A cinnamide compound and its application

Abstract

The present invention discloses a cinnamamide compound and its agriculturally acceptable salt for use as a herbicide. The compound is represented by the general formula (I): #imgabs0#. The definitions of the substituents in the general formula I are as described in the specification. The compound of the general formula I 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, and specifically relates to a cinnamamide compound and its application as a herbicide. Background Art

[0002] Due to the succession and transformation of weed populations, as well as the emergence and rapid development of resistance to chemical pesticides, people are increasingly aware of ecological and environmental protection, and are increasingly concerned about chemical pesticide pollution, the impact of pesticides on non-target organisms, and the fate of pesticides in the ecological environment. The gradual reduction in the world's arable land area, the continuous growth of the population, and the increasing demand for food are forcing people to rapidly develop agricultural production technologies, improve and perfect farming systems, and continuously invent new and improved herbicidal compounds and compositions.

[0003] CN108290846A reports that certain benzamide compounds have herbicidal activity, such as compounds No. 13-30 (KC):

[0004]

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

[0006] The present invention aims to provide a cinnamamide compound which is novel in structure and safe for crops and its application as a herbicide.

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

[0008] 1. A cinnamamide compound, characterized in that: the compound is as shown in general formula I:

[0009]

[0010] Where:

[0011] X1 and X3 are independently selected from hydrogen, cyano, nitro, halogen, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylthio, C1-C6 haloalkylthio, 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, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C3 alkyl, C3-C6 cycloalkyl C1-C3 alkoxy, C3-C6 cycloalkyloxy, C2-C6 alkenyl, C C2-C6 alkynyl, phenyl, unsubstituted or substituted with 1-5 of the following substituents, C2-C6 alkenylsulfonyl, C2-C6 alkynylsulfonyl, phenylsulfonyl, C2-C6 alkenyloxy, C2-C6 alkynyloxy, phenyloxy, C2-C6 alkenylthio, C2-C6 alkynylthio, phenylthio, a 5-7 membered alicyclic heterocycle containing 1-4 heteroatoms, a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms, a 5-7 membered alicyclic heterocycle C1-C6 alkyl containing 1-4 heteroatoms, or a 5-7 membered aromatic heterocycle C1-C6 alkyl containing 1-4 heteroatoms, wherein the following 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 cycloalkylC1-C6 alkyl, C3-C6 halocycloalkylC1-C6 alkyl, Y1oxy, Y1thio, Y1Y2amino, Y1sulfinyl, Y1sulfonyl, Y1oxyC1-C6 alkyl, Y1thioC1-C6 alkyl, Y1Y2aminoC1-C6 alkyl, Y1sulfinylC1-C6 alkyl, Y1sulfonylC1-C6 alkyl, COY1, COOY1, OCOOY1, NY1COOY2, C(O)N Y1Y2, NY1C(O)N Y1Y2, OC(O)NY1Y2, C(O)N(Y1)OY2, NY1SO2Y2, NY1COY2, OSO2Y1, CH=NOY1, C1-C6 alkyl-CH=NOY1, C1-C6 alkyl-ON=CY1Y2, phenyl which is unsubstituted or substituted with 1-5 of the following substituents, 5-7 membered alicyclic rings containing 1-4 heteroatoms, 5-7 membered aromatic rings containing 1-4 heteroatoms heterocycle, a 5-7 membered alicyclic C1-C6 alkyl group containing 1-4 heteroatoms, or a 5-7 membered aromatic heterocyclic C1-C6 alkyl group containing 1-4 heteroatoms, wherein 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 halophenyl;

[0014] Y1 and Y2 are each independently selected from C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C1-C6 alkoxyC1-C6 alkyl, phenyl which is unsubstituted or substituted with 1-5 of the following substituents, a 5-7 membered alicyclic heterocycle containing 1-4 heteroatoms, a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms, a 5-7 membered alicyclic heterocycle C1-C6 alkyl containing 1-4 heteroatoms, or a 5-7 membered aromatic heterocycle C1-C6 alkyl containing 1-4 heteroatoms, wherein 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 cycloalkyloxy, C2-C6 alkenyl, C2-C6 alkynyl, phenyl, or halophenyl;

[0015] Q is selected from Q1, Q2, Q3, Q4, Q5 or Q6 groups;

[0016]

[0017] R1 to R5 are independently selected from hydrogen, hydroxy, cyano, nitro, halogen, phenyl, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio or benzyloxy; wherein

[0018] R1 and R2 can form a benzene ring together with the carbon atoms on the benzene ring to which they are connected, a 5-7 membered aliphatic heterocycle containing 1-4 heteroatoms, or a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms;

[0019] R2 and R3 can form a benzene ring together with the carbon atoms on the benzene ring to which they are connected, a 5-7 membered aliphatic heterocycle containing 1-4 heteroatoms, or a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms;

[0020] R6, R7, and R8 are independently selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, or phenyl;

[0021] R9, R 10 、R 11 are independently selected from hydrogen, halogen, cyano, nitro, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C3 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 or C3-C6 cycloalkyloxy;

[0022] Stereoisomers of the compound of the above general formula I; or, agriculturally acceptable salts of the compound of the above general formula I and its isomers.

