Rapid and mild synthesis of quinazolinones and chromeno[d]pyrimidinones using nanocrystalline copper(I) iodide under solvent-free conditions

Article abstract of DOI:10.1016/j.cclet.2015.08.014

This paper describes a very simple, efficient synthesis of quinazolinones and chromeno[d]pyrimidinones from the reaction of aryl aldehydes, urea/thiourea and active methylene compounds (dimedone/4-hydroxycoumarin) using nano-sized CuI particles under solvent-free conditions. The highlights of this new method are based on using an effective and recyclable catalyst, affording high yields of products, mild reaction conditions, facile work-up and purification.

Full text of DOI:10.1016/j.cclet.2015.08.014

G Model
CCLET 3421 1–5
Chinese Chemical Letters xxx (2015) xxx–xxx
Contents lists available at ScienceDirect
Chinese Chemical Letters
journal homepage: www.elsevier.com/locate/cclet
1
2
Original article
3
4
5
Rapid and mild synthesis of quinazolinones and
chromeno[d]pyrimidinones using nanocrystalline copper(I)
iodide under solvent-free conditions
*
6
7
Q1 Shahrzad Abdolmohammadi , Samira Karimpour
Department of Chemistry, Faculty of Science, East Tehran Branch, Islamic Azad University, PO Box 33955-163 Tehran, Iran
A R T I C L E I N F O
A B S T R A C T
Article history:
This paper describes a very simple, efficient synthesis of quinazolinones and chromeno[d]pyrimidinones
from the reaction of aryl aldehydes, urea/thiourea and active methylene compounds (dimedone/4-
hydroxycoumarin) using nano-sized CuI particles under solvent-free conditions. The highlights of this
new method are based on using an effective and recyclable catalyst, affording high yields of products,
mild reaction conditions, facile work-up and purification.
Received 25 June 2015
Received in revised form 3 August 2015
Accepted 11 August 2015
Available online xxx
ß 2015 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
Published by Elsevier B.V. All rights reserved.
Keywords:
Chromeno[d]pyrimidinones
Copper(I) iodide nanoparticles
Quinazolinones
Solvent-free conditions
8
9
1. Introduction
Thus, the synthesis of heterocycles with a quinazolinone or 30
chromene framework is of particular importance to chemists and, 31
10
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15
16
17
18
19
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23
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25
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27
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The quinazolinone moiety is found, as alterative in a wide
variety of biologically active compounds which can be used as
hypnotic/sedative drugs for treatment of cancer [1]. Furthermore,
quinazolinone derivatives are of interest because they exhibit a
broad spectrum of biological properties, such as analgesic [2], anti-
inflammatory [3], antimicrobial and anti-tubercular [4,5], anti-HIV
[6], antimalarial and antihistamine [7]. Chromenes are also an
important class of nitrogen containing heterocycles, which possess
a range of diverse pharmacological properties, such as antioxidant
[8,9], anticancer [10–13], antimicrobial [14–17], hypotensive [18],
and local anesthetic [19]. In addition, they have been used as
cognitive enhancers [20,21] in the treatment of neurodegenerative
diseases, including Alzheimer’s disease [22] and schizophrenia
[23].
Recent reports reveal that the utility of nanostructured metal
salts, as efficient heterogeneous catalysts, have emerged as a
powerful synthetic tools for the synthesis of many organic
compounds [24–30]. Copper(I) iodide nanoparticles (CuI NPs) as
a Lewis acid catalyst, has attracted intense interest due to its
unique and improved properties [31–38].
hence, various methods have been developed for the synthesis of 32
these compounds as described in the literature [39–43]. Although, 33
most of these procedures offer several advantages, there are also 34
related disadvantages, such as longer reaction times, unsatisfacto- 35
ry yields, harsh reaction conditions and use of high cost or toxic 36
catalysts. To the best of our knowledge, however, no reports to date 37
have revealed the synthesis of these compounds using a CuI NPs 38
catalyst. With this in mind, the central focus of the present article is 39
to investigate the role of nano-sized CuI particles as an 40
inexpensive, readily prepared, recoverable and high yielding 41
heterogeneous catalyst for the synthesis of quinazolinones (4) 42
and chromeno[d]pyrimidinones (6) via a condensation reaction of 43
aryl aldehydes 1, urea/thiourea 2 and active methylene com- 44
pounds including dimedone (3) or 4-hydroxycoumarin (5) under 45
solvent-free conditions (Scheme 1).
