Synthesis of (3,5-aryl/methyl-1H-pyrazol-1-yl)-(5-arylamino-2H-1,2,3- triazol-4-yl)methanone

Article abstract of DOI:10.1002/jccs.200800114

Some new (3,5-aryl/methyl-1H-pyrazol-1-yl)-(5-arylamino-2H-1,2,3-triazol-4- yl)methanones were synthesized and characterized by ¹H NMR, ¹³C NMR, MS, IR spectra data and elemental analyses or high resolution mass spectra (HRMS). Durin

Full text of DOI:10.1002/jccs.200800114

Journal of the Chinese Chemical Society, 2008, 55, 761-767
761
Synthesis of (3,5-Aryl/methyl-1H-pyrazol-1-yl)-(5-arylamino-2H-1,2,3-
triazol-4-yl)methanone
Zi-Ping Caoa (
), Bin Quanb (
) and Heng-Shan Donga* (
)
aState Key Laboratory of Applied Organic Chemistry, Institute of Organic Chemistry, College of Chemistry
and Chemical Engineering, Lanzhou University, Lanzhou, Gansu 730000, P. R. China
bCollege of Chemistry and Chemical Engineering, Guansu Association University,
Lanzhou, Gansu 730000, P. R. China
Some new (3,5-aryl/methyl-1H-pyrazol-1-yl)-(5-arylamino-2H-1,2,3-triazol-4-yl)methanones were
synthesized and characterized by 1H NMR, 13C NMR, MS, IR spectra data and elemental analyses or high
resolution mass spectra (HRMS). During the procedure, Dimroth rearrangement was used in this synthe-
sis.
Keywords: 1H-Pyrazole; 2H-1,2,3-Triazole; Methanone; Synthesis; Dimroth rearrangement.
INTRODUCTION
The synthesis and research of biological activities of
methyl-3-substituted-1H-pyrazol-1-yl)-methanones 6a-e
and [(5-arylamino)-2H-1,2,3-triazol-4-yl]-(3-methyl-5-
substituted-1H-pyrazol-1-yl)-methanones 7a-d have been
synthesized by reaction of benzoylacetone and compounds
5a-e which were prepared by hydrazinolysis and Dimroth
rearrangement of ethyl 5-amino-1-aryl-1H-1,2,3-triazol-
4-carboxylate and hydrazine hydrate. They were separated
completely by chromatographic column (silica gel, eluent
for ethyl acetate: petroleum ether = 1:6) because of their
distinction of polarity. During reaction of compound 5e
with benzoylacetone, product 6e is primary. While acetyl-
acetone reacts with compounds 5a-e, products 6f-j are
triazole derivatives have attracted much attention in recent
years because a set of valuable pharmacological properties
such as anti-inflammatory, anti-rhenmatic, analgesic and
anti-psychotic activities. In addition, compounds of the
pyrazole series have demonstrated their usefulness in
pathological states, and cardiovascular and gastrointestinal
disorders.1-3 Based on these literature studies, the synthesis
and research of biological activities of novel pyrazole de-
rivatives are of great significance. At present, the hetero-
cyclic derivatives with triazole and pyrazole nucleuses are
being developed in good time.4-6 In recent years, we have
reported synthesis of some 7H-s-triazolo[3,4-b]-1,3,4-thia-
diazine derivatives,7 N-[1-(2,5-dichlorophenyl)-5-methyl-
1,2,3-triazol-4-yl]carbamic acid ester derivatives8 and 3,6-
bis(1,2,3-triazolyl)-s-triazolo[3,4-b]-1,3,4-thiadiazole de-
rivatives.9 Thanks to these, we have synthesized some new
(3,5-aryl/methyl-1H-pyrazol-1-yl)-(5-arylamino-2H-1,2,3-
triazol-4-yl)methanones 6a-j, 7a-d in 60-96% yield. The
route of these syntheses is in Scheme I.
The crystal structure of (5-methyl-3-phenyl-1H-pyr-
azol-1-yl)-[5-(p-tolylamino)-2H-1,2,3-triazol-4-yl]meth-
anone 6b was researched by single-crystal X-ray diffrac-
tion. The ORTEP drawing of the title compound 6b show-
ing the atom numbering scheme is shown in Fig. 1.
Fig. 1. ORTEP drawing of the title compound 6b
RESULTS AND DISCUSSION
showing the atom numbering scheme.
The new [(5-arylamino)-2H-1,2,3-triazol-4-yl]-(5-

762 J. Chin. Chem. Soc., Vol. 55, No. 4, 2008
Cao et al.
troscopy data of compounds 6a-e and 7a-d, chemical shift
of 3-CH3 in the pyrazole ring is at 13.80-13.95 ppm, and 5-
CH3 is in the region of 14.34-14.68 ppm.
Scheme I
The IR spectra data character of compounds 5a-e are
tip peaks at 3200-3450 and 1620-1660 cm-1 which could be
found clearly. These peaks could be assigned respectively
to NH or NH2 and C=O. The vibration band of N-N=N is in
the region 970-980 cm-1. We investigated the MS spectra of
5a-e and the results showed that compounds 5a-e have
weak molecular ion peaks.
The IR spectra data character of compounds 6a-j and
7a-d are tip peaks at 3300-3500 and 1640-1670 cm-1. These
peaks could be assigned respectively to NH and C=O. A
chemical shift at 6.00-6.70 ppm can be assigned to the CH
of the pyrazole ring, and usually the chemical shift of NH is
at 8.40 ppm, but we cannot find the NH of the triazole ring.
