An efficient synthesis of 5-aryl-4,5-dihydro-3-(5-methyl-1-p-tolyl-1H-1,2, 3-triazol-4-yl)-1-(4-phenylthiazol-2-yl)pyrazoles

Article abstract of DOI:10.1002/jhet.706

Some new target products 5-aryl-4,5-dihydro-3-(5-methyl-1-p-tolyl-1H-1,2,3- triazol-4-yl)-1-(4-phenylthiazol-2-yl)pyrazoles 5a-j have been synthesized by reaction of 2-bromo-1-phenylethanone and compounds 4a-j which were prepared from the combination of thiosemicarbazide and (E)-3-aryl-1-(5-methyl-1-p-tolyl-1H-1, 2,3-triazol-4-yl)-prop-2-en-1-ones 3a-j. All the structures were established by MS, IR, CHN, and ¹H NMR spectra data. Synthesis of structure diversity is applied.

Full text of DOI:10.1002/jhet.706

1154
An Efficient Synthesis of 5-Aryl-4,5-dihydro-3-(5-methyl-1-p-
tolyl-1H-1,2,3-triazol-4-yl)-1-(4-phenylthiazol-2-yl)pyrazoles
Vol 48
Wang-Jun Dong, Fu-Hong Cui, Zhong-Lian Gao, Rong-Shan Li,
Guo-Liang Shen, and Heng-Shan Dong*
State Key Laboratory of Applied Organic Chemistry, Institute of Organic Chemistry,
College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, Gansu 730000,
People’s Republic of China
*E-mail: donghengshan@lzu.edu.cn
Received April 14, 2010
DOI 10.1002/jhet.706
Published online 8 June 2011 in Wiley Online Library (wileyonlinelibrary.com).
Some new target products 5-aryl-4,5-dihydro-3-(5-methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-1-(4-phenyl-
thiazol-2-yl)pyrazoles 5a–j have been synthesized by reaction of 2-bromo-1-phenylethanone and com-
pounds 4a–j which were prepared from the combination of thiosemicarbazide and (E)-3-aryl-1-(5-
methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-prop-2-en-1-ones 3a–j. All the structures were established by
1
MS, IR, CHN, and H NMR spectra data. Synthesis of structure diversity is applied.
J. Heterocyclic Chem., 48, 1154 (2011).
INTRODUCTION
thiosemicarbazide, and potassium hydroxide in ethanol.
Compounds 4a–j has a 1-unsubstituted thiocarbamoyl
group in the pyrazoline nucleus. Furthermore, the target
compounds 5-aryl-4,5-dihydro-3-(5-methyl-1-p-tolyl-1H-
1,2,3-triazol-4-yl)-1-(4-phenylthiazol-2-yl)pyrazoles 5a–j
was synthesized by compounds 4a–j and 2-bromo-1-
phenylethanone in ethanol in good yields. The synthesis
procedure was shown in Scheme 1.
Substances containing a pyrazoline heterocyclic ring
are important targets in chemical synthesis because of
their pronounced biological activity. Literatures survey
reveals pyrazoline derivatives possess the various bio-
logical activity such as anti-bacterial and antifungal [1],
antidiabetic [2], anti-inflammatory [3], and also active
against many mycobacterias [4–8]. Monoamine oxidases
(MAO) are widely distributed enzymes among mammals
and plants, which are important in the metabolism of
monoamine neurotransmitters. MAO-A inhibitors are
used as antidepressant and antianxiety drugs [9]. MAO-
B inhibitors are coadjuvant in the treatment of Parkin-
son’s disease [10] and Alzheimer’s disease [11]. In the
previous studies, many people focused attention on the
importance of the presence of 1-acetyl group or a 1-thi-
ocarbamoyl in the pyrazoline nucleus for MAO inhibi-
tory activity [12,13].
RESULTS AND DISCUSSIONS
The compounds (E)-3-aryl-1-(5-methyl-1-p-tolyl-1H-
1,2,3-triazol-4-yl)-prop-2-en-1-ones 3a–j were prepared
by the Claisen-Schmidt condensation reaction of 1-(5-
methyl-1-p-tolyl-1,2,3-triazol-4-yl)-ethanone and some
aromatic aldehydes 2. The 5-aryl-4,5-dihydro-3-(5-
methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)pyrazole-1-carbo-
thioamides 4a–j were synthesized by the reactions of 1
equiv 3a–j, 2 equiv thiosemicarbazide, and potassium
hydroxide in ethanol with yields ranging from 75 to
89%. The target products 5-aryl-4,5-dihydro-3-(5-
methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-1-(4-phenylthia-
zol-2-yl)pyrazoles 5a–j were obtained by the reaction
Our interest in pyrazoline derivatives prompted us to
synthesize a novel series of 5-aryl-4,5-dihydro-3-(5-
methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)pyrazole-1-carbo-
thioamides 4a–j by reaction of (E)-3-aryl-1-(5-methyl-
1-p-tolyl-1H-1,2,3-triazol-4-yl)-prop-2-en-1-ones 3a–j,
C
V
2011 HeteroCorporation

September 2011
An Efficient Synthesis of 5-Aryl-4,5-dihydro-3-(5-methyl-1-p-tolyl-
1H-1,2,3-triazol-4-yl)-1-(4-phenylthiazol-2-yl)pyrazoles
1155
1
Scheme 1. The synthesis procedure of compounds 5a–j.
All the products were characterized by IR, H NMR,
CHN, and MS spectral data. Furthermore, the structure
of 5-(4-chlorophenyl)-4,5-dihydro-3-(5-methyl-1-p-tolyl-
1H-1,2,3-triazol-4-yl)-1-(4-phenylthiazol-2-yl)pyrazole
(5c) was established by X-ray analyses (Fig. 1). The
title compound, C24H17N6Cl (I) (Fig. 1).
5-(4-Chlorophenyl)-4,5-dihydro-3-(5-methyl-1-p-
tolyl-1H-1,2,3-triazol-4-yl)-1-(4-phenylthiazol-2-yl)pyra-
zole 5c was obtained by the reaction of 4c and equimolar
2-bromo-1-phenylethanone in ethanol in good yields. The
consists plane of subsituted triazole ring, substituted pyra-
zoline ring, substituted thiazole ring and 3 subsituted phe-
nyl ring, subsituted triazole ring and 4-methylphenyl ring,
4-Clphenyl ring and pyrazoline ring, phenyl ring and thia-
zole ring, pyrazoline ring and thiazole ring is not co-pla-
nar[The dihedral angle of C8-N1-C5-C6 is 151.8(8)ꢀ, C12-
C13-C14-C15 is 71.1(7)ꢀ, N6-C22-C23-C24 is 169.9(7)ꢀ,
N6-C20-N5-C13 is 20.9(10)ꢀ in stable conformation of the
crystal] but only pyrazoline ring and triazole ring is ap-
proximate planar [The dihedral angle of C8-C10-C11-C12
is 177.2(7)ꢀ in stable conformation of the crystal].
On pyrazoline ring, the double bond was indicated
the between N4 and C11, bond length of C11-N4 is
˚
1.277(8)A which is shorter than single bond Csp3-Nsp2
˚
bond C13-N5 1.480(6)A (Table 1).
of 4a–j and equimolar 2-bromo-1-phenylethanone in
ethanol in good yields. In the compounds 4a–j and 5a–
j, the protons of the dihydro-pyrazole ring, which was
give a well-defined system of three double doublets in
positions 4 and 5 indicated the formation of the pyrazo-
line ring.
