Efficient synthesis of pyrano[2,3-d]pyrimidinone and pyrido[2,3-d]pyrimidine derivatives in presence of novel basic ionic liquid catalyst

Article abstract of DOI:10.1016/S1872-2067(17)62827-4

A basic ionic liquid, namely 1,1′-(butane-1,4-diyl)bis(1,4-diazabicyclo [2.2.2]octan-1-ium) hydroxide, was prepared and characterized using Fourier-transform infrared spectroscopy, ¹H nuclear magnetic resonance spectroscopy, and pH measurements. The ionic liquid was used for efficient promotion of the synthesis of pyrano[2,3-d]pyrimidinone and pyrido[2,3-d]pyrimidine derivatives at room temperature under grinding conditions. A simple procedure, short reaction time, high yields, non-column chromatographic separation, commercial availability of the starting materials, and recyclability of the catalyst are attractive features of this process.

Full text of DOI:10.1016/S1872-2067(17)62827-4

Chinese Journal of Catalysis 38 (2017) 1245–1251
a v a i l a b l e a t w w w . s c i e n c e d i r e c t . c o m
j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / c h n j c
Article
Efficient synthesis of pyrano[2,3‐d]pyrimidinone and
pyrido[2,3‐d]pyrimidine derivatives in presence of
novel basic ionic liquid catalyst
Omid Goli Jolodar, Farhad Shirini *, Mohadeseh Seddighi
Department of Chemistry, Faculty of Sciences, University of Guilan, Rasht 41335, Iran
A R T I C L E I N F O
A B S T R A C T
Article history:
A basic ionic liquid, namely 1,1'‐(butane‐1,4‐diyl)bis(1,4‐diazabicyclo [2.2.2]octan‐1‐ium) hydrox‐
ide, was prepared and characterized using Fourier‐transform infrared spectroscopy, 1H nuclear
magnetic resonance spectroscopy, and pH measurements. The ionic liquid was used for efficient
promotion of the synthesis of pyrano[2,3‐d]pyrimidinone and pyrido[2,3‐d]pyrimidine derivatives
at room temperature under grinding conditions. A simple procedure, short reaction time, high
yields, non‐column chromatographic separation, commercial availability of the starting materials,
and recyclability of the catalyst are attractive features of this process.
Received 21 January 2017
Accepted 15 March 2017
Published 5 July 2017
Keywords:
Basic catalyst
Multicomponent reaction
Pyrimidine derivative
Grinding
© 2017, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.
Published by Elsevier B.V. All rights reserved.
1. Introduction
larial, antibacterial, antihypertensive, anti‐inflammatory,
hepatoprotective, cardiotonic, vasodilator, bronchiodilator,
Highly efficient, selective, and cost‐effective catalytic sys‐
tems are the foundation of synthetic chemistry. Ionic liquids
(ILs) have emerged as eco‐friendly catalysts or cata‐
lysts/solvents in various fields of chemistry because of their
distinctive properties such as high thermal stability, negligible
vapor pressure, high loading capacity, and easy recycling [1].
Basic ILs have attracted great interest because, compared
with inorganic bases such as KOH and NaOH, they have good
catalytic efficiencies, are non‐corrosive, recyclable, and produce
no waste [2]. This type of IL has been successfully used in the
industrial production of drugs, fragrances, and chemical inter‐
mediates, and to accelerate various reactions such as Michael
additions, Heck reactions, and Markovnikov additions [3,4].
Pyrano[2,3‐d]pyrimidinones (A) and pyrido[2,3‐d]pyrimid‐
ines (B) (Fig. 1) are two classes of nitrogen‐containing hetero‐
cyclic compounds that show considerable pharmaceutical and
biological activities, including anticancer, antitumor, antima‐
antifolate, and antiallergic activities [5–17]. They are also used
in the preparation of dyes and pigments [18] and flavoring
agents [19], and in luminescence chemistry [20].
The most simple and straightforward protocols for the
preparation of pyrano[2,3‐d]pyrimidinones and pyri‐
do[2,3‐d]pyrimidines are based on three‐component reactions
of substituted aldehydes, malononitrile, and barbituric acid or
6‐amino‐1,3‐dimethyluracil. Various conditions for these reac‐
tions have been reported [21–31]. Although these procedures
Fig. 1. The structure of pyrano[2,3‐d]pyrimidinones (A) and pyri‐
do[2,3‐d]pyrimidines (B).
