WO2021023292A1 - Substituted pyrazolyl pyrazole bisamide 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 bisamide compound or a pesticide acceptable salt or composition thereof, and the use thereof. The compound has a structure of formula (I). Each group in the formula is as defined in the description. The compound having a substituted pyrazolyl pyrazole bisamide 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

A substituted pyrazolylpyrazole bisamide compound or its acceptable salt, composition and use as pesticide Technical field

The present invention belongs to the technical field of pesticides, and specifically relates to a substituted pyrazolylpyrazole bisamide compound or its acceptable salt and composition as a pesticide, and relates to these compounds or their acceptable salt and composition as pesticides. Use of herbicides.

Background technique

Weed control is an important link in realizing high-efficiency agriculture. There are various herbicides on the market. For example, the patent application publication number CN1087342A describes substituted pyrazole derivatives and their preparation methods and their use as herbicides. For application, related substituted pyrazolyl pyrazole derivatives are also disclosed in the patents with application publication numbers CN10518004A and CN105492443A. However, due to the continuous expansion of the market, the resistance of weeds, the service life of drugs, and environmental safety, scientists need to continue to innovate and develop high-efficiency, safe, environmentally friendly and new structures of herbicide compounds with different modes of action.

technical problem

In order to solve the above-mentioned problems in the prior art, the present invention provides a substituted pyrazolylpyrazole bisamide compound or its acceptable salt as a pesticide, a composition and its use. Surprisingly, the above-mentioned pyrazolylpyrazole bisamide-based compounds or their acceptable salts as pesticides have higher herbicidal activity than known compounds, especially for common weeds in paddy fields, they have excellent herbicidal activity, and It has relatively better selectivity and crop safety.

Technical solutions

The technical scheme adopted by the present invention to achieve the above objective is: a substituted pyrazolylpyrazole bisamide compound or its acceptable salt as a pesticide, the structural formula of which is shown in formula (I):

In formula (I),

R ₁ represents H or halogen;

R ₂ represents H, halogen, CN, NO ₂ or COOR ₁ ;

R ₃ represents H, halogen, CN, C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or halo C ₁ -C ₆ alkoxy;

R ₄ represents H, halogen, CN, 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 alkyl substituted sulfonyl, halo C ₁ -C ₆ alkyl substituted sulfonyl;

R ₅ represents H, halogen, CN, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogenated C ₁ -C ₆ alkoxy, C _3- C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyloxy, C ₃ -C ₆ heterocyclyl, C ₃ -C ₆ heterocyclyloxy, C ₃ -C ₆ cycloalkyl substituted C _1- C ₆ alkyl, C ₃ -C ₆ cycloalkenyl substituted C ₁ -C ₆ alkyl and, unsubstituted or by 1-5 independently selected from C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy group, halogenated C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkyl carbonyl group, halogenated C ₁ -C ₆ alkyl carbonyl group, C ₁ -C ₆ alkyl sulfonate Acyl, 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 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 heterocyclyl, C ₃ -C ₆ heterocyclyloxy, C ₁ -C ₆ alkyl substituted C ₃ -C ₆ heterocyclyl or C ₁ -C ₆ Alkoxy substituted C ₁ -C ₆ alkoxy, halogen, nitro, cyano, carboxy, aldehyde or hydroxy group substituted aryl, heteroaryl or cyclic group; that is, R ₅ can Selected from H, halogen, CN, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogenated C ₁ -C ₆ alkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyloxy, C ₃ -C ₆ heterocyclyl, C ₃ -C ₆ heterocyclyloxy, C ₃ -C ₆ cycloalkyl substituted C ₁ -C Any of ₆ alkyl groups, C ₃ -C ₆ cycloalkenyl substituted C ₁ -C ₆ alkyl groups, or R ₅ may be selected from unsubstituted aryl, heteroaryl or cyclic groups, or R ₅ can be selected from aryl, heteroaryl, or cyclic groups substituted with 1-5 substituents, and the aforementioned substituents can be freely selected from 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 alkane Aminocarbonyl 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 cycloalkyl Oxy, C ₃ -C ₆ heterocyclyl, C ₃ -C ₆ heterocyclyloxy, C ₁ -C ₆ alkyl substituted C ₃ -C ₆ heterocyclyl or C ₁ -C ₆ alkoxy substituted C ₁ -C ₆ Alkoxy, halogen, nitro, cyano, carboxy, aldehyde or hydroxyl group;

Or, R ₄ and R ₅ together form a five-membered or six-membered saturated or unsaturated ring that is unsubstituted or substituted by any substituent;

R ₆ represents H, halogen, CN, C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, or halo C ₁ -C ₆ alkoxy.

Further, in formula (I),

R ₁ represents H or halogen;

R ₂ represents H, halogen, CN, NO ₂ ;

R ₃ represents H, halogen, CN, C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkyl;

R ₄ represents H, halogen, CN, C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halo C ₁ -C ₆ alkoxy;

R ₅ represents H, halogen, CN, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogenated C ₁ -C ₆ alkoxy, C _3- C ₆ cycloalkyl, C ₃ -C ₆ heterocyclyl, C ₃ -C ₆ cycloalkyl substituted C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkenyl substituted C ₁ -C ₆ alkyl And, unsubstituted or 1-5 independently selected from C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halo C ₁ -C ₆ alkoxy Group, C ₃ -C ₆ cycloalkyl, halo C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyloxy, halogen, nitro, cyano, carboxy, aldehyde or hydroxyl group Aryl or heteroaryl substituted by a group;

Alternatively, R ₄ and R ₅ together constitute unsubstituted or are selected from H, halogen, CN, C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogen Substituted C ₁ -C ₆ alkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ heterocyclic group substituted by a five-membered or six-membered saturated or unsaturated ring, said five-membered Or the six-membered saturated or unsaturated ring contains or does not contain one or more of O, N and S;

R ₆ represents H, halogen, CN, C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, or halo C ₁ -C ₆ alkoxy.