[0023] The preferred compound has the general formula I:

[0024] X1 and X3 are independently selected from hydrogen, cyano, nitro, halogen, C1-C6 alkylsulfonyl, C1-C6 alkylsulfinyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 alkoxy C1-C3 alkyl, C1-C6 alkoxy C1-C3 alkoxy, C1-C6 alkoxy C1-C3 alkoxy C1-C3 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C3 alkyl, C3- C6 cycloalkyl, C1-C3 alkoxy, C3-C6 cycloalkyloxy, C2-C6 alkenyl, C2-C6 alkynyl, phenyl, phenylsulfonyl, C2-C6 alkenyloxy, phenyloxy, a 5-7 membered aliphatic heterocycle containing 1-4 heteroatoms, a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms, wherein the substituents are selected from nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy or C3-C6 cycloalkyl;

[0025] W is selected from N or CX2;

[0026] X2 is selected from hydrogen, cyano, nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C3-C6 halocycloalkylC1-C6 alkyl, Y1oxy, Y1thio, Y1Y2amino, Y1sulfinyl, Y1sulfonyl, Y1oxyC1-C6 alkyl, Y1thioC1-C6 alkyl, Y1Y2aminoC1-C6 alkyl, Y1sulfinylC1-C6 alkyl, Y1sulfonylC1-C6 alkyl, COY1, COOY1, OCOOY1, NY1COOY2, C(O)N Y1Y2, NY1C(O)N Y1Y2, OC(O)NY1Y2, C(O)N(Y1)OY2, NY1SO2Y2, NY1COY2, OSO2Y1, CH=NOY1, C1-C6 alkyl-CH=NOY1, C1-C6 alkyl-ON=CY1Y2, phenyl which is unsubstituted or substituted with 1-5 of the following substituents, a 5-7 membered alicyclic heterocycle containing 1-4 heteroatoms, a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms, a 5-7 membered alicyclic heterocycle C1-C6 alkyl containing 1-4 heteroatoms, or a 5-7 membered aromatic heterocycle C1-C6 alkyl containing 1-4 heteroatoms, wherein 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;

[0027] Y1 and Y2 are each independently selected from C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C1-C6 alkoxyC1-C6 alkyl, phenyl which is unsubstituted or substituted with 1-5 of the following substituents, a 5-7 membered alicyclic heterocycle containing 1-4 heteroatoms, a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms, a 5-7 membered alicyclic heterocycle C1-C6 alkyl containing 1-4 heteroatoms, or a 5-7 membered aromatic heterocycle C1-C6 alkyl containing 1-4 heteroatoms, wherein the following substituents are selected from nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C6 cycloalkyl, and C3-C6 cycloalkoxy;

[0028] Q is selected from Q1, Q2, Q3, Q4 or Q5 groups;

[0029]

[0030] R1 to R5 are independently selected from hydrogen, hydroxy, cyano, nitro, halogen, phenyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkylthio or benzyloxy; wherein

[0031] R1 and R2 can form a benzene ring together with the carbon atoms on the benzene ring to which they are connected, a 5-7 membered aliphatic heterocycle containing 1-4 heteroatoms, or a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms;

[0032] R2 and R3 can form a benzene ring together with the carbon atoms on the benzene ring to which they are connected, a 5-7 membered aliphatic heterocycle containing 1-4 heteroatoms, or a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms;

[0033] R6, R7, and R8 are independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, or phenyl;

[0034] R9 and R 10 are independently selected from hydrogen, halogen, C1-C6 alkylthio, C1-C6 alkyl, C1-C6 alkoxy, C1-C3 alkoxyC1-C3 alkyl, C1-C6 alkoxyC1-C3 alkoxy, C1-C6 alkoxyC1-C3 alkoxyC1-C3 alkyl or C3-C6 cycloalkyl; stereoisomers of the compound described by the above general formula I.

[0035] Further preferably, the compound, in the general formula I:

[0036] X1 and X3 are each independently selected from hydrogen, cyano, nitro, halogen, C1-C3 alkylsulfonyl, C1-C3 alkylsulfinyl, C1-C3 alkylthio, C1-C3 haloalkylthio, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 alkoxyC1-C3 alkyl, C1-C3 alkoxyC1-C3 alkoxy, C1-C3 alkoxyC1-C3 alkyl, C3-C6 cycloalkyl or C3-C6 cycloalkyloxy;

[0037] W is selected from N or CX2;