* Corresponding author. E‐mail: shirini@guilan.ac.ir
DOI: 10.1016/S1872‐2067(17)62827‐4| http://www.sciencedirect.com/science/journal/18722067 | Chin. J. Catal., Vol. 38, No. 7, July 2017

1246
Omid Goli Jolodar et al. / Chinese Journal of Catalysis 38 (2017) 1245–1251
are better than other methods, they have disadvantages such as
long reaction time, harsh reaction conditions, the need for ex‐
cess amounts of reagents, the use of organic solvents and toxic
reagents, and non‐recoverability of the catalyst. The develop‐
ment of simple, efficient, and mild procedures using easily sep‐
arable and reusable solid catalysts to overcome these problems
is therefore needed.
2. Experimental
Scheme 1. Synthesis of [C4(DABCO)2]·2OH.
2.1. General
Chemicals were purchased from Fluka, Merck, and Aldrich.
The products were characterized by comparison of their melt‐
ing points, and Fourier‐transform infrared (FT‐IR) and nuclear
magnetic resonance (NMR) spectra with those of authentic
samples and those reported in the literature. All yields refer to
isolated products. Thin‐layer chromatography (TLC; Polygram
SILG/UV 254 plates) was used to determine the substrate pu‐
rity and monitor the reaction. FT‐IR spectra were recorded
with a VERTEX 70 (Brucker, Germany) instrument using KBr
disks. 1H NMR and 13C NMR spectra were recorded using a 400
MHz Bruker Avance instrument, with tetramethylsilane as an
internal standard. Melting points were determined using an
Electrothermal 9100 instrument and are uncorrected. Mass
spectrometry (MS) was performed using an Agilent Technology
(HP) instrument at 70 eV.
2.4. Catalyst characterization
2.4.1. FT‐IR analysis
The FT‐IR spectra of DABCO and [C4(DABCO)2]·2OH are
shown in Fig. 2. The DABCO spectrum shows bands from vari‐
ous stretching and bending vibrations. These bands are of low‐
er intensity in the spectrum of [C4(DABCO)2]·2OH, or are ab‐
sent. The strong and broad band between 2700 and 3750 cm−1
(centered at 3424 cm−1) in the spectrum of [C4(DABCO)2]·2OH
can be attributed to the hydroxide stretching mode. The strong
peak at 1407 cm−1 and the small shoulder peak at 702 cm−1 are
assigned to the scissoring and rocking vibrational modes, re‐
spectively, of the CH2 group.
2.4.2. 1H NMR analysis
1
The HNMR spectrum of [C4(DABCO)2]·2OH is show in Fig.
2.2. General procedure for synthesis of 1,1'‐(butane‐1,4‐diyl)bis
(1,4‐diazabicyclo[2.2.2]octan‐1‐ium) chloride ([C4(DABCO)2]·2Cl)
3. The broad multiple peak at 1.7 ppm can be attributed to
chain hydrogen atoms (Ha). The triplet peaks at 3.03 and 3.33
ppm are related to the cyclic hydrogens Hd and Hc, respectively.
The peak at 3.37 ppm, which can be assigned to Hc cyclic hy‐
drogens, confirms that [C4(DABCO)2]·2OH was synthesized.
1,4‐Dichlorobutane (0.547 mL, 5.0 mmol) was added to
DABCO (1.121 g, 10.0 mmol) and the mixture was stirred for 4
h at 80 °C. After completion of the reaction, the solid product
was washed with diethyl ether and dried under vacuum.
[C4(DABCO)2]·2Cl was obtained as a white solid in 98.7% yield
(1.39 g).
(1)
2.3. General procedure for synthesis of 1,1'‐(butane‐1,4‐diyl)bis
(1,4‐diazabicyclo[2.2.2]octan‐1‐ium) hydroxide
([C4(DABCO)2]·2OH)
The amount of chloride in [C4(DABCO)2]·2Cl was deter‐
mined by potentiometric titration to calculate the amount of
KOH needed for complete ion exchange. For this purpose, 10
mL of [C4(DABCO)2]·2Cl in water (0.05 mol/L) was titrated
with AgNO3 (0.55 mol/L); the end‐point occurred after con‐
sumption of 20 mL of AgNO3. This indicates that
[C4(DABCO)2]·2Cl contains 2 equiv of Cl¯ per mole.
