WO2019196731A1 - Substituted pyrazolyl pyrazole sulfonylurea compound or pesticide acceptable salt or composition thereof and use thereof - Google Patents

Abstract

The present invention relates to the field of pesticides, and in particular to a substituted pyrazolyl pyrazole sulfonylurea compound or a pesticide acceptable salt or composition thereof and the use thereof. Said compound has a structure of formula (I). The definitions of groups in formula (I) are as shown in the description. The compound having a substituted pyrazolyl pyrazole sulfonylurea structure of the present invention has higher herbicidal activities than known compounds, and especially has excellent herbicidal activities against common weeds in paddy fields.

Description

Substituted pyrazolyl pyrazole sulfonylurea compound or pesticide acceptable salt thereof, composition and use thereof Technical field

The invention belongs to the technical field of pesticides, in particular to a substituted pyrazolyl pyrazole sulfonylurea compound or a pesticide acceptable salt or composition thereof, and relates to these compounds or their agriculturally acceptable salts and compositions. Use as a herbicide.

Background technique

The substituted pyrazole derivatives are known to have herbicidal activity. The pyrazole sulfonylurea compound and its herbicidal activity are described in the patent application No. CN200580013624.6, and the related pyrazolyl sulfonylurea compounds are also disclosed in CN94195190.1. in. However, for important crops, the activity of these compounds may not be high enough or there may be selectivity issues. However, in the prior art, a pyrazole sulfonylurea compound in which a substituent is bonded to a pyrazole ring of a pyrazole ring is not specifically disclosed.

technical problem

In order to solve the above problems in the prior art, the present invention provides a substituted pyrazolyl pyrazole sulfonylurea compound or a pesticide acceptable salt, composition and use thereof. Surprisingly, the above-mentioned pyrazolyl pyrazole sulfonylurea-based compound or its as an agrochemically acceptable salt has higher herbicidal activity than known compounds, and particularly has excellent herbicidal activity against common weeds in paddy fields.

Technical solution

The technical scheme adopted by the present invention for achieving the above object is: a substituted pyrazolyl pyrazole sulfonylurea compound or a pesticide acceptable salt thereof, and the structural formula is as follows:

In the formula,

R ₁ represents H, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylthio, halogenated C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkoxy Base, halogenated C ₁ -C ₆ alkoxy;

R ₂ represents H, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylthio, halogenated C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkoxy Base, halogenated C ₁ -C ₆ alkoxy;

Or, R ₁ and R ₂ together form a group -(CH ₂ ) _m -, m represents 1-6;

R ₃ represents H or halogen;

CN、卤素、NO ₂、COOR ₁、CONR ₁R ₂； R ₄ represents H,

CN, halogen, NO ₂ , COOR ₁ , CONR ₁ R ₂ ;

R ₅ represents H or halogen;

R ₆ represents a C ₁ -C ₆ alkyl group, a halogenated C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkylthio group, a C ₁ -C ₆ alkylthio group substituted C ₁ -C ₆ alkyl group, halogenated C ₁ -C ₆ alkylthio, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, halogenated C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkylthio, C ₂ -C ₆ Alkenyloxy, C ₁ -C ₆ alkoxy, halo C ₁ -C ₆ alkoxy or C ₁ -C ₆ alkoxy substituted C ₁ -C ₆ alkoxy, either unsubstituted or 1-5 independently selected from halogen, nitro, cyano, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogenated C ₁ -C ₆ alkane Oxyl, C ₁ -C ₆ alkylcarbonyl, halogenated C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkylsulfonyl, halogenated C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ alkoxy Carbonyl group, halogenated C ₁ -C ₆ alkoxycarbonyl group, C ₁ -C ₆ alkylaminocarbonyl group, halogenated C ₁ -C ₆ alkylaminocarbonyl group, carboxyl group, aldehyde group, hydroxyl group, C ₁ -C ₆ alkane Oxy-substituted C ₁ -C ₆ alkoxy, C ₃ -C ₆ cycloalkyl, halogenated C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyloxy, C ₃ -C ₆ ring Alkyloxycarbonyl, C ₃ -C ₆ cycloalkylaminecarbonyl, C ₃ -C ₆ heterocyclyl, C ₃ -C ₆ heterocyclyloxy, C ₃ -C ₆ heterocyclyloxycarbonyl, C ₃ - C ₆ heterocycle An aryl group substituted with a group in a C ₁ -C ₆ alkyl-substituted C ₃ -C ₆ heterocyclic group or a C ₁ -C ₆ alkoxy-substituted C ₁ -C ₆ alkoxy group, a heteroaryl group, an arylamino group, a heteroarylamino group, an aralkyl group, a heteroarylalkyl group, an aryloxy group, a heteroaryloxy group or a cyclo-ring group; that is, R ₆ may be selected from a C ₁ -C ₆ alkyl group, a halogen group. C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylthio substituted C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkylthio, C ₃ - C ₆ cycloalkyl, C ₂ -C ₆ alkenyl group, a halo-C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkenyl group, C ₂ -C ₆ alkenyloxy, C ₁ -C ₆ alkoxy a halogenated C ₁ -C ₆ alkoxy group or a C ₁ -C ₆ alkoxy-substituted C ₁ -C ₆ alkoxy group, or R ₆ may be selected from unsubstituted aryl, hetero An aryl group, an arylamino group, a heteroarylamino group, an aralkyl group, a heteroarylalkyl group, an aryloxy group, a heteroaryloxy group or a cis- ring group, or R ₆ may be selected from an aryl group substituted with 1 to 5 substituents. a heteroaryl group, an arylamino group, a heteroarylamino group, an aralkyl group, a heteroarylalkyl group, an aryloxy group, a heteroaryloxy group or a cycloalkyl group, the aforementioned substituents being freely selected from the group consisting of halogen, nitro and cyanogen group, C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkyl , C ₁ -C ₆ alkoxy, halo C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylcarbonyl, halo C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkylsulfonyl group, a halogen C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ alkoxycarbonyl, halogenated C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ alkylaminocarbonyl, halogenated C ₁ -C ₆ Alkylaminocarbonyl, carboxyl, aldehyde, hydroxy, C ₁ -C ₆ alkoxy substituted C ₁ -C ₆ alkoxy, C ₃ -C ₆ cycloalkyl, halogenated C ₃ -C ₆ cycloalkyl , C ₃ -C ₆ cycloalkyloxy, C ₃ -C ₆ cycloalkyloxycarbonyl, C ₃ -C ₆ cycloalkylaminecarbonyl, C ₃ -C ₆ heterocyclyl, C ₃ -C ₆ heterocycle Alkoxy, C ₃ -C ₆ heterocyclyloxycarbonyl, C ₃ -C ₆ heterocyclylaminocarbonyl, C ₁ -C ₆ alkyl substituted C ₃ -C ₆ heterocyclyl or C ₁ -C ₆ alkane a group in an oxy-substituted C ₁ -C ₆ alkoxy group.

Further, in the formula (I), R ₁ and R ₂ together form a group -(CH ₂ ) _m -, and m represents 1-4.

