A pyrazole carboxylate compound and its application

Abstract

The present invention discloses a pyrazole carboxylate compound and its application. The compound is represented by the general formula (I): Q is one of the following groups: Q1, Q2 or Q3. The definitions of each substituent in the general formula I are described in the specification. The compound of the general formula I of the present invention has excellent herbicidal activity and can be used to control agricultural weeds.

Description

Technical Field

[0001] The present invention belongs to the field of herbicides. Specifically, it is a pyrazole carboxylate compound and its application. Background Art

[0002] Due to the succession and change of weed populations, the emergence and rapid development of resistance to chemical pesticides, the continuous strengthening of people's awareness of ecological environment protection, the increasing understanding of chemical pesticide pollution, the impact of pesticides on non-target organisms, and the increasing attention to the fate of pesticides in the ecological environment. With the gradual reduction of the world's cultivated land area, the continuous growth of the population, and the increasing demand for food, people are forced to rapidly develop agricultural production technologies, improve and perfect farming systems, and continuously invent new and improved herbicidal compounds and compositions.

[0003] CN103980202A reports that certain benzoylpyrazole compounds have herbicidal activity, such as compound No. 21 (KC) therein:

[0004]

[0005] The pyrazole carboxylate compounds as shown in the present invention have not been disclosed. Summary of the Invention

[0006] The object of the present invention is to provide a pyrazole carboxylate compound with a novel structure and safe for crops and its application.

[0007] To achieve the above object, the technical solution of the present invention is as follows:

[0008] A pyrazole carboxylate compound, characterized in that the compound is shown in the general formula I:

[0009]

[0010] In the formula:

[0011] X1 is selected from hydrogen, cyano, nitro, halogen, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C1-C6 alkanesulfinyl, C1-C6 haloalkanesulfinyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C3 alkyl, C1-C6 alkoxyC1-C3 alkoxy, C1-C6 alkoxyC1-C3 alkoxyC1-C3 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C3 alkyl, C3-C6 cycloalkylC1-C3 alkoxy, C3-C6 cycloalkyloxy, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 alkenylsulfonyl, C2-C6 alkynylsulfonyl, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C2-C6 alkenylthio, C2-C6 alkynylthio, phenyl, phenylsulfonyl, phenyloxy, phenylthio, 5-7-membered aliphatic heterocycles containing 1-4 heteroatoms, 5-7-membered aromatic heterocycles containing 1-4 heteroatoms, 5-7-membered aliphatic heterocycles containing 1-4 heteroatoms C1-C6 alkyl or 5-7-membered aromatic heterocycles containing 1-4 heteroatoms C1-C6 alkyl, and the hydrogen on the phenyl, aliphatic heterocycle, aromatic heterocycle can be substituted by one or more of the following substituents, and the substituents are selected from nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy or C3-C6 cycloalkyl;

[0012] W is selected from N or CX2;

[0013] X2 is selected from hydrogen, cyano, nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C3-C6 halocycloalkyl C1-C6 alkyl, Y1 oxy, Y1 thio, Y1Y2 amino, Y1 sulfinyl, Y1 sulfonyl, Y1 sulfinyl C1-C6 alkyl, Y1 sulfonyl C1-C6 alkyl, C(O)Y1, C(O)OY1, OC(O)OY1, N(Y1)C(O)OY2, C(O)N(Y1)Y2, N(Y1)C(O)N(Y1)Y2, OC(O)N(Y1)Y2, C(O)N(Y1)OY2, N(Y1)S(O)2Y2, N(Y1)C(O)Y2, OS(O)2Y1, CH=NOY1, C(Y1)=NOY2, N=CHN(Y1)Y2, phenyl, a 5- to 7-membered aliphatic heterocycle containing 1 to 4 heteroatoms or a 5- to 7-membered aromatic heterocycle containing 1 to 4 heteroatoms, wherein the hydrogen on the phenyl, aliphatic heterocycle, aromatic heterocycle can be substituted by one or more of the following substituents, and the substituents are selected from nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C6 cycloalkyl, C3-C6 cycloalkoxy, C2-C6 alkenyl, C2-C6 alkynyl, phenyl or halogenated phenyl;

[0014] Y1 and Y2 are each independently selected from C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C1-C6 alkoxy C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, phenyl, a 5- to 7-membered aliphatic heterocycle containing 1 to 4 heteroatoms, a 5- to 7-membered aromatic heterocycle containing 1 to 4 heteroatoms, a 5- to 7-membered aliphatic heterocycle C1-C6 alkyl or a 5- to 7-membered aromatic heterocycle C1-C6 alkyl, wherein the hydrogen on the phenyl, aliphatic heterocycle, aromatic heterocycle can be substituted by one or more of the following substituents, and the following substituents are selected from nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C6 cycloalkyl, C3-C6 cycloalkoxy, C2-C6 alkenyl, C2-C6 alkynyl, phenyl or halogenated phenyl;

[0015] X3 is selected from hydrogen, cyano, nitro, halogen, C1-C6 alkylsulfonyl, C1-C6 haloalkyl, C1-C6 haloalkylsulfonyl, C1-C6 alkanesulfinyl, C1-C6 haloalkanesulfinyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C3 alkyl, C1-C6 alkoxyC1-C3 alkoxy, C1-C6 alkoxyC1-C3 alkoxyC1-C3 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C3 alkyl, C3-C6 cycloalkylC1-C3 alkoxy, C3-C6 cycloalkyloxy, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 alkenylsulfonyl, C2-C6 alkynylsulfonyl, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C2-C6 alkenylthio, C2-C6 alkynylthio, phenyl, phenyloxy, phenylthio, phenylsulfonyl, 5-7-membered aliphatic heterocycle containing 1-4 heteroatoms, 5-7-membered aromatic heterocycle containing 1-4 heteroatoms, 5-7-membered aliphatic heterocycle C1-C6 alkyl containing 1-4 heteroatoms or 5-7-membered aromatic heterocycle C1-C6 alkyl containing 1-4 heteroatoms, and the hydrogen on the phenyl, aliphatic heterocycle, aromatic heterocycle can be substituted by one or more of the following substituents, and the substituents are selected from nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy or C3-C6 cycloalkyl;

[0016] When W is selected from CX2, X3 is not C1-C6 haloalkyl;

[0017] Q is selected from Q1, Q2 or Q3,

[0018]

[0019] R1 and R4 may be the same or different and are respectively selected from C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C3-C6 cycloalkylC1-C3 alkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C1-C6 alkoxyC1-C3 alkyl, C1-C6 haloalkoxyC1-C3 alkyl, C1-C6 alkoxyC1-C3 alkoxyC1-C3 alkyl, C1-C6 alkylthioC1-C3 alkyl, C1-C6 haloalkylthioC1-C3 alkyl, C1-C6 alkanesulfinylC1-C3 alkyl, C1-C6 haloalkanesulfinylC1-C3 alkyl, C1-C6 alkylsulfonylC1-C3 alkyl or C1-C6 haloalkylsulfonylC1-C3 alkyl;

[0020] R2 and R3 may be the same or different and are each independently selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C3-C6 halocycloalkyl C1-C3 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, phenyl which is unsubstituted or substituted with 1-5 of the following substituents, and the following substituents are selected from cyano, nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C6 alkoxy or C1-C6 haloalkoxy;

[0021] R5 is selected from hydrogen, halogen, nitro, cyano, C1-C6 alkyl, C1-C6 haloalkyl, phenyl which is unsubstituted or substituted with at least one of the following substituents; and the following substituents are selected from: halogen, cyano, nitro, C1-C6 alkyl, C3-C6 cycloalkyl or C1-C6 haloalkyl.

