Hz), 7.48 (2H, m), 7.27 (1H, m), 7.16 (4H, m),
6.87 (2H, m), 6.75 (2H, m), 6.62 (1H, d, J = 7.6 Hz),
4.67 (1H, d, J = 15.2 Hz), 3.94 (1H, d, J = 15.6 Hz). 13C‐
NMR (100 MHz, DMSO‐d6): δ (ppm) 171.3, 163.1, 148.1,
147.8, 144.9, 137.4, 131.4, 129.7, 128.4, 127.3, 127.1,
126.5, 123.2, 118.0, 116.5, 114.1, 110.2, 105.2, 46.1. Anal.
calcd for C22H16N4O4: C, 65.99; H, 4.02; N, 13.99; found:
C, 66.10; H, 3.82; N, 13.86%.
J = 7.2 Hz), 6.69 (1H, d, J = 7.6 Hz), 6.69 (1H, d,
J = 6.8 Hz). 13C‐NMR (100 MHz, DMSO‐d6): δ (ppm)
172.6, 163.1, 146.4, 144.8, 142.1, 137.1, 131.7, 131.1,
128.7, 126.8, 126.3, 124.7, 118.2, 115.6, 114.1, 110.7,
106.2. Anal. calcd for C21H14N3O2Br: C, 61.12; H, 3.33;
N, 9.72; found: C, 61.10; H, 3.37; N, 9.66%.
2.8.8 | 5‐Chloro‐3′‐phenyl‐1′H‐
spiro[indoline‐3,2′‐quinazoline]‐2,4′(3′H)‐
dione (4h)
2.8.5 | 3′‐Benzyl‐5‐bromo‐1′H‐
spiro[indoline‐3,2′‐quinazoline]‐2,4′(3′H)‐
dione (4e)
m.p. 194–195°C. FT‐IR (KBr) cm−1: 3338, 3240, 2922,
1749, 1615, 1521, 1483, 1278, 1185, 1089, 752, 695. H‐
1
NMR (400 MHz, DMSO‐d6): δ 11.14 (1H, s), 8.39 (1H,
s), 8.10 (1H, d, J = 8.2 Hz), 7.76 (1H, s), 7.73 (1H, d,
J = 7.8 Hz), 7.39 (1H, t, J = 6.8 Hz), 7.21–7.13 (4H, m),
7.10 (1H, d, J = 6.8 Hz), 6.86–6.79 (2H, m), 6.70 (1H, d,
J = 8.2 Hz). 13C‐NMR (100 MHz, DMSO‐d6): δ (ppm)
174.3, 163.2, 145.5, 143.1, 136.9, 132.5, 131.4, 129.1,
128.2, 127.1, 126.4, 125.5, 123.1, 119.0, 115.5, 115.1,
111.2, 76.2, 46.1. Anal. calcd for C21H14N3O2Cl: C, 68.13;
H, 3.63; N, 10.83; found: C, 68.05; H, 3.49; N, 10.67%.
m.p. 301–303°C. FT‐IR (KBr) cm−1: 3264, 2924, 1728,
1615, 1482, 1382, 1184, 751, 697, 532. 1H‐NMR
(400 MHz, DMSO‐d6): δ 10.55 (1H, s), 7.68 (1H, d,
J = 7.6 Hz), 7.44 (2H, m), 7.26 (2H, m), 7.20 (3H, m),
6.83 (2H, m), 6.71 (2H, t, J = 6.8 Hz), 6.59 (1H, d,
J = 7.6 Hz), 4.62 (1H, d, J = 15.0 Hz), 4.11 (1H, d,
J = 15.2 Hz). 13C‐NMR (100 MHz, DMSO‐d6): δ (ppm)
171.3, 163.1, 148.1, 147.8, 144.9, 137.4, 131.4, 129.7,
128.4, 127.3, 127.1, 126.5, 123.2, 118.0, 116.5, 114.1,
110.2, 105.2, 46.1. Anal. calcd for C22H16N3O2Br: C,
60.70; H, 3.70; N, 9.65; found: C, 6.81; H, 3.62; N, 9.44%.
