Facial one-pot, three-component synthesis of thiazole compounds by the reactions of aldehyde/ketone, thiosemicarbazide and chlorinated carboxylic ester derivatives

Article abstract of DOI:10.1016/j.tet.2016.03.053

An efficient, clean and environmentally benign reaction process was developed for the convenient and cheap synthesis of hydrazone derivatives. A series of novel thiazole compounds were synthesized via one-pot three-component reaction of aldehyde/ketone, t

Full text of DOI:10.1016/j.tet.2016.03.053

Accepted Manuscript
Facial one-pot, three-component synthesis of thiazole compounds by the reactions of
aldehyde/ketone, thiosemicarbazide and chlorinated carboxylic ester derivatives
Ma Xiabing, Keyume Ablajan, Mamateli Obul, Mengnisa Seydimemet, Reyhangul
Ruzi, Wenbo Li
PII:
S0040-4020(16)30182-X
10.1016/j.tet.2016.03.053
TET 27593
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 14 December 2015
Revised Date: 13 March 2016
Accepted Date: 15 March 2016
Please cite this article as: Xiabing M, Ablajan K, Obul M, Seydimemet M, Ruzi R, Li W, Facial
one-pot, three-component synthesis of thiazole compounds by the reactions of aldehyde/ketone,
thiosemicarbazide and chlorinated carboxylic ester derivatives, Tetrahedron (2016), doi: 10.1016/
j.tet.2016.03.053.
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Facial one-pot, three-component synthesis of
thiazole compounds by the reactions of
aldehyde/ketone, thiosemicarbazide and
chlorinated carboxylic ester derivatives
Leave this area blank for abstract info.
Xiabing Ma, Keyume Ablajan*, Mamateli Obul, Mengnisa Seydimemet, Reyhangul Ruzi, Wenbo Li
O
S
R
Cl
COOEt
HN
N
COOEt
N
O
Ar
EtOH, CH3COONa, reflux
5a~5j
Ar
R
1a~1j
O
+
S
COOEt
COOEt
CH3
S
H2N
R
HN
N
N
H
2a
NH2
Cl
N
EtOH, CH3COONa, reflux
Ar
6a~6j

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Facial one-pot, three-component synthesis of thiazole compounds by the
reactions of aldehyde/ketone, thiosemicarbazide and chlorinated carboxylic ester
derivatives
Ma Xiabing, Keyume Ablajan*, Mamateli Obul, Mengnisa Seydimemet, Reyhangul Ruzi, Wenbo Li
Key Laboratory of Oil & Gas Fine Chemicals, Ministry of Education & Xinjiang Uyghur Autonomous Region, College of
Chemistry and Chemical Engineering, Xinjiang University, Urumqi 830046, P. R. China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
An efficient, clean and environmentally benign reaction process was developed for the
convenient and cheap synthesis of hydrazone derivatives. A series of novel thiazole compounds
were synthesized via one-pot three-component reaction of aldehyde/ketone, thiosemicarbazide
and chlorinated β-keto ester catalyzed by anhydrous sodium acetate. The reactions had excellent
yields in EtOH solvent. The synthetic method and reaction mechanism were discussed.
Available online
.
Keywords:
chlorinated β-keto ester
thiazole/hydrazone compounds
three-component reaction
one-pot synthesis
2009 Elsevier Ltd. All rights reserved
1. Introductions
for the synthesis of compounds containing thiazolyl-hydrazone
derivatives core.13,14 They have been widely used as medicinal
Many different kinds and large numbers of heterocyclic
compounds are widespread in nature, such as some alkaloids,
vitamins, antibiotics, etc. Due to the differences among the
species and the number of heteroatoms, ring members and the
ring number in heterocyclic drug molecules, they have been
classified into many different categories, such as pyridine,
quinoline, phenothiazine, benzodiazepines, furan, pyrazole
ketones, pyrimidine and thiazole etc. Among them, five-member
heterocyclic compounds are the most important compounds
associated with their bioactivities. Thiazole derivatives are a
kind of important five-member heterocyclic derivatives which
contain nitrogen, sulfur atom and a thiazole functional group,
and have aromaticity. In the past few decades, investigations
pertaining to the development of thiazole compounds toward the
synthesis of novel heterocycles from simple and readily available
substrates have received much attention from synthetic organic
chemists, due to their wide range of biological activities such as
antimicrobial,1 insecticidal,2 and anti-inflammatory.3 Further-
more, compounds containing thiazolyl structure have been
reported to exhibit enzyme inhibition4, anticancer5, antihyperten-
sive,6 anti-tumor,7 anti-HIV8 and antibacterial9,10 activity apart
from being significant intermediates for the construction of
complex heterocycles. Also, many of those compounds play an
essential role in regulating humans and biological metabolism
process.11,12 In view of the biological significance, there has been
extensive attention toward the development of synthetic routes
intermediates because of their useful biological and
pharmacological properties 15,16
.