Further, in formula (I),

R ₁ represents H or halogen;

R ₂ represents H, halogen, CN, NO ₂ ;

R ₃ represents H, halogen, CN, C ₁ -C ₄ alkyl, halo C ₁ -C ₄ alkyl;

R ₄ represents H, halogen, CN, C ₁ -C ₄ alkyl, halo C ₁ -C ₄ alkyl;

R ₅ represents H, halogen, CN, C ₁ -C ₄ alkyl, halogenated C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogenated C ₁ -C ₄ alkoxy, C _3- C ₆ cycloalkyl, C ₃ -C ₆ heterocyclyl, C ₃ -C ₆ cycloalkyl substituted C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkenyl substituted C ₁ -C ₄ alkyl And, unsubstituted or 1-5 independently selected from C ₁ -C ₄ alkyl, halo C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halo C ₁ -C ₄ alkoxy The aryl or heteroaryl substituted by the group in the group;

Alternatively, R ₄ and R ₅ together form an unsubstituted five-membered or six-membered saturated or unsaturated ring, and the five-membered or six-membered saturated or unsaturated ring contains one or more of O, N, and S. Species

R ₆ represents H, halogen, CN, C ₁ -C ₄ alkyl, or halogenated C ₁ -C ₄ alkyl.

Further, in formula (I), the aryl group is phenyl or naphthyl, and the heteroaryl group is pyridyl, pyrazolyl, pyrimidinyl, thiazolyl, isoxazolyl, thienyl, furyl, Pyrrolyl, imidazolyl, pyranyl, pyrazinyl, pyridazinyl, triazinyl.

Further, in formula (I),

R ₁ represents H or halogen;

R ₂ represents H, halogen or CN;

R ₃ represents H, C ₁ -C ₄ alkyl or halo C ₁ -C ₄ alkyl;

R ₄ represents H, C ₁ -C ₄ alkyl or halo C ₁ -C ₄ alkyl;

R ₅ represents H, C ₁ -C ₄ alkyl, halogenated C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ heterocyclic group, C ₃ -C ₆ cycloalkyl substituted C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkenyl substituted C ₁ -C ₄ alkyl and, unsubstituted or 1-3 independently selected from C An aryl or heteroaryl group substituted by a group in a _1- C ₄ alkyl group or a halogenated C ₁ -C ₄ alkyl group, wherein the aryl group is a phenyl group, and the heteroaryl group is a pyridyl group or a pyrazolyl group , Pyrimidinyl, thiazolyl, isoxazolyl or thienyl;

Alternatively, R ₄ and R ₅ together form an unsubstituted five-membered or six-membered saturated or unsaturated ring, and the unsubstituted five-membered or six-membered saturated or unsaturated ring contains O and/or N;

Further, the heteroaryl group is

Or R ₄ and R _{5 are} connected to form an unsubstituted 5-membered or 6-membered saturated or unsaturated ring

R ₆ represents H, C ₁ -C ₄ alkyl, or halogenated C ₁ -C ₄ alkyl.

Further, in formula (I),

R ₁ represents H, F, Cl or Br;

R ₂ represents H, CN;

R ₃ represents H, Me, Et, CHF ₂ , CH ₂ F, CF ₃ , CH ₂ CF ₃ ;

R ₄ represents H, Me, Et;

R ₅ represents H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH ₂ Cl, CHF ₂ , CH ₂ F, CF ₃ , CH ₂ CF _3. Cyclopropanyl, cyclopentylmethyl, tetrahydropyranyl, cyclopentadienylmethyl and, unsubstituted or independently selected from Me, Et, n-Pr, i- Phenyl, pyridyl, pyrazolyl, pyrimidinyl, thiazolyl, isoxazolyl or thienyl substituted by groups in Pr, n-Bu, i-Bu, s-Bu, t-Bu;

Or, R ₄ and R ₅ together form a morpholino group;

R ₆ represents H, H, Me, Et, n-Pr, i-Pr.

Further, the structural compound of formula (I) is selected from:

The pesticide acceptable salt may be a salt prepared by reacting the substituted pyrazolylpyrazole bisamide compound of the present invention with a chemically acceptable acid, wherein the chemically acceptable acid may be an inorganic 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.); the pesticide acceptable salt can also It is a salt prepared by reacting a substituted pyrazolylpyrazole bisamide compound of the present invention with a chemically acceptable base, wherein the chemically acceptable base may be an inorganic base (such as sodium hydroxide, potassium hydroxide, Calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate) or organic bases (such as trimethylamine, triethylamine, etc.).

Further, the pesticide acceptable salt can be potassium salt, sodium salt, ammonium salt, calcium salt, pyridine salt or choline salt.

The present invention also discloses a herbicidal composition, which comprises a herbicidal effective amount of the substituted pyrazolylpyrazole bisamide compound as described above or at least one of its acceptable salts as pesticides.

Preferably, it also includes a preparation carrier or a preparation auxiliary.

The present invention also discloses a method for controlling undesired plants, which comprises adding a herbicidal effective amount of the above substituted pyrazolylpyrazole bisamide compound or at least one of the above-mentioned substituted pyrazolyl pyrazole bisamide compounds or their acceptable salts as pesticides. The herbicidal composition as described above is used on unwanted plants.

The present invention also discloses the use of the above-mentioned substituted pyrazolylpyrazole bisamide compound or at least one of its acceptable salts as pesticides or the above-mentioned herbicidal composition for controlling harmful plants.

In the definition of the above compound structural formula, the professional terms used have the following meanings:

C ₁ -C ₆ alkyl group: a straight or branched chain alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl or n-butyl, isobutyl, sec-butyl, Tert-butyl etc.

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

Halogenated C ₁ -C ₆ alkyl groups: linear or branched alkyl groups with 1-6 carbon atoms. The hydrogen atoms on these alkyl groups may be partially or completely replaced by halogens, for example, chloromethyl, dichloromethane Chloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, etc.

C ₁ -C ₆ alkoxy group: a straight or branched chain alkyl group having 1 to 6 carbon atoms, connected to the structure via an oxygen atom bond.

Halogenated C ₁ -C ₆ alkoxy groups: straight or branched chain alkoxy groups having 1 to 6 carbon atoms. The hydrogen atoms on these alkoxy groups may be partially or completely replaced by halogens, for example, chloroform Oxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, etc.

