1-Methyl-2-oxopyrrolidinium perchlorate ionic liquid in synthesis of 5-ethoxycarbonyl-3,4-dihydropyrimidin-2(1H)-ones

Article abstract of DOI:10.1134/S1070363217110354

A multicomponent Biginelli reaction in a solvent-free conditions catalyzed by 1-methyl-2-oxopyrrolidinium perchlorate ionic liquid was studied. The сondensation of aromatic aldehydes, urea (thiourea), and acetoacetic ester yielded substituted 5-ethoxycarb

Full text of DOI:10.1134/S1070363217110354

ISSN 1070-3632, Russian Journal of General Chemistry, 2017, Vol. 87, No. 11, pp. 2739–2743. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © G.N. Badalova, V.M. Abbasov, I.A. Valiyev, L.I. Alieva, A.H. Talybov, 2017, published in Zhurnal Obshchei Khimii, 2017, Vol. 87,
No. 11, pp. 1917–1921.
LETTERS
TO THE EDITOR
1-Methyl-2-oxopyrrolidinium Perchlorate
Ionic Liquid in Synthesis
of 5-Ethoxycarbonyl-3,4-dihydropyrimidin-2(1H)-ones
G. N. Badalova*, V. M. Abbasov, I. A. Valiyev, L. I. Alieva, and A. H. Talybov
Mamedaliev Institute of Petrochemical Processes, National Academy of Sciences of Azerbaijan,
ave. Khodzhaly 30, Baku, AZ 1025 Azerbaijan
*
e-mail: gunel4ik@mail.ru
Received June 15, 2017
Abstract―A multicomponent Biginelli reaction in a solvent-free conditions catalyzed by 1-methyl-2-oxo-
pyrrolidinium perchlorate ionic liquid was studied. The сondensation of aromatic aldehydes, urea (thiourea),
and acetoacetic ester yielded substituted 5-ethoxycarbonyl-3,4-dihydropyrimidin-2(1H)-ones(thiones) in 75–
97% yield.
Keywords: 3,4-dihydropyrimidin-2-(1H)-ones, ionic liquid, 1-methyl-2-oxopyrrolidinium perchlorate, Biginelli
reaction
DOI: 10.1134/S1070363217110354
The search for eco-friendly and economic methods
for the synthesis of widely used organic compounds
from readily available reagents remains one of the
main problems of organic chemistry. Multicomponent
reactions used in the synthesis of biologically and
physiologically active substances correspond to these
conditions. 3,4-Dihydropyrimidin-2(1H)-ones(thiones)
derivatives obtained from aromatic aldehyde, urea
In recent years, ionic liquids have become a
powerful alternative to traditional molecular organic
catalysts. The advantages of ionic liquids include their
ability to increase the rate and selectivity of reactions,
environmental safety, as well as the possibility of their
recycling. In this regards, ionic liquids are considered
as an excellent alternative to organic solvents.
Combining useful characteristics of solid and mineral
acids, ionic liquids replace traditional mineral acids
(sulfuric and hydrochloric acids) as catalysts in
chemical reactions. These green solvents are also used
as catalysts in the Biginelli reaction for the preparation
of 3,4-dihydropyrimidin-2(1H)-one derivatives [6–11].
(
thiourea) and ethyl acetoacetate by the known
Biginelli reaction have important biological and
pharmacological properties and may be modified with
various functional groups.
Pharmacological properties of 3,4-dihydro-
pyrimidin-2(1H)-one include anticancer [1], analgesic,
antiviral and other activities [2, 3]. Aryl substituted 3,4-
dihydropyrimidine-2(1H)-one and its derivatives play
an important role in organic and medicinal chemistry.
Here we report on a convenient method for the
synthesis of 4-arylsubstituted 3,4-dihydropyrimidin-
2(1H)-ones via three-component reaction of the
substituted aromatic aldehydes, urea (thiourea), and
ethyl acetoacetate at 100°C for 1 h in the presence of
3 mol % of 1-methyl-2-oxopyrrolidinium perchlorate
as a catalyst in the absence of a solvent.
4
-Aryl-1,4-dihydropyridines such as nifedipine [4]
introduced into clinical medicine in 1975 belong to an
important group of calcium channel modulators and
are used to treat cardiovascular diseases [5].