Further, in the formula (I), R ₁ represents H, C ₁ -C ₄ alkyl;

R ₂ represents H, C ₁ -C ₄ alkyl;

Or, R ₁ and R ₂ together form a group -(CH ₂ ) _m -, m represents 3-4;

R ₃ represents H or halogen;

CN、卤素、NO ₂、CONR ₁R ₂； R ₄ represents H,

CN, halogen, NO ₂ , CONR ₁ R ₂ ;

R ₅ represents H or halogen;

R ₆ represents a C ₁ -C ₆ alkyl group, a halogenated C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkylthio group, a C ₁ -C ₆ alkylthio group substituted C ₁ -C ₆ alkyl group, halogenated C ₁ -C ₆ alkylthio, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, halogenated C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkylthio, C ₂ -C ₆ Alkenyloxy, C ₁ -C ₆ alkoxy, halo C ₁ -C ₆ alkoxy or C ₁ -C ₆ alkoxy substituted C ₁ -C ₆ alkoxy, either unsubstituted or 1-5 independently selected from halogen, nitro, cyano, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogenated C ₁ -C ₆ alkane Oxy group, C ₁ -C ₆ alkylcarbonyl group, C ₁ -C ₆ alkylsulfonyl group, C ₁ -C ₆ alkoxycarbonyl group, C ₁ -C ₆ alkylaminocarbonyl group, carboxyl group, aldehyde group, hydroxyl group, C ₁ -C ₆ alkoxy-substituted C ₁ -C ₆ alkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyloxy, C ₃ -C ₆ cycloalkyloxycarbonyl, C ₃ -C ₆ cycloalkylaminecarbonyl, C ₃ -C ₆ heterocyclyl, C ₃ -C ₆ heterocyclyloxy, C ₃ -C ₆ heterocyclyloxycarbonyl or C ₁ -C ₆ alkyl substituted C ₃ -C ₆ heterocyclyl group substituted aryl group, a heteroaryl group, an aryl group, heteroaryl group, aralkyl, heteroaralkyl, aryloxy, or heteroaryloxy .

Further, in the formula (I), the aryl group is a phenyl group, a naphthyl group, and the heteroaryl group is a thiazole, a furan, a pyrrole, a thiophene, an imidazole, a pyran, a pyridine, a pyrazole, a pyrimidine, a pyrene, a fluorene. , pyrimidine, pyrazine, pyridazine, triazine, benzothiazole, benzofuran, quinoline or oxazole.

Further, in the formula (I), R ₁ and R ₂ together form a group -(CH ₂ ) _m -, and m represents 4;

R ₃ represents H, fluorine, chlorine or bromine;

R ₄ represents H or CN;

R ₅ represents H;

R ₆ represents unsubstituted or 1-5 independently selected from the group consisting of fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, propyl, 3-trifluoropropyl, 3-trichloropropyl, Trifluoromethyl, trichloromethyl, methoxy, ethoxy, formyl, acetyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, carboxyl, aldehyde or hydroxy a substituted phenyl group, thiazolyl group, anilino group or a benzyl group; further, R ₆ represents a phenyl group substituted without a substituent, a thiazolyl group, an anilino group, a benzyl group or 1-3 independently selected from fluorine, Chlorine, bromine, nitro, cyano, methyl, ethyl, propyl, 3-trifluoropropyl, trifluoromethyl, methoxy, formyl, methoxycarbonyl or methylaminocarbonyl substituted benzene Base, anilino or benzyl.

Further, the structure of formula I is selected from:

The pesticide acceptable salt may be a salt obtained by reacting a substituted pyrazolyl pyrazole sulfonylurea compound of the present invention with a chemically acceptable acid, wherein the chemically acceptable acid may be a mineral acid. (such as hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid, etc.) or organic acids (such as oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid or benzoic acid, etc.); A salt obtainable by reacting a substituted pyrazolyl pyrazole sulfonylurea compound of the present invention with a chemically acceptable base, wherein the chemically acceptable base may be an inorganic base such as sodium hydroxide or hydroxide. Potassium, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate) or an organic base (such as trimethylamine, triethylamine, etc.).

Further, the pesticide acceptable salt may be a potassium salt, a sodium salt, an ammonium salt, a calcium salt, a pyridinium salt or a choline salt.

The present invention also discloses a herbicidal composition comprising a herbicidally effective amount of at least one of the substituted pyrazolyl pyrazole sulfonylurea compounds as described above or a pesticide acceptable salt thereof.

Preferably, a formulation carrier or formulation adjuvant is also included.

The present invention also discloses a method of controlling an unwanted plant comprising the herbicidally effective amount of a substituted pyrazolyl pyrazole sulfonylurea compound as described above or at least one of the pesticide acceptable salts. Or the herbicidal composition as described above is used on unwanted plants.

The present invention also discloses the use of a substituted pyrazolyl pyrazole sulfonylurea compound as described above or a herbicidal composition thereof as an agrochemically acceptable salt or a herbicidal composition as described above for controlling harmful plants.

In the definition of the structural formula of the above compounds, the terminology used has the following meanings:

C ₁ -C ₆ alkyl: a linear or branched alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group or a t-butyl group.

Halogen or halogen: refers to fluorine, chlorine, bromine, and iodine.

Halogenated C ₁ -C ₆ alkyl group: a straight or branched alkyl group having 1 to 6 carbon atoms, and a hydrogen atom on these alkyl groups may be partially or completely substituted by a halogen, for example, a chloromethyl group, Chloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, and the like.

C ₁ -C ₆ alkoxy group: a linear or branched alkyl group having 1 to 6 carbon atoms bonded to the structure via an oxygen atom bond.

Halogenated C ₁ -C ₆ alkoxy group: a straight or branched alkoxy group having 1 to 6 carbon atoms, and a hydrogen atom on these alkoxy groups may be partially or completely substituted by a halogen, for example, a chlorine group Oxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, and the like.

C ₁ -C ₆ alkylthio group: a linear or branched alkyl group having 1 to 6 carbon atoms bonded to a structure via a sulfur atom bond.

Halogenated C ₁ -C ₆ alkylthio group: a linear or branched alkylthio group having 1 to 6 carbon atoms, and a hydrogen atom on these alkylthio groups may be partially or completely substituted by a halogen atom, for example, chlorine. Methylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio and the like.

C ₁ -C ₆ alkoxy-substituted C ₁ -C ₆ alkoxy group: a group substituted with an alkoxy group having _{1 to 6} carbon atoms and having an alkoxy group having 1 to 6 carbon atoms as a substituent Group, such as

C ₃ -C ₆ heterocyclylaminocarbonyl: a group formed by linking an amino group obtained by substituting an amino group with a heterocyclic group having 3 to 6 carbon atoms as a substituent, such as a group.

C ₁ -C ₆ alkylcarbonyl: a group formed by linking an alkyl group having 1 to 6 carbon atoms to a carbonyl group, such as

C ₁ -C ₆ alkylsulfonyl group: a group formed by linking an alkyl group having 1 to 6 carbon atoms to a sulfonyl group, such as

C ₃ -C ₆ cycloalkyloxycarbonyl: a group formed by sequentially linking a cycloalkyl group having 3 to 6 carbon atoms to an oxygen atom or a carbonyl group, such as

Aryl: Any functional group or substituent derived from a simple aromatic ring.

