An efficient multicomponent reaction for synthesis of 4-amino-6-aryl-2- alkylthiopyrimidine-5-carbonitrile derivatives

Article abstract of DOI:10.1007/s11164-012-0873-6

An efficient and facile synthesis of thiosubstituted pyrimidine derivatives (4-amino-6-aryl-2-alkylthiopyrimidine-5-carbonitrile derivatives) by one-pot multicomponent reaction of aromatic aldehydes, malononitrile, and S-methylisothiouronium sulfate (or S

Full text of DOI:10.1007/s11164-012-0873-6

Res Chem Intermed
DOI 10.1007/s11164-012-0873-6
An efficient multicomponent reaction for synthesis
of 4-amino-6-aryl-2-alkylthiopyrimidine-5-carbonitrile
derivatives
•
Liangce Rong Sheng Xia Shan Yin Shimin Tao
•
•
•
•
Yunyun Zha Shujiang Tu
Received: 23 September 2012 / Accepted: 15 October 2012
Ó Springer Science+Business Media Dordrecht 2012
Abstracts An efficient and facile synthesis of thiosubstituted pyrimidine deriva-
tives (4-amino-6-aryl-2-alkylthiopyrimidine-5-carbonitrile derivatives) by one-pot
multicomponent reaction of aromatic aldehydes, malononitrile, and S-methyliso-
thiouronium sulfate (or S-benzylisothiourea hydrochloride) in ethanolic NaOH is
reported. Because of the simple work-up procedure, low cost, and, especially, high
product yields, this method is a useful and attractive procedure for synthesis of these
thiosubstituted pyrimidine compounds.
Keywords Multicomponent reactions Á 4-Amino-6-aryl-2-alkylthilpyrimidine Á
Heterocyclic compound Á Synthesis
Introduction
The pyrimidine nucleus is found in many biologically active natural products and
has substantial therapeutic potential [1]. Because of the wide range of biological
activity of synthetic pyrimidine-based structures, for example anti-allergic [2],
antitumor [3], anti-inflammatory [4], and antiparasitic [5], a several of these
compounds have attracted much attention. 5-(4-Fluorophenyl)-2-(2-methanesulfi-
nylbenzylsulfanyl)-4-pyridin-4-yl-pyrimidine, a thiosubstituted pyrimidine deriva-
tive (Fig. 1), is the most effective inhibitor of release of tumor necrosis factor-a
(TNF-a) and interleukin-1b (IL-1b) from peripheral blood mononuclear cells [6].
Although several methods have been developed for preparation of the pyrimidine
L. Rong (&) Á S. Xia Á S. Yin Á S. Tao Á Y. Zha Á S. Tu
College of Chemistry and Chemical Engineering, Jiangsu Key Laboratory of Green Synthetic
Chemistry For Functional Materials, Jiangsu Normal University, Xuzhou 221116, Jiangsu,
People’s Republic of China
e-mail: lcrong2005@yahoo.com
123

L. Rong et al.
Fig. 1 The inhibitor of release
of tumor necrosis factor-a
(TNF-a) and interleukin-1b
(IL-1b)
N
N
S
N
S
H3C
O
F
ring [7–12], general and highly selective preparations of the alkylthiol-substituted
pyrimidine skeleton have rarely been studied.
Multicomponent reactions (MCRs) have become extremely important synthetic
methods because they are efficient and powerful means of construction of organic
compounds by one-pot reaction without isolation of intermediates or modification
the reaction conditions [13–16]. Herein, we report an efficient process for synthesis
of 2-alkylthiol-substituted pyrimidine derivatives by means of a multicomponent
reaction.
Results and discussion
First, we wanted to find an efficient method for this synthesis. Reaction of
4-chlorobenzaldehyde, malononitrile, and S-methylisolthiouronium sulfate as
starting materials, catalyzed by Na2CO3, was chosen as the model reaction, and
was investigated under different solvent conditions (Table 1). The results showed
that when nonpolar solvents, for example toluene, CH3CN, and CH2Cl2, were used
reaction did not occur. We also found the reaction was unsuccessful under solvent–
free conditions. However, when polar solvents (95 % EtOH and THF) were used,
the reaction could be performed smoothly with good yields. Taking into account the
toxicity and cost of the solvents, we chose ethanol (95 %) as the preferred solvent
for the reaction.
Although the reaction was catalyzed by Na2CO3, we wished to discover whether
the other catalysts also promoted the reaction, so different catalysts were screened in
ethanol (95 %) under reflux conditions. We found that acid catalysts (HCl, H2SO4)
had no effect on this reaction. In contrast, alkaline catalysts, whether organic or
Table 1 Solvent optimization for synthesis of 4c
Entry
Solvent
Time (h)
Yielda (%)
1
2
3
4
5
6
Toluene
CH3CN
CH2Cl2
EtOH
6
6
6
6
6
6
0
0
0
56
45
0
THF
None
Reagents and conditions: 4-chlorobenzaldehyde (2 mmol), S-methylisothiouronium sulfate (2 mmol),
malononitrile (3 mmol), Na2CO3 (1 mmol), and solvent (10 mL), reflux
a
Isolated yields
123