[0038] X2 is selected from hydrogen, cyano, nitro, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C3 alkyl, C3-C6 halocycloalkylC1-C3 alkyl, Y1oxy, Y1thio, Y1Y2amino, Y1sulfinyl, Y1sulfonyl, Y1oxyC1-C3 alkyl, Y1thioC1-C3 alkyl, Y1Y2aminoC1-C3 alkyl, Y1sulfinylC1-C3 alkyl, Y1sulfonylC1-C3 alkyl, COY1, COOY1, OCOOY1, NY1COOY2, C(O)NY1Y2, NY1C(O)NY1Y2, OC(O)N Y1Y2, NY1SO2Y2, NY1COY2, OSO2Y1, CH=NOY1, (C1-C6)-alkyl-CH=NOY1, phenyl which is unsubstituted or substituted by 1-5 of the following substituents, a 5-7 membered alicyclic heterocycle containing 1-4 heteroatoms, a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms, a 5-7 membered alicyclic heterocycle C1-C3 alkyl containing 1-4 heteroatoms, or a 5-7 membered aromatic heterocycle C1-C3 alkyl containing 1-4 heteroatoms, wherein the following substituents are selected from nitro, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C6 cycloalkyl or C3-C6 cycloalkoxy;

[0039] Y1 and Y2 are each independently selected from C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C1-C6 alkoxyC1-C6 alkyl, phenyl which is unsubstituted or substituted with 1-5 of the following substituents, a 5-7 membered alicyclic heterocycle containing 1-4 heteroatoms, a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms, a 5-7 membered alicyclic heterocycle C1-C6 alkyl containing 1-4 heteroatoms, or a 5-7 membered aromatic heterocycle C1-C6 alkyl containing 1-4 heteroatoms, wherein the following substituents are selected from nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C6 cycloalkyl, or C3-C6 cycloalkoxy;

[0040] Q is selected from Q1, Q2, Q3 or Q4 groups;

[0041]

[0042] R1 to R5 are independently selected from hydrogen, hydroxy, cyano, nitro, halogen, phenyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy or benzyloxy; wherein

[0043] R1 and R2 can form a benzene ring or a 5-7 membered aliphatic heterocycle with 1-4 heteroatoms together with the carbon atoms on the benzene ring to which they are connected;

[0044] R2 and R3 can form a benzene ring or a 5-7 membered aliphatic heterocycle with 1-4 heteroatoms together with the carbon atoms on the benzene ring to which they are connected;

[0045] R6 and R7 are independently selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl or phenyl;

[0046] R8 and R9 are independently selected from hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C3 alkoxy C1-C3 alkyl, C1-C6 alkoxy C1-C3 alkoxy or C3-C6 cycloalkyl;

[0047] Stereoisomers of the compound of the above general formula I.

[0048] More preferably, the compound has the general formula I:

[0049] X1 and X3 are independently selected from hydrogen, cyano, nitro, halogen, C1-C3 alkylsulfonyl, C1-C3 alkyl, C1-C3 haloalkyl;

[0050] W is selected from N or CX2;

[0051] X2 is selected from hydrogen, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C3 alkyl, C3-C6 halocycloalkyl C1-C3 alkyl, Y1oxy, Y1thio, Y1Y2amino, Y1sulfonyl, Y1oxy C1-C3 alkyl, Y1thio C1-C3 alkyl, Y1Y2amino C1-C3 alkyl, Y1sulfonyl C1-C3 alkyl, COY1, COOY1, OCOOY1, NY1COOY2, C(O)N Y1Y2, NY1C(O)N Y1Y2, NY1SO2Y2, NY1COY2, OSO2Y1, CH=NOY1, (C1-C6)-alkyl-CH=NOY1, phenyl which is unsubstituted or substituted by 1-5 of the following substituents, a 5-7 membered alicyclic heterocycle containing 1-4 heteroatoms, a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms, a 5-7 membered alicyclic heterocycle C1-C3 alkyl containing 1-4 heteroatoms, or a 5-7 membered aromatic heterocycle C1-C3 alkyl containing 1-4 heteroatoms, wherein the following substituents are selected from nitro, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C6 cycloalkyl or C3-C6 cycloalkoxy;

[0052] Y1 and Y2 are each independently selected from C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl, C1-C6 alkoxyC1-C6 alkyl, phenyl which is unsubstituted or substituted with 1-5 of the following substituents, a 5-7 membered alicyclic heterocycle containing 1-4 heteroatoms, a 5-7 membered aromatic heterocycle containing 1-4 heteroatoms, a 5-7 membered alicyclic heterocycle C1-C6 alkyl containing 1-4 heteroatoms, or a 5-7 membered aromatic heterocycle C1-C6 alkyl containing 1-4 heteroatoms, wherein the following substituents are selected from nitro, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C6 cycloalkyl, or C3-C6 cycloalkoxy;

[0053] Q is selected from Q1, Q2, Q3 or Q4 groups;

[0054]

[0055] R1 to R5 are independently selected from hydrogen, hydroxy, cyano, nitro, halogen, phenyl, methyl, ethyl, propyl, vinyl, propenyl, ethynyl, propynyl, methoxy, ethoxy, benzyloxy, trifluoromethyl or trifluoromethoxy;

[0056] R1 and R2 can form a benzene ring together with the carbon atoms on the benzene ring to which they are connected;

[0057] R2 and R3 can form a benzene ring, a 1,3-dioxane ring or a 1,4-dioxane ring together with the carbon atoms on the benzene ring to which they are connected;

[0058] R6 and R7 are independently selected from hydrogen, methyl or ethyl;

[0059] R8 and R9 are independently selected from hydrogen, chlorine or methyl;

[0060] The trans stereoisomer of the compound of the above general formula I.