2.8.9 | 5‐Nitro‐3′‐phenyl‐1′H‐
spiro[indoline‐3,2′‐quinazoline]‐2,4′(3′H)‐
dione (4i)
2.8.6 | 3′‐Phenyl‐1′H‐spiro[indoline‐3,2′‐
quinazoline]‐2,4′(3′H)‐dione (4f)
m.p. 276–278°C. FT‐IR (KBr) cm−1: 3337, 3243, 2925,
1752, 1616, 1522, 1486, 1275, 1188, 1087, 748, 696. H‐
1
m.p. 351–353°C. FT‐IR (KBr) cm−1: 3442, 3267, 1727,
1642, 1617, 1488, 1359, 1193, 749, 694.1H‐NMR
(400 MHz, DMSO‐d6): δ 10.42 (1H, s), 7.65 (1H, d,
J = 8), 7.63 (s, 1H), 7.54 (1H, d, J = 7.2 Hz,), 7.31–7.29
(1H, m), 7.20–7.15 (3H, m), 6.99 (2H, t), 7.03–6.97 (m,
2H), 6.93 (1H, t, J = 7.6 Hz), 6.73–6.68 (m, 2H), 6.64 (d,
J = 7.6 Hz, 1H). 13C‐NMR (100 MHz, DMSO‐d6): δ
(ppm) 175.67, 163.56, 146.10, 141.65, 138.08, 133.64,
130.79, 128.60, 127.61, 127.59, 127.40, 127.29, 126.47,
122.08, 117.65, 114.57, 114.08, 110.07, 76.35. Anal. calcd
for C21H15N3O2: C, 73.89; H, 4.42; N, 12.31; found: C,
73.95; H, 4.21; N, 12.57%.
NMR (400 MHz, DMSO‐d6): δ 11.16 (1H, s), 8.40 (1H,
s), 8.11 (1H, d, J = 8.4 Hz), 7.77 (1H, s), 7.70 (1H, d,
J = 7.6 Hz), 7.35 (1H, t, J = 6.8 Hz), 7.25–7.17 (4H, m),
7.03 (1H, d, J = 6.8 Hz), 6.87–6.80 (2H, m), 6.71 (1H, d,
J = 8 Hz). 13C‐NMR (100 MHz, DMSO‐d6): δ (ppm)
170.3, 162.2, 147.8, 145.6, 143.9, 138.4, 132.5, 131.3,
129.0, 127.6, 127.1, 124.3, 119.4, 115.4, 113.6, 110.2,
107.8. Anal. calcd for C21H14N4O4: C, 68.75; H, 3.67; N,
10.93; found: C, 68.68; H, 3.94; N, 10.71%.
2.8.10 | 3′‐(4‐chlorophenyl)‐1′H‐
Spiro[indoline‐3,2′‐quinazoline]‐2,4′(3′H)‐
dione (4j)
2.8.7 | 5‐Bromo‐3′‐phenyl‐1′H‐
spiro[indoline‐3,2′‐quinazoline]‐2,4′(3′H)‐
dione (4g)
m.p. 265–267°C. FT‐IR (KBr) cm−1: 3256, 1726, 1644,
1615, 1489, 1357, 1149, 750. 1H‐NMR (400 MHz,
DMSO‐d6): δ 10.36 (s, 1H), 7.69 (s, 1H), 7.60(d, 1H,
J = 7.4 Hz), 7.57 (d, 1H, J = 7.4 Hz), 7.30–7.26 (m, 3H),
7.18 (t, 1H, J = 7. Hz), 7.03–6.93 (m, 3H), 6.84–6.79 (m,
3H). 13C‐NMR (100 MHz, DMSO‐d6): δ (ppm) 174.3,
163.2, 145.5, 143.1, 136.9, 132.5, 131.4, 129.1, 128.2,
127.1, 126.4, 125.5, 123.1, 119.0, 115.5, 115.1, 111.2, 76.2,
m.p. 276–277°C. FT‐IR (KBr) cm−1: 3401, 3236, 2893,
1735, 1612, 1522, 1485, 1277, 1180, 751.1H‐NMR
(400 MHz, DMSO‐d6): δ 10.57 (1H, s), 7.75 (1H, s), 7.68
(1H, d, J = 6.8 Hz), 7.65 (1H, s), 7.33–7.23 (4H, m), 7.19
(1H, d, J = 6.2 Hz), 7.02 (2H, d, J = 5.6 Hz), 6.76 (1H, t,

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SAFAEI‐GHOMI AND TEYMURI
46.1. Anal. calcd for C21H14N3O2Cl: C, 68.13; H, 3.63; N,
10.83; found: C, 68.25; H, 3.41; N, 10.77%.