Heteroaryl: a five- or six-membered ring containing one or more N, O, S heteroatoms such as pyridine, furan, thiophene, pyrazole, pyrimidine, pyrazine, pyridazine, triazine, quinoline, Thiazole, benzothiazole, benzofuran, and the like.

Aromatic amine group: an amine group obtained by substituting an aryl group as a substituent for an amino group.

Heteroaralkyl: an alkyl group obtained by substituting a hydrogen of an alkyl group as a substituent.

Heteroaryloxy: A heteroaryl group is bonded to an oxygen atom and bonded to the structure via an oxygen atom.

And a group of double or triple rings, such as

A method for synthesizing a compound of formula I, characterized by a compound of formula II and a compound of formula III (in the formulae listed below, as long as it is not otherwise defined, a substituent and a symbol and a substituent as defined in formula I) The same meaning as the symbol) The product is obtained after carrying out the reaction with or without a solvent. The compound represented by the general formula II can be synthesized by the method described in the patent JPS61191602A, and the compound represented by the general formula III can be synthesized by referring to the method described in the patent CN1060478C:

Wherein R ₁ represents H, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylthio, halo C ₁ -C ₆ alkylthio, C ₁ -C ₆ Alkoxy, halogenated C ₁ -C ₆ alkoxy;

R ₂ represents H, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylthio, halogenated C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkoxy Base, halogenated C ₁ -C ₆ alkoxy;

Or, R ₁ and R ₂ together form a group -(CH ₂ ) _m -, m represents 1-6;

R ₃ represents H or halogen;

CN、卤素、NO ₂、COOR ₁、CONR ₁R ₂； R ₄ represents H,

CN, halogen, NO ₂ , COOR ₁ , CONR ₁ R ₂ ;

R ₅ represents H or halogen;

R ₆ represents a C ₁ -C ₆ alkyl group, a halogenated C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkylthio group, a C ₁ -C ₆ alkylthio group substituted C ₁ -C ₆ alkyl group, halogenated C ₁ -C ₆ alkylthio, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, halogenated C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkylthio, C ₂ -C ₆ Alkenyloxy, C ₁ -C ₆ alkoxy, halo C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkoxy substituted C ₁ -C ₆ alkoxy or unsubstituted or 1- 5 independently selected from halogen, nitro, cyano, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogenated C ₁ -C ₆ alkoxy , C ₁ -C ₆ alkylcarbonyl, halogenated C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkylsulfonyl, halogenated C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ alkoxycarbonyl Halogenated C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ alkylaminocarbonyl, halogenated C ₁ -C ₆ alkylaminocarbonyl, carboxyl, aldehyde, hydroxy, C ₁ -C ₆ alkoxy Substituted C ₁ -C ₆ alkoxy, C ₃ -C ₆ cycloalkyl, halo C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyloxy, C ₃ -C ₆ cycloalkyl Oxycarbonyl, C ₃ -C ₆ cycloalkylaminecarbonyl, C ₃ -C ₆ heterocyclyl, C ₃ -C ₆ heterocyclyloxy, C ₃ -C ₆ heterocyclooxycarbonyl, C ₃ -C ₆ Heterocyclic amine a carbonyl group, an alkyl-substituted C ₃ -C ₆ heterocyclic group, a C ₁ -C ₆ alkoxy-substituted C ₁ -C ₆ alkoxy group-substituted aryl group, a heteroaryl group, an arylamine group, Heteroarylamino, aralkyl, heteroarylalkyl, aryloxy, heteroaryloxy, and cycloalkyl.

Further, the solvent is selected from the group consisting of acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, benzene, toluene, xylene, dichloroethane One or more solvents in ethyl acetate.

Further, the compound of the formula II and the formula III is reacted with a compound having a benzoate structure with or without a solvent to obtain a compound in which a sulfonylurea structure is bonded to an an alkoxycarbonyl-substituted anilino group.

The compounds of formula I of the present invention can be prepared as follows:

The compound represented by the formula I is obtained by reacting a compound of the formula II with a compound of the formula III under neutral conditions; the reaction can be carried out in the absence of a solvent or in a suitable solvent. Suitable solvents may be selected from, for example, chloroform, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, acetone, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, benzene, toluene, xylene, One or more solvents of N-methylpyrrolidone, dichloroethane, ethyl acetate, etc.; the reaction temperature may be between room temperature and the boiling point of the solvent, usually 20-100 ° C; the reaction time is 30 minutes to 24 Hours, usually 1-10 hours.

For many annual monocotyledonous and dicotyledonous harmful plants, the compounds of formula I of the present invention have outstanding herbicidal activity. The active substances of the present invention are also effective for perennial weeds which grow from rhizomes, rhizomes, or other perennial organs. As for the timing of use of the active substance of the present invention, it may be before sowing, before germination or after germination. With particular reference to representative examples of monocotyledonous and dicotyledonous weed populations which can be controlled by the compounds of the present invention, representative examples of weed species in which the active substance of the present invention can function effectively include monocotyledons: annual oats, ryegrass, Look at the genus Aquila, cockroach, genus, genus, and sedge, and perennial genus of Agropyron, Bermudagrass, Rhizoma and sorghum, and perennial sedge.

With regard to dicotyledonous weed species, species whose effects can be extended to, for example, the annual genus Polyporus, Amaranth, Pomna, Wild Sesame, Stellaria, Amaranthus, White Mustard, Ipomoea, and Yellow Flower Genus, Matricaria and genus, and perennial weeds, genus, genus and genus. The active substance of the present invention can still effectively control harmful plants under the specific conditions of rice seeding, such as cockroaches, genus, genus, genus, genus, cane, and sedge. If the compound of the present invention is applied to the surface of the soil before germination, the weeds of the weeds can be completely prevented before the weeds grow, or when the weeds grow out of the cotyledons, and finally completely die after three to four weeks. Although the compounds of the present invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, they are not harmful to important economic crop plants such as wheat, barley, rye, rice, corn, sugar beets, cotton, and soybeans, or The damage is very small. Thus, the compounds of the invention are highly suitable for the selective control of unwanted plants in agricultural or ornamental plants. In addition, the compounds of the invention can significantly modulate the growth of crop plants. By modulating the involvement of plant metabolism, these compounds are used to orient the components of the plant and promote harvesting, such as drying and dwarfing the plants. Moreover, they are also suitable for regulating and inhibiting unwanted plant growth without destroying the growth of the crop. Inhibition of plant growth plays a very important role in many monocotyledonous and dicotyledonous crops, as this reduces or completely prevents lodging.