[0022] For the preferred compounds, in general formula I:

[0023] X1 is selected from halogen, C1-C6 alkylsulfonyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkoxy C1-C3 alkyl, C1-C6 alkoxy C1-C3 alkoxy, C1-C6 alkoxy C1-C3 alkoxy C1-C3 alkyl, a 5-7-membered aliphatic heterocycle containing 1-4 heteroatoms, a 5-7-membered aromatic heterocycle containing 1-4 heteroatoms, a 5-7-membered aliphatic heterocycle C1-C6 alkyl or a 5-7-membered aromatic heterocycle C1-C6 alkyl, and the hydrogen on the aliphatic heterocycle or aromatic heterocycle may be substituted with one or more of the following substituents, and the substituents are selected from nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy or C3-C6 cycloalkyl;

[0024] W is selected from CX2;

[0025] X2 is selected from cyano, C1-C6 alkyl, C1-C6 haloalkyl, Y1 oxy, Y1 thio, Y1Y2 amino, Y1 sulfinyl, Y1 sulfonyl, Y1 sulfinyl C1-C6 alkyl, Y1 sulfonyl C1-C6 alkyl, C(O)Y1, C(O)OY1, OC(O)OY1, N(Y1)C(O)OY2, C(O)N(Y1)Y2, N(Y1)C(O)N(Y1)Y2, OC(O)N(Y1)Y2, C(O)N(Y1)OY2, N(Y1)S(O)2Y2, N(Y1)C(O)Y2, OS(O)2Y1, CH=NOY1, phenyl, a 5-7 membered aliphatic heterocycle containing 1-4 heteroatoms or a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms, and the hydrogen on the phenyl, aliphatic heterocycle, aromatic heterocycle can be substituted by one or more of the following substituents, and the substituents are selected from nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C6 cycloalkyl, C3-C6 cycloalkoxy, C2-C6 alkenyl, C2-C6 alkynyl, phenyl or halogenated phenyl;

[0026] Y1 and Y2 are each independently selected from C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy C1-C6 alkyl, phenyl, a 5-7 membered aliphatic heterocycle containing 1-4 heteroatoms, a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms, a 5-7 membered aliphatic heterocycle C1-C6 alkyl or a 5-7 membered aromatic heterocycle C1-C6 alkyl, and the hydrogen on the phenyl, aliphatic heterocycle, aromatic heterocycle can be substituted by one or more of the following substituents, and the following substituents are selected from nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C6 cycloalkyl, C3-C6 cycloalkoxy, C2-C6 alkenyl, C2-C6 alkynyl, phenyl or halogenated phenyl;

[0027] X3 is selected from cyano, nitro, halogen, C1-C6 alkylsulfonyl, C1-C6 alkanesulfinyl, C1-C6 haloalkanesulfinyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkoxyC1-C3 alkyl, C1-C6 alkoxyC1-C3 alkoxy, C1-C6 alkoxyC1-C3 alkoxyC1-C3 alkyl, a 5-7-membered heteroalicyclic ring containing 1-4 heteroatoms, a 5-7-membered heteroaromatic ring containing 1-4 heteroatoms, a 5-7-membered heteroalicyclic ring C1-C6 alkyl containing 1-4 heteroatoms or a 5-7-membered heteroaromatic ring C1-C6 alkyl containing 1-4 heteroatoms, and the hydrogen on the heteroalicyclic ring and heteroaromatic ring may be substituted by one or more of the following substituents, and the substituents are selected from nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy or C3-C6 cycloalkyl;

[0028] Q is selected from Q1, Q2 or Q3;

[0029] R1 and R4 may be the same or different and are each independently selected from C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkylC1-C3 alkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C1-C6 alkoxyC1-C3 alkyl, C1-C6 haloalkoxyC1-C3 alkyl, C1-C6 alkoxyC1-C3 alkoxyC1-C3 alkyl, C1-C6 alkylthioC1-C3 alkyl, C1-C6 haloalkylthioC1-C3 alkyl, C1-C6 alkylsulfonylC1-C3 alkyl or C1-C6 haloalkylsulfonylC1-C3 alkyl;

[0030] R2 and R3 may be the same or different and are each independently selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl or C3-C6 halocycloalkyl;

[0031] R5 is selected from hydrogen, halogen, cyano, C1-C6 alkyl or C1-C6 haloalkyl.

[0032] In the further preferred compound, in general formula I:

[0033] X1 is selected from halogen, C1-C6 alkylsulfonyl, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkoxyC1-C3 alkyl, C1-C6 alkoxyC1-C3 alkoxyC1-C3 alkyl, a 5-7-membered heteroalicyclic ring containing 1-4 heteroatoms or a 5-7-membered heteroaromatic ring containing 1-4 heteroatoms, and the hydrogen on the heteroalicyclic ring and heteroaromatic ring may be substituted by one or more of the following substituents, and the substituents are selected from nitro, halogen, C1-C6 alkyl or C1-C6 haloalkyl;

[0034] W is selected from CX2;

[0035] X2 is selected from C1-C6 alkyl, Y1 oxy group, Y1 thio group, Y1Y2 amino group, Y1 sulfinyl group, Y1 sulfonyl group, Y1 sulfinyl C1-C6 alkyl, Y1 sulfonyl C1-C6 alkyl, C(O)Y1, C(O)OY1, CH=NOY1, phenyl, a 5-7 membered aliphatic heterocycle containing 1-4 heteroatoms or a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms, and the hydrogen on the phenyl, aliphatic heterocycle, aromatic heterocycle can be substituted by one or more of the following substituents, and the substituents are selected from nitro, halogen, C1-C6 alkyl or C1-C6 haloalkyl;

[0036] Y1 and Y2 are each independently selected from C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy C1-C6 alkyl, a 5-7 membered aliphatic heterocycle containing 1-4 heteroatoms, a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms, a 5-7 membered aliphatic heterocycle C1-C3 alkyl or a 5-7 membered aromatic heterocycle C1-C3 alkyl, and the hydrogen on the aliphatic heterocycle, aromatic heterocycle can be substituted by one or more of the following substituents, and the following substituents are selected from nitro, halogen, C^1-C6 alkyl or C1-C6 haloalkyl;

[0037] X3 is selected from cyano, halogen, C1-C6 alkylsulfonyl, a 5-7 membered aliphatic heterocycle containing 1-4 heteroatoms or a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms, and the hydrogen on the aliphatic heterocycle, aromatic heterocycle can be substituted by one or more of the following substituents, and the substituents are selected from nitro, halogen or C1-C3 alkyl;

[0038] Q is selected from Q1, Q2 or Q3;

[0039] R1 and R4 can be the same or different and are each independently selected from C1-C6 alkyl, C1-C3 alkylsulfonyl, C1-C3 alkoxy C1-C3 alkyl or C1-C3 alkylsulfonyl C1-C3 alkyl;

[0040] R2 and R3 can be the same or different and are each independently selected from hydrogen, C1-C3 alkyl or C3-C6 cycloalkyl;

[0041] R5 is selected from hydrogen.