C ₁ -C ₆ Alkylcarbonyl: A group formed by connecting an alkyl group with 1 to 6 carbon atoms and a carbonyl group, such as

C ₁ -C ₆ alkylsulfonyl group: a group formed by connecting an alkyl group with 1-6 carbon atoms and a sulfonyl group, such as

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 as a substituent of an alkoxy group having 1 to 6 carbon atoms Group, such as

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

Heteroaryl: a polycyclic ring containing one or more N, O, S heteroatoms, such as pyridine, furan, thiophene, pyrazole, pyrimidine, pyrazine, pyridazine, triazine, thiazole, etc.

Bucyclic group: a group consisting of bicyclic or tricyclic rings, such as

The method for synthesizing the compound of formula I is specifically combining the compound of formula II and the compound of formula III (in the following chemical formulas, unless otherwise defined, the substituents and symbols are the same as those defined in formula I Significance) The intermediate is obtained after the reaction is carried out with or without solvent, and then reacted with the compound of formula IV to obtain the target compound of formula I. The compound represented by formula II can be synthesized with reference to the method described in patent CN1036397C, and the compound represented by formula III and IV can be obtained commercially:

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

For many annual monocotyledonous and dicotyledonous harmful plants, the compound of formula I of the present invention has outstanding herbicidal activity. The active substance of the present invention is also effective against 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. Special mention is made of representative examples of monocotyledonous and dicotyledonous weeds that can be controlled by the compounds of the present invention. Representative examples of weed species for which the active substance of the present invention can play an effective role include monocots: annual oats, ryegrass, Look at the genus Aegilops, Barnyard, Crabgrass, Setaria and Cyperus, and the perennial Wheatgrass, Bermudagrass, Imperata and Sorghum, and the perennial Cyperus.

Regarding the species of dicotyledonous weeds, its role can be extended to species such as the annual genus Asparagus, Viola, Pona, Sesamum, Stellaria, Amaranthus, White mustard, Ipomoea, Nimbus Genus, Matricaria and Abutilon, and perennial weeds Convolvulus, Thistle, Rumex and Artemisia. The active substance of the present invention can still effectively control harmful plants, such as barnyardgrass, Aquilaria, Alisma, water chestnut, saccharum and Cyperus under the specific conditions of rice sowing. If the compound of the present invention is applied to the soil surface before germination, the seedling of the weed can be prevented completely before the weed grows, or the growth of the weed can be stopped when the cotyledon grows, and finally died completely after three to four weeks. Although the compound of the present invention has excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, it has no damage to important economic crop plants such as wheat, barley, rye, rice, corn, sugar beet, cotton and soybean, or The damage is very small. Therefore, the compound of the present invention is very suitable for selectively controlling useless plants in agricultural crops or ornamental plants. In addition, the compounds of the present invention can significantly regulate the growth of crop plants. By regulating the involvement of plant metabolism, these compounds are used to control plant components and promote harvest, such as drying and stunting plant growth. And they are also suitable for regulating and inhibiting the growth of undesirable plants without destroying the growth of crops. Inhibiting plant growth plays a very important role in many monocot and dicot crops, because it can reduce or completely prevent lodging.

General formulations can be used to apply the compounds of the present invention, and wettable powders, soluble powders, emulsifiable concentrates, water emulsions, suspensions, dispersible oil suspensions, powders, microcapsule suspensions, water dispersible granules, water-soluble granules can be used.剂 etc. Thus, the present invention also provides herbicidal compositions comprising the compound of formula I. According to general biological and/or chemical physical parameters, the compound of formula I can be formulated in a variety of ways. Examples of suitable formulation choices are: wettable powder (WP), wettable liquid (SL), soluble powder (SP), dispersible liquid (DC), water (AS), microemulsion (ME), emulsifiable concentrate ( EC), water emulsion (EW), sprayable solution, suspension (SC), dispersible oil suspension (OD), powder (DP), microcapsule suspension (CS), water dispersible granules (WG), water soluble Granules (SG), large granules (GG), granules (GR) for broadcast and soil application, aerosols (AE), ultra-low volume agents (ULV) and wax products. Necessary formulation aids, such as inert substances, surfactants, solvents and other additives.