46
2. Experimental
47
48
2.1. Materials and methods
All of the chemical materials used in this work were purchased 49
from Merck or Sigma–Aldrich and used without further purifica- 50
tion. Melting points were determined on an Electrothermal 9100 51
apparatus and are uncorrected. IR spectra were obtained on an ABB 52
FT-IR (FTLA 2000) spectrometer. The 1H NMR spectra were 53
*
Corresponding author.
E-mail addresses: s.abdolmohamadi@yahoo.com, s.abdolmohamadi@iauet.ac.ir
(S. Abdolmohammadi).
http://dx.doi.org/10.1016/j.cclet.2015.08.014
1001-8417/ß 2015 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.
Please cite this article in press as: S. Abdolmohammadi, S. Karimpour, Rapid and mild synthesis of quinazolinones and
chromeno[d]pyrimidinones using nanocrystalline copper(I) iodide under solvent-free conditions, Chin. Chem. Lett. (2015), http://
dx.doi.org/10.1016/j.cclet.2015.08.014

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CCLET 3421 1–5
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S. Abdolmohammadi, S. Karimpour / Chinese Chemical Letters xxx (2015) xxx–xxx
1655, 1619, 1447, 1370. 1H NMR (400 MHz, DMSO-d6):
d
0.78 (s,
80
3H, CH3), 0.83 (s, 3H, CH3), 1.85 (m, 2H, CH2), 2.16 (m, 2H, CH2),
5.33(s, 1H, CH), 7.12 (m, 4H, HAr), 7.51 (s, 1H, NH), 9.29 (s, 1H, NH)
ppm. Anal. Calcd. for C16H17ClN2O2 (304.78): C 63.05, H 5.62, N
9.19; found: C 63.23, H 5.77, N 9.38.
81
82
83
84
7,7-Dimethyl-4-phenyl-2-thioxo-2,3,4,6,7,8-hexahydro-5(1H)-
quinazolinone (4f): Yield 263 mg (92%). White powder. M.p. 281–
283 8C. IR (KBr, cmÀ1): nmax 3280, 3204, 1711, 1620, 1572, 1451,
85
86
87
88
1383. 1H NMR (400 MHz, DMSO-d6):
d
0.90 (s, 3H, CH3), 1.02 (s, 3H,
CH3), 2.21 (m, 2H, CH2), 2.42 (m, 2H, CH2), 5.23 (s, 1H, CH), 7.26 (m,
3H, HAr), 7.33 (m, 2H, HAr), 9.70 (s, 1H, NH), 10.61 (s, 1H, NH) ppm.
Anal. Calcd. for C16H18N2OS (286.39): C 67.10, H 6.33, N 9.78;
found: C 66.91, H 6.41, N 9.56.
89
90
91
92
Scheme 1. Synthesis of quinazolinone and chromeno[d]pyrimidinone derivatives.
7,7-Dimethyl-4-(4-methylphenyl)-2-thioxo-2,3,4,6,7,8-hexa-
hydro-5(1H)-quinazolinone (4h): Yield 273 mg (91%). White
powder. M.p. 279–280 8C. IR (KBr, cmÀ1): nmax 3307, 3184,
93
94
95
96
54
55
56
recorded on a Bruker DRX-400 AVANCE at 400 MHz, using TMS as
internal standard and DMSO-d6 as solvent. Elemental analyses
were carried out using a Heraeus CHN rapid analyzer.
1639, 1565, 1431, 1344. 1H NMR (400 MHz, DMSO-d6):
d
0.91
(s, 3H, CH3), 1.04 (s, 3H, CH3), 2.08 (m, 2H, CH2), 2.20 (s, 2H, CH2),
2.26 (s, 3H, CH3), 5.17 (s, 1H, CH), 7.13 (m, 4H, HAr), 9.63 (s, 1H,
NH), 10.56 (s, 1H, NH) ppm. Anal. Calcd. for C17H20N2OS (300.42): C
67.97, H 6.71, N 9.32; found: C 67.61, H 6.53, N 9.23.
97
98
99
57
2.2. General procedure for preparation of compounds 4a–h and 6a–f
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
A mixture of aryl aldehyde (1 mmol), urea/thiourea (1.2 mmol),
active methylene compound (dimedone/4-hydroxycoumarin)
(1 mmol) and CuI NPs (1.9 mg, 10 mol%) was stirred at 70 8C for
appropriate times. After completion of the reaction, indicated by
TLC, the reaction mixture was diluted with DMF (5 mL) and
centrifuged for five min at 2000–3000 rpm, to separate the catalyst
by filtration which then was washed with EtOH, and dried under
vacuum for several hours. The filtrate was then poured into ice-cold
water (10 mL) to give a solid precipitate, which was filtered, washed
with water and recrystallized from EtOH to generate the pure
product.