2.8.14 | 5‐Nitro‐3′‐(p‐tolyl)‐1′H‐
spiro[indoline‐3,2′‐quinazoline]‐2,4′(3′H)‐
dione (4n)
m.p. 171–173°C. FT‐IR (KBr) cm−1: 3440, 1750, 1612,
1516, 1483, 1338, 1252, 1188, 1085. 752. 1H‐NMR
(400 MHz, DMSO‐d6): δ 11.13 (1H, s), 8.40 (1H, s), 8.12
(1H, dd, J = 6.8, 1.6 Hz), 7.74 (1H, s), 7.69 (1H, d,
J = 7.6), 6.34 (1H, t), 7.03 (2H, d, J = 8.4 Hz), 6.90 (2H,
d, J = 8.4 Hz), 6.86 (1H, d, J = 8.4 Hz), 6.80 (1H, t,
J = 7.6 Hz), 6.69 (1H, d, J = 8 Hz), 2.17 (1H, s). 13C‐
NMR (100 MHz, DMSO‐d6): δ (ppm) 173.3, 165.2, 151.6,
149.3, 146.2, 138.8, 132.1, 134.6, 133.5, 132.1, 130.8,
129.2, 127.4, 118.1, 116.9, 115.2, 110.7, 107.9, 23.5. Anal.
calcd for C22H16N4O4: C, 65.99; H, 4.02; N, 13.99; found:
C, 65.86; H, 3.77; N, 13.69%.
2.8.11 | 3′‐(4‐bromophenyl)‐1′H‐
Spiro[indoline‐3,2′‐quinazoline]‐2,4′(3′H)‐
dione (4k)
m.p. 212–214°C. FT‐IR (KBr) cm−1: 3448, 3271, 2923,
1726, 1642, 1615, 1512, 1360, 1193, 751. 1H‐NMR
(400 MHz, DMSO‐d6): δ 10.52 (s, 1H), 7.68 (d, 1H,
J = 7.2 Hz), 7.59 (s, 1H), 7.57 (d, 1H, J = 7.4 Hz), 7.45
(d, 2H, J = 8.2 Hz), 7.29 (t, 1H, J = 7.4 Hz), 7.18 (t, 1H,
J = 7.8 Hz), 6.96–6.89 (m, 3H), 6.77–6.68 (m, 3H). 13C‐
NMR (100 MHz, DMSO‐d6): δ (ppm) 77.2, 109.8, 113.5,
114.8, 117.6, 120.3, 121.4, 127.1, 127.6, 128.0, 131.2,
131.8, 133.1, 134.6, 137.8, 142.2, 146.7, 163.9, 175.7. Anal.
calcd for C21H14N3O2Br: C, 61.12; H, 3.26; N, 9.72; found:
C, 61.03; H, 3.28; N, 9.83%.