In the compounding formulation or the tank-mixing formulation, the suitable active material that can be mixed with the active material of the present invention is, for example, the known material in the "Encyclopedia of World Pesticide New Variety Technology" (China Agricultural Science and Technology Press, 2010.9). For example, the herbicide active substances mentioned below can be mixed with the mixture of formula I, (Note: the name of the compound, or the common name according to the International Organization for Standardization (ISO), or the chemical name, with the code when appropriate): Amine, Butachlor, Alachlor, Propolachlor, Metolachlor, Fine Metolachlor, Pretilachlor, Tetrachlor, Mesochlor, Naprolam, R-Naproxen Mefenacet, propanyl, mefenacet, difenacet, diflufenican, chlorfenazone, flufenacet, bromobutyramide, dimethenamid, high-efficiency dimethyl Thienachlor, ethoxyfen, flufenacet, metolachlor, metazachlor, clomazone, high-efficiency wheat straw fluoromethyl, high-efficiency wheat straw fluorine propyl ester, propenyl chlor, clethamine , Butachlor, cyprofen, fenoxsulam, enantholac, ibutachlor, propitrachlor, terbutachlor, xylene chlor, dimethenamid, chlorpropamide, Trimethochlor, melachlor, propargyl, dimethenamid, valerolachlor, carmethochlor, syllanine, dimethenamid, butenamid, formachlor, promethazine, quinone Pingamine, fenfluramide, naprolamine, acetochlor, naphthachlor, dimethochlor, metamethochlor, promethacin, chlorophthalimide, butamidine, flumipyr Amine, atrazine, simazine, promethazine, cyanochloride, siprogin, atrazine, permethionine, isopropion, fluroxylin, terbutyrin, terbuthine, triazine , Cyprodinol, glyphosate, sadagine, simatong, simatong, azide, diquat, isoprazine, metatrol, other dingjin, zhongdingtong, tedingtong, A Oxypropane, cyanochloride, indosulfuron, colazin, atrtoton, metoxetone, glycyrrhizin, cyanuric acid, Indaziflam, chlorsulfuron, metsulfuron, bensulfuron-methyl, chlorimuron-methyl, Trisulfuron-methyl, Thisulfuron-methyl, Pyrimsulfuron-methyl, Methsulfuron-methyl, Iodosulfuron-methyl sodium salt, Formamisulfuron-methyl, Trisulfuron-methyl, Tribenuron-methyl, Mesulfuron-methyl, Nicotinol Sulfur-methyl, sulfamesulfuron, sulfimuron-methyl, ethoxysulfuron-methyl, ciprosulfuron-methyl, sulfone sulfuron-methyl, pyrimsulfuron-methyl, flazasulfuron, monosulfuron-methyl, monosulfuron ester , Fluzosulfuron, flufensulfuron-methyl, flufensulfuron-methyl, epoxysulfuron-methyl, zoflufensulfuron-methyl, flufensulfuron-methyl, propasulfuron-methyl, trifluprosulfuron-methyl, sulfensulfuron-methyl , Triflufensulfuron, Fluasulfuron, Triflusulfuron-methyl, Metsulfuron-methyl sodium salt, Flufensulfuron-methyl, Methiosulfuron-methyl, Pimesulfuron-methyl, Propyrisulfuron, Propyrisulfuron Pyrimsulfuron, acifluorfen, fomesafen, lactofop-p-ethyl, oxyfluorfen, oxyfluorfen, fluroxyfen, aclofen, ethyl chlorflufen, methyl Carboflufen, fenflufen, methoxyfen, flufenox, flufenox, flufenoxan, flufenox, chlorfenapyr, dimethyl fluoride, flufenoxafen, fluoride Glyfoxyfen, Halosafen, Chlorotoluron, Isoproturon, Liururon, Diuron, Saprouron, Flururon, Benthuron, Methiophene, Probenuron, Sulthiuron, Isoxazone Methoxuron, Tebutthiazur, Clodinafon, Chlorobromuron, Methoxyuron, Methoxyuron, Methoxyuron, Bromosulfuron, Methoxuron, Luvaluron, Meturon, Ringgrass Sulfuron, fenuron, trifluthuron, grass not Cyclomethonium, Cyclomethuron, Cyclofenon, Isofluorocarbon, Cyclocapuron, Thiefuron, Buthiazolone, Cyclomethuron, Parafluon, Metthiazolone, Cyclofen, Trimethylisourea, Oxazolone, Monisouron , Anisuron, Methiuron, Chloreturon, Tetraflon, Betanin, Betanin-Ethyl, Betalan, Sulfentrazone, Teraqualin, Omatizin, Aniline, Chlorophenazine, Promethalin, Perachlor , Chlorpropargyl, Carboxazole, Chlorprocarb, Fenasulam, BCPC, CPPC, Carbasulam, Butachlor, Melanopsis, Dimethoate, Melanin, Melanopsis, Metrapyrin, Mediram, Barnyardgrass, Ringgrass Enemy, Oatme, Methiobencarb, Ethionate, Pingcaotan, Kecaomeng, Prosyloxytome, Zhongcaotan, Thiochloride, Methiobencarb, Isopolinate, Methiobencarb, 2,4-Dbutyl ester , 2 methyl 4 sodium chloride, 2,4-drops isooctyl ester, 2 methyl 4 chloro isooctyl ester, 2,4-drops sodium salt, 2,4-drops dimethylamine salt, 2 methyl 4 chloro ethyl thioester, 2 methyl 4 chloride, 2,4-d propionic acid, high 2,4-d propionate, 2,4-d butyric acid, 2 methyl 4 chloropropionic acid, 2 methyl 4 chloropropionate, 2 methyl 4 chloro Butyric acid, 2,4,5-butyric acid, 2,4,5-butyric acid, 2,4,5-butyric acid, 2-methyl-4 chloramine salt, dicamba, chlorophyll, valtox, saccharin Pine, Triclofenac, Diclofenac, Methoxytrichlorobenzoic acid, Propoxyfen, fluoxyfop-ethyl, fluoxyfop-ethyl, fluoxyfop-p-ethyl, high-efficiency fluoxyfop-ethyl, Quizalofop-p-ethyl, quizalofop-p-ethyl, fenoxaprop-p-ethyl, fenoxaprop-p-ethyl, oxachlor, cyhalofop-ethyl, oxadifen, clodinafop-propargyl, thiazoxyprop-p-ethyl, propadiop-ethyl, Pendimethalin, trifluoromethane oxime, clomazone, paraquat, diquat, acesulfame, ethalofen, isoprofen, metsulfuryl, ciprofluran, aminopropyl Trifluralin, etfluralin, chloretfluralin, aminoetfluralin, dilotin, chloretfluralin, methalpropalin, propionol, glyphosate, barnylphosate, glufosinate, methyl amine Phosphorus, phosphinothricin, phosphinothricin, bialaphos, diazaphos, glufosinate, triaphos, valonphos, methamidophos, glufosinate, imidazole nicotinic acid, imidazole nicotinic acid, imidazolinic acid , Imazamox, imazamox ammonium salt, imazethapyr nicotinic acid, imazamox, fluroxypyr, fluroxypyr isooctyl, diclopyridine, pyridine acid, three Clopyroxyacetic acid, fluthiopyr, halodipyr, triclopyr, thiaclopyr, flupyridone, clopyridin, fluroxypyr hydrazone, butoxyethyl triclopyr, Cliodinate , Clethodim, clethodim, clofenazone, chlorfenazone, chlorfenazone, buclofen, oxatrione, pyratrione, Buthidazole, trimethoprim, cyprozinone, fentrazone , Ethazinon, Ametridione, Amibuzin, bromoxynil, octanoyl bromoxynil, octanoyl iodobenzonitrile, iodobenzonitrile, dipropionitrile, diphenylacetonitrile, difentrazone, oxydipropioni, Iodobonil, Flumetsulam, double Sulfentrazone, Penoxsulam, Sulfentrazone, Chlorfentrazone, Diclofentrazone, Flaxsulam, Fluroxyfen, Bifentrazone, Saflufenacil, Cyfentrazone , Safentrazone, Sulfentrazone, Sulcotrione, Methiotrione, Sulcotrione, Tempotrione, Tefuryltrione, Bicyclopyrone, Ketodpiradox, Isoxaflutole, Clomazone, Fenoxasulfone, Methiozolin, Isopropyl Metazachlor, Metazachlor, Pyrazolate, Yeyanquat, Prozac, Metazachlor, Meclofen, Pyrasulfotole, Mefentrazone, Pyroxasulfone, Carfentrazone, Flufentrazone, Flufenazone , Chlorfenazone, fentrazone, flufentrazone, sulfentrazone, Bencarbazone, difentrazone, fluprofen-p-ethyl, chlordiazep, clomazone, cyclapyr, terchlorfen, Flupropacil, indoxacil, flufenoxalic acid, flumioxal, clodinafop, phthalobenzyl ether, Flumezin, pentachlorophenol (sodium), dioxol, telofol, teloxalate, pentonitrophenol , Dinitrophenol, Chloronitrophenol, Dioxin, Dilact, Oxachlor, Oxachlor, Penoxazone, Mefentrazone, Methoxalate, Tetrafenacet, Fluorine Pyridazine, fluroxyfen, bromoatramine, dimethyl pyraclosporin, pyridafen, chlorpyridone, chlorpyridone, pyridalphos, Pyridafol, quinclorac, quinclorac, quinclorac Pine, pyridachlor, oxazimone, chlorfenazone, clomazone, cyprofen, isopropafen, profentopyr, indanachlor, sodium chlorate, oxadifen, trichloroacetic acid , Monochloroacetic acid, hexachloroacetone, tetrafluoropropionic acid, forage fast, bromophenol oxime, triazole sulfonate, diazepam, furaflutole, oxaflufen, sulfentrazone, chlorophthalic acid, flurochloridone , Barnyardzein, acrolein, benflufen, difenazone, oat esters, thiadifenac, methenamine, oxytodone, methoxenone, saflufenacil, phosphinothricin, three Chloropropionic acid, Alorac, Diethamquat, Etnipromid, Iprymidam, Ipfencarbazone, Thiencarbazonemethyl, Pyrimisulfan, Chlorflurazole, Tripropindan, Sulglycapin, Methioprine, Cambendichlor, Cyclopyridine, Fluclopyridin, Flupyridin.