[0061] In the definition of compounds of general formula I given above, the terms used are collectively defined as follows:

[0062] Alkyl refers to a straight or branched chain form, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl and the like. Cycloalkyl refers to a cyclic chain form, such as cyclopropyl, methylcyclopropyl, cyclopropylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. Alkenyl refers to a straight or branched chain alkenyl, such as vinyl, 1-propenyl, 2-propenyl, butenyl, pentenyl and hexenyl and the like. Alkyl refers to a straight or branched chain alkynyl, such as 1-propynyl, 2-propynyl, butynyl, pentynyl and hexynyl and the like. Alkoxy refers to a group with an oxygen atom attached to the end of an alkyl group, such as methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy and the like. A 5-7 membered aliphatic heterocycle containing 1-4 heteroatoms refers to a 5-7 membered heterocyclic compound without aromatic characteristics containing 1-4 heteroatoms, such as ethylene oxide, tetrahydrofuran, imidazolinone, caprolactam, 1,3-dioxane, and 1,4-dioxane. A 5-7 membered aromatic heterocycle containing 1-4 heteroatoms refers to a 5-7 membered heterocyclic compound with aromatic characteristics containing 1-4 heteroatoms, such as furan, thiophene, pyrazole, and pyridine. A stereoisomer refers to a compound in Formula I in which the hydrogen atoms on the carbon-carbon double bond B are on the same side (cis) or on both sides (trans) of the bond B.

[0063] The general formula compound I of the present invention can be prepared by the following method:

[0064] Method 1:

[0065]

[0066] The compound of general formula II is reacted with the compound of general formula III 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.

[0067] 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.

[0068] Adding a suitable base to the reaction system may be beneficial to the reaction. Suitable bases are selected from organic bases such as triethylamine, N,N-dimethylaniline or pyridine, or inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium tert-butoxide or potassium tert-butoxide.

[0069] The compound of formula III can be prepared from the corresponding acid (commercially available). The method can be referred to WO2009123714.

[0070] Method 2:

[0071]

[0072] The compound of formula IV is reacted with the compound of formula V in a suitable solvent at a temperature ranging from -10°C to the boiling point of the suitable solvent for 0.5-48 hours to obtain the target compound I.

[0073] 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.

[0074] Adding a suitable base to the reaction system may be beneficial to the reaction. Suitable bases are selected from organic bases such as triethylamine, N,N-dimethylaniline or pyridine, or inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium tert-butoxide or potassium tert-butoxide.

[0075] The compound of formula V can be prepared from the corresponding acid (commercially available). The method can be referred to WO2009123714.

[0076] The preparation method of the compound of formula II is as follows:

[0077]

[0078] A compound of formula VI (commercially available) and a compound of formula VII (commercially available) are reacted in a suitable base and solvent with a suitable activating agent at a temperature of -10°C to the boiling point of the suitable solvent for 0.5-48 hours to produce a compound of formula II; the suitable solvent is selected from petroleum ether, hexane, benzene, toluene, chlorobenzene, ethyl acetate, acetonitrile, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, pyridine, 2-methylpyridine, 3-methylpyridine, or 4-methylpyridine. The suitable activating agent is selected from phosgene, triphosgene, CDI, DCC, thionyl chloride, oxalyl chloride, phosphorus oxychloride, or phosphorus pentachloride. The suitable base is selected from N-methylimidazole or DMAP.

[0079] The preparation method of the compound of formula IV can refer to the preparation method of formula II.

[0080] The compounds of Formula I, their stereoisomers, or agriculturally acceptable salts of the compounds of Formula I and their isomers of the present invention exhibit herbicidal activity and can be used to control various weeds in agriculture. Compared to compounds disclosed in the prior art, the pyrazole amide compounds of the present invention not only exhibit excellent herbicidal activity but are also safe for crops.

[0081] The present invention also includes a herbicidal composition comprising a compound of formula I, a stereoisomer thereof, or an agriculturally acceptable salt of a compound of formula I or an isomer thereof as an active ingredient. The active ingredient is present in an amount of 1-99% by weight in the herbicidal composition. The herbicidal composition also includes an agriculturally acceptable carrier.

[0082] The herbicidal compositions of the present invention can be applied in a variety of formulations. Typically, the compounds of the present invention are dissolved or dispersed in a carrier to prepare formulations that facilitate their dispersibility when used as herbicides. For example, these chemical formulations can be formulated as wettable powders or emulsifiable concentrates. Therefore, these compositions require at least one liquid or solid carrier and typically require the addition of a suitable surfactant.