In view of broad application
prospects of these types of compound, according to the
principles of drug design, it would probably produce more bio-
active compounds by introducing the thiazole ring into the
molecules of hydrazone compounds.17,18
Multi-component reactions (MCRs) effectively combine three,
or sometimes more, reactants simultaneously in a one-pot
synthesis that does not require the separation of intermediate
products.19 MCRs reactions constitute one of the best tools for
modern organic synthesis because they can use most of the
constituent atoms of several reactant molecules to form a product
molecule. They are also highly selective and are simply operated
under mild conditions, and have been used industrially. Most
multi-component reactions have been widely used in synthetic,
medicinal and combinatorial chemistry.20-23
For many synthetic methods of thiazole derivatives, Hantzsch
synthesis method is simple, which can introduce many functional
groups and is used widely at present,24-26 so there is still certain
application prospect in the future. However, its shortcomings are
obvious, including the use of toxic solvents, requirement of
expensive catalyst, low reaction rate, harsh reaction conditions
and difficult post-processing. As part of our ongoing research
programs, current study was directed at the development of
efficient methodologies for the preparation of thiazolyl

2
Tetrahedron
derivatives and our continued work on the synthesis of
Scheme 2. Three-component one-pot reactions for the synthesis of
ACCEPTED MANUSCRIPT
thiazolyl-hydrazone compounds via multi-component synthetic
method. To our delight, a series of thiazole compounds were
successfully synthesized using one-pot reaction route.
5a and 6a
S
O
S
O
+
HN
N
H
CH3COONa
EtOH reflux
+
COOEt
Cl
COOEt
COOEt
N
H2N
N
H
NH2
Ph
H
Ph
1a
2a
3a
5a
2. Results and discussion
COOEt
CH3
O
S
The synthetic methods of heterocyclic thiazole compounds
had been reported,27 in which one-pot multi-component reaction
was one of the most successful methods. In this study, we
prepared 20 target compounds 5a~5j and 6a~6j via one-pot
three-component reaction of aromatic aldehyde/ketone,
thiosemicarbazide and β-keto ester catalyzed by CH3COONa in
EtOH. The synthetic route of compounds 5a~5j and 6a~6j were
shown in Scheme 1.
S
O
CH3COONa
EtOH reflux
HN
N
H
H2N
+
+
N
N
NH2
Ph
H
Cl
4a
Ph
H
1a
2a
6a
Table 1 Optimization of the reaction conditions and catalyst
screening for products 5a and 6a
Time
(h)
Yielda (%)
Entry
Solvet
Catalyst
5a
6a
1
2
EtOH
CH3COONa
TEBA
4
4
4
4
6
6
6
6
4
4
4
4
4
4
89
53
61
59
22
23
15
9
87
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
MeOH
CH3CN
DMSO
THF
50
57
56
24
20
13
7
Scheme 1. Three-component one-pot reaction for the synthesis of
5a~5j and 6a~6j
3
Et3N
4
Piperidine
NaOH
5
O
6
KOH
S
R
Cl
COOEt
HN
N
7
Na2CO3
COOEt
N
8
NaHCO3
CH3COONa
CH3COONa
CH3COONa
CH3COONa
CH3COONa
CH3COONa
O
Ar
EtOH, CH COONa, reflux
3
9
69
43
45
32
21
38
63
42
41
27
17
35
5a~5j
Ar
R
10
11
12
13
14
1a~1j
O
+
S
COOEt
COOEt
S
H N
2
R
HN
N
N
H
2a
NH
2
Cl
CH2Cl2
H2O
N
CH
3
EtOH, CH COONa, reflux
Ar
3
6a~6j
a Isolated yield for three-component reaction.