The compound of the present invention can be applied using a general formulation, and a wettable powder, a soluble powder, an emulsifiable concentrate, an aqueous emulsion, a suspending agent, a dispersible oil suspension, a powder, a microcapsule suspension, a water-dispersible granule, a water-soluble granule can be used. Agents, etc. Thus the invention also provides a herbicidal composition comprising a compound of formula I. The compounds of formula I can be formulated in a variety of ways, depending on the usual biological and/or chemical physical parameters. Examples of suitable formulation options are: wettable powder (WP), wettable liquid (SL), soluble powder (SP), dispersible liquid (DC), aqueous (AS), microemulsion (ME), emulsifiable concentrate ( EC), water emulsion (EW), sprayable solution, suspending agent (SC), dispersible oil suspension (OD), powder (DP), microcapsule suspension (CS), water-dispersible granule (WG), water-soluble Granules (SG), large granules (GG), granules (GR) for aerosol and soil application, aerosol (AE), ultra low volume (ULV) and wax products. Necessary formulation auxiliaries such as inerts, surfactants, solvents and other additives.

Among the compounding preparations or tank mixes, suitable active substances which can be mixed with the active substance of the present invention are, for example, known substances in the "World Pesticide New Variety Technology Encyclopedia" (China Agricultural Science and Technology Press, 2010.9). For example, the herbicide active substance mentioned below may be mixed with the mixture of the formula I (note: the name of the compound, or a common name according to the International Organization for Standardization (ISO), or a chemical name, if appropriate, a code): Amine, butachlor, alachlor, propisochlor, metolachlor, stilben, acetochlor, chlorfenapyr, acetochlor, naproxen, R-levoperin Acetochlor, dipivoxil, thiaceuramide, dibenzoylamine, piracetamide, herbicide, flufenic acid, bromobutyramide, dimethoprim, high-efficiency dimethyl Thiachlor, acetophene, flufenacet, methoxymethafen, metazachlor, isoxachlor, high-efficiency wheat fluoromethyl ester, high-efficiency wheat fluoropropyl ester, dipropenamide, acetochlor , butyrylamine, cyclopropamide, flufenacetamide, heptylacetate, ibutachlor, propargylamine, chlorfenapyr, xetylene, dimethyl chloramine, chloramine, Trimethoprim, chloroformylamine, propyzamide, valproate, carbamachlor, neoxanthine, tricyclothiamatine, butachlor, forage, benzylamine, Indapamide, phenylsulfonamide, naphthylamine, acetochlor, naphthylamine, thiamatine, cyanochlor, benzodiazepine, turkey, chloropurine, butylamine, fluoropyridin Oxalamine, atrazine, simazine, chlorpyrifos, cyanaceton, cilostaz, chlorhexidine, chlorpyrifos, isopropyl, flufenate, tertidine, terbutin, triazine Amine, cyclopropazine, gansujin, chlordazin, chlorpyrifos, simazine, azide net, dichlorpyrifos, isoprene, chlorpyrifos, another dingjin, zhongdingtong, tedingtong, Methotrexate, cyanaceate, oxalozin, colazi, sputum, scutellaria, licorice, cyanuric acid, Indaziflam, chlorsulfuron, metsulfuron, bensulfuron-methyl, chlorsulfuron-methyl , benzosulfuron, thiasulfuron, pyrazosulfuron, methyl disulfuron, methyl iodsulfuron sodium, formylaminosulfuron, ethersulfuron, ether sulfuron, mesulfuron, smoke Sulfoxsulfuron, amphetsulfuron, sulfonamide, ethoxysulfuron, cyprosulfuron, sulfimsulfuron, tetrazincsulfuron, flazasulfuron, monosulfuron, monosulfur Ester, flufensulfuron, fluridine, flupirsulfuron, epoxy Sulfonamide, oxazolsulfuron-methyl, flusulfuron-methyl, propylsulfuron-methyl, trifluoropropanesulfuron, sulfonylsulfuron, triflusulfuron, flucarbazone, trifluorosulfuron, metsulfuron Sodium salt, flurbisulfuron, thiosulfuron-methyl, pyrimethanil, propyrisulfuron, pyrazursulfuron, acifluorfen, flufenazone, flufenacil , flufenacetate, oxyfluorfen, oxalic acid ether, dipyridamole, flufenacetate ethyl ester, carbaryl herbicide, trifluoromethane ether, methoxy herbicide ether, triflurane, Fluorinated herbicide ether, flufenic acid ether, herbicide ether, acetochlor, dimethyl oxalate, flufenacetate, flufenate, Halosafen, chloromeron, isoproturon, Ligulong, diuron , sapphire, fluroxypyr, benzothiazol, methamphetamine, benzalkon, sulfothyron, isoxon, tetrandil, acetylene, chlorbromide, methyl chlorpyrifos , oxacillin, methoxapril, bromogluta, methoxyuron, glutamate, chlorpyrifos, hyaluros, non-grass, thiosulfuron, chlorpyrifos, hazel, sedum, Xicaolong, Cyclosporon, Teflon, Butylthiazide, Kudzuron, Fluorone, methazamide, primate, trimethylisourea, oxazolone, Monisouron, Anisuron, Methiuron, Chlureturon, tetrafluorolong, beetin, beetin-ethyl ester, beet, sulforaphane, special grass Ling, oatmeal, aniline, chlorpheniramine, diclofenac, chlorpyrifos, chlorinated alkaloids, Carboxazole, Chlorprocarb, Fenasulam, BCPC, CPPC, Carbasulam, chlorpyrifos, grass, and grass Hecao Te, Wild Maidi, Piperdam, Hecao, Valerian, Ring Grass, Oats, Bactericide, Ethylthiophene, Pingcao Dan, Kecao Meng, Bencao Dan, Qiu Dan , thiamethasone, chlorfenapyr, Isopolinate, Methiobencarb, 2,4-butyl butyl ester, 2 methyl 4-chlorosodium chloride, 2,4-diisooctyl ester, 2 methyl 4-chloroisooctyl ester, 2,4-D Sodium salt, 2,4-D dimethylamine salt, 2 methyl 4-chloroethyl thioester, 2 methyl 4 chloro, 2,4-dipropionic acid, high 2,4-D-propionate, 2,4-dibutyl Acid, 2, 4-chloropropionic acid, 2, 4-chloropropionate, 2, 4-chlorobutyric acid, 2,4,5-indole, 2,4,5-propionic acid, 2,4,5-methyl Acid, 2,4,4 chloramine salt, dicamba, hibiscus, valeric acid, saison, trichlorobenzoic acid, aminodichlorobenzoic acid, methoxy trichloride Acid, grass herb, flurazepam, flupirtine, flupirtine, high-efficiency flupirtine, quizalofop, fine quizalofop, oxazolyl and oxazolidine Hecao Ling, valerate, cyhalofoprin, oxazolamide, clodinafop, thiazolyl, acetylene, valprofloxacin, trifluoromethane, estrone, paraquat , Diquat, Ansulphate, Ethylbutafluoride, Isoproterone, Metol-Lingling, Cyclopropanol, Aminopropionin, Ethyl Fluoride, Chloroflurane, Ethyltrifluoroethyl, Diltrin, chlorhexidine, Methalpropalin, propofol, glyphosate, samarium phosphine, glufosinate, methylammonium, sulforaphane, piperidin, bialaphos, disperse , oxalophos, chlorpyrifos, ruthenium phosphate, dimethicin, turf, imidazolium, imidazolium, imidazoquinone, imazamox, imazamox, amimidate Acid, imazethapyr, flufenoxyacetic acid, isooctyl chlorofluoropyroxyacetate, clopyralidic acid, ampicillin, triclopyridinic acid, flurazepam, haloformin, trichloropyridinol , thiacilidine, fluroxypyr, Citamidic acid, fluroxypyr, trichloropyroxyacetate butoxyethyl ester, Cliodinate, allene, butoxanes, thiazolone, chlorfen, benzophenone, butyl benzophenone, hydrazine Oxalone, pyrethone, Buthidazole, oxazinone, cycloazinone, oxazinone, oxazinone, Ametridione, Amibuzin, bromoxynil, octanoyl bromoxynil, octanoyl iodide, iodobenzene Nitrile, dichlorvotrile, diphenylacetonitrile, oxazolonitrile, hydroxydicarbonitrile, Iodobonil, oxasulfuron, diflufenacil, penoxsulam, sulfazolamide, chlorsulfuron , chlorfenapamide, acesulfame, furazo yellow, bispyribyl ether, pyrithione, cyclic ester, pyrimethanil, pyrimethanil, dicyclohexanone, mesotrione, sulfonate Oxalone, Tembotrione, Tefuryltrione, Bicyclopyrone, Ketodpiradox, Isoxaflutole, Isoxachlorone, Fenoxasulfone, Methiozolin, Isoprofen, Pyrazepam, Pyrazol, Wild Yant, Benzopyraz, Pyridine Oxalone, chlorhexidine, pyrasulfotole, oxazolone, Pyroxasulfone, oxazinamide, fluoxazole, chlorpyrifos, oxazolone, oxazolidinone, fluazole Oxalone, Methotrexate, Bencarbazone, Dipyrimazone, Fluroxypyrazine, Herbicide, Isochloridine, Cyclohexadel, Tesaldine, Flupropacil, Indolinone, Fluoric Acid, C Arsenicin, ethinamide, benzyl ether, Flumezin, pentachlorophenol (sodium), dinose, tromethool, tromethoate, pentoxide, dinitrophenol, chloronitrophenol, dexamethasone, Diloate, propargyl oxalofenone, oxadiazon, cyclopentazone, fluoxetamine, methyl oxazate, tetrazolam, flurazazine, herbicide, bromine, Dimethoate, valerian, oxazolone, valerian, valerian, Pyridafol, quinclorac, chloroquinoline, bentazon, valerate, oxazinone, herbicide Ling, Isooxalin, Cyclopentyl ether, Isopropyl oxalate, Propyl oxalate, oxadiazon, sodium chlorate, thatch, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoropropionic acid , forage fast, bromophenolphthalein, triazole sulfonate, triazodazole, furazolidone, fenfuransulfonate, pyrimethamine, chlorinated acid, fluroxypyr, valerian, acrolein, benzoic acid, extinction Grass ring, oat ester, thiazolamide, cotton amine Nitrate, oxybenzone, methoxybenzophenone, saflufenacil, chlorhexylphosphine, trichloropropionic acid, Alorac, Diethamquat, Etnipromid, Iprymidam, Ipfencarbazone, Thiencarbazonemethyl, Pyrimisulfan, Chlorflurazole, Tripropindan, Sulglycapin, Methionine Ling, Cambendichlor, cyprodinil, thiocyananilide, oxalofen, oxadiazepine, chlorpyrifos, oxacillin, oxaloquine, oxalic acid, oxalic acid, sulfacetonitrile, cumin, Pyrazolyl ester, furazosalazine, valerian, dibenzoxazole acid, dichloropropenylamine, fluorochloropyridinium ester, chlorofluoropyridinium ester.

