Organocatalysis by p-sulfonic acid calix[4]arene: A convenient and efficient route to 2,3-dihydroquinazolin-4(1H)-ones in water

Article abstract of DOI:10.1039/c4ra16374e

An efficient and eco-friendly method is reported for the synthesis of 2,3-dihydroquinazolin-4(1H)-ones from the direct cyclocondensation of anthranilamide with aldehydes using p-sulfonic acid calix[4]arene (p-SAC) as a recyclable organocatalyst in excellent yields in water at room temperature. The catalyst was reusable without significant loss of catalytic efficiency. Operational simplicity, the compatibility with various functional groups, non-chromatographic purification technique, high yields and mild reaction conditions are the notable advantages of this procedure. Large scale reaction demonstrated the practical applicability of this methodology.

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Graphical Abstract
Organocatalysis by p-sulfonic acid calix[4]arene: a convenient and efficient
route to 2,3-dihydroquinazolin-4(1H)-ones in water
Matiur Rahman, Irene Ling, Norbani Abdullah, Rauzah Hashim*and Alakananda Hajra*
Reaction
O
O
NH2
Catalyst (1 mol%)
20-25 mins, RT
NH
O
R2
NH2
R2
N
H
R1
R1
≥ 90 %
ꢀ Green protocol
SO
3
H
SO H
3
SO
3
H
SO
3
H
ꢀ Water as reaction media
ꢀ Shorter reaction time
ꢀ Low catalyst loading
ꢀ Recyclable catalyst
OH
OH
OH
OH
ꢀNon-chromatographic technique
ꢀ Gram-scale synthesis

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DOI: 10.1039/C4RA16374E
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ARTICLE TYPE
Organocatalysis by p-sulfonic acid calix[4]arene: a convenient and
efficient route to 2,3-dihydroquinazolin-4(1H)-ones in water
Matiur Rahman,a Irene Ling,a Norbani Abdullah,a Rauzah Hashima*and Alakananda Hajrab*
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
a challenging task in the field of green catalysis. Aqueous
biphasic reaction systems using water-soluble catalysts have the
50 practical advantages that the catalysts can be reused after simple
decantation or extraction of the water-insoluble products and the
catalysts show high catalytic activity in water.10 The thought of
environmental factor (E-factor) and atom economy have
gradually become incorporated into conventional organic
55 synthesis in both industry and academia. Solvents are the main
reason for an insufficient E-factor, especially in synthesis of fine
chemicals and pharmaceutical industries.11
The calixarenes are a class of cyclooligomers formed via
condensation between para substituted phenols and
60 formaldehyde.12 Calixarenes are good receptors for the
complexation with various kinds of guests such as anions, cations
and neutral organic/inorganic molecules.13 Calixarenes have been
widely used in sensors, enzyme-mimics, ion carriers, solid-phase
support materials, ion selective electrodes, drug-delivery agents
65 etc.14 The discovery of water-soluble calixarenes as catalyst in
organic reaction has attracted the attention of researchers with the
objective of faster reaction and use of lower amount of catalyst.15
In this sense, water-soluble calix[n]arenes could be used as
surfactant-type Brønsted acid catalyst to facilitate the reactions
An efficient and eco-friendly method is reported for the
synthesis of 2,3-dihydroquinazolin-4(1H)-ones from the direct
cyclocondensation of anthranilamide with aldehydes using p-
sulfonic acid calix[4]arene (p-SAC) as
a
recyclable
10 organocatalyst in excellent yields in water at room
temperature. The catalyst was reusable without significant
loss of catalytic efficiency. Operational simplicity, the
compatibility with various functional groups, non-
chromatographic purification technique, high yields and mild
15 reaction conditions are the notable advantages of this
procedure. Large scale reaction demonstrated the practical
applicability of this methodology.