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
4-Phenyl-3,4-dihydro-2H-chromeno[4,3-d]pyrimidine-
2,5(1H)-dione (6a): Yield 278 mg (95%). White powder. M.p. 162–
163 8C. IR (KBr, cmÀ1): nmax 3404, 2952, 2677, 2344, 1673, 1439,
1391. 1H NMR (400 MHz, DMSO-d6):
d
6.31 (s, 1H, CH), 7.38 (m, 9H,
HAr), 7.90 (s, 1H, NH), 8.03 (s, 1H, NH) ppm. Anal. Calcd. for
17H12N2O3 (292.29): C 69.86, H 4.14, N 9.58; found: C 69.64, H
C
3.96, N 9.69.
4-(Dimethylaminophenyl)-3,4-dihydro-2H-chromeno[4,3-
d]pyrimidine-2,5(1H)-dione (6c): Yield 322 mg (96%). Brick-red
powder. M.p. 242–244 8C. IR (KBr, cmÀ1): nmax 3412, 3115, 2904,
2716, 2584, 1685, 1606, 1560, 1536, 1441, 1359. 1H NMR (400 MHz,
7,7-Dimethyl-4-phenyl-4,6,7,8-tetrahydro-2,5(1H,3H)-quina-
zolinedione (4a): Yield 254 mg (94%). White powder. M.p. 285–
287 8C. IR (KBr, cmÀ1): nmax 3333, 3254, 2960, 1706, 1678, 1611,
DMSO-d6):d3.17(s, 6H,CH3), 6.50(s, 1H, CH), 7.30(m, 8H, HAr),7.84
(s, 1H, NH), 8.01 (s, 1H, NH) ppm. Anal. Calcd. for C19H17N3O3
(335.36): C 68.05, H 5.11, N 12.53; found: C 68.21, H 5.24, N 12.60.
4-(4-Methoxyphenyl)-2-thioxo-1,2,3,4-tetrahydro-5H-chro-
meno[4,3-d]pyrimidine-5-one (6f): Yield 315 mg (93%). White
powder. M.p. 265–267 8C. IR (KBr, cmÀ1): nmax 3389, 3102, 1953,
1705, 1622, 1605, 1578, 1491, 1450, 1326. 1H NMR (400 MHz,
DMSO-d6): d 3.77 (s, 3H, OCH3), 6.44 (s, 1H, CH), 6.94 (m, 8H, HAr),
8.04 (s, 1H, NH), 8.07 (s, 1H, NH) ppm. Anal. Calcd. for C18H14N2O3S
(338.38): C 63.89, H 4.17, N 8.28; found: C 63.71, H 4.07, N 8.11.
1474, 1364. 1H NMR (400 MHz, DMSO-d6):
d 0.98 (s, 3H, CH3), 1.09
(s, 3H, CH3), 2.21 (q, 2H, J = 16.0 Hz, CH2), 2.38 (q, 2H, J = 16.7 Hz,
CH2), 5.29 (d, 1H, J = 2.8 Hz, CH), 7.27 (m, 5H, HAr), 7.46 (s, 1H, NH),
9.35 (s, 1H, NH) ppm. Anal. Calcd. for C16H18N2O2 (270.33): C 71.09,
H 6.71, N 10.36; found: C 70.86, H 6.61, N 10.58.
7,7-Dimethyl-4-(2-chlorophenyl)-4,6,7,8-tetrahydro-
2,5(1H,3H)-quinazolinedione (4b): Yield 283 mg (93%). White
powder. M.p. 269–270 8C. IR (KBr, cmÀ1): nmax 3427, 3211, 1680,
Fig. 1. XRD pattern of the synthesized CuI NPs.
Please cite this article in press as: S. Abdolmohammadi, S. Karimpour, Rapid and mild synthesis of quinazolinones and
chromeno[d]pyrimidinones using nanocrystalline copper(I) iodide under solvent-free conditions, Chin. Chem. Lett. (2015), http://
dx.doi.org/10.1016/j.cclet.2015.08.014

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S. Abdolmohammadi, S. Karimpour / Chinese Chemical Letters xxx (2015) xxx–xxx
3
Fig. 3. TEM image of the synthesized CuI NPs.
Fig. 2. SEM image of the synthesized CuI NPs.
