Synthesis of some new 1-acyl-5-aryl-3-(5-methyl-1-p-tolyl-1H- 1,2,3-triazol-4-yl)-4,5-dihydro-1H-pyrazole

Article abstract of DOI:10.1002/jhet.726

Some new compounds (E)-3-aryl-1-(5-methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)- prop-2-en-1-ones 5a-e were prepared by 1-(5-methyl-1-p-tolyl-1H-1,2,3-triazol-4- yl)-ethanone and various aromatic aldehydes. Then one pot reaction was happened by compounds 5a-e with hydrazine hydrate in acetic acid or propionic acid, respectively, to give the title compounds 1acyl-5-aryl-3-(5-methyl-1-p-tolyl-1H- 1,2,3-triazol- 4-yl)-4,5-dihydro-1H-pyrazoles 6a-i. All structures were established by MS, IR, CHN, 1H-NMR and ¹³C-NMR spectral data..

Full text of DOI:10.1002/jhet.726

January 2012
Synthesis of Some New 1-Acyl-5-aryl-3-(5-methyl-1-p-tolyl-1H-
1,2,3-triazol-4-yl)-4,5-dihydro-1H-pyrazole
149
Heng-Shan Dong,a* Yan-Fei Wang,a Guo-Liang Shen,a Bin Quan,b
and Wang-Jun Donga
aState 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
bCollege of Chemistry and Chemical Engineering, Guansu Association University, Lanzhou,
Gansu 730000, People’s Republic of China
*E-mail: donghengshan@lzu.edu.cn
Received June 12, 2010
DOI 10.1002/jhet.726
Published online 17 October 2011 in Wiley Online Library (wileyonlinelibrary.com).
Some new compounds (E)-3-aryl-1-(5-methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-prop-2-en-1-ones 5a–e
were prepared by 1-(5-methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-ethanone and various aromatic aldehydes.
Then one pot reaction was happened by compounds 5a–e with hydrazine hydrate in acetic acid or propi-
onic acid, respectively, to give the title compounds 1acyl-5-aryl-3-(5-methyl-1-p-tolyl-1H-1,2,3-triazol-
4-yl)-4,5-dihydro-1H-pyrazoles 6a–i. All structures were established by MS, IR, CHN, 1H-NMR and
13C-NMR spectral data.
J. Heterocyclic Chem., 49, 149 (2012).
INTRODUCTION
1,2,3-triazol-4-yl)-prop-2-en-1-ones and 1-acyl-5-aryl-3-(5-
methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-4,5-dihydro-1H-pyr-
azoles and the steps are shown in Scheme 1. All struc-
Among infectious diseases, tuberculosis (TB) is consid-
ered to be one of the most dangerous chronic communica-
ble diseases with over 2 million casualties annually in the
world [1]. At the same time, the emergence of AIDS
which reduced emphasis on tuberculosis control programs
contributed to the disease’s resurgence in industrialized
countries [2]. Resistance of Mycobacterium tuberculosis
(MTB) strains to antimycobacterial agents is also an
increasing problem worldwide [3–5]. However, the key
problem in the chemotherapy of tuberculosis is no new
powerful anti-TB drugs with new mechanism of action
have been developed in recent years. Thus, the exploitation
of new anti-TB drugs that are effective against a persistent
MTB infection is urgently desired. Literature survey
reveals that pyrazoline derivatives possess the various bio-
logical activities such as anti-bacterial and anti-fungal [6],
anti-diabetic [7], anti-inflammatory [8], and are also active
against many mycobacterials [9–13]. Therefore, we have
synthesized some new (E)-3-aryl-1-(5-methyl-1-p-tolyl-1H-
1
tures are established by MS, IR, CHN, H-NMR, and
13C-NMR spectral data.