[0042] For the further preferred compound, in general formula I:

[0043] X1 is selected from halogen, C1-C3 alkylsulfonyl, C1-C3 alkyl, C1-C3 alkoxy C1-C3 alkyl or C1-C3 alkoxy C1-C3 alkoxy C1-C3 alkyl;

[0044] W is selected from CX2;

[0045] X2 is selected from Y1 oxy group, Y1 thio group, Y1Y2 amino group, Y1 sulfinyl group, Y1 sulfonyl group, Y1 sulfonyl C1-C6 alkyl group, C(O)Y1, C(O)OY1, CH=NOY1, a 5-7 membered aliphatic heterocycle containing 1-4 heteroatoms or a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms. The hydrogen on the aliphatic heterocycle or aromatic heterocycle may be substituted by one or more of the following substituents, and the substituents are selected from halogen, C1-C3 alkyl group or C1-C3 haloalkyl group;

[0046] Y1 and Y2 are each independently selected from C1-C6 alkyl group, C1-C6 haloalkyl group, C1-C3 alkoxy C1-C3 alkyl group, a 5-7 membered aliphatic heterocycle containing 1-4 heteroatoms, a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms, a 5-7 membered aliphatic heterocycle C1-C3 alkyl group or a 5-7 membered aromatic heterocycle C1-C3 alkyl group. The hydrogen on the aliphatic heterocycle or aromatic heterocycle may be substituted by one or more of the following substituents, and the following substituents are selected from halogen, C1-C3 alkyl group or C1-C3 haloalkyl group;

[0047] X3 is selected from halogen, C1-C3 alkylsulfonyl group, a 5-7 membered aliphatic heterocycle containing 1-4 heteroatoms or a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms. The hydrogen on the aliphatic heterocycle or aromatic heterocycle may be substituted by one or more of the following substituents, and the substituents are selected from halogen or C1-C3 alkyl group;

[0048] Q is selected from Q1, Q2 or Q3;

[0049] R1 and R4 may be the same or different and are each independently selected from C1-C3 alkyl group, C1-C3 alkylsulfonyl group or C1-C3 alkylsulfonyl C1-C3 alkyl group;

[0050] R2 and R3 may be the same or different and are each independently selected from hydrogen, C1-C3 alkyl group or C3-C6 cycloalkyl group;

[0051] R5 is selected from hydrogen.

[0052] In the definition of the general formula I compound given above, the definitions of the terms used are as follows:

[0053] Alkyl refers to straight-chain or branched-chain forms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl and other groups. Cycloalkyl refers to groups including cyclic-chain forms, such as cyclopropyl, methylcyclopropyl, cyclopropylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and other groups. Alkenyl refers to straight-chain or branched-chain alkenyl groups, such as 1-propenyl, 2-propenyl, butenyl, pentenyl and hexenyl and other groups. Alkynyl refers to straight-chain or branched-chain alkynyl groups, such as 1-propynyl, 2-propynyl, butynyl, pentynyl and hexynyl and other groups. Alkoxy refers to a group in which an alkyl group is connected to an oxygen atom at the end, such as methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy and the like. A 5- to 7-membered aliphatic heterocycle containing 1 to 4 heteroatoms refers to a 5- to 7-membered heterocyclic compound without aromatic characteristics containing 1 to 4 heteroatoms, such as ethylene oxide, tetrahydrofuran, imidazolinone, caprolactam and the like. A 5- to 7-membered aromatic heterocycle containing 1 to 4 heteroatoms refers to a 5- to 7-membered heterocyclic compound with aromatic characteristics containing 1 to 4 heteroatoms, such as furan, thiophene, pyrazole, pyridine and the like.

[0054] The general formula compound I of the present invention can be prepared by the following method:

[0055]

[0056] The compound of general formula II (commercially available or prepared by referring to the following method) and the compound of general formula III are reacted in a suitable solvent at a temperature of -10°C to the boiling point of the suitable solvent for 0.5 - 48 hours to obtain the target compound I.

[0057] The suitable solvents are selected from dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, acetic acid, tetrahydrofuran, dioxane, N,N-dimethylformamide or dimethyl sulfoxide and the like.

[0058] Adding a suitable basic substance is beneficial to the reaction. Suitable bases are selected from organic bases such as triethylamine, N,N-dimethylaniline or pyridine and the like, or inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium tert-butoxide or potassium tert-butoxide and the like.

[0059] The compound of general formula III can be prepared from the corresponding acid, and the acid is commercially available or prepared by referring to the operations in WO2009123714.

[0060] The preparation method of the compound of general formula II is as follows:

[0061]

[0062] In the above formula, General Formula IV reacts in the presence of a base and a catalyst in a suitable solvent at a temperature of -10°C to the boiling point of the suitable solvent for 0.5 - 48 hours to obtain the compound of General Formula II; the suitable solvent is selected from dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, acetic acid, tetrahydrofuran, dioxane, N,N-dimethylformamide or dimethyl sulfoxide, etc. The suitable base is selected from sodium carbonate, potassium carbonate or triethylamine, etc. The suitable catalyst is selected from sodium carbonate, potassium carbonate, acetone cyanohydrin, azide, azide quaternary ammonium salt, metal cyanide or DMAP, etc.

[0063] The preparation method of the compound of General Formula IV is as follows:

[0064]

[0065] The compound of General Formula V and the compound of General Formula VI (prepared by the method described in the commercially available or reference document EP0240001) react in a suitable solvent at a temperature of -10°C to the boiling point of the suitable solvent for 0.5 - 24 hours to obtain the compound of General Formula IV. The suitable solvent is selected from dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, acetic acid, tetrahydrofuran, dioxane, N,N-dimethylformamide or dimethyl sulfoxide, etc.

[0066] Adding a suitable basic substance is beneficial to the reaction. The suitable base is selected from organic bases such as triethylamine, N,N-dimethylaniline or pyridine, etc., or inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium tert-butoxide or potassium tert-butoxide, etc.