3 | RESULTS AND DISCUSSION
The FT‐IR spectra of bis(2‐aminobenzamide), Al‐SBA‐15,
CTPES@Al‐SBA‐15, bis(2‐aminobenzamide)@Al‐SBA‐15,
V‐bis(2‐aminobenzamide)@Al‐SBA‐15 are shown in
Figure 3. The peaks at 600–1200 cm−1 can be attributed
to the vibration of Si–O groups in the mesoporous silica
framework. The absorption bands of Al‐SBA‐15‐based
materials at 1078, 802 and 460 cm−1 are attributed to
the Si–O–Si anti‐stretching vibration, the Si–O–Si
stretching vibration, and the bending vibration of Si–O,
respectively. The silanol groups of pure Al‐SBA‐15 pres-
ent a characteristic weak peak at 956 cm−1. Because of
the functionalization of Al‐SBA‐15 with CPTES
(Figure 3c), the weak peak declines and even disappears,
signifying the formation of –Si–O– bands. This happens
due to the reaction between the silanol groups of Al‐
SBA‐15 and (C2H5O)3Si– groups of silylation reagent.[34]
Therefore, weaker vibration intensity in the FT‐IR spectra
is observed possibly due to decrease of silanol groups. The
characteristic bands at 2893 and 2892 cm−1 were associ-
ated with C‐H stretching (Figure 4c).[35] The signals that
appeared at 2892 cm−1 and 2993 cm−1 in curve ‘c’ indi-
cated the existence of the organic propylchloride moiety
in the Al‐SBA. The absorption peaks at 3477, 3298, 1629
and 1546 were observed and attributed to the characteris-
tic peaks of bis(2‐aminobenzamide), due to the presence
of the NH2, C=O bonds. Accordingly, these signals at
1546 cm−1, 1629 cm−1 and 3298 in curve ‘d’ show the suc-
cessful attachment of bis(2‐aminobenzamide) to SBA‐15.
After bis(2‐aminobenzamide) coordinated with V, this
2.8.12 | 5‐Bromo‐3′‐(4‐bromophenyl)‐1′H‐
spiro[indoline‐3,2′‐quinazoline]‐2,4′(3′H)‐
dione (4l)
m.p. 296–298°C. FT‐IR (KBr) cm−1: 3268, 2924,1738,
1
1646, 1615, 1485, 1355, 1275, 1191, 753. 532. H‐NMR
(400 MHz, DMSO‐d6): δ 10.62 (1H, s), 7.81 (1H, s), 7.72
(1H, s), 7.66 (1H, d, J = 7.6 Hz), 7.46 (2H, d, J = 8 Hz),
7.36 (1H, t, J = 8 Hz), 7.32 (2H, t, J = 7.2 Hz), 6.99 (1H,
d, J = 7.6 Hz), 6.77 (1H, t, J = 7.2 Hz), 6.69 (1H, d,
J = 8 Hz), 6.64 (1H, d, J = 8.4 Hz). 13C‐NMR (100 MHz,
DMSO‐d6): δ (ppm) 171.2, 162.7, 148.1, 141.2, 139.6,
134.1, 133.6, 133.1, 132.4, 130.5, 129.4, 128.4, 123.8,
122.3, 120.1, 176.4, 115.1, 113.6, 107.8. Anal. calcd for
C21H13N3O2Br2: C, 51.69; H, 2.56; N, 8.22; found: C,
51.44; H, 2.63; N, 8.14%.
2.8.13 | 5‐Bromo‐3′‐(p‐tolyl)‐1′H‐
spiro[indoline‐3,2′‐quinazoline]‐2,4′(3′H)‐
dione (4m)
m.p. 153–155°C. FT‐IR (KBr) cm−1: 3443, 1751, 1610,
1514, 1486, 1337, 1249, 1188, 1083. 751. 1H‐NMR
(400 MHz, DMSO‐d6): δ 10.51 (s, 1H), 7.78 (s, 1H), 7.61
(m, 2H), 7.29–7.31 (m, 2H), 7.00 (d, 1H, J = 7.8 Hz),
6.86 (d, 2H, J = 6.7 Hz), 6.72 (t, 1H), 6.66 (d, 1H,
J = 7.7 Hz), 6.58 (d, 1H, J = 8.2 Hz), 2.11 (s, 3H). 13C‐
NMR (100 MHz, DMSO‐d6): δ (ppm) 22.0, 77.3, 111.9,
114.6, 114.7, 114.9, 117.8, 126.3, 128.5, 128.3, 131.4,
133.7, 134.1, 135.4, 136.6, 141.7, 145.9, 162.6, 176.3. Anal.
calcd for C22H16N3O2Br: C, 60.84; H, 3.71; N, 9.67; found:
C, 60.96; H, 3.58; N, 10.02%.