EXPERIMENTAL
All melting points were determined on a XT-100X kofler
melting point apparatus and are uncorrected. IR spectra were
1
obtained in KBr discs on a Shimadzu IR-435 spectrometer. H
When the type pyrazolin-1-carbothioamides 4a–j were
synthesized by reaction of 1,3-diarylpre-2-en-1-one anal-
ogous 3a–j, 1,3-diphenylpre-2-en-1-one and semicarba-
zide give its semicarbazone [14]. The reaction of 4- phe-
nylbut-3-en-2-one and thiosemicarbazide give its
thiosemicarbazone [15]. While the reaction of 4-phenyl-
but-3-en-2-one and 3-amino-2(1H)-thioxo-4(3H)-quina-
zolinone, its products is given by 1,4-addication of amino
to 4-phenylbut-3-en-2-one [16]. Synthesis of structure di-
versity is applied, when the 5-aryl-4,5-dihydro-3-(5-
methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)pyrazole-1-carbo-
thioamides 4a–j were synthesized by the reactions of 1
equiv 3a–j, 2 equiv thiosemicarbazide, and potassium hy-
droxide in ethanol with yields ranging from 75 to 89%.
In summary, we conveniently prepared a series of
pyrazoline derivatives by a simple synthetic method
from a,b-unsaturated ketones. The title compounds 5a–j
containing a 1H-1,2,3-triazole ring, a thiazole ring and a
pyrazoline heterocyclic ring are the compound of struc-
ture diversity, which possess also the diversified biologi-
cal activity [17–24]. So the title compounds could
exhibit the interesting biological activity which is under
investigated.
NMR spectroscopy (CDCl3) was recorded on Avance Mercury
plus-300 instrument with TMS as an internal standard. The
mass spectrum of compounds 1, 3a–j, 4a–i were recorded on a
HP-5988A spectrometer (EI at 70 eV), compound 4j and 5a–j
were performed on ESQ6K instrument. Elemental analyses
were carried out on a Yanaco CHN Corder MT-3 analyzer.
1-(5-Methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-ethanone
[25]. Compound 1 were prepared by the reaction of 1-azido-4-
1
methylbenzene [26,27] with pentane-2,4-dione. A cold solution
Figure 1. Mercury diagram of compound 5c. [Color figure can be
at
viewed
in
the
online
issue,
which
is
available
wileyonlinelibrary.com.]
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

1156
W.-J. Dong, F.-H. Cui, Z.-L. Gao, R.-S. Li, G.-L. Shen, and H.-S. Dong
Vol 48
Table 1
Selected geometric parameters (A, ꢀ).
˚
Pyrazoline ring
Thiazole ring
Atom-atom
Triazole ring
Atom-atom
ꢀ
ꢀ
ꢀ
˚
Bond (A, )
˚
Bond (A,
˚
Bond (A,
Atom-atom
)
)
C11-N4
C11-C12
C12-C13
C12-H12A
C12-H12B
C13-N5
C13-C14
C13-H13
N4-N5
1.277(8)
1.505(8)
1.526(9)
0.9700
C20-N6
C21-C22
C21-H21
C22-N6
C22-C23
S1-C21
1.274(7)
1.367(8)
0.9300
1.403(7)
1.472(9)
1.722(7)
1.742(5)
1.392(7)
N1-N2
N2-N3
N1-C5
1.358(6)
1.293(7)
1.426(8)
1.362(8)
1.374(8)
1.373(7)
1.456(9)
C8-N1
0.9700
1.480(6)
1.502(10)
0.9800
1.388(7)
102.8(5)
114.5(6)
113.6(5)
100.4(5)
107.1(5)
71.1(7)
C8-C10
C10-N3
C10-C11
S1-C20
C20-N5
C11-C12-C13
N4-C11-C12
N4-N5-C13
N5-C13-C12
C11-N4-N5
C12-C13-C14-C15
N6-C20-N5-C13
N6-C20-S1
C22-C21-S1
C21-C22-N6
117.1(4)
112.6(4)
112.5(6)
110.8(4)
86.8(3)
N1-C8-C10
N3-C10-C8
N2-N1-C8
105.2(5)
107.9(6)
109.3(5)
109.0(5)
108.6(5)
151.8(8)
C20-N6-C22
C20-S1-C21
N2-N3-C10
N3-N2-N1
C8-N1-C5-C6
N6-C22-C23-C24
C8-C10-C11-C12
169.9(7)
177.2(7)
20.9(10)
of CH3ONa (0.23 mole, in 120 mL absolute methanol) was
added to the mixture of pentane-2,4-dione(17 mL) and 1-
azido-4-methylbenzene (about 0.15 mole) and stirred for 1 h at
0–5ꢀC. Then the mixture was heated under reflux on an oil-
bath for 10 h. Finally, the mixture was acidified with concen-
trated hydrochloric acid. Compound 1 was separated and
crystallized from methanol. Whiter power, yield 52.6%, mp
105–107ꢀC, IR(KBr, cmꢁ1): 3459, 3345, 3050, 1924, 1688,
1549, 1515, 1414, 1367, 1276, 1214, 1078, 949, 825, 671, 558,
CH¼¼CACO), 7.650–7.622 (d, 2H, J ¼ 8.4 Hz, Ar-H), 7.405–
7.226 (m, 6H, Ar-H), 2.659 (s, 3H, Tr-CH3), 2.476 (s, 3H,
Ar1-CH3), 2.403 (s, 3H, Ar2-CH3); MS(EI, 70 ev) (m/z, %):
317 (Mþ., 14.2), 288 (4.9), 261 (57.9), 208 (42.7), 145 (46.4),
132 (100), 115 (40.2), 91 (97.9), 65 (56.5), 43 (34.5); IR
(KBr, cmꢁ1): 1663, 1597, 1111, 1074, 1034, 994, 888, 817,
733.
(E)-3-(4-Chlorophenyl)-1-(5-methyl-1-p-tolyl-1H-1,2,3-tri-
azol-4-yl)-prop-2-en-1-one (3c). White solid; mp: 177–
179ꢀC; Yield: 79.1%; 1H NMR (300 MHz, CDCl3): d (ppm)
8.050–8.105 (d, 1H, J ¼ 16.5 Hz, CH¼¼CACO), 7.833–7.888
(d, 1H, J ¼ 16.5 Hz, C¼¼CHACO), 7.644–7.671 (d, 2H, J ¼
8.1 Hz, Ar2-2,6-H), 7.386–7.413 (d, 2H, J ¼ 8.1 Hz, Ar2-3,5-
H), 7.337–7.376 (m, 4H, Ar1-H), 2.657 (s, 3H, CH3), 2.476 (s,
3H, CH3); MS (m/z, %) 337 (Mþ, 1.2), 308 (2.7), 281 (32.1),
228 (28.4), 165 (37.5), 137 (26.2), 132 (91.4), 102 (34.8), 91
(100), 65 (79.0), 39 (35.6); IR (KBr, cmꢁ1): 1664, 1605, 1032,
993, 887, 824, 786, 756.
