# US 11,076,594 B2 · Pyrazolone compound or salt thereof, preparation method therefor, herbicide composition and use thereof

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- Number: US 11,076,594 B2
- Document ID: US11076594B2
- Status: Granted
- Kind: B2
- Application number: 15/559,614
- Filed: 2016-01-08
- Published: 2018-03-01
- Granted: 2021-08-03
- Earliest claimed: 2015-11-06
- Applicants: Qingdao Kingagroot Chemical Compounds Co., Ltd.
- Inventors: Lei Lian; Yurong Zheng; Bin He; Xuegang Peng; Tao Jin; Qi Cui
- Web page: https://patentgrep.com/patent/US11076594B2

## CPC

- A01N 43/56: 1,2-Diazoles; Hydrogenated 1,2-diazoles
- A01N 43/60: 1,4-Diazines; Hydrogenated 1,4-diazines
- A01N 43/84: six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
- A01N 47/06: containing —O—CO—O— groups; Thio analogues thereof
- C07D 231/20: One oxygen atom attached in position 3 or 5
- C07D 401/10: linked by a carbon chain containing aromatic rings
- C07D 401/14: containing three or more hetero rings
- C07D 403/10: linked by a carbon chain containing aromatic rings
- C07D 403/14: containing three or more hetero rings
- C07D 413/10: linked by a carbon chain containing aromatic rings
- C07D 413/14: containing three or more hetero rings
- C07D 417/10: linked by a carbon chain containing aromatic rings
- C07D 417/14: containing three or more hetero rings
- A01N: PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF (preservation of food or foodstuff A23); BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES (preparations for medical, dental or toiletry purposes which kill or prevent the growth or proliferation of unwanted organisms A61K); PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)

## Abstract

The present invention belongs to the field of pesticides, particularly relates to a pyrazolone compound or a salt thereof, a preparation method therefor, a herbicidal composition and use thereof. The pyrazolone compound is as described in formula I: In the formula, R1R2N represents substituted or unsubstituted 3-8 membered nitrogen-containing heterocyclic group containing 1-3 heteroatoms; or R1 and R2 each represent hydrogen or C1-8 alkyl; R3 represents hydrogen, C1-4 alkyl, alkenyl, alkynyl, unsubstituted C3-6 cycloalkyl or C3-6 cycloalkyl substituted by C1-4 alkyl; R4 represents methyl, ethyl, n-propyl, isopropyl or cyclopropyl; X represents hydrogen, —S(O)nR6, —R7 or substituted or unsubstituted 3-8 membered heterocyclic group containing 1-4 heteroatoms, wherein, n represents 1, 2 or 3, R6 represents substituted or unsubstituted alkyl or aryl, and R7 represents substituted or unsubstituted alkyl, aryl, alkyl acyl or aroyl. The active substance of the invention exhibits good herbicidal effect, and is convenient to use, low in cost and has great commercial value.

## Claims

### Claim 1

A pyrazolone compound of formula I or a salt thereof:
wherein, R1R2N represents substituted or unsubstituted 4-8 membered lactam group containing 0-2 heteroatoms selected from O, S and N; or,
R1 and R2 each represent hydrogen, C1-8 alkyl, substituted alkyl containing 1-4 heteroatoms, alkenyl, alkynyl, substituted or unsubstituted C1-4 acyl, unsubstituted C3-6 cycloalkyl or C3-6 cycloalkyl substituted by C1-4 alkyl;
R3 represents hydrogen, C1-4 alkyl, alkenyl, alkynyl, unsubstituted C3-6 cycloalkyl or C3-6 cycloalkyl substituted by C1-4 alkyl;
R4 represents methyl, ethyl, n-propyl, isopropyl or cyclopropyl;
X represents hydrogen, —S(O)nR6, —R7, —(C═O)R8 or substituted or unsubstituted 3-8 membered heterocyclic group containing 1-4 heteroatoms, wherein, n represents 1, 2 or 3, R6 represents substituted or unsubstituted alkyl or aryl, R7 represents substituted or unsubstituted alkyl, aryl, alkyl acyl or aroyl, and R8 represents alkoxy, aryloxy, substituted or unsubstituted alkyl or aryl, or substituted or unsubstituted 3-8 membered heterocyclic group containing 1-4 heteroatoms.