Synthesis of 4-amino-6-aryl-2-alkylthiopyrimidine-5-carbonitrile derivatives
Table 2 Effect of catalyst and temperature on the model reaction
Entry
Catalyst (mmol)
Temperature (°C)
Time (h)
Yielda (%)
1
2
3
4
5
6
7
8
9
10
None
60
60
60
60
60
60
70
80
80
90
8
8
8
6
6
6
2
2
4
2
0
0
HCl (1)
H2SO4 (1)
Piperidine (1)
Et3N (1)
0
34
37
80
81
89
88
87
NaOH (1)
NaOH (1)
NaOH (1)
NaOH (1)
NaOH (1)
Reagents and conditions: 4-chlorobenzaldehyde (2 mmol), S-methylisothiouronium sulfate (2 mmol), and
malononitrile (3 mmol), 95 % ethanol (10 mL)
a
Isolated yields
inorganic alkalis, all promote the reaction with different yields. Study of the results
obtained from the reaction revealed that inorganic alkali catalysts were more
efficient than organic alkalis. Further research revealed sodium hydroxide was the
best catalyst for this synthesis. The results obtained are summarized in Table 2.
Using these optimized conditions, different aromatic aldehydes were reacted with
malononitrile, and S-methylisothiouronium sulfate and a series of 4-amino-6-aryl-2-
methylthiopyrimidine-5-carbonitrile derivatives were obtained with high yields
(Scheme 1). The results, summarized in Table 3, revealed that highly sterically
hindered aromatic aldehydes, for example 3,4,5-trimethoxybenzaldehyde and
1-naphthaldehyde, reacted well with malononitrile and S-methylisothiouronium to
give corresponding products.
To extend the range of this synthesis, S-benzylisothiouronium chloride was
reacted with aromatic aldehydes and malononitrile under the same conditions
(Scheme 2). To our delight, we found the reaction proceeded smoothly and different
products, 4-amino-6-aryl-2-benzylthiopyrimidine-5-carbonitrile derivatives, were
obtained with excellent yields. The results are summarized in Table 4.
The structures of all the products were confirmed on the basis of spectroscopic
data, particularly nuclear magnetic resonance (1H NMR) spectroscopy and high-
SCH3
N
N
CHO
NH
SCH3
CN
CN
NaOH
ethanol
H2N
+
H2SO4
+
R
R
H2N
2
CN
2
1
3
4
Scheme 1 Synthesis of 4-amino-6-aryl-2-(methylthio)pyrimidine-5-carbonitrile derivatives
123

