Poly(4-vinylpyridine) supported acidic ionic liquid: A novel solid catalyst for the efficient synthesis of 2,3-dihydroquinazolin-4(1H)-ones under ultrasonic irradiation

Article abstract of DOI:10.1016/j.ultsonch.2013.05.009

A novel poly(4-vinylpyridine) supported acidic ionic liquid catalyst was synthesized by the reaction of 4-vinylpyridine with 1,3-propanesultone, followed by the polymerization and the addition of the heteropolyacid. Due to the combination of polymer features and ionic liquid, it acted as a heterogeneous catalyst to effectively catalyze the cyclocondensation reaction of anthranilamide with aldehydes under ultrasonic irradiation and afforded the corresponding 2,3-dihydro-4(1H)-quinazolinones compounds in good to excellent yields. In addition, the catalyst could be easily recovered by the filtration and reused six times without significant loss of catalytic activity. More importantly, the use of ultrasonic irradiation can obviously accelerate the reaction.

Full text of DOI:10.1016/j.ultsonch.2013.05.009

Accepted Manuscript
Short communication
Poly(4-vinylpyridine) supported acidic ionic liquid: a novel solid catalyst for
the efficient synthesis of 2,3-dihydroquinazolin-4(1H)-ones under ultrasonic ir‐
radiation
Junke Wang, Yingxiao Zong, Rugang Fu, Yuying Niu, Guoren Yue, Zhengjun
Quan, Xicun Wang, Yi Pan
PII:
S1350-4177(13)00117-X
DOI:
http://dx.doi.org/10.1016/j.ultsonch.2013.05.009
ULTSON 2315
Reference:
To appear in:
Ultrasonics Sonochemistry
Received Date:
Revised Date:
Accepted Date:
18 March 2013
7 May 2013
17 May 2013
Please cite this article as: J. Wang, Y. Zong, R. Fu, Y. Niu, G. Yue, Z. Quan, X. Wang, Y. Pan, Poly(4-vinylpyridine)
supported acidic ionic liquid: a novel solid catalyst for the efficient synthesis of 2,3-dihydroquinazolin-4(1H)-ones
under ultrasonic irradiation, Ultrasonics Sonochemistry (2013), doi: http://dx.doi.org/10.1016/j.ultsonch.
2
013.05.009
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Poly(4-vinylpyridine) supported acidic ionic liquid:
a novel solid catalyst for the efficient synthesis of
2
,3-dihydroquinazolin-4(1H)-ones under ultrasonic irradiation
,a,c
,a
a
a
a
b
Junke Wang* , Yingxiao Zong* , Rugang Fu, Yuying Niu , Guoren, Yue , Zhengjun Quan ,
b
c
Xicun Wang and Yi Pan
a
Key Laboratory of Hexi corridor resources utilization of Gansu Universities, College of Chemistry and Chemical Engineering,
Hexi University, Zhangye 734000, China
b
Gansu Key Laboratory of Polymer Materials, College of Chemistry and Chemical Engineering, Northwest Normal University,
Lanzhou 730070, China
c
School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China
E-mail:wangjk@hxu.edu.cn
Abstract: A novel poly(4-vinylpyridine) supported acidic ionic liquid catalyst was synthesized by the reaction of
4
-vinylpyridine with 1,3-propanesultone, followed by the polymerization and the addition of the heteropolyacid.
Due to the combination of polymer features and ionic liquid, it acted as a heterogeneous catalyst to effectively
catalyze the cyclocondensation reaction of anthranilamide with aldehydes under ultrasonic irradiation and afforded
the corresponding 2,3-dihydro-4(1H)-quinazolinones compounds in good to excellent yields. In addition, the
catalyst could be easily recovered by the filtration and reused six times without significant loss of catalytic activity.
More importantly, the use of ultrasonic irradiation can obviously accelerate the reaction.