IR absorption peak shifted from 1629 to 1646 cm−1
,
which is indicative of the formation of a V–ligand bond.
The results above imply the presence of bis(2‐
aminobenzamide) bonded on the surface of Al‐SBA‐15,

SAFAEI‐GHOMI AND TEYMURI
7 of 13
FIGURE 4 N2 adsorption–desorption isotherms of Al‐SBA‐15, N‐
C@Al‐SBA‐15, V‐N‐C@Al‐SBA‐15
TABLE 1 Structural and textural parameters of SBA‐15, N‐
C@Al‐SBA‐15 and V‐N‐C@Al‐SBA‐15
BET
surface
Pore
diameter
Total pore
volume (m3/
Sample
area (m2/g) (BJH) (nm) g)
Al‐SBA‐15
873
5.618
3.461
3.112
1.226
0.475
0.319
FIGURE 3 Fourier transform‐infrared (FT‐IR) spectra of: (a)
bis(2‐aminobenzamide); (b) Al‐SBA‐15; (c) CPES@Al‐SBA‐15; (d)
bis(2‐aminobenzamide)@Al‐SBA‐15; (e) V‐bis(2‐aminobenzamide)
@Al‐SBA‐15; and (f) the used V‐bis(2‐aminobenzamide)@Al‐SBA‐
15
N‐C@Al‐SBA‐15 549
V‐N‐C@Al‐SBA‐ 410
15
BET, Brunauer–Emmett–Teller; BJH, Barrett–Joyner–Halenda.
and that the molecular structure of these functional moi-
eties can be perfectly retained in the complex of V‐bis(2‐
aminobenzamide)@Al‐SBA‐15.
incorporation of bis(2‐aminobenzamide) into the pore
channels. The even smaller pore size of V‐N‐C@Al‐SBA‐
15 suggested the distribution of vanadium inside the pore
channels.
The N2 adsorption/desorption isotherms and pore‐size
distribution curves of the samples are displayed in
Figure 4. As shown in Figure 4, all the isotherms exhib-
ited a typical type IV isotherm with an H1 hysteresis loop
starting from P/P0 = 0.6. This is characteristic of mesopo-
rous Al‐SBA‐15 with ordered pore structures, which is
quite important to disperse and stabilize the supported
vanadium species. Compared with the BET surface area
(873 m2/g) of Al‐SBA‐15, the surface area of V‐N‐C@Al‐
SBA‐15 was decreased to 410 m2/g after Al‐SBA‐15 was
functionalized. Table 1 displays the narrow pore size dis-
tribution centred on 5.618, 3.461 and 3.112 nm for Al‐
SBA‐15, N‐C@Al‐SBA‐15 and V‐N‐C@Al‐SBA‐15 sam-
ples, respectively. N‐C@Al‐SBA‐15 represent a smaller
pore size than the parent Al‐SBA‐15 due to the
These results are in excellent agreement with the fact
that the surface of mesoporous Al‐SBA‐15 has been suc-
cessfully modified by bis(2‐aminobenzamide). V species
have entered into the channels of the Al‐SBA‐15 mate-
rials, resulting in the decrease in its pore size.
In order to obtain the morphology and particle size of
nanoparticles, FE‐SEM images of the mesopores were
obtained and are presented in Figure 5. As shown in the
FE‐SEM images of Figure 5(a), the Al‐SBA‐15 sample is
that with the bagel‐shaped particles with relatively uni-
form sizes. After being functionalized with V‐N‐C@Al‐
SBA‐15, the shape of Al‐SBA‐15 is noticeably unchanged
(Figure 5b).