L. Rong et al.
Yielda (%)
Table 3 Results from synthesis
of compounds 4
Entry
Ar
Product
1
C6H5
4a
4b
4c
4d
4e
4f
88
89
81
80
82
80
82
88
83
84
2
4-ClC6H4
3
4-CH3C6H4
4
2-CH3OC6H4
3,4-(CH3)2C6H3
2,5-(CH3O)2C6H3
3,4-(CH3O)2C6H3
3,4-OCH2OC6H3
3,4,5-(CH3O)3C6H2
1-naphthalenyl
5
6
7
4g
4h
4i
8
9
10
4j
Ph
N
S
N
CHO
NH
CN
CN
NaOH
ethanol
H2N
+
HCl
+
R
R
H2N
SCH2Ph
CN
1
5
3
6
Scheme 2 Synthesis of 4-amino-6-aryl-2-(benzylthio)pyrimidine-5-carbonitrile derivatives
Table 4 Results from synthesis
of compounds 6
Entry
Ar
Product
Yielda (%)
1
2
3
4
5
6
C6H5
6a
6b
6c
6d
6e
6f
85
86
84
83
88
89
4-FC6H4
4-BrC6H4
3,4-Cl2C6H3
3,4-(CH3O)2C6H3
3,4-OCH2OC6H3
resolution mass spectroscopy (HRMS). We take 4c and 6f as examples to analyze
1
their structures. The H NMR spectrum of 4c contained singlet signals at d = 2.43
(3H) and 2.58 (3H) ppm from CH3 and SCH3 protons. Doublet signals at d = 7.42
(1H, J = 8.0 Hz) and 7.92 (1H, J = 8.4 Hz) and a triplet signal at d = 7.33 (2H,
J = 8.4 Hz) were ascribed to four phenyl protons. A singlet signal at d = 5.70 (2H)
should be the amino protons. In the infrared (IR) spectrum, amino peaks were
observed at 3,480 and 3,346 cm-1 and a nitrile peak at 2,212 cm-1. In the HRMS
spectrum, the calculated m/z (C13H12N4S [M ? Na]?) of 4c is 279.0680 and the
found m/z is 279.0661.
1
The H NMR spectrum of 6e contained singlet signals at d = 3.78 (3H), 3.82
(3H), and 4.54 (2H) ppm from 2 9 OCH3 and PhCH2 protons. Singlet signals at
d = 7.11 (2H) and 7.18 (1H) ppm, triplet signals at d = 7.26 (1H, J = 7.2 Hz) and
123

Synthesis of 4-amino-6-aryl-2-alkylthiopyrimidine-5-carbonitrile derivatives
7.33 (2H, J = 6.8), and a doublet at d = 7.52 (2H, J = 6.8 Hz) were attributed to
eight phenyl protons. A singlet signal at d = 8.10 (2H) was attributed to amino
protons. In the IR spectrum, the amino peaks appear at 3,474 and 3,330 cm-1 and
the nitrile peak at 2,216 cm-1. In the HRMS spectrum, the calculated m/z
(C20H18N4O2S [M ? H]?) of 6e is 379.1229 and the found m/z is 379.1284.
Conclusions
We report a facile and efficient one-pot reaction for synthesis of 4-amino-6-aryl-2-
alkylthiopyrimidine-5-carbonitrile derivatives from aromatic aldehydes, malononit-
rile, and methyl carbamimidothioate sulfate or S-benzylisothiourea hydrochloride.
Because of the simple work-up procedure, low cost, and, especially, high product
yield, this method is a useful and attractive procedure for synthesis of these
thiosubstituted pyrimidine compounds.
Experimental
Melting points were determined on an XT-5 microscopic melting-point apparatus
and were uncorrected. IR spectra were recorded on an FT IR-8101 spectrometer. 1H
NMR spectra were obtained from solution in DMSO-d6, with Me4Si as internal
standard, using a Bruker-400 spectrometer. HRMS spectra were obtained with a
Bruker micrOTOF-Q 134 instrument.
General procedure for synthesis of 4-amino-6-aryl-2-alkylthiopyrimidine-5-
carbonitrile derivatives
A mixture of aromatic aldehyde 1 (2 mmol), methyl carbamimidothioate sulfate (or
S-benzylisothiourea hydrochloride) 2 (2 mmol), malononitrile 3 (3 mmol), sodium
hydroxide (1 mmol), and ethanol (10 mL) was reacted under reflux conditions for
approximately 2 h. When the reaction was complete, the reaction mixture was
poured into water, then washed thoroughly with water. The product was isolated by
filtration, dried, and recrystallized from 95 % ethanol.
4-Amino-2-methylthio-6-phenylpyrimidine-5-carbonitrile (4a)
m.p.[280 °C; IR (KBr) v: 3460, 3324, 3218, 1625, 1533, 1526, 1428, 1300, 1269,
1238, 1045, 756, 707 cm-1; 1H NMR (400 MHz, DMSO-d6) d: 2.59 (3H, s, SCH3),
7.54 (2H, t, J = 4.0 Hz, ArH), 7.57 (3H, t, J = 3.6 Hz, ArH), 8.07 (2H, s, NH2).
HRMS m/z calculated for C12H10N4S [M ? Na]?: 265.0524, found: 265.0533.
4-Amino-6-(4-chlorophenyl)-2-(methylthio)pyrimidine-5-carbonitrile (4b)
m.p. 228–230 °C; IR (KBr) v: 3469, 3329, 3214, 2930, 2812, 2225, 2210, 1620,
1525, 1477, 1385, 1350, 1300, 1235, 1158, 1124, 1033, 993, 965, 860, 761, 703,
123