(2)
In the next step, solid KOH (0.561 g, 10 mmol) was added to
a solution of [C4(DABCO)2]·2Cl (1.44 g, 5 mmol) in dry metha‐
nol and the mixture was stirred at room temperature (r.t.) for 3
h. The produced solid (KCl) was removed by filtration, and the
filtrate was evaporated under reduced pressure. The obtained
viscous liquid was washed with ethyl acetate (3  10 mL) and
dried to give the pure IL, i.e., [C4(DABCO)2]·2OH (1.35 g,
96.42%) (Scheme 1).
ρ (CH2)
δs (CH2)
ν (OH‒)
3500
3000
2500
2000
1500
1000
500
Wavenumber (cm‒1
)
Fig. 2. FT‐IR spectra of DABCO (1) and [C4(DABCO)2]·2OH (2).

Omid Goli Jolodar et al. / Chinese Journal of Catalysis 38 (2017) 1245–1251
1247
Fig. 3. 1H NMR spectrum of [C4(DABCO)2]·2OH.
2.4.3. Titration curve for [C4(DABCO)2]·2OH with HCl
2.4.4. Leaching test
The basicity of [C4(DABCO)2]·2OH was determined by ac‐
id‐base titration. An aqueous solution of the IL (0.05 mol/L, 10
mL) was titrated with a standard solution of HCl (0.1 mol/L)
using a calibrated glass electrode pH meter at 25 °C. Fig. 4
shows that 20 mL of HCl were needed to neutralize all the basic
groups in [C4(DABCO)2]·2OH. According to equation (1), 5 mL
of HCl are needed to neutralize each basic group, therefore it
can be concluded that this IL has four basic groups. Neutraliza‐
tion occurred in two stages, which indicates that
[C4(DABCO)2]·2OH has two types of basic group. These results
confirm the structure of the prepared reagent.
The probability of hydroxide groups leaching from the
[C4(DABCO)2]·2OH framework was determined using an in situ
filtration technique. [C4(DABCO)2]·2OH (50 mg) was stirred in
dichloromethane (10 mL) for 24 h at room temperature. The
[C4(DABCO)2]·2OH was separated by filtration, and the filtrate
was transferred to a 50 mL round‐bottomed flask and evapo‐
rated to dryness. After drying, the pH values of fresh and tested
[C4(DABCO)2]·2OH were determined using pH‐indicator strips.
The images of the pH‐indicator strips show that no leaching of
the basic hydroxyl groups occurred (Fig. 5).
M
(acid) × V(acid) = M(base) × V(base)
0.05 (mol/L) × 10 (mL) = 0.10 (mol/L) × V(acid) (1)
(acid) = 5 mL
2.5. General procedure for synthesis of 2‐amino‐3‐cyano‐4H‐
pyran derivatives
V
A mixture of an aldehyde (1 mmol), malononitrile (1 mmol),
barbituric acid or 6‐amino‐1,3‐dimethyluracil (1 mmol), and
[C4(DABCO)2]·2OH (2 mol%) was prepared. The mixture was
ground for 5–11 min at room temperature using a mortar and
14
12
10
8
0
-0.2
-0.4
-0.6
-0.8
-1
Tested [C4(DABCO)2]·2OH
Fresh [C4(DABCO)2]·2OH
6
4
-1.2
-1.4
-1.6
2
Titration
First derivative
0
0
5
10
15
20
25
30
Volume of HCl in mL
Fig. 5. Images of pH‐indicator strips for fresh and tested
[C4(DABCO)2]·2OH.
Fig. 4. Titration curve and its first derivative for IL with HCl (0.1
mol/L).

1248
Omid Goli Jolodar et al. / Chinese Journal of Catalysis 38 (2017) 1245–1251
(a)
(b)
(c)
(d)
(e)
(f)
Fig. 6. Reaction process (a‒f) using grinding method.
pestle; a solid mass was obtained (Fig. 6). After completion of
the reaction (monitored using TLC), water (3 mL) was added to
the mortar, and the mixture was filtered to separate the crude
product. The product was purified by recrystallization from
ethanol.