In the first stage urea (thiourea) 1 reacted with
aldehyde 2 to form intermediate A, which under
One of the advantages of Biginelli reaction is the
possibility of varying the initial reagents, catalysts or
solvents. Various organic and inorganic acids, Lewis
acids, and also ionic liquids are used as catalysts for
this reaction.
the
action
of
the
catalyst
(1-methyl-2-
oxopyrrolidinium perchlorate) was converted to
intermediate B. The latter added acetoacetate to form
intermediate C, which underwent cyclization into the
2
739

2
740
BADALOVA et al.
Scheme 1.
+
_
NH
CH3
O ClO4
O
H
X
R
OH
R
R
X
H
NH
H
4
N
NH2
+
_
H N
NH2
X
H O
2
2
H N
2
1
2
A
B
R
R
R
C H O
CH3
2
5
O
O
O
O
O
3
C H O
C H O
NH
2
5
NH
2
5
C H O
NH
2
5
_H
O
X
2
H C
O
H C
3
3
N
H
X
H C
N
3
X
H N
2
HO
H
C
5_19
(8, 15), 3-ClC
D
Х = О (5–12), S (13–19); R = Ph (5, 13), 2-НОС
6
Н
4
(6), 4-НОС
6
Н
4
(7, 14), 4-СН
3
ОС
6
Н
4
6
H
4
(9, 19),
2
-ClC (10), 4-ClC (16), 4-(СН NC (11, 17), 4-NO
6
H
4
6
H
4
3
)
2
6
H
4
2
C
6
H
4
(12), 4-CH C H
3 6 4
(18).
intermediate D that dehydrated into the final product
(NH), 3111.3, 2976.8, 1721.6 s (C=O), 1697.4, 1643.6,
(
Scheme 1).
1598.6, 1418.5, 1312.4, 1289.2, 1217.2, 1085.8,
1
1
025.9, 771.2, 755.5, 697.5, 659.7. Н NMR spectrum,
The improved Biginelli reaction, which involves
-methyl-2-oxopyrrolidinium perchlorate ionic liquid,
δ, ppm: 1.11 t (3H, СН , J = 6.9 Hz), 2.46 s (3H, CH ),
3
3
1
3
.96–4.03 d (2Н, СН , J = 7.2 Hz), 5.14 s (1H, PhCH,
2
led to the formation of dihydropyrimidin-2-ones 5–19
in a yield of 75 to 97%. Mild reaction conditions, high
yields, simple experimental procedure, and availability
of the catalyst are among the advantages of the
proposed method for preparing compounds 5–19.
J = 3.0 Hz), 7.34–7.22 m (4H ), 7.74 s (1H, NH), 9.19
Ar
1
3
s (1H, NH). С NMR spectrum, δ , ppm: 14.53,
С
1
1
6
8.24, 39.94, 54.41, 59.65, 99.70, 126.70, 127.73,
28.85, 145.32, 148.83, 152.60, 165.80. Found, %: C
4.65; H 6.18; N 10.74. C H N O . Calculated, %: C
14
16
2
3
Structure of the obtained compounds was con-
firmed by IR and NMR spectroscopy data. The
physico-chemical constants of the synthesized com-
pounds coincided with the reported data [12–17].
64.60; H 6.20; N 10.76.
5-Ethoxycarbonyl-4-(2-hydroxyphenyl)-6-methyl-
3
,4-dihydropyrimidin-2(1H)-one (6). Yield 88%, mp
–1
214–215°C (mp 210–212°C [13]). IR spectrum, ν, cm :
General procedure for the synthesis of
compounds 5–19. A mixture of aromatic aldehyde (10
mmol), acetoacetic ester (10 mmol), urea (thiourea)
3348.5, 3244.7 br (N–H), 3082.0, 2989.2, 2845.0,
1686.3 s (C=O), 1638.3, 1515.4, 1462.0, 1232.8,
1087.2, 759.4. Н NMR spectrum, δ, ppm: 1.25 t (3H,
1
(
30
mmol),
and
1-methyl-2-oxopyrrolidinium
CH
4.18 q (2H, CH
(4HAr, J = 7.2 Hz), 6.92 d (4HAr, J = 7.5 Hz), 7.25 s
3
, J = 7.2 Hz), 1.73 s (3H, CH
3
), 2.49 s (1H, OH),
perchlorate (3 mol %) was stirred at 100°C for 1 h.