### Claim 2 (depends on 1)

The pyrazolone compound or the salt thereof according to claim 1, which is characterized in that,
R1R2N represents substituted or unsubstituted 4-8 membered lactam group containing 0-2 heteroatoms selected from O, S and N; or,
one of R1 and R2 represents C1-4 acyl containing O , S or N, which is unsubstituted or substituted by halogen, and the other one represents hydrogen, C1-8 alkyl and substituted alkyl containing 1-4 heteroatoms, alkenyl, alkynyl, unsubstituted C3-6 cycloalkyl or C3-6 cycloalkyl substituted by C1-4 alkyl;
R3 represents hydrogen, C1-4 alkyl, alkenyl, alkynyl, unsubstituted C3-6 cycloalkyl or C3-6 cycloalkyl substituted by C1-4 alkyl;
R4 represents methyl, ethyl, n-propyl, isopropyl or cyclopropyl;
X represents hydrogen, —S(O)nR6, —R7 or substituted or unsubstituted 3-8 membered heteroaryl containing 1-4 heteroatoms, wherein n represents 1, 2 or 3, R6 represents substituted or unsubstituted alkyl or aryl, and R7 represents substituted or unsubstituted alkyl, aryl, alkyl acyl or aroyl.

### Claim 3 (depends on 1)

The pyrazolone compound or the salt thereof according to claim 1, which is characterized in that,
R1R2N represents substituted or unsubstituted 4-8 membered lactam group containing 0-2 heteroatoms selected from O, S and N; or
one of R1 and R2 represents C1-4 acyl containing O, S or N, which is unsubstituted or substituted by halogen, and the other one represents hydrogen, C1-8 alkyl, substituted C1-8 alkyl containing 1-4 heteroatoms, unsubstituted C3-6 cycloalkyl or C3-6 cycloalkyl substituted by C1-4 alkyl;
R3 represents hydrogen, methyl, ethyl or cyclopropyl;
R4 represents methyl, ethyl or isopropyl;
X represents hydrogen, —SO2R6, or —(C═O)R8, wherein R6 represents substituted or unsubstituted alkyl or aryl, R8 represents alkoxy, aryloxy, substituted or unsubstituted alkyl or aryl, or substituted or unsubstituted 3-8 membered heterocyclic group containing 1-4 heteroatoms.

### Claim 4 (depends on 1)

The pyrazolone compound or the salt thereof according to claim 1, which is characterized in that,
R1R2N represents a group selected from butyrolactam group, valeroalctam group, caprolactam group, oenantholactam group, piperazinone group, morpholinone group and thiomorpholinone group, each of which is unsubstituted or substituted on ring by one or more groups selected from fluorine, chlorine, methyl, ethyl, methoxyl and ethoxyl; or
R1 represents acetyl, fluoroacetyl, difluoroacetyl, trifluoroacetyl, methoxy acetyl, ethoxy acetyl, methoxy propionyl or ethoxy propionyl, R2 represents hydrogen; cycloprropyl; or a group selected from methyl, ethyl, propyl, butyl and pentyl, each of which is unsubstituted or substituted by one or more groups selected from fluorine, methoxyl, ethyoxyl, propoxy, butoxy and methoxyethoxy;
R3 represents hydrogen, methyl, ethyl or cyclopropyl;
R4 represents methyl, ethyl or isopropyl;
X represents hydrogen, —SO2R6, —(C═O)R8, wherein R6 represents substituted or unsubstituted alkyl or aryl, R8 represents alkoxy, aryloxy, substituted or unsubstituted alkyl or aryl, unsubstituted N-alkylpyrazolyl or N-alkylpyrazolyl substituted on ring by one or more groups selected from methyl, ethyl, methoxyl and ethoxyl.

### Claim 5 (depends on 1)

A method for preparing the pyrazolone compound or the salt thereof according to claim 1, comprising the following steps:
(1) a compound of formula II is reacted with an excessive amount of compound R1R2NH to prepare a compound of formula III;
(2) the compound of formula III is reacted with compound X-A to obtain the compound of formula I;
wherein A represents halogen, methylsulfonyl or p-tosyl, and the reaction route is as follows:

### Claim 6 (depends on 5)

The method according to claim 5, which is characterized in that, said step (1) and step (2) are conducted in an aprotic solvent in the presence of a base; at a reaction temperature of −30° C. −180° C.