(E)-3-(3-Chlorophenyl)-1-(5-methyl-1-p-tolyl-1H-1,2,3-tri-
azol-4-yl)-2-en-1-one (3d). White powder; mp 144–146ꢀC;
Yield: 89.2%; 1H NMR (300 MHz, CDCl3) d (ppm) 7.978–
8.031 (d, 1H, J ¼ 15.9 Hz, CH¼¼CACO), 7.866–7.919 (d, 1H,
J ¼ 15.9 Hz, C¼¼CHACO), 7.679–7.708 (d, 2H, J ¼ 8.4 Hz,
Ar2-2,6-H), 7.374–7.403 (d, 2H, J ¼ 8.7 Hz, Ar1-2,6-H),
7.337–7.366 (d, 2H, J ¼ 8.7Hz, Ar1-3,5-H), 6.934–6.963 (d,
2H, J ¼ 8.7 Hz, Ar2-3,5-H), 3.080 (s, 3H, OCH3), 2.659 (s,
3H, Ar1-CH3), 2.474 (s, 3H, CH3); MS (EI, 70 ev) (m/z, %)
333 (Mþ, 12.6), 334 (Mþ1, 4.3), 304 (4.0), 277 (17.2), 262
(23.6), 247 (6.2), 224 (56.9), 161 (69.9), 145 (31.3), 132
(60.0), 91 (100), 65 (67.0); IR (KBr, cmꢁ1): 1657, 1592, 974,
995, 1011, 1033, 1113, 813, 733.
(E)-3-(4-Methoxyphenyl)-1-(5-methyl-1-p-tolyl-1H-1,2,3-
triazol-4-yl)-2-en-1-one (3e). Yellow powder; mp: 177–
178ꢀC; Yield: 88.2%; 1H NMR (300 MHz, CDCl3) d (ppm)
8.048–8.101 (d, 1H, J ¼ 15.9 Hz, CH¼¼CACO), 7.851–7.904
(d, 1H, J ¼ 15.9 Hz, C¼¼CHACO), 7.323–7.368 (w, 5H, Ar1-
H and Ar2-H), 7.241–7.261 (d, 2H, J ¼ 6 Hz, Ar2-H), 6.966
(s, 1H, Ar2-H), 3.887 (s, 3H, OCH3), 2.661 (s, 3H, Ar1-CH3),
1
499; N HMR (300 MHz, CDCl3): d 7.360–7.384 (d, 2H, J ¼
7.2 Hz, Ar-2,6), 7.306–7.333 (d, 2H J ¼ 8.1 Hz, Ar-3,5), 2.757
(s, 3H, CH3CO), 2.573 (s, 3H, Tr-CH3), 2.468 (s, 3H, Ar-CH3);
MS(EI, 70 ev) (m/z, %): 215 (Mþ., 19), 187 (5), 172 (31), 144
(100), 130 (16), 117 (17), 91 (88), 77 (11), 65 (76), 43 (91).
General method for the synthesis of (E)-3-aryl-1-(5-
methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-prop-2-en-1-ones 3a–j
[25]. A mixture solution of the aromatic aldehyde (0.012
mole) and compound 1 (0.01 mole) in ethanol (70 mL) was
added slowly to an aqueous solution of potassium hydroxide
(0.0128 mole) in water (10 mL). The mixture was stirred in
crushed-ice bath for 2 h, stirred at 20–25ꢀC for 4 h. The mix-
ture was filtrated and the solid was washed with cold water
and alcohol. The product was crystallized from ethanol to give
3a–j.
(E)-1-(5-Methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-3-phenyl-
prop-2-en-1-one (3a)[26]. White powder; mp: 173–175ꢀC;
1
Yield: 91.3%; H NMR (300 MHz, CDCl3) d 8.080–8.132 (d,
1H, J ¼ 15.6 Hz, CH¼¼CACO), 7.809–7.862 (d, 1H, J ¼ 15.6
Hz, C¼¼CHACO), 7.721 (s, 1H, Ar2-2-H), 7.581–7.608 (w,
1H, Ar2-H), 7.342–7.410 (w, 6H, Ar1-H and Ar2-H), 2.666 (s,
3H, Ar1-CH3), 2.479 (s, 3H, CH3); MS (EI, 70ev) (m/z, %)
337 (Mþ, 1.3), 281 (21.9), 228 (30.0), 165 (44.2), 132 (95.0),
91 (100), 65 (71.3); IR (KBr, cmꢁ1): 1664, 1611, 1110, 1034,
1074, 997, 979, 899, 855, 838, 815, 789, 684.
(E)-1-(5-Methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-3-p-tolyl-
prop-2-en-1-one (3b). Whiter power, mp 186–188ꢀC, yield
1
88%; N HMR (300 MHz, CDCl3): d 8.105–8.052 (d, 1H, J ¼
15.9 Hz, C¼¼CHACO), 7.941–7.888 (d, 1H, J ¼ 15.9 Hz,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

September 2011
An Efficient Synthesis of 5-Aryl-4,5-dihydro-3-(5-methyl-1-p-tolyl-
1H-1,2,3-triazol-4-yl)-1-(4-phenylthiazol-2-yl)pyrazoles
1157
2.476 (s, 3H, CH3); MS (EI, 70 ev) (m/z, %) 333(Mþ, 7.8),
277 (18.1), 224 (38.8), 161 (43.6), 132 (100), 118 (27.7), 91
(95.8), 65 (60.4); IR (KBr, cmꢁ1): 1664, 1602, 1049, 1001,
983, 859, 824, 777, 734, 699, 679.
(28.9), 44 (42.1); IR (KBr, cmꢁ1): 1648, 1611, 1034, 1017,
996, 981, 891, 819, 798, 703.
Synthesis of 5-aryl-4,5-dihydro-3-(5-methyl-1-p-tolyl-1H-
1,2,3-triazol-4-yl)pyrazole-1-carbothioamide 4a-j [28]. Com-
pounds 3a–j (5 mmol) and thiosemicarbazide (10 mmol) was
dissolved in ethanol (70 mL), the mixture was stirred at 90ꢀC
for several mintuters, and then an aqueous solution of potas-
sium hydroxide (10 mmol) in ethanol (70 mL) was added
dropwise. The mixture was refluxed for 8 h, and stirred over
night at room temperature. The precipitate was separated by
filtration, washed with ethanol, and the crude product was
crystallized from ethanol to give 4a–j.
(E)-3-(3-Methoxyphenyl)-1-(5-methyl-1-p-tolyl-1H-1,2,3-
triazol-4-yl)prop-2-en-1-one (3f). White powder; mp: 144–
146ꢀC; Yield: 90.0%; 1H NMR (300 MHz, CDCl3), d (ppm)
8.097–8.150 (d, 1H, J ¼ 15.9 Hz, CH¼¼CACO), 7.897–7.950
(d, 1H, J ¼ 15.9 Hz, C¼¼CHACO), 7.721–7.434 (m, 2H, Ar2-
3,5-H), 7.417–7.434 (m, 3H, Ar2-2,4,6-H), 7.376–7.405 (d, 2H,
J ¼ 8.7 Hz, Ar1-2,6-H), 7.339–7.368 (d, 2H, J ¼ 8.7 Hz, Ar1-
5-H), 2.665 (s, 3H, Ar1-CH3), 2.475 (s, 3H, CH3); MS (EI, 70
ev) (m/z, %) 303 (Mþ, 5.1), 274 (2.8), 260 (3.2), 247 (30.6),
194 (35.8), 144 (12.9), 132 (98.4), 115 (34.3), 103 (64.6), 91
(100), 77 (63.3), 65 (78.6), 51 (35.3), 39 (31.5); IR (KBr,
cmꢁ1): 1666, 1602, 1111, 1071, 1035, 1018, 989, 733, 693.