The reaction progress was monitored by thin layer
chromato-graphy (eluent EtOAc : hexane = 1 : 4).
After the reaction completed the mixture was washed
with ice water. The precipitate was filtered off, washed
with 500 mL of distilled water, dried, and recrys-
tallized from ethanol.
2
, J = 4.5 Hz), 4.48 s (1H, CH), 6.79 d
13
(1H, NH), 7.61 s (1H, NH). С NMR spectrum, δ ,
С
ppm: 14.48, 24.40, 44.30, 48.16, 60.98, 83.54, 117.01,
120.94, 125.85, 127.82, 129.09, 129.77, 151.08,
154.99, 168.87. Found, %: C 60.79; H 5.60; N 10.24.
C
14
H
16
N
2
O
4
. Calculated, %: C 60.86; H 5.84; N 10.14.
5
-Ethoxycarbonyl-4-phenyl-6-methyl-3,4-dihyd-
5-Ethoxycarbonyl-4-(4-hydroxyphenyl)-6-methyl-
ropyrimidin-2(1H)-one (5). Yield 95%, mp 207–208°C
mp 205–206°C [12]). IR spectrum, ν, cm : 3233.9 br
3,4-dihydropyrimidin-2(1H)-one (7). Yield 93%, mp
–
1
–1
(
234–236°C (mp 230–232°C [14]). IR spectrum, ν, cm :
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 11 2017

1
-METHYL-2-OXOPYRROLIDINIUM PERCHLORATE IONIC LIQUID
2741
3
1
274.8 (O–H), 3232.4 (N–H), 1714.2 (C–H), 1614.4,
J = 3.6 Hz), 7.26–7.32 m (2H ), 7.38–7.41 d (2H ,
Ar
Ar
3
1
506.9 (C=C), 1681.3, 1230.4 (C=O), 827.9, 750.7
J = 7.5 Hz), 7.71 s (1H, NH), 9.28 s (1H, NH).
С
1
(
Ar). Н NMR spectrum, δ, ppm: 1.09 t (3H, СН , J =
NMR spectrum, δ , ppm: 14.35, 18.12, 51.93, 59.54,
3
С
7
6
7
.2 Hz), 2.22 s (3H, СН ), 3.96 q (2H, СН , J =
98.35, 128.20, 129.23, 129.54, 129.81, 132.14, 142.16,
149.76, 151.82, 165.43. Found, %: C 57.09; H 5.10; Cl
12.05; N 9.54. C H ClN O . Calculated, %: C 57.05;
3
2
.9 Hz), 5.03 s (1H, СН), 6.69 d (2H , J = 2.1 Hz),
Ar
.03 d (2H , J = 9.0 Hz), 7.61 s (1H, NH), 9.09 s (1H,
Ar
14 15
3
5
1
3
NH), 9.32 s (1H, OH). С NMR spectrum, δ , ppm:
H 5.13; Cl 12.03; N 9.50.
С
1
1
6
6
4.56, 18.20, 53.88, 59.57, 101.19, 115.44, 127.87,
35.90, 148.22, 152.64, 156.99, 165.88. Found, %: C
0.83; H 5.85; N 10.15. C H N O . Calculated, %: C
5
-Ethoxycarbonyl-4-(4-dimethylaminophenyl)-6-
methyl-3,4-dihydropyrimidin-2(1H)-one (11). Yield
5%, mp 232–234°C (mp 230–232°C [15]). IR spec-
14
16
2
4
7
0.86; H 5.84; N 10.14.
-Ethoxycarbonyl-4-(4-methoxyphenyl)-6-methyl-
,4-dihydropyrimidin-2(1H)-one (8). Yield 97%, mp
–
1
trum, ν, cm : 3237.13 br (N–H), 3137.62, 2955.28,
719.19 s (C=O), 1700.80, 1647.42, 1617.71, 1525.22,
457.65, 1288.70, 1218.84 [N(CH ) ], 1087.24, 782.98
5
1
1
(
3
2
3
1
1
1
3
2
–
1
07°C (mp 202–204°C [14]). IR spectrum, ν, cm :
233.0 br (N–H), 3104.0, 2981.2, 2955.0, 2834.3,
721.1 s (С=О), 1702.0, 1646.2, 1612.8, 1583.9,
511.7, 1455.1, 1440.1, 1383.3, 1366.4, 1330.9, 1306.0,
276.5, 1255.7, 1218.2, 1174.8, 1109.9, 1083.8, 1030.1,
52.3, 835.0, 778.9, 761.2, 680.1, 657.4, 632.0, 605.9.