Beneficial effect

In summary, due to the adoption of the above technical solutions, the beneficial effects of the present invention are:

By chemically modifying and molecularly designing the substituted pyrazolyl pyrazole compound, a sulfonylurea structure has been introduced, which has obtained a series of more efficient, better selective and safe methods for agricultural or forestry weeding. Herbicidally active compounds, especially for common weeds in paddy fields, have good activity and selectivity.

Embodiments of the invention

The technical solutions in the embodiments of the present invention will be clearly and completely described in the following with reference to the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention.

By considering the economics, diversity, and biological activity of the synthesized compounds, it is preferred that some of the compounds are listed in the following table. The specific compound structure is shown in Table 1, and the specific compound physical property data is shown in Table 2. The compounds in Table 1-2 are for illustrative purposes only and are not intended to limit the invention, and those skilled in the art should not understand that the scope of the present invention is limited to the following compounds.

Table 1 Structure of the compound of formula I

Table 2 ¹ H NMR data

Methods of preparing the compounds of the present invention are illustrated in the following technical schemes and examples. The starting materials can be purchased commercially or can be prepared by methods known in the literature or as shown in detail. Those skilled in the art will appreciate that other synthetic routes can also be utilized to synthesize the compounds of the present invention. Although specific materials and conditions in the synthetic route have been described below, they can be easily replaced with other similar materials and conditions, such as compounds produced by variations or variants of the preparation methods of the invention. Various isomers and the like are included in the scope of the present invention. Additionally, the methods of preparation described below can be further modified in accordance with the present disclosure, using conventional chemical methods well known to those skilled in the art. For example, the appropriate groups are protected during the reaction, and the like.

Example 1

2-(N-((1-(3-Cl-4,5,6,7-tetrahydropyrazolo[1,5A]pyridin-2-yl)4-cyano-1H-pyrazole-5-) Synthesis of carbamoyl)sulfonamide)methyl benzoate (Compound 1):

Add 5-amino-1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-A]pyridin-2-yl)-1H-pyrazole-4-A to the reaction flask 2.72 g (10 mmol) of nitrile and 30 mL of acetonitrile were added, and 2.4 g (10 mmol) of 2-sulfonyl isocyanate methyl benzoate was added with stirring. The reaction was stirred at room temperature for 6 h, and the reaction was observed by TLC (ethyl acetate: petroleum ether = 1:1, GF254 , UV color development), after completion of the reaction, the solvent was spun off, and the compound was purified by column chromatography to give the object compound 3.15 g, white solid powder, melting point: 110-112 ° C; ¹ H-NMR (CDCl ₃ -d ₆ , 500 MHz) δ: 8.12-8.09 (m, 1H), 7.79-7.76 (s, 1H), 7.72-7.69 (m, 1H), 7.48-7.54 (m, 2H), 4.34-4.30 (t, 2H), 3.90-3.86 (s, 3H), 2.73-2.69 (t, 2H), 1.73-1.69 (m, 2H), 1.46-1.42 (m, 2H).