(E)-3-(3,4-Dimethoxyphenyl)-1-(5-methyl-1-p-tolyl-1H-1,2,
3-triazol-4-yl)-prop-2-en-1-one (3g). Yellow powder, mp:
154–156ꢀC; Yield: 79.7%; 1H NMR (300 MHz, CDCl3) d
(ppm) 7.962–8.014 (d, 1H, J ¼ 15.6 Hz, CH¼¼CACO), 7.855–
7.907 (d, 1H, J ¼ 15.6 Hz, C¼¼CHACO), 7.339–7.405 (m,
4H, Ar1-H), 7.276–7.290 (d, 2H, J ¼ 8.7 Hz, Ar2-5,6-H),
6.893–6.923 (d, 1H, J ¼ 8.7 Hz, Ar2-2-H), 3.980 (s, 3H,
OCH3), 3.959 (s, 3H, OCH3), 2.663 (s, 3H, CH3), 2.472 (s,
3H, CH3); MS (m/z, %) 363 (Mþ, 36.8), 335 (6.7), 292 (36.0),
281 (35.8), 254 (55.3), 219 (34.7), 191 (32.5), 132 (100), 91
(51.9); IR (KBr, cmꢁ1): 1656, 1590, 1024, 997, 973, 850, 825,
808, 762, 690.
(E)-3-(Furan-2-yl)-1-(5-methyl-1-p-tolyl-1H-1,2,3-triazol-
4-yl)-prop-2-en-1-one (3h). White powder; mp: 188–189ꢀC;
Yield: 93.8%; 1H NMR (300 MHz, CDCl3) d (ppm) 7.980–
7.927 (d, 1H, J ¼ 15.6 Hz, CH¼¼CACO), 7.671–7.723 (d, 1H,
J ¼ 15.6 Hz, C¼¼CHACO), 7.552–7.556 (d, 1H, J ¼ 1.8 Hz,
5-furanyl-H), 7.362–7.399 (d, 2H, J ¼ 8.7 Hz, Ar2-2,6-H),
7.333–7.362 (d, 2H, J ¼ 8.7 Hz, Ar2-3,5-H), 6.770–6.781 (d,
1H, J ¼ 3.3 Hz, 3-furanyl-H), 6.512–6.529 (dd, 1H, J ¼ 1.8
Hz, J ¼ 3.3 Hz, 4-furanyl-H), 2.650 (s, 3H, CH3), 2.472 (s,
3H, CH3); MS (m/z, %) 293 (Mþ, 10.9), 294 (Mþ1, 2.5), 265
(2.1), 237 (17.4), 222 (2.6), 210 (8.1), 132 (57.3), 91 (64.9),
65 (100), 51 (32), 39 (52); IR (KBr, cmꢁ1): 1661, 1598, 1036,
1013, 993, 976, 877, 860, 822, 771, 698.
4,5-Dihydro-3-(5-methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-5-
phenylpyrazole-1-carbothioamide (4a). Whiter power, yield
86%, mp 182–184ꢀC, IR(KBr, cmꢁ1): 3432, 3250, 1614, 1586,
1516, 1467, 1035, 1001, 869, 828, 756, 718, 670; 1N
HMR(300 MHz, CDCl3): d 7.397–7.370 (d, 2H, J ¼ 8.1 Hz,
Ar1-H), 7.346–7.319 (d, 2H, J ¼ 8.1 Hz, Ar1-H), 7.282–7.229
(m, 5H, Ar2-H ), 6.069–6.018 (dd, 1H, Jx,a ¼ 11.4 Hz, Jx,b
¼
3.6 Hz, Hx), 4.091–3.992 (dd, 1H, Ja,x ¼ 11.4 Hz, Ja,b ¼ 18.3
Hz, Ha), 3.601–3.527 (dd, 1H, Jb,x ¼ 3.6 Hz, Jb,a ¼ 18.3 Hz,
Hb), 2.610 (s, 3H, Tr-CH3), 2.472 (s, 3H, Ar1-CH3); MS(EI,
70 ev) (m/z, %): 376 (Mþ, 5.1), 60 (100). Anal. Calcd for
C20H20N6S: C, 63.81; H, 5.35; N, 22.32; Found: C, 63.96; H,
5.25; N, 22.20.
4,5-Dihydro-3-(5-methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-5-
p-tolylpyrazole-1-carbothioamide (4b). Whiter power, yield
90%, mp 204–206ꢀC, IR(KBr, cmꢁ1): 3438, 3249, 1614, 1588,
1516, 1467, 1087, 1038, 1000, 869, 836, 812, 670; 1N HMR
(300 MHz, CDCl3): d 7.395–7.360 (d, 2H, J ¼ 8.7 Hz, Ar1-
H), 7.346–7.317 (d, 2H, J ¼ 8.7 Hz, Ar1-H), 7.133(s, 4H, Ar2-
H), 6.023–5.975 (dd, 1H, Jx,a ¼ 11.1 Hz, Jx,b ¼ 3.3 Hz, Hx),
4.068–3.968 (dd, 1H, Ja,x ¼ 11.1 Hz, Ja,b ¼ 18.3 Hz, Ha),
3.581–3.509 (dd, 1H, Jb,x ¼ 3.3 Hz, Jb,a ¼ 18.3 Hz, Hb),
2.602 (s, 3H, Tr-CH3), 2.467 (s, 3H, Ar1-CH3), 2.313 (s, 3H,
Ar2-CH3); MS(EI, 70 ev) (m/z, %): 390 (Mþ, 6.7), 60 (100).
Anal. Calcd for C21H22N6S: C, 64.59; H, 5.68; N, 21.52;
Found: C, 64.39; H, 5.78; N, 21.40.
5-(4-Chlorophenyl)-4,5-dihydro-3-(5-methyl-1-p-tolyl-1H-
1,2,3-triazol-4-yl)pyrazole-1-carbothioamide
(4c). Whiter
power, yield 94%, mp 276–248ꢀC, IR(KBr, cmꢁ1): 3439,
3240, 1590, 1515, 1478, 1086, 1036, 918, 876, 843, 670; 1N
HMR (300 MHz, CDCl3): d 7.403–7.376 (d, 2H, J ¼ 8.1 Hz,
Ar1-H), 7.353–7.326 (d, 2H, J ¼ 8.1 Hz, Ar1-H), 7.298–7.271
(d, 2H, J ¼ 8.1 Hz, Ar2-H), 7.202–7.175 (d, 2H, J ¼ 8.1 Hz,
Ar2-H), 6.032–5.981 (dd, 1H, Jx,a ¼ 11.7 Hz, Jx,b ¼ 3.6 Hz,
Hx), 4.093–4.000 (dd, 1H, Ja,x ¼ 11.7 Hz, Ja,b ¼ 18.9 Hz, Ha),
3.570–3.495 (dd, 1H, Jb,x ¼ 3.6 Hz, Jb,a ¼ 18.9 Hz, Hb),
2.610 (s, 3H, Tr-CH3), 2.476 (s, 3H, Ar1-CH3); MS(EI, 70 ev)
(m/z, %): 410 (Mþ., 2.6), 60 (100). Anal. Calcd for
C20H19ClN6S: C, 58.46; H, 4.66; N, 20.45; Found: C, 58.35;
H, 4.84; N, 20.27.