1
Ar), 658.98. Н NMR spectrum, δ, ppm: 1.11 t (3H,
CH , J = 7.2 Hz), 2.22 s (3H, CH ), 2.84 s [6H,
3
3
N(CH ) ], 3.98 q (2H, CH , J = 7.2 Hz), 5.03 d (1H,
PhCH, J = 3.0 Hz), 6.66 d (2H , J = 8.7 Hz), 7.04 d
3
2
2
Ar
(
2H , J = 8.7 Hz), 7.58 s (1H, NH), 9.08 s (1H, NH).
Ar
9
13
С NMR spectrum, δ , ppm: 14.60, 18.18, 39.95,
С
1
Н NMR spectrum, δ, ppm: 1.09 t (3H, CH , J =
3
5
1
1
1
3.76, 59.56, 100.35, 112.67, 127.34, 133.10, 148.01,
50.21, 152.76, 165.95. Found, %: C 63.33; H 7.00; N
3.87. C H N O . Calculated, %: C 63.35; H 6.98; N
6
.9 Hz), 2.44 s (3H, CH ), 3.71 s (3H, OCH ), 3.98 q
3 3
(
2H, CH , J = 7.2 Hz), 5.10 d (1H, PhCH, J = 3.3 Hz),
2
1
6
21
3
3
6
7
.88 d (2H , J = 1.8 Hz), 7.16 d (2H , J = 6.9 Hz),
Ar Ar
3.85.
1
3
.68 s (1H, NH), 9.16 s (1H, NH). С NMR spectrum,
δС, ppm: 14.55, 18.21, 53.98, 55.49, 59.62, 100.03,
5-Ethoxycarbonyl-4-(4-nitrophenyl)-6-methyl-
1
1
14.15, 127.86, 137.51, 148.47, 152.65, 158.90,
65.83. Found, %: C 62.07; H 6.19; N 9.67.
3,4-dihydropyrimidin-2(1H)-one (12). Yield 86%,
mp 208–209°C (mp 207–209°C [15]). IR spectrum, ν,
–
1
C H N O . Calculated, %: C 62.06; H 6.25; N 9.65.
cm : 3415.81 (N–H), 3240.74, 1715.98 (C=O),
1
5
18
2
4
1
1
674.44, 1644.62. Н NMR spectrum, δ, ppm: 1.09 t
5
-Ethoxycarbonyl-4-(3-chlorophenyl)-6-methyl-
(
3H, СН , J = 7.2 Hz), 2.24 s (3H, СН ), 3.76 q (2H,
3
3
3
1
3
1
1
,4-dihydropyrimidin-2(1H)-one (9). Yield 97%, mp
–1
CH ), 5.19 d (1H, ArCH, J = 3.6 Hz), 7.62–8.10 m
2
94–196°C (mp 195–196°C [12]). IR spectrum, ν, cm :
213.94 br (NH), 3086.13, 1699.41 s (C=O), 1649.41,
473.90, 1424.42, 1328.92, 1221.97, 1087.42,
1
3
(
4H ), 7.92 s (1H, NH), 9.28 s (1H, NH). С NMR
Ar
spectrum, δ , ppm: 14.24, 18.72, 55.82, 60.17, 101.61,
С
1
118.16, 130.39, 138.37, 152.28, 153.41, 159.14, 165.87.
Found, %: C 55.19; H 4.90; N 13.62. C H N O .
020.61, 868.07, 766.45, 749.27, 689.75, 669.60. Н
1
4
15
3
5
NMR spectrum, δ, ppm: 1.11 t (3H, CH , J = 7.2 Hz),
2
3
Calculated, %: C 57.08; H 4.95; N 13.76.