L. Rong et al.
1
667 cm-1; H NMR (400 MHz, DMSO-d6) d: 2.61 (3H, s, SCH3), 7.54 (2H, d,
J = 4.4 Hz, ArH), 7.58–7.62 (1H, m, ArH), 7.70 (1H, d, J = 7.6 Hz, ArH), 8.19
(2H, s, NH2). HRMS m/z calculated for C12H9ClN4S [M]?: 276.0236, found:
276.0263.
4-Amino-2-methylthio-6-p-tolylpyrimidine-5-carbonitrile (4c)
m.p. 195–196 °C; IR (KBr) v: 3480, 3346, 2927, 2212, 1624, 1542, 1513, 1329,
1
1300, 1239, 1190, 1153, 1040, 994, 864, 811, 774 cm-1; H NMR (400 MHz,
DMSO-d6) d: 2.43 (3H, s, CH3), 2.58 (3H, s, SCH3), 5.70 (2H, s, NH2), 7.33 (2H, t,
J = 8.4 Hz, ArH), 7.42 (1H, d, J = 8.0 Hz, ArH), 7.92 (1H, d, J = 8.4 Hz, ArH).
HRMS m/z calculated for C13H12N4S [M ? Na]?: 279.0680, found: 279.0661.
4-Amino-6-(2-methoxyphenyl)-2-(methylthio)pyrimidine-5-carbonitrile (4d)
m.p. 269–270 °C; IR (KBr) v: 3450, 3343, 2812, 2214, 1632, 1545, 1496, 1384,
1
1349, 1249, 1118, 1014, 824, 756 cm-1; H NMR (400 MHz, DMSO-d6) d: 2.58
(3H, s, SCH3), 3.80 (3H, s, OCH3), 7.11 (1H, t, J = 7.6 Hz, ArH), 7.21 (1H, d,
J = 8.4 Hz, ArH), 7.32 (1H, d, J = 7.6 Hz, ArH), 7.53 (1H, t, J = 8.0 Hz, ArH),
8.00 (2H, s, NH2). HRMS m/z calculated for C13H12N4OS [M ? H]?: 273.0810,
found: 273.0896.
4-Amino-6-(3,4-dimethylphenyl)-2-(methylthio)pyrimidine-5-carbonitrile (4e)
m.p. 223–225 °C; IR (KBr) v: 3324, 3217, 2225, 2210, 1637, 1542, 1527, 1428,
1306, 1264, 1241, 670 cm-1; 1H NMR (400 MHz, DMSO-d6) d: 2.29 (3H, s, CH3),
2.30 (3H, s, CH3), 2.58 (3H, s, SCH3), 7.23 (1H, d, J = 7.6 Hz, ArH), 7.31 (2H, t,
J = 5.6 Hz, ArH), 7.95 (2H, s, NH2). HRMS m/z calculated for C14H14N4S
[M ? H]?: 271.1017, found: 271.1055.
4-Amino-6-(2,5-dimethoxyphenyl)-2-(methylthio)pyrimidine-5-carbonitrile (4f)
m.p.[280 °C; IR (KBr) v: 3447, 3343, 3220, 2932, 2837, 2213, 1638, 1625, 1541,
1
1491, 1221, 1157, 1049, 1015, 846, 809, 731, 669 cm-1; H NMR (400 MHz,
DMSO-d6) d: 2.59 (3H, s, SCH3), 3.75 (3H, s, OCH3), 3.75 (3H, s, OCH3), 6.94
(1H, dd, J = 2.8 Hz, J = 14.8 Hz, ArH), 7.09 (1H, dd, J = 2.8 Hz, J = 8.8 Hz,
ArH), 7.16 (1H, d, J = 9.2 Hz, ArH), 7.95 (2H, s, NH2). HRMS m/z calculated for
C14H14N4O2S [M]?: 302.0837, found: 302.0840.
4-Amino-6-(3,4-dimethoxyphenyl)-2-(methylthio)pyrimidine-5-carbonitrile (4g)
m.p.[280 °C; IR (KBr) v: 3421, 3329, 3234, 2933, 2835, 2212, 1639, 1547, 1500,
1
1466, 1428, 1260, 1224, 1141, 1024, 855, 814, 782, 756, 669 cm-1; H NMR
(400 MHz, DMSO-d6) d: 2.58 (3H, s, SCH3), 3.80 (3H, s, OCH3), 3.85 (3H, s,
OCH3), 7.10–7.15 (2H, m, ArH), 7.18 (1H, s, ArH), 7.95 (2H, s, NH2). HRMS m/z
calculated for C14H14N4O2S [M]?: 302.0837, found: 302.0823.
123