(E)-3-(Benzo[d][1,3]dioxol-5-yl)-1-(5-methyl-1-p-tolyl-1H-
1,2,3-triazol-4-yl)-prop-2-en-1-one (3i). Yellow powder, mp:
183–185ꢀC; Yield: 82.6%; 1H NMR (300 MHz, CDCl3) d
(ppm) 7.921–7.974 (d, 1H, J ¼ 15.9 Hz, CH¼¼CACO), 7.808–
7.861 (d, 1H, J ¼ 15.9 Hz, C¼¼CHACO), 7.362 (s, 4H, Ar1-
H), 7.267 (s, 1H, Ar2-2-H), 7.177–7.204 (d, 1H, J ¼ 8.1 Hz,
Ar2-6-H), 6.837–6.864 (d, 1H, J ¼ 8.1 Hz, Ar2-5-H), 6.030 (s,
2H, CH2), 2.651 (s, 3H, CH3), 2.470 (s, 3H, CH3); MS (m/z,
%) 347 (Mþ, 18.8), 319 (11.2), 291 (46.9), 238 (45.3), 144.9
(36.6), 132 (100), 90.9 (55.0), 40 (46.4); IR (KBr, cmꢁ1):
1662, 1589, 1036, 996, 926, 860, 815, 756, 695.
(E)-3-[4-(Dimethylamino)phenyl]-1-(5-methyl-1-p-tolyl-1H-
1,2,3-triazol-4-yl)-prop-2-en-1-one (3j). Yellow powder; mp:
210–212ꢀC; Yield: 82.5%; 1H NMR (300 MHz, CDCl3) d
(ppm) 7.911 (s, 2H, CH¼¼CH), 7.626–7.657 (d, 2H, J ¼ 8.7
Hz, Ar2-2,6-H), 7.366 (b, 4H, Ar1-2,3,5,6-H), 6.696–6.725 (d,
2H, J ¼ 8.7 Hz, Ar2-3,5-H), 3.056 (s, 6H, N(CH3)2), 2.657 (s,
3H, Ar1-CH3), 2.472 (s, 3H, CH3); MS (m/z, %) 346 (Mþ,
11.6), 347 (Mþ1, 1.4), 318 (3.4), 290 (5.2), 275 (2.3), 237
(5.0), 174 (8.2), 158 (7.4), 144 (16.1), 132 (100), 91 (63.5), 65
5-(3-Chlorophenyl)-4,5-dihydro-3-(5-methyl-1-p-tolyl-1H-
1,2,3-triazol-4-yl)pyrazole-1-carbothioamide
(4d). Whiter
power, yield 89%, mp 225–227ꢀC, IR (KBr, cmꢁ1): 3432,
3248, 1591, 1517, 1470, 1081, 1039, 1000, 975, 879, 819,
1
674; N HMR (300 MHz, CDCl3): d 7.405–7.376 (d, 2H, J ¼
8.7 Hz, Ar1-H), 7.356–7.327 (d, 2H, J ¼ 8.7 Hz, Ar1-H),
7.311–7.142 (m, 4H, Ar2-H ), 6.036–5.985 (dd, 1H, Jx,a
11.4 Hz, Jx,b ¼ 3.9 Hz, Hx), 4.095–3.994 (dd, 1H, Ja,x ¼ 11.4
Hz, Ja,b ¼ 18.6 Hz, Ha), 3.572–3.497 (dd, 1H, Jb,x ¼ 3.9 Hz,
¼
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

1158
W.-J. Dong, F.-H. Cui, Z.-L. Gao, R.-S. Li, G.-L. Shen, and H.-S. Dong
Vol 48
Jb,a ¼ 18.6 Hz, Hb), 2.616 (s, 3H, Tr-CH3), 2.494 (s, 3H, Ar1-
CH3); MS(EI, 70 ev) (m/z, %): 410 (Mþ., 1.9), 60 (100). Anal.
Calcd for C20H19ClN6S: C, 58.46; H, 4.66; N, 20.45; Found:
C, 58.37; H, 4.66; N, 20.55.
5-(Benzo[d][1,3]dioxol-5-yl)-4,5-dihydro-3-(5-methyl-1-p-tolyl-
1H-1,2,3-triazol-4-yl)pyrazole-1-carbothioamide (4i). Whiter
power, yield 87%, mp 223–225ꢀC, IR (KBr, cmꢁ1): 3434,
3235, 1594, 1488, 1432, 1087, 1035, 1001, 927, 891, 837,
1
4,5-Dihydro-5-(4-methoxyphenyl)-3-(5-methyl-1-p-tolyl-1H-
1,2,3-triazol-4-yl)-5-phenylpyrazole-1-carbothioamide (4e). Whiter
power, yield 96%, mp 215–217ꢀC, IR(KBr, cmꢁ1): 3408,
3261, 1592, 1512, 1468, 1079, 1026, 999, 913, 867, 820, 671;
1N HMR (300 MHz, CDCl3): d 7.401–7.374 (d, 2H, J ¼ 8.1
Hz, Ar1-H), 7.354–7.327 (d, 2H, J ¼ 8.1 Hz, Ar1-H), 7.200–
7.171 (d, 2H, J ¼ 8.7 Hz, Ar2-H), 6.877–6.848 (d, 2H, J ¼
671; N HMR (300 MHz, CDCl3): d 7.406–7.378 (d, 2H, J ¼
8.4 Hz, Ar1-H), 7.357–7.329 (d, 2H, J ¼ 8.4 Hz, Ar1-H),
6.791–6.693 (m, 3H, Ar2-H), 5.972–5.922 (dd, 1H, Jx,a ¼ 11.4
Hz, Jx,b ¼ 3.6 Hz, Hx), 5.938( s, 2H, Ar2-OCH2OA), 4.061–
3.952 (dd, 1H, Ja,x ¼ 11.4 Hz, Ja,b ¼ 18.6 Hz, Ha), 3.569–
3.495 (dd, 1H, Jb,x ¼ 3.6 Hz, Jb,a ¼ 18.6 Hz, Hb), 2.602 (s,
3H, Tr-CH3), 2.477 (s, 3H, Ar1-CH3); MS(EI, 70 ev) (m/z, %):
420 (Mþ, 5.0), 60 (100). Anal. Calcd for C21H20N6O2S: C,
59.98; H, 4.79; N, 19.99; Found: C, 58.74; H, 4.82; N, 20.04.
4,5-Dihydro-5-(4-dimethylaminophenyl)-3-(5-methyl-1-p-tolyl-
1H-1,2,3-triazol-4-yl)pyrazole-1-carbothioamide (4j). Whiter
power, yield 93%, mp 232–234ꢀC, IR(KBr, cmꢁ1): 3428, 3243,
8.7 Hz, Ar2-H), 6.014–5.965 (dd, 1H, Jx,a ¼ 11.1 Hz, Jx,b
¼
3.6 Hz, Hx), 4.064–3.963 (dd, 1H, Ja,x ¼ 11.1 Hz, Ja,b ¼ 18.6
Hz, Ha), 3.785 (s, 3H, Ar2-OCH3), 3.595–3.521 (dd, 1H, Jb,x
¼ 3.6 Hz, Jb,a ¼ 18.6 Hz, Hb), 2.608 (s, 3H, Tr-CH3), 2.474
(s, 3H, Ar1-CH3); MS(EI, 70 ev) (m/z, %): 406 (Mþ, 1.3), 60
(100). Anal. Calcd for C21H22N6OS: C, 62.05; H, 5.45; N,
20.67; Found: C, 62.24; H, 5.47; N, 20.44.