Further exploration is in progress.
We investigated the MS spectra of 6a-j and 7a-d and
the results showed that compounds 6a-j and 7a-d have
weak molecular ion peaks. While analyzing the cleavage
fragments of the molecular ions, we found that the MS
spectra of 6a-j exhibit some important ion peaks at m/z 159,
M-159, 97, M-97.
EXPERIMENTAL
All melting points are uncorrected and determined on
an XT4-100x microscopic melting point apparatus. IR
spectra were obtained in KBr discs on a Nicolet NEXUS
670 FT-IR spectrometer. MS were performed on an HP-
5988A spectrometer (EI at 70 eV). High resolution mass
spectra (HRMS) were tested on Bruker Daltonics Apex2
47e ft-icr mass spectra apparatus. 1H NMR spectroscopy
(CDCl3) was recorded on a Varian Mercury Plus-300 in-
strument with TMS as an internal standard. 13C NMR spec-
troscopy was performed on a Bruker DRX-200 spectrome-
ter. Elemental analyses were carried out on a Yanaco CHN
Corder MT-3 analyzer.
given exclusively. To differentiate pairs of compounds 6a-
e and 7a-d, compound 6b’ single-crystal structure and all
of the compounds’1H NMR spectrum were performed. Ac-
tually, in the pyrazole ring of these compounds, chemical
shifts of CH3 at the 3- and 5-parts are different, one is in a
range of 2.439-2.452 ppm, while the other is in an area of
2.770-2.794 ppm. 6b’s correct structure is due to its crystal
structure; consequently the 5-CH3 chemical shift which is
2.782 ppm is determined. So we extrapolate that the 5-CH3
chemical shift is in a range of 2.770-2.794 ppm and 3-CH3
is in the region of 2.439-2.452 ppm. Finally, compounds
6a-e and 7a-d are distinguishable. In their 13C NMR spec-
Preparation of ethyl 5-amino-1-aryl-1H-1,2,3-tria-
zol-4-carboxylates 4a-e followed a method in the litera-
ture.10-11
Ethyl 5-amino-1-phenyl-1H-1,2,3-triazol-4-carboxyl-
ate 4a m.p. 125-126 °C (Lit.10a m.p. 124.5-125.5 °C)
Ethyl 5-amino-1-p-tolyl-1H-1,2,3-triazol-4-carboxylate
4b m.p. 151-152 °C (Lit.10a m.p. 152-153 °C)
Ethyl 5-amino-1-o-tolyl-1H-1,2,3-triazol-4-carboxylate
4c
1
Compound is white powder, m.p. 124-125 °C. H

1H-Pyrazol-1-yl-2H-1,2,3-triazol-4-yl Methanone
J. Chin. Chem. Soc., Vol. 55, No. 4, 2008 763
NMR (CDCl3-d) (ppm), 1.426-1.473 (t, 3H, J = 7.2 Hz,
CH3), 2.163 (s, 3H, CH3), 4.408-4.480 (q, 2H, J = 7.2 Hz,
CH2), 5.043 (b, 2H, NH2), 7.296-7.321 (d, 1H, J = 7.5 Hz,
5-o-Tolylamino-2H-1,2,3-triazol-4-carbohydrazide 5c
Compound is white powder, yield 43%, m.p. 214-216
°C. 1H NMR (DMSO-d6) (ppm), 2.261 (s, 3H, CH3), 4.501
(b, 2H, NH2), 6.860-6.901 (m, 1H, Ar-H), 7.011-7.108 (m,
3H, Ar-H), 8.435 (s, 1H, NH), 9.769 (b, 1H, NH); MS m/z:
+
.
Ar-H), 7.358-7.505 (m, 3H, Ar-H); MS m/z: 246 (
,
M
26.2), 247 (M+1, 4.0), 248 (M+2, 0.5), 201 (2.8), 172
(22.0), 157 (9.4), 145 (90.3), 118 (59.2), 91 (100). IR: 3366
(NH2), 3289, 3223, 3173 (Ar-H), 2982, 2929 (CH3), 1691
(s, C=O), 1639, 1571, 1514, 1410 (s, Ar or triazole ring),
974 (N=N-N) cm-1. Anal. Calcd for C12H14N4O2: C, 58.53;
H, 5.73; N, 22.75; Found: C, 58.40; H, 5.69; N, 22.62.
Ethyl 5-amino-1-(4-chlorophenyl)-1H-1,2,3-triazol-4-
carboxylate 4d m.p. 165-166 °C (Lit.10b m.p. 165-167 °C)
Ethyl 5-amino-1-(3-chlorophenyl)-1H-1,2,3-triazol-4-
carboxylate 4e m.p. 134-135 °C (Lit.10b m.p. 134-135 °C)
1. General synthesis of 5-arylamino-2H-1,2,3-triazol-
4-carbohydrazides 5a-e
+
.
232 (
, 100), 233 (M+1, 12), 201 (60), 173 (18), 146
M
(27), 118 (41), 91 (86), 77 (35), 65 (62). IR: 3371, 3316
(NH2, NH), 1621 (CO), 973 (N=N-N) cm-1. Anal. Calcd for
C10H12N6O: C, 51.72; H, 5.21; N, 36.19; Found: C, 51.61;
H, 5.29; N, 36.32.