Synthesis of 4-amino-6-aryl-2-alkylthiopyrimidine-5-carbonitrile derivatives
4-Amino-6-(benzo[d][1,3]dioxol-5-yl)-2-(methylthio)pyrimidine-5-carbonitrile (4h)
m.p.[280 °C; IR (KBr) v: 3461, 3219, 2850, 2220, 1633, 1593, 1540, 1506, 1417,
1386, 1350, 1248, 669 cm-1 1H NMR (400 MHz, DMSO-d6) d: 2.57 (3H, s,
;
SCH3), 6.15 (2H, s, CH2), 7.03 (1H, d, J = 8.0 Hz, ArH), 7.10 (1H, d, J = 8.0 Hz,
ArH), 7.16 (1H, s, ArH), 8.02 (2H, s, NH2). HRMS m/z calculated for C13H10N4O2S
[M ? H]?: 287.0603, found: 287.0629.
4-Amino-2-methylthio-6-(3,4,5-trimethoxyphenyl)pyrimidine-5-carbonitrile (4i)
m.p.[280 °C; IR (KBr) v: 3480, 3337, 3223, 2960, 2842, 2219, 1638, 1544, 1509,
1
1473, 1417, 1253, 1131, 1005, 840, 778, 669 cm-1; H NMR (400 MHz, DMSO-
d6) d: 2.59 (3H, s, SCH3), 3.75 (3H, s, OCH3), 3.81 (3H, s, OCH3), 3.81 (3H, s,
OCH3), 6.90 (2H, s, ArH), 8.30 (2H, s, NH2). HRMS m/z calculated for
C15H16N4O3S [M - H]?: 331.0865, found: 331.0870.
4-Amino-2-methylthio-6-(naphthalen-1-yl)pyrimidine-5-carbonitrile (4j)
m.p. 237–239 °C; IR (KBr) v: 3458, 3329, 3213, 3054, 2929, 2215, 1621, 1551,
1
1525, 1455, 1385, 1258, 1239, 1059, 1026, 958, 809, 723, 621 cm-1; H NMR
(400 MHz, DMSO-d6) d: 2.65 (3H, s, SCH3), 7.59 (3H, t, J = 5.6 Hz, ArH), 7.62
(1H, s, ArH), 7.68 (1H, t, J = 7.6 Hz, ArH), 8.07 (1H, d, J = 8.0 Hz, ArH), 8.13
(1H, d, J = 8.0 Hz, ArH). HRMS m/z calculated for C16H12N4S [M ? Na]?:
315.0602, found: 315.0626.
4-Amino-2-benzylthio-6-phenylpyrimidine-5-carbonitrile (6a)
m.p. 192–193 °C; IR (KBr) v: 3441, 3329, 3217, 2220, 1644, 1633, 1539, 1495,
1455, 1263, 669 cm-1; 1H NMR (400 MHz, DMSO-d6) d: 4.52 (2H, s, SCH2), 7.26
(1H, t, J = 7.6 Hz, ArH), 7.33 (2H, t, J = 7.6 Hz, ArH), 7.52-7.56 (7H, m, ArH),
8.29 (2H, s, NH2). HRMS m/z calculated for C18H14N4S [M ? H]?: 319.1017,
found: 319.1022.
4-Amino-2-benzylthio-6-(4-fluorophenyl)pyrimidine-5-carbonitrile (6b)
m.p. 191–193 °C; IR (KBr) v: 3469, 3329, 3214, 2930, 2812, 2225, 2210, 1620,
1525, 1477, 1385, 1350, 1300, 1235, 1158, 1124, 1033, 993, 965, 860, 761, 703,
1
667 cm-1; H NMR (400 MHz, DMSO-d6) d: 4.04 (2H, s, SCH2), 7.25(1H, t,
J = 7.6 Hz, ArH), 7.31(2H, t, J = 7.2 Hz, ArH), 7.40 (2H, t, J = 7.6 Hz, ArH),
7.45(2H, d, J = 7.6 Hz, ArH), 7.92 (2H, t, J = 7.2 Hz, ArH), 8.22 (2H, s, NH2).
HRMS m/z calculated for C18H13FN4S [M ? H]?: 337.0923, found: 337.0940.
4-Amino-2-benzylthio-6-(4-bromophenyl)pyrimidine-5-carbonitrile (6c)
m.p. 195–196 °C; IR (KBr) v: 3459. 3120, 2210, 1641, 1590, 1573, 1538, 1493,
1397, 1312, 1243, 1067, 995, 839, 792, 768, 701 cm-1
;
1H NMR (400 MHz,
123