Table 1
Synthesis of 4b by the reaction of 2-chlorobenzaldehyde, urea and dimedone under
different conditions.
122
3. Results and discussion
Entry Mole ratio of the
reactants
Catalyst
(mol%)
Solvent Temp. Time Yield
(8C)
(min) (%)a
123
124
125
126
127
128
129
In continuation of our research program towards highly
expedient methodologies for the synthesis of heterocyclic com-
pounds using nanostructured catalysts, we have found that CuI
nanoparticles (CuI NPs) are suitable for the preparation of
quinazolinones 4(a–h) and chromeno[d]pyrimidinones 6(a–f) by
the three-component coupling reaction of aryl aldehydes, urea/
thiourea and active methylene compounds (dimedone/4-hydro-
(2-
chlorobenzaldehyde:
urea:dimedone)
1
1:1.2:1
1:1.2:1
1:1.2:1
1:1.2:1
1:1.2:1
1:1.2:1
1:1.2:1
1:1.2:1
1:1.2:1
1:1.2:1
5:6:5
No catalyst
Neat
Neat
100
80
90
60
60
60
90
80
90
90
60
60
60
43
68
93
93
69
73
70
79
94
94
95
2
CuI NPs (5%)
3
CuI NPs (10%) Neat
CuI NPs (15%) Neat
CuI NPs (10%) CH2Cl2
CuI NPs (10%) DMF
CuI NPs (10%) H2O
CuI NPs (10%) Neat
CuI NPs (10%) Neat
CuI NPs (10%) Neat
CuI NPs (10%) Neat
70
4
70
5
70
130 Q2 xycoumarin) at 70 8C under solvent-free conditions (Fig. 1).
6
100
90
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
In a preliminary study, CuI NPs were prepared according to the
published procedure of Salavati-Niasari et al. [44]. The crystalline
structure and purity of the CuI NPs was confirmed from XRD
analyses. The XRD results confirmed the presence of CuI NPs with
high crystallinity and a cubic structure with space groupings of F-
7
8
60
9
80
10
11
100
70
a
Isolated yield.
˚
43m and cell constants 6.0545 A (JCPDS 82-2111 of CuI for
confirmation). The SEM image of CuI NPs is presented in Fig. 2
which shows triangular shapes with a size range of 30–40 nm of
nanoparticles. The TEM image of CuI NPs is also shown in Fig. 3.
We then studied on the optimization of the reaction conditions
using a model reaction of 2-chlorobenzaldehyde (1b), urea (2b)
and dimedone (3) to afford the corresponding product (4b) under
various reaction conditions. The results are summarized in Table 1.
First, we checked the efficiency of CuI NPs as a heterogeneous
catalyst using different amounts of CuI NPs. The results in Table 1
show that using just 10 mol% of catalyst affected the efficiency of the
reaction (Table 1, entries 1–4). In investigating the effect of the 147
reaction media, several solvents were also examined. Thus, the best 148
yield of product was obtained under solvent-free conditions 149
(Table 1, entries 3 and 5–7). To determine the optimized reaction 150
temperature, the model reaction was carried out at different 151
temperatures. It was observed that the optimal temperature of 70 8C 152
was best and higher temperatures up to 80 and 100 8C did not 153
improve the yield of product (Table 1, entries 3 and 8–10). During 154
Table 2
CuI NPs catalyzed syntheses of quinazolinones 4(a–h) and chromeno[d]pyrimidinones 6(a–f) under solvent-free conditions.
Active methylene
compounds
Product
Ar
X
Time (min)
Yield (%)a
MP (8C)
Obs.
Lit.
3
3
3
3
3
3
3
3
5
5
5
5
5
5
4a
4b
4c
4d
4e
4f
C6H5
O
O
O
O
O
S
50
60
50
45
45
60
60
50
45
60
50
50
60
45
94
93
90
90
93
92
93
91
95
92
96
92
90
93
285–287
269–270
274–276
298–300
300–301
281–283
271–273
279–280
162–163
205–206
242–244
187–189
233–234
265–267
288–290 [42]
271–273 [42]
272–274 [42]
300–302 [42]
297–299 [42]
280–282 [42]
268–270 [42]
280–282 [42]
160–162 [43]
205–207 [43]
239–241 [43]
188–190 [43]
232–234 [43]
264–266 [43]
2-ClC6H4
4-MeOC6H4
4-MeC6H4
3-NO2C6H4
C6H5
4g
4h
6a
6b
6c
6d
6e
6f
4-MeOC6H4
4-MeC6H4
C6H5
S
S
O
O
O
S
2-ClC6H4
4-N(CH3)2C6H4
C6H5
4-N(CH3)2C6H4
4-MeOC6H4
S
S
a
Isolated yield.