1
1613, 1592, 1520, 1481, 1085, 1037, 999, 944, 867, 812, 670; N
HMR(300 MHz, CDCl3): d 7.402–7.374 (d, 2H, J ¼ 8.4 Hz, Ar1-
H), 7.358–7.330 (d, 2H, J ¼ 8.4 Hz, Ar1-H), 7.152–7.123 (d, 2H, J
¼ 8.7 Hz, Ar2-H), 6.700–6.671 (d, 2H, J ¼ 8.7 Hz, Ar2-H), 5.979–
5.930 (dd, 1H, Jx,a ¼ 11.4 Hz, Jx,b ¼ 3.6 Hz, Hx), 4.040–3.941
(dd, 1H, Ja,x ¼ 11.4 Hz, Ja,b ¼ 18.9 Hz, Ha), 3.610–3.536 (dd, 1H,
Jb,x ¼ 3.6 Hz, Jb,a ¼ 18.9 Hz, Hb), 2.922 (s, 6H, Ar2-N(CH3)2),
2.604(s, 3H, Tr-CH3), 2.474 (s, 3H, Ar1-CH3); MS (LOWmass.m):
420 (MþH), 442 (MþNa); Anal. Calcd for C22H25N7S: C, 62.98;
H, 6.01; N, 23.37; Found: C, 62.77; H, 5.90; N, 23.55.
Synthesis of 5-aryl-4,5-dihydro-3-(5-methyl-1-p-tolyl-1H-1,
2,3-triazol-4-yl)-1-(4-phenylthiazol-2-yl)pyrazoles 5a-j. Com-
pounds 4a–j (2 mmol) and 2-bromo-1-phenylethanone (2
mmol) wad dissolved in ethanol (15 mL), and then the mixture
was refluxed for 2 h. The precipitate was separated by filtra-
tion, washed with ethanol, and the crude product was crystal-
lized from ethanol to give 5a–j.
4,5-Dihydro-3-(5-methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-5-
phenyl-1-(4-phenylthiazol-2-yl)pyrazole (5a). Light yellow
power, yield 82%, mp 191–193ꢀC, IR(KBr, cmꢁ1): 3440, 3094,
1603, 1541, 1514, 1441, 1055, 1026, 1004, 975, 820, 735, 695;
1N HMR(300 MHz, CDCl3): d 7.702–7.675 (d, 2H, J ¼ 8.1 Hz,
Ar-H), 7.480–7.454 (d, 2H, J ¼ 7.8 Hz, Ar-H), 7.382–7.210 (m,
10H, Ar-H), 6.803 (s, 1H, Thiazole-H), 5.707 (b, 1H, Hx), 4.209–
4.107 (dd, 1H, Ja,x ¼ 12.0 Hz, Ja,b ¼ 18.6 Hz, Ha), 3.721–3.638
(dd, 1H, Jb,x ¼ 6.6 Hz, Jb,a ¼ 18.6 Hz, Hb), 2.685(s, 3H, Tr-
CH3), 2.478 (s, 3H, Ar1-CH3); MS (LOW mass. m): 477
(MþH), 499 (MþNa); Anal. Calcd for C28H24N6S: C, 70.56; H,
5.08; N, 17.63; Found: C, 70.82; H, 4.95; N, 17.55.
4,5-Dihydro-5-(3-methoxyphenyl)-3-(5-methyl-1-p-tolyl-
1H-1,2,3-triazol-4-yl)-5-phenylpyrazole-1-carbothioamide
(4f). Whiter power, yield 95%, mp 197–199ꢀC, IR(KBr,
cmꢁ1): 3365, 3259, 1591, 1516, 1479, 1083, 1047, 1001,
975, 821, 776, 670; 1N HMR (300 MHz, CDCl3): d 7.399–
7.372 (d, 2H, J ¼ 8.1 Hz, Ar1-H), 7.351–7.340 (d, 2H, J ¼
8.1 Hz, Ar1-H), 7.321–7.235 (m, 1H, Ar2-H), 6.839–6.780
(m, 3H, Ar2-H ), 6.040–5.988 (dd, 1H, Jx,a ¼ 12.0 Hz, Jx,b
¼ 3.6 Hz, Hx), 4.074–3.974 (dd, 1H, Ja,x ¼ 12.0 Hz, Ja,b
¼
18.9 Hz, Ha), 3.796 (s, 3H, Ar2-OCH3), 3.589–3.515 (dd,
1H, Jb,x ¼ 3.6 Hz, Jb,a ¼ 18.9 Hz, Hb), 2.603 (s, 3H, Tr-
CH3), 2.472 (s, 3H, Ar1-CH3); MS(EI, 70 ev) (m/z, %): 406
(Mþ., 4.2), 60 (100). Anal. Calcd for C21H22N6OS: C,
62.05; H, 5.45; N, 20.67; Found: C, 61.92; H, 5.64; N,
20.55.
4,5-Dihydro-5-(3,4-dimethoxyphenyl)-3-(5-methyl-1-p-tolyl-
1H-1,2,3-triazol-4-yl)pyrazole-1-carbothioamide (4g). Whiter
power, yield 92%, mp 185–187ꢀC, IR (KBr, cmꢁ1): 3346,
3277, 1593, 1516, 1475, 1082, 1026, 1002,919, 871, 825, 763,
1
672; N HMR (300 MHz, CDCl3): d 7.403–7.376 (d, 2H, J ¼
8.1 Hz, Ar1-H), 7.356–7.329 (d, 2H, J ¼ 8.1Hz, Ar1-H),
6.807–6.755 (m, 3H, Ar2-H), 6.018–5.967 (dd, 1H, Jx,a ¼ 11.7
Hz, Jx,b ¼ 3.6 Hz, Hx), 4.070–3.970 (dd, 1H, Ja,x ¼ 11.7 Hz,
Ja,b ¼ 18.6 Hz, Ha), 3.880 (s, 3H, Ar2-OCH3), 3.851 (s, 3H,
Ar2-OCH3), 3.621–3.546 (dd, 1H, Jb,x ¼ 3.6 Hz, Jb,a ¼ 18.6
Hz, Hb), 2.610( s, 3H, Tr-CH3), 2.476 (s, 3H, Ar1-CH3);
MS(EI, 70 ev) (m/z, %): 436 (Mþ., 1.8), 60 (100). Anal. Calcd
for C22H24N6O2S: C, 60.53; H, 5.54; N, 19.25; Found: C,
60.70; H, 5.43; N, 19.19.
4,5-Dihydro-3-(5-methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-1-
(4-phenylthiazol-2-yl)-5-p-tolylpyrazole (5b). Light yellow
power, yield 76%, mp 237–239ꢀC, IR(KBr, cmꢁ1): 3437,
3092, 1602, 1536, 1513, 1443, 1055, 1029, 1003, 971, 817,
4,5-Dihydro-5-(furan-2-yl)-3-(5-methyl-1-p-tolyl-1H-1,2,3-
triazol-4-yl)pyrazole-1-carbothioamide (4h). Whiter power,
yield 90%, mp 175–177ꢀC, IR (KBr, cmꢁ1): 3462, 3351, 1575,
1518, 1467, 1073, 1039, 1004, 948, 868, 815, 747, 670; 1N
HMR (300 MHz, CDCl3): d 7.403–7.375 (d, 2H, J ¼ 8.4 Hz,
Ar1-H), 7.359–7.331 (d, 2H, J ¼ 8.4Hz, Ar1-H), 7.311–7.307
(d, 1H, J ¼ 1.2 Hz, furan-H), 6.467–6.455 (d, 1H, J ¼ 3.6 Hz,
furan-H), 6.344–6.328 (dd, 1H, J ¼ 1.8 Hz, J ¼ 3.0 Hz, furan-
H), 6.156–6.107 (dd, 1H, Jx,a ¼ 11.2 Hz, Jx,b ¼ 4.5 Hz, Hx),
3.931–3.837 (dd, 1H, Ja,x ¼ 11.2 Hz, Ja,b ¼ 18.6 Hz, Ha),
3.841–3.765 (dd, 1H, Jb,x ¼ 4.5 Hz, Jb,a ¼ 18.6 Hz, Hb),
2.688 (s, 3H, Tr-CH3), 2.473 (s, 3H, Ar1-CH3); MS(EI, 70 ev)
(m/z, %): 366 (Mþ., 5.6), 60 (100). Anal. Calcd for
C18H18N6OS: C, 59.00; H, 4.95; N, 22.93; Found: C, 59.23;
H, 4.82; N, 22.70.