The spectral data of new compounds are as follows.
7‐Amino‐2,4‐dioxo‐5‐(o‐tolyl)‐1,3,4,5‐tetrahydro‐2H‐pyrano
[2,3‐d]pyrimidine‐6‐carbonitrile (Table 1, entry 5): m.p. =
223–225 C; FT‐IR (KBr, cm−1): 3302, 3070, 2962, 2223, 1698,
1606, 1481, 1377, 1275, 1212, 1065; MS: m/z = 297 (M+ + 1);
1H NMR (DMSO‐d6, 400 MHz, ppm): δ = 2.45 (s, 3H, CH3), 4.52
(s, 1H, CH), 7.10–7.16 (m, 6H, ArH and NH2), 11.059 (s, 1H, NH),
12.080 (s, 1H, NH).
7'‐Amino‐2,2',4'‐trioxo‐1',2',3',4'‐tetrahydrospiro[indoline‐
3,5'‐pyrano[2,3‐d]pyrimidine]‐6'‐carbonitrile (Table 1, entry
14): m.p. = 243–245 °C; FT‐IR (neat, cm−1): 3352, 3303, 3140,
2202, 1723, 1672, 1531, 1389, 1333, 1108, 995, 635; MS: m/z =
323 (M+); 1H NMR (DMSO‐d6, 400 MHz, ppm): δ = 6.8 (d, J = 7.6
Hz, 1H), 6.9 (1H, td, J1 = 7.6 Hz, J2 = 0.8 Hz), 7.2 (2H, m), 7.4 (2H,
s, NH2), 10.5 (1H, s, NH), 11.145 (1H, s, NH), 12.3 (1H, s, NH);
13C NMR (DMSO‐d6, 100 MHz, ppm): δ = 58, 87, 109, 117, 122,
124, 128, 133, 142, 149, 153, 158, 161, 178.
Table 1
Preparation of pyrano[2,3‐d]pyrimidinone derivatives using
7‐Amino‐2,4‐dioxo‐5‐(pyridin‐4‐yl)‐1,3,4,5‐tetrahydro‐2H‐
pyrano[2,3‐d]pyrimidine‐6‐carbonitrile (Table 1, entry 15):
m.p. = 211–212 °C; FT‐IR (neat, cm−1) 3418, 3316, 3179, 2958,
2883, 2187, 1683, 1599, 1369, 1214, 1146, 1040; MS: m/z =
[C4(DABCO)2]·2OH as catalyst.
283 (M+); H NMR (DMSO‐d6, 500 MHz, ppm): δ = 4.38 (a, 1H,
1
CH), 7.28 (2H, s, NH2), 7.46–7.49 (1H, dd, ArH), 7.82–7.85 (1H,
dd, ArH), 8.5–8.52 (1H, dd, ArH), 8.55–8.58 (1H, dd, ArH), 9.38
(1H, s, NH), 11.12 (1H, s, NH); 13C NMR (DMSO‐d6, 100 MHz,
ppm): δ = 26.02, 33.92, 57.83, 82.83, 87.6, 114.80, 115.26,
119.48, 124.93, 138.06, 138.99, 141.03, 146.68, 146.83, 150.09,
153.16, 158.31, 163.05, 164.58.
7‐Amino‐5‐(4‐cyanophenyl)‐1,3‐dimethyl‐2,4‐dioxo‐1,2,3,4‐
tetrahydropyrido[2,3‐d]pyrimidine‐6‐carbonitrile (Table 2,
entry 9): m.p. > 300 °C; FT‐IR (KBr, cm−1): 3469, 3319, 3217,
2212, 1708, 1649, 1622, 1554, 1508, 1276, 1226, 973, 850,
806, 752; MS: m/z = 332 (M+ + 1); 1H NMR (DMSO‐d6, 500 MHz,
ppm): δ = 3.09 (s, 3H, CH3), 3.53 (s, 3H, CH3), 7.28–7.31 (d, 2H),
7.36 (s, 2H, NH2), 7.44–7.45 (d, 2H); 13C NMR (DMSO‐d6, 100
MHz, ppm): δ = 24.56, 28.21, 28.31, 30.12, 34.85, 35.43, 43.05,
88.96, 99.11, 114.64, 115.76, 127.64, 128.01, 128.19, 128.73,
129.20, 134.99, 137.22, 151.36, 154.10, 158.91, 159.39, 160.75,
166.81.