8 of 13
SAFAEI‐GHOMI AND TEYMURI
FIGURE 6 Low‐angle X‐ray diffraction (XRD) patterns of Al‐
SBA‐15 and V‐N‐C@Al‐SBA‐15
in the 2q range of 0–2, which can be indexed as (1 0 0),
(1 1 0) and (2 0 0) reflections of the two‐dimensional hex-
agonal structure of the SBA‐15 material. As can be seen
the regularity of Al‐SBA‐15 is decreased.
The ordered structure of V‐N‐C@Al‐SBA‐15 has
remained intact, as supported by the XRD results. Also
there is no major change in the crystallinity of Al‐SBA‐
15 after functionalization and V immobilization. Further-
more, the diffraction peaks of V species cannot be
detected, which also shows that the V species were
immobilized into the pore channels of Al‐SBA‐15 in the
atom dispersion, and no crystal V species existed in the
sample.
FIGURE 5 Field emission‐scanning electron microscopy (FE‐
SEM) images of: (a) Al‐SBA‐15; (b) V‐N‐C@Al‐SBA‐15; (e) the
used V‐N‐C@Al‐SBA‐15; and transmission electron microscopy
(TEM) image of: (c) Al‐SBA‐15; (d) V‐N‐C@Al‐SBA‐15; (f) the used
V‐N‐C@Al‐SBA‐15
Figure 7 shows the XPS wide scan spectrum; the pres-
ence of V 2p, C 1s, N 1s and O 1s signals further confirms
the composition of V‐N‐C @Al‐SBA‐15.
The TEM images of the Al‐SBA‐15 (Figure 5c) and V‐
N‐C@Al‐SBA‐15 (Figure 5d) samples reveal that the
porous structure was not disrupted after the post‐grafting
synthesis. Accordingly, it can be concluded that the regu-
larity of the mesoscopic channels was well retained after
the modification procedure, which further highlights the
stability of the catalyst during the functionalization pro-
cess. These observations are also in very good agreement
with the data obtained from the small‐angle XRD and
nitrogen adsorption–desorption analyses.
The evaluation of the used catalyst structure by
FE‐SEM and TEM evidences that the morphology of the
catalyst remained unchanged after the 5th cycle
(Figure 5e and f).
The small‐angle XRD patterns of Al‐SBA‐15 and V‐N‐
C@Al‐SBA‐15 are shown in Figure 6. The Bragg peaks
The result (Figure 7a) demonstrated that all the V spe-
cies in the V‐N‐C @Al‐SBA‐15 catalyst were present in
the V4+ state, corresponding to the binding energies of
517.2 and 523.50 eV in V 2p3/2 and V 2p1/2 levels, sug-
gesting that the V (IV) species deposited on V‐N‐C @Al‐
SBA‐15 support.[36–38] To determine the chemical micro-
environment of the organic functional groups in the
mesoporous silica, the electronic states of carbon, nitro-
gen and oxygen elements were also analyzed by the XPS
spectrum. As shown in Figure 7(b), the C 1s spectra
clearly indicated the V‐N‐C @Al‐SBA‐15 sample has
peaks at 284.8 eV and 286.9 eV corresponding to the
non‐oxygenated carbon in the phenyl ring and C=O in
the amide group. Meanwhile, two peaks with
binding energy at 400.7 eV could be observed in N 1s
spectra of the V‐N‐C @Al‐SBA‐15 sample (Figure 7c).

SAFAEI‐GHOMI AND TEYMURI
9 of 13
FIGURE 7 High‐resolution X‐ray
photoelectron spectroscopy (XPS) spectra
of: (a) V 2P; (b) C 1s; (c) N 1s; (d) O 1s; and
(e) XPS survey spectrum of V‐N‐C@Al‐
SBA‐15
This peak shows binding energy for the amide group
(CO–NH‐C).[39,40]
and vanadium amounts of the V‐N‐C @Al‐SBA‐15 were
24.14, 9.67, 33.91, 2.10, 19.40, 3.62 (wt %).