1
736, 693; N HMR(300 MHz, CDCl3): d 7.726–7.702 (d, 2H,
J ¼ 7.2 Hz, Ar-H), 7.380–7.216 (m, 9H, Ar-H), 7.177–7.149
(d, 2H, J ¼ 8.4 Hz, Ar-H), 6.796 (s, 1H, Thiazole-H), 5.701
(b, 1H, Hx), 4.183–4.082 (dd, 1H, Ja,x ¼ 12.0 Hz, Ja,b ¼ 18.3
Hz, Ha), 3.712–3.630 (dd, 1H, Jb,x ¼ 6.6 Hz, Jb,a ¼ 18.3 Hz,
Hb), 2.679 (s, 3H, Tr-CH3), 2.476 (s, 3H, Ar1-CH3), 2.327 (s,
3H, Ar2-CH3); MS (LOW mass. m): 491 (MþH), 513
(MþNa); Anal. Calcd for C29H26N6S: C, 70.99; H, 5.34; N,
17.13; Found: C, 71.05; H, 5.19; N, 17.09.
5-(4-Chlorophenyl)-4,5-dihydro-3-(5-methyl-1-p-tolyl-1H-1,
2,3-triazol-4-yl)-1-(4-phenylthiazol-2-yl)pyrazole (5c). Light
yellow power, yield 85%, mp 203–205ꢀC, IR(KBr, cmꢁ1):
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

September 2011
An Efficient Synthesis of 5-Aryl-4,5-dihydro-3-(5-methyl-1-p-tolyl-
1H-1,2,3-triazol-4-yl)-1-(4-phenylthiazol-2-yl)pyrazoles
1159
3435, 3092, 1600, 1536, 1514, 1438, 1085, 1055, 1031, 1007,
973, 820, 714, 691; 1N HMR(300 MHz, CDCl3): d 7.694–
7.667 (d, 1H, J ¼ 8.1 Hz, Ar-H), 7.425–7.224 (m, 12H, Ar-
H), 6.821 (s, 1H, Thiazole-H), 6.000 (b, 1H, Hx), 4.203–4.103
(dd, 1H, Ja,x ¼ 11.7 Hz, Ja,b ¼ 18.3 Hz, Ha), 3.669–3.584 (dd,
1H, Jb,x ¼ 6.9 Hz, Jb,a ¼ 18.3 Hz, Hb), 2.677 (s, 3H, Tr-CH3),
2.418 (s, 3H, Ar1-CH3); MS (LOW mass. m): 511 (MþH),
533 (MþNa); Anal. Calcd for C28H23ClN6S: C, 65.81; H,
4.54; N, 16.44; Found: C, 65.77; H, 4.40; N, 16.59.
Jb,a ¼ 18.0 Hz, Hb), 2.677 (s, 3H, Tr-CH3), 2.474 (s, 3H, Ar1-
CH3); MS (LOW mass. m): 507 (MþH), 529 (MþNa); Anal.
Calcd for C29H26N6OS: C, 68.75; H, 5.17; N, 16.59; Found:
C, 67.58; H, 5.32; N, 16.49.
4,5-Dihydro-5-(3,4-dimethoxyphenyl)-3-(5-methyl-1-p-
tolyl-1H-1,2,3-triazol-4-yl)-1-(4-phenylthiazol-2-yl)pyrazole
(5g). Light yellow power, yield 80%, mp 244–246ꢀC, IR(KBr,
cmꢁ1): 3443, 3083, 1600, 1540, 1514, 1462, 1055, 1025, 1005,
977, 821, 727, 690; 1N HMR (300 MHz, CDCl3): d 7.737–
7.714 (d, 2H, J ¼ 6.9 Hz, Ar-H), 7.380–7.216 (m, 8H, Ar-H),
7.050–7.011 (m, 1H, Ar-H), 6.868–6.841 (d, 1H, J ¼ 8.1 Hz,
Ar-H), 6.815 (s, 1H, Thiazole-H), 5.627 (b, 1H, Hx), 4.179–
4.080 (dd, 1H, Ja,x ¼ 11.7 Hz, Ja,b ¼ 18.0 Hz, Ha), 3.892(s,
3H, Ar2-OCH3), 3.865(s, 3H, Ar2-OCH3), 3.744–3.658 (dd,
1H, Jb,x ¼ 6.9 Hz, Jb,a ¼ 18.6 Hz, Hb), 2.851(s, 3H, Tr-CH3),
2.474 (s, 3H, Ar1-CH3); MS (LOW mass. m): 537 (MþH),
559 (MþNa); Anal. Calcd for C30H28N6O2S: C, 67.14; H,
5.26; N, 15.66; Found: C, 67.00; H, 5.33; N, 15.69.
X-ray structure determination of 5c. Colorless, Block,
C28H23ClN6S, Mr ¼ 511.03, Triclinic, space group P-1, a ¼
˚
11.276 (11), b ¼ 11.690 (11), c ¼ 11.757 (11) A, a ¼ 64.111
3
ꢀ
˚
(14), b ¼ 67.034 (14), c ¼ 79.882 (13) , V ¼ 1284 (22)A , Z
¼ 2, Dx ¼ 1.322 Mg mꢁ3, F000 ¼ 532, l ¼ 0.259 mmꢁ1. In-
tensity data were collected using a Siemens SMART diffrac-
tometer at 293 (2) K, graphite monochromator MoKa radiation
(k ¼ 0.071073 nm), using the x-2y scan technique to a maxi-
mum 1.9–25.1ꢀ. A total of 4298 reflections were collected
with 2261 unique ones (R ¼ 0.0614), of which 5597 reflec-
tions were observed with I > 2r (I). The final int R and wR
values were 0.0989 and 0.2463, s ¼ 1.090, (D/r)max ¼ 0.000.
The maximum peak and minimum peak in the final difference
4,5-Dihydro-5-(furan-2-yl)-3-(5-methyl-1-p-tolyl-1H-1,2,3-
triazol-4-yl)-1-(4-phenylthiazol-2-yl)pyrazole
(5h). Light
yellow power, yield 75%, mp 179–181ꢀC, IR(KBr, cmꢁ1):
3449, 3090, 1603, 1541, 1479, 1073, 1054, 1005, 974, 819,
1
map is 0.470 and ꢁ0.403 eAꢁ3. The crystal structure has been
802, 731, 698; NHMR(300MHz, CDCl3): d 7.823–7.798 (d,
˚
2H, J ¼ 7.5 Hz, Ar-H), 7.399–7.253 (m, 8H, Ar-H ), 6.836
(s, 1H, Thiazole-H), 6.594 (s, 1H, furan-H), 6.358 (s, 1H,
furan-H), 5.801 (b, 1H, Hx), 3.984–3.955 (m, 2H, Ha, Hb),
2.657 (s, 3H, Tr-CH3), 2.476 (s, 3H, Ar1-CH3); MS (LOW
mass. m): 467 (MþH), 489 (MþNa); Anal. Calcd for
C26H22N6OS: C, 66.93; H, 4.75; N, 18.01; Found: C, 66.83;
H, 4.55; N, 18.26.
deposited at the Cambridge Crystallographic Data Centre and
allocated the deposition number is CCDC 793215.