Time Yielda
m.p. (°C)
Entry
Aldehyde
(min) (%)
Found
Reported
1
2
3
4
5
6
7
8
C6H5CHO
2‐ClC6H4CHO
2‐NO2C6H4CHO
2‐OHC6H4CHO
2‐CH3C6H4CHO
3‐ClC6H4CHO
3‐NO2C6H4CHO
4‐ClC6H4CHO
4‐BrC6H4CHO
4‐OCH3C6H4CHO
4‐NO2C6H4CHO
4‐CH3C6H4CHO
4‐NMe2C6H4CHO
Isatin
5
6
4
7
6
6
5
5
5
4
6
6
10
4
92
94
95
95
94
90
95
94
94
96
93
85
92
95
215–217 215–217[30]
211–212 211–212[30]
253–256 253–256[30]
160–162 160–162[30]
223–225
—
240–241 240–241 [30]
267–269 267–269 [30]
245–247 245–247 [30]
231–233 231–233 [30]
280–281 280–281 [30]
236–237 237–238 [30]
9
10
11
12
13
14
225–227
225 [30]
231–233 230–232 [30]
243–245
211–212
—
—
Pyridine‐4‐carbal‐
dehyde
15
7
94
a Isolated yields.

Omid Goli Jolodar et al. / Chinese Journal of Catalysis 38 (2017) 1245–1251
1249
by
Table 2
Preparation
[C4(DABCO)2]·2OH as catalyst.
Table 3
of
pyrido[2,3‐d]pyrimidine
derivatives
using
Optimization
of
conditions
Solvent
for
reactions
catalyzed
Time
(min)
60
60
60
60
60
5
[C4(DABCO)2]·2OHa.
Catalyst
Entry
Temperature
Yieldb
(mol%)
(°C)
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
(%)
Trace
Trace
Trace
70
80
94
95
85
1
2
3
4
5
7
8
9
—
—
—
10
10
10
15
5
EtOH
H2O
Grinding
EtOH
Time Yielda
(min) (%)
m.p. (°C)
Reported
H2O
Entry
Aldehyde
Found
Grinding
Grinding
Grinding
1
2
3
4
5
6
7
8
9
10
C6H5CHO
2‐ClC6H4CHO
3‐ClC6H4CHO
4‐ClC6H4CHO
3‐NO2C6H4CHO
4‐NO2C6H4CHO
3‐BrC6H4CHO
4‐FC6H4CHO
8
11
8
7
7
8
8
10
10
8
92
93
92
94
93
95
92
91
93
91
>300
>300
>300
>300
>300
>300
>300
>300
>300
>300
>300 [31]
>300 [31]
>300 [31]
>300 [31]
>300 [31]
>300 [31]
>300 [31]
>300 [31]
—
5
25
a Reaction conditions: 4‐chlorobenzaldehyde (1 mmol), barbituric acid
(1 mmol), malononitrile (1 mmol), in the presence of [C4(DABCO)2]·2OH
as the catalyst.
b Isolated yields.
products were obtained in high isolated yields in short reaction
times (Table 1, entries 1–13). The heterocyclic aldehydes isatin
and pyridine‐4‐carbaldehyde were also used under these con‐
ditions, and the desired products were obtained in high yields
(Table 1, entries 14 and 15).
Next, [C4(DABCO)2]·2OH was used to promote the conden‐
sation of aldehydes, malononitrile, and 6‐amino‐1,3‐dimethy‐
luracil to give pyrido[2,3‐d]pyrimidines. The reaction condi‐
tions were optimized using the reaction between
4‐CNC6H4CHO
2‐Naphthaldehyde
—
a Isolated yields.