5-(4-Chlorophenylamino)-2H-1,2,3-triazol-4-carbohy-
drazide 5d
Compound is white powder, yield 79.3%, m.p. 217-
218 °C. 1H NMR (DMSO-d6) (ppm), 4.511 (b, 2H, NH2),
7.213-7.241 (d, 2H, J = 8.4 Hz, Ar-H), 7.486-7.514 (d, 2H,
J = 8.4 Hz, Ar-H), 8.449 (s, 1H, NH), 9.775 (b, 1H, NH);
+
.
Ethyl 5-amino-1-arlyl-1H-1,2,3-triazol-4-carboxyl-
ate 4a-e (0.003 mol) and hydrazine hydrate (0.012 mol)
were added in a 100 mL flask; the mixture was heated at 80
°C for a hour, then refluxed in EtOH (25 mL) for 5-10
hours. The mixture was cooled to room temperature and the
solid was filtered, washed with cool anhydrous ethanol and
dried. The compound which Dimroth rearrangement hasn’t
happened was given. The filtrate was neutralized with di-
luted HCl, the solid was filtered and dried. Compounds
5a-e were given.
MS m/z: 252 (
, 100), 253 (M+1, 12), 254 (M+2, 29),
M
221 (39), 195 (12), 166 (29), 138 (28), 111 (77), 102 (34),
75 (66), 63 (18). IR: 3390, 3352, 3308, 3267 (NH2, NH),
1659 (CO), 970 (N=N-N) cm-1. Anal. Calcd for C9H9ClN6O:
C, 42.78; H, 3.59; N, 33.26; Found: C, 42.93; H, 3.66; N,
33.03.
5-(3-Chlorophenylamino)-2H-1,2,3-triazol-4-carbohy-
drazide 5e
Compound is white needles, yield 73.8%, m.p. 218-
219 °C. 1H NMR (DMSO-d6) (ppm), 4.511 (b, 2H, NH2),
6.897-7.029 (t, 1H, Ar-H), 7.119-7.146 (d, 1H, J = 8.1 Hz,
Ar-H), 7.364-7.391 (d, 1H, J = 8.1 Hz, Ar-H), 7.629 (s, 1H,
5-Phenylamino-2H-1,2,3-triazol-4-carbohydrazide 5a
Compound is white powder, yield 41.3%, m.p. 179-
180 °C. 1H NMR (DMSO-d6) (ppm), 4.509 (b, 2H, NH2),
6.807-6.855 (t, 1H, J = 7.8 Hz, Ph), 7.157-7.210 (t, 2H, J =
7.8 Hz, Ph), 7.487-7.516 (d, 2H, J = 7.8 Hz, Ph), 8.444 (s,
Ar-H), 8.443 (b, 1H, NH), 9.768 (b, 1H, NH); MS m/z: 252
+
.
(
, 97), 253 (M+1, 12), 254 (M+2, 37.5), 221 (56), 193
M
(19), 166 (33), 138 (43), 113 (36), 111 (100), 102 (39), 75
(94), 63 (22). IR: 3348, 3323, 3266 (NH2, NH), 1635 (CO),
972 (N=N-N) cm-1. Anal. Calcd for C9H9ClN6O: C, 42.78;
H, 3.59; N, 33.26; Found: C, 42.96; H, 3.62; N, 33.50.
2. General synthesis of [(5-arylamino)-2H-1,2,3-
triazol-4-yl]-(5-methyl-3-substituted-1H-pyrazol-1-
yl)methanones 6a-j and [(5-arylamino)-2H-1,2,3-
triazol-4-yl]-(3-methyl-5-substituted-1H-pyrazol-1-
yl)methanones 7a-d
+
.
1H, NH), 9.772 (b, 1H, NH); MS m/z: 218 (
, 93), 219
M
(M+1, 10.0), 187 (37), 161 (9), 132 (29), 104 (31), 77
(100). IR: 3370, 3320, 3248, 3206 (NH2, -NH), 1625 (CO),
974 (N=N-N)cm-1. Anal. Calcd for C9H10N6O: C, 49.54; H,
4.62; N, 38.51; Found: C, 49.36; H, 4.51; N, 38.62.
5-p-Tolylamino-2H-1,2,3-triazol-4-carbohydrazide 5b
Compound is white powder, yield 35%, m.p. 199-200
°C. 1H NMR (DMSO-d6) (ppm), 2.241(s, 3H, CH3), 4.506
(b, 2H, NH2), 7.089-7.116 (d, 2H, J = 8.1 Hz, Ar-H),
7.403-7.430 (d, 2H, J = 8.1 Hz, Ar-H), 8.440 (s, 1H, NH),
To add 5-arylamino-2H-1,2,3-triazol-4-carbohydra-
zide 5a-e (3 mmol), 1,3-diketone (3 mmol) and EtOH (25
mL) in a 100 mL flask. When the mixture was controlled at
80 °C till completely dissolved under stirring, 5 drops of di-
lute HCl was added, and refluxed for 0.5-2 hours. The mix-
ture was cooled to room temperature and the solid was fil-
tered, washed with cool anhydrous ethanol and dried. The
+
.