Taking the synthesis of compound 5a and 6a for example
(Scheme 2 and Scheme 3), effects of solvent and catalyst on the
reaction yields were investigated. The obtained results were
Next, the optimal solvent for the synthesis of products 5a and
6a were found from among EtOH, CH2Cl2, MeOH, THF,
CH3CN, DMSO and H2O. CH3COONa catalyst was used at the
previously optimized level as 20 mol% in all reactions. Low
yields were obtained using CH2Cl2, THF, CH3CN and DMSO
(Table 2, entries 11-14). Reactions conducted in MeOH gave
higher yields than those in other organic solvent (Table 3, entry
10). However, the best yield was afforded using EtOH as a
solvent (Table 2, entry 1). In addition, when the H2O was used as
solvent, lower yields of 5a and 6a were obtained (Table 2, entry
14). The boiling point of CH2Cl2 and THF were low that it does
not meet the temperature requirements. Both solvents were not a
green organic solvent.
summarized in Table 1. The effects of different catalysts were
further evaluated for this model reaction. The results showed that
the reaction catalyzed by CH3COONa gave a highest yield.
CH3COONa is an efficient and eco-friendly catalyst, which
provides advantages such as low cost, high yield and simple
operation for the synthesis of the titled products. Then, the
reaction was conducted using different bases in ethanol under
refluxing condition. In the presence of Et3N, the reaction
afforded better yields for compounds 5a and 6a (61% and 57%).
While TEBA was used as a catalyst, the yield of compound 5a
reached to 53% and yield of compound 6a reached to 50%
(Table 1, entry 2). The test reaction was then carried out in the
presence of piperidine, which afforded a moderate yields (Table
1, entry 4). When the reactions were catalyzed by common bases,
such as NaOH, KOH, Na2CO3 and NaHCO3, even if the reaction
was refluxed longer, the yield was not increased (Table 1, entries
5-8).
Table 2 Optimization of reaction time and temperature for the
synthesis of 5a and 6a via three-component reactions
Yielda (%)
CH3COONa
Entry
Temp (°C)
Time (h)
(mol%)
5a
6a
Next we investigated the effects of the loads of the catalyst
and reaction temperature. The next optimization was of catalyst
loading: 5, 10, 20, and 30 mol% CH3COONa (Table 2，entries
9-12). The optimal amount of CH3COONa was 20 mol%, and
higher dosage of catalyst would not improve the production rate.
Furthermore, the reactions were compared at different
temperatures (40-80 °C) within different durations (60-240 min)
(Table 2, entries1-8 and 10). For any given temperature,
increasing the reaction time improved the yield. However,
excessive reaction time and temperature would reduce the
reaction yield. Therefore, the reaction conducted at 80°C for 4h
was chosen as a optimal condition (Table 2，entry 10).
1
2
40
60
80
40
60
80
40
60
80
80
80
1
1
1
3
3
3
4
4
4
4
4
20
20
20
20
20
20
20
20
5
10
28
38
13
54
65
16
63
40
10
26
34
11
48
58
13
59
37
3
4
5
6
7
8
9
10
11
10
20
73
89
68
87

3
89
87
12
80
4
30
generate intermediate B. The loss of H2O molecule from the
ACCEPTED MANUSCRIPT
intermediate B resulted in the final product 5. In addition, the
possible mechanism for the formation of compounds 6a~6j
depicted in Scheme 4 were similar to the Scheme 3.
a Isolated yield for three-component reaction.
Finally, a series of compounds 5a~5j and 6a~6j were
obtained by using similar reaction condition. The results were
listed in Table 3. Due to good functional adaptability of the
aromatic aldehyde, they can react with thiosemicarbazide and β-
keto ester smoothly to get target products in 74%~89%. At the
same time, we have investigated the influence of the electric
effect and steric hindrance effect of the substituents to the yields
and regioselectivity. With the increasing of the substituents
space steric hindrace, low yield of product was obtained (Table 3,
entries 8, 9 and entries18, 19). In contrast, good yields were
achieved when aromatic aldehydes possessing electron-donating
substituent groups such as H or CH3O (Table 3, entries 3, 11 and
15).