7‐Amino‐1,3‐dimethyl‐5‐(naphthalen‐2‐yl)‐2,4‐dioxo‐1,2,3,
4‐tetrahydropyrido[2,3‐d]pyrimidine‐6‐carbonitrile (Table 2,
entry 10): m.p. >300 °C; FT‐IR (KBr, cm−1): 3431, 3047, 3229,
2908, 2202, 1658, 1621, 1575, 1372, 1264, 741; MS: m/z = 357
(M+); 1H NMR (DMSO‐d6, 500 MHz, ppm): δ = 3.07 (s, 3H, CH3),
3.55 (s, 3H, CH3), 7.35–7.37 (dd, 2H), 7.57–7.63 (m, 2H), 7.81 (s,
1H), 7.92–8.01 (m, 3H); 13C NMR (DMSO‐d6, 100 MHz, ppm): δ =
19.05, 28.16, 30.14, 56.51, 89.11, 99.30, 115.95, 126.29, 126.33,
126.78, 126.98, 127.57, 128.11, 128.54, 132.90, 133.10, 135.53,
151.39, 154.16, 159.01, 159.70, 160.79.
4‐chlorobenzaldehyde,
malononitrile,
and
6‐amino‐
1,3‐dimethyluracil as a model reaction. The best results were
obtained by grinding 1 mmol of aldehyde, 1 mmol of malono‐
nitrile, 1 mmol of 6‐amino‐1,3‐dimethyluracil, and 10 mol%
[C4(DABCO)2]·2OH at room temperature. Under the optimal
conditions, various aromatic aldehydes containing elec‐
tron‐releasing and electron‐withdrawing substituents on the
aromatic ring gave the corresponding products in high yields in
short reaction time (Table 2).
We compared the results obtained using our newly devel‐
oped method for the [C4(DABCO)2]·2OH‐catalyzed synthesis of
7‐amino‐5‐(4‐chlorophenyl)‐2,4‐dioxo‐1,3,4,5‐tetrahydro‐2H‐p
yrano[2,3‐d]pyrimidine‐6‐carbonitrile (Table 1, entry 8) and
7‐amino‐5‐(4‐nitrophenyl)‐2,4‐dioxo‐1,3,4,5‐tetrahydro‐2H‐py
rano[2,3‐d]pyrimidine‐6‐carbonitrile (Table 1, entry 11) with
the results reported in the literature for other synthetic meth‐
ods (Table 4). The data in Table 4 show that this method avoids
some of the difficulties associated with other procedures such
as long reaction time, low yields, harsh conditions for catalyst
preparation, e.g., IR or microwave irradiation, and high catalyst
loadings.
3. Results and discussion
The structure of [C4(DABCO)2]·2OH suggests that this rea‐
gent has good potential as a basic catalyst for reactions that are
accelerated by this type of catalyst. We therefore investigated
the use of this reagent for promotion of the synthesis of pyra‐
no[2,3‐d]pyrimidinone and pyrido[2,3‐d]pyrimidine deriva‐
tives.
First, we optimized the reaction conditions in the synthesis
of pyrano[2,3‐d]pyrimidinone derivatives by performing the
condensation of 4‐chlorobenzaldehyde, barbituric acid, and
malononitrile in the absence or presence of [C4(DABCO)2]·2OH
under various conditions (Table 3). The best results were ob‐
tained using
a grinding method with 10 mol% of
[C4(DABCO)2]·2OH at room temperature under solvent‐free
conditions.
A
proposed mechanism for the synthesis of pyra‐
After optimization of the reaction conditions, the effective‐
ness and suitability of this method were investigated by per‐
forming the reaction using a variety of simple and readily
available substrates under the optimal conditions.
For this purpose, various aromatic aldehydes containing
electron‐withdrawing and electron‐donating groups, i.e., Cl, Br,
CH3, OCH3, and NO2, in the ortho, meta, and para positions of
the benzene ring were reacted with barbituric acid and malo‐
nonitrile under the optimal conditions. The corresponding
no[2,3‐d]pyrimidinone and pyrido[2,3‐d]pyrimidine deriva‐
tives is shown in Scheme 2. In this procedure,
[C4(DABCO)2]·2OH effectively catalyzes the formation of olefin
(V), which is readily prepared by Knoevenagel condensation of
an aldehyde and active methylene nitrile (I), via intermediate
(IV). Barbituric acid or 6‐amino‐1,3‐dimethyluracil then reacts
with V to give VII or VII', followed by intermolecular cyclization
to VIII or VIIIʹ. Finally, the products are formed by tautomeriza‐
tion.