9.771 (b, 1H, NH); MS m/z: 232 (
, 90), 233 (M+1, 10),
M
201 (51), 173 (20), 146 (35), 118 (40), 91 (100). IR: 3388,
3355, 3325, 3304 (NH, NH2), 1641 (C=O), 974 (N=N-N)
cm-1. Anal. Calcd for C10H12N6O: C, 51.72; H, 5.21; N,
36.19; Found: C, 51.91; H, 5.19; N, 36.05.

764 J. Chin. Chem. Soc., Vol. 55, No. 4, 2008
Cao et al.
solid was separated by chromatographic column (silica gel,
eluent for ethyl acetate:petroleum ether = 1:6). The titled
compounds 6a-j, 7a-d were given.
Phenyl), 7.315-7.421 (m, 3H, Ar-H), 7.496-7.514 (m, 3H,
Ar-H), 7.834-7.853 (d, 2H, Ar-H), 8.462, 8.495 (b, 2H,
NH); 13C NMR (CDCl3-d) (ppm), 14.66 (CH3), 17.81
(CH3), 108.47 (CH), 111.30 (C), 117.91 (CH), 121.92
(CH), 125.03 (C), 126.38 (2CH), 127.16 (CH), 129.02
(2CH), 129.82 (CH), 130.28 (CH), 130.87 (C), 138.34 (C),
146.27 (C), 155.11 (C), 155.41 (C), 156.96 (C=O); MS
(5-Methyl-3-phenyl-1H-pyrazol-1-yl)-(5-phenylamino-
2H-1,2,3-triazol-4-yl)methanone 6a
Compound is light yellow powder, yield 19.3%, m.p.
1
186-188 °C. H NMR (CDCl3-d) (ppm), 2.784 (s, 3H,
+
.
CH3), 6.619 (s, 1H, CH), 7.050-7.831 (m, 10H, Ph), 8.462
(b, 1H, NH); 13C NMR (CDCl3-d) (ppm), 14.68 (CH3),
108.59 (CH), 117.88 (2CH), 120.29 (C), 121.95 (CH),
126.42 (2CH), 129.05 (2CH), 129.20 (2CH), 129.87 (CH),
130.85 (C), 139.94 (C), 146.28 (C), 155.18 (C), 155.76
m/z: 358 (
, 18), 359 (M+1, 4.3), 330 (5.2), 315 (1), 301
M
(3.5), 287 (2.7), 260 (1.5), 212 (3), 200 (2.0), 184 (5.1),
172 (4.4), 159 (100), 117 (53), 91 (56), 77 (40), 65 (37); IR:
3474, 3338 (b, NH), 3060 (Ar-H), 2924 (w, CH3), 1659 (s,
C=O), 1618, 1596 (s, triazole or pyrazole ring), 1573,
1519, 1468, 1449, 1429 (s, Ar), 1261 (m, C=N-N), 943 (w,
N=N-N) cm-1. Anal. Calcd for C20H18N6O: C, 67.02; H,
5.06; N, 23.45; Found: C, 67.13; H, 5.11; N, 23.34.
[5-(p-Chlorophenylamino)-2H-1,2,3-triazol-4-yl]-(5-
methyl-3-phenyl-1H-pyrazol-1-yl)methanone 6d
+
.
(C), 156.92 (C=O); MS m/z: 344 (
, 12), 345 (M+, 3.2),
M
316 (6.5), 287 (5.0), 273 (1.7), 260 (3.1), 246 (2.3), 212
(3.3), 196 (5.7), 159 (69), 103 (48), 77 (100), 69 (55), 57
(56), 55 (49), 43 (45); IR: 3357, 3321 (b, NH), 3141, 3113
(Ar-H), 2924 (w, CH3), 1665 (s, C=O), 1611 (s, triazole or
pyrazole ring), 1576, 1520, 1469, 1440 (s, Ar), 1261 (s,
C=N-N), 946 (w, N=N-N) cm-1. Anal. Calcd for C19H16N6O:
C, 66.27; H, 4.68; N, 24.40; Found: C, 66.01; H, 4.46; N,
24.58.
Compound is light yellow powder, yield 21%, m.p.
1
209-211 °C. H NMR (CDCl3-d) (ppm), 2.778 (s, 3H,
CH3), 6.627 (s, 1H, CH), 7.313-7.342 (d, 2H, J = 8.7 Hz,
Ar-H), 7.499-7.524 (d, 3H, Ph), 7.706-7.735 (d, 2H, J = 8.7
Hz, Ar-H), 7.825-7.850 (d, 2H, J = 7.5 Hz, Ph), 8.464 (b,
1H, NH); 13C NMR (CDCl3-d) (ppm), 14.68 (CH3), 108.77
(CH), 111.32 (C), 119.05 (2CH), 126.46 (2CH), 126.80
(C), 129.14 (2*2CH), 129.99 (CH), 130.81 (C), 138.52
(C), 146.36 (C), 154.87 (C), 155.41 (C), 156.91 (C=O);
(5-Methyl-3-phenyl-1H-pyrazol-1-yl)-[5-(p-tolyl-amino)-
2H-1,2,3-triazol-4-yl]methanone 6b
Compound is light yellow powder, yield 39%, m.p.