The elemental composition of V‐N‐C @Al‐SBA‐15 was
shown by energy‐dispersive X‐ray spectroscopy (EDS)
spectrum (Figure 8). Elemental analysis results showed
that the carbon, nitrogen, oxygen, aluminum, silicon
As a result of our great interest in preparation of het-
erocyclic compounds by applying heterogeneous cata-
lysts,[41,42] herein we wish to report an efficient
procedure to synthesize spiro[indoline‐3,2′‐quinazoline]
derivatives through a three‐component one‐pot conden-
sation of isatoic anhydride, isatins and primary
amines/or ammonium acetate using V‐N‐C@Al‐SBA‐15
as catalyst (Scheme 1). Beforehand, the reaction of isatoic
anhydride, isatin and aniline was picked out as a model
reaction. And now the effect of experimental factors com-
prising type and amount of catalyst and solvent were
investigated to find the best conditions for this reaction,
and the results are listed in Table 2. When the reaction
was carried out in EtOH/H2O, the expected product was
obtained in high yield (95%) and with better reaction
times compared with other organic solvents (Table 2,
entry 10). With non‐polar dichloromethane, the desired
adduct was produced in trace amounts, likely due to
insolubility of the isatoic anhydride.
According to the table, comparison of this entry with
entries 10–15 of Table 2 reveals that the V‐N‐C@Al‐
FIGURE 8 Energy‐dispersive X‐ray spectroscopy (EDS) of V‐N‐
C@Al‐SBA‐15

10 of 13
SAFAEI‐GHOMI AND TEYMURI
TABLE 2 The effect of reaction conditions on the synthesis of spiro[indoline‐3,2′‐quinazoline]‐2,4′(3′H)‐dione under various conditions
Entry
Solvent (condition)
Catalyst
Time (min)
Yielda (%)
1
Solvent‐free
V‐N‐C@Al‐SBA‐15 (0.03 g)
V‐N‐C @Al‐SBA‐15 (0.03 g)
V‐N‐C@Al‐SBA‐15 (0.03 g)
V‐N‐C@Al‐SBA‐15 (0.03 g)
V‐N‐C@Al‐SBA‐15 (0.03 g)
V‐N‐C @Al‐SBA‐15 (0.03 g)
V‐N‐C@Al‐SBA‐15 (0.03 g)
V‐N‐C@Al‐SBA‐15 (0.02 g)
V‐N‐C@Al‐SBA‐15 (0.03 g)
V‐N‐C@Al‐SBA‐15 (0.03 g)
Al‐SBA‐15 (0.03 g)
120
125
150
150
125
100
75
42
50
2
Water (reflux)
3
DCM (reflux)
trace
20
4
Acetone (reflux)
5
Acetonitrile (reflux)
Methanol (reflux)
Ethanol (reflux)
35
6
72
7
74
8
Ethanol/H2O (1:1) (reflux)
Ethanol/H2O (2:1) (reflux)
Ethanol/H2O (1:1) (reflux)
Ethanol (reflux)
70
84
9
70
88
10
11
12
13
14
15
70
95
120
420
100
300
240
62
EtOH (reflux)
KAl (SO4)2·12H2O(alum) (0.4 g)
1‐Methylimidazolium hydrogen sulfate (1.59 ml)
Ethylenediamine diacetate (0.036)
nano CeO2 (5 mol%)
91
Acetonitrile
94
H2O (reflux)
94
Ethanol/H2O (1:1) (reflux)
85
aIsolated yields.
SBA‐15 is the most efficient catalyst for the synthesis of
spiro[indoline‐3,2′‐quinazoline] derivatives.
The optimized quantity of V‐N‐C@Al‐SBA‐15 for this
synthesis is 0.03 g (Table 2, entry 10).
Various spiro[indoline‐3,2′‐quinazoline] were pre-
pared by V‐N‐C @Al‐SBA‐15 using the obtained opti-
mized conditions (Table 3).
