Studies on the reaction of α-chloroformylarylhydrazine hydrochloride with imidazole and 1,2,4-triazole

Article abstract of DOI:10.1002/jccs.200200144

α-Imidazolformylarylhydrazine 2 and α-[1,2,4] triazolformylarylhydrazine 3 have been synthesized through the nucleophilic substitution reaction of 1 with imidazole and 1,2,4-triazole, respectively. 2,2′-Diaryl-2H,2′H-[4,4′]bi[[1,2,4]-triazolyl]-3, 3′-dione 4 was obtained from the cycloaddition of α- chloroformylarylhydrazine hydrochloride 1 with 1,2,4-triazole at 60 °C and in absence of n-Bu₃N. The inducing factor for cycloaddition of 1 with 1,2,4-triazole was ascertained as hydrogen ion by the formation of 4 from the reaction of 3 with hydrochloric acid. 4 was also acquired from the reaction of 3 with 1 and this could confirm the reaction route for cycloaddition of 1 with 1,2,4-triazole. Some acylation reagents were applied to induce the cyclization reaction of 2 and 3. 1 possessing chloroformyl group could induce the cyclization of 2 to give 2-aryl-4-(2-aryl-4-vinyl-semicarbazide-4-yl)-2,4- dihydro-[1,2,4]-triazol-3-one 6. 7 was obtained from the cyclization of 2 induced by some acyl chlorides. Acetic acid anhydride like acetyl chloride also could react with 2 to produce 7D. 5-Substituted-3-aryl-3H-[1,3,4]oxadiazol-2-one 8 was produced from the cyclization reaction of 3 induced by some acyl chlorides or acetic acid anhydride. The 1,2,4-triazole group of 3 played a role as a leaving group in the course of cyclization reaction. This was confirmed by the same product 8 which was acquired from the reaction of 1, possessing a better leaving group: Cl, with some acyl chlorides or acetic acid anhydride.

Full text of DOI:10.1002/jccs.200200144

Journal of the Chinese Chemical Society, 2002, 49, 1003-1014
1003
Studies on the Reaction of -Chloroformylarylhydrazine Hydrochloride
with Imidazole and 1,2,4-Triazole
Chun-Yen Chiua,b
Wen-Fa Kuoa (
(
), Jen-Hua Chunga (
),
)
) and Mou-Yung Yeh*a (
aDepartment of Chemi s t r y, National Cheng Kung University, Tainan, Taiwan 70101, R.O.C.
bDepartment of Environmental Engineering and Health, Tajen Institute of Technology,
Pingtung, Taiwan 907, R.O.C.
-Imidazolformylarylhydrazine 2 and -[1,2,4]triazolformylarylhydrazine 3 have been synthesized
through the nucleophilic substitution reaction of 1 with imidazole and 1,2,4-triazole, respectively. 2,2 -
Diaryl-2H,2 H-[4,4 ]bi[[1,2,4]-triazolyl]-3,3 -dione 4 was obtained from the cycloaddition of -chloro-
formylarylhydrazine hydrochloride 1 with 1,2,4-triazole at 60 C and in absence of n-Bu3N. The inducing fac-
tor for cycloaddition of 1 with 1,2,4-triazole was ascertained as hydrogen ion by the formation of 4 from the
reaction of 3 with hydrochloric acid. 4 was also acquired from the reaction of 3 with 1 and this could confirm
the reaction route for cycloaddition of 1 with 1,2,4-triazole. Some acylation reagents were applied to induce
the cyclization reaction of 2 and 3. 1 possessing chloroformyl group could induce the cyclization of 2 to give
2-aryl-4-(2-aryl-4-vinyl-semicarbazide-4-yl)-2,4-dihydro-[1,2,4]-triazol-3-one 6. 7 was obtained from the
cyclization of 2 induced by some acyl chlorides. Acetic acid anhydride like acetyl chloride also could react
with 2 to produce 7D. 5-Substituted-3-aryl-3H-[1,3,4]oxadiazol-2-one 8 was produced from the cyclization
reaction of 3 induced by some acyl chlorides or acetic acid anhydride. The 1,2,4-triazole group of 3 played a
role as a leavi n g group in the course of cyclization reaction. This was confirmed by the same product 8 which
was acquired from the reaction of 1, possessing a better leaving group: Cl, with some acyl chlorides or acetic
acid anhydride.
INTRODUCTION
Although -chloroformylarylhydrazine hydrochloride
1 since they could react with acyl chloride easily. It was of
great interest to introduce a heterocyclic ring into the acyl
group of 1 because this work had never been done, and this
kind of product was not obtained easily through the other syn-
thetic reaction route. The anticipated products also had not
been reported in other papers as yet. This focused our efforts
on the study of their derivative reactions.
1 possesses a chloroformyl group like acyl chloride, its chem-
ical behavior is not the same. Possessing both active amino
and chloroformyl groups which occupy advantaged sites for
cycloaddition reaction, 1 readily proceeds to intermolecular
cycloaddition with itself or some other reagents.1,2,3,4 The
synthetic reactions of some desirable compounds through 1
were often limited to mild conditions. At higher temperature
or in more basic conditions, 1 was easily transformed into
dimer products.1 Therefore, successful attempts to undergo a
series of derivative reactions from one functional group of 1
often could not be attained.
RESULTS AND DISCUSSION
Imidazole dissolved in iPrOH was stirred with
-
chloroformyl arylhydrazine hydrochloride 1 in the presence
of n-Bu3N at room temperature. When the reaction was com-
In our past report,3,4 many N-heterocyclic compounds
reacted with 1 through cycloaddition to obtain the derivates
of 2,4-dihydro-1,2,4-triazol-3-one under mildly basic and
heating conditions. We thought if some N-heterocyclic com-
pounds possess a second order nitrogen atom which has
stronger nucleophility, they can go ahead with nucleophilic
substitution reaction but not cycloaddition with 1 under the
control of reaction conditions. In this paper, imidazole and
1,2,4-triazole were tried to undergo substitution reaction with
pleted, the major product was isolated and identified as -
imidazolformylarylhydrazine 2 by x-ray spectrum analysis
(Fig. 1). Following the same step, 1,2,4-triazole was tested to
react with 1. The product obtained was ascertained as
-
[1,2,4]triazolformylarylhydrazine 3 by elemental analysis,
1H NMR and MASS spectrum analysis. The yields of the
above two products are shown in Table 1. According to the re-
sults of the above two reactions (Scheme I), we found imida -
zole and 1,2,4-triazole underwent nucleophilic substitution

1004 J. Chin. Chem. Soc., Vol. 49, No. 6, 2002
Chiu et al.
Table 1. The Reactions of 1 with Imidazole (A) and 1,2,4-
Scheme I
Triazole (B) at Room Temperature and in the Presence
of n-Bu3N
O
O
n-Bu3N, 25 0
iPrOH
C
C
N
N
Ar
N
Ar
N
Cl
N
Product
Ar
C6H5
4-ClC6H4
4-CH3C6H4
C6H5
Yield
Reagent
+
+
.
NH2
NH2
H Cl
N
2a
2b
2c
3a
3b
3c
36
52
57
32
36
70
A
A
A
B
B
B
2
1
O
O
N
N
n-Bu3N, 25 0
iPrOH
Ar
N
Cl
4-ClC6H4
4-CH3C6H4
Ar
N
N
N
N
.
NH2
H Cl
N
NH2
1
3
Table 2. The Reaction of 1 with 1,2,4-Triazole at 60 C and in
iPrOH
the Absence of n-Bu3N
iPrOH, 600C
O
1
60 0
C
Product
Ar
C6H5
4-ClC6H4
4-CH3C6H4
Yield
O
4aa
4bb
4cc
15
13
18
Ar
N
N
N
N
Ar
N
N
4
spectrum analysis. In order to study the fact o r inducing the
cycloaddition of 1 with 1,2,4-triazole, we designed that com-
pound 3 was tested to undergo intramolecular cyclization un-
der three types of conditions. The first condition was at 60 C
and in the presence of n-Bu3N; the second one was at 60 C
but in the absence of n-Bu3N; and the third one was at 60 C
and with the addition of concentrated hydrochloric acid. The
result (Scheme II) indicated that und e r the third condition, 5
and 4 were obtained and und e r the other ones, there was no re-
action taking place. 5 was confirmed as 4-amino-2-aryl-2,4-
dihydro-3H-1,2,4-triazol-3-one by comparing their spectrum
in another paper.5 The reaction route for production of 5 and
4, we guessed, is shown in Scheme II. According to these re-
sults, the factor inducing the cycloaddition of 1 with 1,2,4-
triazole was ascertained to be a hydrogen ion. From the poor
result for the cycloaddition of 1 with 1,2,4-triazole, we made
a guess that as 1 could provide a hydrogen ion itself duri n g
the reaction, 1 underwent cycloaddition with 1,2,4-triazole in
the absence of n-Bu3N, but on this acidic condition, the inter-
mediate product 3 was not easily produced, and therefore, the
yield of the final product 4 was low. In order to confirm our
inference, 3 was tested to react with 1 at 60 C in the absence
reaction with 1.
In one of our previous papers,4 3-amino-1,2,4-triazole
could proceed to cycloaddition with 1 at 60 C to obtain
5-amino-bis(2-aryl-2,4-dihydro-1,2,4-triazol-3-on-4-yl).
This made us believe that 1,2,4-triazole could also undergo
cycloaddition with 1 under some conditions. Therefore, 1,2,4-
triazole was attempted to go ahead with cycloaddition with 1
by changing the reaction condition. We found cycloaddition
product 4 was isolated from the reaction of 1 with 1,2,4-
triazole at 60 C and in the absence of n-Bu3N (Scheme I), but
the yield (Table 2) was low. The structure of 4 was ascer-
tained as 2,2 -diaryl-2H,2 H-[4,4 ]bi[[1,2,4]-triazolyl]-3,3 -
dione by elemental analy s i s , 1H NMR, 13C NMR and MASS
Table 3. The Reaction of 3 with Hydrochloric Acid at 60 C
Product 1
Yield
Product 2
Yield
Ar
C6H5
4-ClC6H4
4-CH3C6H4
4aa
4bb
4cc
17
14
19
5a
5b
5c
48
45
42
Fig. 1. Molecular Structure of -Imidazolformyl-4-
methylphenyl hydrazine 2c.

Reaction of -Chloroformylarylhydrazine
J. Chin. Chem. Soc., Vol. 49, No. 6, 2002 1005
Scheme II
,
n-Bu3N
iPrOH
No reaction
No reaction
600C
iPrOH
600C
O
N
Ar
N
N
N
NH2
3
O
HCl
,
iPrOH
600C
N
+
N
Ar
N
N
H
NH2
O
O
O
Ar
hydrolysis
N
N N
Ar
N
N NH2
Ar
N
N N C NH2
H
N
N
N
N
H
H
5
3
+
O
O
O
O
N
Ar
Ar
N
N N
N
Ar
Ar
N
N
N
N
N
N
N
H
NH3
+
4
of n-Bu3N. The product 4 was also acquired and the yield
demonstrated in Table 4 was enhanced. This result could as-
certain the reaction route in Scheme I.
given. According to the structure of 6, this reaction route
could be suggested as that in Scheme III. Investigating this
reaction route, we guessed that the factor inducing the
cyclization reaction of 2 was the chloroformyl group of 1. In
order to confirm this inference, some acyl chlorides were
tested to react with 2. The results shown in Table 5 indicate
that 2 could undergo cyclization reaction induced by acyl
chloride to obtain 7. The structure of 7Db was identified as
2 was also attempted to execute intramolecular cycliza-
tion by addition of hydrochloric acid, but the anticipated re-
sult was not obtained. Another test for the cycloaddition rea c -
tion of 2 with 1 was done and 2-aryl-4-(2-aryl-4-vinyl-
semicarbazide-4-yl)-2,4-dihydro-[1,2,4]-triazol-3-one 6 was
Table 4. The Reaction of 3 with 1 at 60 C
Reactant 3
Reactant 1
Product
Ar
C6H5
C6H5
C6H5
4-ClC6H4
4-ClC6H4
4-ClC6H4
4-CH3C6H4
4-CH3C6H4
4-CH3C6H4
Ar
C6H5
4-ClC6H4
4-CH3C6H4
C6H5
4-ClC6H4
4-CH3C6H4
C6H5
4-ClC6H4
4-CH3C6H4
Yield
3a
3a
3a
3b
3b
3b
3c
3c
3c
1a
1b
1c
1a
1b
1c
1a
1b
1c
4aa
4ab
4ac
4ab
4bb
4bc
4ac
4bc
4cc
46
44
48
43
42
45
48
46
52

1006 J. Chin. Chem. Soc., Vol. 49, No. 6, 2002
Chiu et al.
Scheme III
N-{2-[1-(4-chlorophenyl)-5-oxo-1,5-dihydro-[1,2,4]triazol-
4-yl]vinyl}-acetamide (Fig. 2) by x-ray spectrum analysis.
Acetic acid anhydride like acyl chlorides was also
tested to react with 2; we found the product was the same as
that obtained from the cyclization reaction induced by acetyl-
chloride. According to the above results, we concluded that 2
could undergo intramolecular cyclization induced by some
acylation reagents.
clization of 3 and the product obtained (Table 6) was ascer-
tained as 5-substituted-3-aryl-3H-[1,3,4]oxadiazol-2-one 8
by comparing their spectrum in other papers.1,6,7 This result
was different from that obtained through the cyclization rea c -
tion of 3 induced by hydrogen ion. According to the structure
of 8, the synthetic reaction route of 8 given from 3 could be
shown in Scheme IV and, we thought, the 1,2,4-triazole
group of 3 played a role as a leaving group in the course of
cyclization reaction. In order to confirm this reaction route, 1
Some acylation reagents were also applied to the cy-

Reaction of -Chloroformylarylhydrazine
J. Chin. Chem. Soc., Vol. 49, No. 6, 2002 1007
Table 5. The Reactions of 2 with 1; 4-Nitrobenzoyl Chloride (A); Benzoyl Chloride (B);
Ethoxalyl Chloride (C); Acetyl Chloride (D); Ethoxycarbonyl Chloride (E) and
Acetic Acid Anhydride (F)
Reactant 2
Reagent
Product
Ar
C6H5
4-CH3C6H4
4-ClC6H4
4-CH3C6H4
4-ClC6H4
4-CH3C6H4
4-ClC6H4
4-CH3C6H4
4-ClC6H4
4-CH3C6H4
4-ClC6H4
4-CH3C6H4
4-ClC6H4
4-CH3C6H4
R
Yield
2a
2c
2b
2c
2b
2c
2b
2c
2b
2c
2b
2c
2b
2c
1a
1c
A
A
B
B
C
C
D
D
E
E
F
6aa
6cc
52
67
84
81
82
83
76
72
73
63
55
36
73
66
7Ab
7Ac
7Bb
7Bc
7Cb
7Cc
7Db
7Dc
7Eb
7Ec
7Db
7Dc
4-NO2C6H4
4-NO2C6H4
C6H5
C6H5
COOC2H5
COOC2H5
CH3
CH3
OC2H5
OC2H5
CH3
F
CH3
Table 6. The Reactions of 3 with 4-Nitrobenzoyl Chloride (A); Benzoyl Chloride (B);
Ethoxalyl Chloride (C); Acetyl Chloride (D) and Acetic Acid Anhydride (E)
Reactant
Reagent
Product
Ar
R
Yield
3c
3c
3c
3c
3c
A
B
C
D
E
8Ac
8Bc
8Cc
8Dc
8Dc
4-CH3C6H5
4-CH3C6H4
4-CH3C6H4
4-CH3C6H4
4-CH3C6H4
4-NO2C6H4
C6H5
COOC2H5
CH3
52
67
84
81
82
CH3
possessing a better leaving group: Cl was tested to react with
acyl chlorides or acetic acid anhydride. The product 8 was
also obtained and the yield is shown in Table 7.
CONCLUSION
2 and 3 have been synthesized through the nucleophilic
substitution reaction of 1 with imidazole and 1,2,4-triazole,
respectively. 4 was obtained from the cycloaddition of 1 with
1,2,4-triazole at 60 C and in the absence of n-Bu3N. The in-
ducing fact o r for cycloaddition of 1 with 1,2,4-triazole was
ascertained as hydrogen ion by the formation of 4 from the re-
action of 3 with hydrochloric acid. 4 was also acquired from
the reaction of 3 with 1 and this could confirm the reaction
route for cycloaddition of 1 with 1,2,4-triazole.
Some acylation reagents were applied to induce the
cyclization reaction of 2 and 3. 1 possessing chloroformyl
group could induce the cyclization of 2 to give 6. 7 was ob-
tained from the cyclization of 2 induced by some acyl chlo-
rides. Acetic acid anhydride like acetyl chloride also could
react with 2 to produce 7D.
Fig. 2. Molecular Structure of N-{2-[1-(4-Chloro-
phenyl)-5-oxo-1,5-dihydro-[1,2,4]triazol-4-yl]
vinyl}acetamide 7Db.
The result from the cyclization reaction of 3 induced by
some acylation reagents was different from that induced by
hydrogen ion. Some acyl chlorides or acetic acid anhydride

1008 J. Chin. Chem. Soc., Vol. 49, No. 6, 2002
Chiu et al.
Scheme IV
O
O
R
Cl
Ar
Ar
N
O
N
iPrOH, 50 0C
R
O
R
N
Ar
8
4-CH3C6H4
Ar
N
N
4-NO2C6H4
C6H5
8Ac
N
O
O
O
NH2
8Bc
8Cc
8Dc
H3C
O
CH3
COOC2H5
CH3
N
O
3
N
iPrOH, 50 0C
CH3
8Dc
O
R
Cl
8
THF, 25 0C
O
Ar
N
Cl
O
O
.
NH2
HCl
H3C
O
CH3
1
8Dc
THF, 25 0C
Reaction route:
O
R
O
N
O
N
Cl
O
Ar
N
N
N
Ar
N
N
N
N
NH2
O
or
R
O
H
O
R
3
R
O
Ar
N
O
N
R
8
could react with 3 to obtain 8. The 1,2,4-triazole group of 3
played a role as a leaving group in the course of cyclization re-
action. This was confirmed by the same product 8 which was
acquired from the reaction of 1, possessing a better leavi n g
group: Cl, with some acyl chlorides or acetic acid anhydride.
tro-photometer. NMR spectra were measured on a Bruker
AMX-200 NMR spectrometer with tetramethylsilane as in-
ternal standard. The mass spectra were registered on a
Finnigan MAT TSQ-46C spectrometer at an ionizing poten-
tial of 70 eV. Elemental analyses were performed on Heraeus
CHN-O-Rapid and Tacussel Coulomax 78 analyzers. X-ray
analyses were made with a Nonius CAD-4 diffractometer.
Column chromatography was carried out on silica gel
(Kieselgel 100, 70-230 mesh, E. Merck).
EXPERIMENTAL SECTION
General
Melting points (Buchi 535 apparatus) are uncorrected.
IR spectra were recorded on a Hitachi 270-30 infrared spec-
Synthesis of 2 from the reaction of 1 with imidazole
Imidazole (0.34 g, 5 mmol) dissolved in iPrOH was

Reaction of -Chloroformylarylhydrazine
J. Chin. Chem. Soc., Vol. 49, No. 6, 2002 1009
Table 7. The Reactions of 1 with 4-Nitrobenzoyl Chloride (A); Benzoyl Chloride (B);
Ethoxalyl Chloride (C); Acetyl Chloride (D) and Acetic Acid Anhydride (E)
Reactant
Reagent
Product
Ar
R
Yield
1c
1c
1c
1c
1c
A
B
C
D
E
8Ac
8Bc
8Cc
8Dc
8Dc
4-CH3C6H5
4-CH3C6H4
4-CH3C6H4
4-CH3C6H4
4-CH3C6H4
4-NO2C6H4
C6H5
COOC2H5
CH3
62
79
80
70
72
CH3
Table 8. Crystal Data for 2c, 7Db
Table 9. Bond Distances/Å of 2c
Compound
2c
7Db
C(1)-C(2)
C(1)-H(1a)
C(1)-H(1b)
C(1)-H(1c)
C(2)-C(3)
C(2)-C(7)
C(3)-C(4)
C(3)-H(3)
C(4)-C(5)
C(4)-H(4)
C(5)-C(6)
C(5)-N(1)
C(6)-C(7)
C(6)-H(6)
C(7)-H(7)
1.514(14)
0.955
0.938
C(8)-O(1)
C(8)-N(1)
C(8)-N(3)
C(9)-C(10)
C(9)-N(3)
C(9)-H(9)
C(10)-N(4)
C(10)-H(10)
C(11)-N(3)
C(11)-N(4)
C(11)-H(11)
N(1)-N(2)
N(2)-H(n2)
N(2)-H(n21)
1.202(11)
1.354(12)
1.426(14)
1.270(15)
1.378(12)
0.962
1.369(16)
0.958
1.399(14)
1.361(16)
0.952
Formula
fw
cryst system
space group
a, Å
b, Å
c, Å
, deg
, deg
C11H12N4O
216.24
Triclinic
P-1
11.6071(9)
5.6841(8)
16.6714(11)
90.000(11)
103.344(10)
89.960(9)
1070.22(19)
2
C12H11ClN4O2
288.42
Triclinic
P-1
4.2449(24)
12.700(5)
23.933(3)
100.333(21)
95.080(22)
99.54(3)
1242.4(9)
2
0.945
1.370(21)
1.359(24)
1.380(13)
0.967
1.358(22)
0.952
1.387(18)
1.449(11)
1.366(14)
0.975
, deg
1.435(10)
0.957
0.961
V, Å3
Z
Dcalcd, g cm-3
(?Mo-K ), Å
F000
1.342
1.49
0.963
0.70930
456.18
0.70930
595.00
Range, deg
24, 9.84-34.66 24, 12.60-28.26
2
max ,deg
49.9
-2
44.9
-2
Table 10. Bond Angles/deg of 2c
scan type
/cm-1
0.09
2202
2183
1029
249
0.31
3435
3257
1827
343
C(2)-C(1)-H(1a)
C(2)-C(1)-H(1b)
C(2)-C(1)-H(1c)
H(1a)-C(1)-H(1b) 108.6
H(1a)-C(1)-H(1c) 107.8
H(1b)-C(1)-H(1c) 108.5
110.8
111.3
109.9
C(6)-C(7)-H(7)
O(1)-C(8)-N(1)
O(1)-C(8)-N(3)
N(1)-C(8)-N(3)
C(10)-C(9)-N(3)
C(10)-C(9)-H(9)
120.9
125.2(10)
118.2(9)
116.6(8)
112.0(9)
125.8
Reflections measured
Unique reflections
Observed reflections
Refined parameters
Rf for significant reflections 0.079
Rw for significant reflections 0.083
0.051
0.051
2.16
C(1)-C(2)-C(3)
C(1)-C(2)-C(7)
C(3)-C(2)-C(7)
C(2)-C(3)-C(4)
C(2)-C(3)-H(3)
C(4)-C(3)-H(3)
C(3)-C(4)-C(5)
C(3)-C(4)-H(4)
C(5)-C(4)-H(4)
C(4)-C(5)-C(6)
C(4)-C(5)-N(1)
C(6)-C(5)-N(1)
C(5)-C(6)-C(7)
C(5)-C(6)-H(6)
C(7)-C(6)-H(6)
C(2)-C(7)-C(6)
C(2)-C(7)-H(7)
119.4(15) N(3)-C(9)-H(9)
122.8(14) C(9)-C(10)-N(4)
117.8(10) C(9)-C(10)-H(10)
121.9(15) N(4)-C(10)-H(10)
122.1
107.2(9)
128.2
124.4
105.0(10)
127.9
GOF
3.02
stirred with 1a (0.517 g, 2.56 mmol) and n-Bu3N (1.5 g) at
room temperature for 2 hours. After the reaction, iPrOH was
removed from the reaction mixture and the residue was sub-
jected to column separation (eluent: EtOAc/n-hexane = 4:1)
to give 2a. According to this procedure, the reactions of 1b
and1c with imidazole were undergone, but there was precipi-
tate produced in the reaction mixture. The precipitate was fil-
tered and then recrystalized from EtOAc + iPrOH to give 2b,
2c.
119.7
118.1
N(3)-C(11)-N(4)
N(3)-C(11)-H(11)
119.0(13) N(4)-C(11)-H(11)
127.1
124.5
116.5
120.2(9)
C(5)-N(1)-C(8)
C(5)-N(1)-N(2)
C(8)-N(1)-N(2)
126.0(8)
117.9(7)
115.5(6)
109.6
121.3(11) N(1)-N(2)-H(n2)
118.5(13) N(1)-N(2)-H(n21)
119.0(14) H(n2)-N(2)-H(n21) 108.0
109.8
120.2
120.7
C(8)-N(3)-C(9)
C(8)-N(3)-C(11)
121.8(9)
132.5(9)
105.7(8)
110.1(10)
122.1(13) C(9)-N(3)-C(11)
117.0 C(10)-N(4)-C(11)
-Imidazolformylphenyl hydrazine 2a
mp 99-100 C; IR (KBr) 3316, 3178, 1680 cm-1; H
1

1010 J. Chin. Chem. Soc., Vol. 49, No. 6, 2002
Table 11. Bond Distances/Å of 7Db
Chiu et al.
1H NMR (DMSO-d6) 8.38 (s, 1H), 7.68 (d, J = 2.2 Hz, 1H),
7.58 (d, J = 9.0 Hz, 2H), 7.46 (d, J = 9.0 Hz, 2H), 6.96 (d, J =
2.2 Hz, 1H), 5.71 (s, 2H); EIMS (70 eV) m/z: 238 (M++2, 31),
236 (M+, 72), 209 (46), 169 (26), 153 (57), 141 (96), 77 (100),
68 (72), 63 (33). Anal. Calcd for C10H10ClN4O: C, 50.75; H,
3.83; N, 23.67; Cl, 14.98. Found: C, 50.64; H, 3.89; N, 23.63;
Cl, 15.00.
C(1)-C(2)
C(1)-C(6)
C(1)-H(1)
C(2)-C(3)
C(2)-N(1)
C(3)-C(4)
C(3)-H(3)
C(4)-C(5)
C(4)-H(4)
C(5)-C(6)
C(5)-C(1)
C(6)-H(6)
C(7)-N(2)
C(7)-N(3)
C(7)-H(7)
C(8)-O(1)
1.366(8)
1.385(10)
0.961
1.384(9)
1.425(8)
1.367(9)
0.957
1.356(9)
0.981
1.380(10)
1.733(6)
0.941
C(8)-N(1)
C(8)-N(3)
C(9)-C(10)
C(9)-N(3)
C(9)-H(9)
C(10)-N(4)
C(10)-H(10)
C(11)-C(12)
C(11)-O(2)
C(11)-N(4)
C(12)-H(12a)
C(12)-H(12b)
C(12)-H(12c)
N(1)-N(2)
1.359(8)
1.397(8)
1.311(10)
1.394(9)
0.953
1.394(9)
0.947
1.506(10)
1.207(8)
1.353(9)
0.954(6)
0.961(7)
0.941(6)
1.389(7)
0.952
-Imidazolformyl-4-methylphenyl hydrazine 2c
mp 135-136 C; IR (KBr) 3334, 3292, 3190, 3136,
1725, 1692 cm-1; 1H NMR (DMSO-d6) 8.32 (s, 1H), 7.60 (d,
J = 0.8 Hz, 1H), 7.39 (d, J = 8.5 Hz, 2H), 7.19 (d, J = 8.5 Hz,
2H), 6.93 (d, J = 0.8 Hz, 1H), 5.63 (s, 2H), 2.31 (s, 3H); EIMS
(70 eV) m/z: 216 (M+, 100), 189 (12), 149 (13), 133 (20), 121
(57), 77 (45), 68 (72), 63 (10). Anal. Calcd for C11H12N4O: C,
61.11; H, 5.56; N, 25.93. Found: C, 61.19; H, 5.50; N, 25.73.
1.273(9)
1.355(8)
0.978(7)
1.224(8)
N(4)-H(n4)
Table 12. Bond Angles/deg of 7Db
120.1(6) C(10)-C(9)-H(9)
Synthesis of 3 from the reaction of 1 with 1,2,4-triazole
1,2,4-Triazole (0.69 g, 10 mmol) dissolved in iPrOH
was stirred with 1a (0.517 g, 2.56 mmol) and n-Bu3N (1.5 g)
at room temperature for 2 hours. After the reaction, iPrOH
was removed from the reaction mixture and the residue was
subjected to column separation (eluent: EtOAc/n-hexane =
6:1) to give 3a. According to this procedure, the reactions of
various 1 with 1,2,4-triazole were achieved.
C(2)-C(1)-C(6)
C(2)-C(1)-H(1)
C(6)-C(1)-H(1)
C(1)-C(2)-C(3)
C(1)-C(2)-N(1)
C(3)-C(2)-N(1)
C(2)-C(3)-C(4)
C(2)-C(3)-H(3)
C(4)-C(3)-H(3)
C(3)-C(4)-C(5)
C(3)-C(4)-H(4)
C(5)-C(4)-H(4)
C(4)-C(5)-C(6)
C(4)-C(5)-C(1)
C(6)-C(5)-C(1)
C(1)-C(6)-C(5)
C(1)-C(6)-H(6)
C(5)-C(6)-H(6)
N(2)-C(7)-N(3)
N(2)-C(7)-H(7)
N(3)-C(7)-H(7)
O(1)-C(8)-N(1)
O(1)-C(8)-N(3)
N(1)-C(8)-N(3)
114.2
116.1
127.5(6)
116.7
115.8
121.5(6)
115.3(6)
123.3(6)
111.6
110.8
111.8
119.9
120.0
N(3)-C(9)-H(9)
C(9)-C(10)-N(4)
120.2(6) C(9)-C(10)-H(10)
118.8(5) N(4)-C(10)-H(10)
121.0(5) C(12)-C(11)-O(2)
119.2(5) C(12)-C(11)-N(4)
120.1
120.7
121.0(6) C(11)-C(12)-H(12b)
119.9
119.1
120.3(6) H(12a)-C(12)-H(12c) 107.7
120.7(5) H(12b)-C(12)-H(12c) 108.9
119.0(5) C(2)-N(1)-C(8)
119.1(5) C(2)-N(1)-N(2)
120.8
120.1
O(2)-C(11)-N(4)
C(11)-C(12)-H(12a)
-[1,2,4]-triazolformylphenylhydrazine 3a
C(11)-C(12)-H(12c)
H(12a)-C(12)-H(12b) 105.9
mp 124-125 C; IR (KBr) 3352, 3220, 3166, 3106,
1695 cm-1; 1H NMR (DMSO-d6) 9.14 (s, 1H), 8.12 (s, 1H),
7.20-7.49 (m, 5H), 5.75 (s, 2H); EIMS (70 eV) m/z: 203 (M+,
47), 146 (67), 107 (59), 91 (23), 77 (100), 70 (60), 64 (17).
Anal. Calcd for C9H9N5O: C, 53.20; H, 4.43; N, 34.48.
Found: C, 53.24; H, 4.37; N, 34.69.
128.8(5)
118.6(5)
112.4(5)
103.0(5)
105.7(5)
125.4(5)
128.8(5)
121.2(5)
117.5
C(8)-N(1)-N(2)
C(7)-N(2)-N(1)
115.2(6) C(7)-N(3)-C(8)
121.6
123.2
129.8(6) C(10)-N(4)-C(11)
126.5(6) C(10)-N(4)-H(n4)
103.7(5) C(11)-N(4)-H(n4)
C(7)-N(3)-C(9)
C(8)-N(3)-C(9)
-[1,2,4]-triazolformyl-4-chlorophenylhydrazine 3b
mp 141-142 C; IR (KBr) 3304, 3238, 3184, 3130,
1740, 1704 cm-1; 1H NMR (DMSO-d6) 9.17 (s, 1H), 8.14 (s,
1H), 7.48 (d, J = 8.5 Hz, 2H), 7.47 (d, J = 8.5 Hz, 2H), 5.78 (s,
2H); EIMS (70 eV) m/z: 239 (M++2, 10), 237 (M+, 36), 180
(92), 141 (83), 111 (47), 77 (100), 70 (77). Anal. Calcd for
C9H8ClN5O: C, 45.57; H, 3.38; N, 29.54; Cl, 14.77. Found: C,
45.65; H, 3.43; N, 29.48; Cl, 14.84.
121.3
C(10)-C(9)-N(3) 129.6(6)
NMR (DMSO-d6) 8.35 (s, 1H), 7.63 (d, J = 2.1 Hz, 1H),
7.21-7.62 (m, 5H), 6.94 (d, J = 2.1 Hz, 1H), 5.7 (s, 2H); EIMS
(70 eV) m/z: 202 (M+, 100), 175 (84), 135 (69), 119 (51), 107
(90), 77 (86), 68 (40), 64 (28). Anal. Calcd for C10H10N4O: C,
59.41; H, 4.95; N, 27.72. Found: C, 59.64; H, 5.01; N, 27.56.
-[1,2,4]-triazolformyl-4-methylphenylhydrazine 3c
mp 161-162 C; IR (KBr) 3340, 3220, 3172, 3106,
1680 cm-1; 1H NMR (DMSO-d6) 9.11 (s, 1H), 8.11 (s, 1H),
7.35 (d, J = 8.3 Hz, 2H), 7.16 (d, J = 8.3 Hz, 2H), 5.69 (s, 2H),
2.29 (s, 3H); EIMS (70 eV) m/z: 217 (M+, 73), 160 (100), 121
(91), 91 (95), 77 (47), 70 (27). Anal. Calcd for C10H11N5O: C,
-Imidazolformyl-4-chlorophenyl hydrazine 2b
mp 115-116 C; IR (KBr) 3364, 3280, 3172, 1680 cm-1;

Reaction of -Chloroformylarylhydrazine
J. Chin. Chem. Soc., Vol. 49, No. 6, 2002 1011
55.30; H, 5.07; N, 32.26. Found: C, 55.25; H, 4.89; N, 32.09.
hexane = 3:2) to give 5c. According to this procedure, the re-
actions of various 3 with hydrochloric acid were achieved.
The reaction of 1 with 1,2,4-triazole in the absence of
n-Bu3N
4-Amino-2-phenyl-2,4-dihydro-3H-1,2,4-triazol-3-one 5a
mp 161-162 C; IR (KBr) 3322, 3280, 3214, 1716 cm-1;
1H NMR (DMSO-d6) 8.23 (s, 1H), 7.89 (d, J = 8.4 Hz, 2H),
7.45 (t, J = 8.4 Hz, 2H), 7.22 (t, J = 8.4 Hz, 1H), 5.55 (s, 2H);
FABMS m/z: 177 (M++1, 100), 176 (M+, 52), 136 (19). Anal.
Calcd for C8H8N4O: C, 54.54; H, 4.58; N, 31.80. Found: C,
54.58; H, 4.65; N, 31.78.
[1,2,4]-Triazole (0.86 g, 12.5 mmol) dissolved in
iPrOH (10 mL) was stirred with 1a (0.517 g, 2.56 mmol) at 60
C for thirty minutes. After the reaction, the white precipitate
was filtered to obtain 4aa. According to this procedure, the
reactions of various 1 with 1,2,4-triazole were achieved.
2,2 -Diphenyl-2H,2 H-[4,4 ]bi[[1,2,4]-triazolyl]-3,3 -dione
(4aa)
4-Amino-2-(4-chlorophenyl)-2,4-dihydro-3H-1,2,4-triazol-
mp > 250 C; IR (KBr) 3142, 3088, 1728, 1704 cm-1; 1H
3-one 5b
NMR (DMSO-d6)) 8.80 (s, 2H), 7.33-7.86 (m, 10H); 13
C
mp 184-185 C; IR (KBr) 3334, 3226, 1710 cm-1; H
1
NMR (DMSO-d6)) 147.85, 137.15, 136.91, 129.48, 126.31,
118.31; EIMS (70 eV) m/z: 321 (M++1, 18), 320 (M+, 85), 260
(31), 132 (12), 119 (13),104 (22), 91 (32), 77 (100), 64 (13).
Anal. Calcd for C16H12N6O2: C, 60.00; H, 3.78; N, 26.24.
Found: C, 59.87; H, 3.69; N, 26.18.
NMR (DMSO-d6) 8.26 (s, 1H), 7.92 (d, J = 8.8 Hz, 2H),
7.51 (d, J = 8.8 Hz, 2H), 5.55 (s, 2H); FABMS m/z: 211
(M++1, 100), 210 (M+, 62). Anal. Calcd for C8H7ClN4O: C,
45.62; H, 3.35; N, 26.60. Found: C, 45.53; H, 3.35; N, 26.66.
4-Amino-2-(4-methylphenyl)-2,4-dihydro-3H-1,2,4-triazol-
3-one 5c
2,2 -Bis(4-chlorophenyl)-2H,2 H-[4,4 ]bi[[1,2,4]-triazolyl]-
3,3 -dione (4bb)
mp 163-164 C; IR (KBr) 3340, 3298, 3232, 1698 cm-1;
1H NMR (DMSO-d6) 8.19 (s, 1H), 7.75 (d, J = 8.4 Hz, 2H),
7.25 (d, J = 8.4 Hz, 2H), 5.52 (s, 2H), 2.29 (s, 3H); FABMS
m/z: 191 (M++1, 100), 190 (M+, 66), 154 (19). Anal. Calcd for
C9H10N4O: C, 56.83; H, 5.30; N, 29.50. Found: C, 56.83; H,
5.37; N, 29.63.
mp > 250 C; IR (KBr) 3130, 3082, 1728, 1704 cm-1; 1H
NMR (DMSO-d6) 8.79 (s, 2H), 7.89 (d, J = 8.9 Hz, 4H),
7.59 (d, J = 8.9 Hz, 4H); 13C NMR (DMSO-d6) 147.81,
135.78, 131.54, 129.01, 127.11, 118.34; EIMS (70 eV) m/z:
392 (M++4, 10) 390 (M++2, 15), 388 (M+, 22), 194 (25), 138
(25), 125 (28), 111 (100), 89 (29), 75 (37), 63 (21). Anal.
Calcd for C16H10Cl2N6O2: C, 49.38; H, 2.59; N, 21.59; Cl,
18.22. Found: C, 49.20; H, 2.50; N, 21.48; Cl, 18.00.
The reaction of 3 with 1
3a (0.203 g, 1 mmol) dissolved in iPrOH (10 mL) was
stirred with 1a (0.207 g, 1 mmol) at 60 C for 30 minutes. Af-
ter the reaction, the precipitate was filtered to obtain 4aa. Ac-
cording to this procedure, the reactions of various 3 with vari -
ous 1 were achieved.
2,2 -Di-p-tolyl-2H,2 H-[4,4 ]bi[[1,2,4]-triazolyl]-3,3 -dione
(4cc)
mp > 250 C; IR (KBr) 3136, 3088, 1728, 1704, 1515,
1386 cm-1; 1H NMR (DMSO-d6) 8.77 (s, 2H), 7.76 (d, J =
8.6 Hz, 4H), 7.35 (d, J = 8.6 Hz, 4H), 2.34 (s, 6H); 13C NMR
(DMSO-d6) 147.77, 136.93, 135.63, 134.56, 129.82, 118.35,
20.54; EIMS (70 eV) m/z: 349 (M++1, 22), 348 (M+, 100),
174 (27), 146 (8), 132 (8), 118 (12), 105 (12), 91 (51), 73
(10), 65 (12). Anal. Calcd for C18H16N6O2: C, 62.06; H, 4.63;
N, 24.12. Found: C, 62.00; H, 4.58; N, 23.98.
2-Phenyl-2 -(4-chlorophenyl)-2H,2 H-[4,4 ]bi[[1,2,4]-
triazolyl]-3,3 -dione (4ab)
mp > 250 C; IR (KBr) 3136, 3088, 1728, 1704 cm-1; 1H
NMR (DMSO-d6) 8.82 (s, 1H), 8.81 (s, 1H), 7.29-7.93 (m,
9H); EIMS (70 eV) m/z: 356 (M++2, 32), 354 (M+, 100), 320
(37), 194 (17), 160 (25),125 (11), 111 (25), 91 (24), 77 (63),
63 (9). Anal. Calcd for C16H11ClN6O2: C, 54.17; H, 3.13; N,
23.69; Cl, 9.99. Found: C, 54.01; H, 3.03; N, 23.41; Cl, 9.84.
The reaction of 3 with hydrochloric acid
3c (0.217 g, 1 mmol) dissolved in iPrOH (8 mL) was
stirred with concentrated hydrochloric acid (5 mL) at 60 C
for 2 hours. After the reaction, the precipitate was filtered to
obtain 4c. iPrOH was removed from the filtrate and the resi -
due was subjected to column separation (eluent: EtOAc/n-
2-Phenyl-2 -p-tolyl-2H,2 H-[4,4 ]bi[[1,2,4]-triazolyl]-3,3 -
dione (4ac)
mp > 250 C; IR (KBr) 3133, 3084, 1730, 1704 cm-1; 1H
NMR (DMSO-d6) 8.80 (s, 1H), 8.77 (s, 1H), 7.89 (d, J = 8.8