Example 2

2-(N-((1-(3-Cl-4,5,6,7-tetrahydropyrazolo[1,5A]pyridin-2-yl)4-cyano-1H-pyrazol-5yl) Synthesis of carbamoylsulfonamide) benzoic acid (Compound 2):

To the reaction flask was added 2-(N-((1-(3-Cl-4,5,6,7-tetrahydropyrazolo[1,5A]pyridin-2-yl)4-cyano-1H-) Pyrazolyl-yl)carbamoylsulfonamide)methyl benzoate 5.03 g (10 mmol), methanol 30 mL, 0.41 g (1.1 mmol) of sodium hydroxide and 1 mL of water were added with stirring, and the reaction was stirred at room temperature for 6 h, and the reaction was followed by TLC. (ethyl acetate: petroleum ether = 1:1, GF254, UV color development), after the reaction was completed, the solvent was spun off, 50 mL of dichloromethane, 10 mL of saturated brine was added, and the solvent was separated, and the solvent was evaporated. The title compound was obtained as 2.93 g,yield of pale yellow solid powder, m.p.: 111-113 ° C; ¹ H-NMR (CDCl ₃ -d ₆ , 500 MHz) δ: 8.18-8.14 (d, 1H), 8.09-8.06 (d, 1H) ), 7.91-7.88(s,1H), 7.72-7.68(m,2H), 4.25-4.23(t,2H),2.82-2.78(t,2H),2.11-2.07(m,2H),1.97-1.92 (m, 2H).

Example 3

Synthesis of Compound 3:

Add 5-amino-1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-A]pyridin-2-yl)-1H-pyrazole-4carbonitrile to the reaction flask 2.62g (10mmol), 30mL of acetonitrile, add 2.6g (10mmol) of 2-((isocyanatesulfonyl)methyl)benzoate methyl ester under stirring, stir the reaction at room temperature for 6h, and observe the reaction by TLC (ethyl acetate: petroleum ether = 1:1, GF254, UV color development), after completion of the reaction, the solvent was spun off, and the compound was purified by column chromatography to give the object compound: 3.04 g, white solid powder, melting point: 115-117 ° C; ¹ H-NMR (CDCl ₃ - d ₆ , 500MHz) δ: 7.92-7.88 (d, 1H), 7.78-7.76 (s, 1H), 7.53-7.49 (d, 1H), 7.48-7.43 (m, 1H), 7.32-7.28 (m, 1H) ), 5.07-5.04 (s, 2H), 4.05-4.03 (t, 2H), 3.84-3.80 (s, 3H), 2.72-2.68 (t, 2H), 2.04-1.99 (m, 2H), 1.87-1.84 (m, 2H).

Example 4

Synthesis of Compound 4:

Add 5-amino-1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-A]pyridin-2-yl)-1H-pyrazole-4-A to the reaction flask 2.62 g (10 mmol) of nitrile and 30 mL of acetonitrile, 1.4 g (10 mmol) of chlorosulfonyl isocyanate was added with stirring, and the reaction was stirred at room temperature for 2 h. 1.5 g of methyl salicylate and 480 mg of sodium hydroxide were added under stirring at room temperature, and the reaction was followed by TLC. Ethyl acetate: petroleum ether = 1:1, GF254, UV color development). After the reaction was completed, the solvent was evaporated, and the compound was purified by column chromatography to give the title compound 3.63 g, pale yellow solid powder, melting point: 120-122 ° C; ¹ H-NMR (CDCl ₃ -d ₆ , 500 MHz) δ: 7.94 - 7.91 (m, 2H), 7.43 - 7.38 (m, 2H), 6.97 - 6.95 (m, 1H), 3.97 - 3.95 (s, 3H) , 3.84-3.81 (t, 2H), 2.82-2.78 (t, 2H), 2.08-2.04 (m, 2H), 1.89-1.84 (m, 2H).

Example 5

Synthesis of Compound 5:

Add 5-amino-1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-A]pyridin-2-yl)-1H-pyrazole-4-A to the reaction flask 2.62 g (10 mmol) of nitrile and 30 mL of acetonitrile were added, 1.4 g (10 mmol) of chlorosulfonyl isocyanate was added with stirring, and the reaction was stirred at room temperature for 2 h. 1.5 g of methyl anthranilate and 480 mg of sodium hydroxide were added under stirring at room temperature, and the reaction was followed by TLC. (ethyl acetate: petroleum ether = 1:1, GF254, UV color development). After the reaction was completed, the solvent was evaporated, and the compound was purified by column chromatography to give the title compound 3.28 g, white solid powder, melting point: 116-118 ° C; ¹ H-NMR (CDCl ₃ -d ₆ , 500 MHz) δ: 7.72-7.68 (m, 2H), 7.32-7.30 (m, 1H), 7.12-7.09 (m, 1H), 7.02-6.99 (m, 1H) , 4.01-3.99 (s, 3H), 3.82-3.79 (t, 2H), 2.72-2.70 (t, 2H), 2.06-2.03 (m, 2H), 1.93-1.91 (m, 2H).

Example 6

Synthesis of Compound 6:

Add 5-amino-1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-A]pyridin-2-yl)-1H-pyrazole-4-A to the reaction flask 2.52 g (10 mmol) of amide and 30 mL of acetonitrile were added, and 2.4 g (10 mmol) of 2-sulfonyl isocyanate methyl ester was added with stirring. The reaction was stirred at room temperature for 6 h, and the reaction was observed by TLC (ethyl acetate: petroleum ether = 1:1, GF254) , UV color development), after completion of the reaction, the solvent was spun off, and the compound was purified by column chromatography to give the title compound: 3.64 g, white solid powder, melting point: 135-137 ° C; ¹ H-NMR (CDCl ₃ -d ₆ , 500 MHz δ: 8.18-8.15 (m, 1H), 7.93-7.91 (m, 1H), 7.84-7.81 (m, 1H), 7.78-7.75 (m, 1H), 7.73-7.70 (m, 1H), 3.97- 3.95 (s, 3H), 3.82-3.79 (t, 2H), 2.72-2.70 (t, 2H), 2.06-2.03 (m, 2H), 1.93-1.91 (m, 2H).

Example 7

Evaluation of biological activity (post-emergence):

The test compound was dissolved in a small amount of acetone, and then diluted to the desired concentration with water containing 0.1% Tween 80. Prepare the nutrient soil into a paper cup with a diameter of 7cm, sprinkle the quantitative weed seeds into the paper cup, cover the soil 1.5cm after sowing, culture in the greenhouse after suppression and watering, and the seedlings and fixed plants after emergence (grass weed 10) -20 strains/cup, 2-4 plants/cup of broadleaf weeds, wait for 2-3 leaf stage of weeds, broadleaf weeds to 2-4 leaf stage, stalks with spray tower according to experimental design dose Leaf spray treatment, the test was set to 3 repetitions. After the drug solution is naturally air-dried, it is placed in the greenhouse and managed according to the conventional method. The growth and development of the test material are regularly observed. According to the pesticide indoor bioassay test standard, part 4, and according to the actual situation, it is regularly investigated by visual inspection after treatment. The control effect of the test agent on weeds. Control effect grading standards:

Grade 9: equivalent to 67.6-100% of weeds in the blank control area;

Grade 8: equivalent to 35.1-67.5% of weeds in the blank control area;

Grade 7: equivalent to 25.1-35% of weeds in the blank control area;

Level 6: equivalent to 15.1-25% of weeds in the blank control area;

Grade 5: equivalent to 10.1-15% of weeds in the blank control area;

Grade 4: equivalent to 5.1-10% of weeds in the blank control area;

Level 3: equivalent to 2.6-5% of weeds in the blank control area;

Grade 2: equivalent to 0-2.5% of weeds in the blank control area;

Level 1: All deaths.