Please cite this article in press as: S. Abdolmohammadi, S. Karimpour, Rapid and mild synthesis of quinazolinones and
chromeno[d]pyrimidinones using nanocrystalline copper(I) iodide under solvent-free conditions, Chin. Chem. Lett. (2015), http://
dx.doi.org/10.1016/j.cclet.2015.08.014

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S. Abdolmohammadi, S. Karimpour / Chinese Chemical Letters xxx (2015) xxx–xxx
Scheme 2. Proposed mechanism for the reaction of aryl aldehyde, urea/thiourea and dimedone as active methylene compound, catalyzed by CuI NPs.
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
optimization, wethenexplored theroleofmoleratioofthereactants
and determined, that the present method is effective for large-scale
synthesis as well as routine scale (Table 1, entries 3 and 11).
To determine the utility of this new procedure, we examined
some substituted benzaldehydes for the reaction with urea/
thiourea and active methylene compounds, including dimedone or
4-hydroxycoumarin, to obtain desired products under optimized
conditions (Table 2). The isolated compounds 4(a–h) and 6(a–f)
were characterized by IR and 1H NMR spectroscopic data and also
by elemental analyses. The analytical, spectroscopic and physical
data are in good agreement with those described in the literature.
Selected spectroscopic data are reported in Section 2.2.
A plausible mechanism for the formation of product 4 is given in
Scheme 2. It is feasible that CuI NPs participates in two following
catalytic cycles. The initial event is the formation of copper
oxonium salt 7 which then undergoes a Knoevenagel condensation
with dimedone 3, to generate alkene 9 via intermediate 8. The
urea/thiourea 2 then adds to alkene 9 to produce the Michael
adduct 10. Further cyclization of 10 gives product 4, after
dehydration. The formation of product 6 is likely to occur via a
tandem Knoevenagel–Michael condensation as that was explained
in Scheme 2, for the formation of product 4.
175
176
177
178
179
180
181
182
183
Moreover, we evaluated separation, isolation and recycling of
the CuI NPs catalyst, which was successfully recycled as mentioned
in Section 2.2 and reused several times in the model reaction with
no significant loss of activity (Fig. 4). From the XRD patterns of the
second and third recycled catalyst reuse, the character of CuI in the
cubic phase is not changed and could be compared to the original
one (Fig. 5).
Fig. 5. XRD patterns of (a) original catalyst, (b) 2nd recycled catalyst use, and (c) 3rd
Fig. 4. Reuse of CuI NPs for the synthesis of 4b.
recycled catalyst use.
Please cite this article in press as: S. Abdolmohammadi, S. Karimpour, Rapid and mild synthesis of quinazolinones and
chromeno[d]pyrimidinones using nanocrystalline copper(I) iodide under solvent-free conditions, Chin. Chem. Lett. (2015), http://
dx.doi.org/10.1016/j.cclet.2015.08.014

G Model
CCLET 3421 1–5
S. Abdolmohammadi, S. Karimpour / Chinese Chemical Letters xxx (2015) xxx–xxx
5
[18] V.K. Tandon, M. Vaish, S. Jain, D.S. Bhakuni, R.C. Srimal, Synthesis, carbon-13 NMR 249
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4. Conclusion
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In summary, we have developed an efficient and less wasteful
manufacturing method for the synthesis of some of quinazolinone
and chromeno[d]pyrimidinone derivatives from aryl aldehydes,
urea/thiourea and active methylene compounds, including dime-
done or 4-hydroxycoumarin, using CuI NPs as reusable and
inexpensive heterogeneous catalysts under solvent-free condi-
tions. This new catalytic method has several advantages including
high yields of products, short reaction time, simple operation and
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Acknowledgment
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Shahrzad Abdolmohammadi is pleased to acknowledge the
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coupling of diaryl diselenide with aryl halides under ligand-free conditions, Org. 269
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Lett. 11 (2009) 951–953.
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N-alkylation of amines with alcohols, Der Pharma Chemica 3 (2011) 180–189.
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Islamic Azad University.
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Please cite this article in press as: S. Abdolmohammadi, S. Karimpour, Rapid and mild synthesis of quinazolinones and
chromeno[d]pyrimidinones using nanocrystalline copper(I) iodide under solvent-free conditions, Chin. Chem. Lett. (2015), http://
dx.doi.org/10.1016/j.cclet.2015.08.014