[0067] The corresponding raw material carboxylic acid of the compound of General Formula V (prepared by the method described in the commercially available or reference document WO0017194) reacts with an acyl halide reagent in a suitable solvent at a temperature of -10°C to the boiling point of the suitable solvent for 0.5 - 48 hours to obtain the compound of General Formula V. The acyl halide reagent is selected from oxalyl chloride, thionyl chloride, phosphorus oxychloride, phosphorus trichloride or phosphorus pentachloride, etc. The suitable solvent is selected from dichloromethane, 1,2-dichloroethane, hexane, benzene, toluene, acetonitrile, acetic acid, dioxane or liquid acyl halide reagent, etc.

[0068] The compound of General Formula I of the present invention has herbicidal activity and can be used for controlling various weeds in agriculture.

[0069] The present invention also includes a herbicidal composition with the compound of General Formula I as the active ingredient. The weight percentage content of the active ingredient in the herbicidal composition is 1 - 99%. The herbicidal composition also includes an agriculturally acceptable carrier.

[0070] The herbicidal composition of the present invention can be applied in the form of various preparations. Usually, the compounds of the present invention are dissolved or dispersed in a carrier to prepare a preparation for easier dispersion when used as a herbicide. For example, these chemical preparations can be made into wettable powders or emulsifiable concentrates, etc. Therefore, in these compositions, at least one liquid or solid carrier is added, and usually a suitable surfactant needs to be added.

[0071] The present invention also provides an implementation method for controlling weeds, which includes applying an herbicidally effective amount of the herbicidal composition of the present invention to the surface of the weeds or the place where the weeds grow or their growth medium. A more suitable effective dose is 1 gram to 1000 grams per hectare, and the preferred effective dose is 10 grams to 500 grams per hectare. For certain applications, one or more other herbicides can be added to the herbicidal composition of the present invention, and additional advantages and effects can thus be produced.

[0072] The compounds of the present invention can be used alone or in combination with other known insecticides, fungicides, plant growth regulators or fertilizers, etc.

[0073] It should be clear that within the protection scope of the present invention, various transformations and modifications can be carried out.

[0074] Advantages of the present invention:

[0075] Compared with the known pyrazole carboxylate compounds, the general formula compounds of the present invention contain a benzoyl group and a pyrazoloyl group substitution, with a novel structure, and the pyrazole carboxylate compounds of the present invention have unexpectedly high herbicidal activity, and also have high herbicidal activity at lower doses. They are not only highly efficient, but also reduce the usage amount of pesticides, lower the cost, and reduce environmental pollution. Detailed implementation manners

[0076] The following examples and bioassay test results can be used to further illustrate the present invention, but do not mean to limit the present invention.

[0077] Synthesis examples

[0078] Example 1. Synthesis of compound 1-1:

[0079] (1) Synthesis of 1-ethyl-5-methyl-3-pyrazolecarbonyl chloride

[0080]

[0081] Add 1-ethyl-5-methyl-3-pyrazolecarboxylic acid (0.19 g, 1.3 mmol) and toluene (10 mL) into the reaction flask, slowly add thionyl chloride (0.5 g, 4 mmol), heat the mixture under reflux for 4 hours, evaporate the solvent under reduced pressure to obtain 0.21 g of yellow oil, and directly proceed to the next step.

[0082] (2) Synthesis of Compound 1-1

[0083]

[0084] Add 4-(2-methyl-3-isoxazolyl-4-methylsulfonylbenzoyl)-1-methyl-5-hydroxypyrazole (0.3 g, 0.8 mmol, commercially available), dichloromethane (10 mL), and triethylamine (0.13 g, 1.3 mmol) into the reaction flask, and slowly add a dichloromethane solution (5 mL) of 1-ethyl-5-methyl-3-pyrazolecarbonyl chloride from the previous step dropwise. Stir at room temperature for 1 hour, evaporate the solvent under reduced pressure, add ethyl acetate (100 mL) to the residue, and perform liquid-liquid extraction with water (50 mL). The organic phase is washed successively with saturated brine (50 mL), dried over anhydrous magnesium sulfate, the solvent is evaporated under reduced pressure, and the residue is separated by column chromatography to obtain 0.35 g of a yellow oil with a purity of 92% and a yield of 77%.

[0085] Example 2 Synthesis of Compound 1-31

[0086] (1) Synthesis of 2-methylsulfonyl-4-chlorobenzoyl chloride

[0087]

[0088] Add 2-methylsulfonyl-4-chlorobenzoic acid (3 g, 12.8 mmol) and toluene (20 mL) into the reaction flask, slowly add thionyl chloride (7.6 g, 4.6 mmol), heat the mixture under reflux for 4 hours, evaporate the solvent under reduced pressure to obtain 3.2 g of a yellow oil, which is directly used in the next step.

[0089] (2) Synthesis of 2-methylsulfonyl-4-chlorobenzoyl-1,3-dimethyl-5-hydroxypyrazole ester

[0090]

[0091] Add 1,3-dimethyl-5-hydroxypyrazole (1.4 g, 12.8 mmol), dichloromethane (20 mL), and triethylamine (1.9 g, 19.2 mmol) into the reaction flask, and slowly add a dichloromethane solution (10 mL) of 2-methylsulfonyl-4-chlorobenzoyl chloride from the previous step dropwise. Stir at room temperature for 2 hours, wash the organic phase with water (50 mL) once, dry over anhydrous magnesium sulfate, evaporate the solvent under reduced pressure, and separate the residue by column chromatography to obtain 3.3 g of a yellow solid with a yield of 78%.

[0092] (3) Synthesis of 4-(2-methylsulfonyl-4-chlorobenzoyl)-1,3-dimethyl-5-hydroxypyrazole

[0093]

[0094] Add 2-(methylsulfonyl)-4-chlorobenzoyl-1,3-dimethyl-5-hydroxypyrazole ester (3.3 g, 10 mmol), toluene (20 mL), and potassium carbonate (2.1 g, 15 mmol) into a reaction flask. Reflux the reaction for 4 hours, cool to room temperature, add water (30 mL), and stir for half an hour. Adjust the aqueous phase to pH = 2 - 3 with 10% dilute hydrochloric acid, extract twice with ethyl acetate (50 mL * 2), wash the combined organic phase with saturated brine (50 mL), dry over anhydrous magnesium sulfate, and evaporate the solvent under reduced pressure to obtain 2.3 g of a yellow solid with a yield of 70%.

[0095] (4) Synthesis of 1-ethyl-5-methyl-3-pyrazolecarbonyl chloride

[0096]

[0097] Add 1-ethyl-5-methyl-3-pyrazolecarboxylic acid (0.35 g, 2.3 mmol) and toluene (10 mL) into a reaction flask, slowly add thionyl chloride (0.9 g, 7.6 mmol), heat the mixture under reflux for 4 hours, evaporate the solvent under reduced pressure to obtain 0.4 g of a yellow oil, and directly proceed to the next step.

[0098] (5) Synthesis of compound 1-31

[0099]

[0100] Add 4-(2-(methylsulfonyl)-4-chlorobenzoyl)-1,3-dimethyl-5-hydroxypyrazole (0.5 g, 1.5 mmol), dichloromethane (10 mL), and triethylamine (0.2 g, 2 mmol) into a reaction flask, and dropwise add a dichloromethane solution (5 mL) of 1-ethyl-5-methyl-3-pyrazolecarbonyl chloride from the previous step. Stir at room temperature for 1 hour, evaporate the solvent under reduced pressure, add ethyl acetate (100 mL) to the residue, perform liquid-liquid extraction with water (50 mL), wash the organic phase successively with saturated brine (50 mL), dry over anhydrous magnesium sulfate, evaporate the solvent under reduced pressure, and separate the residue by column chromatography to obtain 0.32 g of a white solid with a purity of 95% and a yield of 42%.

[0101] Example 3 Synthesis of compound ********

[0102] (1) Synthesis of 2,3-dichloro-4-(methylsulfonyl)benzoyl chloride

[0103]

[0104] Add 2,3-dichloro-4-(methylsulfonyl)benzoic acid (5 g, 18.6 mmol) and toluene (20 mL) into a reaction flask, slowly add thionyl chloride (6.6 g, 55.7 mmol), heat the mixture under reflux for 4 hours, evaporate the solvent under reduced pressure to obtain 5.3 g of a yellow oil, and directly use it for the next step.

[0105] (2) Synthesis of 2,3 - dichloro - 4 - (methylsulfonyl)benzoyl - 1,3 - dimethyl - 5 - hydroxypyrazole ester

[0106]

[0107] Add 1,3 - dimethyl - 5 - hydroxypyrazole (2.1 g, 18.6 mmol), 1,2 - dichloroethane (50 mL), and triethylamine (5.6 g, 55.7 mmol) into the reaction flask, and dropwise add the 1,2 - dichloroethane solution (20 mL) of 2,3 - dichloro - 4 - (methylsulfonyl)benzoyl chloride obtained in the previous step. Stir at room temperature for 2 hours. Wash the organic phase once with water (50 mL), dry it over anhydrous magnesium sulfate, evaporate the solvent under reduced pressure, and separate the residue by column chromatography to obtain 5.1 g of yellow oil with a yield of 76%.

[0108] (3) Synthesis of 4 - (2,3 - dichloro - 4 - (methylsulfonyl)benzoyl) - 1,3 - dimethyl - 5 - hydroxypyrazole

[0109]

[0110] Add 2,3 - dichloro - 4 - (methylsulfonyl)benzoyl - 1,3 - dimethyl - 5 - hydroxypyrazole ester (4 g, 11 mmol), 1,2 - dichloroethane (20 mL), triethylamine (1.7 g, 16.5 mmol), and 2 drops of acetone cyanohydrin into the reaction flask. Stir at room temperature overnight, add water (50 mL) and stir for half an hour. Adjust the pH of the aqueous phase to 2 - 3 with 10% dilute hydrochloric acid, extract twice with ethyl acetate (50 mL × 2), wash the combined organic phase with saturated brine (50 mL), dry it over anhydrous magnesium sulfate, and evaporate the solvent under reduced pressure to obtain 3.5 g of yellow oil with a yield of 88%.

[0111] (4) Synthesis of 1 - ethyl - 5 - methyl - 3 - pyrazolecarbonyl chloride

[0112]

[0113] Add 1 - ethyl - 5 - methyl - 3 - pyrazolecarboxylic acid (0.2 g, 1.3 mmol) and toluene (10 mL) into the reaction flask, slowly add thionyl chloride (0.4 g, 3.3 mmol), heat the mixture under reflux for 4 hours, evaporate the solvent under reduced pressure to obtain 0.22 g of yellow oil, which is directly used in the next step.

[0114] (5) Synthesis of Compound 1 - 145

[0115]

[0116] Add 4-(2,3-dichloro-4-methylsulfonylbenzoyl)-1,3-dimethyl-5-hydroxypyrazole (0.4 g, 1.1 mmol), dichloromethane (10 mL), and triethylamine (0.33 g, 3.3 mmol) to the reaction flask, and slowly add a dichloromethane solution (5 mL) of 1-ethyl-5-methyl-3-pyrazolecarbonyl chloride from the previous step dropwise. Stir at room temperature for 1 hour, evaporate the solvent under reduced pressure, add ethyl acetate (100 mL) to the residue, extract with water (50 mL) by liquid separation, wash the organic phase successively with saturated brine (50 mL), dry over anhydrous magnesium sulfate, evaporate the solvent under reduced pressure, and separate the residue by column chromatography to obtain 0.11 g of a white solid with a purity of 98% and a yield of 20%.

[0117] Example 4. Synthesis of Compound 1-147

[0118] (1) Synthesis of 2-chloro-3-methyl-4-methylsulfonylbenzoyl chloride

[0119]

[0120] Add 2-chloro-3-methyl-4-methylsulfonylbenzoic acid (5.6 g, 22.7 mmol) and toluene (20 mL) to the reaction flask, slowly add thionyl chloride (13.5 g, 114 mmol), heat the mixture under reflux for 4 hours, evaporate the solvent under reduced pressure to obtain 6 g of a yellow oil, which is directly used in the next step.

[0121] (2) Synthesis of 4-(2-chloro-3-methyl-4-methylsulfonylbenzoyl)-1,3-dimethyl-5-hydroxypyrazole

[0122]

[0123] Add 1,3-dimethyl-5-hydroxypyrazole (2.8 g, 25 mmol), dichloromethane (50 mL), and triethylamine (4.6 g, 45.4 mmol) to the reaction flask, and slowly add a dichloromethane solution (20 mL) of 2-chloro-3-methyl-4-methylsulfonylbenzoyl chloride from the previous step dropwise. Stir at room temperature for 1 hour, wash the organic phase with water (50 mL) once, dry over anhydrous magnesium sulfate, add triethylamine (3.8 g, 37.5 mmol) and 2 drops of acetone cyanohydrin, stir at room temperature overnight, add water (50 mL) and stir for half an hour, adjust the aqueous phase to pH = 2-3 with 10% dilute hydrochloric acid, extract with ethyl acetate (50 mL × 2) twice, wash the combined organic phase with saturated brine (50 mL), dry over anhydrous magnesium sulfate, evaporate the solvent under reduced pressure to obtain 4 g of a yellow oil with a yield of 51%.

[0124] (3) Synthesis of 1-ethyl-5-methyl-3-pyrazolecarbonyl chloride

[0125]

[0126] Add 1-ethyl-5-methyl-3-pyrazolecarboxylic acid (0.16 g, 1 mmol) and toluene (10 mL) into a reaction flask, slowly add thionyl chloride (0.3 g, 2.6 mmol), heat the mixture under reflux for 4 hours, evaporate the solvent under reduced pressure to obtain 0.2 g of yellow oil, and directly proceed to the next step.

[0127] (4) Synthesis of Compound 1-147

[0128]

[0129] Add 4-(2-chloro-3-methyl-4-methylsulfonylbenzoyl)-1,3-dimethyl-5-hydroxypyrazole (0.3 g, 0.9 mmol), dichloromethane (10 mL), and triethylamine (0.25 g, 2.5 mmol) into a reaction flask, and dropwise add a dichloromethane solution (5 mL) of 1-ethyl-5-methyl-3-pyrazolecarbonyl chloride from the previous step. Stir at room temperature for 1 hour, evaporate the solvent under reduced pressure, add ethyl acetate (100 mL) to the residue, perform liquid-liquid extraction with water (50 mL), wash the organic phase successively with saturated brine (50 mL), dry over anhydrous magnesium sulfate, evaporate the solvent under reduced pressure, and separate the residue by column chromatography to obtain 0.26 g of white solid with a purity of 98% and a yield of 60%.

[0130] Other compounds represented by General Formula I can be obtained by replacing the starting materials according to the method described above. For some compounds of General Formula I, see Table 1 and Table 2.

[0131] For the compound of General Formula I, where W is CX2.

[0132]

[0133] Q is one of the following groups: Q1, Q2, or Q3

[0134]

[0135] Structures and Physical Properties of Some Compounds of General Formula I in Table 1

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156] A compound of general formula I, wherein W is N.

[0157]

[0158] Q is one of the following groups: Q1, Q2 or Q3

[0159]

[0160] Structures and physical properties of some compounds of general formula I in Table 2

[0161]

[0162]

[0163]

[0164] For some compounds 1 The 1H NMR (300 MHz, CDCl3) data are as follows:

[0165] Compound 1-1: 7.94 (s, 1H), 7.85 (d, 1H), 7.47 (d, 1H), 6.34 (s, 1H), 4.51 (t, 2H), 4.17 (q, 2H), 3.71 (s, 3H), 3.21 (t, 2H), 3.05 (s, 3H), 2.30 (s, 3H), 2.19 (s, 3H), 1.42 (s, 3H).

[0166] Compound 1-8: 7.92 (s, 1H), 7.87 - 7.88 (d, 1H), 7.68 (d, 1H), 7.49 - 7.50 (d, 1H), 6.79 (d, 1H), 4.49 - 4.52 (t, 2H), 3.76 (s, 3H), 3.21 - 3.23 (m, 2H), 3.06 (s, 3H), 2.22 (s, 3H).

[0167] Compound 1-9: 7.96 (s, 1H), 7.85 - 7.84 (d, 1H), 7.48 - 7.50 (d, 1H), 6.40 (s, 1H), 5.90 - 5.97 (m, 1H), 5.24 - 5.46 (d, 1H), 5.04 - 5.07 (d, 1H), 4.78 - 4.79 (d, 2H), 4.51 - 4.54 (t, 2H), 3.72 (s, 3H), 3.49 - 3.54 (m, 2H), 3.08 (s, 3H), 2.29 (s, 3H), 2.20 (s, 3H).

[0168] Compound 1-10: 7.92 (s, 1H), 7.88 - 7.90 (d, 1H), 7.48 - 7.48 (d, 1H), 6.43 (s, 1H), 5.62 - 5.64 (d, 2H), 4.50 - 4.54 (t, 2H), 3.72 (s, 3H), 3.21 - 3.22 (m, 2H), 3.06 (s, 3H), 2.37 (s, 3H), 2.21 (s, 3H).

[0169] Compound 1-11: 7.92 (s, 1H), 7.85 - 7.90 (d, 1H), 7.48 - 7.49 (d, 1H), 6.43 (s, 1H), 5.62 - 5.64 (d, 2H), 4.50 - 4.54 (t, 2H), 3.72 (s, 3H), 3.31 (s, 1H), 3.21 - 3.22 (m, 2H), 3.06 (s, 3H), 2.37 (s, 3H), 2.21 (s, 3H).

[0170] Compound 1-12: 7.94 (s, 1H), 7.86 - 7.87 (d, 1H), 7.49 - 7.50 (d, 1H), 6.35 (s, 1H), 4.51 - 4.54 (t, 2H), 4.09 - 4.12 (t, 2H), 3.73 (s, 3H), 3.20 - 3.23 (t, 2H), 3.07 (s, 3H), 2.31 (s, 3H), 2.21 (s, 3H), 1.77 - 1.82 (m, 2H), 1.35 - 1.38 (m, 2H), 0.94 - 0.96 (t, 3H).

[0171] Compound 1-13: 7.90 - 7.91 (d, 1H), 7.87 (s, 1H), 7.50 - 7.52 (d, 1H), 6.32 (s, 1H), 4.50 - 4.53 (t, 2H), 4.19 - 4.25 (m, 1H), 3.73 (s, 3H), 3.18 - 3.22 (m, 2H), 3.09 (s, 3H), 2.30 (s, 3H), 2.23 (s, 3H), 1.97 - 2.02 (m, 1H), 1.79 - 1.83 (m, 1H), 1.51 - 1.52 (d, 3H), 0.80 - 0.82 (t, 3H).

[0172] Compound 1-14: 7.92 (s, 1H), 7.86 - 7.88 (d, 1H), 7.49 - 7.50 (d, 1H), 6.37 (s, 1H), 4.51 - 4.55 (t, 2H), 3.92 - 3.93 (d, 2H), 3.74 (s, 3H), 3.21 - 3.24 (m, 2H), 3.08 (s, 3H), 2.38 (s, 3H), 2.22 - 2.24 (m, 1H), 2.21 (s, 3H), 0.91 - 0.92 (d, 6H).

[0173] Compound 1-15: 7.93 (s, 1H), 7.84 - 7.86 (d, 1H), 7.48 - 7.49 (d, 1H), 6.44 (s, 1H), 5.16 (s, 2H), 4.51 - 4.55 (t, 2H), 3.73 (s, 3H), 3.24 - 3.25 (m, 2H), 3.08 (s, 3H), 2.39 (s, 3H), 2.20 (s, 3H), 2.15 (s, 3H).

[0174] Compound 1-16: 7.92 (s, 1H), 7.84 - 7.85 (d, 1H), 7.47 - 7.49 (d, 1H), 6.53 (s, 1H), 4.53 - 4.56 (t, 2H), 3.74 (s, 3H), 3.24 - 3.27 (m, 2H), 3.10 (s, 3H), 3.00 (s, 3H), 2.46 (s, 3H), 2.21 (s, 3H).

[0175] Compound 1-17: 7.97 (s, 1H), 7.81 - 7.82 (d, 1H), 7.60 - 7.61 (d, 1H), 6.43 (s, 1H), 4.42 - 4.46 (t, 2H), 3.91 (s, 3H), 3.68 (s, 3H), 3.18 - 3.21 (t, 2H), 3.11 (s, 3H), 2.09 (s, 3H), 1.85 - 1.90 (m, 1H), 0.94 - 0.97 (m, 2H), 0.70 - 0.73 (m, 2H).

[0176] Compound 1-18: 7.95 (s, 1H), 7.83 - 7.84 (d, 1H), 7.61 - 7.63 (d, 1H), 6.43 (s, 1H), 4.42 - 4.45 (t, 2H), 4.26 - 4.30 (q, 2H), 3.69 (s, 3H), 3.18 - 3.21 (t, 2H), 3.11 (s, 3H), 2.10 (s, 3H), 1.88 - 1.93 (m, 1H), 1.38 - 1.41 (t, 3H), 0.96 - 0.98 (m, 2H), 0.71 - 0.74 (m, 2H).

[0177] Compound 1-30: 8.42 (s, 1H), 7.95 (d, 1H), 7.50 (d, 1H), 6.24 (s, 1H), 4.13 - 4.16 (m, 2H), 3.59 (s, 3H), 2.96 (s, 3H), 2.60 (s, 3H), 2.29 (s, 3H), 1.42 - 1.45 (t, 3H).

[0178] Compound 1-31: 7.79 (s, 1H), 7.57 (d, 1H), 7.33 (d, 1H), 6.29 (s, 1H), 4.15 (q, 2H), 3.56 (s, 3H), 3.27 (s, 3H), 2.31 (s, 3H), 2.30 (s, 3H).

[0179] Compound 1-56: 7.65 (d, 1H), 7.12 (d, 1H), 6.20 (s, 1H), 4.14 (q, 2H), 3.78 (q, 2H), 3.61 (s, 3H), 3.07 (s, 3H), 2.55 (s, 3H), 2.29 (s, 3H), 2.17 (s, 3H), 1.38 - 1.42 (m, 6H).

[0180] Compound 1-63: 7.67 (d, 1H), 7.19 (d, 1H), 6.18 (s, 1H), 4.05 - 4.25 (m, 4H), 3.57 (s, 3H), 3.06 (s, 3H), 2.53 (s, 3H), 2.27 (s, 3H), 2.17 (s, 3H), 1.39 (t, 3H).

[0181] Compound 1-143: 7.68 (s, 1H), 7.56 (d, 1H), 7.37 (d, 1H), 6.26 (s, 1H), 4.13 - 4.17 (m, 2H), 3.63 (s, 3H), 2.91 (s, 3H), 2.56 (s, 3H), 2.29 (s, 3H), 1.41 - 1.44 (t, 3H).

[0182] Compound 1-145: 7.84 (d, 1H), 7.27 (d, 1H), 6.30 (s, 1H), 4.15 - 4.19 (m, 2H), 3.63 (s, 3H), 3.11 (s, 3H), 2.58 (s, 3H), 2.30 (s, 3H), 1.40 - 1.42 (t, 3H).

[0183] Compound 1-147: 7.78 (d, 1H), 7.21 (d, 1H), 6.23 (s, 1H), 4.13 - 4.17 (m, 2H), 3.62 (s, 3H), 2.94 (s, 3H), 2.58 (s, 3H), 2.29 (s, 3H), 2.09 (s, 3H), 1.39 - 1.41 (t, 3H).

[0184] Compound 1-148: 7.07 (d, 1H), 6.95 (d, 1H), 6.26 (s, 1H), 4.17 (q, 2H), 3.61 (s, 3H), 2.51 (s, 3H), 2.32 (s, 3H), 2.29 (s, 3H).

[0185] Compound 1-208: 7.84 (d, 1H), 7.40 (d, 1H), 6.24 (s, 1H), 5.28 (s, 2H), 4.13 - 4.16 (m, 2H), 3.60 (s, 3H), 3.21 (s, 3H), 3.03 (s, 3H), 2.54 (s, 3H), 2.28 (s, 3H), 1.38 - 1.40 (t, 3H).

[0186] Compound 1-231: 7.99 (s, 1H), 7.83 - 7.84 (d, 1H), 7.61 - 7.63 (d, 1H), 4.44 - 4.47 (t, 2H), 3.95 (s, 3H), 3.74 (s, 3H), 3.54 - 3.57 (m, 2H), 3.12 (s, 3H), 2.14 (s, 3H).

[0187] Compound 1-367: 7.99 - 8.00 (d, 1H), 7.71 (s, 1H), 7.53 - 7.55 (d, 1H), 6.69 (s, 1H), 5.23 - 5.27 (m, 1H), 4.54 - 4.57 (t, 2H), 3.77 (s, 3H), 3.25 - 3.31 (m, 2H), 3.07 (s, 3H), 2.31 (s, 3H), 2.27 (s, 3H), 1.48 - 1.49 (d, 6H).

[0188] Compound 1-368: 8.00 - 8.01 (d, 1H), 7.68 (s, 1H), 7.54 - 7.55 (d, 1H), 6.70 (s, 1H), 5.05 - 5.10 (m, 2H), 4.55 - 4.58 (t, 2H), 3.77 (s, 3H), 3.27 - 3.36 (m, 2H), 3.09 (s, 3H), 2.32 (s, 3H), 2.27 (s, 3H), 1.92 - 2.00 (m, 1H), 1.73 - 1.80 (m, 1H), 1.48 - 1.49 (d, 3H), 0.78 - 0.80 (t, 3H).

[0189] Compound 1-369: 7.99 - 8.00 (d, 1H), 7.70 (s, 1H), 7.55 - 7.55 (d, 1H), 6.71 (s, 1H), 4.54 - 4.58 (t, 2H), 4.25 - 4.27 (d, 2H), 3.76 (s, 3H), 3.25 - 3.29 (m, 2H), 3.09 (s, 3H), 2.31 (s, 3H), 2.26 (s, 3H), 2.13 - 2.18 (m, 1H), 0.88 - 0.89 (d, 6H).

[0190] Compound 1-370: 7.98 - 8.00 (d, 1H), 7.72 (s, 1H), 7.53 - 7.54 (d, 1H), 6.69 (s, 1H), 4.54 - 4.58 (t, 2H), 4.41 - 4.43 (t, 2H), 3.77 (s, 3H), 3.19 - 3.27 (m, 2H), 3.07 (s, 3H), 2.30 (s, 3H), 2.27 (s, 3H), 1.75 - 1.80 (m, 2H), 1.30 - 1.36 (m, 2H), 0.90 - 0.93 (t, 3H).

[0191] Compound 1-371: 7.94 (s, 1H), 7.86 - 7.87 (d, 1H), 7.49 - 7.50 (d, 1H), 6.36 (s, 1H), 4.51 - 4.54 (t, 2H), 4.07 - 4.09 (t, 2H), 3.73 (s, 3H), 3.20 - 3.24 (m, 2H), 3.07 (s, 3H), 2.31 (s, 3H), 2.21 (s, 3H), 1.83 - 1.87 (m, 2H), 0.94 - 0.96 (t, 3H).

[0192] Compound 1-372: 8.01 - 8.02 (d, 1H), 7.72 (s, 1H), 7.53 - 7.55 (d, 1H), 6.81 (s, 1H), 5.71 (s, 2H), 4.55 - 4.58 (t, 2H), 3.77 (s, 3H), 3.27 - 3.29 (m, 2H), 3.10 (s, 3H), 2.93 (s, 3H), 2.35 (s, 3H), 2.27 (s, 3H), 1.39 - 1.41 (t, 3H), 0.94 - 0.98 (m, 2H), 0.75 - 0.78 (m, 2H).

[0193] Compound 1-373: 7.98 - 7.99 (d, 1H), 7.69 (s, 1H), 7.56 - 7.58 (d, 1H), 6.86 (s, 1H), 4.55 - 4.59 (t, 2H), 4.10 (s, 3H), 3.79 (s, 3H), 3.22 - 3.31 (m, 2H), 3.09 (s, 3H), 2.29 (s, 9H).

[0194] Compound 1-374: 7.97 - 7.98 (d, 1H), 7.74 (s, 1H), 7.55 - 7.56 (d, 1H), 4.55 - 4.58 (t, 3H), 4.06 (s, 3H), 3.79 (s, 3H), 3.30 - 3.37 (m, 2H), 3.06 (s, 3H), 2.59 - 2.63 (m, 2H), 2.28 (s, 3H), 2.23 (s, 3H), 1.21 - 1.24 (t, 3H).

[0195] Compound 1-375: 7.98 - 7.99 (d, 1H), 7.72 (s, 1H), 7.53 - 7.55 (d, 1H), 6.61 (s, 1H), 5.23 - 5.27 (m, 1H), 4.54 - 4.58 (t, 2H), 4.43 - 4.47 (q, 2H), 3.77 (s, 3H), 3.27 - 3.34 (m, 2H), 3.07 (s, 3H), 2.27 (s, 3H), 1.91 - 1.95 (m, 1H), 1.39 - 1.41 (t, 3H), 0.94 - 0.98 (m, 2H), 0.75 - 0.78 (m, 2H).

[0196] Biological assay examples

[0197] Example 5. Determination of herbicidal activity

[0198] Seeds of broad-leaved weeds (Zinnia elegans, Abutilon theophrasti) or gramineous weeds (Setaria viridis, Echinochloa crusgalli) were sown separately in paper cups with a diameter of 7 cm filled with nutrient soil. After sowing, the soil was covered with a 1-cm layer, compacted, and watered. Then, they were cultivated in a greenhouse according to the conventional method. After the weeds reached the 2 - 3 leaf stage, they were treated by spraying the stems and leaves.

[0199] The original drug was dissolved in acetone, and then the test solution with the required concentration was prepared by standing in tap water with 1‰ Tween 80 according to the test requirements. According to the test design dose, the spraying treatment was carried out on a crawler-type crop sprayer (designed and produced by Engineer Research Ltd., UK) (spraying pressure 1.95 kg / cm 2 , spraying liquid volume 500 L / hm 2 , crawler speed 1.48 km / h). The test was set with 3 replicates. After the test materials were treated, they were placed in the operation hall. After the liquid medicine dried naturally, they were placed in the greenhouse and managed according to the conventional method. The reaction of the weeds to the medicine was observed and recorded. After the treatment, the control effect of the test medicine on the weeds was visually inspected regularly, which was expressed by 0 - 100%, with "0" representing no control effect and "100%" representing complete killing.

[0200] The test results show that the compounds of general formula I generally have high control efficacy against various weeds. Among some of the tested compounds, such as compounds 1-1, 1-9, 1-10, 1-12, 1-13, 1-14, 1-15, 1-16, 1-17, 1-18, 1-31, 1-143, 1-145, 1-147, 1-208, 1-231, 1-367, 1-368, 1-369, 1-370, 1-371, 1-372, 1-373, 1-374 and 1-375, at the application rate of 600 g a.i. / hm 2 showed good control efficacy against *Zinnia elegans*, *Abutilon theophrasti*, *Setaria viridis* or *Echinochloa crusgalli*, with the control efficacy being greater than or equal to 90%.

[0201] According to the above test method, some compounds of general formula I were selected for the activity test of controlling *Abutilon theophrasti* with KC, and the results are shown in Table 3.

[0202] Table 3: Activity of some compounds of general formula I and the control compound KC against *Abutilon theophrasti* (post-emergence, control efficacy %)

[0203]

[0204]

[0205] “ / ” in the table indicates not tested.

[0206] According to the above test method, some compounds of general formula I were selected for the activity test of controlling *Setaria viridis* with KC, and the results are shown in Table 4.

[0207] Table 4: Activity of some compounds of general formula I and the control compound KC against *Setaria viridis* (post-emergence, control efficacy %)

[0208]

[0209] “ / ” in the table indicates not tested.

[0210] According to the above test method, some compounds of general formula I were selected for the activity test of controlling *Echinochloa crusgalli* with KC, and the results are shown in Table 5.

[0211] Table 5: Activity of some compounds of general formula I and the control compound KC against *Echinochloa crusgalli* (post-emergence, control efficacy %)

[0212]

[0213]

[0214] “ / ” in the table indicates not tested.

[0215] In summary, the pyrazole carboxylate compounds of the present invention have excellent herbicidal activity, high herbicidal activity even at low doses, and are safe for crops, and can be used in agriculture to control various weeds.

Claims

1. A pyrazole carboxylate compound, characterized in that: The compound is shown by general formula I: In the formula: X1 is selected from halogen, C1-C6 alkyl; W is selected from CX2; X2 is selected from Y1 sulfonyl C1-C6 alkyl; Y1 is selected from C1-C6 alkyl; X3 is selected from C1-C6 alkyl sulfonyl; Q is selected from Q1 or Q3, ； R1 is selected from C1-C6 alkyl, C1-C6 haloalkyl; R2 and R3 may be the same or different and are respectively selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl; R4 is selected from C1-C6 alkyl; R5 is selected from hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyl.

2. The compound according to claim 1, characterized in that, In general formula I: X1 is selected from halogen; W is selected from CX2; X2 is selected from Y1 sulfonyl C1-C6 alkyl; Y1 is selected from methyl; X3 is selected from methyl sulfonyl; Q is selected from Q1 or Q3; R1 is selected from methyl; R2 and R3 are selected from methyl; R4 is selected from ethyl; R5 is selected from hydrogen.

3. The compound according to claim 2, characterized in that, In general formula I: X1 is selected from chlorine; W is selected from CX2; X2 is selected from methylsulfonylmethyl; X3 is selected from methyl sulfonyl; Q is selected from Q1; R1 is selected from methyl; R2 and R3 are selected from methyl; R4 is selected from ethyl; R5 is selected from hydrogen.

4. Use of the general formula I compound according to claim 1 for controlling weeds.

5. A herbicidal composition, characterized in that: The herbicidal composition is an active substance and an agriculturally acceptable carrier, the active component is the general formula I compound according to claim 1, and the weight percentage content of the active component in the composition is 1-99%.

6. A method for controlling weeds with the herbicidal composition as claimed in claim 5, characterized in that: Apply a herbicidally effective dose of the herbicidal composition according to claim 5 to weeds or the growth medium or location of weeds.

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