)、对照化合物A(CAS登记号为194542-15-9、具体结构为

)进行了除草活性的平行测定。施药3周后的除草活性实验效果如下表所示： According to the above method, select some compounds (Compound No. 1-127) and Nicosulfuron (the specific structure is

), control compound A (CAS registration number is 194542-15-9, the specific structure is

) A parallel determination of herbicidal activity was performed. The experimental results of herbicidal activity after 3 weeks of application are shown in the following table:

Table 3 defense level

Through the above experiments, it can be found that the compound protected by the present invention has excellent biological activity and has a good commercial application prospect.

Example 8

Paddy field biological activity evaluation (post-emergence):

The test compound was dissolved in a small amount of acetone, and then diluted to the desired concentration with water containing 0.1% Tween 80. Prepare a special variegated flower pot with a diameter of 11cm, a bottom diameter of 7cm and a height of 11cm at 3/4 in the rice field. Add 120mL of water to each pot, mix the soil and water evenly and keep the surface smooth. . The quantitative weed seeds and rice seeds are sprinkled into the pots, the seeds are pressed into the soil, and placed in the greenhouse according to the conventional method (the water layer is always kept at about 2 cm), and the weeds grow to the 2-3 leaf stage. When the sputum sputum grows to the 2 leaf stage, the genus of the genus is up to the 2-3 leaf stage, and the rice grows to the 2-3 leaf stage, the application is designed according to the experimental design dose by the pipette (according to the dosage of 30g/ha, 15g/ Ha is applied, the specific application amount of the flower pot is converted according to the specific area of the flower pot, and each treatment is set to two repetitions. After the application, the growth and development of the test material are periodically observed in the greenhouse, and according to the actual situation, After the treatment, the control effect of the test agent on weeds and the safety of the crops were investigated by visual inspection. According to the pesticide indoor bioassay test guidelines, part 8 and part 9, according to the test symptoms and severity of the target weeds and crops, the herbicidal activity and crop safety of the pesticides are evaluated, and a uniform level is used for investigation:

Performance grading standards:

Grade 9: equivalent to 67.6-100% of weeds in the blank control area (this level is non-phytotoxic, no obvious phytotoxicity or slight phytotoxicity for crops);

Grade 8: equivalent to 35.1-67.5% of weeds in the blank control area;

Grade 7: equivalent to 25.1-35% of weeds in the blank control area;

Level 6: equivalent to 15.1-25% of weeds in the blank control area;

Grade 5: equivalent to 10.1-15% of weeds in the blank control area;

Grade 4: equivalent to 5.1-10% of weeds in the blank control area;

Level 3: equivalent to 2.6-5% of weeds in the blank control area;

Grade 2: equivalent to 0-2.5% of weeds in the blank control area;

Level 1: All deaths;

The main symptoms of phytotoxicity are:

1) color change (yellow, white, purple, etc.);

2) morphological changes (new leaf deformities, distortions, etc.);

3) Growth changes (dehydration, withering, dwarfing, clustering, etc.).

According to the above method, a part of the compound (Compound No. 1-6, Compound 9, Compound 12, Compound 15, Compound 17, Compound 20, Compound 31, Compound 35, Compound 49, Compound 51, Compound 53, Compound 55, Compound 62, Compound 85, compound 96) was tested in parallel with dioxazolidine for herbicidal activity and crop safety. The effects of weed control activity and crop safety after 3 weeks of application are shown in the following table:

Table 4 Paddy field effectiveness level

Through the above experiments, it can be found that the compound protected by the present invention has excellent biological activity of paddy weeds, has good effects on common weeds in paddy fields, and has good commercial application prospect; in addition, the current dosage is The compounds protected by the present invention are basically non-phytotoxic (the degree of phytotoxicity is 0) or no obvious phytotoxicity (the degree of phytotoxicity is 1-10%) for the visual observation of rice, so that the crop is especially suitable for crops at a suitable dose. Rice has good safety.

Example 9

Crop safety assessment:

Prepare the nutrient soil into a paper cup of 7cm in diameter, sprinkle the quantitative crop seeds into the paper cup, cover the soil 1.5cm after sowing, squash and water, and then dilute in the greenhouse for 2 weeks, then dilute with water containing 0.1% Tween 80. Dissolve the acetone solution of the original drug to be tested to the desired concentration, spray the stem and leaf with a spray tower according to the test design dose (3 repetitions per treatment), then store it in the greenhouse according to the conventional method, and observe it regularly. The growth and development of the material, according to the pesticide indoor bioassay test guidelines, part 8 and according to the actual situation, after the treatment, the effect of the test agent on the crop is investigated regularly by visual inspection, and the symptoms of the drug damage are described. The main symptoms are:

1) color change (yellow, white, purple, etc.);

2) morphological changes (new leaf deformities, distortions, etc.);

3) Growth changes (dehydration, withering, dwarfing, clustering, etc.).

Classification of phytotoxicity evaluation:

Grade a: no phytotoxicity;

Grade b: The degree of phytotoxicity is 1-10%, no obvious phytotoxicity;

Grade c: The degree of phytotoxicity is 11-30%, slightly phytotoxic;

Grade d: the degree of phytotoxicity is 31-50%, moderate phytotoxicity;

Grade e: The degree of phytotoxicity is 51-100%, which is a serious phytotoxicity.

记载于CN1069368B说明书第17页实施例1中)进行了作物安全性的平行测定。施药3周后的作物安全性实验效果如下表所示： According to the above method, a part of the compound (Compound No. 1, Compound 9, Compound 15, Compound 17, Compound 20, Compound 31, Compound 35, Compound 49) and Compound B were selected (Structure:

Parallel measurement of crop safety was carried out as described in Example 1 on page 17 of the CN 1069368B specification. The effect of the crop safety test after 3 weeks of application is shown in the following table:

Table 5 Crop safety test

Compound number Application rate (g ai/ha) wheat corn 1 15 a a 9 15 b a 15 15 a a 17 15 a b 20 15 a b 31 15 b b 35 15 a b B 15 d e

It can be seen that the compounds protected by the present invention have no phytotoxicity or obvious phytotoxicity for the visual observation of wheat or corn under the current dosage, and therefore have good properties for crops, especially wheat or corn, at suitable dosages. safety.

The above embodiments are only intended to illustrate the technical concept and the features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the contents of the present invention and to implement the present invention. Equivalent variations or modifications made in accordance with the substance of the invention are intended to be included within the scope of the invention.

Industrial applicability

The compounds of the present invention are useful as selective herbicides for grass crop fields or rice fields.