.25 s (3H, CH ), 3.99 q (2H, CH ), 5.15 d (1H, CH,
3 2
J = 3.6 Hz), 7.18–7.39 m (4H ), 7.79 s (1H, NH), 9.26
Ar
5
-Ethoxycarbonyl-4-phenyl-6-methyl-3,4-dihyd-
1
3
s (1H, NH). С NMR spectrum, δ , ppm: 14.50,
С
ropyrimidine-2(1H)-thione (13). Yield 96%, mp 204–
06°C (mp 205–206°C [12]). IR spectrum, ν, cm :
324.7 br (N–H), 3166.2, 3101.2, 2978.2, 1665.0 s
C=O), 1570.5, 1463.4, 1368.4, 1325.1, 1192.9 s
–
1
1
1
8.28, 54.06, 59.77, 99.06, 125.37, 126.69, 127.72,
30.96, 133.35, 147.70, 149.43, 152.38, 165.6. Found,
2
3
(
(
%
: C 57.10; H 5.08; Cl 12.01; N 9.35. C H ClN O .
14 15 2 3
1
Calculated, %: C 57.05; H 5.13; Cl 12.03; N 9.50.
-Ethoxycarbonyl-4-(2-chlorophenyl)-6-methyl-
,4-dihydropyrimidin-2(1H)-one (10). Yield 75%,
mp 221–223°C (mp 222–224°C [15]). IR spectrum, ν,
С=S), 1172.8, 1114.0 1024.2, 755.2, 688.2, 648.6. Н
5
NMR spectrum, δ, ppm: 1.11 t (3H, СН
2.95 s (3H, CH ), 4.01 q (2Н, СН , J = 9.0 Hz), 5.18 s
(1H, PhCH, J = 3.0 Hz), 7.36–7.21 m (4HAr), 9.65 s
(1H, NH), 10.33 s (1H, NH). С NMR spectrum, δ ,
ppm: 14.46, 17.63, 54.51, 60.06, 101.17, 126.85,
128.14, 129.02, 143.96, 145.50, 165.59, 174.69. Found,
3
, J = 7.2 Hz),
3
3
2
–
1
13
cm : 3349.95 br (NH), 3229.86, 3103.34, 1695.87 s
C=O), 1639.87, 1442.18, 1219.25, 1077.21, 1028.13,
С
(
7
1
93.22, 754.57, 698.35, 675.41, 658.17, 625.85. Н
NMR spectrum, δ, ppm: 1.01 t (3H, СН , J = 7.2 Hz),
%: C 60.65; H 5.78; N 10.66; S 11.68. C14
H N O S.
16 2 2
3
2
.29 s (3H, СН ), 3.92 q (2H, CH ), 5.63 s (1H, PhCH,
3 2
Calculated, %: C 60.85; H 5.84; N 10.14; S 11.60.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 11 2017

2
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BADALOVA et al.
5
-Ethoxycarbonyl-4-(4-hydroxyphenyl)-6-methyl-
Yield 90%, mp 211°C (mp 208–210°C [13]). IR
–
1
3
,4-dihydropyrimidin-2(1H)-thione (14). Yield 87%,
spectrum, ν, cm : 3321.9 br (N–H), 3166.5, 3099.0,
2979.7, 2896.4, 2798.2, 1705.5 s (C=O), 1663.7,
1612.4, 1560.6, 1520.2, 1442.6, 1361.3, 1326.0,
mp 192–194°C (mp 194–196°C [16]). IR spectrum, ν,
–
1
cm : 3504.84 (O–H), 3358.64, 3234.90, 3111.44 br
N–H), 2979.39, 1679.10 s (C=O), 1642.58, 1459.55,
(
1283.4, 1181.0 s (C=S), 1163.1, 1114.7, 803.5, 752.9,
1
1
8
1
367.67, 1293.99, 1228.50 s (C=S), 1169.63, 1087.66,
22.69, 750.75, 649.55. Н NMR spectrum, δ, ppm:
.09 t (3H, CH , J = 7.2 Hz), 2.22 s (3H, CH ), 3.98 q
648.5. Н NMR spectrum, δ, ppm: 1.11 t (3H, CH , J =
3
1
6.9 Hz), 2.27 s (3H, CH ), 2.85 s [6H, N(CH ) ], 3.98
3
3 2
q (2H, CH , J = 6.9 Hz), 5.03 s (1H, CH, J = 3.6 Hz),
3
3
2
(
2H, OCH , J = 6.9 Hz), 5.04 d (1H, CH, J = 3.0 Hz),
6.65 d (2H , J = 9.0 Hz), 7.00 d (2H , J = 9 Hz), 9.52
2
Ar
Ar
13
6
7
.69 d (2H , J = 8.4 Hz), 7.03 d (2H , J = 8.4 Hz),
s (1H, NH), 10.21 s (1H, NH). С NMR spectrum, δ ,
Ar
Ar
С
.61 s (1H, NH), 9.09 s (1H, NH), 9.33 s (1H, OH).