[0083] The present invention also provides a method for controlling weeds, comprising applying a herbicidally effective amount of the herbicidal composition of the present invention to the weeds, the locus where the weeds grow, or the surface of the growth medium thereof. A preferred effective dose is 1 to 1000 grams per hectare, with a preferred effective dose being 10 to 500 grams per hectare. For certain applications, one or more other herbicides may be added to the herbicidal composition of the present invention to provide additional advantages and effects.

[0084] The compounds of the present invention can be used alone or in combination with other known insecticides, fungicides, plant growth regulators or fertilizers.

[0085] It should be understood that various changes and modifications can be made within the scope of the present invention as defined by the claims.

[0086] The advantages of the present invention are:

[0087] Compared with known benzamide compounds, the general formula compound of the present invention contains a benzoyl group and a cinnamoyl group as substitutions and has a novel structure. In addition, the amide compound of the present invention has unexpectedly high herbicidal activity, even at a lower dosage. It is not only highly effective, but also reduces the amount of pesticide used, lowers costs, and reduces pollution to the environment. DETAILED DESCRIPTION

[0088] The following examples and biological test results can be used to further illustrate the present invention, but are not intended to limit the present invention.

[0089] Synthesis Example

[0090] Example 1, Synthesis of Compound 1-1:

[0091] (1) Synthesis of N-(1-methyl-tetrazol-5-yl)-2-methylsulfonyl-4-trifluoromethylbenzamide

[0092]

[0093] To the reaction flask, 2-methylsulfonyl-4-trifluoromethylbenzoic acid (19.1 g, 71.2 mmol), 1-methyl-5-aminotetrazole (8.5 g, 85.4 mmol), 3-methylpyridine (100 ml), N-methylimidazole (11.7 g, 142.0 mmol) were added and stirred at room temperature for half an hour. The mixture was cooled to below 10 degrees Celsius in an ice-water bath and thionyl chloride (13.6 g, 114.0 mmol) was slowly added dropwise. The mixture was stirred at room temperature for 2 hours, the temperature was raised to 50 degrees Celsius and the reaction was kept warm for 2 hours. The mixture was cooled to below 10 degrees Celsius in an ice-water bath and cold water was slowly added dropwise. Solid precipitated and filtered. The filter cake was washed twice with 100 ml of water and dried to give 17.5 g of an off-white solid with a yield of 70%.

[0094] (2) Synthesis of cinnamoyl chloride

[0095]

[0096] Cinnamic acid (10.0 g, 67.5 mmol), dichloromethane (300 ml) and DMF (3 drops) were added to a reaction flask, and oxalyl chloride (42.8 g, 337.5 mmol) was slowly added. The mixture was stirred at room temperature for 2 hours, and the solvent was evaporated under reduced pressure. Toluene (150 ml) was added to the residue, stirred for 3 minutes, and the solvent was evaporated under reduced pressure to obtain 11.3 g of a yellow solid, which was used directly in the next step.

[0097] (3) Synthesis of compound 1-1

[0098]

[0099] To a reaction flask were added N-(1-methyl-tetrazol-5-yl)-2-methanesulfonyl-4-trifluoromethylbenzamide (1.2 g, 3.4 mmol), dichloromethane (20 ml), and triethylamine (0.7 g, 6.8 mmol). A solution of cinnamoyl chloride in dichloromethane (1.1 g, 6.8 mmol dissolved in 15 ml of dichloromethane) was then added dropwise. The mixture was stirred at room temperature for 40 minutes. The solvent was evaporated under reduced pressure. Ethyl acetate (50 ml) was added to the residue, and the mixture was extracted with water (50 ml). The organic phase was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was separated by column chromatography to obtain 1.3 g of a light yellow solid with a purity of 94% and a yield of 82%.

[0100] Example 2, Synthesis of Compound 1-24:

[0101] (1) Synthesis of N-(1-methyl-tetrazol-5-yl)-2-chloro-3-methoxymethyl-4-methylsulfonylbenzamide

[0102]

[0103] To the reaction flask, 2-chloro-3-methoxymethyl-4-methanesulfonylbenzoic acid (5.0 g, 17.9 mmol), 1-methyl-5-aminotetrazole (2.1 g, 21.5 mmol), 3-methylpyridine (30 ml), N-methylimidazole (3.0 g, 35.9 mmol) were added and stirred at room temperature for half an hour. The mixture was cooled to below 10 degrees Celsius in an ice-water bath and thionyl chloride (3.4 g, 28.7 mmol) was slowly added dropwise. The mixture was stirred at room temperature for 2 hours, the temperature was raised to 50 degrees Celsius and the reaction was kept warm for 2 hours. The mixture was cooled to below 10 degrees Celsius in an ice-water bath and cold water was slowly added dropwise. Solid precipitated and filtered. The filter cake was washed twice with 30 ml of water and dried to give 3.29 g of an off-white solid with a yield of 51%.