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Omid Goli Jolodar et al. / Chinese Journal of Catalysis 38 (2017) 1245–1251
Table 4
Comparison of results obtained for synthesis of selected compounds in presence of [C4(DABCO)2]·2OH with those obtained using other catalysts.
Product
Catalyst (mol%)
Zn[(L)proline]2 (17)
[BMIm]BF4 (1.5 g)
DABCO`(10)
SBA‐Pr‐SO3H (0.02 g)
KBr (100)
Reaction condition
EtOH / reflux
90 °C
Ethanol‐H2O (1:1) / r.t.
Neat / 140 °C
Electrolysis
Time (min)
Yielda (%)
90
Ref.
[22]
50
180
120
45
92
89
30
77
[23]
[25]
[26]
[29]
20
[C4(DABCO)2]·2OH (10)
L‐proline (5)
Grinding/ r.t.
aq. EtOH, r.t.
5
45
94
73
This work
[21]
Zn[(L)proline]2 (17)
DAHP (10)
DABCO`(10)
SBA‐Pr‐SO3H (0.02 g)
TBAB (10)
EtOH / reflux
aq. EtOH / r.t.
Ethanol‐H2O (1:1) / r.t
Neat / 140 °C
H2O / reflux
30
92
72
92
90
[22]
[24]
[25]
[26]
120
120
15
35
80
[27]
KBr (100)
Electrolysis
20
73
[29]
[C4(DABCO)2]·2OH (10)
Grinding/ r.t.
6
93
This work
a Isolated yields.
4. Conclusions
In summary, we synthesized pyrano[2,3‐d]pyrimidinone
and pyrido[2,3‐d]pyrimidine derivatives using 1,1'‐(butane‐
1,4‐diyl)bis(1,4‐diazabicyclo[2.2.2]octan‐1‐ium) hydroxide as
an effective IL catalyst with dual basic functional groups. This
synthesis has various advantages: preparation of the basic IL
catalyst is simple, and the IL is not harmful to the environment;
the starting materials are readily available; mild reaction con‐
ditions can be used; the reaction profile is clean; high reaction
rates and excellent yields are achieved; and column chromato‐
graphic separation of the products is not needed.
Acknowledgments
The authors are thankful to the University of Guilan Re‐
search Council for the partial support of this work.
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Scheme 2. Proposed mechanism for synthesis of pyra‐
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Omid Goli Jolodar et al. / Chinese Journal of Catalysis 38 (2017) 1245–1251
1251
Graphical Abstract
Chin. J. Catal., 2017, 38: 1245–1251 doi: 10.1016/S1872‐2067(17)62827‐4
R
Efficient synthesis of pyrano[2,3‐d]pyrimidinone and
pyrido[2,3‐d]pyrimidine derivatives in presence of
novel basic ionic liquid catalyst
O
HN
NH
O
CN
O
O
HN
Omid Goli Jolodar, Farhad Shirini *, Mohadeseh Seddighi
University of Guilan, Iran
O
N
H
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C4(DABCO)2.2OH
Grinding, r.t.
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新型碱性离子液体催化剂高效催化合成吡喃酮[2,3-d]嘧啶酮和[2,3-d]嘧啶衍生物
Omid Goli Jolodar, Farhad Shirini *, Mohadeseh Seddighi
桂兰大学理学院化学系, 雷什特41335, 伊朗
摘要: 制备了碱性离子液体1,1'-(丁烷-1,4-二基)双(1,4-二氮杂二环[2.2.2]辛烷-1-ium)羟化物, 并采用红外光谱、1H核磁共振
谱和pH值分析对其进行了表征. 然后将它用于室温研磨条件下高效催化合成吡喃酮[2,3-d]嘧啶酮和[2,3-d]嘧啶. 该法步骤
简单, 反应时间短, 产物收率高, 无需柱色谱分离, 原料易得, 且可回收利用.
关键词: 碱性催化剂; 多组分反应; 嘧啶衍生物; 研磨
收稿日期: 2017-01-21. 接受日期: 2017-03-15. 出版日期: 2017-07-05.
*通讯联系人. 电子信箱: shirini@guilan.ac.ir
本文的英文电子版由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18722067).