1
170-171 °C. H NMR (CDCl3-d) (ppm), 2.341 (s, 3H,
CH3), 2.782 (s, 3H, CH3), 6.616 (s, 1H, CH), 7.173-7.200
(d, 2H, J = 8.1 Hz, p-MeC6H4-H), 7.636-7.663 (d, 2H, J =
8.1 Hz, p-MeC6H4-H), 7.495-7.519 (m, 3H, Ph-H), 7.825-
7.851 (d, 2H, Ph-H), 8.382 (b, 1H, NH); 13C NMR (CDCl3-
d) (ppm), 14.60 (CH3), 20.67 (CH3), 108.42 (CH), 110.84
(C), 117.90 (2CH), 126.33 (2CH), 128.97 (2CH), 129.62
(2CH), 129.75 (CH), 130.83 (C), 131.36 (C), 137.39 (C),
146.14 (C), 154.98 (C), 155.28 (C), 156.80 (C=O); MS
+
.
MS m/z: 378 (
, 19), 381 (M+3, 0.4), 380 (M+2, 6.7),
M
379 (M+1, 4.5), 350 (6.7), 321 (4.1), 315 (3.2), 294 (2.3),
287 (5.8), 212 (3.9), 196 (5.8), 184 (5.6), 159 (100), 137
(38), 111 (28), 77 (39), 51 (26); IR: 3444, 3347 (NH), 3061
(m, Ar-H), 2924 (CH3), 1653 (s, C=O), 1605 (s, triazole or
pyrazole ring), 1570, 1522, 1490, 1448, 1408 (s, Ar), 1264
(C=N-N), 943 (N=N-N) cm-1. Anal. Calcd for C19H15ClN6O:
C, 60.24; H, 3.99; N, 22.19; Found: C, 60.52; H, 3.87; N,
22.06.
+
.
m/z: 358 (
, 27), 359 (M+1, 6.3), 330 (7.1), 301 (7.4),
M
212 (3.6), 159 (100), 117 (63), 91 (78), 77 (47), 65 (38), 57
+
.
(30), 51 (25), 43 (27), 39 (16); HRMS (ESI, M ) calcd
[5-(m-Chlorophenylamino)-2H-1,2,3-triazol-4-yl]-(5-
methyl-3-phenyl-1H-pyrazol-1-yl)methanone 6e
Compound is light yellow powder, yield 61%, m.p.
for C20H18N6O 358.1542, found 358.1537, 301.1481,
158.0837; IR: 3437, 3348 (b, NH), 3106 (Ar-H), 2922 (w,
CH3), 1661 (s, C=O), 1607 (s, triazole or pyrazole ring),
1570, 1510, 1448, 1408 (s, Ar), 1261 (m, C=N-N), 945 (w,
N=N-N) cm-1.
1
187-188 °C. H NMR (CDCl3-d) (ppm), 2.770 (s, 3H,
CH3), 6.619 (s, 1H, CH), 6.981-7.014 (dd, 1H, J = 8.7 Hz, J
= 1.2 Hz, Ar1-H), 7.249-7.303 (m, 1H, Ar1-H), 7.497-7.536
(m, 3H, Ar2-H), 7.588-7.616 (d, 1H, Ar1-H), 7.821-7.848
(m, 2H, Ar2-H), 7.880 (s, 1H, Ar1-H), 8.487 (b, 1H, NH);
13C NMR (CDCl3-d) (ppm), 14.34 (CH3), 108.80 (CH),
115.88 (CH), 117.75 (CH), 121.89 (CH), 126.48 (2CH),
129.11 (2CH), 130.00 (CH), 130.17 (CH), 130.74 (C),
(5-Methyl-3-phenyl-1H-pyrazol-1-yl)-[5-(o-tolyl-amino)-
2H-1,2,3-triazol-4-yl]methanone 6c
Compound is light yellow powder, yield 11%, m.p.
1
183-184 °C. H NMR (CDCl3-d) (ppm), 2.442 (s, 3H,
CH3), 2.794 (s, 3H, CH3), 6.616 (s, 1H, CH), 6.984 (t, 1H,

1H-Pyrazol-1-yl-2H-1,2,3-triazol-4-yl Methanone
J. Chin. Chem. Soc., Vol. 55, No. 4, 2008 765
134.90 (C), 141.73 (C), 146.07 (C), 146.16 (C), 154.67
ring), 1569, 1511, 1447, 1411 (s, Ar), 1261 (m, C=N-N),
967 (N=N-N) cm-1.
+
.
(C), 155.45 (C), 156.93 (C=O); MS m/z: 378 (M , 17), 380
(M+2, 4.5), 379 (M+1, 3.5), 350 (7.7), 321 (5.0), 294 (2.7),
287 (8.0), 280 (1.3), 266 (0.5), 212 (6.0), 196 (7.5), 184
(10), 159 (100), 137 (39), 111 (48), 91 (12), 77 (57); IR:
3464, 3330 (b, NH), 3059 (Ar-H), 2922 (CH3), 1648 (s,
C=O), 1610, 1596 (s, triazole or pyrazole ring), 1566,
1519, 1472, 1452, 1423 (s, Ar), 1261 (b, C=N-N), 942 (w,
N=N-N) cm-1. Anal. Calcd for C19H15ClN6O: C, 60.24; H,
3.99; Cl, 9.36; N, 22.19; O, 4.22; Found: C, 60.18; H, 3.94;
N, 22.03.
(3,5-Dimethyl-1H-pyrazol-1-yl)-[5-(o-tolylamino)-2H-
1,2,3-triazol-4-yl]methanone 6h
Compound is light yellow powder, yield 85%, m.p.
1
205-206 °C. H NMR (CDCl3-d) (ppm), 2.362 (s, 3H,
CH3), 2.424 (s, 3H, CH3), 2.686 (s, 3H, CH3), 6.092 (s, 1H,
CH), 6.938-6.985 (m, 1H, Ph-H), 7.198-7.297 (m, 3H, Ph-
H), 8.417-8.495 (b, 2H, NH); 13C NMR (CDCl3-d) (ppm),
13.90 (CH3), 14.46 (CH3), 17.86 (CH3), 111.27 (CH),
111.70 (C), 117.87 (CH), 122.93 (C), 125.00 (CH), 127.20
(CH), 130.29 (CH), 138.52 (C), 147.89 (C), 153.76 (C),
(3,5-Dimethyl-1H-pyrazol-1-yl)-(5-phenylamino-2H-
1,2,3-triazol-4-yl)methanone 6f
+
.
155.27 (C), 155.80 (C=O); MS m/z: 296 (
, 21), 297
M
Compound is white powder, yield 95.7%, m.p. 196-
1
198 °C. H NMR (CDCl3-d) (ppm), 2.350 (s, 3H, CH3),
(M+1, 4.4), 268 (7.2), 239 (2.0), 225 (3.9), 212 (1.5), 198
(4.3), 171 (2.7), 144 (16), 117 (52), 97 (100), 91 (39), 65
(35); IR: 3369 (b, NH), 3137, 2975 (Ar-H), 2926 (w, CH3),
1661 (s, C=O), 1597 (s, triazole or pyrazole ring), 1571,
1515, 1472, 1431 (s, Ar), 1261 (s, C=N-N), 987, 967 (w,
N=N-N) cm-1. Anal. Calcd for C15H16N6O: C, 60.80; H,
5.44; N, 28.36; Found: C, 60.99; H, 5.34; N, 28.20.
[5-(p-Chlorophenylamino)-2H-1,2,3-triazol-4-yl]-(3,5-
dimethyl-1H-pyrazol-1-yl)methanone 6i
2.676 (s, 3H, CH3), 6.100 (s, 1H, CH), 6.897-7.045 (t, 1H, J
= 7.8 Hz, Ph), 7.338-7.391 (t, 2H, J = 7.8 Hz, Ph), 7.737-
7.766 (d, 2H, J = 7.8 Hz, Ph), 8.409 (b, 1H, NH); 13C NMR
(DMSO-d6) (ppm), 13.34 (CH3), 13.84 (CH3), 111.53
(CH), 116.95 (2CH and C), 120.73 (C), 128.95 (3CH),
+
.
140.89 (C), 144.39 (2C), 152.65 (C=O); MS m/z: 282 (
,
M
20), 283 (M+1, 4.1), 254 (12.7), 225 (3.8), 211 (2.1), 198
(9.3), 184 (4.4), 158 (5.0), 150 (4.0), 130 (8.4), 103 (46),
97 (100), 91 (3), 77 (51); IR: 3365 (s, NH), 3141, 3065
(Ar-H), 2930 (CH3), 1662 (s, C=O), 1598 (s, triazole or
pyrazole ring), 1569, 1488, 1462, 1428 (s, Ar), 1254 (b,
C=N-N), 987, 971 (N=N-N) cm-1. Anal. Calcd for
C14H14N6O: C, 59.56; H, 5.00; N, 29.77; Found: C, 59.42;
H, 5.09; N, 29.98.
Compound is light yellow powder, yield 94.8%, m.p.
1
204-206 °C. H NMR (CDCl3-d) (ppm), 2.352 (s, 3H,
CH3), 2.667 (s, 3H, CH3), 6.104 (s, 1H, CH), 7.295-7.301,
7.325-7.331 (q, 2H, J = 8.7 Hz, Ph-H), 7.688-7.694,
7.717-7.723 (q, 2H, J = 8.7 Hz, Ph-H); 8.409 (b, 1H, NH);
13C NMR (CDCl3-d) (ppm), 13.90 (CH3), 14.42 (CH3),
111.48 (CH), 118.94 (2CH), 126.62 (C), 129.11 (2CH),
137.07 (C), 138.71 (C), 145.66 (C), 153.95 (C), 154.60
(3,5-Dimethyl-1H-pyrazol-1-yl)-[5-(p-tolylamino)-2H-
1,2,3-triazol-4-yl]methanones 6g
+
.
(C), 156.27 (C=O); MS m/z: 316 (
, 8), 318 (M+2, 2.8),
M
Compound is light yellow powder, yield 84%, m.p.
1
191-193 °C. H NMR (CDCl3-d) (ppm), 2.331 (s, 3H,
317 (M+1, 1.7), 288 (4.3), 253 (3.8), 232 (2.8), 225 (7.6),
137 (27), 111 (22), 97 (100), 75 (29); IR: 3361 (b, NH),
3194 (Ar-H), 2925 (CH3), 1660 (s, C=O), 1614 (s, triazole
or pyrazole ring), 1567, 1515, 1492, 1454 (s, Ar), 1263 (s,
C=N-N), 966 (w, N=N-N) cm-1. Anal. Calcd for C14H13ClN6O:
C, 53.09; H, 4.14; N, 26.53; Found: C, 53.20; H, 4.05; N,
26.70.
CH3), 2.349 (s, 3H, CH3), 2.671 (s, 3H, CH3), 6.092 (s, 1H,
CH), 7.157-7.184 (d, 2H, J = 8.1 Hz, Ar-H), 7.620-7.648
(d, 2H, J = 8.4 Hz, Ar-H), 8.329 (b, 1H, NH); 13C NMR
(CDCl3-d) (ppm), 13.84 (CH3), 14.40 (CH3), 20.68 (CH3),
111.25 (CH), 117.84 (2CH), 129.63 (2CH), 131.22 (C),
137.57 (C), 145.50 (2C), 153.65 (C), 155.14 (C), 156.79
[5-(m-Chlorophenylamino)-2H-1,2,3-triazol-4-yl]-(3,5-
dimethyl-1H-pyrazol-1-yl)methanones 6j
+
.
(C=O); MS m/z: 296 (
, 9), 297 (M+1, 1.2), 268 (3.3),
M
239 (1.7), 225 (2.0), 212 (3.4), 198 (1.9), 172 (1.4), 145
(6.3), 133 (5.2), 117 (37), 97 (100), 91 (33), 65 (23);
Compound is light yellow powder, yield 91%, m.p.
1
203-204 °C. H NMR (CDCl3-d) (ppm), 2.356 (s, 3H,
+
.
HRMS (ESI, M ) calcd for C15H16N6O 296.1386, found
CH3), 2.671 (s, 3H, CH3), 6.107 (s, 1H, CH), 6.969-7.002
(t, 1H, Ph-H), 7.268-7.295 (d, 1H, J = 8.1 Hz, Ph-H),
7.577-7.604 (d, 1H, J = 8.1 Hz, Ph-H), 7.880 (s, 1H, Ph-H),
8.448 (b, 1H, NH); 13C NMR (DMSO-d6) (ppm), 13.25
296.1380, 297.1418, 268.1322, 239.1300, 225.1144,
212.1202, 145.0780; IR: 3364 (NH), 3198, 3140 (Ar-H),
2922 (CH3), 1663 (s, C=O), 1606 (s, triazole or pyrazole

766 J. Chin. Chem. Soc., Vol. 55, No. 4, 2008
Cao et al.
(CH3), 13.79 (CH3), 111.41, 115.38, 116.17, 120.04, 130.04,
1275 (b, C=N-N), 973 (m, N=N-N) cm-1. Anal. Calcd for
C20H18N6O: C, 67.02; H, 5.06; N, 23.45; Found: C, 66.90;
H, 5.00; N, 23.63.
+
.
133.52, 142.20, 144.34, 152.67; MS m/z: 316 (
, 10),
M
318 (M+2, 3.4), 317 (M+1, 2.1), 288 (7.0), 225 (13), 137
(26), 111 (20), 97 (100), 75 (28), 54 (12), 42 (15); HRMS
(3-Methyl-5-phenyl-1H-pyrazol-1-yl)-[5-(o-tolylamino)-
2H-1,2,3-triazol-4-yl]methanone 7c
+
.
(ESI,
) calcd for C14H13ClN6O 316.0839, found
M
316.0834, 318.0793, 288.0777, 253.1094, 225.1150,
137.0046, 97.0778; IR: 3434, 3364 (b, NH), 3130, 2983
(Ar-H), 2926 (w, CH3), 1662 (s, C=O), 1602 (s, triazole or
pyrazole ring), 1564, 1511, 1480, 1453, 1422 (s, Ar), 1259
(s, C=N-N), 987, 965 (w, N=N-N) cm-1.
Compound is light yellow powder, yield 53%, m.p.
1
170-172 °C. H NMR (CDCl3-d) (ppm), 2.276 (s, 3H,
CH3), 2.439 (s, 3H, CH3), 6.331 (s, 1H, CH), 6.952 (m, 1H,
Ar-H), 7.395-7.472 (m, 7H, Ar-H), 7.944 (m, 1H, Ar-H),
8.171 (b, 1H, NH), 8.332 (b, 1H, NH); 13C NMR (CDCl3-d)
(ppm), 13.95 (CH3), 17.82 (CH3), 112.14 (C), 112.98 (CH),
118.45 (CH), 122.19 (CH), 125.75 (C), 127.04 (CH),
128.00 (2CH), 129.00 (2CH), 129.10 (CH), 130.31 (CH
and C), 138.31 (C), 148.20 (C), 153.65 (C), 155.31 (C),
(3-Methyl-5-phenyl-1H-pyrazol-1-yl)-(5-phenylamino-
2H-1,2,3-triazol-4-yl)methanone 7a
Compound is light yellow powder, yield 77.5%, m.p.
1
167-168 °C. H NMR (CDCl3-d) (ppm), 2.448 (s, 3H,
+
.
CH3), 6.332 (s, 1H, CH), 6.996 (t, 1H, Ph), 7.299-7.352 (t,
2H, Ph), 7.479-7.489 (d, 5H, Ph), 7.671-7.696 (d, 2H, Ph),
8.239 (b, 1H, NH); 13C NMR (CDCl3-d) (ppm), 13.88
(CH3), 112.39 (C), 112.99 (CH), 117.7 (2CH), 121.75
(CH), 128.02 (2CH), 128.89 (2CH), 129.03 (2CH), 129.12
(CH), 130.40 (C), 139.91 (C), 148.07 (C), 153.77 (C),
155.90 (C=O); MS m/z: 358 (
, 14), 359 (M+1, 2.6), 330
M
(6.0), 301 (1.7), 287 (1.9), 260 (0.7), 212 (2.3), 196 (1),
185 (5.1), 171 (4.3), 159 (100), 117 (54), 91 (55); IR: 3368,
3203 (b, NH), 3051, 2965 (Ar-H), 2923 (w, CH3), 1665 (s,
C=O), 1616, 1598 (s, triazole or pyrazole ring), 1571,
1503, 1468, 1444, 1427 (s, Ar), 1272, 1246 (C=N-N), 972
(N=N-N) cm-1. Anal. Calcd for C20H18N6O: C, 67.02; H,
5.06; N, 23.45; Found: C, 67.08; H, 5.14; N, 23.57.
[5-(p-Chlorophenylamino)-2H-1,2,3-triazol-4-yl]-(3-
methyl-5-phenyl-1H-pyrazol-1-yl)methanone 7d
+
.
154.87 (C), 156.19 (C=O); MS m/z: 344 (
, 14), 345
M
(M+1, 2.6), 316 (8.5), 287 (5.4), 260 (2.8), 212 (1), 196
(1.2), 184 (6.4), 170 (1.5), 159 (100), 130 (15), 103 (49),
+
.
77 (71); HRMS (ESI,
) calcd for C19H16N6O 344.1386,
M
found 344.1380, 316.1305, 287.1292, 196.0883, 159.0937;
IR: 3356 (NH), 3132, 3058 (Ar-H), 2933 (w, CH3), 1667 (s,
C=O), 1600 (s, triazole or pyrazole ring), 1569, 1526,
1499, 1467, 1444 (s, Ar), 1237 (s, C=N-N), 980 (w,
N=N-N) cm-1.
Compound is light yellow powder, yield 67%, m.p.
1
188-190 °C. H NMR (CDCl3-d) (ppm), 2.452 (s, 3H,
CH3), 6.338 (s, 1H, CH), 7.252-7.288 (d, 2H, J = 6.9 Hz,
Ar-H), 7.475 (s, 5H, Ph), 7.624-7.653 (d, 2H, J = 6.9 Hz,
Ar-H), 8.239 (b, 1H, NH); 13C NMR (DMSO-d6) (ppm),
13.80 (CH3), 112.99 (C), 119.13 (CH), 124.71 (C), 128.49
(2CH and C), 128.84 (2CH), 128.93 (CH and C), 129.02
(2*2CH), 130.72 (C), 140.36 (C), 147.16 (C), 152.79
(3-Methyl-5-phenyl-1H-pyrazol-1-yl)-[5-(p-tolylamino)-
2H-1,2,3-triazol-4-yl]methanone 7b
Compound is light yellow powder, yield 34%, m.p.
1
179-180 °C. H NMR (CDCl3-d) (ppm), 2.305 (s, 3H,
+
.
(C=O); MS m/z: 378 (
, 13), 380 (M+2, 5), 379 (M+1,
M
CH3), 2.444 (s, 3H, CH3), 6.324 (s, 1H, CH), 7.114-7.143
(d, 2H, J = 8.7 Hz, p-MeC6H4-H), 7.549-7.577 (d, 2H, J =
8.4 Hz, p-MeC6H4-H), 7.475 (s, 5H, Ph-H), 8.161 (b, 1H,
NH); 13C NMR (CDCl3-d) (ppm), 13.94 (CH3), 20.68
(CH3), 111.32 (C), 112.95 (CH), 118.04 (2CH), 128.06
(2CH), 128.97 (2CH), 129.19 (CH), 129.60 (2CH), 130.47
(C), 131.38 (C), 137.41 (C), 148.08 (C), 153.65 (C),
3), 350 (4.8), 321 (2.3), 315 (2.8), 294 (2), 287 (5.1), 212
(2.5), 196 (2.8), 184 (4.5), 170 (2.1), 159 (100), 137 (30),
111 (26); IR: 3572, 3363 (b, NH), 3143, 2968 (Ar-H), 2837
(w, CH3), 1661 (s, C=O), 1601 (s, triazole or pyrazole ring),
1565, 1494, 1449, 1406 (s, Ar), 1280, 1237 (C=N-N), 978
(N=N-N) cm-1. Anal. Calcd for C19H15ClN6O: C, 60.24; H,
3.99; N, 22.19; Found: C, 60.06; H, 3.89; N, 22.35.
+
.
155.26 (C), 155.92 (C=O); MS m/z: 358 (
, 8), 359
M
(M+1, 0.9), 330 (1.4), 301 (1), 232 (4.7), 188 (2.4), 158
(52), 117 (26), 91 (61), 77 (43), 65 (32), 57 (100), 51 (25),
43 (94), 39 (22); IR: 3359 (b, triazole-NH), 3210, 3135 (b,
ACKNOWLEDGEMENT
The authors wish to acknowledge that this project is
supported by Lanzhou University SKLAOC.
…
N-H O=C), 2919 (w, CH3), 1668 (s, C=O), 1613 (s, tri-
Received October 23, 2007.
azole or pyrazolering), 1570, 1512, 1444, 1409 (s, Ar),

1H-Pyrazol-1-yl-2H-1,2,3-triazol-4-yl Methanone
J. Chin. Chem. Soc., Vol. 55, No. 4, 2008 767
6. Menozzi, G.; Mosti, L.; Bruno, O.; Presti, E. L.; Musiu, C.;
Longu, S.; Colla, P. L.; Filippelli, W.; Falcone, G.; Piucci, B.
Il Farmaco, 1999, 54, 416.
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