Scheme 3. A plausible mechanism for the synthesis of components
5a~5j in the one-pot three-component reaction system
S
COOEt
SH
O
O
HN
N
-H2O
-HCl
R
H2N
H2N
+
+
Cl
COOEt
N
NH2
NH O
Ar
R
Ar
1a~1j
2a
3a
A
S
N
H
NH2
H
S
S
HN
N
R
-H2O
HN
N
R
COOEt
N
COOEt
N
OH
Ar
Ar
5a~5j
B
Table 3 Three- component one-pot syntheses of 5a~5j and 6a~6j in
EtOH catalyzed by CH3COONa
Scheme 4. A plausible mechanism for the synthesis of components
6a~6j in the one-pot three-component reaction system
Time Temp
Yielda
(%)
No Product
Ar-
R-
(h)
( °C)
COOEt
S
Cl
1
2
3
4
5
6
7
5a
5b
5c
5d
5e
5f
Ph-
4-COOH-Ph-
Furanyl-
H
H
4
4
4
4
4
4
4
80
80
80
80
80
80
80
89
79
82
83
87
83
81
SH
NH2
O
HN
N
CH3
-H2O
-HCl
R
H3C
H2N
H2N
+
COOEt
+
NH O
N
Ar
R
Ar
O
C
2a
1a~1j
4a
H
Thiophene-
4-CH3O-Ph-
4-Cl-Ph-
H
S
H
H
N
H
NH2
COOEt
CH3
S
H
COOEt
CH3
S
HN
R
-H2O
HN
N
R
N
N
5g
4-Cl-Ph-
CH3
N
O
Ar
H
Ar
1-phenyl-5-met-
hyl-1-pyrzle-4-yl-
8
5h
CH3
4
80
76
6a~6j
D
9
5i
5j
β-Naphthyl-
4-Br-Ph-
Ph-
CH3
CH3
H
4
4
4
4
4
4
4
4
4
80
80
80
80
80
80
80
80
80
79
77
87
84
82
83
85
83
81
10
11
12
13
14
15
16
17
3. Conclusions
6a
6b
6c
6d
6e
6f
4-COOH-Ph-
Furanyl-
H
In summary, we have successfully developed a simple and
efficient method for the synthesis of thiazole derivatives, through
the one-pot three-component reaction of aldehyde/ketone,
thiosemicarbazide and chlorinated β-keto ester in EtOH, using
CH3COONa as a catalyst. It was suggested that the method
offered several advantages such as high yields, broader substrate
scope, and a safe, cheap and environmentally benign procedure,
which make it a useful and attractive process for the synthesis of
similar type of compounds.
H
Thiophene-
4-CH3O-Ph-
4-Cl-Ph-
H
H
H
6g
4-Cl-Ph-
CH3
1-phenyl-5-meth-
yl-1-pyrazle-4-yl-
18
6h
CH3
4
80
74
19
20
6i
6j
β-Naphthyl-
CH3
CH3
4
4
80
80
75
75
4-Br-Ph-
4. Experimental
4.1 General
a Isolated yield for three-component reaction.
1
All target compounds were characterized by their H NMR,
In the mass spectra of compounds 5a~5j and 6a~6j, the
IR, and MS spectra. 1H NMR spectra were obtained on a Bruker
Inova-400 instrument using CDCl3 as solvent. Chemical shifts
were given in ppm relative to TMS as an internal standard, and J
values were given in Hz. IR spectra were recorded on a Bruker
EQUINOX55 spectrophotometer using samples as KBr pellets.
Mass spectra were recorded on a HP 1100 (LC–MS, ESI source)
mass spectrometer with 120 eV ionization potential. SHB- S
recycled water vacuum pump was purchased from Zhengzhou
Great Wall Industry & Trade Co. Ltd.. All reagents used are
analytical pure and employed directly untreated except for
special instructions.
[M+Na]+ and [M+H]+ peak can be found, so we can infer to the
1
accurate molecular weight of products. In the H-NMR spectra,
the proton signals of saturated alkane and aromatic ring appeared
between 1.2~4.3 ppm and 6.4~7.5 ppm respectively, and the
proton of secondary amine appeared between 8~12 ppm as a
short and wide peak. In the IR spectra, 3200 cm-1 corresponded
to N-H stretching vibration peak, near 1600 cm-1 was attributed
to carbonyl absorption peak.
A plausible mechanism for the formation of compounds
5a~5j was depicted in Scheme 3. First, the nitrogen atom with
lone pair electrons in compound 2 attacked the carbon of
carbonyl group of compound 1, and a loss of H2O molecule to
generate thiosemicarbazide. Next, sulfur with lone pair electrons
in compound 2 attacked the carbon atom connected with chlorine
in compound 3 led to the formation of intermediate A. And then
the intramolecular ring closing reaction in intermediate A to
4.2 General procedure for the syntheses of compounds 5a-5j
and 6a~6j
A mixture of substituted benzaldehyde (1mmol), thiosemi-
carbazide (1 mmol) and 4-chloro-ethyl acetoacetate (2-chloro-
ethyl acetoacetate) (1mmol) and CH3COONa (0.02 mmol) in

4
Tetrahedron
EtOH (20 mL) was refluxed at 80 °C for 4h, After the
4.3.7 2-(N'-Furan-2-ylmethylene-hydrazino)-4-methyl-thiazole-
ACCEPTED MANUSCRIPT
completion of the reaction had been confirmed by TLC, the
reaction mixture was cooled at room temperature. The
precipitated product was filtered off and purified by
recrystallization from EtOH to give the desired product 5a and
6a in good yield.