Claims (10)

A substituted pyrazolyl pyrazole sulfonylurea compound or a pesticide acceptable salt thereof having the following structural formula: In the formula,

R ₁ represents H, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylthio, halogenated C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkoxy Base, halogenated C ₁ -C ₆ alkoxy; R ₂ represents H, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylthio, halogenated C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkoxy Base, halogenated C ₁ -C ₆ alkoxy; Or, R ₁ and R ₂ together form a group -(CH ₂ ) _m -, m represents 1-6; R ₃ represents H or halogen; R ₄ represents H,

CN, halogen, NO ₂ , COOR ₁ , CONR ₁ R ₂ ; R ₅ represents H or halogen; R ₆ represents a C ₁ -C ₆ alkyl group, a halogenated C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkylthio group, a C ₁ -C ₆ alkylthio group substituted C ₁ -C ₆ alkyl group, halogenated C ₁ -C ₆ alkylthio, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, halogenated C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkylthio, C ₂ -C ₆ Alkenyloxy, C ₁ -C ₆ alkoxy, halo C ₁ -C ₆ alkoxy or C ₁ -C ₆ alkoxy substituted C ₁ -C ₆ alkoxy, either unsubstituted or 1 - 5 independently selected from the group consisting of halogen, nitro, cyano, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogenated C ₁ -C ₆ alkoxy a C ₁ -C ₆ alkylcarbonyl group, a halogenated C ₁ -C ₆ alkylcarbonyl group, a C ₁ -C ₆ alkylsulfonyl group, a halogenated C ₁ -C ₆ alkylsulfonyl group, a C ₁ -C ₆ alkoxy group Carbonyl, halogenated C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ alkylaminocarbonyl, halogenated C ₁ -C ₆ alkylaminocarbonyl, carboxyl, aldehyde, hydroxy, C ₁ -C ₆ alkoxy Substituted C ₁ -C ₆ alkoxy, C ₃ -C ₆ cycloalkyl, halogenated C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyloxy, C ₃ -C ₆ naphthenic Alkyloxycarbonyl, C ₃ -C ₆ cycloalkylaminecarbonyl, C ₃ -C ₆ heterocyclyl, C ₃ -C ₆ heterocyclyloxy, C ₃ -C ₆ heterocyclooxycarbonyl, C ₃ -C ₆ heterocyclic group Aminocarbonyl, C ₁ -C ₆ alkyl substituted C ₃ -C ₆ heterocyclyl or C ₁ -C ₆ alkoxy-substituted C ₁ -C ₆ alkoxy groups substituted aryl, heteroaryl Aryl, arylamino, heteroarylamino, aralkyl, heteroarylalkyl, aryloxy, heteroaryloxy or a cis-cyclic group. A substituted pyrazolyl pyrazole sulfonylurea compound according to claim 1 or a pesticide acceptable salt thereof, wherein, in the formula (I), R ₁ and R ₂ together form a group - (CH ₂ ) _m -, m represents 1-4. A substituted pyrazolyl pyrazole sulfonylurea compound according to claim 1 or a pesticide acceptable salt thereof, wherein, in the formula (I), R ₁ represents H, C ₁ - C ₄ alkyl; R ₂ represents H, C ₁ -C ₄ alkyl; Or, R ₁ and R ₂ together form a group -(CH ₂ ) _m -, m represents 3-4; R ₃ represents H or halogen; R ₄ represents H,

CN, halogen, NO ₂ , COOR ₁ , CONR ₁ R ₂ ; R ₅ represents H or halogen; R ₆ represents a C ₁ -C ₆ alkyl group, a halogenated C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkylthio group, a C ₁ -C ₆ alkylthio group substituted C ₁ -C ₆ alkyl group, halogenated C ₁ -C ₆ alkylthio, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, halogenated C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkylthio, C ₂ -C ₆ Alkenyloxy, C ₁ -C ₆ alkoxy, halo C ₁ -C ₆ alkoxy or C ₁ -C ₆ alkoxy substituted C ₁ -C ₆ alkoxy, either unsubstituted or 1-5 independently selected from halogen, nitro, cyano, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogenated C ₁ -C ₆ alkane Oxy group, C ₁ -C ₆ alkylcarbonyl group, C ₁ -C ₆ alkylsulfonyl group, C ₁ -C ₆ alkoxycarbonyl group, C ₁ -C ₆ alkylaminocarbonyl group, carboxyl group, aldehyde group, hydroxyl group, C ₁ -C ₆ alkoxy-substituted C ₁ -C ₆ alkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyloxy, C ₃ -C ₆ cycloalkyloxycarbonyl, C ₃ -C ₆ cycloalkylaminecarbonyl, C ₃ -C ₆ heterocyclyl, C ₃ -C ₆ heterocyclyloxy, C ₃ -C ₆ heterocyclyloxycarbonyl or C ₁ -C ₆ alkyl substituted C ₃ -C ₆ heterocyclyl group substituted aryl group, a heteroaryl group, an aryl group, heteroaryl group, aralkyl, heteroaralkyl, aryloxy, or heteroaryloxy . A substituted pyrazolyl pyrazole sulfonylurea compound or a pesticide acceptable salt thereof according to any one of claims 1 to 3, wherein in the formula (I), the aryl group Is phenyl, naphthyl, the heteroaryl is thiazole, furan, pyrrole, thiophene, imidazole, pyran, pyridine, pyrazole, pyrimidine, indole, indole, pyrimidine, pyrazine, pyridazine, triazine, benzene And thiazole, benzofuran, quinoline or oxazole. A substituted pyrazolyl pyrazole sulfonylurea compound according to Claim 2 or a pesticide acceptable salt thereof, wherein, in the formula (I), R ₁ and R ₂ together form a group - (CH ₂ ) _m -, m represents 4; R ₃ represents H, fluorine, chlorine or bromine; R ₄ represents H, CN; R ₅ represents H; R ₆ represents unsubstituted or 1-5 independently selected from the group consisting of fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, propyl, 3-trifluoropropyl, 3-trichloropropyl, Trifluoromethyl, trichloromethyl, methoxy, ethoxy, formyl, acetyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, carboxyl, aldehyde, hydroxyl Substituted phenyl, thiazolyl, anilino, benzyl. A substituted pyrazolyl pyrazole sulfonylurea compound according to claim 5 or a pesticide acceptable salt thereof, wherein R ₆ represents a phenyl group, a thiazolyl group or an aniline substituted with no substituent. Or benzyl or 1-3 independently selected from the group consisting of fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, propyl, 3-trifluoropropyl, trifluoromethyl, methoxy , formyl, methoxycarbonyl, methylamino substituted phenyl, anilino, benzyl. A substituted pyrazolyl pyrazole sulfonylurea compound according to any one of claims 1 to 6 or a pesticide acceptable salt thereof, which is selected from the group consisting of:

A herbicidal composition comprising a herbicidally effective amount of at least one of the substituted pyrazolyl pyrazole sulfonylurea compounds according to any one of claims 1 to 7 or as an agrochemically acceptable salt thereof. Preferred; further comprising a formulation carrier or a formulation aid. A method of controlling an unwanted plant, characterized by comprising a herbicidally effective amount of the substituted pyrazolyl pyrazole sulfonylurea compound according to any one of claims 1 to 7 or as a pesticide acceptable At least one of the salts or the herbicidal composition of claim 8 is used on unwanted plants. The substituted pyrazolyl pyrazole sulfonylurea compound according to any one of claims 1 to 7 or at least one of the pesticide-acceptable salts or the herbicidal composition according to claim 8 under control Use on harmful plants.