Introduction
Catalysis has played a crucial role in the success of the chemistry
20 in the twentieth century.1 Nowadays organocatalysis is one of the
hot research topics in advanced organic chemistry. In the past
decade, organocatalysis has opened a new window for carrying
out organic transformations and has become a powerful tool in
the synthesis of biologically active and structurally complex
25 compounds.2 Compared with transition-metal catalysts, the cost
and toxicity of organocatalysts are low, thus making
organocatalysts beneficial for the production of pharmaceutical
intermediates.2,3 Moreover, organocatalysts are tolerant of water
and air, are usually easy to use and finally avoidance of expensive
30 metal reagents or catalysts.4
70 through the formation of
a host-guest complex, with a
nucleophile component in the organic-aqueous interfacial layer.10
So the use of calix[n]arenes as catalyst in water is in demand
from the aspect of green chemistry. However the use of
calixarenes as catalyst in water is very rare.15a
75
The N-containing heterocyclic compounds play a crucial role
in the field of drug scaffolds, synthetic organic chemistry,
medicinal chemistry as well as material sciences.16 2,3-
Dihydroquinazolinone derivatives act as important intermediates
in the synthesis of drug molecules, and natural products.17 These
The development of eco‐friendly methodologies that are
environmentally benign and waste‐free, as well as being able to
produce the desired products in high purity, have received much
attention in recent years because of the increasing tendency of the
35 chemical industry towards greener processes.5 The major drive
towards this idea is the replacement of volatile organic solvents
by green solvents,6 as organic solvents are the major contributors
to environmental pollution. In this view, water is the most ideal
solvent7 and the use of water in organic reactions as solvent has
80 also exhibit various activities such as antitumor, anti-cancer,
antibiotic, antidefibrillatory, antipyretic, analgesic,
antihypertonic, diuretic, antihistamine, antidepressant, and
vasodilating agents18 (Fig 1).
40 received much attention.8 Water is
a safe, harmless and
O
O
N
environmentally benign solvent in comparison with a large
number of harmful organic solvents; the unique physicochemical
properties of water can even accelerate some reactions.9
However, the poor solubility of most organic compounds in water
45 often makes an unfavorable impact on water mediated organic
synthesis. Therefore, the development of water-tolerant catalysts
that allow organic reactions to be carried out in aqueous media is
Cl
NH
N
OMe
N
H
O
N
Anticancer activity
Diuretic
85
Fig. 1 Biologically important quinazolinone derivatives.
This journal is © The Royal Society of Chemistry [year]
[journal], [year], [vol], 00–00 | 1

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In view of their significant uses, green methodologies for the
synthesis of 2,3-dihydroquinazolin-4(1H)-ones should be
The reaction did not proceed well in absence of any solvent
(Table 1, entry 11). The chain length of calixarenes also played a
benefited in the synthetic and medicinal chemistry. Although 50 significant role. By increasing the chain length of 4 to 6 (n = 1 to
numerous protocols have been developed for the synthesis of 2,3-
dihydroquinazolinones,19 regardless their efficiency and
reliability, most of these methods suffer from one or more of
these disadvantages, such as the use of hazardous organic
3) the yield of the desired product decreased noticeably (Table 1,
entry 12). To explore the role of p-sulfonic acid calix[4]arene (p-
SAC) we used p-hydroxy benzenesulfonic acid (p-HSA) as a
catalyst. It was observed that p-HSA was less efficient than p-
5
solvents, requires higher temperature, low yields, strongly acidic 55 SAC (Table 1, entry 13). This indicates that the sulfonyl and
conditions, expensive moisture sensitive catalysts, and tedious
phenolic groups in calixarene moiety are not solely responsible
for fast and efficient reaction. On the other hand, p-TSA was not
also effective for this conversion (Table 1, entry 14). Phenol was
less efficient than p-SAC (Table 1, entry 15). Other Brønsted acid
10 work-up procedure. Therefore, it is important to develop
economically and environmentally more viable procedure for the
synthesis of 2,3-dihydroquinazolin-4(1H)-ones. Very recently, we
have developed an environmentally benign greener strategy using 60 catalyst like p-dodecylbenzenesulfonic acid (DBSA, Kobayashi’s
recyclable nano indium oxide as catalyst for the one-pot synthesis
15 of 2,3-dihydroquinazolin-4(1H)-ones by three-component
catalyst2m) was also tested, but no improvement of the yield was
observed (Table 1, entries 16). Thus, optimal reaction conditions
a
condensation of isatoic anhydride with primary amines or
ammonium salts and aromatic aldehydes in ethanol.19o As a part
were obtained using anthranilamide (1,
methylbenzaldehyde (2a, 1 mmol) in presence of 1 mol% of p-
1
mmol), 4-
of our ongoing research for the synthesis of heterocycles through 65 sulfonic acid calix[4]arene (p-SAC) in water (1 mL) at room
a greener way,19o,20 herein we report a simple and practical
20 metal-free method for the synthesis of 2,3-dihydroquinazolin-
4(1H)-ones by the cyclocondensation of anthranilamide with
aldehydes using p-sulfonic acid calix[4]arene (p-SAC) as a
recyclable organocatalyst in water at room temperature (Scheme
1).
temperature for 20 min (Table 1, entry 1).
Table 1 Optimization of the reaction conditionsa
O
CHO
O
Catalyst
NH
NH2
+
Solvent, rt
N
H
NH2
O
O
CH3
CH3
Catalyst (1mol%)
NH
R2
R1
O
3a
1
2a
NH2
+
R1
R2
H2O (1 mL), rt
N
H
Solvent
(1 mL)
Time
(min)
Yields
(%)b
NH2
Entry
Catalyst (mol%)
3
1
2
1
p-SAC (1)
p-SAC (1)
p-SAC (5)
p-SAC (0.5)
-
H2O
20
60
20
20
20
20
20
20
20
20
20
92
92
93
84
n. r.c
80
72
38
75
32
20
R
1 = aryl, heteroaryl,allycyclic, alkyl
2
H2O
R2 = H, Me
3
H2O
4
H2O
SO3H
SO3H
HO3S
HO3S
5
H2O
n = 1, p-sulfonic acid calix[4]arene
n = 3, p-sulfonic acid calix[6]arene
Catalyst =
6
p-SAC (1)
p-SAC (1)
p-SAC (1)
p-SAC (1)
p-SAC (1)
p-SAC (1)
p-Sulfonic acid
MeOH
MeCN
Toluene
DMF
DCE
-
7
n
OH
OH
OH
OH
25
8
9
Scheme 1 Synthesis of 2,3-dihydroquinazolin-4(1H)-ones.
10
11
We started our study with preparing p-sulfonic acid
calix[n]arenes in our laboratory according to the literature
12
H2O
20
67
30 procedure.21 Next the catalytic activity of these organocatalyst
were investigated for the synthesis of 2,3-dihydroquinazolin-
4(1H)-ones. In order to find out the optimum reaction conditions,
we have selected the reaction of anthranilamide 1 and 4-
methylbenzaldehyde 2a as the model reaction (Table 1). To our
35 delight, the desired product 3a was obtained in 92% yield in
presence of 1 mol% p-sulfonic acid calix[4]arene (p-SAC) in
water at room temperature for 20 min (Table 1, entry 1). No
further improvement was noticed by increasing the reaction time
(Table 1, entry 2). Increasing the amount of catalyst (5 mol%) did
40 not improve the yield noticeably (Table 1, entry 3,) whereas
decreasing the amount of catalyst (0.5 mol%) decreased the yield
(Table 1, entry 4). To clarify the role of the catalyst (p-SAC) in
this process, the same reaction was carried out without p-SAC
(Table 1, entry 5). However the reaction did not proceed at all
45 without the catalyst after 20 min of reaction. Water appeared to
be the best choice as solvent among the common solvents like
MeOH, MeCN, toluene, DMF, 1,2-DCE (Table 1, entries 6-10).
calix[6]arene [n = 3] (1)
13
14
15
16
p-HSA (1)
H2O
H2O
H2O
H2O
20
20
20
20
60
57
18
58
p-TSA (1)
Phenol (1)
DBSA (5)
a
Reaction conditions: 1 mmol of 1 and 1 mmol of 2a in the presence of
70 catalyst and solvent (1 mL) at room temperature. Isolated yields. No
reaction. p-SAC p-Sulfonic acid calix[4]arene. p-HSA p-
Hydroxybenzenesulfonic acid. p-TSA = p-Toluenesulfonic acid. TBAB =
Tetrabutyl ammonium bromide. DBSA = p-Dodecylbenzenesulfonic acid.
b
c
=
=
75
Next, we studied the scope and limitation of this reaction by
employing a wide range of aldehydes (2) under optimized
reaction conditions. The results are summarized in Table 2. To
our delight, the corresponding dihydroquinazolin-4(1H)-ones (3)
were obtained with good to excellent yields in all cases. Aromatic
80 aldehydes with electron-donating as well as electron-withdrawing
substituents reacted very well, affording good to excellent yields
2
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of 2,3-dihydroquinazolinones. The chloro- and bromo-
have successfully synthesized the dihydroquinazolinone 3a in
substituted benzaldehydes afforded the corresponding products 35 86% yield by the reaction of anthranilamide (1, 20 mmol) and 4-
3d and 3e in 87% and 86% yields respectively. Substituent at the
ortho position of the phenyl ring also afforded the corresponding
products with excellent yields (3j and 3k). Heteroaryl aldehyde
like 2-thiophenecarboxaldehyde was also compatible under this
methylbenzaldehyde (2a, 20 mmol) (Table 2, entry 1).
Finally the single crystal X-ray diffraction analysis of 3n was
carried out for further confirmation of the structure of product
(Fig. 2).23 In crystalline state the compound shows the 2,3-
5
reaction conditions to give the desired product (3p) without 40 dihydroquinazoline moiety is planar. The pyrimidine ring is in a
polymerization. Gratifyingly, the current methodology is also
applicable for the aliphatic aldehydes. Cyclohexane
10 carboxaldehyde gave the desired product (3q) with high yield.
flattened half-chair conformation. The nitro-substituted benzene
ring forms dihedral angle of 85.91o, with the benzene ring of the
dihydroquinazoline group. In the crystal, molecules are arranged
in crisscross manner along a-axis, with N—O…H hydrogen
Butyraldehyde also afforded the corresponding 2,3-
dihydroquinazolinone (3r) with good yield however longer 45 bonds linking molecules at 2.451 to 2.708 Å in the extended
reaction time is required. Moreover, ketone like acetone also
afforded the desired product (3s) with moderate yield. The all
15 synthesized compounds have been characterized by spectral and
analytical data. Results in Table 2 clearly show that the present
protocol is indeed superior to several reported methods in terms
of product yields, reaction time, avoiding the use of volatile
organic solvents, and reaction temperature. Moreover, we have
20 developed a greener reaction conditions bearing lower E-
factor11,22 of 0.17 and 0.15 in the cases of synthesizing 3a and 3b
respectively (see Supporting Information).
network. Short contacts of hydrogen bonding interaction related
to carbonyl oxygen atoms with neighboring hydrogen atoms is
observed with O…H distances ranging from 2.080 to 2.636 Å.
Table 2 Substrates scopes of the reactiona
O
O
O
Catalyst
R2
H2O, rt
NH
R2
R1
NH2
R1
+
N
H
3
NH2
1
2
Time Yields
(min) (%)b
Entry
R1
R2
Products
92, 86c
50
Fig. 2 The single crystal XRD structure of compound 3n.
1
4-Me-C6H4
Ph
H
H
H
H
H
H
H
H
H
H
H
3a
3b
3c
3d
3e
3f
20
18
20
22
22
25
20
22
24
20
22
2
94
Next, we turned our attention towards the recovery and
reusability of the catalyst. For this purpose, we have chosen the
reaction of anthranilamide (1) with 4-methylbenzaldehyde (2a) in
presence of 1 mol% p-sulfonic acid calix[4]arene (p-SAC) in
3
4-MeO-C6H4
4-Cl-C6H4
4-Br-C6H4
4-NO2-C6H4
4-MeS-C6H4
4-CN-C6H4
4-OH-C6H4
2-Cl-C6H4
2-OH-C6H4
90
4
87
5
86
6
82
55 water at room temperature as the model reaction. After
completion of the reaction distilled water was added to the
reaction mixture. The reaction mixture was then filtered off and
the catalyst was recovered by evaporating the water. Pure product
was obtained by recrystallizing the residue from hot ethanol. The
60 recovered catalyst was reused for a subsequent fresh batch of the
reaction. The catalytic activity was checked upto fourth cycle and
it showed similar (Table 3).
7
3g
3h
3i
88
8
86
9
82
10
11
3j
90
3k
88
4-OH-3,5-
(OMe)2-C6H2
12
H
3l
24
84
13
14
15
16
17
18
19
5-Br-2-OH-C6H3
3-NO2-C6H4
1-Pyrenyl
2-Thiophenyl
Cyclohexyl
C3H7
H
3m
3n
3o
3p
3q
3r
22
24
26
22
30
40
90
85
88
82
86
82
68
64
H
H
Table 3 Recycling of the p-sulfonic acid calix[4]arene (p-SAC) for
65 synthesizing 3aa
H
H
Entry
Run
1st
Yield (%)b
H
1
2
3
4
5
92
92
90
89
87
CH3
CH3
3s
2nd
3rd
4th
5th
25 a Reaction conditions: 1 (1 mmol), 2 (1 mmol) in water (1 mL) at room
temperature in presence of 1 mol% of p-SAC. Isolated yields. 1 (20
mmol), 2a (20 mmol) in water (20 mL) at room temperature in presence
of 1 mol% of p-SAC.
b
c
a Carried out with 1 mmol of 1 and 1 mmol of 2a in presence of catalyst
in water (1 mL) at room temperature. b Isolated yields.
30
The dihydroquinazolinones were generally precipitated from
the reaction mixtures and the solid precipitation was filtered off
and recrystallized from hot ethanol to obtain pure products. This
methodology is also applicable on a gram-scale synthesis. We
Based o the literature reports,19g a plausible mechanistic
70 pathway to 2,3-dihydroquinazolin-4(1H)-ones (3) is illustrated in
This journal is © The Royal Society of Chemistry [year]
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Scheme 2. In the initial step, condensation of anthranilamide (1)
evaporating the water. The recovered catalyst was reused for a
with the aldehyde (2) gives imine A, which upon intramolecular 45 subsequent fresh batch of the reaction after reactivation. The
cyclization afforded the final product 3. The catalyst might
activate the aldehyde through the co-ordination with the oxygen
of the corresponding carbonyl group which facilitates the
subsequent nucleophilic attack by the nitrogen atom on the
carbonyl carbon.
crude product was recrystallized from hot ethanol to afford the
pure product.
5
Acknowledgements
We thank the University of Malaya and the Malaysian Ministry
50 of Higher Education High Impact Research Grant
UM.C/625/1/HIR/MOHE/05 for financial support.
O
O
H
Calixarene
H2O
NH2
NH2
NH2
C
R1
O
+
R2
R1
R2
N
Notes and references
A
a
Department of Chemistry, University of Malaya, 50603 Kuala Lumpur,
Malaysia. E-mail: rauzah@um.edu.my
b
55
Department of Chemistry, Visva-Bharati (A Central University),
Santiniketan 731235, India. E-mail: alakananda.hajra@visva-
bharati.ac.in
O
NH
R2
R1
†Electronic Supplementary Information (ESI) available: [1H, 13C NMR
data and Spectra, crystallographic data, E-factor calculations]. See
60 DOI: 10.1039/b000000x/
N
H
3
1
(a) R. A. Sheldon, Chemtech, 1994, 25, 38-47; (b) R. A.
Sheldon and H. van Bekkum, Eds., Fine Chemicals Through
Heterogeneous Catalysis, Wiley-VCH, Weinheim, Germany,
2001.
10
Scheme 2 Plausible mechanistic pathway
65
70
2
(a) P. I. Dalko and L. Moisan, Angew. Chem., Int. Ed., 2001,
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Conclusions
In summary, we have demonstrated a remarkable catalytic
activity of p-sulfonic acid calix[4]arene (p-SAC) as an
organocatalyst for the synthesis of 2,3-dihydroquinazolin-4(1H)-
15 ones by the condensation between various aldehydes and
anthranilamide in water at room temperature. This protocol is
also applicable on a gram-scale synthesis. Clean reaction, ease of
product isolation, short reaction time, mild reaction conditions
(room temperature), low catalyst loading, low E-factor, and use
20 of water as solvent are the notable advantages of the present
methodology and these features make this procedure to be a green
synthetic protocol. We believe that our novel procedure will open
up a new practical and convenient route for the synthesis of
biologically important 2,3-dihydroquinazolin-4(1H)-ones.
75
80
3
25 Experimental section
85
General: Melting points were determined on a glass disk with an
electric hot plate and are uncorrected. H NMR (400 MHz) and
1
13C NMR (100 MHz) spectra were run in in CDCl3 & DMSO-d6
solutions (Bruker Avance 400). Chemical shift were recorded as
30 δ values in parts per million (ppm), and the signals were reported
as s (singlet), d (doublet), t (triplet), m (multiplet) and coupling
constants J were given in Hz. IR spectra were taken in a Perkin
Elmer FTIR-Spectrum 400. Commercially available substrates
were freshly distilled before the reaction. Solvents, reagents and
35 chemicals were purchased from Sigma Aldrich and Merck.
4
5
(a) Organic Catalysis; Wiley-VCH: Weinheim, Germany,
2004; pp. 1007-1249; (b) Organocatalysis; American
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95
General procedure for the synthesis of 2,3-dihydroquinazolin-
100
105
4(1H)-ones
p-Sulfonic acid calix[4]arene (1 mol%) was added to a solution of
anthranilamide (1 mmol) and aldehyde/ketone (1 mmol) in water
40 (1 mL) and the mixture was stirred at room temperature for a
specified period of time. After completion of the reaction, cold
distilled water (5 mL) was added to the reaction mixture. Then
the product was filtered off and the catalyst was recovered by
4
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