ppm: 14.53, 17.57, 53.94, 59.94, 101.69, 112.66,
127.57, 131.66, 144.77, 150.42, 165.74, 174.28.
Found, %: C 60.06; H 6.58; N 13.12; S 10.04.
C H N O S. Calculated, %: C 60.16; H 6.63; N
1
3
С NMR spectrum, δ , ppm: 14.56, 18.20, 53.88,
С
5
1
9.57, 100.19, 115.44, 127.87, 135.90, 148.22, 152.64,
56.99, 165.88. Found, %: C 58.00; H 5.79; N 10.12;
1
6
21
3
2
S 11.58. C H N O S. Calculated, %: C 57.52; H
13.16; S 10.04.
14
16
2
2
5
.52; N 9.58; S 10.97.
5
-Ethoxycarbonyl-4-(4-methylphenyl)-6-methyl-
5-Ethoxycarbonyl-4-(4-methoxyphenyl)-6-methyl-
3
,4-dihydropyrimidin-2(1H)-thione (18). Yield 90%,
mp 193°C (mp 192–194°C [12]). IR spectrum, ν, cm :
324.28, 3171.62 br (N–H), 1671.50 s (C=O),
573.81, 1463.78 (CH), 1370.42, 1283.22 s (C=S),
195.49, 1185.45, 1117.99, 1029.03, 786.50, 758.71,
3
8
,4-dihydropyrimidine-2(1H)-thione (15). Yield
–1
2%, mp 143–145°C (mp 140–142°C [13]). IR spec-
3
1
1
7
–
1
trum, ν, cm : 3321.7 br (N–H), 3166.2, 1704.3 s
C=O), 1663.7, 1560.6, 1519.6, 1443.2, 1361.3, 1283.3
s (C=S), 1181.5, 1162.9, 1114.3, 1020.3, 943.8, 802.7,
(
1
36.08, 650.03. Н NMR spectrum, δ, ppm: 1.24 t
3H, CH , J = 7.2ꢀHz), 2.28 s (3H, CH ), 2.25 s (3H,
1
7
50.2, 647.1. Н NMR spectrum, δ, ppm: 1.17 t (3H,
(
3
3
OCH CH , J = 7.11 Hz), 2.27 s (3H, CH ), 2.85 s (3H,
OCH ), 3.98 q (2H, OCH , J = 3.6 Hz), 5.04 d (1H,
CH, J = 3.6 Hz), 6.67 d (2H , J = 8.7), 7.02 d (2H ,
J = 8.7), 9.52 s (1H, NH), 10.21 s (1H, NH). С NMR
2
3
3
CH ), 3.03 q (2H, CH , J = 6.95 Hz), 5.14 d (1H, CH),
3
2
3
2
7
(
2
1
5
.06 m (2H , J = 8.4ꢀHz), 9.61 s (1H, NH), 10.30 s
1H, NH). С NMR spectrum, δ , ppm: 14.48, 17.60,
1.12, 54.19, 60.03, 101.27, 126.76, 129.52, 137.37,
41.05, 145.34, 165.61, 174.60. Found, %: C 60.34; H
.79; N 10.11; S 11.53. C H N O S. Calculated, %:
Ar
13
Ar
Ar
1
3
С
spectrum, δ , ppm: 14.32, 18.05, 55.24, 55.49, 60.45,
С
1
1
1
01.84, 114.32, 127.74, 137.25, 147.15, 159.45,
65.62, 182.48. Found, %: C 58.68; H 5.79; N 9.62; S
1.08. C H N O S. Calculated, %: C 58.80; H 5.92;
1
4
16
2
2
C 62.04; H 6.25; N 9.65; S 11.04.