5-(3-Chlorophenyl)-4,5-dihydro-3-(5-methyl-1-p-tolyl-1H-1,
2,3-triazol-4-yl)-1-(4-phenylthiazol-2-yl)pyrazole (5d). Light
yellow power, yield 73%, mp 226–228ꢀC, IR(KBr, cmꢁ1):
3441, 3097, 1597, 1536, 1515, 1478, 1075, 1055, 1002, 973,
1
863, 774, 693; N HMR(300 MHz, CDCl3): d 7.702–7.677 (d,
5-(Benzo[d][1,3]dioxol-5-yl)-4,5-dihydro-3-(5-methyl-1-
p-tolyl-1H-1,2,3-triazol-4-yl)-1-(4-phenylthiazol-2-yl)pyr-
azole (5i). Light yellow power, yield 77%, mp 229–231ꢀC,
IR(KBr, cmꢁ1): 3478, 3093, 1604, 1535, 1514, 1487, 1038,
2H, J ¼ 7.5 Hz, Ar-H), 7.476 (s, 1H, Ar-H ), 7.374–7.214 (m,
10H, Ar-H), 6.823 (s, 1H, Thiazole-H), 5.641–5.578 (dd, 1H,
Jx,a ¼ 11.7 Hz, Jx,b ¼ 7.2 Hz, Hx), 4.203–4.142 (dd, 1H, Ja,x
¼ 11.7 Hz, Ja,b ¼ 18.0 Hz, Ha), 3.681–3.597 (dd, 1H, Jb,x
¼
1
1008, 976, 934, 818, 744, 697; N HMR (300 MHz, CDCl3): d
7.2 Hz, Jb,a ¼ 18.0 Hz, Hb), 2.671(s, 3H, Tr-CH3), 2.468 (s,
3H, Ar1-CH3); MS (LOW mass. m): 511 (MþH), 533
(MþNa); Anal. Calcd for C28H23ClN6S: C, 65.81; H, 4.54; N,
16.44; Found: C, 65.70; H, 4.41; N, 16.58.
7.739–7.714 (d, 2H, J ¼ 7.5Hz, Ar-H), 7.380–7.243 (m, 8H,
Ar-H), 6.989-6.897 (m, 1H, Ar-H), 6.815 (s, 1H, Thiazole-H),
6.784-6.774 (m, 1H, Ar-H), 5.998 (s, 2H, Ar2-OCH2O-), 5.604
(b, 1H, Hx), 5.516–4.056 (dd, 1H, Ja,x ¼ 11.7 Hz, Ja,b ¼ 18.3
Hz, Ha), 3.673–3.589 (dd, 1H, Jb,x ¼ 6.3 Hz, Jb,a ¼ 18.3 Hz,
Hb), 2.673(s, 3H, Tr-CH3), 2.476 (s, 3H, Ar1-CH3); MS (LOW
mass. m): 521 (MþH), 543 (MþNa); Anal. Calcd for
C29H24N6O2S: C, 66.90; H, 4.65; N, 16.14; Found: C, 66.86;
H, 4.85; N, 16.19.
4,5-Dihydro-5-(4-methoxyphenyl)-3-(5-methyl-1-p-tolyl-1H-
1,2,3-triazol-4-yl)-1-(4-phenylthiazol-2-yl)pyrazole (5e). Light
yellow power, yield 83%, mp 223–225ꢀC, IR (KBr, cmꢁ1):
3426, 3087, 1606, 1537, 1515, 1479, 1055, 1030, 1002, 971,
1
825, 735, 692; N HMR (300 MHz, CDCl3): d 7.728–7.702 (d,
2H, J ¼ 8.7 Hz, Ar-H), 7.411–7.210 (m, 9H, Ar-H), 6.897–
6.868 (d, 2H, J ¼ 8.7 Hz, Ar-H), 6.796 (s, 1H, Thiazole-H),
5.655–5.594 (dd, 1H, Jx,a ¼ 11.7 Hz, Jx,b ¼ 6.6 Hz, Hx),
4.164–4.064 (dd, 1H, Ja,x ¼ 11.7 Hz, Ja,b ¼ 18.3 Hz, Ha),
3.777 (s, 3H, Ar2-OCH3), 3.703–3.619 (dd, 1H, Jb,x ¼ 6.6 Hz,
Jb,a ¼ 18.0 Hz, Hb), 2.667 (s, 3H, Tr-CH3), 2.462 (s, 3H, Ar1-
CH3); MS (LOW mass. m): 507 (MþH), 529 (MþNa); Anal.
Calcd for C29H26N6OS: C, 68.75; H, 5.17; N, 16.59; Found:
C, 68.90; H, 5.01; N, 16.44.
4,5-Dihydro-5-(4-dimethylaminophenyl)-3-(5-methyl-1-
p-tolyl-1H-1,2,3-triazol-4-yl)-1-(4-phenylthiazol-2-yl)pyr-
azole (5j). Light yellow power, yield 82%, mp 215–217ꢀC,
IR(KBr, cmꢁ1): 3434, 3095, 1613, 1539, 1518, 1478, 1053,
1
1027, 1002, 972, 814, 711, 692; N HMR (300 MHz, CDCl3):
d 7.763–7.749 (d, 2H, J ¼ 7.2 Hz, Ar-H), 7.380–7.257 (m,
9H, Ar-H), 7.237-7.214 (d, 2H, J ¼ 6.9Hz, Ar-H), 7.003 (s,
1H, Thiazole-H), 5.629-5.569 (dd, 1H, Jx,a ¼ 11.7Hz, Jx,b
¼
6.3Hz, Hx), 4.140-4.039 (dd, 1H, Ja,x ¼ 12.0 Hz, Ja,b ¼ 18.3
Hz, Ha), 3.732–3.648 (dd, 1H, Jb,x ¼ 6.3 Hz, Jb,a ¼ 18.3 Hz,
Hb), 2.935 (s, 6H, Ar2-N(CH3)2), 2.675(s, 3H, Tr-CH3), 2.474
(s, 3H, Ar1-CH3); MS (LOW mass. m): 520 (MþH), 542
(MþNa); Anal.Calcd for C30H29N7S: C, 69.34; H, 5.62; N,
18.87; Found: C, 69.17; H, 5.55; N, 18.96.
4,5-Dihydro-5-(3-methoxyphenyl)-3-(5-methyl-1-p-tolyl-
1H-1,2,3-triazol-4-yl)-1-(4-phenylthiazol-2-yl)pyrazole (5f). Light
yellow power, yield 89%, mp 194–196ꢀC, IR (KBr, cmꢁ1):
3448, 3095, 1607, 1537, 1515, 1485, 1003, 1052, 975, 868,
1
819, 777, 695; N HMR (300 MHz, CDCl3): d 7.722–7.698 (d,
2H, J ¼ 7.2 Hz, Ar-H), 7.378–7.210 (m, 9H, Ar-H), 7.059–
7.014 (m, 2H, Ar-H), 6.809 (s, 1H, Thiazole-H), 5.692 (b, 1H,
Hx), 4.191–4.090 (dd, 1H, Ja,x ¼ 12.3 Hz, Ja,b ¼ 18.0 Hz, Ha),
3.804 (s, 3H, Ar2-OCH3), 3.712–3.631 (dd, 1H, Jb,x ¼ 6.3 Hz,
Acknowledgments. The authors acknowledge that this project is
supported by Lanzhou University SKLAOC.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

1160
W.-J. Dong, F.-H. Cui, Z.-L. Gao, R.-S. Li, G.-L. Shen, and H.-S. Dong
Vol 48
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet