Synthesis and herbicidal activities of a series of di(aminopyrazoly) ketone derivatives

Article abstract of DOI:10.1002/jhet.5570440401

(Chemical Equation Presented) In order to obtain new lead compounds with high herbicidal activity, a series of 5-amino pyrazole derivatives were designed and synthesized using a series of relational synthons. Their structures were determined by IR, ¹H NMR, and elemental analyses. These compounds were screened for herbicidal activities against rape and barnyard grass. Their structure-activity relationships are discussed.

Full text of DOI:10.1002/jhet.5570440401

Jul-Aug 2007
749
Synthesis and Herbicidal Activities of a Series of
Di(aminopyrazoly) Ketone Derivatives
Jun-fei Li1,2, You-quan Zhu, Xin Wang and Hua-zheng Yang*
1. State Key Laboratory of Element-Organic Chemistry, Institute of Element-Organic Chemistry,
Nankai University, Tianjin 300071, P. R. China. E-mail: nk_yanghz@126.com
2. School of Chemistry and Material Science, Shanxi Normal University, Linfen 041004, Shanxi, P. R. China
Received January 6, 2006
H2N
O
COOEt
R1
N
R1
N
R1
N
COOEt
NH2
CONHNH2
NH2
N
R1
R2
CN
NHNH2 H2O
N
A
RNHNH2
R3
NH2
N
R
N
R
N
R
COOEt
A
R=CH3, C6H5, C4H9 ; R1,R3= SMe, H, CH3; R2= SMe, OEt, OCH3
In order to obtain new lead compounds with high herbicidal activity, a series of 5-amino pyrazole
derivatives were designed and synthesized using a series of relational synthons. Their structures were
1
determined by IR, H NMR, and elemental analyses. These compounds were screened for herbicidal
activities against rape and barnyard grass. Their structure-activity relationships are discussed.
J. Heterocyclic Chem., 44, 749 (2007).
INTRODUCTION
derivatives classified as the inhibitors of 4-HPPD
displayed excellent herbicidal activities, such as
pyrazolynate 1, pyrazoxyfen 2 and benzofenap 3 [6-9]
(Figure 1). By comparisons with other HPPD inhibitors, it
was concluded that their main pharmacophore was 5-
hydroxyl-4-benzoyl pyrazole. It was also noticed that
amino group possessed a similar capability of forming
complex compounds with hydroxyl group, and according
to the bioisosterism theory, both pyrazole ring and
benzene ring were ring equivalents. However, the
pyrazole derivatives containing two pyrazole rings used as
herbicide have been rarely reported. In order to find
valuable lead compounds with high herbicidal activity, a
series of the title compounds 4 (Figure 1) were designed
and synthesized.
4-Hydoxyphenylpyruvate dioxygenase (4-HPPD)
catalyzes the conversion of the 4-hydroxyphenylpyruvate
to homogentisate in the biosynthesis pathway of
plastoquinone and tocopherol. Inhibition of the production
of homogentisate by 4-HPPD inhibitors down-regulates
the production of plastoquinone, which is thought to be an
acceptor of hydrogen from phytoene. Therefore, the
absence of plastoquinone leads to an accumulation of the
phytoene, which results in the impairment of carotenoid
biosynthesis that is essential for the growth and survival
of herbs. Generally, potent herbicides of this kind must
possess the following structural features: (1) a di- or
tricarbonyl methane structure, with one of the carbonyl
groups being a substituted benzoyl group; (2) the
compound must be able to enolize so that the enolate is
capable of inhibiting the HPPD enzyme by competitive
combination with Fe2+, the reaction center of the HPPD
enzyme [1-5]. As reported, many 4-carbonyl pyrazole
Schemes 1
R1
N
COOEt
NH2
R1
R2
CN
RNHNH2
i
6
Cl
R2
COOEt
N
R
O
1 Pyrazolate: R1=4-CH3C6H4SO2, R2=H
2 Pyroxyfen: R1=C6H5COCH2, R2=H
3 Benzofenap: R1=C6H5COCH2, R2=CH3
Cl
a R1= SMe, R2=SMe
b R = H, R =OEt
R=CH3, C6H5, C4H9
6
7
5
c R11= CH3,2R2=OCH3
N
OR1
H2N
N
ii
NHNH2 H2O
CONHNH2
H2N
O
COOEt
O
COOEt
4 R= CH3, C6H5, t-C4H9
R1
N
N
R1
N
5
R1
N
N
N
N
R1,3= H, CH3, SMe
R3
R3
iii
NH2
NH2
N
R
NH2
N
R
N
R
4
8
i: ethanol, reflux; ii: relux; iii: DMF, reflux
Figure 1. Chemical structure 1-4

750
J.-f. Li, Y.-q. Zhu, X. Wang and H.-z. Yang
Vol 44
only the compounds 4w and 4x exhibited some extent
inhibition against rape; 3) the compounds with R1 = SMe
delivere no inhibited activity on Rape root. When the
substitute R was phenyl group, the compounds displayed
some inhibition against rape root but have no influence on
barnyard grass. In general, the results indicated that all the
compounds possessed a certain extent inhibiting activities
against the rape root growth and exhibited activities
against barnyard grass, but their activities are not as good
as the diketone herbicides.
RESULTS AND DISCUSSION
1. Synthesis. The title compounds were synthesized
according to Scheme 1 by in a parallel synthesis fashion,
by which
a number of compounds with various
substitution patterns could be efficiently prepare in a short
time. First, three ethyl 2-cyano-acrylates (5) were reacted
with three substituted hydrazine (6) to obtained nine ethyl
1,3-disubstituted-5-amino-pyrazoly-4-carboxyacate (7)
according to a reported procedure [10], then (7) was
transformed to its hydrazine derivatives (8). Finally, the
title compounds (4) were prepared by reaction of (8)
with synthons (5). This pathway had the advantages of
mild reaction conditions and high yields (listed in
Tables 1 and 2).
Scheme 2
CN
COOEt
O
H3CS
CONHNH2
NH2
H3CS
N
H
N
C
N
N
H3CO
H
N
N
COOEt
N
NH2
During the reaction of the pyrazole carbohydrazide 8g
and intermediate 5c in ethanol at room temperature a solid
(mp 159-160 °C) was obtained. Its infrared spectrum
showed that the cyano group still existed (2204 cm-1) and
5c
10
8g
1
the H NMR spectrum showed there were two singlets at
H2N
8.97 and 10.90 ppm which corresponded to the NH and
CONH, so its structure was confirmed to be 10 and the
reaction from 8g to 4u was thought to proceed according
to Scheme 2 [11].
2. Herbicidal activity. These compounds were
screened for herbicidal activities against rape and
barnyard grass (Table 2). The results showed that, when R
was t-butyl group, 1) compounds 4 always possessed
better herbicidal activities against barnyard grass than
methyl or phenyl group at 100ug/mL; 2) among them, the
compound 4z and 4aa exhibited bleaching activities and
HN
O
COOEt
O
COOEt
H3CS
N
R1
N
N
N
H
N
N
NH2
N
NH2
N
R
4u
3. Crystal structure [22]. The compound 4r was
recrystallized from ethanol and obtained a light crystal.
The data of crystal structure was collected by BRUKER
SMART 1000 CCD diffractometer and the structure
(Figure 2) was solved by using differential techniques
using SHELX-97 [23]. It was surprising to find that the
two hydrogen atoms in N4 combine with the oxygen O1
Table 1
Physical and Analytical Data of Compounds 2
Compd
R
R1
Mp(°C)
Yield(%)
93
7a
CH3
CH3S
181-183
(litt. [12] 182-183)
98-99
7b
7c
CH3
CH3
H
85
88
(litt. [13] 99-101)
107-109
CH3
(litt. [14] 111)
7d
7e
7f
7g
7h
7i
C6H5
C6H5
C6H5
t-C4H9
t-C4H9
t-C4H9
CH3
CH3S
H
CH3
CH3S
H
99-100(litt. [15]
98-100(litt. [16]
)
)
91
82
87
78
83
85
96-98(litt. [17]
37-38
)
liquid(litt. [18]
61-63
)
CH3
CH3S
Figure 2
8a
243-245
75
70
(litt. [19] 245-247)
245-247
8b
CH3
H
and O2 and constitute two intramolecular hydrogen
bonds, the hydrogen atom in N1 associate with O1 in
another molecule and form a hydrogen intermolecular
bond. he data showed that the hydrogen bond between O1
and N4 was stronger than the bond between N4 and O2,
the bonds, by which the molecules constitute a sandwich.
The one between N1 and O2 in another molecule is the
(litt. [20] 245-247)
205-207
65
78
75
70
75
74
79
8c
8d
8e
8f
8g
8h
CH3
CH3
CH3S
H
CH3
CH3S
H
C6H5
C6H5
C6H5
t-C4H9
t-C4H9
153-154
183-184(litt. [21]
115-116
)
73-75
165-167
156-158
8i
t-C4H9
CH3

Jul-Aug 2007
Synthesis and Herbicidal Activities of a Series of Di(aminopyrazoly) Ketone Derivatives
751
weakest. The rings O1/C5/N5/C6/N4, N4/C6/C7/C16/O2
and the pyrazole ring (N5/N6/C8/C7/C6) formed a
coplanar structure by the action of the association, the
ratio of deviation is 0.0187. The data was found to be
accorded with our assumption and exhibits the
conjunction of the compounds and the HPPD enzyme
indirectly.
temperature, and then poured into 100 mL water, the
precipitate was collected by filtration and the solid was
purified by recrystallization with ethanol to afford desired
product 7.
Ethyl 5-amino-1-t-butyl-3-(thiomethyl)-1H-pyrazole-
4-carboxylate (7g). This compound is obtained as
1
colorless solid (alcohol), yield 78%, mp 37~38°. H nmr
(400 MHz, ꢀ ppm, CDCl3): 1.36 (t, J = 7.2, 3H, CH3),
1.60 (s, 9H, t-C4H9), 2.46 (s, 3H, SCH3), 4.30 (q, J = 7.20,
2H, CH2 ), 5.28 (s, 2H, NH2); ir (potassium bromide):
3423, 3332 (NH), 1670 (C=O), 1524 (C=N), 1231 (O=C-
O)cm-1. Anal. Calcd. for C11H19N3O2S: C, 51.34; H, 7.44;
N, 16.33. Found C, 51.12; H, 7.51; N, 16.38.
Ethyl 5-amino-1-t-butyl-3-methyl-1H-pyrazole-4-
carboxylate (7i). This compound is obtained as colorless
solid (alcohol), yield 85%; mp 61~63°. 1H nmr (400 MHz,
CONCLUSION
In conclusion, a number of diaminopyrazolyl ketone
compounds were synthesized and tested for herbicidal
activity. However, only a few compounds exhibited
moderate activity against rape or barnyard grass. Further
biological evaluation and structure modifications are in
progress in our laboratory.
ꢀ ppm, CDCl3): 1.34 (t, J = 7.2, 3H, CH3), 1.60 (s, 9H, t-
C4H9), 2.36 (s, 3H, 3-CH3), 4.30 (q, J = 7.20, 2H, CH2),
5.28 (s, 2H, NH2); ir (potassium bromide): 3425, 3333
(NH), 1669 (C=O), 1520 (C=N), 1210 (O=C-O)cm-1.
Anal. Calcd. for C11H19N3O2: C, 58.64; H, 8.50; N, 18.65.
Found C, 58.52; H, 8.51; N, 18.38.
2. General Procedure for the Reaction of 5-amino-
1H-pyrazole-4-carbohydrazide (8) [20,25,26]. A sus-
pension of pyrazole derivatives 7 (0.05mol) in 14.7mL
85% hydrazine hydrate is heated at 105° for 6 h. Then the
solution is evaporated under vacuum and cooled to room
temperature. The residue is filtrated; washed with 25 mL
diethyl ether three times. A white crystalline solid 8 is
obtained.
EXPERIMENTAL
General Methods. Melting points were measured on a
Thomas-Hoover apparatus and are not corrected.
Infrared spectra were recorded on a Bruker Equinox55
spectrophotometer as potassium bromide tablets. 1H-
NMR spectra were measured on
a Varian 400
spectrometer (400 MHz). Elemental analyses were
performed on Yanaco-CHN CORDER MT-3 elementary
analyzer. Compounds 5 were prepared according to
literature [24-25].
1. Preparation of ethyl 5-amino-1H-pyrazole-4-
carboxylates (7) [9-10]. To a solution of 5 (0.10 mol) in
40 mL ethanol, hydrazine 6 (0.11 mol) was added. The
mixture was refluxed for 4 h and cooled to room
5-amino-3-methyl-1-methyl-1H-pyrazole-4-carbo-
hydrazide (8c). This compound is obtained as colorless
Table 2
Structure and herbicidal activity of targeted compounds.
Rape root test
Barnyardgrass cup test
Compound
R
R1
Yield(%)
Rꢀ
Mp(ꢁ)
10ug/mL
3.70
15.05
20.96
0.00
100ug/mL
13.50
51.80ꢂ
40.10ꢂ
0.00
10ug/mL
5.10
0.00
100ug/mL
30.10
5.00
4a
4b
4c
4d
4e
4f
4g
4h
4i
4j
4k
4l
4m
4n
4o
4p
4q
4r
4s
- CH3
- CH3
- CH3
- CH3
- CH3
- CH3
- CH3
- CH3
- CH3
- Ph
- Ph
- Ph
- Ph
- Ph
- Ph
- Ph
- Ph
- Ph
t-C4H9
t-C4H9
t-C4H9
t-C4H9
t-C4H9
t-C4H9
t-C4H9
t-C4H9
t-C4H9
- SMe
- SMe
- SMe
- H
- H
- H
- CH3
- CH3
- CH3
- SMe
- SMe
- SMe
- H
-SMe
-H
- CH3
-SMe
-H
- CH3
-SMe
-H
- CH3
-SMe
-H
- CH3
-SMe
-H
- CH3
-SMe
-H
- CH3
-SMe
-H
- CH3
-SMe
-H
156-158
198-200
200-202
191-192
198-200
193-198
103-104
166-168
196-198
192-194
159-160
169-170
146-148
185-186
145-147
184-185
213-215
169-171
203-205
101-102
135-137
173-175
165-166
108-110
134-135
116-118
101-103
85
78
87
92
82
83
77
88
79
80
75
85
90
83
80
79
81
75
85
85
76
90
81
85
76
87
79
0.00
8.71
0.00
18.08
21.25
23.88
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
17.66
11.19
23.01
48.88
26.37
36.18
0.00
5.00
5.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
25.21
0.00
0.00
32.84
22.99ꢂ
27.61ꢂ
33.51
34.28
31.50
28.06
66.08ꢂ
18.87ꢂ
32.99
0.00
0.00
0.00
0.00
60.13
54.62
0.00
11.29
7.72
15.23ꢂ
9.43ꢂ
14.85
13.23
5.27
21.86
39.48ꢂ
8.97
24.33
0.00
0.00
0.00
- H
- H
0.00
10.00
5.00
- CH3
- CH3
- CH3
- SMe
- SMe
- SMe
- H
- H
- H
- CH3
- CH3
- CH3
0.00
8.96
43.28
8.08
0.00
0.00
0.00
0.00
30.85
26.62
15.00
18.66
47.89
17.66
18.69
9.95
20.40
6.47
48.01
45.15
4t
4u
4v
4w
4x
4y
4z
4aa
0.00
52.69
26.74
0.00
0.00
0.00
- CH3
-SMe
-H
- CH3

752
J.-f. Li, Y.-q. Zhu, X. Wang and H.-z. Yang
Vol 44
(O=C-O)cm-1. Anal. Calcd. for C13H18N6O3S: C, 46.14; H, 5.36;
N, 24.84. Found C, 46.18; H, 5.12; N, 25.10.
1
solid, yield 65%; mp 205~207°. H nmr (400 MHz, ꢀ
ppm, CDCl3): 2.33 (s, 3H, 3-CH3), 3.55 (s, 3H, 3-CH3),
3.97 (s, 2H, NH2), 5.19 (s, 2H, 5-NH2), 6.68 (s, 1H,
CONH) ; ir (potassium bromide): 3410, 3280 (NH), 1615
(C=O), 1548 (C=N), 1401 (O=C-N)cm-1. Anal. Calcd. for
C6H11N5O: C, 42.60; H, 6.55; N, 41.39. Found C, 42.55;
H, 6.53; N, 41.59.
5-Amino-3-(methylthio)-1-phenyl-1H-pyrazole-4-carbohy-
drazide (8d). This compound is obtained as colorless solid,
yield 78%; mp 153~154°; H nmr (400 MHz, ꢀ ppm, DMSO-
d6): 2.47 (s, 3H, SCH3), 4.34 (s, 2H, NH2), 6.34 (s, 2H, 5-NH2),
6.92 (s, 1H, CONH) 7.34-7.52 (m, 5H, Ph); ir (potassium
bromide): 3456, 3344 (NH), 1615 (C=O), 1595, 1501(-Ph), 1389
(O=C-N) cm-1. Anal. Calcd. for C11H13N5OS: C, 50.17; H, 4.98;
N, 26.60. Found C, 50.11; H, 4.82; N, 26.84.
5-Amino-3-methyl-1-phenyl-1H-pyrazole-4-carbohydra-
zide (8f). This compound is obtained as colorless solid, yield
70%; mp 115~116°. 1H nmr (400 MHz, ꢀ ppm, CDCl3): 2.42 (s,
3H, CH3), 4.01 (s, 2H, NH2), 5.55 (s, 2H, 5-NH2), 6.80 (s, 1H,
CONH), 7.3-7.512 (m, 5H, Ph); ir (potassium bromide): 3432,
3320 (NH), 1608 (C=O), 1550, 1501 (-Ph), 1396 (O=C-N) cm-1.
Anal. Calcd. for C11H13N5O: C, 57.13; H, 5.65; N, 30.28. Found
C, 56.87; H, 5.53; N, 30.59.
Ethyl 5-amino-1-(5'-amino-1'-methyl-1H-pyrazole-4'-car-
bonyl)-3-(methylthio)-1H-pyrazole-4-carboxylate (4d). This
compound is obtained as colorless solid (alcohol), yield 92%,
1
mp 191~192°. H nmr (400 MHz, ꢀ ppm, CDCl3): 1.38 (t, J =
7.2, 3H, CH3), 2.55 (s, 3H, SCH3), 3.64 (s, 3H, 1'-CH3), 4.32 (q,
J = 7.2, 2H, CH2), 5.58 (s, 2H, 5'-NH2), 7.20 (s, 2H, 5-NH2),
8.43 (s, 1H, 3'-H); ir (potassium bromide): 3455, 3329 (NH),
1686, 1622 (C=O), 1515 (C=N), 1398 (O=C-N ), 1198 (O=C-O)
cm-1. Anal. Calcd. for C12H16N6O3S: C, 44.43; H, 4.97; N, 25.91.
Found C, 44.71; H, 4.63; N, 25.88.
Ethyl 5-amino-1-(5'-amino-1'-methyl-1H-pyrazole-4'-car-
bonyl)-1H-pyrazole-4-carboxylate (4e). This compound is
obtained as colorless solid (alcohol), yield 82%, mp 198~200°.
1H nmr (400 MHz, ꢀ ppm, CDCl3): 1.35 (t, J = 7.2, 3H, CH3),
3.64 (s, 3H, 1'-CH3), 4.28 (q, J = 7.2, 2H, CH2), 5.59 (s, 2H, 5'-
NH2), 7.15 (s, 2H, 5-NH2), 7.73 (s, 1H, 3-H), 8.44 (s, 1H, 3'-H);
ir (potassium bromide): 3469, 3336 (NH), 1698, 1632 (C=O),
1521 (C=N), 1396 (O=C-N ), 1167 (O=C-O)cm-1. Anal. Calcd.
for C11H13N6O3: C, 47.48; H, 5.07; N, 30.20. Found C, 47.31; H,
4.79; N, 29.98.
1
Ethyl 5-amino-1-(5'-amino-1'-methyl-1H-pyrazole-4'-car-
bonyl)-3-methyl-1H-pyrazole-4-carboxylate (4f). This
compound is obtained as colorless solid (alcohol), yield 83%,
5-Amino-1-t-butyl-3-(methylthio)-1H-pyrazole-4-carbohy-
drazide (8g). This compound is obtained as colorless solid,
yield 75%; mp 73~75°; H nmr (400 MHz, ꢀ ppm, DMSO-d6):
1
mp 193~195°. H nmr (400 MHz, ꢀ ppm, CDCl3): 1.36 (t, J =
1
7.2, 3H, CH3), 2.38 (s, 3H, 3-CH3), 3.64 (s, 3H, 1'-CH3), 4.28 (q,
J = 7.2, 2H, CH2), 5.57 (s, 2H, 5'-NH2), 7.20 (s, 2H, 5-NH2),
8.49 (s, 1H, 3'-H); ir (potassium bromide): 3448, 3334 (NH),
1686, 1627 (C=O), 1506 (C=N), 1400 (O=C-N ), 1200 (O=C-
O)cm-1. Anal. Calcd. for C12H16N6O3: C, 49.31; H, 5.52; N,
28.75. Found C, 49.03; H, 5.57; N, 28.78.
1.61(s, 9H, t-C4H9), 2.46 (s, 3H, SCH3), 3.90 (s, 2H, NH2), 5.34
(s, 2H, 5-NH2), 8.15 (s, 1H, NH, CONH) ; ir (potassium
bromide): 3436, 3318 (NH), 1610 (C=O), 1508 (C=N), 1398
(O=C-N)cm-1. Anal. Calcd. for C9H17N5OS: C, 44.42; H, 7.04;
N, 28.78. Found C, 44.23; H, 6.82; N, 28.84.
5-Amino-1-t-butyl-1H-pyrazole-4-carbohydrazide (8h).
This compound is obtained as colorless solid, yield 74%; mp
Ethyl 5-amino-1-(5'-amino-3'-methyl-1'-methyl-1H-pyra-
zole-4'-carbonyl)-3-(methylthio)-1H-pyrazole-4-carboxylate
(4g). This compound is obtained as colorless solid (alcohol),
1
165~167°. H nmr (400 MHz, ꢀ ppm, CDCl3): 1.62(s, 9H, t-
C4H9), 3.96 (s, 2H, NH2), 5. 30 (s, 2H, 5-NH2), 6.84 (s, 1H,
CONH), 7.58(s, 1H, 3-H); ir (potassium bromide): 3430, 3315
(NH), 1614 (C=O), 1556 (C=N), 1400 (O=C-N)cm-1. Anal.
Calcd. for C8H15N5O: C, 48.72; H, 7.67; N, 35.51. Found C,
48.77; H, 7.76; N, 35.49.
5-Amino-1-t-butyl-3-methyl-1H-pyrazole-4-carbohydrazide
(8i). This compound is obtained as colorless solid, yield 79%;
mp 156~158°. 1H nmr (400 MHz, ꢀ ppm, CDCl3): 1.62(s, 9H, t-
C4H9), 2.42 (s, 3H, CH3), 3.98 (s, 2H, NH2), 5.40 (s, 2H, 5-NH2),
6.80 (s, 1H, CONH); ir (potassium bromide): 3437, 3312 (NH),
1600 (C=O), 1533 (C=N), 1401 (O=C-N)cm-1. Anal. Calcd. for
C9H17N5O: C, 51.17; H, 8.11; N, 33.15. Found C, 51.10; H, 8.23;
N, 33.29.
3. General procedure for the synthesis of title compounds
4 [10-11]. To a solution of intermediate 5 (5.0 mmol) in 15mL
DMF is added compound 8 (5.5 mmol). The mixture is refluxed
for 8 h and cooled to room temperature, then poured into 30 mL
water. The precipitate is collected by filtration and a white solid
is obtained. The solid is purified by recrystallization from
ethanol/water. Desired product 4 is obtained.
1
yield 77%, mp 103~104°. H nmr (400 MHz, ꢀ ppm, CDCl3):
1.38 (t, J = 7.2, 3H, CH3), 2.36 (s, 3H, 3'-CH3), 2.47 (s, 3H, 3-
SCH3), 3.58 (s, 3H, 1'-CH3), 4.32 (q, J = 7.2, 2H, CH2), 5.56 (s,
2H, 5'-NH2), 7.28 (s, 2H, 5-NH2); ir (potassium bromide): 3447,
3341 (NH), 1688, 1608 (C=O), 1518 (C=N), 1405 (O=C-N ),
1201 (O=C-O)cm-1. Anal. Calcd. for C13H18N6O3S: C, 46.14; H,
5.36; N, 24.84. Found C, 46.17; H, 5.32; N, 24.75.
Ethyl 5-amino-1-(5'-amino-3'-methyl-1'-methyl-1H-pyra-
zole-4'-carbonyl)-1H-pyrazole-4-carboxylate (4h). This
compound is obtained as colorless solid (alcohol), yield 88%,
1
mp 166~168°. H nmr (400 MHz, ꢀ ppm, CDCl3): 1.35 (t, J =
7.2, 3H, CH3), 2.38 (s, 3H, 3'-CH3), 3.58 (s, 3H, 1'-CH3), 4.30
(q, J = 7.2, 2H, CH2), 5.69 (s, 2H, 5'-NH2), 7.18 (s, 2H, 5-NH2),
7.74 (s, 1H, 3-H); ir (potassium bromide): 3470, 3362 (NH),
1688, 1624 (C=O), 1546 (C=N), 1401 (O=C-N ), 1151 (O=C-
O)cm-1. Anal. Calcd. for r C12H16N6O3: C, 49.31; H, 5.52; N,
28.75. Found C, 49.45; H, 5.55; N, 28.53.
Ethyl 5-amino-1-(5'-amino-3'-methyl-1'-methyl-1H-pyra-
zole-4'-carbonyl)-3-methyl-1H-pyrazole-4-carboxylate (4i).
This compound is obtained as colorless solid (alcohol), yield
79%, mp 196~198°. 1H nmr (400 MHz, ꢀ ppm, CDCl3): 1.36 (t,
J = 7.2, 3H, CH3), 2.38 (s, 6H, 3, 3'- CH3), 3.59 (s, 3H, 1'-CH3),
4.31 (q, J = 7.2, 2H, CH2), 5.74 (s, 2H, 5'-NH2), 7.30 (s, 2H, 5-
NH2); ir (potassium bromide): 3462, 3391 (NH), 1679, 1606
(C=O), 1544 (C=N), 1403 (O=C-N ), 1200 (O=C-O)cm-1. Anal.
Calcd. for C13H18N6O3: C, 50.90; H, 5.92; N, 27.44. Found C,
50.64; H, 5.79; N, 27.73.
Ethyl 5-amino-1-(5'-amino-3'-(methylthio)-1'-methyl-1H-
pyrazole-4'-carbonyl)-3-methyl-1H-pyrazole-4-carboxylate
(4c). This compound is obtained as colorless white crystals
1
(alcohol), yield 87%, mp 200~202 °; H nmr (400 MHz, ꢀ ppm,
CDCl3): 1.4 (t, J = 7.2, 3H, CH3), 2.3 (s, 3H, 3-CH3), 2.5 (s, 3H,
SCH3), 3.6 (s, 3H, 1'-CH3), 4.3 (q, J = 7.2, 2H, CH2), 5.6 (s, 2H,
5'-NH2), 7.1 (s, 2H, 5-NH2); ir (potassium bromide): 3445, 3349
(NH), 1675, 1624 (C=O), 1508 (C=N), 1400 (O=C-N ), 1223

Jul-Aug 2007
Synthesis and Herbicidal Activities of a Series of Di(aminopyrazoly) Ketone Derivatives
753
Ethyl 5-amino-1-(5'-amino-3'-(methylthio)-1'-phenyl-1H-
pyraz ole-4'-carbonyl)-3-(methylthio)-1H-pyrazole-4-carbox-
ylate (4j). This compound is obtained as colorless solid
(alcohol), yield 80%, mp 192~194oC. 1H nmr (400 MHz, ꢀ ppm,
CDCl3): 1.38 (t, J = 7.2, 3H, CH3), 2.46 (s, 3H, 3-SCH3), 2.52 (s,
3H, 3'-SCH3), 4.33 (q, J = 7.20, 2H, CH2), 6.40(s, 2H, 5'-NH2),
7.36 (s, 2H, 5-NH2), 7.43-7.55 (m, 5H, Ph); ir (potassium
bromide): 3423, 3343 (NH), 1685, 1621(C=O), 1520, 1437 (-
Ph), 1410 (O=C-N), 1196(O=C-O)cm-1. Anal. Calcd. for
C18H20N6O3S2: C, 49.98; H, 4.66; N, 19.43. Found C, 49.62; H,
4.31; N, 19.56.
Ethyl 5-amino-1-(5'-amino-3'-methyl-1'-phenyl-1H-pyra-
zole-4'-carbonyl)-3-(methylthio)-1H-pyrazole-4-carboxylate
(4p). This compound is obtained as colorless solid (alcohol),
1
yield 79%, mp 184~185°. H nmr (400 MHz, ꢀ ppm, CDCl3):
1.36 (t, J = 7.2, 3H, CH3), 2.45 (s, 3H, 3'-CH3), 2.50(s, 3H,
SCH3), 4.32 (q, J = 7.2, 2H, CH2), 6.0 (s, 2H, 5'-NH2), 7.18 (s,
2H, 5-NH2), 7.42-7.55 (m, 5H, -Ph); ir (potassium bromide):
3435, 3366 (NH), 1685, 1610 (C=O), 1535, 1455 (-Ph),
1391(O=C-N), 1197(O=C-O)cm-1. Anal. Calcd. for
C18H20N6O3S: C, 53.99; H, 5.03; N, 20.99. Found C, 53.72; H,
5.32; N, 21.15.
Ethyl 5-amino-1-(5'-amino-3'-(methylthio)-1'-phenyl-1H-
pyrazole-4'-carbonyl)-1H-pyrazole-4-carboxylate (4k). This
compound is obtained as colorless solid (alcohol), yield 75%,
Ethyl 5-amino-1-(5'-amino-3'-methyl-1'-phenyl-1H-pyra-
zole-4'-carbonyl)-1H-pyrazole-4-carboxylate (4q). This
compound is obtained as colorless solid (alcohol), yield 81%,
1
1
mp 159~160 °; H nmr (400 MHz, ꢀ ppm, CDCl3): 1.35 (t, J =
mp 213~215°. H nmr (400 MHz, ꢀ ppm, CDCl3): 1.35 (t, J =
7.2, 3H, CH3), 2.52 (s, 3H, SCH3), 4.30 (q, J = 7.2, 2H, CH2),
6.53 (s, 2H, 5'-NH2), 7.21 (s, 2H, 5-NH2), 7.43-7.55 (m, 5H, -
Ph), 7.74 (s, 1H, 3-H); ir (potassium bromide): 3481, 3360
(NH), 1685, 1610 (C=O), 1500, 1455 (-Ph), 1404 (O=C-N),
Anal. Calcd. for
C17H18N6O3S: C, 52.84; H, 4.70; N, 21.75. Found C, 52.57; H,
4.70; N, 21.75.
7.2, 3H, CH3), 2.45 (s, 3H, 3'-CH3), 4.30 (q, J = 7.2, 2H, CH2),
5.97 (s, 2H, 5'-NH2), 7.19 (s, 2H, 5-NH2), 7.42-7.52 (m, 5H, Ph),
7.75 (s, 1H, 3-H); ir (potassium bromide): 3458, 3372 (NH),
1684, 1599 (C=O), 1518, 1478 (-Ph), 1398(O=C-N),
1197(O=C-O )cm-1. Anal. Calcd. for C17H18N6O3: C, 57.62; H,
5.12; N, 23.72. Found C, 57.45; H, 5.25; N, 23.53.
1298 (HC=C), 1179(O=C-O)cm-1.
Ethyl 5-amino-1-(5'-amino-3'-methyl-1'-phenyl-1H-pyra-
zole-4'-carbonyl)-3-methyl-1H-pyrazole-4-carboxylate (4r).
This compound is obtained as colorless white crystals (alcohol),
Ethyl 5-amino-1-(5'-amino-3'-(methylthio)-1'-phenyl-1H-
pyrazole-4'-carbonyl)-3-methyl-1H-pyrazole-4-carboxylate
(4l). This compound is obtained as colorless solid (alcohol),
1
yield 75%, mp 169~171°. H nmr (400 MHz, ꢀ ppm, CDCl3):
1
yield 85%, mp 169~170°; H nmr (400 MHz, ꢀ ppm, CDCl3):
1.36 (t, J = 7.2, 3H, CH3), 2.36 (s, 3H, 3-CH3), 2.45 (s, 3H, 3'-
CH3), 4.32 (q, J = 7.2, 2H, CH2), 6.03 (s, 2H, 5'-NH2), 7.29 (s,
2H, 5-NH2), 7.4-7.5 (m, 5H, -Ph); ir (potassium bromide): 3458,
3400 (NH), 1679, 1604 (C=O), 1517, 1466 (-Ph), 1402(O=C-N),
1198(O=C-O)cm-1. Anal. Calcd. for C18H20N6O3: C, 58.69; H,
5.47; N, 22.81. Found C, 58.64; H, 5.29; N, 22.74.
1.36 (t, J = 7.2, 3H, CH3), 2.36 (s, 3H, 3-CH3), 2.51 (s, 3H,
SCH3), 4.30 (q, J = 7.2, 2H, CH2), 6.61 (s, 2H, 5'-NH2), 7.15 (s,
2H, 5-NH2), 7.41-7.55 (m, 5H, -Ph); ir (potassium bromide):
3423, 3343 (NH), 1685, 1621 (C=O), 1520, 1437 (-Ph), 1410
(O=C-N ), 1196(O=C-O)cm-1. Anal. Calcd. for C18H20N6O3S: C,
53.99; H, 5.03; N, 20.99. Found C, 53.78; H, 4.92; N, 21.10.
Ethyl 5-amino-1-(5'-amino-1'-phenyl-1H-pyrazole-4'-car-
bonyl)-3-(methylthio)-1H-pyrazole-4-carboxylate (4m). This
compound is obtained as colorless solid (alcohol), yield 90%,
Ethyl 5-amino-1-(5'-amino-1'-t-butyl-3'-(methylthio)-1H-
pyrazole-4'-carbonyl)-3-(methylthio)-1H-pyrazole-4-carbox-
ylate (4s). This compound is obtained as colorless solid
1
(alcohol), yield 85%, mp 203~205°. H nmr (400 MHz, ꢀ ppm,
1
mp 146~148 °. H nmr (400 MHz, ꢀ ppm, CDCl3): 1.39 (t, J =
CDCl3): 1.38 (t, J = 7.2, 3H, CH3), 1.63 (s, 9H, t-C4H9 ), 2.43 (s,
3H, 3'-SCH3), 2.52 (s, 3H, 3-SCH3), 4.30 (q, J = 7.2, 2H, CH2),
6.00 (s, 2H, 5'-NH2), 7.20 (s, 2H, 5-NH2); ir (potassium
bromide): 3458, 3337 (NH), 1687, 1611 (C=O), 1493 (C=N),
7.2, 3H, CH3), 2.58 (s, 3H, SCH3), 4.31 (q, J = 7.20, 2H, CH2),
5.93 (s, 2H, 5'-NH2), 7.19 (s, 2H, 5-NH2), 7.43-7.56 (m, 5H, Ph),
8.65 (s, 1H, 3'-H); ir (potassium bromide): 3401, 3343 (NH),
1671, 1601 (C=O), 1519, 1467 (-Ph), 1403 (O=C-N),
1201(O=C-O)cm-1. Anal. Calcd. For. C17H18N6O3S: C, 52.84; H,
4.70; N, 21.75. Found C, 52.74; H, 4.63; N, 21.88.
1400 (O=C-N ), 1224 (O=C-O)cm-1.
Anal. Calcd. for
C16H24N6O3S2: C, 46.85; H, 5.86; N, 20.37. Found C, 46.62; H,
5.73; N, 20.56.
Ethyl 5-amino-1-(5'-amino-1'-phenyl-1H-pyrazole-4'-car-
bonyl)-1H-pyrazole-4-carboxylate (4n). This compound is
obtained as colorless solid (alcohol), yield 83%, mp 185~186°.
1H nmr (400 MHz, ꢀ ppm, CDCl3): 1.36 (t, J = 7.2, 3H, CH3),
4.30 (q, J = 7.2, 2H, CH2), 5.94 (s, 2H, 5'-NH2), 7.18 (s, 2H, 5-
NH2),7.24-7.55 (m, 5H, -Ph), 7.77 (s, 1H, 3-H), 8.7 (s, 1H, 3'-
H); ir (potassium bromide): 3425, 3326 (NH), 1677, 1600
(C=O), 1531, 1456 (-Ph), 1398 (O=C-N), 1201(O=C-O)cm-1.
Anal. Calcd. For. C16H16N6O3: C, 56.47; H, 4.74; N, 24.65.
Found C, 52.48; H, 4.74; N, 24.64.
Ethyl 5-amino-1-(5'-amino-1'-t-butyl -3'-(methylthio)-1H-
pyrazole-4'-carbonyl)-1H-pyrazole-4-carboxylate (4t). This
compound is obtained as colorless solid (alcohol), yield 85%,
1
mp 101~102 °; H nmr (400 MHz, ꢀ ppm, CDCl3): 1.35 (t, J =
7.2, 3H, CH3), 1.63(s, 9H, t-C4H9 ), 2.45 (s, 3H, 3'-SCH3), 4.30
(q, J = 7.2, 2H, CH2), 6.27 (s, 2H, 5'-NH2), 7.17 (s, 2H, 5-NH2),
7.72 (s, 1H, 3-H); ir (potassium bromide): 3466, 3345 (NH),
1690, 1614 (C=O), 1535 (C=N), 1401 (O=C-N ), 1194 (O=C-
O)cm-1. Anal. Calcd. for C15H22N6O3S: C, 49.17; H, 6.05; N,
22.93. Found C, 49.26; H, 6.10; N, 22.75.
Ethyl 5-amino-1-(5'-amino-1'-phenyl-1H-pyrazole-4'-car-
bonyl)-3-methyl-1H-pyrazole-4-carboxylate (4o). This
compound is obtained as colorless solid (alcohol), yield 80%,
Ethyl 5-amino-1-(5'-amino-1'-t-butyl-3'-(methylthio)-1H-
pyrazole-4'-carbonyl)-3-methyl-1H-pyrazole-4-carboxylate
(4u). This compound is obtained as colorless solid (alcohol),
1
1
mp 145~147°. H nmr (400 MHz, ꢀ ppm, CDCl3): 1.37 (t, J =
yield 76%, mp 135~137 °; H nmr (400 MHz, ꢀ ppm, CDCl3):
7.2, 3H, CH3), 2.40 (s, 3H, 3-CH3), 4.30 (q, J = 7.2, 2H, CH2),
5.92 (s, 2H, 5'-NH2), 7.19 (s, 2H, 5-NH2), 7.42-7.55 (m, 5H, Ph),
8.70 (s, 1H, 3'-H); ir (potassium bromide): 3458, 3360 (NH),
1679, 1604 (C=O), 1501, 1459 (-Ph), 1397 (O=C-N),
1208(O=C-O )cm-1. Anal. Calcd. for C17H18N6O3: C, 57.62; H,
5.12; N, 23.72. Found C, 57.90; H, 5.07; N, 23.78.
1.35 (t, J = 7.2, 3H, CH3), 1.64 (s, 9H, t-C4H9 ), 2.38 (s, 3H, 3-
CH3), 2.44 (s, 3H, 3'-SCH3), 4.30 (q, J = 7.2, 2H, CH2), 5.60 (s,
2H, 5'-NH2), 7.21 (s, 2H, 5-NH2); ir (potassium bromide): 3454,
3348 (NH), 1688, 1610(C=O), 1529(C=N), 1400(O=C-N ),
1225(O=C-O)cm-1; Anal. Calcd. for C16H24N6O3S: C, 50.51; H,
6.36; N, 22.09. Found C, 50.78; H, 6.32; N, 21.99.

754
J.-f. Li, Y.-q. Zhu, X. Wang and H.-z. Yang
Vol 44
Ethyl 5-amino-1-(5'-amino-1'-t-butyl-1H-pyrazole-4'-car–
bonyl)-3-(methylthio)-1H-pyrazole-4-carboxylate (4v). This
compound is obtained as colorless solid (alcohol), yield 90%,
hydrazineyl)-2-cyanobut-2-enoate (10). To
a
solution of
intermediate 5c (1.0 mmol) in 40 mL ethanol, the pyrazole
carbohydrazide 8g (1.1 mmol) is added. The mixture is stirred
for 2 h at room temperature and poured into 100 mL water. The
solid precipitate is collected by filtration and purified by
recrystallization from ethanol to give a white solid 0.35 g, yield
92%, mp 159-160°. 1H nmr (400 MHz, ꢀ ppm, CDCl3): 1.32 (t, J
= 7.2, 3H, CH3), 1.62 (s, 9H, t-C4H9), 2.31 (s, 3H, SCH3), 2.52
(s, 3H, CH3), 4.26 (q, J = 7.2, 2H, CH2), 5.62 (s, 2H, 5'-NH2),
8.97 (s, 1H, NH), 10.90 (s, 1H, CONH); ir (potassium bromide):
3451, 3334 (NH), 2204 (CN), 1688, 1602 (C=O), 1402 (O=C-
N), 1233 (O=C-O)cm-1. Anal. Calcd. for C16H24N6O3S: C,
50.51; H, 6.36; N, 22.09. Found C, 50.28; H, 6.36; N, 22.13.
1
mp 173~175 °. H nmr (400 MHz, ꢀ ppm, CDCl3): 1.38 (t, J =
7.2, 3H, CH3), 1.66 (s, 9H, t-C4H9 ), 2.54 (s, 3H, 3-SCH3), 4.31
(q, J = 7.2, 2H, CH2), 5.91 (s, 2H, 5'-NH2), 7.2 (s, 2H, 5-NH2),
8.46 (s, 1H, 3'-H); ir (potassium bromide): 3441, 3352 (NH),
1686, 1607 (C=O), 1500 (C=N), 1392 (O=C-N ), 1226 (O=C-
O)cm-1. Anal. Calcd. for C15H22N6O3S: C, 49.17; H, 6.05; N,
22.93. Found C, 49.14; H, 6.03; N, 22.88.
Ethyl 5-amino-1-(5'-amino-1'-t-butyl-1H-pyrazole-4'-car-
bonyl)-1H-pyrazole-4-carboxylate (4w). This compound is
obtained as colorless solid (alcohol), yield 81%, mp 165~166°.
1H nmr (400 MHz, ꢀ ppm, CDCl3): 1.4 (t, J = 7.2, 3H, CH3), 1.6
(s, 9H, t-C4H9 ), 4.28 (q, J = 7.2, 2H, CH2), 5.90 (s, 2H, 5'-NH2),
7.18 (s, 2H, 5-NH2), 7.72 (s, 1H, 3-H), 8.43 (s, 1H, 3'-H); ir
(potassium bromide): 3457, 3327 (NH), 1692, 1611 (C=O),
1508 (C=N), 1401 (O=C-N ), 1233 (O=C-O)cm-1. Anal. Calcd.
for C14H20N6O3: C, 52.49; H, 6.29; N, 26.23. Found C, 52.48; H,
6.54; N, 26.34.
Herbicidal Activity Tests [27-28]
1. Inhibition of the root-growth of rape
(Brassicacampestris L). The compounds to be tested are made
into emulsions to aid dissolution. Rape seeds are soaked in
distilled water for 4 h before being placed on a filter paper in a
6-cm Petri plate, to which 2 ml of inhibitor solution had been
added in advance. Usually, 15 seeds are used on each plate. The
plate is placed in a dark room and allowed to germinate for 65 h
at 28° (±1). The lengths of 10 rape roots selected from each
plate are measured and the means are calculated. The percentage
inhibition is calculated relative to controls using distilled water
instead of the inhibitor solution.
Ethyl 5-amino-1-(5'-amino-1'-t-butyl-1H-pyrazole-4'-car-
bonyl)-3-methyl-1H-pyrazole-4-carboxylate (4x). This
compound is obtained as colorless solid (alcohol), yield 85%,
1
mp 108~110°. H nmr (400 MHz, ꢀ ppm, CDCl3): 1.35 (t, J =
7.2, 3H, CH3), 1.65 (s, 9H, t-C4H9 ), 2.35 (s, 3H, 3-CH3), 4.29 (q,
J = 7.2, 2H, CH2), 5.87 (s, 2H, 5'-NH2), 7.25 (s, 2H, 5-NH2),
8.50 (s, 1H, 3'-H); ir (potassium bromide): 3463, 3346 (NH),
1686, 1619 (C=O), 1508 (C=N), 1400 (O=C-N ), 1238 (O=C-
O)cm-1. Anal. Calcd. for C15H22N6O3: C, 53.88; H, 6.63; N,
25.13. Found C, 53.90; H, 6.47; N, 25.18.
2. Inhibition of the seedling growth of barnyard
grass (Echinochloacrus-galli (L) Beauv). The compounds
to be evaluated are made into emulsions to aid
dissolution. Ten barnyard grass seeds are placed into a
50-ml cup covered with a layer of glass beads and a
piece of filter paper at the bottom, to which 5 ml of
inhibitor solution had been added in advance. The cup is
placed in a bright room and the seeds allowed to
germinate for 65 h at 28° (±1). The height of the above-
ground parts of the seedlings in each cup is measured
and the means calculated. The percentage inhibition is
calculated relative to controls using distilled water
instead of the inhibitor solution. The results of herbicidal
activity listed in Table 2.
Ethyl 5-amino-1-(5'-amino-1'-t-butyl-3'-methyl-1H-pyra-
zole-4'-carbonyl)-3-(methylthio)-1H-pyrazole-4-carboxylate
(4y). This compound is obtained as colorless solid (alcohol),
1
yield 76%, mp 134~135°. H nmr (400 MHz, ꢀ ppm, CDCl3):
1.38 (t, J = 7.2, 3H, CH3), 1.63 (s, 9H, t-C4H9 ), 2.31 (s, 3H, 3'-
CH3), 2.47 (s, 3H, 3-SCH3), 4.32 (q, J = 7.2, 2H, CH2), 5.55 (s,
2H, 5'-NH2), 7.16 (s, 2H, 5-NH2); ir (potassium bromide): 3459,
3342 (NH), 1688, 1604 (C=O), 1521 (C=N), 1400 (O=C-N ),
1232 (O=C-O)cm-1.Anal. Calcd. for C16H24N6O3S: C, 50.51; H,
6.36; N, 20.09. Found C, 50.72; H, 6.32; N, 20.15.
Acknowledgement. This work is supported by the National
Key Project for Basic Research (2003CB114400) and the
National Natural Science Foundation of China (20572054) and
the Research Found for the Doctoral Program of Higher
Education.
Ethyl 5-amino-1-(5'-amino-1'-t-butyl-3'-methyl-1H-pyra-
zole-4'-carbonyl)-1H-pyrazole-4-carboxylate (4z). This
compound is obtained as colorless solid (alcohol), yield 87%,
1
mp 116~118°. H nmr (400 MHz, ꢀ ppm, CDCl3): 1.35 (t, J =
7.2, 3H, CH3), 1.63 (s, 9H, t-C4H9 ), 2.29 (s, 3H, 3'-CH3), 4.30
(q, J = 7.2, 2H, CH2), 5.68 (s, 2H, 5'-NH2), 7.05 (s, 2H, 5-NH2),
7.72 (s, 1H, 3-H); ir (potassium bromide): 3475, 3353 (NH),
1688, 1615 (C=O), 1539 (C=N), 1401 (O=C-N ), 1194 (O=C-
O)cm-1. Anal. Calcd. for C15H22N6O3: C, 53.88; H, 6.63; N,
25.13. Found C, 53.75; H, 6.65; N, 25.23.
Ethyl 5-amino-1-(5'-amino-1'-t-butyl-3'-methyl-1H-pyra-
zole-4'-carbonyl)-3-methyl-1H-pyrazole-4-carboxylate (4aa).
This compound is obtained as colorless solid (alcohol), yield
79%, mp 101~103°. 1H nmr (400 MHz, ꢀ ppm, CDCl3): 1.36 (t,
J = 7.2, 3H, CH3), 1.63 (s, 9H, t-C4H9 ), 2.30 (s, 3H, 3'-CH3),
2.36 (s, 6H, 3-CH3), 4.30 (q, J = 7.2, 2H, CH2), 5.73 (s, 2H, 5'-
NH2), 7.14 (s, 2H, 5-NH2); ir (potassium bromide): 3455, 3340
(NH), 1688, 1610 (C=O), 1529 (C=N), 1397 (O=C-N ), 1236
(O=C-O)cm-1. Anal. Calcd. for C16H24N6O3: C, 55.16; H, 6.94;
N, 24.12. Found C, 55.24; H, 6.99; N, 24.14.
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