[0104] (2) Synthesis of Compound 1-24

[0105]

[0106] To a reaction flask, add N-(1-methyl-tetrazol-5-yl)-2-chloro-3-methoxymethyl-4-methanesulfonylbenzamide (0.5 g, 1.4 mmol), dichloromethane (20 ml), and triethylamine (0.3 g, 2.8 mmol). Then, add dropwise a prepared dichloromethane solution of cinnamoyl chloride (0.5 g of cinnamoyl chloride dissolved in 15 ml of dichloromethane). Stir at room temperature for 40 minutes, evaporate the solvent under reduced pressure, and add ethyl acetate (50 ml) to the residue. Extract the mixture with water (50 ml). The organic phase is washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and evaporated under reduced pressure to remove the solvent. The residue is separated by column chromatography to obtain 0.4 g of a light yellow solid with a purity of 95% and a yield of 56%.

[0107] Example 3, Synthesis of Compound 1-41:

[0108] (1) Synthesis of N-(1-methyl-tetrazol-5-yl)cinnamamide

[0109]

[0110] Cinnamic acid (5.0 g, 33.7 mmol), 1-methyl-5-aminotetrazole (3.7 g, 37.1 mmol), 3-methylpyridine (50 ml), and N-methylimidazole (5.5 g, 67.5 mmol) were added to the reaction flask and stirred at room temperature for half an hour. The mixture was cooled to below 10 degrees Celsius in an ice-water bath and thionyl chloride (6.4 g, 54.0 mmol) was slowly added dropwise. The mixture was stirred at room temperature for 2 hours, and the temperature was raised to 50 degrees Celsius and kept for 2 hours. The mixture was cooled to below 10 degrees Celsius in an ice-water bath and cold water was slowly added dropwise. Solid precipitated and filtered. The filter cake was washed twice with 50 ml of water and dried to give 3.3 g of a yellow solid with a yield of 42%.

[0111] (2) Synthesis of 2-chloro-3-{[(tetrahydrofuran-2-yl)methoxy]methyl}-4-methylsulfonylbenzoyl chloride

[0112]

[0113] To a reaction flask were added 2-chloro-3-{[(tetrahydrofuran-2-yl)methoxy]methyl}-4-methanesulfonylbenzoic acid (1.3 g, 3.8 mmol), dichloromethane (20 ml) and DMF (1 drop), and oxalyl chloride (2.4 g, 19.0 mmol) was slowly added. The mixture was stirred at room temperature for 2 hours, and the solvent was evaporated under reduced pressure. Toluene (10 ml) was added to the residue, stirred for 3 minutes, and the solvent was evaporated under reduced pressure to obtain 1.3 g of a yellow solid, which was used directly in the next step.

[0114] (3) Synthesis of Compound 1-41

[0115]

[0116] To a reaction flask were added N-(1-methyltetrazol-5-yl)cinnamamide (0.4 g, 1.9 mmol), dichloromethane (20 ml), and triethylamine (0.4 g, 3.8 mmol). A dichloromethane solution of 2-chloro-3-{[(tetrahydrofuran-2-yl)methoxy]methyl}-4-methanesulfonylbenzoyl chloride (1.3 g of 2-chloro-3-{[(tetrahydrofuran-2-yl)methoxy]methyl}-4-methanesulfonylbenzoyl chloride dissolved in 15 ml of dichloromethane) was then added dropwise. The mixture was stirred at room temperature for 40 minutes. The solvent was evaporated under reduced pressure, and ethyl acetate (50 ml) was added to the residue. The mixture was then separated and extracted with water (50 ml). The organic phase was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was separated by column chromatography to obtain 0.3 g of a yellow solid with a purity of 88% and a yield of 25%.

[0117] By replacing the starting materials according to the method described above, other compounds of general formula I can be obtained. Some compounds of general formula I are shown in Tables 1 and 2; wherein, in Table 1, W is selected from CX2 and the stereo configuration is trans; in Table 2, W is selected from N and the stereo configuration is trans.

[0118] The compound of formula I, wherein W is CX2 and the stereo configuration is trans.

[0119]

[0120] Table 1 Structures and physical properties of some compounds of formula I

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136] Table 1 Some compounds 1 H NMR (600 MHz, DMSO-d6) data are as follows:

[0137] Compound 1-1: 8.40 (s, 1H), 8.28 (d, 1H), 8.18 (d, 1H), 7.79 (d, 1H), 7.63 (d, 2H),

[0138] 7.40-7.47(m,3H),6.56(s,1H),4.17(s,3H),3.41(s,3H).

[0139] Compound 1-8: 8.39 (s, 1H), 8.31 (s, 1H), 8.27 (d, 1H), 8.16 (d, 1H), 7.70 (d, 1H), 7.34 (s, 1H), 7.17 (d, 1H), 6.96 (d, 1H), 6.09 (s, 2H), 4.16 (s, 3H), 3.39 (s, 3H).