These results indicate the fact that the use of as low as
0.03 g of V‐N‐C@Al‐SBA‐15 exhibits marked efficiency
on all of the aliphatic and aromatic amines tested under
desired reaction conditions (Table 3). As shown in
Table 3, the product 4c was formed through the reaction
between isatoic anhydride, benzylamine and isatin in
high yield. This reaction was fairly general, clean,
extremely rapid and efficient under the optimized reac-
tion conditions in the presence of V‐N‐C @Al‐SBA‐15.
All novel and known products were characterized by
comparing their physical data, 1H‐NMR, 13C‐NMR,
FT‐IR spectroscopy and elemental analysis spectra.
On the basis of the point mentioned above, a reason-
able mechanism for the preparation of spiro[indoline‐
3,2′‐quinazoline]‐2,4′(3′H)‐dione derivatives by the V‐N‐
C@Al‐SBA‐15 is suggested in Scheme 3. The first point
was the interaction of V‐N‐C@Al‐SBA‐15 as a catalyst
and isatoic anhydride to produce a reactive intermediate
I. And now, the N‐nucleophilic primary amine attacks
on the carbonyl unit of I to produce a reactive intermedi-
ate II, which in turn affords III through decarboxylation
reaction. Subsequently, the proton transfer of III affords
2‐amino‐N‐substituted‐amide IV. Also the reaction of an
activated isatin with IV proceeds to produce the imine
intermediate V. The part of the amide functional group
in intermediate IV could be formed using tautomerism
phenomenon in the presence of V‐N‐C@Al‐SBA‐15.
Accordingly, intermediate VI could be prepared by an
intermolecular nucleophilic attack of the amide nitrogen
on activated imine carbon, followed by a 1,5‐proton trans-
fer to yield the final spiro[indoline‐3,2′‐quinazoline]‐2,4′
(3′H)‐dione as the concluding product. Without a cata-
lyst, the reaction occurred under the conditions to give
18% yield. Active sites on the porous surface of the cata-
lyst were considerably increased by adding the catalyst,
and reached the best yield value (95%) with 0.03 g of
V‐N‐C@Al‐SBA‐15 catalyst. Also, the results established
the superior catalytic activity of this catalyst compared
with some conventional catalysts, for example bare
Al‐SBA‐15 (Table 2, entry 11). For the aforementioned
mechanism, the significant roles of V‐N‐C@Al‐SBA‐15

SAFAEI‐GHOMI AND TEYMURI
11 of 13
TABLE 3 Synthesis of monosubstituted spiro[indoline‐3,2′‐
quinazoline]‐2,4′(3′H)‐dione using V‐N‐C@Al‐SBA‐15
TABLE 3 (Continued)
Time/yield%
m.p.[Ref]
Time/yield%
m.p.[Ref]
Time/yield%
m.p.[Ref]
Time/yield%
m.p.[Ref]
4l
4k
4a
4b
80 min/89
72 min/90
38 min/95
35 min/96
212–2146[7]
296–2987[8]
262–2648[9]
253–255
4m
4n
4c
4d
58 min/94
48 min/95
47 min/97
46 min/96
153–1559[10]
171–1739[10]
212–2148[9]
289–291
4f
4e
44 min/95
70 min/95
301–303
251–2537[8]
4g
4h
65 min/94
62 min/94
276–2778[9]
194–1959[10]
4j
4i
50 min/95
52 min/90
276–278
265–2676[7]
SCHEME 3 Proposed reaction mechanism for the formation of
substituted spiro[indoline‐3,2′‐quinazoline]‐2,4′(3′H)‐diones using
V‐N‐C@Al‐SBA‐15
(Continues)

12 of 13
SAFAEI‐GHOMI AND TEYMURI
FIGURE 9 Recyclability study of V‐N‐C@Al‐SBA‐15 as a heterogeneous catalyst for the reaction of isatoic anhydride, isatin and aniline
under optimized conditions
are activation of carbonyl groups and efficient develop-
ment of the reaction on its high surface area.
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