### Claim 7 (depends on 6)

The method according to claim 6, which is characterized in that, said solvent is acetonitrile, diethyl ether, tetrahydrofuran, DMF or DMSO; said base is sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, triethylamine, DIPEA or DBU.

### Claim 8 (depends on 1)

A herbicidal composition, which is characterized in that, it comprises a herbicidally effective amount of at least one pyrazolone compound or the salt thereof according to claim 1.

### Claim 9 (depends on 8)

The herbicidal composition according to claim 8, which is characterized in that, it also comprises a preparation auxiliary.

### Claim 10 (depends on 1)

A method for controlling a harmful plant, comprising a step of applying a herbicidally effective amount of at least one pyrazolone compound or the salt thereof according to claim 1 to the harmful plant or an area with the harmful plant.

### Claim 11 (depends on 1)

A The pyrazolone compound or the salt thereof according to claim 1, wherein the compound is selected from
compound
ID
R1R2N-
R3
R4
X
001
Me
Me
H
002
Me
Me
H
003
Me
Me
H
004
Me
Me
H
005
Me
Me
H
006
Me
Me
H
007
Me
Me
H
008
Me
Me
H
009
Me
Me
H
010
Me
Me
H
011
Me
Me
H
012
Me
Me
H
013
Me
Me
H
014
H
Me
H
015
H
Me
016
H
Me
017
H
Me
018
Me
Me
H
019
Me
Me
EtSO2—
020
Me
Me
021
Me
Me
022
Me
Me
023
Me
Me
024
Me
Me
H
025
Me
H
026
Me
027
Me
028
Me
029
H
Me
H
030
H
Me
Ac—
031
H
Me
EtSO2—
032
H
Me
033
H
Me
034
H
Me
035
Me
Me
H
036
Me
Me
037
Me
Me
038
Me
Me
039
Me
Me
040
Me
Me
H
041
Me
Me
042
Me
Me
H
043
Me
Me
044
Me
Me
H
045
Me
Me
046
Me
H
047
Me
048
Me
049
Me
050
H
Me
H
051
H
Me
052
H
Me
053
H
Me
054
Me
Me
H
055
Me
Me
056
Me
Me
057
Me
Me
058
Me
Me
059
Me
H
060
Me
061
Me
062
Me
096
H
Et
H
097
H
Et
098
Me
Et
H
099
Me
Et
100
Et
Me
H
101
Et
Me
102
Et
Et
H
103
Et
Et
104
Et
H
105
Et
106
H
Et
H
107
H
Et
108
Me
Et
H
109
Me
Et
110
Et
Me
H
111
Et
Me
112
Et
Et
H
113
Et
Et
114
Et
H
115
Et
116
H
Et
H
117
H
Et
118
Me
Et
H
119
Me
Et
120
Et
Me
H
121
Et
Me
122
Et
Et
H
123
Et
Et
124
Et
H
125
Et
146
H
147
H
148
H.

### Claim 12 (depends on 6)

The method according to claim 6, wherein said step (1) and step (2) are both conducted at −5° C. −90° C.

### Claim 13 (depends on 6)

The method according to claim 6, wherein the solvent is acetonitrile, tetrahydrofuran or DMF.

### Claim 14 (depends on 6)

The method according to claim 6, wherein the base is NaH, triethylamine or potassium carbonate.

### Claim 15 (depends on 1)

A method for controlling a harmful plant growing in a desirable crop, comprising a step of applying a herbicidally effective amount of at least one pyrazolone compound or the salt thereof according to claim 1 to the harmful plant or an area with the harmful plant.

### Claim 16 (depends on 15)

The method according to claim 15, wherein the desirable crop is a genetically modified crop or a crop treated by a genome editing technique.

### Claim 17 (depends on 8)

A method for controlling a harmful plant, comprising a step of applying a herbicidally effective amount of the herbicidal composition according to claim 8 to the harmful plant or an area with the harmful plant.

### Claim 18 (depends on 8)

A method for controlling a harmful plant growing in a desirable crop, comprising a step of applying a herbicidally effective amount the herbicidal composition according to claim 8 to the harmful plant or an area with the harmful plant.

### Claim 19 (depends on 18)

The method according to claim 18, wherein the desirable crop is a genetically modified crop or a crop treated by a genome editing technique.