[0140] Compound 1-12:8.78(s,1H),8.52(s,1H),8.27(s,1H),7.79(d,1H),7.65(s,2H),

[0141] 7.42-7.45(m,3H),6.56(d,1H),4.22(s,3H),3.46(s,3H).

[0142] Compound 1-13: 8.76 (s, 1H), 8.50 (d, 1H), 8.24 (d, 1H), 7.70 (d, 1H), 7.37 (s, 1H), 7.18 (d, 1H), 6.96 (d, 1H), 6.07-6.09 (m, 3H), 4.20 (s, 3H), 3.46 (s, 3H).

[0143] Compound 1-14: 8.43 (d, 1H), 8.07 (dd, 1H), 7.98 (d, 1H), 7.79 (d, 1H), 7.65 (d, 2H), 7.41-7.43 (m, 3H), 6.65 (d, 1H), 4.17 (s, 3H).

[0144] Compound 1-15: 7.81-7.83 (m, 3H), 7.67 (d, 2H), 7.59 (d, 1H), 7.43-7.47 (m, 3H), 6.90 (d, 1H), 4.09 (s, 3H).

[0145] Compound 1-16: 7.80-7.82 (m, 2H), 7.72-7.75 (m, 1H), 7.58 (dd, 1H), 7.34 (s, 1H), 7.22 (d, 1H), 6.98 (d, 1H), 6.65 (d, 1H), 6.10 (s, 2H), 4.08 (s, 3H).

[0146] Compound 1-17: 8.14 (s, 1H), 8.10 (d, 1H), 8.02 (d, 1H), 7.83 (d, 1H), 7.67 (d, 2H), 7.42-7.49 (m, 3H), 6.82 (s, 1H), 4.14 (s, 3H), 3.35 (s, 3H).

[0147] Compound 1-18: 8.14 (s, 1H), 8.08 (d, 1H), 8.01 (dd, 1H), 7.74 (d, 1H), 7.37 (s, 1H), 7.22 (d, 1H), 6.98 (d, 1H), 6.56 (d, 1H), 6.10 (s, 2H), 4.12 (s, 3H), 3.36 (s, 3H).

[0148] Compound 1-19: 8.03 (d, 1H), 7.89 (d, 1H), 7.82 (d, 1H), 7.66 (d, 2H), 7.39-7.49 (m, 3H), 6.79 (d, 1H), 4.14 (s, 3H), 3.32 (s, 3H), 2.72 (s, 3H).

[0149] Compound 1-20: 8.02 (d, 1H), 7.88 (d, 1H), 7.73 (d, 1H), 7.36 (s, 1H), 7.21 (d, 1H), 6.98 (d, 1H), 6.54 (d, 1H), 6.10 (s, 2H), 4.13 (s, 3H), 3.34 (s, 3H), 2.72 (s, 3H).

[0150] Compound 1-21: 8.02 (d, 1H), 7.87 (d, 1H), 7.78 (d, 1H), 7.63 (d, 2H), 6.98 (d, 2H), 6.58 (d, 1H), 4.13 (s, 3H), 3.80 (s, 3H), 3.33 (s, 3H), 2.72 (s, 3H).

[0151] Compound 1-22: 8.03 (d, 1H), 7.86-7.91 (m, 2H), 7.71-7.76 (m, 6H), 7.49 (t, 2H), 7.41 (t, 1H), 6.82 (d, 1H), 4.15 (s, 3H), 3.34 (s, 3H), 2.73 (s, 3H).

[0152] Compound 1-24: 8.10 (d, 1H), 8.06 (d, 1H), 7.82 (d, 1H), 7.66 (d, 2H), 7.42-7.49 (m, 3H), 6.76 (d, 1H), 4.95 (s, 2H), 4.15 (s, 3H), 3.39 (s, 3H), 3.35 (s, 3H).

[0153] Compound 1-41: 8.06-8.11 (m, 2H), 7.82 (d, 1H), 7.65 (d, 2H), 7.43-7.48 (m, 4H), 5.06 (s, 2H), 4.15 (s, 3H), 3.69-3.72 (m, 1H), 3.50-3.62 (m, 4H), 3.38 (s, 3H), 1.75-1.78 (m, 3H), 1.49-1.54 (m, 1H).

[0154] Compound 1-53: 8.09 (s, 2H), 7.82 (d, 1H), 7.66 (d, 2H), 7.43-7.47 (m, 3H), 6.78 (d, 1H), 5.05 (s, 2H), 4.16 (s, 3H), 3.68 (s, 2H), 3.49 (s, 2H), 3.37 (s, 3H), 3.23 (s, 3H).

[0155] Compound 1-90: 8.15 (d, 1H), 8.07 (d, 1H), 7.85 (d, 1H), 7.67 (d, 2H), 7.43-7.48 (m, 3H), 6.76 (d, 1H), 4.16 (s, 3H), 3.48 (s, 3H).

[0156] Compound 1-97: 7.81 (d, 1H), 7.75 (d, 1H), 7.67-7.68 (m, 3H), 7.44-7.49 (m, 3H), 7.07 (d, 1H), 4.06-4.11 (m, 5H), 3.74 (t, 2H), 3.36 (s, 3H), 3.33 (s, 3H), 2.44 (s, 3H).

[0157] Compound 1-154: 8.25 (s, 1H), 8.22 (d, 1H), 8.05 (d, 1H), 7.93 (d, 1H), 7.75-7.77 (m, 2H), 7.73 (s, 1H), 7.46-7.50 (m, 3H), 3.63 (s, 3H), 2.66 (s, 3H).

[0158] The compound of formula I, wherein W is N and the stereo configuration is trans.

[0159]

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

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172] Biotest Examples

[0173] Example 4: Determination of herbicidal activity

[0174] Broadleaf weeds (zinnia, velvetleaf) or grass weeds (setaria, barnyard grass) seeds were sown in 7 cm diameter paper cups filled with nutrient soil, covered with 1 cm of soil after sowing, pressed and watered, and then cultured in a greenhouse according to conventional methods. After the weeds reached the 2-3 leaf stage, the stems and leaves were sprayed.

[0175] After the original drug was dissolved in acetone, the test solution of the required concentration was prepared by adding 1‰ Tween 80 to tap water according to the test requirements. According to the designed dose, the spray treatment was carried out on a crawler crop sprayer (designed and produced by Engineer Research Ltd., UK) (spray pressure 1.95kg / cm 2 , spray volume 500L / hm 2 , crawler speed 1.48 km / h). The test was repeated three times. After treatment, the test materials were placed in the operating hall. After the pesticide solution dried naturally in the shade, they were placed in the greenhouse and managed according to conventional methods. The response of the weeds to the pesticide was observed and recorded. After treatment, the control effect of the test pesticide on weeds was visually inspected regularly. The control effect is expressed on a scale of 0 to 100%, with "0" representing no control effect and "100%" representing complete kill.

[0176] The test results show that the compounds of general formula I generally have high control effects on a variety of weeds. Among some of the tested compounds, such as compounds 1-1, 1-8, 1-15, 1-17, 1-19, 1-24, 1-41, and 1-53, the application dose is 600 g ai / hm 2 It has good control effect on zinnia, velvetleaf, foxtail grass or barnyard grass, with a control effect greater than or equal to 90%.

[0177] According to the above test method, some compounds of general formula I were selected and KC were tested for their activity against zinnia and velvetleaf. The results are shown in Table 3.

[0178] Table 3: Activity of some compounds of formula I and control compound KC against zinnia and velvetleaf

[0179] (Post-emergence, prevention effect%)

[0180]

[0181] The compound of the general formula of the present invention is safe to crops such as wheat, rice or corn.

[0182] The general compound of the present invention has herbicidal activity, is safe to crops, and can be used for preventing and controlling various weeds in agriculture.

Claims

1. A cinnamamide compound, characterized in that: The compound is shown in the general formula I: Where: X1 and X3 are independently selected from halogen, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C1-C6 alkyl or C1-C6 haloalkyl; W is selected from CX2; X2 is selected from Y1oxy C1-C6 alkyl; Y1 is selected from C1-C6 alkyl or C1-C6 alkoxy C1-C6 alkyl; Q is selected from ； R1 to R5 are each independently selected from hydrogen; R6 is selected from C1-C6 alkyl or C1-C6 haloalkyl; The hydrogen atoms on the carbon-carbon double bond B of the compound of the general formula I are on both sides of the bond B; or, the compound of the general formula I is an agriculturally acceptable salt.

2. The compound according to claim 1, characterized in that In the general formula I: X1 and X3 are independently selected from halogen, C1-C3 alkylsulfonyl, C1-C3 alkylsulfinyl, C1-C3 alkyl or C1-C3 haloalkyl; W is selected from CX2; X2 is selected from Y1oxy C1-C3 alkyl; Y1 is selected from C1-C6 alkyl or C1-C6 alkoxy C1-C6 alkyl; Q is selected from ； R1 to R5 are each independently selected from hydrogen; R6 is selected from C1-C6 alkyl.

3. The compound according to claim 2, characterized in that In the general formula I: X1 and X3 are independently selected from halogen, C1-C3 alkylsulfonyl, C1-C3 alkyl or C1-C3 haloalkyl; W is selected from CX2; X2 is selected from Y1oxy C1-C3 alkyl; Y1 is selected from C1-C6 alkyl or C1-C6 alkoxy C1-C6 alkyl; Q is selected from ； R1 to R5 are each independently selected from hydrogen; R6 is selected from methyl or ethyl.

4. Use of the compound of general formula I according to claim 1, characterized in that: Use of the compound of general formula I or the agriculturally acceptable salt of the compound of general formula I in controlling weeds.

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

6. A method for controlling weeds using the herbicidal composition according to claim 5, characterized in that: Applying a herbicidally effective amount of the herbicidal composition according to claim 5 to weeds or a growth medium or site of weeds.

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