1012 J. Chin. Chem. Soc., Vol. 49, No. 6, 2002
Chiu et al.
Hz, 2H), 7.74 (d, J = 8.4 Hz, 2H), 7.54 (t, J = 8.8 Hz, 2H), 7.33
(m, 3H), 2.3 (s, 3H); EIMS (70 eV) m/z: 335 (M++1, 22), 334
(M+, 100), 174 (33), 160 (25), 105 (11), 91 (33), 77 (65).
Anal. Calcd for C17H14N6O2: C, 61.07; H, 4.22; N, 25.14.
Found: C, 60.98; H, 4.20; N, 25.09.
The reaction of 2 with acyl chloride or acetic acid anh y -
dride
2 (1 mmol) dissolved in iPrOH (10 mL) was stirred with
various acyl chlorides or acetic acid anhydride (2 mmol) at 50
C for 2 hours. After the reaction, if there was precipitate pro-
duced in the reaction mixture, the precipitate was filtered to
obtain 7; if there was no precipitate in the reaction mixture,
iPrOH was removed from the filtrate and the residue was sub-
jected to column separation (eluent: EtOAc/n-hexane = 1:3)
to give 7.
2-(4-Chlorophenyl)-2 -p-tolyl-2H,2 H-[4,4 ]bi[[1,2,4]-
triazolyl]-3,3 -dione (4bc)
mp > 250 C; IR (KBr) 3448, 3136, 3084, 1726, 1707
cm-1; 1H NMR (DMSO-d6) 8.79 (s, 1H), 8.76 (s, 1H), 7.89
(d, J = 8.9 Hz, 2H), 7.75 (d, J = 8.6 Hz, 2H), 7.59 (d, J = 8.9
Hz, 2H), 7.35 (d, J = 8.6 Hz, 2H), 2.3 (s, 3H); EIMS (70 eV)
m/z: 370 (M++2, 33), 368 (M+, 100), 348 (82), 194 (7), 174
(38),146 (17), 111 (26), 91 (90), 65 (17). Anal. Calcd for
C17H13ClN6O2: C, 55.37; H, 3.55; N, 22.79; Cl, 9.61. Found:
C, 55.24; H, 3.45; N, 22.63; Cl, 9.52.
N-{2-[1-(4-Chlorophenyl)-5-oxo-1,5-dihydro-[1,2,4]triazol-
4-yl]vinyl}-4-nitrobenzamide 7Ab
mp 249-250 C; IR (KBr) 3112, 1713, 1680, 1605 cm-1;
1H NMR (DMSO-d6) 10.71 (d, J = 10.0 Hz, 1H), 8.45 (s,
1H), 8.37 (d, J = 8.9 Hz, 2H), 8.12 (d, J = 8.9 Hz, 2H), 7.95 (d,
J = 8.9 Hz, 2H), 7.56 (d, J = 8.9 Hz, 2H), 6.98 (dd, J = 10.0,
7.2 Hz, 1H), 6.00 (d, J = 7.2 Hz, 1H); EIMS (70 eV) m/z: 387
(M++2, 11), 385 (M+, 32), 150 (100), 120 (9), 104 (27), 76
(10). Anal. Calcd for C17H12ClN5O4: C, 52.99; H, 3.12; N,
18.18; Cl, 9.09. Found: C, 52.88; H, 3.25; N, 18.06; Cl, 9.14.
The reaction of 2 with 1
2a (0.202 g, 1 mmol) was dissolved in iPrOH (10 mL)
and then stirred with 1a (0.517 g, 2.5 mmol) at 60 C for 30
minutes. After the reaction, iPrOH was removed from the re-
action mixture and the residue was subjected to column sepa -
ration (eluent: EtOAc/n-hexane = 1:3) to give 6aa. Accord-
ing to this procedure, the reaction of 2c with 1c was achieved.
N-{2-[1-(4-Methylphenyl)-5-oxo-1,5-dihydro-[1,2,4]triazol-
4-yl]vinyl}-4-nitrobenzamide 7Ac
mp 189-190 C; IR (KBr) 3094, 1710, 1671, 1605 cm-1;
1H NMR (DMSO-d6) 10.86 (d, J = 10.1 Hz, 1H), 8.40 (s,
1H), 8.36 (d, J = 8.5 Hz, 2H), 8.11 (d, J = 8.5 Hz, 2H), 7.80 (d,
J = 8.5 Hz, 2H), 7.29 (d, J = 8.5 Hz, 2H), 6.93 (dd, J = 10.1,
7.3 Hz, 1H), 6.02 (d, J = 7.3 Hz, 1H); EIMS (70 eV) m/z: 366
(M++1, 16), 365 (M+, 84), 336 (11), 263 (32), 175 (20), 150
(100), 133 (28), 120 (29), 104 (63), 91 (33), 76 (34), 65 (19).
Anal. Calcd for C18H15N5O4: C, 59.18; H, 4.11; N, 19.18.
Found: C, 59.07; H, 4.21; N, 19.04.
2-Phenyl-4-(2-phenyl-4-vinylsemicarbazide-4-yl)-2,4-
dihydro-[1,2,4]triazol-3-one 6aa
mp 193-194 C; IR (KBr) 3328, 3262, 3208, 3100,
1
2926, 1713, 1692, 1656 cm-1; H NMR (DMSO-d6) 10.11
(d, J = 10.8 Hz, 1H), 8.34 (s, 1H), 7.87-7.08 (m, 10H), 6.63
(dd, J = 10.8, 7.4 Hz, 1H), 5.78 (d, J = 7.4 Hz, 1H), 5.44 (s,
2H); EIMS (70 eV) m/z: 336 (M+, 6), 293 (48), 229 (43), 161
(19), 133 (19), 119 (23), 108 (100), 91 (62), 77 (92), 65 (33).
Anal. Calcd for C17H16N6O2: C, 60.70; H, 4.80; N, 25.00.
Found: C, 60.73; H, 4.86; N, 24.88.
N-{2-[1-(4-Chlorophenyl)-5-oxo-1,5-dihydro-[1,2,4]triazol-
4-yl]vinyl}benzamide 7Bb
2-(4-Methylphenyl)-4-(2-(4-methylphenyl)-4-vinylsemi-
carbazide-4-yl)-2,4-dihydro-[1,2,4]triazol-3-one 6cc
mp 213-214 C; IR (KBr) 3328, 3274, 3208, 3100,
mp 206-207 C; IR (KBr) 3166, 3088, 1713, 1680,
1659 cm-1; 1H NMR (DMSO-d6) 10.50 (d, J = 10.1 Hz, 1H),
8.41 (s, 1H), 7.91-7.57 (m, 9H), 6.97 (dd, J = 10.1, 7.3 Hz,
1H), 5.93 (d, J = 7.3 Hz, 1H); EIMS (70 eV) m/z: 342 (M++2,
8), 340 (M+, 23), 153 (5), 125 (7), 105 (100), 77 (53). Anal.
Calcd for C17H13ClN4O2: C, 60.00; H, 3.82; N, 16.47; Cl,
10.3. Found: C, 59.90; H, 3.82; N, 16.41; Cl, 10.40.
1
2920, 1713, 1692, 1653, 1635 cm-1; H NMR (DMSO-d6)
10.07 (d, J = 10.8 Hz, 1H), 8.31 (s, 1H), 7.75 (d, J = 8.5 Hz,
2H), 7.42 (d, J = 8.5 Hz, 2H), 7.29 (d, J = 8.5 Hz, 2H), 7.11 (d,
J = 8.5 Hz, 2H), 6.63 (dd, J = 10.8, 7.4 Hz, 1H), 5.76 (d, J =
7.4 Hz, 1H), 5.34 (s, 2H), 2.32 (s, 3H), 2.26 (s, 3H); EIMS (70
eV) m/z: 364 (M+, 6), 321 (16), 243 (41), 175 (14), 133 (13),
122 (100), 105 (27), 91 (41), 77 (20), 65 (12). Anal. Calcd for
C19H20N6O2: C, 62.65; H, 5.50; N, 23.10. Found: C, 62.43; H,
5.44; N, 22.82.
N-{2-[1-(4-Methylphenyl)-5-oxo-1,5-dihydro-[1,2,4]triazol-
4-yl]vinyl}benzamide 7Bc
mp 199-200 C; IR (KBr) 3424, 3148, 3088, 2962,
1713, 1674, 1605 cm-1; 1H NMR (DMSO-d6) 10.68 (d, J =