5-carboxylic acid ethyl ester (6c). Brown crystalline power; m.p.
1
171-172 °C; H NMR (CDCl3, 400 MHz) δ: 1.25~1.29 (3H, t,
CH3), 2.47 (3H, s, CH3), 4.17~4.22 (2H, q, CH2), 6.62~7.84 (3H,
m, C4H3O), 7.97 (1H, s, CH), 12.41 (1H, s, NH); IR (KBr) ν:
3445, 3206, 3093, 2976, 1788, 1669, 1616, 1570, 1526, 1479,
1409, 1369, 1318, 1271, 1089, 1013, 931, 883, 811, 756, 724
cm-1; HRMS (ESI) m/z calcd for C12H13N3O3S+ [M+H]+
280.07504 found 280.07492.
4.3.1. 4-[(4-Ethoxycarbonylmethylene-4,5-dihydro-thiazol-2-yl)-
hydrazonomethyl]-benzoic acid (5b). Yellow crystalline power;
m.p. 235-237 °C; 1H NMR (CDCl3, 400 MHz) δ: 1.18~1.21 (3H,
t, CH3), 3.59 (2H, s, CH2), 4.06~4.11 (2H, q, CH2), 6.69 (1H, s,
CH), 7.72~7.98 (4H, d*d, C6H4), 12.71 (1H, s, COOH); IR
(KBr) ν: 3138, 3045, 2963, 2909, 2868, 2668, 2549, 1754, 1687,
1570, 1429, 1401, 1383, 1318, 1295, 1262, 1172, 1157, 1129,
1025, 938, 857, 804, 766, 729 cm-1; HRMS (ESI) m/z calcd for
C15H16N3O4S+ [M+H]+ 334.08560 found 334.08566.
4.3.8
Ethyl4-methyl-2-(2-(thiophen-2-ylmethylene)hydrazinyl)
thiazole-5-carboxylate acid ethyl ester (6d). Yellow crystalline
power; m.p. 208-210 °C; 1H NMR (CDCl3, 400 MHz) δ:
1.25~1.28 (3H, t, CH3), 2.46 (3H, s, CH3), 4.18~4.23 (2H, q,
CH2), 7.11~7.64 (3H, m, C4H3S), 8.28 (1H, s, CH), 12.44 (1H, s,
NH); IR (KBr) ν: 3544, 3127, 2988, 2899, 2812, 1688, 1570,
1516, 1439, 1416, 1368, 1314, 1281, 1215, 1099, 1043, 967, 919,
4.3.2. Ehyl 2-(2-(2-(furan-2-ylmethylene)hydrazinyl)thiazol-4
(5H)-ylidene)acetate (5c). Yellowish crystalline power; m.p.
182-183 °C; H NMR (CDCl3, 400 MHz) δ: 1.25~1.28 (3H, t,
857, 761, 711 cm-1; HRMS (ESI) m/z calcd for C12H14N3O2S2
+
[M+H]+ 296.05219 found 296.05203.
1
CH3), 3.63 (2H, s, CH2), 4.16~4.21 (2H, q, CH2), 6.47~7.51 (3H,
m, C4H3O), 6.51 (1H, s, CH), 7.74 (1H, s, CH); IR (KBr) ν:
3157, 3118, 3048, 2983, 2942, 2827, 2238, 1726, 1573, 1550,
1426, 1353,1305, 1156, 1124, 1026, 974, 938, 844, 815, 748,
734 cm-1; HRMS (ESI) m/z calcd for C12H14N3O3S+ [M+H]+
280.07504 found 280.07492.
4.3.9 4-Methyl-2-{N'-[1-(5-methyl-1-phenyl-1H-pyrazol-4-yl)-
ethylidene]-hydrazino}-thiazole-5-carboxylic acid ethyl ester
1
(6h). Reddish crystalline power; m.p. 209-211 °C; H NMR
(CDCl3, 400 MHz) δ: 1.33~1.37 (3H, t, CH3), 2.27 (3H, s, CH3),
2.60 (3H, s, CH3), 2.62 (3H, s, CH3), 4.27~4.32 (2H, q, CH2),
7.26~7.53 (5H, m, C6H5), 7.81 (1H, s, CH); IR (KBr) ν: 3264,
3090, 2979, 1753, 1659, 1561, 1503, 1450, 1371, 1330, 1283,
1239, 1190, 1102, 1039, 1011, 953, 927, 850, 764, 712 cm-1;
HRMS (ESI) m/z C19H22N5O2S+ [M+H]+ 384.14887 found
384.14880.