Beneficial effect

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

Through the chemical modification and molecular design of substituted pyrazolyl pyrazole compounds, the bisamide structure was introduced, and a series of more efficient, better selectivity and safety for weeding in agriculture or forestry were obtained. The active compound has good activity and selectivity especially against common weeds in paddy fields, and has excellent crop safety for paddy field crops, especially rice.

Embodiments of the invention

The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention.

Through comprehensive consideration of the economy, diversity and biological activity of the synthesized compounds, some of the compounds are preferably listed in the following table. The specific compound structure is shown in Table 1, and the specific compound physical data is shown in Table 2. The compounds in Table 1-2 are only to better illustrate the present invention, and do not limit the present invention. Those skilled in the art should not interpret this as the scope of the above subject of the present invention is limited to the following compounds.

Table 1 Structure of formula I compound

Table 2 ¹ H NMR data

The method for preparing the compound of the present invention is illustrated in the following technical scheme and examples. The raw materials can be purchased on the market or can be prepared by methods known in the literature or as shown in the detailed description. Those skilled in the art should understand that other synthetic routes can also be used to synthesize the compounds of the present invention. Although the specific raw materials and conditions in the synthetic route have been described in the following, they can be easily replaced with other similar raw materials and conditions. These modifications or variations of the preparation method of the present invention produce such compounds as Various isomers and the like are included in the scope of the present invention. In addition, the preparation method described below can be further modified according to the disclosure of the present invention using conventional chemical methods well known to those skilled in the art. For example, protecting appropriate groups during the reaction and so on.

Example 1

Synthesis of compound 3:

Add compound II-1 (2.62g, 10mmol) and acetonitrile (30ml) into the reaction flask, add compound III-1 (2.32g, 10mmol) with stirring at 10°C, add potassium carbonate (2eq) to the reaction at 10°C, TLC followed the reaction (ethyl acetate: petroleum ether = 1:1, GF254, UV color). After the reaction was complete, the solvent was spun off and dried to obtain Intermediate 1. Continue to feed the next step, add 20 mL of toluene and compound IV-1 (Ie acetyl chloride, 780mg, 10mmol) was heated to reflux, and reacted for 8h under reflux conditions to obtain compound 3, 1.83g, white solid powder, melting point: 203-205℃; ¹ H-NMR (CDCl ₃ -d ₆ , 500MHz) δ: 7.68 (s, 1H), 5.02-4.98 (m, 1H), 4.15-4.11 (t, 2H), 3.87-3.84 (m, 2H), 2.76-2.73 (t, 2H), 2.36-2.33 (s , 3H), 2.12-2.08 (m, 2H), 1.94-1.91 (m, 2H), 1.74-1.71 (d, 3H) ppm.

Example 2

Synthesis of compound 5:

Add compound II-1 (2.62g, 10mmol) and acetonitrile (30ml) into the reaction flask, add compound III-1 (1.64g, 10mmol) with stirring at 10°C, add potassium carbonate (2eq) to the reaction at 10°C, The reaction was followed by TLC (ethyl acetate: petroleum ether=1:1, GF254, UV color). After the reaction was completed, the solvent was spun off and dried to obtain Intermediate 2. Continue to feed the next step, add 20 mL of toluene and compound IV-1 (I.e. acetyl chloride, 780mg, 10mmol) was heated to reflux, and reacted for 8h under reflux conditions to obtain compound 5, 1.61g, white solid powder, melting point: 208-210℃; ¹ H-NMR (CDCl ₃ -d ₆ , 500MHz) δ: ¹ H-NMR (CDCl ₃ -d ₆ , 500MHz) δ: 7.69 (s, 1H), 5.57-5.53 (d, 2H), 5.02-4.98 (m, 1H), 4.15-4.11 (t, 2H) , 2.76-2.73 (t, 2H), 2.36-2.33 (s, 3H), 2.12-2.08 (m, 2H), 1.94-1.91 (m, 2H), 1.74-1.71 (d, 3H) ppm.