Reaction of -Chloroformylarylhydrazine
J. Chin. Chem. Soc., Vol. 49, No. 6, 2002 1013
10.0 Hz, 1H), 8.36 (s, 1H), 7.89-7.56 (m, 9H), 6.92 (dd, J =
10.0, 7.3 Hz, 1H), 5.95 (d, J = 7.3 Hz, 1H), 2.32 (s, 3H); EIMS
(70 eV) m/z: 321 (M++1, 24), 320 (M+, 75), 133 (12), 105
(100), 91 (17), 77 (78). Anal. Calcd for C18H16N4O2: C,
67.50; H, 5.00; N, 17.50. Found: C, 67.47; H, 5.12; N, 17.45.
(12), 91 (32). Anal. Calcd for C13H14N4O2: C, 60.47; H, 5.43;
N, 21.71. Found: C, 60.38; H, 5.47; N, 21.62.
2-(4-Chlorophenyl)-4-(ethyl-N-vinylcarbamate)-2,4-
dihydro-[1,2,4]triazol-3-one 7Eb
mp 233-234 C; IR (KBr) 3454, 3184, 3100, 2986,
1
N-{2-[1-(4-Chlorophenyl)-5-oxo-1,5-dihydro-[1,2,4]triazol-
4-yl]vinyl}oxalamic acid ethyl ester 7Cb
1725, 1713, 1695 cm-1; H NMR (DMSO-d6) 9.62 (d, J =
10.6 Hz, 1H), 8.19 (s, 1H), 7.91 (d, J = 8.9 Hz, 2H), 7.53 (d, J
= 8.9 Hz, 2H), 6.65 (dd, J = 10.6, 6.8 Hz, 1H), 5.58 (d, J = 6.8
Hz, 1H), 4.09 (q, J = 7.0 Hz, 2H), 1.19 (t, J = 7.0 Hz, 3H);
EIMS (70 eV) m/z: 310 (M++2, 39), 308 (M+, 100), 262 (39),
153 (37), 125 (62), 111 (28), 85 (59), 75 (17), 69 (30), 63 (19),
56 (27). Anal. Calcd for C13H13ClN4O3: C, 50.56; H, 4.22; N,
18.18; Cl, 11.36. Found: C, 50.45; H, 4.23; N, 18.13; Cl,
11.51.
mp 146-147 C; IR (KBr) 3100, 3064, 2986, 1761,
1
1713, 1683 cm-1; H NMR (DMSO-d6) 11.23 (d, J = 10.2
Hz, 1H), 8.39 (s, 1H), 7.90 (d, J = 8.9 Hz, 2H), 7.56 (d, J = 8.9
Hz, 2H), 6.64 (dd, J = 10.2, 7.7 Hz, 1H), 6.06 (d, J = 7.7 Hz,
1H), 4.26 (q, J = 7.0 Hz, 2H), 1.25 (t, J = 7.0 Hz, 3H); EIMS
(70 eV) m/z: 338 (M++2, 10), 336 (M+, 32), 263 (100), 153
(14), 125 (21), 111 (12), 75 (7). Anal. Calcd for
C14H13ClN4O4: C, 50.00; H, 3.87; N, 16.67; Cl, 10.42. Found:
C, 49.91; H, 3.90; N, 16.72; Cl, 10.34.
2-(4-Methylphenyl)-4-(ethyl-N-vinylcarbamate)-2,4-
dihydro-[1,2,4]triazol-3-one 7Ec
N-{2-[1-(4-Methylphenyl)-5-oxo-1,5-dihydro-[1,2,4]triazol-
4-yl]vinyl}oxalamic acid ethyl ester 7Cc
mp 164-165 C; IR (KBr) 3304, 3088, 2980, 1722,
1710, 1698 cm-1; 1H NMR (DMSO-d6) 9.60 (d, J = 10.2 Hz,
1H), 8.10 (s, 1H), 7.73 (d, J = 8.5 Hz, 2H), 7.58 (d, J = 8.5 Hz,
2H), 6.61 (dd, J = 10.2, 7.3 Hz, 1H), 5.23 (d, J = 7.3 Hz, 1H),
3.94 (q, J = 7.0 Hz, 2H), 2.30 (s, 3H), 1.11 (t, J = 7.0 Hz, 3H);
EIMS (70 eV) m/z: 288 (M+, 6), 189 (100), 133 (8), 117 (9),
105 (6), 89 (6). Anal. Calcd for C14H16N4O3: C, 58.33; H,
5.59; N, 19.43. Found: C, 58.20; H, 5.45; N, 19.40.
mp 195-196 C; IR (KBr) 3136, 3064, 2986, 1755,
1
1701, 1680 cm-1; H NMR (DMSO-d6) 11.36 (d, J = 10.2
Hz, 1H), 8.35 (s, 1H), 7.75 (d, J = 8.4 Hz, 2H), 7.29 (d, J = 8.4
Hz, 2H), 6.61 (dd, J = 10.2, 7.7 Hz, 1H), 6.08 (d, J = 7.7 Hz,
1H), 4.26 (q, J = 7.0 Hz, 2H), 2.32 (s, 3H), 1.27 (t, J = 7.0 Hz,
3H); EIMS (70 eV) m/z: 316 (M+, 33), 243 (100), 133 (12),
105 (15), 91 (16), 55 (11). Anal. Calcd for C15H16N4O4: C,
56.96; H, 5.06; N, 17.72. Found: C, 56.76; H, 5.08; N, 17.71.
The reaction of 3 with acyl chloride or acetic acid anh y -
dride
N-{2-[1-(4-Chlorophenyl)-5-oxo-1,5-dihydro-[1,2,4]triazol-
4-yl]vinyl}acetamide 7Db
3c (0.217 g, 1 mmol) dissolved in iPrOH (10 mL) was
stirred with various acyl chlorides or acetic acid anhydride (2
mmol) at 70 C for 2 hours. After the reaction, the precipitate
was filtered and then recrystalized from EtOAc + iPrOH to
obtain 8.
mp 181-182 C; IR (KBr) 3184, 3106, 1719, 1680 cm-1;
1H NMR (DMSO-d6) 9.88 (d, J = 10.6 Hz, 1H), 8.28 (s, 1H),
7.94 (d, J = 9.0 Hz, 2H), 7.54 (d, J = 9.0 Hz, 2H), 6.87 (dd, J =
10.6, 6.9 Hz, 1H), 5.65 (d, J = 6.9 Hz, 1H), 1.97 (s, 3H); EIMS
(70 eV) m/z: 280 (M++2, 38), 278 (M+, 97), 236 (100), 153
(29), 125 (58), 111 (20), 85 (86), 75 (18), 69 (20), 63 (20),
56(38). Anal. Calcd for C12H11ClN4O2: C, 51.80; H, 3.96; N,
20.14; Cl, 12.59. Found: C, 51.75; H, 4.04; N, 20.22; Cl,
12.55.
5-(4-Nitrophenyl)-3-p-tolyl-3H-[1,3,4]oxadiazol-2-one 8Ac
mp 203-204 C; IR (KBr) 3106, 3070, 3034, 2920,
1782 cm-1; 1H NMR (DMSO-d6) 8.40 (d, J = 9.2 Hz, 2H),
8.14 (d, J = 9.2 Hz, 2H), 7.73 (d, J = 8.5 Hz, 2H), 7.35 (d, J =
8.5 Hz, 2H), 2.34 (s, 3H); EIMS (70 eV) m/z: 297 (M+, 30),
105 (100), 78 (13), 65 (5). Anal. Calcd for C15H11N3O4: C,
60.60; H, 3.70; N, 14.10. Found: C, 60.53; H, 3.76; N, 14.15.
N-{2-[1-(4-Methylphenyl)-5-oxo-1,5-dihydro-[1,2,4]triazol-
4-yl]vinyl}acetamide 7Dc
mp 168-169 C; IR (KBr) 3274, 3208, 3130, 3076,
5-Phenyl-3-p-tolyl-3H-[1,3,4]oxadiazol-2-one 8Bc
3034, 1707, 1662 cm-1; H NMR (DMSO-d6) 9.88 (d, J =
mp 165-166 C; IR (KBr) 3133, 3084, 2920, 1776 cm-1;
1H NMR (DMSO-d6) 7.90 (m, 2H), 7.71 (d, J = 8.5 Hz, 2H),
7.61 (m, 3H), 7.33 (d, J = 8.5 Hz, 2H), 2.34 (s, 3H); EIMS (70
eV) m/z: 252 (M+, 56), 105 (100), 77 (13), 65 (5). Anal. Calcd
for C15H12N2O2: C, 71.40; H, 4.80; N, 11.10. Found: C, 71.25;
1
10.6 Hz, 1H), 8.23 (s, 1H), 7.77 (d, J = 8.5 Hz, 2H), 7.27 (d, J
= 8.5 Hz, 2H), 6.83 (dd, J = 10.6, 6.9 Hz, 1H), 5.66 (d, J = 6.9
Hz, 1H), 2.31 (s, 3H) 1.97 (s, 3H); EIMS (70 eV) m/z: 259
(M++1, 28), 258 (M+, 100), 153 (22), 133 (29), 125 (60), 105