4.3.3. Ethyl 2-(2-(2-(thiophen-2-ylmethylene)hydrazinyl)thia-
zol-4(5H)-ylidene)acetate (5d). Yellow crystalline power; m.p.
1
139-141 °C; H NMR (CDCl3, 400 MHz) δ: 1.24~1.28 (3H, t,
CH3), 3.62 (2H, s, CH2), 4.15~4.20 (2H, q, CH2), 6.50 (1H, s,
CH), 7.02~7.34 (3H, m, C4H3S), 7.98 (1H, s, CH); IR (KBr) ν:
3437, 3152, 3046, 2915, 2827, 1730, 1564, 1534, 1444, 1420,
1364, 1306, 1230, 1123, 1029, 973, 946, 916, 824, 776, 734 cm-
4.3.10 2-[N'-(4-Bromo-benzylidene)-hydrazino]-4-methyl-thia-
zole-5-carboxylic acid ethyl ester (6j). Reddish crystalline power;
m.p. 176-178 °C; 1H NMR (CDCl3, 400 MHz) δ: 1.35~1.39 (3H,
t, CH3), 2.21 (3H, s, CH3), 2.59 (3H, s, CH3), 4.28~4.34 (2H, q,
CH2), 7.46~7.72 (4H, d*d, C6H4), 8.80 (1H, s, NH); IR (KBr) ν:
3225, 3065, 2982, 2920, 1907, 1653, 1550, 1484, 1400, 1373,
1318, 1100, 1077, 1039, 952, 823, 760 cm-1; HRMS (ESI) m/z
calcd for C15H17BrN3O2S+ [M+H]+ 382.02194 found 382.02220.
+
1; HRMS (ESI) m/z calcd for C12H14N3O2S2 [M+H]+ 296.05219
found 296.05182.
4.3.4. {2-[N'-(4-Methoxy-benzylidene)-hydrazino]-thiazol-4-yli-
dene}-acetic acid ethyl ester (5e ). Yellow crystalline power; m.p.
1
148-149 °C; H NMR (CDCl3, 400 MHz) δ: 1.25~1.29 (3H, t,
CH3), 3.63 (2H, s, CH2), 3.84 (3H, s, CH3), 4.16~4.22 (2H, q,
CH2), 6.50 (1H, s, CH), 6.91~7.62 (4H, d*d, C6H4), 7.79 (1H, s,
CH); IR (KBr) ν: 3441, 3180, 3071, 2973, 2930, 2870, 2562,
2359, 1729, 1607, 1554, 1510, 1479, 1442, 1408, 1363, 1326,
1307, 1251, 1180, 1119, 1103, 1032, 979, 912, 874, 833, 717
cm-1; HRMS (ESI) m/z calcd for C15H18N3O3S+ [M+H]+
320.10634 found 320.10611.
Acknowledgments
This work was supported financially by the National Natural
Science Foundation of China (No. 21462041) and the Tianshan
Talent Cultivation Project of Xinjiang Uyghur Autonomous
Region.
4.3.5 (2-{N'-[1-(5-Methyl-1-phenyl-1H-pyrazol-4-yl)ethylidene]
hydrazino}thiazol-4-ylidene)acetic acid ethyl ester (5h). Reddish
crystalline power; m.p. 206-209 °C; 1H NMR (CDCl3, 400 MHz)
δ: 1.33~1.36 (3H, t, CH3), 3.04 (3H, s, CH3), 2.59 (2H, s, CH2),
2.62 (3H, s, CH3), 4.27~4.32 (2H, q, CH2), 7.42~7.54 (5H, m,
C6H5), 7.81 (1H, s, CH); IR (KBr) ν: 3264, 2978, 1659, 1562,
1503, 1450, 1391, 1371, 1330, 1284, 1190, 1102, 1040, 1012,
954, 928, 851, 764 cm-1; HRMS (ESI) m/z calcd for
C19H22N5O2S+ (M+H)+ 384.14887, found 384.14868.
Supplementary data
Supplementary data associated with this article can be found
in the online version, at http://
MOL files and InChikeys of the most important compounds
described in this article.
. These data include
References and notes
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