Example 3

Synthesis of compound 21:

Add compound II-1 (2.62g, 10mmol) and acetonitrile (30ml) into the reaction flask, add compound III-3 (1.50g, 10mmol) under stirring at 10°C, add potassium carbonate (2eq) to the reaction under stirring at 10°C, The reaction was followed by TLC (ethyl acetate: petroleum ether=1:1, GF254, UV color). After the reaction was completed, the solvent was spun off and dried to obtain Intermediate 3. Continue feeding to the next step, adding 20 mL of dichloromethane and compound IV -2 (i.e. trifluoroacetic anhydride, 2.10g, 10mmol) was heated to reflux and reacted for 8h under reflux conditions to obtain compound 21, 2.05g, white solid powder, melting point: 197-199°C; ¹ H-NMR(CDCl ₃ -d ₆ ,500MHz)δ:7.69(s,1H),4.57-4.54(s,2H),4.14-4.10(t,2H),2.92-2.88(d,3H),2.76-2.73(t,2H) ,2.11-2.07(m,2H),1.93-1.90(m,2H)ppm.

Example 4

Synthesis of compound 78:

Add compound II-1 (2.62g, 10mmol) and acetonitrile (30ml) into the reaction flask, add compound III-4 (2.06g, 10mmol) with stirring at 10°C, and add potassium carbonate (2eq) with stirring at 10°C, The reaction was followed by TLC (ethyl acetate: petroleum ether = 1:1, GF254, UV color). After the reaction was complete, the solvent was spun off and dried to obtain the intermediate. Continue feeding to the next step, adding 20 mL of dichloromethane and compound IV- 2 (i.e. trifluoroacetic anhydride, 2.10g, 10mmol) was heated to reflux and reacted for 8h under reflux conditions to obtain compound 78, 2.4g, yellow-white solid powder, melting point: 211-213°C; ¹ H-NMR(CDCl _3- d ₆ ,500MHz)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

Preparation of the formulation:

1. Powder: 20% of the compound of formula (I) is weighed, 80% of kaolin is mixed uniformly, and the product is obtained by pulverization.

2. Wettable powder: weigh 20% of the compound of formula (I), 8% calcium lignosulfonate, 2% sodium lauryl sulfate, 3% white carbon black, and kaolin and add to 100%. The mixture is evenly mixed and the product is obtained after air jet pulverization.

3. Water dispersible granules: weigh 60% of the compound of formula (Ⅰ), 6% sodium lignosulfonate, 4% NNO (alkyl naphthalene sulfonate formaldehyde condensate), 2% open powder BX (dibutyl Sodium naphthalene sulfonate), 3% K-12 (sodium lauryl sulfate), 5% carboxymethyl (ethyl) cellulose, 5% diatomaceous earth, 5% glucose, and kaolin are added to 100%. The mixture is evenly mixed, after being pulverized by air flow, the powder is weighed and mixed with water, granulated in a granulator, then dried and sieved to obtain a granular product.

4. Emulsifiable concentrate: weigh 15% of the compound of formula (I), 5% Nongru 700#, 5% Nongru 500#, 6% Nongru 1601#, 10% cyclohexanone, 3% N-methylpyrrolidone, Solvent oil 150 is added to 100%, and the product is obtained by dissolving completely and mixing uniformly.

5. Suspending agent: weigh 15% of the compound of formula (Ⅰ), 4% FS3000 (phosphate ester type anionic surfactant), 2% NS-500LQ (non-ionic hydroxyl polyethylene oxide block copolymer), 0.2% xanthan gum, 1% magnesium aluminum silicate, 5% ethylene glycol, 0.1% BIT (1,2-benzisothiazolin-3-one), 0.3% organically modified siloxane defoamer, The deionized water is added to 100% to form a slurry, and the product is obtained after sanding.

The above are percentages by weight.

Example 6

Evaluation of biological activity (post-emergence):

The original drug of the test compound is dissolved in DMF to prepare a 2.5% mother liquor, and then diluted with 0.1% Tween-80 water for use. Prepare nutrient soil and put it in a plastic pot with a diameter of 10 cm and a height of 9 cm. Sprinkle the target seeds (barnyard grass, amaranthus retroflexus) into it, cover with soil 0.5-1 cm after sowing, and place the bottom in a greenhouse after absorbing water for cultivation. Amaranth 3-4 leaf stage and barnyard grass grow to 2-3 leaf stage, the stems and leaves were sprayed with a spray tower according to the designed dose of the experiment, and the experiment was set up to repeat 3 times. After the liquid is naturally air-dried, it is placed in the greenhouse and managed according to conventional methods, and the growth and development of the test materials are regularly observed. According to Part 4 of the guidelines for the indoor bioassay test of pesticides, and according to the actual situation, the supply is regularly inspected by visual inspection after treatment. The control effect of the test agent on weeds. Control effect classification standard:

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

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

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

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

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

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

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

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

Level 1: All died.

According to the above method, select some compounds (compound numbers shown in Table 3) to perform parallel determination of herbicidal activity with the following compounds:

Pafenpyril (specific structure is

),

Control compound 4.179 (documented in CN1036397C, the specific structure is

),

Control compound 4.238 (documented in CN1036397C, the specific structure is

),

Control compound 4.254 (documented in CN1036397C, the specific structure is

),

Reference compound 443.1 (documented in CN1036397C, the specific structure is

),

Reference compound 443.2 (documented in CN1036397C, the specific structure is

).

The experimental results of herbicidal activity after application are shown in the table below:

Table 3 Prevention level

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

Example 7

Paddy field biological activity evaluation (post-emergence):

The original drug of the test compound is dissolved in DMF, and then diluted with water containing 0.1% Tween 80 to the desired concentration. Prepare the special soil for paddy field and install it to 3/4 of the flowerpots with 11cm diameter, 7cm bottom diameter and 11cm high plastic opaque flowerpots. Add 120mL of water to each flowerpot, mix the soil and water evenly and keep the surface flat . Sprinkle quantitative weed seeds and rice seeds into flower pots, press the seeds into the soil, and place them in the greenhouse according to conventional methods (the water layer is always about 2cm), and wait until the barnyard grass grows to the 4-leaf stage and the firefly When the plant grows to the 3-leaf stage, the ducklings grows to the 3-leaf stage, and the rice grows to the 2-leaf stage, it is sprayed with a pipette according to the experimental design dose (according to the dosage of 30g/ha, the specific dosage of the flowerpot is based on the flower The specific area of the pot is converted, and there are two replicates for each treatment), after applying the pesticide, continue to be placed in the greenhouse to regularly observe the growth and development of the test material, and according to the actual situation, regularly observe the test drug’s effect on weeds after treatment. The control effect and the safety to crops. According to Part 8 and Part 9 of the Guidelines for the Indoor Bioassay of Pesticides, the herbicidal activity and crop safety of the pesticides are evaluated according to the symptoms and severity of the target weeds and crops, and the investigation is conducted at a uniform level:

Effect classification standard:

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

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

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

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

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

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

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

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

Level 1: All died;

The main symptoms of phytotoxicity are:

1) Color change (yellowing, whitening, purple, etc.);

2) Morphological changes (new leaf deformity, distortion, etc.);

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

According to the above method, select some compounds (Compound No. 1-8, Compound 12, Compound 14, Compound 17-21, Compound 40, Compound 45-48, Compound 70, Compound 78, Compound 80, Compound 93, Compound 104, Compound 123 ) And pyrenpyril, compounds 4.179, 4.238, 4.254, 443.1, 443.2 (the specific structure is shown above) were tested in parallel for herbicidal activity and crop safety. The experimental results of weed control activity and crop safety after 3 weeks of application are shown in the following table:

Table 4 Paddy field control effect level

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

Example 8

Crop safety evaluation:

The original drug of the test compound is dissolved in DMF to prepare a 2.5% mother liquor, and then diluted with 0.1% Tween-80 water for use. Prepare nutrient soil and put it in a plastic pot with a diameter of 10 cm and a height of 9 cm. Sprinkle the target seeds (barnyard grass, amaranthus retroflexus) into it, cover with soil 0.5-1 cm after sowing, and place the bottom in a greenhouse after absorbing water for cultivation. Amaranth 3-4 leaf stage, barnyardgrass grow to 2-3 leaf stage, the stem and leaves were sprayed with a spray tower according to the designed dose of the experiment, and the experiment was set up to 3 times. After the liquid is naturally air-dried, it is placed in a greenhouse for management according to conventional methods, and the growth and development of the test materials are regularly observed. According to Part 8 of the Guidelines for Pesticide Indoor Bioassay Tests, and according to the actual situation, the supply is regularly inspected by visual inspection after treatment. The effect of the test agent on crops, and the symptoms of phytotoxicity are described. The main symptoms are:

1) Color change (yellowing, whitening, purple, etc.);

2) Morphological changes (new leaf deformity, distortion, etc.);

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

Pesticide evaluation classification:

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%, slight phytotoxicity;

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

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

According to the above method, select some compounds (Compound No. 3, Compound 12, Compound 14, Compound 21, Compound 40, Compound 45, Compound 70,) and Pafenpyril, Compound 4.179, 4.238, 4.254, 443.1, 443.2 (specific structure As shown above) parallel determination of crop safety was carried out. The effect of the crop safety experiment after 3 weeks of application is shown in the following table:

Table 5 Crop safety test

Compound number	Application amount (g ai/ha)	wheat	corn
3	30	a	a
12	30	a	a
14	30	a	b
twenty one	30	a	a
40	30	a	b
45	30	a	b
70	30	b	a
Pafenpyril	30	a	a
4.179	30	a	b
4.238	30	a	b
4.254	30	b	b
443.1	30	a	b
443.2	30	a	b

It can be seen that the compound protected by the present invention has basically no phytotoxicity or no obvious phytotoxicity to wheat or corn by visual observation under the current dosage. Therefore, it is very good for crops, especially wheat or corn, at a suitable dosage. safety.

The above-mentioned embodiments are only to illustrate the technical concept and characteristics of the present invention, and their purpose is to enable those of ordinary skill in the art to understand the content of the present invention and implement them accordingly, and should not limit the protection scope of the present invention. All equivalent changes or modifications made according to the essence of the present invention should be covered by the protection scope of the present invention.

Industrial applicability

The compounds of the present invention can be used as selective herbicides in gramineous crop fields or rice fields.

Claims (10)

1. A substituted pyrazolylpyrazole bisamide compound or its acceptable salt as a pesticide, its structural formula is as shown in formula (I):

   

   In formula (I),

   R ₁ represents H or halogen;

   R ₂ represents H, halogen, CN, NO ₂ or COOR ₁ ;

   R ₃ represents H, halogen, CN, C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or halo C ₁ -C ₆ alkoxy;

   R ₄ represents H, halogen, CN, 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 alkyl substituted sulfonyl, halo C ₁ -C ₆ alkyl substituted sulfonyl;

   R ₅ represents H, halogen, CN, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogenated C ₁ -C ₆ alkoxy, C _3- C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyloxy, C ₃ -C ₆ heterocyclyl, C ₃ -C ₆ heterocyclyloxy, C ₃ -C ₆ cycloalkyl substituted C _1- C ₆ alkyl, C ₃ -C ₆ cycloalkenyl substituted C ₁ -C ₆ alkyl and, unsubstituted or by 1-5 independently selected from C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy group, halogenated C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkyl carbonyl group, halogenated C ₁ -C ₆ alkyl carbonyl group, C ₁ -C ₆ alkyl sulfonate Acyl, 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 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 heterocyclyl, C ₃ -C ₆ heterocyclyloxy, C ₁ -C ₆ alkyl substituted C ₃ -C ₆ heterocyclyl or C ₁ -C ₆ Alkoxy substituted C ₁ -C ₆ alkoxy, halogen, nitro, cyano, carboxyl, aldehyde or hydroxyl group substituted aryl, heteroaryl or cyclic group;

   Or, R ₄ and R ₅ together form a five-membered or six-membered saturated or unsaturated ring that is unsubstituted or substituted by any substituent;

   R ₆ represents H, halogen, CN, C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, or halo C ₁ -C ₆ alkoxy.
2. A substituted pyrazolylpyrazole bisamide compound or its acceptable salt as a pesticide as claimed in claim 1, characterized in that, in formula (I),

   R ₁ represents H or halogen;

   R ₂ represents H, halogen, CN, NO ₂ ;

   R ₃ represents H, halogen, CN, C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkyl;

   R ₄ represents H, halogen, CN, C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halo C ₁ -C ₆ alkoxy;