1014 J. Chin. Chem. Soc., Vol. 49, No. 6, 2002
Chiu et al.
H, 4.78; N, 11.15.
Key Words
-Chloroformylarylhydrazine hydrochloride;
5-Oxo-4-p-tolyl-4,5-dihydro-[1,3,4]oxadiazol-2-carboxylic
acid ethyl est e r 8Cc
Imidazole; 1,2,4-Triazole; -Imidazolformylaryl-
hydrazine; -[1,2,4]Triazolformylarylhydrazine;
2,2 -Diaryl-2H,2 H-[4,4 ]bi[[1,2,4]-triazolyl]-3,3 -
dione; Cycloaddition; 2-Aryl-4-(2-aryl-4-vinyl-
semicarbazide-4-yl)-2,4-dihydro-[1,2,4]-triazol-3-one;
Acyl chloride; Acetic acid anhydride;
The spectrum of 8Cc was the same as that reported in
another paper.7
5-Methyl-3-p-tolyl-3H-[1,3,4]oxadiazol-2-one 8Dc
The spectrum of 8Dc was the same as that reported in
another paper.1,6
5-Substituted-3-aryl-3H-[1,3,4]oxadiazol-2-one.
The reaction of 1 with acyl chloride or acetic acid anh y -
dride
REFERENCES
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Yeh, M. Y. J. Chin. Chem. Soc. 1994, 41, 849.
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Chem. Soc. 2001, 48, 215.
3. Chiu, C. Y.; Kuo, C. N.; Kuo, W. F.; Yeh, M. Y. J. Chin.
Chem. Soc. 2001, 48, 1135.
1c (0.217 g, 1 mmol) suspended in THF (5 mL) was
stirred with various acyl chloride or acetic acid anhydride (2
mmol) at room temperature for 2 hours. After the reaction,
THF was removed from the reaction mixture and then the res-
idue was stirred with cold iPrOH for 30 minutes. The precipi-
tate was filtered to obtain 8.
4. Chiu, C. Y.; Kuo, C. N.; Kuo, W. F.; Yeh, M. Y. J. Chin.
Chem. Soc. 2002, 49, 239.
5. Ehrhardt, Heinz; Heubach, Guenther; Mildenberger, Hilmar
Liebigs Ann.Chem. 1982, 5, 994.
ACKNOWLEDGMENT
6. Mallur, Shanta G.; Badami, Bharati V. Farmaco 2000, 55,
65.
7. Freund, M.; Thilo, J. Chem.Ber. 1891, 24, 4199.
We thank the National Science Council of the Republic
of China for financial support of this study.
Received April 19, 2002.