RESULTS AND DISCUSSION
The compounds (E)-3-aryl-1-(5-methyl-1-p-tolyl-1H-
1,2,3-triazol-4-yl)-prop-2-en-1-one 5a–e were prepared
by the Claisen-Schmidt condensation reaction of 1-(5-
methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-ethanone and some
aromatic aldehydes. The target compounds 1-acyl-5-aryl-
3-(5-methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-4,5-dihydro-
1H-pyrazoles 6a–e were prepared from 5a–e, hydrazine
and acetic/propionic acid by sequence reactions involving
in intermolecular conjugated addition, hydrazone forma-
tion and N-acylation [14].
In their IR spectral, mc¼o vibration bands are at 1648–1666
cmꢀ1 in 5a–e, and 1654–1665cmꢀ1 in 6a–i. Moreover, mC¼N
C
V
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150
H.-S. Dong, Y.-F. Wang, G.-L. Shen, B. Quan, and W.-J. Dong
Vol 49
Scheme 1
In summary, a series of pyrazoline derivatives were
conveniently prepared by a simple synthetic method
from aromatic amine. Its structure was characterized by
1
MS, IR, CHN, H-NMR, and 13C-NMR spectral data.
EXPERIMENTAL
All melting points were determined on a XT4-100x Kofler
melting point apparatus and are uncorrected. IR spectra were
obtained in KBr discs on a Shimadzu IR-435 spectrometer. MS
were performed on a HP-5988A spectrometer (EI at 70 eV).
1H-NMR and 13C-NMR spectroscopy (CDCl3) was recorded on
Avance Mercury plus-300 instrument with TMS as an internal
standard. Elemental analysis was carried out on a Yanaco CHN
Corder MT-3 analyzer.
1-Azido-4-methylbenzene 3. Compound 3 was prepared by
the method reported in the literature [20,21].
1-(5-Methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-ethanone 4.
Compound 4 was prepared by the reaction of 1-azido-4-meth-
ylbenzene 3 with pentane-2,4-dione [22]. A cold solution of
CH3ONa (0.23 mol, 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 mol) and stirred for 1 h at 0–5ꢁC.
Then the mixture was heated under reflux on an oil-bath for
10 h. Finally, the mixture was acidified with concentrated hy-
drochloric acid. Compound 4 was separated and crystallized
from methanol. Yield is 52.6%, mp 106–107ꢁC 1H-NMR
(CDCl3): 2.45 (s, 3H, CH3), 2.56 (s, 3H, CH3), 2.73 (s, 3H,
CH3CO), 7.343 (s, 4H, Ar).
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-one 5a–e. A mix-
ture of the aromatic aldehyde (0.012 mol) and compound 4
(0.01 mol) dissolved in ethanol (70 mL) was added slowly to
an aqueous solution of potassium hydroxide (0.0128 mol) in
water (10 mL) [21,23]. The reaction mixture was stirred in
crushed-ice bath for 2 h, stirred at 20–25ꢁC for 4 h. The mix-
ture was filtrated and the solid was washed with cold water
and cold alcohol. The product was crystallized from ethanol to
give 5a–e. All the products were new compounds, which were
1
characterized by IR, H-NMR, and mass spectral data.
(E)-1-(5-Methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-3-phenylprop-
2-en-1-one 5a. White powder, yield 90%, mp 173–175ꢁC (Lit
178–180ꢁC) [21].
(E)-3-(3-Chlorophenyl)-1-(5-methyl-1-p-tolyl-1H-1,2,3-triazol-
4-yl)-2-en-1-one 5b. White powder, yield 88%, mp 144–146ꢁC,
IR (KBr, cmꢀ1): 1664 (C¼¼O), 1611 (C¼¼N), 979, 997, 1034,
1074, 1110 (NAN¼¼N), 899, 855, 838, 815, 789, 684 (Ph-H);
1H-NMR (300 MHz, CDCl3) d 2.479 (s, 3H, CH3), 2.666
(s, 3H, Ar1-CH3), 7.342–7.410 (m, 6H, Ar1 and Ar2-H),
7.581–7.608 (m, 1H Ar2-H), 7.721 (s, 1H, Ar2-2-H), 7.809–
7.862 (d, 1H, J ¼ 15.6Hz, C¼¼CHACO), 8.080–8.132 (d, 1H,
J ¼ 15.6Hz, CH¼¼CACO); 13C-NMR d 183.98, 151.02,
143.72, 141.73, 140.36, 138.65, 136.72, 134.83, 132.74,
130.18, 130.06, 128.31, 126.83, 125.03, 124.18, 21.23, 10.29;
MS (EI, 70 eV) (m/z, %) 337 (Mþꢂ, 1.3%), 339 (Mþ2, 0.4),
281 (21.9), 228 (30.0), 165 (44.2), 132 (95.0), 91 (100), 65
(71.3). Anal. Calcd for C19H16ClN3O: C, 67.56; H, 4.77; N,
12.44; Found: C, 67.86; H, 4.90; N, 12.02.
stretching bands are shown in the region 1592–1611
cmꢀ1 in 5a–e and 1571–1605 cmꢀ1 in the pyrazoline ring
6a–i [15–18]. The 1H-NMR spectrum of 6a showed a sin-
glet signal at d 2.35 ppm corresponding to the acetyl
group in accordance with the reported data [19]. The
chemical shifts of Ha and Hb protons are discernible in the
regions d 3.40–3.55 and 3.70–3.95 ppm as double dou-
blets, respectively, in the pyrazoline ring. The HX proton
is observed at d 5.45–5.62 ppm as double doublets (Jab
4.50–4.80 Hz, Jbx ¼ 18.2–18.6 Hz, Jxa ¼ 11.5–11.7 Hz).
¼
(E)-3-(3-Methoxyphenyl)-1-(5-methyl-1-p-tolyl-1H-1,2,3-tri-
azol-4-yl)-2-en-1-one 5c. White powder, yield 91%, mp 177–
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

January 2012
Synthesis of Some New 1-Acyl-5-aryl-3-(5-methyl-1-p-tolyl-1H-
1,2,3-triazol-4-yl)-4,5-dihydro-1H-pyrazole
151
178ꢁC, IR(KBr, cmꢀ1): 1657 (C¼¼O), 1592 (C¼¼N), 974, 995,
11.7Hz, HX), 7.235–7.401 (m, 9H, Ar1-H and Ar2-H); 13C-NMR
d 168.46, 149.38, 141.44, 140.09, 137.79, 133.34, 133.05, 130.11,
128.71, 127.50, 125.53, 124.84, 58.77, 43.27, 21.84, 21.16, 10.33;
MS (EI, 70 eV) (m/z, %): 359 (Mþꢂ, 6.3), 360 (Mþ1, 1.3), 331
(0.25), 288 (3.4), 260 (3.6), 244 (2.9), 212 (4.9), 184 (3.2), 169
(4.7), 145 (6.9), 128 (6.2), 115 (6.2), 104 (3.4), 91 (27.1), 43
(100). Anal. Calcd for C21H21N5O: C, 70.17; H, 5.89; N, 19.48;
Found: C, 69.80; H, 5.78; N, 19.87.
1
1011, 1033, 1113 (NAN¼¼N), 813, 733 (Ph-H); H-NMR (300
MHz, CDCl3) d 2.476 (s, 3H, CH3), 2.661 (s, 3H, Ar1-CH3),
3.877 (s, 3H, OACH3), 6.966 (s, 1H, Ar2-2-H), 7.241–7.270
(d, 2H, J ¼ 8.7Hz, Ar2-4,6-H), 7.323–7.352 (d, 1H, J ¼
8.7Hz, Ar2-5-H), 7.368 (s, 4H, Ar1-H), 7.870–7.923 (d, 1H, J ¼
15.9Hz, C¼¼CHACO), 8.068–8.120 (d, 1H,
J
¼
15.9Hz,
CH¼¼CACO); 13C-NMR d 184.26, 159.83, 143.82, 143.48,
140.29, 138.50, 136.21, 132.77, 130.15, 129.78, 125.01, 123.09,
121.65, 116.73, 112.91, 55.30, 21.19, 10.59; MS (EI, 70 eV)
(m/z, %): 333 (Mþꢂ, 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). Anal. Calcd for C20H19N3O2: C,
72.05; H, 5.74; N, 12.60; Found: C, 71.88; H, 5.64; N, 12.28.
3-(5-Methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-5-phenyl-1-pro-
pionyl-4,5-dihydro-1H-pyrazole 6b. White powder, yield 56%,
mp 116–118ꢁC, IR (KBr, cmꢀ1): 1654 (C¼¼O), 1605 (C¼¼N),
1079, 1038, 1000, 978, 953 (NAN¼¼N), 847, 822, 763, 700
(Ph-H); 1H-NMR (300 MHz, CDCl3): d 1.170–1.220 (t, 3H,
J ¼ 7.5Hz, COCH2CH3), 2.476 (s, 3H, CH3), 2.633 (s, 3H,
Ar1-CH3), 2.732–2.807 (q, 2H, J ¼ 7.5Hz, COCH2CH3), 3.459–
3.537 (dd, 1H, JA,X ¼ 4.8Hz, JA,B ¼ 18.6Hz, HA), 3.891–3.992
(dd, 1H, JB,X ¼ 11.7Hz, JA,B ¼ 18.6Hz, HB), 5.543–5.599 (dd,
1H, JA,X ¼ 4.8Hz, JB,X ¼ 11.7Hz, HX), 7.117–7.402 (m, 9H,
Ar1-H and Ar2-H); 13C-NMR d 171.46, 149.44, 143.43, 143.17,
140.47, 134.07, 130.80, 130.56, 129.30, 127.66, 125.78, 125.52,
59.48, 43.87, 27.85, 21.01, 10.39, 8.88; MS (EI, 70 eV) (m/z,
%): 373 (Mþꢂ, 7.9), 345 (0.23), 289 (7.9), 260 (5.4), 244 (3.3),
212 (5.6), 184 (4.4), 169 (5.1), 157 (3.5), 91 (37.8), 77 (9.7), 57
(100). Anal. Calcd for C22H23N5O: C, 70.76; H, 6.21; N, 18.75;
Found: C, 70.88; H, 6.18; N, 18.86.
(E)-3-(Furan-2-yl)-1-(5-methyl-1-p-tolyl-1H-1,2,3-triazol-4-
yl)-2-en-1-one 5d. White powder, yield 92%, mp 188–189ꢁC, IR
(KBr, cmꢀ1): 1661 (C¼¼O), 1598 (C¼¼N), 1036, 1013, 993, 976
(NAN¼¼N), 877, 860, 822, 771, 698 (Ph-H); 1H-NMR (300 MHz,
CDCl3): d 2.472 (s, 3H, CH3), 2.650 (s, 3H, Ar1-CH3), 6.512–6.529
(dd, 1H, J ¼ 1.8Hz, J ¼ 3.3Hz furan-4), 6.770–6.781 (d, 1H, J ¼
3.3Hz, furan-3), 7.333- 7.362 (d, 2H, J ¼ 8.7Hz, Ar1-3,5-H),
7.362–7.399 (d, 2H, J ¼ 8.7Hz, Ar1-2,6-H), 7.552–7.556 (d, 1H,
J
¼
1.8Hz, furan-5), 7.671–7.723 (d, 1H,
J
¼
15.6Hz,
C¼¼CHACO), 7.980–7.927 (d, 1H, J ¼ 15.6Hz, CH¼¼CACO);
13C-NMR d 184.16, 151.79, 145.01, 143.83, 140.22, 138.29,
132.83, 130.13, 129.60, 125.02, 120.86, 115.89, 112.52, 21.20,
10.25; MS (EI, 70 eV) (m/z, %): 293 (Mþꢂ, 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). Anal. Calcd for C17H15N3O2: C, 69.61; H,
5.15; N, 14.33; Found: C, 69.45; H, 5.33; N, 14.52.
1-Acetyl-5-(3-chlorophenyl)-3-(5-methyl-1-p-tolyl-1H-1,2,3-
triazol-4-yl)-4,5-dihydro-1H-pyrazole 6c. White powder, yield
86%, mp 158–159ꢁC, IR(KBr, cmꢀ1): 1660 (C¼¼O), 1595
(C¼¼N), 1092, 1037, 1002, 973, 960 (NAN¼¼N), 867, 822, 786,
693 (Ph-H); 1H-NMR (300 MHz, CDCl3): d 2.400 (s, 3H,
COCH3), 2.478 (s, 3H, CH3), 2.637 (s, 3H, Ar1-CH3), 3.441–
3.518 (dd, 1H, JA,X ¼ 4.5Hz, JA,B ¼ 18.6Hz, HA), 3.913–4.014
(dd, 1H, JB,X ¼ 11.7Hz, JA,B ¼ 18.6Hz, HB), 5.519–5.573 (dd,
1H, JA,X ¼ 4.5Hz, JB,X ¼ 11.7Hz, HX), 7.148–7.177 (dd, 1H,
J1 ¼ 1.8Hz, J2 ¼ 6.9Hz, Ar2-5-H), 7.204 (m, Ar2-6-H), 7.241–
7.254 (q, 1H, J ¼ 1.8Hz, Ar2-4-H), 7.261 (m, 1H, Ar2-2-H),
7.341–7.360 (d, 2H, J ¼ 5.7Hz, Ar1-3,5-H), 7.379–7.408 (d,
2H, J ¼ 5.7Hz, Ar1-2,6-H); 13C-NMR d 168.58, 149.34,
143.53, 140.19, 137.63, 134.62, 133.51, 133.05, 130.17, 130.09,
127.81, 125.63, 124.89, 124.02, 58.32, 43.22, 21.84, 21.21,
10.38; MS (EI, 70 eV) (m/z, %): 393 (Mþꢂ, 4.2), 395 (Mþ2,
1.3), 365 (1.9), 323 (2.6), 294 (1.9), 258 (1.4), 244 (1.5), 91
(22.9), 43 (100). Anal. Calcd for C21H20ClN5O: C, 64.04; H,
5.12; N, 17.78; Found: C, 63.89; H, 5.32; N, 17.53.
(E)-3-[4-(Dimethylamino)phenyl]-1-(5-methyl-1-p-tolyl-1H-
1,2,3–triazol-4-yl)prop-2-en-1-one 5e. White powder, yield
86%, mp 210–212ꢁC, IR (KBr, cmꢀ1): 1648 (C¼¼O), 1611
(C¼¼N), 1034, 1017, 996, 981 (NAN¼¼N), 891, 819, 798, 703
(Ph-H); 1H-NMR (300 MHz, CDCl3): d 2.472 (s, 3H, CH3),
2.657 (s, 3H, Ar1-CH3), 3.056 (s, 6H, N(CH3)2), 6.696–6.725
(d, 2H, J ¼ 8.7Hz, Ar2-3,5-H), 7.366 (b, 4H, Ar1-2,3,5,6-H),
7.626–7.657 (d, 2H, J ¼ 8.7Hz, Ar2-2,6-H), 7.911 (s, 2H,
CH¼¼CH); 13C-NMR
d 184.35, 151.97, 144.48, 144.22,
140.10, 137.90, 132.99, 130.70, 130.11, 126.57, 125.06,
117.76, 111.71, 40.08, 21.22, 10.29; MS (EI, 70 eV) (m/z, %):
346 (Mþꢂ, 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 (28.9), 44 (42.1). Anal. Calcd for C21H22N4O: C,
72.81; H, 6.40; N, 16.17; Found: C, 72.25; H, 6.55; N, 15.97.
5-(3-Chlorophenyl)-3-(5-methyl-1-p-tolyl-1H-1,2,3-triazol-4-
yl)-1-propionyl-4,5-dihydro-1H-pyrazole 6d. Orange yellow
powder, yield 83.5%, mp 110–112ꢁC, IR (KBr, cmꢀ1): 1663
(C¼¼O), 1595 (C¼¼N), 1080, 1039, 1002, 976 (NAN¼¼N), 860,
General method for the synthesis of 1-acyl-5-aryl-3-(5-
methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-4,5-dihydro-1H-pyra-
zoles 6a–i. A mixture of compound 5 (0.01 mol), hydrazine
hydrate (0.03 mol), acetic acid or propionic acid (50 mL) was
refluxed for 3 h, then poured into crushed-ice [24]. The precipitate
was separated by filtration, washed with water and the crude
products 6a–i were obtained, which were crystallized from etha-
nol. All the products were new compounds.
1
819, 784, 691 (Ph-H); H-NMR (300 MHz, CDCl3): d 1.148–
1.197 (t, 3H, J ¼ 7.5Hz, COCH2CH3), 2.476 (s, 3H, CH3),
2.632 (s, 3H, Ar1-CH3), 2.745–2.803 (q, 2H, J ¼ 7.5Hz,
COCH2CH3), 3.431–3.490 (dd, 1H, JA,X ¼ 4.8Hz, JA,B
18.6Hz, HA), 3.906–3.981 (dd, 1H, JB,X ¼ 11.7Hz, JA,B
¼
¼
1-Acetyl-3-(5-methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-5-phenyl-
4,5-dihydro-1H-pyrazole 6a. White powder, yield 67.5%, mp
183–185ꢁC, IR(KBr, cmꢀ1): 1655 (C¼¼O), 1571 (C¼¼N), 1090,
1031, 999, 956 (NAN¼¼N), 870, 822, 750, 700 (Ph-H); 1H-
NMR (300 MHz, CDCl3): d 2.389 (s, 3H, COCH3), 2.473 (s, 3H,
CH3), 2.63 (s, 3H, Ar1-CH3), 3.476–3.552 (dd, 1H, JA,X ¼ 4.8Hz,
JA,B ¼ 18.6Hz, HA), 3.903–4.005 (dd, 1H, JB,X ¼ 11.7Hz, JA,B
18.6Hz, HB), 5.503–5.545 (dd, 1H, JA,X ¼ 4.8Hz, JB,X ¼ 11.7Hz,
HX), 7.144–7.167 (dd, 1H, J1 ¼ 1.6Hz, J2 ¼ 8.7Hz, Ar2-5-H),
7.201–7.197 (d, 1H, J ¼ 1.6Hz, Ar2-6-H), 7.233–7.247 (dd, 1H,
J1 ¼ 1.6HZ, J2 ¼ 4Hz, Ar2-4-H), 7.262 (s, 1H, Ar2-2-H), 7.344–
7.366 (d, 2H, J ¼ 8.8Hz, Ar1-3,5-H), 7.378–7.400 (d, 2H, J ¼
8.8Hz, Ar1-2,6-H); 13C-NMR d 171.92, 149.02, 143.67, 140.05,
137.59, 134.45, 133.38, 132.95, 130.06, 130.00, 127.63, 125.57,
124.76, 123.91, 58.37, 43.89, 27.39, 21.09, 10.28, 8.70; MS (EI,
¼ 18.6Hz, HB), 5.560–5.615 (dd, 1H, JA,X ¼ 4.8Hz, JB,X
¼
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70 eV) (m/z, %): 407 (Mþꢂ, 5.5), 409(Mþ2, 1.5), 379 (2.3), 323
(9.8), 294 (4.8), 212 (10.3), 145 (10.3), 91 (30.2), 57 (100), 45
(78.9). Anal. Calcd for C22H22ClN5O: C, 64.78; H, 5.44; N,
17.17; Found: C, 64.89; H, 5.51; N, 16.89.
yield 74%, mp 162–164ꢁC, IR (KBr, cmꢀ1): 1660 (C¼¼O),
1576 (C¼¼N), 1092, 1063, 1039, 1003 (NAN¼¼N), 868, 818
(Ph-H); 1H-NMR (300 MHz, CDCl3):
COCH3), 2.473 (s, 3H, CH3), 2.626 (s, 3H, Ar1-CH3), 2.918
d 2.353 (s, 3H,
(s, 6H, N(CH3)2), 3.492–3.568 (dd, 1H, JA,X ¼ 4.5Hz, JA,B
¼
1-Acetyl-5-(3-methoxyphenyl)-3-(5-methyl-1-p-tolyl-1H-1,2,3-
triazol-4-yl)-4,5-dihydro-1H-pyrazole 6e. Gray powder, yield
59.5%, mp 185–187ꢁC, IR(KBr, cmꢀ1): 1654 (C¼¼O), 1583
(C¼¼N), 1112, 1088, 1025, 1003, 959 (NAN¼¼N), 875, 823
18.3Hz, HA), 3.845–3.946 (dd, 1H, JB,X ¼ 11.7Hz, JA,B
¼
18.3Hz, HB), 5.489–5.542 (dd, 1H, JA,X ¼ 4.8Hz, JB,X ¼ 11.7
Hz, HX), 6.666–6.694 (d, 2H, J ¼ 8.4Hz, Ar2-3,5-H), 7.137–
7.166 (d, 2H, J ¼ 8.4Hz, Ar2-2,6-H), 7.339–7.367 (d, 2H, J ¼
8.4Hz, Ar1-3,5-H), 7.375–7.403 (d, 2H, J ¼ 8.4Hz, Ar1-2,6-
H); 13C-NMR d 168.35, 149.94, 149.42, 140.02, 137.95,
133.20, 133.08, 130.08, 129.30, 126.68, 124.83, 112.56, 58.37,
42.94, 40.47, 21.90, 21.15, 10.33; MS (EI, 70 eV) (m/z, %):
402 (Mþꢂ, 1.57), 279 (5.14), 261 (37.4), 220 (24.7), 191 (35.9),
135 (58.3), 9 1(19.7), 57 (100). Anal. Calcd for C23H26N6O:
C, 68.63; H, 6.51; N, 20.88; Found: C, 68.45; H, 6.64; N,
20.25.
(Ph-H); 1H-NMR (300 MHz, CDCl3):
d 2.390 (s, 3H,
COCH3), 2.466 (s, 3H, CH3), 2.624 (s, 3H, Ar1-CH3), 3.451–
3.529 (dd, 1H, JA,X ¼ 4.8Hz, JA,B ¼ 18.2Hz, HA), 3.785(s,
3H, OACH3), 3.886–3.988 (dd, 1H, JB,X ¼ 11.7Hz, JA,B
18.2Hz, HB), 5.526–5.580 (dd, 1H, JA,X ¼ 4.8Hz, JB,X
¼
¼
11.7Hz, HX), 6.776–6.790 (m, 2H, J ¼ 2.1Hz, Ar2-4,6-H),
6.825–6.850 (d, 1H, J ¼ 7.5Hz, Ar2-5-H), 7.212–7.267 (dd,
1H, J ¼ 7.5Hz, 2.1Hz, Ar2-2-H), 7.333–7.396 (q, 4H, J ¼
8.1Hz, Ar1-H); 13C-NMR d 168.50, 159.86, 149.45, 143.16,
140.16, 137.85, 133.39, 133.14, 130.18, 129.91, 124.92,
117.76, 112.57, 111.59, 58.78, 55.17, 43.37, 21.90, 21.24,
10.41; MS (EI, 70 eV) (m/z, %): 389 (Mþꢂ, 5.1), 361 (0.4),
212 (2.4), 184 (3.3), 169 (5.2), 145 (10.1), 121 (16.2), 91
(18.4), 65 (12.2), 43 (100). Anal. Calcd for C22H23N5O2: C,
67.85; H, 5.95; N, 17.98; Found: C, 67.55; H, 5.78; N, 17.37.
5-(4-Dimethylaminophenyl)-3-(5-methyl-1-p-tolyl-1H-1,2,3-
triazol-4-yl)-1-propionyl-4,5-dihydro-1H-pyrazole 6i. Orange
yellow powder, yield 79%, mp 141–143ꢁC, IR(KBr, cmꢀ1):
1665 (C¼¼O), 1571 (C¼¼N), 1095, 1064, 1040, 1002, 978
(NAN¼¼N), 852, 818 (Ph-H); 1H-NMR (300 MHz, CDCl3): d
1.173 (t, 3H, J ¼ 5.4Hz, COCH2CH3), 2.473 (s, 3H, CH3),
2.622 (s, 3H, Ar1-CH3), 2.735 (q, 2H,
J
¼
5.4Hz,
5-(3-Methoxyphenyl)-3-(5-methyl-1-p-tolyl-1H-1,2,3-triazol-4-
yl)-1-propionyl-4,5-dihydro-1H-pyrazole 6f. Light gray powder,
yield 68.4%, mp 128–130ꢁC, IR(KBr, cmꢀ1): 1659 (C¼¼O),
1591 (C¼¼N), 1034, 1002, 976 (NAN¼¼N), 859, 825, 800, 741
(Ph-H); 1H-NMR (300 MHz, CDCl3): d 1.176–1.227 (t, 3H,
J ¼ 7.5Hz, COCH2CH3), 2.466 (s, 3H, CH3), 2.622 (s, 3H,
Ar1-CH3), 2.735–2.812 (q, 2H, J ¼ 7.5Hz, COCH2CH3),
3.433–3.509 (dd, 1H, JA,X ¼ 4.8Hz, JA,B ¼ 18.2Hz, HA),
3.779(s, 3H, OACH3), 3.865–3.972 (dd, 1H, JB,X ¼ 11.7Hz,
JA,B ¼ 18.2Hz, HB), 5.508–5.563 (dd, 1H, JA,X ¼ 4.8Hz, JB,X
¼ 11.7Hz, HX), 6.768–6.790(m, 2H, J ¼ 2.2Hz, Ar2-4,6-H),
6.819–6.845 (d, 1H, J ¼ 7.8Hz, Ar2-5-H), 7.206–7.263 (dd,
1H, J ¼ 7.8Hz, 2.2Hz, Ar2-2-H), 7.331–7.394 (q, 4H, J ¼
8.1Hz, Ar1-H); 13C-NMR d 171.85, 159.73, 149.11, 143.30,
140.02, 137.81, 133.25, 133.02, 130.06, 129.79, 124.79,
117.65, 112.49, 111.38, 58.81, 55.01, 43.04, 27.46, 21.11,
10.29, 8.81; MS (EI, 70 eV) (m/z, %): 403 (Mþꢂ, 12.9), 404
(Mþ1, 3.1), 318 (6.8), 290 (4.7), 212 (7.3), 184 (5.0), 169
(7.1), 145 (21.3), 121 (43.6), 91 (49.6), 57 (100). Anal. Calcd
for C23H25N5O2: C, 68.47; H, 6.25; N, 17.36; Found: C,
68.64; H, 6.37; N, 17.02.
COCH2CH3), 2.923 (s, 6H, N(CH3)2), 3.481–3.544 (dd, 1H,
JA,X ¼ 4.5Hz, JA,B ¼ 18.3Hz, HA), 3.839–3.943 (dd, 1H, JB,X
¼ 11.7Hz, JA,B ¼ 18.3Hz, HB), 5.474–5.515 (dd, 1H, JA,X
¼
4.5Hz, JB,X ¼ 11.7Hz, HX), 6.658–6.686 (d, 2H, J ¼ 8.4Hz,
Ar2-3,5-H), 7.131–7.159 (d, 2H, J ¼ 8.4Hz, Ar2-2,6-H),
7.339–7.367 (d, 2H, J ¼ 8.4Hz, Ar1-3,5-H), 7.373–7.401 (d,
2H, J ¼ 8.4Hz, Ar1-2,6-H); 13C-NMR d 171.76, 149.95,
149.17, 140.04, 138.13, 133.15, 130.12, 129.58, 126.78,
124.89, 112.63, 58.58, 42.73, 40.53, 27.57, 21.20, 10.38, 8.86;
MS (EI, 70 eV) (m/z, %): 416 (Mþꢂ, 7.94), 417 (Mþ1, 2.07),
218 (23.9), 203 (24.6), 189 (57.5), 134 (100), 91 (44.5), 57
(78.7). Anal. Calcd for C24H28N6O: C, 69.21; H, 6.78; N,
20.18; Found: C, 69.45; H, 6.87; N, 19.84.
Acknowledgment. The authors acknowledge the support given
by the Lanzhou University SKLAOC.
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