Keywords: Ultrasonic irradiation; Poly(4-vinylpyridine); 2,3-Dihydroquinazolin-4(1H)-ones; Ionic liquid
1.Introduction
Quinazoline frameworks are pervasive in both pharmaceutical industry and academic research [1,2]. They
play an essential roles in cell growth, signaling, proliferation, and sensing. Among of them,
,3-dihydro-4(1H)-quinazolinone is an important calss of heterocycles, because they serve as an essential core
2
structure for a wide range of natural products, and are important pharmacophore of synthetic drugs demonstrating
anti-inflammatory, antiviral, anticancer agents, anticonvulsants, antimalarial, antibacterial analgesic, and
anti-Alzheimer properties [3-5]. Recently, they have been found that some 3,4-dihydroquinazoline derivatives act
2+
2+
as potent T-type Ca channel blockers, particularly against two isoforms of T-type Ca channel [6-9].
Furthermore, 2,3-dihydro-4(1H)-quinazolinones could be easily oxidized to 4-(3H)-quinazolinones, which are
important
2,3-dichloro-5,6-dicyano-1,4-benzoquinone) [10,11].
Many classical methods for the synthesis of 2, 3-dihydro-4(1H)- quinazolinones have been reported [12-27].
For example, they were obtained by reductive cyclization of o-nitrobenzamide or o-azidobenzamide with
aldehydes and ketones promoted by metallic samarium and a catalytic amount of iodine or SmI [17, 22]. The
privileged
structures
in
medicinal
chemistry,
by
NaHSO
3
or
DDQ
(
2
synthesis of 2,3-dihydroquinazolinones was also achieved with the aid of a low valent titanium reagent [18-21].
There was also a recent report of carrying out these reactions in ionic liquids [23, 24]. These ionic liquids have
6 4
been shown to have serious drawbacks, especially imidazoliums with PF and BF anions that are as toxic as
benzene on certain aquatic ecosystems and also liberate hazardous HF during recycling [25]. A few procedures in
water have been reported in the literature [26, 27]. However, the reported reactions in water have been carried out
in the presence of surfactants such as SDS (sodium dodecyl sulfate). Unfortunately, normal-phase separation is
difficult during workup due to the formation of emulsions because of the SDS [28]. Moreover, this method needed
the multifarious procedures, and the reuse of catalyst was satisfied in water reaction [27].
1

Ionic liquids (ILs) have been attracting significant attention as alternative solvents and catalysts for chemical
reactions because of their negligible volatility, remarkable solubility, and potential recyclability [29]. In recent
years, the use of heteropolyacid-based IL (HPA-IL) to catalyze organic reactions is an ongoing research area [30].
Some HPA-IL composites have been reported and employed as catalysts for acid-catalyzed reactions[31].
Considering that ionic polymers containing IL units are potentially capable of acting the bifunctions of IL and
polymer, such as high thermal stability, easily shaping, corrosion resistance, and variety of available
structures[32], the catalytic stabilities of theses catalysts need to be improved.
Ultrasound irradiation has been established as a significant technique in synthetic organic chemistry [33–36].
Shorter reaction time is the main benefit of ultrasound-assisted reactions. Simple experimental procedure, high
yields, improved selectivity and clean reaction of many ultrasound induced organic transformations offers
additional convenience in the field of synthetic organic chemistry. Most recently, Ultrasound-assisted has been
used for the synthesis of coumarins, 2-amino-4H-chromenes, coumarin thioglycopyranoside derivatives and
hymecromone as insecticide intermediate [37-41].
With these considerations in mind, based on our previous works, which focus on the synthesis of polymer
supported catalyst and the utilization in organic reaction[27,42-45], herein, we report a novel poly(4-vinylpyridine)
supported acidic ionic liquid catalyst (Poly(VPyPS)-PW) and its application as a highly efficient and recoverable
catalyst for the synthesis of 2,3-dihydroquinazolin-4(1H)-ones compounds under sonication irradiation (Scheme
1
).
H
N
R
NH
2
O
H
Poly(VPyPS)-PW, ))))
EtOH, R. T.
+
R2
NH
NH
2
R1
R
1
O
O
2
*
1
*
3
3
n
Poly(VPyPS)-PW:
3-
PW12
SO
O
40
N
3
H
Scheme 1 The synthesis of 2,3-dihydroquinazolin-4(1H)-ones catalyzed by Poly(VPyPS)-PW under sonication
2. Experimental
2.1 General information
Melting points were determined on a Perkin-Elmer differential scanning calorimeter and was uncorrected. The
1
13
IR spectra were run on a Nicolete spectrometer (KBr). NMR spectra were recorded at 400 ( H) and 100 ( C)
MHz, respectively, on a Varian Mercury plus-400 instrument using CDCl as solvent and TMS as the internal
3
standard. Mass spectrawere obtained with an automated FININIGAN TSQ Advantage mass spectrometer.
Thermogravimetric analysis was carried out under nitrogen using a Shimadzu TGA-50 spectrometer. X-Ray
diffraction (XRD) images were obtained from a Bruker XRD D8 Advance instrument with Cu Ka radiation. All
the solvents used were strictly dried according to standard operation. Ultrasonic irradiation was performed in an
ultrasound cleaning bath (KQ-250B, China) with a frequency of 40 Hz and voltage of 220 V. The reaction vessel
placed inside the ultrasonic bath containing water.
2.2 Preparation of VPyPS
To a solution of 1,3-propane-sultone (0.1 mol, 12.2 g) in dry toluene (50 mL), 4-vinyl pyridine (0.1 mol, 10.5
g) was slowly at room temperature and the mixture was stired overnight until the solid formed. which was
washed with ether and dried in vacuo at room temperature. The solid was used in next step without further
purification.
2

2.3 Preparation of Poly(VPyPS)
The obtained VPyPS (2.5 g) was dissolved in methanol (20 mL) , and azobisisobutyronitrile (AIBM) (0.05 g)
were added under nitrogen atmosphere, and the mixture was refluxed at 70 °C for 24 h with stirring. Then the
solvent was removed by distillation, and the residue was washed with ethanol to give a white solid Poly(VPyPS).
2
.4 Poly(VPyPS)-PW and control samples
The solution of H 40 (PW) (4 g, 1.39 mmol) was added dropwise into the obtained Poly(VPyPS) (0.88 g,
monomer molar quantity 4.17 mmol) in methanol, followed by the refluxing for 24 h. On completion, methanol
was removed in vacuum to give the final product Poly(VPyPS)-PW as a white solid. Poly(VPyPS)-HSO was
prepared by reacting Poly(VMPS) and H SO with the monomer molar ratio of 1:1 at 0 °C.
.5 General procedure for the synthesis of β-amino carbonyl compounds
To the mixture of anthranilamide (2 mmol) and aldehydes (2.1 mmol) in 5 mL of ethanol, Poly(VPyPS)-PW
0.2 g) was added. The mixture was irradiated at room temperature under sonication (with a frequency of 40 kHz
3
PW12O
4
2
4
2
(
and a nominal power 250 W) for appropriate time indicated in Table 3 until the reaction was completed as
monitored by TLC. After the resulting mixture was heated to refluxing, the hot ethanol solution was filtered to
recover the catalyst. The analytical sample was obtained by recrystallization of the filtrate. The separated catalyst
was washed with ethanol, dried at 60 °C under vacuum for 4 h. The recovered catalyst was directly used for the
next run. The product was collected from the filtrate after cooling to room temperature and recrystallized from the
ethanol to give compounds 3a–3m. The 2,3-dihydroquinazolin-4(1H)-one compounds were characterized by the
use of spectral data and comparison of their physical data with the literature. Spectral data for compound 3b:
-1 1
6
white solid, IR (KBr): ν 3439, 1672 cm , H NMR (400 MHz, DMSO-d ): d 7.98 (s, 1H), 7.68 (d, 1H, J = 7.8 Hz),
13
7
.34 (d, 1H, J = 8.0 Hz), 7.21–7.24 (m, 1H), 7.08 (s, 1H), 6.74–6.65 (m, 3H), 5.88 (s, 1H), 3.95–3.85 (m, 9H). C
6
NMR (100 MHz, DMSO-d ): d 163.2, 161.3, 158.2, 148.3, 132.1, 127.6, 127.8, 122.4, 117.3, 114.9, 114.4, 104.6,
-1
1
9
8.6, 56.5, 55.5. Spectral data for compound 3m: IR (KBr): ν 3376, 2984, 1675, cm , H NMR (400 MHz,
6
DMSO-d ): d 7.82 (d, 1H, J = 8.2 Hz), 7.80 (d, 1H, J = 8.0 Hz), 7.60 (m, 1H), 7.36 (d, 1H, J = 8.2 Hz), 7.18–7.21
13
(
6
m, 1H), 7.10 (d, 1H, J = 8.0 Hz), 5.90 (s, 1H). C NMR (100 MHz, DMSO-d ): d 169.8, 165.2, 147.2, 146.3,
1
34.9, 129.2, 121.5, 118.4, 115.2, 114.8, 62.3.
3
. Results and discussion
3
.1 Preparation of the catalyst
Poly(4-vinylpyridine) supported acidic ionic liquid [Poly(VPyPS)-PW] was prepared following the procedure
shown in Scheme 2. The precursor Poly(VPyPS) was prepared by quaternization of 4-vinyl pyridine(Vpy) with
,3-propanesultone, followed by the polymerization with AIBN. Ultimately, The obtained Poly(VPyPS) was
dissolved in methanol at 60 °C with stirring, an aqueous solution of H 40(PW) with an methanol solution
1
3
PW12O
of the precursor was refluxed for 24 h, which afforded Poly(VPyPS)-PW catalyst.
O
O
AIBN, 60 oC,
S
Toluene
+
O
0oC, 12 h
methanol, 24 h
6
N
N
VPy
VPyPS
PS
SO -
3
*
n
*
n
*
*
H
3
PW12
O40(PW)
3
-
PW12O
40
methanol, 24 h
N
N
SO -
Poly(VPyPS)
3
SO H
3
Poly(VPyPS)-PW
Scheme 2 Synthesis of the Poly(VPyPS)-PW catalyst.
3

3
.2 Characterization of the catalyst
The Poly(VPyPS)-PW have a high melting point of above 250 °C, and it was observed to be insoluble in the
polar solvents, which enable Poly(VPyPS)-PW to be a solid catalyst for organic reaction. In order to warrant the
successful functionalization of Poly(VPyPS) with H 40(PW), FT-IR was employed to give a detailed
investigation of the blank H 40(PW) and Poly(VPyPS)-PW. As can be seen from Fig. 1, both of the samples
show peaks in the wavenumber region of 800–1100 cm . There are absorb peaks 1081 cm (P–Oa), 981 cm
3
PW12O
3
PW12O
-
1
-1
-1
-1
-1
-1
(
(
[
3
W=Od), 891 cm (W–Ob–W) (corner-sharing), and 807 cm (W–Oc–W) in H PW12O40(PW), while 1081 cm
-
1
-1
-1
P–Oa), 977 cm (W=Od), 900 cm (W–Ob–W) (corner-sharing), and 822 cm (W–Oc–W) in Poly(VPyPS)-PW
31f].
3
Compared with H PW12O40(PW), the slight shifts of the Keggin bands for Poly(VPyPS)-PW appeared, which
are resulted from the strong ionic interaction between the polymeric cations and heteropolyanions. The FT-IR
-1
spectra of Poly(VPyPS)-PW shows that the peak at 1205 and 1040 cm could be due to the asymmetric and
-1
symmetric stretching vibrations of S=O, respectively, and that the broad and asymmetric peak at 3424 cm could
be due to O-H vibrations. Thus, the above results indicate that the Poly(VPyPS) was successfully combined with
3
H PW12O40(PW) via ionic linkages.
3
Fig. 1 FT-IR spectra of (A) H PW12O40 and (B) Poly(VPyPS)-PW
The stability of the Poly(VPyPS)-PW and H
analysis (Fig. 2). The TG curve indicates that the decomposition temperature of Poly(VPyPS)-PW was about
02°C. which is remarkably lower than that(>400°C) for H 40(PW). This fact indicates Poly(VPyPS)-PW is
not a physical mixture of Poly(VMPS) with HPA, but a ionic hybrid.
3
PW12O40(PW) was compared by the thermogravimetric (TG)
3
3
PW12O
3
Fig. 2 TG pattern of (A) H PW12O40 and (B) Poly(VPyPS)-PW
4

3
Fig. 3 XRD pattern of (A) H PW12O40 and (B) Poly(VMPS)-PW
In order to further clarify the structure, The XRD pattern of Poly(VPyPS)-PW and H
3
PW12O40(PW) were
investigated(Fig. 3). H 40(PW) possess the characteristic peak of the Keggin anions. However, all of the
3
PW12O
peaks disappeared in the XRD pattern of Poly(VPyPS)-PW. This phenomenon demonstrates that the
rearrangement took place between heteropolyanions and polymeric cations by self-assembly. All these results
suggest that Poly(VPyPS)-PW has the structure illustrated in Scheme 1.
3
.3 Synthesis of 2,3-dihydroquinazolin-4(1H)-one compounds catalyzed by Poly(VPyPS)-PW
To optimize the reaction conditions, we chose anthranilamide and benzaldehyde as model reaction to
investigate effect of temperature, solvent, amount of catalyst on the synthesis of 2,3-dihydroquinazolin-4(1H)-one.
Firstly, without ultrasonic irradiation, the reaction was carried out under various reaction conditions at variety of
temperature with Poly(VPyPS)-PW as the catalyst. The results are shown in Table 1. Without the addition of
catalyst, no product were detected after 6 h of the reaction time (entry 1 in Table 1). With the increase of catalyst
amount, the yield of product increase(entry 2, 3, 4 in Table 1). Several solvents were tested for the reaction, such
2 2 2 2 2 2
as EtOH, MeCN, CH Cl , H O and PhMe. The reaction hardly proceeded in CH Cl , H O or PhMe. However, the
reaction in EtOH afforded product in high selectivity with nearly complete conversion. It seemed that the solvents
also played an important role in the cyclocondensation reaction catalyzed by Poly(VPyPS)-PW. Therefore, EtOH
was selected as the reaction solvent in the following investigation. It is found that the temperature is a key factor,
which affects the yield. With the improve of the temperature of system, the yield of product was improved. When
the solution was refluxed, the maximal value of yield was realized(entry 10, 11, 12 in Table 1).
Table 1
The optimization for the cyclocondensation reaction of anthranilamide with aldehydes without ultrasonic irradiation
H
NH
2
N
O
H
Poly(VPyPS)-PW
Solvent
+
NH
2
NH
O
O
o
a
Time( h)
2
Entry
1
Catalyst (g)
No catalyst
Solvent
Temperature ( C)
Yield
0
EtOH
Reflux
2
3
4
5
6
7
8
9
Poly(VPyPS)-PW (0.3 g)
Poly(VPyPS)-PW (0.2 g)
Poly(VPyPS)-PW (0.1g)
Poly(VPyPS)-PW (0.05 g)
Poly(VPyPS)-PW (0.2 g)
Poly(VPyPS)-PW (0.2 g)
Poly(VPyPS)-PW (0.2 g)
Poly(VPyPS)-PW (0.2 g)
Poly(VPyPS)-PW (0.2 g)
Poly(VPyPS)-PW (0.2 g)
Poly(VPyPS)-PW (0.2 g)
EtOH
EtOH
EtOH
EtOH
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
80
2
2
2
2
2
2
2
2
2
2
2
90
87
76
40
70
0
MeCN
2
CH Cl ,
2
H
2
O
trace
trace
68
PhMe
EtOH
EtOH
EtOH
Reflux
60
1
1
1
0
1
2
R. T.
40
40
48
a
Isolated yield.
In order to demonstrate the superiority of Poly(VPyPS)-PW as the catalyst, the contrast tests were conducted.
When H 40, which has the well-known strong acidity arising from the three protons in the cation position,
was used as the catalyst, it presents a conversion of 80% (entry 1 in Table 2). Although H 40 can catalyze
3
PW12O
3
PW12O
the reaction with high yield in water, the reuse of catalyst was not satisfied [27]. Poly(VPyPS) as catalysts hardly
5

produced the product (entry 2 in Table 2). Yet, their analogous combination in the form of Poly(VPyPS)-PW
increased the yield up to 87% in a shorter reaction time (entry 3 in Table 2). In contrast, Poly(VPyPS)-HSO was
used as the catalyst for the reaction, and it gave a low conversion 73% (entry 4 in Table 2). The conversion was
lower than that of H 40, implying that the heteropolyanion in the polymeric hybrid is indispensable for both
the solid nature and the high activity of Poly(VPyPS)-PW. This fact demonstrate that the SO H functional groups
4
3
PW12O
3
in the polymeric cations are responsible for the high yield of Mannich reaction. Morever, there is maybe bulk-type
catalysis mode for Poly(VPyPS)-PW because of the specific secondary structures of heteropolyanion-based
salts[46].
Table 2
Screening of catalysts for the the cyclocondensation reaction
H
NH
2
N
O
H
Poly(VPyPS)-PW
EtOH
+
NH
2
NH
O
O
a
Entry
Catalyst (g)
Time( h)
Yield
1
2
3
4
H
3
PW12
O
40(0.3 g)
2
2
2
2
2
80
Poly(VPyPS)(0.3 g)
trace
87
Poly(VPyPS)-PW (0.2 g)
Poly(VPyPS)-HSO (0.5 g)
4
73
b
5
Poly(VPyPS)-PW (0.2 g)
87
a
b
Isolated yield.
The catalyst after the first run.
Compared with the conventional heating, the cyclocondensation reaction catalyzed by Poly(VPyPS)-PW under
ultrasonic irradiation showed a more effective catalytic activity. As shown Table 3, without the catalyst, the
corresponding imine was formed. However, the cyclocondensation reaction can not take place under ultrasonic
irradiation. The fact imply that the catalyst is prerequisite to the reaction. Under ultrasonic irradiation, in present of
0
.1 g Poly(VPyPS)-PW, the reaction can proceed, which have taken 10 min, and yield was significantly higher
under the conventional reflux. Obviously, ultrasound irradiation could accelerate the cyclocondensation reaction.
The chemical effects of ultrasounds resulted from implosive collapse of the cavitations period of the sound waves.
The bubbles are generated at localized sites in the liquid mixture that contain small amounts of dissolved gases.
The bursting of these bubbles produces high temperature and high pressure which the intermolecular reaction.
When a solid exist in the reaction system, the ultrasonic irradiation has several additional enhancement effects, and
this is especially useful when the solid acts as a catalyst [37, 47].
Table 3
The cyclocondensation reaction of anthranilamide with aldehydes in the presence of different amount of Poly(VPyPS)-PW under
ultrasonic irradiation。
H
NH
2
N
O
H
Poly(VPyPS)-PW, )))
EtOH
+
NH
2
NH
O
O
a
Entry
Catalyst (g)
Time( min.)
Yield
1
2
3
4
H
3
PW12
O
40(0.3 g)
10
10
10
10
83
Poly(VPyPS)(0.3 g)
trace
95
Poly(VPyPS)-PW (0.2 g)
Poly(VPyPS)-HSO (0.5 g)
4
82
6

b
5
Poly(VPyPS)-PW (0.2 g)
10
95
a
b
Isolated yield.
The catalyst after the first run.
Encouraged by this result, in order to build the generality of the reaction, our attention moved to the reactions of
other aldehydes, and the results are summarized in Table 4. As expected, this reaction proceeded smoothly and the
desired products were obtained in good to excellent yields. A series of aldehydes with either electron-donating or
electron-withdrawing groups attaching to aromatic ring were investigated. The substitution groups on the aromatic
ring had no obvious effect on the yield. When aromatic aldehydes were replaced by aromatic heterocyclic
aldehydes, the corresponding products were obtained with high yields as well (entries 12 and 13 Table 2). From
these experiments, it is clearly demonstrated that the synthesis of 2,3-dihydroquinazolin-4(1H)-ones using
Poly(VPyPS)-PW as catalyst under ultrasonic irradiation is indeed an effective method and is undoubtedly
superior to other procedures with respect to reaction time, availability of catalyst, work-up procedure and yields.
Table 4
a
Poly(VPyPS)-PW catalyzed the synthesis of 2,3-dihydroquinazolin-4(1H)-ones compounds under ultrasonic irradiation
b
Entry
R1
R
2
Time(min.)
Product
Yield (%)
Mp (°C)
Reported
c
c
UI
CH
Found
1
2
3
4
5
6
7
8
9
H
H
H
H
H
H
H
H
H
Cl
C6H5
6
6
3a
3b
3c
3d
3e
3f
95
88
90
93
74
89
80
96
94
93
20
219-220
174-175
202-204
184-186
201-203
199-201
191-193
185-187
230-232
217-218
215–216[19]
173–174[27]
202–204[19]
183–184[13]
203–204[13]
197–200[22]
190–192[22]
183–185[14]
231–233[19]
215–216[19]
2,3,4,-(CH3O)3C6H2
4-(Cl)C6H4
trace
15
8
2,4-(CH3O)2C6H3
4-(F)C6H4
6
35
16
6
trace
35
4-(NO2)C6H4
2-(NO2)C6H4
4-(CH3O)C6H4
4-(CH3)C6H4
4-(CH3O)C6H4
6
3g
3h
3i
trace
30
6
8
35
1
0
9
3j
10
1
1
1
2
Cl
H
4-(CH3)C6H4
2-furyl
16
8
3k
3l
83
88
24
241-243
165-167
242–244[19]
164–165[13]
trace
1
3
H
2-thiazolyl
12
3m
90
trace
169-171
-
a
b
c
Reaction condition: benzaldehyde(2 mmol), anthranilamide (2 mmol) and catalyst(0.2g) were irradiation under ultrasonic
Isolated yields.
UI = ultrasonic irradiation; CH = conventional heat
3
.4 Reuse of catalyst Poly(VPyPS)-PW
The recovery and reuse of a catalyst is highly preferable for a greener process. Thus, the recyclability of
Poly(VPyPS)-PW was investigated by using anthranilamide and benzaldehyde as model substrates. The catalyst
was easily separated by filtration after the reaction and washed with ethyl acetate, dried under vacuum and reused
in a subsequent reaction. The yields remained unchanged even after the catalyst had been recycled six times
(Table 5).
Table 5
a
Catalyst recycling of catalyst for the synthesis of 2,3-dihydroquinazolin-4(1H)-ones compounds
b
Entry
Cycle
Fresh
yield(%)
1
2
3
95
94
94
1st recycle
2nd recycle
7

4
5
6
7
3rd recycle
4th recycle
5th recycle
6th recycle
95
94
93
93
a
b
Reaction condition: benzaldehyde(0.2 mmol), anthranilamide (0.2 mmol) and catalyst(0.2g) were irradiation under ultrasonic
Isolated yields.
4
.Conclusions
In conclusion, we developed a poly(4-vinylpyridine) supported acidic ionic liquid catalyst, and used it into the
3
synthesis of 2,3-dihydroquinazolin-4(1H)-ones under ultrasonic irradiation. Owing to the combination of SO H
functional groups, the polymeric framework of IL-cation and the large heteropolyanion, the Mannich reactions can
be conducted effectively with the handling of the catalyst, effective recovering and reusability of the catalyst, use
of inexpensive catalyst with lower loading and simple experimental procedure. Most importantly, the use of
ultrasonic
irradiation
can
obviously
accelerate
the
reaction.
Besides
the
synthesis
of
2
,3-dihydroquinazolin-4(1H)-ones compounds, such an environmentally benign catalyst should find a wider
application in various acid-catalyzed organic transformations, which is in progress.
.
Acknowledgements
This work was financially supported by Key Laboratory of Hexi Corridor Resources Utilization of Gansu
Universities (No. XZ1011), the President’s Funds of Hexi University (No. XZ-2009-9), and the National Natural
Science Foundation of China (No. 21262010).
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2
1
0

Highlights
1
2
3
4
) Poly(VPyPS)-PW hybrid catalyst were firstly synthesized;
) Poly(VPyPS)-PW was combined with polymer features and ionic liquid;
) The catalyst demonstrated high performance in synthesis of quinazolinones under ultrasonic irradiation
) The catalyst reused six times without significant loss of catalytic activity.
11