   R ₅ represents H, halogen, CN, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogenated C ₁ -C ₆ alkoxy, C _3- C ₆ cycloalkyl, C ₃ -C ₆ heterocyclyl, C ₃ -C ₆ cycloalkyl substituted C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkenyl substituted C ₁ -C ₆ alkyl And, unsubstituted or 1-5 independently selected from C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halo C ₁ -C ₆ alkoxy Group, C ₃ -C ₆ cycloalkyl, halo C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyloxy, halogen, nitro, cyano, carboxy, aldehyde or hydroxyl group Aryl or heteroaryl substituted by a group;

   Alternatively, R ₄ and R ₅ together constitute unsubstituted or are selected from H, halogen, CN, C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogen Substituted C ₁ -C ₆ alkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ heterocyclic group substituted by a five-membered or six-membered saturated or unsaturated ring, said five-membered Or the six-membered saturated or unsaturated ring contains or does not contain one or more of O, N and S;

   R ₆ represents H, halogen, CN, C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, or halo C ₁ -C ₆ alkoxy.
3. A substituted pyrazolylpyrazole bisamide compound or its acceptable salt as a pesticide as claimed in claim 1, characterized in that, in formula (I),

   R ₁ represents H or halogen;

   R ₂ represents H, halogen, CN, NO ₂ ;

   R ₃ represents H, halogen, CN, C ₁ -C ₄ alkyl, halo C ₁ -C ₄ alkyl;

   R ₄ represents H, halogen, CN, C ₁ -C ₄ alkyl, halo C ₁ -C ₄ alkyl;

   R ₅ represents H, halogen, CN, C ₁ -C ₄ alkyl, halogenated C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogenated C ₁ -C ₄ alkoxy, C _3- C ₆ cycloalkyl, C ₃ -C ₆ heterocyclyl, C ₃ -C ₆ cycloalkyl substituted C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkenyl substituted C ₁ -C ₄ alkyl And, unsubstituted or 1-5 independently selected from C ₁ -C ₄ alkyl, halo C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halo C ₁ -C ₄ alkoxy The aryl or heteroaryl substituted by the group in the group;

   Alternatively, R ₄ and R ₅ together form an unsubstituted five-membered or six-membered saturated or unsaturated ring, and the five-membered or six-membered saturated or unsaturated ring contains one or more of O, N, and S. Species

   R ₆ represents H, halogen, CN, C ₁ -C ₄ alkyl, or halogenated C ₁ -C ₄ alkyl.
4. A substituted pyrazolylpyrazole bisamide compound or a pesticide acceptable salt thereof according to any one of claims 1 to 3, wherein in formula (I), the aryl group is Phenyl, naphthyl, and the heteroaryl group is pyridyl, pyrazolyl, pyrimidinyl, thiazolyl, isoxazolyl, thienyl, furyl, pyrrolyl, imidazolyl, pyranyl, pyrazinyl, Pyridazinyl, triazinyl.
5. A substituted pyrazolylpyrazole bisamide compound or its acceptable salt as a pesticide as claimed in claim 4, characterized in that, in formula (I), in formula (I),

   R ₁ represents H or halogen;

   R ₂ represents H, halogen or CN;

   R ₃ represents H, C ₁ -C ₄ alkyl or halo C ₁ -C ₄ alkyl;

   R ₄ represents H, C ₁ -C ₄ alkyl or halo C ₁ -C ₄ alkyl;

   R ₅ represents H, C ₁ -C ₄ alkyl, halogenated C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ heterocyclic group, C ₃ -C ₆ cycloalkyl substituted C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkenyl substituted C ₁ -C ₄ alkyl and, unsubstituted or 1-3 independently selected from C An aryl or heteroaryl group substituted by a group in a _1- C ₄ alkyl group or a halogenated C ₁ -C ₄ alkyl group, wherein the aryl group is a phenyl group, and the heteroaryl group is a pyridyl group or a pyrazolyl group , Pyrimidinyl, thiazolyl, isoxazolyl or thienyl;

   Alternatively, R ₄ and R ₅ together form an unsubstituted five-membered or six-membered saturated or unsaturated ring, and the unsubstituted five-membered or six-membered saturated or unsaturated ring contains O and/or N;

   R ₆ represents H, C ₁ -C ₄ alkyl, or halogenated C ₁ -C ₄ alkyl.
6. A substituted pyrazolylpyrazole bisamide compound or its acceptable salt as a pesticide according to claim 5, wherein in formula (I), R ₁ represents H, F, Cl or Br;

   R ₂ represents H, CN;

   R ₃ represents H, Me, Et, CHF ₂ , CH ₂ F, CF ₃ , CH ₂ CF ₃ ;

   R ₄ represents H, Me, Et;

   R ₅ represents H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH ₂ Cl, CHF ₂ , CH ₂ F, CF ₃ , CH ₂ CF _3. Cyclopropanyl, cyclopentylmethyl, tetrahydropyranyl, cyclopentadienylmethyl and, unsubstituted or independently selected from Me, Et, n-Pr, i- Phenyl, pyridyl, pyrazolyl, pyrimidinyl, thiazolyl, isoxazolyl or thienyl substituted by groups in Pr, n-Bu, i-Bu, s-Bu, t-Bu;

   Or, R ₄ and R ₅ together form a morpholino group;

   R ₆ represents H, H, Me, Et, n-Pr, i-Pr.
7. A substituted pyrazolylpyrazole bisamide compound or its acceptable salt as a pesticide as claimed in any one of claims 1 to 6, wherein the compound of formula (I) is selected from:

   

   
8. A herbicidal composition, characterized in that it comprises a herbicidal effective amount of the substituted pyrazolylpyrazole bisamide compound according to any one of claims 1-7 or at least one of its pesticide-acceptable salts ; Preferably, it also includes a formulation carrier or formulation auxiliary.
9. A method for controlling unwanted plants, which is characterized in that it comprises adding a herbicidal effective amount of the substituted pyrazolylpyrazole bisamide compound according to any one of claims 1 to 7 or its acceptable salt as a pesticide At least one of or the herbicidal composition of claim 8 is used on unwanted plants.
10. The substituted pyrazolylpyrazole bisamide compound according to any one of claims 1-7 or at least one of its acceptable salts as pesticides or the herbicidal composition according to claim 8 is effective in controlling harmful Use on plants.