L. Rong et al.
DMSO-d6) d: 4.40 (2H, s, SCH2), 7.24 (1H, t, J = 7.2 Hz, ArH), 7.31 (2H, t,
J = 7.6 Hz, ArH), 7.44 (2H, d, J = 7.2 Hz, ArH), 7.72 (4H, dd, J = 8.8 Hz,
J = 12.0 Hz, ArH), 8.27 (2H, s, NH2). HRMS m/z calculated for C18H13BrN4S [M]:
396.0044, found: 396.0082.
4-Amino-2-benzylthio-6-(3,4-dichlorophenyl)pyrimidine-5-carbonitrile (6d)
m.p. 197–199 °C; IR (KBr) v: 3458, 3345, 3231, 2213, 1640, 1523, 1475, 1396,
1308, 1245, 1150, 1031, 892, 788, 711, 696 cm-1; 1H NMR (400 MHz, DMSO-d6)
d: 4.39 (2H, s, SCH2), 7.25 (2H, t, J = 7.6 Hz, ArH), 7.32 (3H, t, J = 7.2 Hz, ArH),
7.45 (2H, t, J = 7.2 Hz, ArH), 8.03 (1H, s, ArH), 8.52 (2H, s, NH2). HRMS m/z
calculated for C18H12Cl2N4S [M ? H]?: 387.0238, found: 387.0246.
4-Amino-2-benzylthio-6-(3,4-dimethoxyphenyl)pyrimidine-5-carbonitrile (6e)
m.p. 194–196 °C; IR (KBr) v: 3474, 3330, 3211, 2216, 1616, 1595, 1545, 1454,
1
1420, 1261, 1227, 1141, 1017, 818, 778, 720 cm-1; H NMR (400 MHz, DMSO-
d6) d: 3.78 (3H, s, OCH3), 3.82 (3H, s, OCH3), 4.51 (2H, s, SCH2), 7.11 (2H, s,
ArH), 7.18 (1H, s, ArH), 7.26 (1H, t, J = 7.2 Hz, ArH), 7.33 (2H, t, J = 7.6 Hz,
ArH), 7.52 (2H, d, J = 6.8 Hz, ArH), 8.10 (2H, s, NH2). HRMS m/z calculated for
C20H18N4O2S [M ? H]?: 379.1229, found: 379.1284.
4-Amino-6-(benzo[d][1,3]dioxol-5-yl)-2-(benzylthio)pyrimidine-5-carbonitrile (6f)
m.p. 214–215 °C; IR (KBr) v: 3476, 3331, 2906, 2218, 1618, 1549, 1487, 1443,
1
1349, 1249, 1033, 920, 776, 720, 677 cm-1; H NMR (400 MHz, DMSO-d6) d:
4.50 (2H, s, SCH2), 6.14 (2H, s, CH2), 7.02 (1H, d, J = 8.0 Hz, ArH), 7.09 (1H, d,
J = 8.0 Hz, ArH), 7.16 (1H, s, ArH), 7.25 (1H, t, J = 7.2 Hz, ArH), 7.32 (2H, t,
J = 7.6 Hz, ArH), 7.52 (2H, d, J = 7.2 Hz, ArH), 7.95 (2H, s, NH2). HRMS m/z
calculated for C19H14N4O2S [M ? H]?: 363.0916, found: 363.0920.
Acknowledgments This work was supported by the National Natural Science Foundation of China
(NSFC) (21172188), the Foundation of Xuzhou Normal University (10XLS02), and the Priority
Academic Program Development of Jiangsu Higher Education Institutions.
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