1
5
18
2
3
N 9.14; S 10.47.
5-Ethoxycarbonyl-4-(3-chlorophenyl)-6-methyl-
,4-dihydropyrimidine-2(1H)-thione (19). Yield
1%, mp 200–202°C (mp 196–198°C [16]). IR
3
8
5
-Ethoxycarbonyl-4-(4-chlorophenyl)-6-methyl-
3
,4-dihydropyrimidine-2(1H)-thione (16). Yield
–
1
spectrum, ν, cm : 3110.49 br (N–H), 3179.52,
8
9%, mp 208–211°C (mp 209–210°C [17]). IR
–
1
3
1
1
7
1
(
7
9
103.50, 2976.29, 1660.71 s (C=O), 1564.46, 1456.70,
372.59, 1333.76, 1282.43 s (C=S), 1193.89, 1173.73,
113.64, 1080.66, 1025.88, 1000.06, 871.88, 778.41,
spectrum, ν, cm : 3326.3 br (N‒H), 3172.6, 3101.8,
2
1
1
982.1, 1668.9 s (C=O), 1572.1, 1463.2, 1370.5,
334.7, 1280.5 s (C=S), 1194.4, 1175.3, 1115.0, 1090.6,
013.1, 803.3, 758.9, 744.5, 645.3. Н NMR spectrum,
1
1
42.09, 679.82, 652.17. Н NMR spectrum, δ, ppm:
.10 t (3H, CH , J = 6.9 Hz), 2.98 s (3H, CH ), 4.02 q
δ, ppm: 1.9 t (3H, CH , J = 7.2 Hz), 2.29 s (3H, CH ),
3
3
3
3
2H, CH , J = 4.2 Hz), 5.17 s (1H, PhCH, J = 3.6 Hz),
3
.99 q (2H, CH , J = 6.9 Hz), 5.17 s (1H, CH), 7.21 d
2
2
.24 d (2H , J = 12.6 Hz), 7.42 d (2H , J = 7.8 Hz),
Ar Ar
(
2H , J = 8.7 Hz), 7.42 d (2H , J = 8.4 Hz), 9.67 s
Ar
Ar
13
1
3
.68 s (1H, NH), 10.41 s (1H, NH). С NMR spec-
(1H, NH), 10.38 s (1H, NH). С NMR spectrum, δ ,
С
trum, δ , ppm: 14.44, 17.67, 54.06, 60.16, 100.57,
ppm: 14.46, 17.65, 53.91, 60.12, 100.75, 128.78,
С
1
1
1
25.50, 126.80, 128.14, 131.13, 133.53, 146.04,
46.25, 165.42, 174.82. Found, %: C 60.75; H 5.79; N
1
5
29.05, 132.73, 142.84, 165.45, 174.70. Found, %: C
4.06; H 5.39; Cl 11.31; N 10.00; S 10.58.
0.12; S 11.58. C H N O S. Calculated, %: C 60.85;
C H ClN O S. Calculated, %: C 54.10; H 4.86; Cl
14 16
2
2
1
4
15
2
2
H 5.84; N 10.14; S 11.60.
1
1.41; N 9.01; S 10.32.
-Ethoxycarbonyl-4-(4-dimethylaminophenyl)-6-
methyl-3,4-dihydropyrimidine-2(1H)-thione (17).
5
IR spectra were recorded on an ALPHA IR Fourier
spectrometer (Bruker, Germany) in the range of 600–
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 11 2017

1
-METHYL-2-OXOPYRROLIDINIUM PERCHLORATE IONIC LIQUID
2743
–
1
1
13
4
000 cm from SeZn crystals. H and C NMR
Jain, S., Arch. Appl. Sci. Res., 2012, vol. 4, no. 2,
p. 988.
9. Liu, Z., Ma, R., Cao, D., and Liu, C., Molecules, 2016,
spectra (DMSO-d ) were registered on a Bruker
Fourier spectrometer (300 MHz). Melting points were
measured on a DSC Q20 apparatus.
6
vol. 21, p. 462. doi 10.3390/molecules21040462
1
0. Zhang, Y., Wang, B., Zhang, X., Huang, J., and Liu, C.,
Molecules, 2015, vol. 20, p. 381. doi 10.3390/
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 11 2017