Trifluoroolefin compounds with nematicidal activity and preparation method and use thereof

Abstract

The present invention relates to a trifluoroolefin compound having nematicidal activity, a preparation method and use thereof. Specifically, the present invention discloses a compound having formula (I) or its optical isomers, cis-trans isomers or pesticide-acceptable salts, and a preparation method thereof. The above-mentioned compound has excellent nematicidal activity.

Description

Technical Field

[0001] The present invention belongs to the field of pesticides and specifically relates to a trifluoroolefin compound having nematicidal activity and a preparation method and use thereof. Background Art

[0002] Plant parasitic nematodes are a type of extremely harmful pathogenic microorganisms. They are widely distributed, diverse in species, and highly adaptable to the environment. They can parasitize the roots, stems, leaves, seeds, young shoots, and fruits of plants. They can cause mechanical damage to host plants through feeding activities and plunder the nutrients of host plants. In particular, their esophageal gland secretions can cause a series of lesions in host plants. They can also infect host plants with other pathogenic microorganisms, causing complex diseases and resulting in yield losses. Globally, plant parasitic nematodes cause agricultural losses of more than $100 billion each year, seriously restricting the development of the agricultural economy.

[0003] There are many means of controlling nematodes in agriculture, and chemical control is currently the main method. Widely used chemical nematicides are mainly highly toxic, high-residue organophosphorus or carbamate pesticides, such as thiosulfuron, chlorpyrifos, fenamiphos, thiathion, aldicarb, oxamyl and carbofuran, which have low safety for humans and other non-target organisms, and also cause varying degrees of pollution to soil, water sources and agricultural products. In addition, due to the single variety, such nematicides are excessively and frequently used, which has caused serious drug resistance, making the control of nematodes increasingly difficult. Therefore, it has become a technical problem in this field to urgently solve to find a novel chemical nematicide with high efficiency, low toxicity and good environmental compatibility.

[0004] In summary, there is an urgent need in the art to develop new compounds with nematicidal activity. Summary of the invention

[0005] The purpose of the present invention is to provide a novel chemical nematicide with high efficiency, low toxicity and good environmental compatibility.

[0006] Another object of the present invention is to provide a preparation method and application of the chemical nematicide.

[0007] In the first aspect, the present invention provides a compound represented by formula (I), or an optical isomer, a cis-trans isomer or a pesticide-acceptable salt thereof:

[0008]

[0009] In the formula,

[0010] n is an integer of 0-5, preferably an integer of 1-3, more preferably 1;

[0011] A is an oxygen or sulfur atom;

[0012] G is selected from the group consisting of H, substituted or unsubstituted C 1-6 Alkyl, substituted or unsubstituted C 3-6 Cycloalkyl, substituted or unsubstituted C 2-6 Alkenyl, substituted or unsubstituted C 2-6 Alkynyl, substituted or unsubstituted C 5-7 Cycloalkenyl, substituted or unsubstituted 5-10 membered aryl (preferably phenyl, naphthyl), substituted or unsubstituted 5-membered or 6-membered aromatic heterocyclic group, substituted or unsubstituted 5-membered or 6-membered aliphatic heterocyclic group;

[0013] M is a substituted or unsubstituted 5-7 membered aromatic ring, a substituted or unsubstituted 5-7 membered carbocyclic ring, a substituted or unsubstituted 5-7 membered aromatic heterocyclic ring or a 9-12 membered condensed aromatic heterocyclic ring, or a substituted or unsubstituted 5-7 membered aliphatic heterocyclic ring, CH2SN2, CO, SO, SO2, (CH2) m , wherein m is an integer of 0-5; the substituent of the ring M is selected from the following group: H, halogen, substituted or unsubstituted C 1-6 Alkyl or alkoxy, substituted or unsubstituted C 3-6 Cycloalkyl, substituted or unsubstituted C 2-6 Alkenyl, substituted or unsubstituted C 2-6 Alkynyl, substituted or unsubstituted C 5-7 Cycloalkenyl, substituted or unsubstituted 5-10 membered aryl (preferably phenyl, naphthyl), substituted or unsubstituted 5-membered or 6-membered aromatic heterocyclic group, substituted or unsubstituted 5-membered or 6-membered aliphatic heterocyclic group;

[0014] Q is a substituted or unsubstituted 5-12 membered aromatic ring, a substituted or unsubstituted 5-12 membered carbocyclic ring, a substituted or unsubstituted 5-12 membered aromatic heterocyclic ring, a substituted or unsubstituted 5-12 membered alicyclic ring (including fully or partially unsaturated alicyclic rings), a substituted or unsubstituted alkenyl group, or is selected from the following U-1 to U-34:

[0015]

[0016] wherein p is an integer of 0-7, preferably an integer of 0-5, most preferably an integer of 0-3;

[0017] Wherein R1 is selected from the following group: =O, substituted or unsubstituted C 1-6 Alkyl or alkoxy, halogen, substituted or unsubstituted C 3-7 Cycloalkyl, substituted or unsubstituted C 2-6 Alkenyl, substituted or unsubstituted C 2-6 Alkynyl, substituted or unsubstituted C 5-7 Cycloalkenyl, substituted or unsubstituted 5-10 membered aryl (preferably phenyl, naphthyl), substituted or unsubstituted 5- or 6-membered aromatic heterocyclic group, substituted or unsubstituted 5- or 6-membered aliphatic heterocyclic group.

[0018] In a preferred embodiment, Q is a 5-12 membered aromatic ring or an aromatic heterocyclic ring.

[0019] In a further preferred embodiment, Q is a 5-12 membered benzoaromatic heterocycle or a 5-12 membered benzoaromatic heterocycle.

[0020] In a specific embodiment, the compound is as shown in Formula II, I-II, I-III or I-IV:

[0021]

[0022] wherein m, n, A, G and Q are as defined above.

[0023] In a specific embodiment, the compound is as shown in Formula II,

[0024] Wherein, m is 0 or 1;

[0025] n is an integer from 1 to 3;

[0026] A is an oxygen atom or a sulfur atom;

[0027] G is H, substituted or unsubstituted C 1-6 Alkyl or alkoxy (preferably halogen-substituted alkyl), five-membered or six-membered aromatic heterocycle;

[0028] Q is a substituted or unsubstituted 5-12 membered aromatic ring, a substituted or unsubstituted 5-12 membered aromatic heterocyclic ring, or a substituted or unsubstituted 5-12 membered aliphatic heterocyclic ring.

[0029] In a preferred embodiment, the aromatic ring is a substituted or unsubstituted aromatic ring-linked aromatic ring, preferably a substituted or unsubstituted phenyl-linked phenyl ring;

[0030] In a preferred embodiment, the aromatic heterocycle is a nitrogen-containing aromatic heterocycle, a five-membered or six-membered aromatic heterocycle, an aromatic ring (preferably a benzene ring) and an aromatic heterocycle, a condensed aromatic heterocycle, an aromatic heterocycle connected to an aromatic heterocycle, or an aromatic heterocycle connected to an aromatic heterocycle;

[0031] In a preferred embodiment, the five-membered aromatic heterocycle includes, but is not limited to: substituted or unsubstituted oxazole, substituted or unsubstituted thiadiazole, substituted or unsubstituted oxadiazole, substituted or unsubstituted isoxazole, substituted or unsubstituted isoxazoline;

[0032] The six-membered heterocyclic ring includes, but is not limited to, substituted or unsubstituted pyridine, substituted or unsubstituted triazine ring, substituted or unsubstituted oxadiazine;

[0033] The aromatic ring and aromatic heterocycle are benzoaromatic heterocycles, including but not limited to: benzoxazole, benzotriazole, benzoquinadione ring;

[0034] The fused aromatic heterocycle includes but is not limited to: thiazolyl pyrazole, triazolothiadiazole,;

[0035] The aromatic ring-linked aromatic heterocycle includes but is not limited to a benzo-linked aromatic heterocycle, such as benzopyrazole, benzothiazole, or benzoisoxazoline;

[0036] The aromatic heterocycle-linked aromatic heterocycle includes, but is not limited to, pyrazine bipyridine and pyridine bipyrazole.

[0037] In a specific embodiment, the compound is as shown in Formula II,

[0038] Wherein, m is 0 or 1;

[0039] n is an integer from 1 to 2;

[0040] A is an oxygen atom or a sulfur atom;

[0041] G is H, substituted or unsubstituted C 1-6 Alkyl or alkoxy (preferably C 1-3 alkyl or alkoxy);

[0042] Q is a substituted or unsubstituted five-membered or six-membered aromatic heterocycle, a substituted or unsubstituted five-membered or six-membered alicyclic ring, a substituted or unsubstituted 5-12-membered aromatic ring (preferably a benzene ring) and aromatic heterocycle, a substituted or unsubstituted 5-12-membered aromatic heterocycle and aromatic heterocycle, or a substituted or unsubstituted 5-12-membered aromatic ring and aromatic ring.

[0043] In a specific embodiment, the compound represented by formula II is a compound selected from the following:

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053] The compound represented by formula I-II is selected from the following compounds:

[0054]

[0055]

[0056] The compound represented by formula I-III is selected from the following compounds:

[0057]

[0058] The compound represented by formula I-IV is selected from the following compounds:

[0059]

[0060]

[0061] In a second aspect, the present invention provides a pesticide composition comprising the compound described in the first aspect, or its optical isomers, cis-trans isomers or pesticide-acceptable salts, and optionally a pesticide-acceptable excipient.

[0062] In a third aspect, the present invention provides the use of the compound of the first aspect, or its optical isomers, cis-trans isomers or pesticide-acceptable salts, for killing nematodes or for preparing a nematicidal pesticide composition.

[0063] In a fourth aspect, the present invention provides use of the pesticide composition of the second aspect for killing nematodes.

[0064] In a fifth aspect, the present invention provides a method for controlling and eliminating nematodes, the method comprising the step of administering an effective amount of the compound described in the first aspect, or its optical isomers, cis-trans isomers or pesticide-acceptable salts, or the pesticide composition described in the second aspect to plants or crops that need to control and eliminate nematodes.

[0065] In a sixth aspect, the present invention provides a method for preparing the compound described in the first aspect, wherein the compound is prepared using the following synthetic route:

[0066] 1) When M is a substituted or unsubstituted 5-7 membered aromatic ring, a substituted or unsubstituted 5-7 membered carbocyclic ring, a substituted or unsubstituted 5-7 membered aromatic heterocyclic ring, or a substituted or unsubstituted 5-7 membered heterocyclic ring, (CH2) m Wherein m=0-5 is prepared by the method shown in the following reaction formula:

[0067]

[0068] a) chlorinating the compound of formula 1-1 to obtain the compound of formula 1-2;

[0069] b) reacting the compound represented by formula 1-2 with the corresponding amine or sulfonamide in the presence of a base or a condensing agent to obtain the compound represented by formula 1-3;

[0070] c) reacting the compound of formula 1-3 with a bromide in the presence of to generate a compound of formula 1-4;

[0071] or

[0072] 2) When M is CH2SN2, the following reaction formula is used to prepare:

[0073]

[0074] a) chlorinating the compound of formula 2-1 to obtain the compound of formula 2-2;

[0075] b) reacting the compound of formula 2-2 with the corresponding ammonium thiocyanate to obtain the corresponding isothiocyanate, i.e., the compound of formula 2-3; and

[0076] c) reacting the compound represented by formula 2-3 with an amino compound to produce a compound represented by formula 2-4;

[0077] or

[0078] 3) When M is SO2, the following reaction formula is used for preparation:

[0079]

[0080] a) reacting the compound represented by formula 3-1 with the corresponding sulfonamide in the presence of a condensing agent to obtain the compound represented by formula 3-2;

[0081] b) reacting the compound represented by formula 3-2 with a bromide in the presence of a base to generate a compound represented by formula 3-3.

[0082] It should be understood that within the scope of the present invention, the above-mentioned technical features of the present invention and the technical features specifically described below (such as embodiments) can be combined with each other to form a new or preferred technical solution. Due to space limitations, they will not be described one by one here. BRIEF DESCRIPTION OF THE DRAWINGS

[0083] Figure 1 The construction ideas of the compounds of the present invention are shown;

[0084] Figure 2 The calculation method of the disease index grade is shown. DETAILED DESCRIPTION

[0085] After long-term and in-depth research, the inventors have designed and synthesized a series of trifluoroolefin compounds with novel structures and significant insecticidal activity. The compounds have the advantages of high efficiency, low toxicity and good environmental compatibility. On this basis, the inventors have completed the present invention.

[0086] Group Definition

[0087] The term "C 1-6 The term "alkyl" refers to a straight or branched chain alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, or the like.

[0088] The term "C 2-6 The term "alkenyl" refers to a straight or branched alkenyl group having 2 to 6 carbon atoms, such as vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, or the like.

[0089] The term "C 2-6 The term "alkynyl" refers to a straight or branched chain alkynyl group having 2 to 6 carbon atoms, such as ethynyl, propynyl, or the like.

[0090] The term "C 3-7 The term "cycloalkyl" refers to a cyclic alkyl group having 3 to 7 carbon atoms, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or the like.

[0091] The term "C 5-7 The term "cycloalkenyl" refers to a cyclic alkenyl group having 5 to 7 carbon atoms and having one or more double bonds, such as cyclopentenyl, cyclohexenyl, cycloheptenyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, or the like.

[0092] As used herein, the term “C 1-4 The term "alkoxy" refers to a straight or branched alkoxy group having 1 to 4 carbon atoms, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, or the like.

[0093] The term "halogen" refers to fluorine, chlorine, bromine, or iodine. The term "halogenated" refers to a group substituted by the same or different one or more halogen atoms mentioned above, for example trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl, or the like.

[0094] The term "ring" or "ring system" refers to a carbocyclic or heterocyclic ring.

[0095] The term "heterocycle" means that at least one of the atoms forming the heterocycle skeleton is not carbon, but a heteroatom such as nitrogen, oxygen or sulfur. It is well known to those skilled in the art that heterocycles can be divided into two categories: aliphatic heterocycles and aromatic heterocycles; heterocycles usually contain no more than 4 nitrogen atoms, no more than 2 oxygen atoms and / or no more than 2 sulfur atoms. Unless otherwise specified, heterocycles can be saturated, partially unsaturated or fully unsaturated rings.

[0096] The term "ring system" refers to two or more rings fused together.

[0097] As used herein, the term "5-membered or 6-membered heterocyclyl" refers to a 5-membered or 6-membered ring containing one or more heteroatoms selected from nitrogen, oxygen or sulfur, for example, pyridyl, thiazolyl, isothiazolyl, thienyl, furanyl, pyrrolyl, pyrazolyl, pyrimidinyl, tetrahydrofuranyl, 4,5-dihydrothiazol-2-yl, 2-cyano-4-oxo-1,3-thiazolidin-3-yl, 2-cyano-imino-4-oxo-1,3-thiazolidin-3-yl, 2-cyano-imino- -4-oxo-1,3-thiazin-3-yl, oxazolyl, isoxazolyl, 1H-tetrazolyl, 1H-1,2,3-triazolyl, 4H-1,2,4-triazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl or tetrazolyl, etc.

[0098] The term "heterocyclic ring system" refers to a ring system wherein at least one ring in the ring system is a heterocyclic ring.

[0099] The term "heteroaromatic ring system" refers to a system in which at least one ring in the ring system is aromatic.

[0100] The term "alkyl" refers to a group formed by removing one hydrogen atom from an alkane molecule; the term "alkylene" refers to a group formed by removing two hydrogen atoms from an alkane molecule. Similarly, the definitions of "alkenylene", "alkynylene", "cycloalkylene", "cycloalkenylene", "phenylene", "naphthylene", "heterocyclylene" or "heteroaromatic bicyclic or tricyclic ring system" are similar.

[0101] Unless otherwise specified as "substituted or unsubstituted", the groups of the present invention may be substituted by substituents selected from the following groups: halogen, cyano, nitro, C 1-6 Alkyl, C 1-6 Haloalkyl, C 2-6 Alkenyl, C 2-6 Halogenated alkenyl, C 2-6 Alkynyl, C 2-6 Haloalkynyl, hydroxyl, hydroxyl C 1-4 Alkyl, OR', Si(R')3, NR'R", C(O)R', C(O)OR', C(O)NR'R", SR', S(O) m R', S(O)2NR'R", OC(O)R', OC(O)NR'R", OS(O)2R', OS(O)2NR'R", N(R")C(O)R', NCH2R', N(R")C(O)NR'R", N(R")S(O)2R' or N(R')S(O)2NR'R", etc.;

[0102] Wherein, R' and R" are each independently H, C 1-6 Alkyl or cycloalkyl, C 1-6 Haloalkyl, C2-6 Alkenyl, C 2-6 Halogenated alkenyl, C 2-6 Alkynyl or C 2-6 Haloalkynyl.

[0103] Inert solvents refer to various solvents that do not react with raw materials, including various linear, branched or cyclic alcohols, ethers or ketones, halogenated alkanes, 1,4-dioxane, acetonitrile, tetrahydrofuran, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and the like.

[0104] Compounds having nematicidal activity of the present invention

[0105] The term "active substance of the present invention" or "active compound of the present invention" refers to a compound having a structure represented by the general formula (I) or an agrochemically acceptable salt thereof.

[0106] In a specific embodiment, the compound of the present invention is a compound represented by the general formula I:

[0107]

[0108] wherein n, A, G, M and Q are as described above.

[0109] In a further embodiment, according to the different connecting bridges M in the general formula I, the compounds of the present invention can be divided into several different types of compounds:

[0110] When M is (CH2) m , wherein m = 0-5, an amide compound II is obtained, and its specific structural example is shown in Table 1;

[0111] When M is When sulfonamide compounds I-II are obtained, specific examples of which are shown in Table 2;

[0112] When M is When , thiosemicarbazide compounds I-III are obtained, and specific examples thereof are shown in Table 3;

[0113] When M is a six-membered aromatic (hetero) ring, compound I-IV is obtained, wherein when Q is When the bisamide compounds are obtained, specific examples are shown in Table 4.

[0114] The active substance of the present invention can be used to control and eliminate a wide range of parasitic nematodes of agricultural and forestry plants. In this specification, "nematicide" is a general term for substances that have the effect of controlling all plant parasitic nematodes mentioned herein.

[0115] Examples of plant parasitic nematodes include, but are not limited to, root-knot nematodes, such as Meloidogynearenaria, Meloidogyne chitwoodi, Meloidogyneexigua, Meloidogyne hapla, Meloidogyneincognita, Meloidogyne javanica, and other Meloidogyne species; cyst nematodes, such as Globodera rostochiensis, Globodera pallida, Globodera tabacum, and other Globodera species; heterodermal nematodes, such as Heterodera avenae, Heterodera spp. glycines), beet cyst nematode (Heterodera schachtii), clover cyst nematode (Heterodera trifolii), and other Heterodera species; seed nematodes, such as Anguina funesta, Anguina tritici, and other Anguina species; stem and leaf bud nematodes, such as Aphelenchoides besseyi, Aphelenchoides fragariae, Aphelenchoides ritzemabosi, and other Aphelenchoides species; thorn nematodes, such as Belonolaimus longicaudatus and other Belonolaimus species; pine nematodes, such as Bursaphelenchus xylophilus xylophilus and other Bursaphelenchus species; ring nematodes, such as Criconema, Criconemella, Criconemoides, and Mesocriconema; bulb nematodes, such as Ditylenchus destructor, Ditylenchus dipsaci, Ditylenchus myceliophagus, and other Ditylenchus species;Cone nematodes, such as Dolichodorus; spiral nematodes, such as Helicotylenchus dihystera, Helicotylenchus multicintus, and other Helicotylenchus; sheath nematodes, such as Hemicycliophora and Hemicriconemoides; crown nematodes, such as Hoploaimus columbus and other Hoploaimus; pseudorhizobium nematodes, such as Nacobbus aberrans and other Nacobbus; needle nematodes, such as Longidorus elongatus and other Longidorus species; nail nematodes, such as Paratylenchus; root rot nematodes, such as Pratylenchus brachyurus, Pratylenchus coffee, Pratylenchus zeae, Pratylenchus penetrans, and other Pratylenchus species; boring nematodes, such as Radopholus similis and other Radopholus species; reniform nematodes, such as Rotylenchus robustus and other Rotylenchus species; stump nematodes, such as Trichodorus rufipogonus and other primitivus and other Trichodorus; dwarf nematodes such as Tylenchorhynchus claytoni, Tylenchorhynchus dubius, and other Tylenchorhynchus; citrus nematodes such as Tylenchulus semipipenetrans and other Tylenchulus; Xiphinema such as Xiphinema americanum, Xiphinema index, Xiphinema diversicaudatum, and other Xiphinema.

[0116] The compound of the present invention has a good control effect on the southern root-knot nematode (Meloidogyne incognita).

[0117] Nematicide composition containing the active substance of the present invention

[0118] The active substances of the present invention can be prepared into nematicide compositions by conventional methods. These active compounds can be made into conventional formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active substances, microcapsules in polymers, coating compounds for seeds, and formulations for use with combustion devices, such as fumigation cartridges, fumigation pots and fumigation trays, and ULV cold mist and hot mist formulations.

[0119] These preparations can be produced in a known manner, for example by mixing the active compound with an extender, i.e. a liquid, liquefied gas or solid diluent or carrier and optionally a surfactant, i.e. an emulsifier and / or dispersant and / or foam former. For example, when water is used as the extender, an organic solvent can also be used as an auxiliary agent.

[0120] When a liquid solvent is used as a diluent or carrier, it is basically suitable, such as: aromatic hydrocarbons, for example xylene, toluene or alkylnaphthalene; chlorinated aromatic or chlorinated aliphatic hydrocarbons, for example chlorobenzene, vinyl chloride or methylene chloride; aliphatic hydrocarbons, for example cyclohexane or paraffins, for example mineral oil fractions; alcohols, for example ethanol or ethylene glycol and their ethers and lipids; ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; or unusual polar solvents, for example dimethylformamide and dimethyl sulfoxide, and water.

[0121] A diluent or carrier for liquefied gas refers to a liquid that will become a gas at normal temperature and pressure, such as an aerosol propellant, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.

[0122] Solid carriers can be ground natural minerals, such as kaolin, clay, talc, quartz, atavistic clay, montmorillonite, or diatomaceous earth; and ground synthetic minerals, such as highly dispersed silicic acid, alumina and silicates. Solid carriers for particles are ground and classified natural zircons, such as calcite, marble, pumice, sepiolite and dolomite, and inorganic and organic coarse powders and particles of organic materials such as sawdust, coconut shells, corn cobs and tobacco stems.

[0123] Nonionic and anionic emulsifiers can be used as emulsifiers and / or foam formers. For example, polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, such as alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and albumin hydrolysates. Dispersants include lignin sulfite waste liquor and methylcellulose.

[0124] Binders such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or emulsions, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, may be used in the formulation.

[0125] Colorants such as inorganic dyes, such as iron oxide, cobalt oxide and Prussian blue; organic dyes, such as azo dyes or metal phthalocyanine dyes; and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, aluminum and zinc, etc. may be used.

[0126] The active compounds of the present invention may be mixed with other active compounds in their commercial preparations or in the use formulations prepared from these preparations, and these other active compounds are insecticides, bactericides, fungicides, herbicides, growth control agents, etc. Insecticides include, for example, phosphates, carbamates, chlorinated hydrocarbons, and substances produced by microorganisms, such as avermectin, etc., and fungicides include strobilurins, amides, triazoles, etc.

[0127] In addition, the active compounds of the present invention may also be mixed with synergists in their commercial preparations or dosage forms prepared from these preparations. These synergists are compounds that enhance the effects of the active compounds. Since the active compounds themselves are active, it is not necessary to add synergists.

[0128] These preparations usually contain 0.001-99.99% by weight, preferably 0.01-99.9% by weight, more preferably 0.05-90% by weight of the active compound of the present invention, based on the total weight of the nematicidal composition. The concentration of the active compound in the commercial preparations or use forms may vary over a wide range. The concentration of the active compound in the use form may be from 0.0000001 to 100% (g / v), preferably between 0.0001 and 1% (g / v).

[0129] Preparation method of the compound of the present invention

[0130] The compound shown in the general formula of the present invention can be prepared by the following method, but the conditions of the method, such as the amount of reactants, solvents, alkalis, compounds used, reaction temperature, reaction time required, etc. are not limited to the following explanation. The compounds of the present invention can also be prepared conveniently by combining various synthetic methods described in this specification or known in the art, and such a combination can be easily carried out by a technician in the field to which the present invention belongs. If feasible, the reagent can be purchased through commercial channels.

[0131] Typical embodiments of the compounds of the present invention can be synthesized using the following general reaction schemes. It is apparent from the description given herein that the general scheme can be changed by replacing with other materials with similar structures to obtain corresponding different products. The synthetic method can provide a large amount of production as required. The raw materials can be obtained by commercial methods or synthesized using disclosed methods. The examples given herein, through simple inspection steps, the characteristics of the final product usually make the characteristics of the necessary raw materials obvious.

[0132] Synthesis reaction parameters can use, for example, the following general methods and procedures to prepare compounds of the present invention from readily available starting materials. It will be appreciated that other process conditions may also be used where typical or optimized process conditions (i.e., reaction temperature, time, molar ratio of reactants, solvent, catalyst, pressure, etc.) are given, unless otherwise noted. Optimum reaction conditions may vary with specific reactants or solvents used, but such conditions may be determined by conventional optimization procedures by those skilled in the art.

[0133] The starting materials for the following reactions are generally known compounds or can be prepared by known procedures or obvious modifications thereof. For example, many starting materials can be obtained from commercial suppliers, and others can be prepared by procedures described in standard reference texts or obvious modifications thereof.

[0134] In the preparation method of the present invention, each reaction is usually carried out in an inert solvent at a reaction temperature of -20 to 120°C (preferably -10 to 0°C or 20 to 30°C or 80 to 100°C). The reaction time is usually 2 to 24 hours, preferably 4 to 18 hours, and the reaction time can be appropriately extended according to the reaction requirements. The specific reaction time is determined according to the degree of reaction.

[0135] The base used in the reaction includes (but is not limited to): triethylamine, pyridine, diisopropylethylamine, diethylamine, piperidine, piperazine, morpholine, N-methylmorpholine, triethylenediamine (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, or a combination thereof.

[0136] The condensing agent used in the reaction includes (but is not limited to): 4-dimethylaminopyridine (4-DMAP, PyBop), diphenylphosphoryl azide (DPPA), dicyclohexylcarbodiimide (DCC), HATU, diphenylphosphinyl chloride (DPP-Cl).

[0137] Synthesis route:

[0138] 1. When M is a substituted or unsubstituted 5-7 membered aromatic ring, a substituted or unsubstituted 5-7 membered carbocyclic ring, a substituted or unsubstituted 5-7 membered aromatic heterocyclic ring, or a substituted or unsubstituted 5-7 membered heterocyclic ring, (CH2) m When m=0-5, the method in Scheme 1 is adopted.

[0139] Scenario 1:

[0140]

[0141] In one embodiment, 1-1 is chlorinated and then reacted with the corresponding amine or sulfonamide in the presence of a base or a condensing agent to obtain 1-3, which is then reacted with a bromide under basic conditions to produce compound 1-4.

[0142] When M is CH2SN2, the method in Scheme 2 is adopted.

[0143] Option 2:

[0144]

[0145] In one embodiment, 2-1 is chlorinated and then reacted with the corresponding ammonium thiocyanate to obtain the corresponding isothiocyanate 2-3, which is then reacted with an amino compound to produce compound 2-4.

[0146] When M is SO2, use option 3:

[0147]

[0148] In one scheme, 3-1 is reacted with the corresponding sulfonamide in the presence of a condensing agent to obtain 3-2, and 3-2 is then reacted with a bromide in the presence of a base to produce compound 3-3.

[0149] Synthesis Example

[0150] 1. Preparation of Compound II

[0151] Take the preparation of II-2N-(5-chlorothiazol-2-yl)-4,5,5-trifluoropentene-4-amide as an example.

[0152] (1) Preparation of intermediate II-2.

[0153] Synthesis of 4,5,5-trifluoropentenoyl chloride

[0154]

[0155] 2mmol of 4,5,5-trifluoropentenoyl chloride and 15mL of dichloromethane were added to a 50mL single-mouth bottle, and a dichloromethane solution of 2.5mmol of oxalyl chloride was added dropwise in an ice bath. After the addition was complete, 0.05mL of DMF was added. Stir at room temperature for 3h. After the reaction was completed, dichloromethane was removed by distillation to obtain a crude product of 4,5,5-trifluoropentenoyl chloride with a yield of 91%. It was directly used for the next step without purification.

[0156] Synthesis of 2-amino-4-chlorothiazole

[0157]

[0158] 5mmol of 2-aminothiazole, 10mL of acetic acid, and 6mmol of NCS were added to a 100mL single-mouth bottle, stirred at room temperature for reaction, and followed by TLC. After the reaction was completed, the reaction solution was poured into 50mL of distilled water, and the pH was adjusted to 7 with a saturated sodium bicarbonate aqueous solution. The mixture was extracted with dichloromethane (15mL×3), the organic layers were combined, dried with anhydrous sodium sulfate, filtered, and the filtrate was concentrated. The pure product of 2-amino-4-chlorothiazole was obtained by column chromatography with petroleum ether / ethyl acetate = 3 / 1, with a yield of 72%.

[0159] (2) Preparation of II-2

[0160]

[0161] Take N-(5-chlorothiazol-2-yl)-4,5,5-trifluoropentene-4-amide as an example. 3mmol of 2-amino-5-chlorothiazol, 3mmol of 4,5,5-trifluoropentenoyl chloride, 4.5mmol of triethylamine, and 20mL of dichloromethane were added to a single-mouth bottle and stirred at room temperature for reaction. TLC tracking, after the reaction was completed, the solvent was removed under reduced pressure, 30mL of saturated ammonium chloride aqueous solution was added to the residue, and dichloromethane (15mL×3) was used for extraction, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, the filtrate was collected and concentrated, and the pure product N-(5-chlorothiazol-2-yl)-4,5,5-trifluoropentene-4-amide was obtained by petroleum ether ethyl acetate column chromatography.

[0162] 2. Preparation of Compound I-II

[0163] Taking the preparation of I-II-1 4,5,5-trifluoro-N-(thiazol-2-ylsulfonyl)pent-4-enamine as an example

[0164]

[0165] Thiazole-2-sulfonamide 1.7mmol, 4,5,5-trifluoropentenoic acid 3mmol, triethylamine 4.5mmol, dichloromethane 20mL, were added to a single-mouth bottle, stirred at room temperature for reaction. TLC tracking, after the reaction was completed, the solvent was removed under reduced pressure, saturated ammonium chloride aqueous solution 30mL was added to the residue, and dichloromethane (15mL×3) was used for extraction, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, the filtrate was collected and concentrated, and the pure product N-(5-chlorothiazol-2-yl)-4,5,5-trifluoropentene-4-amide was obtained by petroleum ether ethyl acetate column chromatography.

[0166] 3. Preparation of Compounds I-III

[0167] Taking the preparation of I-III-1 4,5,5-trifluoro-N-(2-(thiazol-2-yl)hydrazine-1-thiocarbonyl)pent-4-enamide as an example

[0168] (1) Preparation of the intermediate 4,5,5-trifluoropent-4-enoyl isothiocyanate

[0169]

[0170] Add 2mmol of ammonium thiocyanate, 2mmol of 4,5,5-trifluoropentenoyl chloride, and 20mL of dimethyl carbonate to a single-mouth bottle, stir and heat to reflux. After 30 minutes, stop heating and cool to room temperature. Remove the solvent under reduced pressure, add 30mL of saturated sodium chloride aqueous solution to the residue, extract with dichloromethane (15mL×3), combine the organic phases, dry with anhydrous sodium sulfate, filter, collect and concentrate the filtrate to obtain crude 4,5,5-trifluoropent-4-enoyl isothiocyanate.

[0171] (2) Preparation of 4,5,5-trifluoro-N-(2-(thiazol-2-yl)hydrazine-1-thiocarbonyl)pent-4-enamide

[0172]

[0173] 2mmol of 4,5,5-trifluoropent-4-enoyl isothiocyanate, 2mmol of 2-thiazole hydrazine, and 20mL of ethyl acetate were added to a single-mouth bottle, stirred, cooled to 0°C for reaction. TLC tracking, after the reaction was completed, 30mL of saturated sodium chloride aqueous solution was added for extraction, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was collected and concentrated, and 4,5,5-trifluoro-N-(2-(thiazol-2-yl)hydrazine-1-thiocarbonyl)pent-4-enoamide was obtained by column chromatography.

[0174] 4. Preparation of Compounds I-IV

[0175] To prepare I-IV-6N 2 ,N 6 -Bis(4,5,5-trifluoropent-4-en-1-yl)pyrazine-2,6-amide as an example

[0176]

[0177] 1.5 mmol of 2,6-diaminopyrazine, 3 mmol of 4,5,5-trifluoropentenoic acid, 4.5 mmol of pyridine, and 20 mL of dichloromethane were added to a single-mouth bottle and stirred at room temperature for reaction. TLC tracking, after the reaction was completed, the solvent was removed under reduced pressure, 30 mL of saturated aqueous ammonium chloride solution was added to the residue, and dichloromethane (15 mL×3) was used for extraction. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was collected and concentrated. The pure product N was obtained by petroleum ether ethyl acetate column chromatography. 2 ,N 6 -bis(4,5,5-trifluoropent-4-en-1-yl)pyrazine-2,6-amide.

[0178] NMR data of target compound:

[0179] Table 1: NMR data of compound II

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190] Table 2: NMR data of compound I-II:

[0191]

[0192]

[0193]

[0194] Table 3: NMR data of compounds I-III

[0195]

[0196]

[0197]

[0198] Table 4: NMR data of compounds I-IV:

[0199]

[0200]

[0201]

[0202] Test Example. Nematicidal activity test of the compounds of the present invention

[0203] Root-knot nematodes belong to the phylum Nematoda, order Tylenchida, suborder Tylenchida, superfamily Heteroderidea, subfamily Meloidogyninae, and genus Meloidogyne. They are a serious plant parasitic nematode.

[0204] Live activity

[0205] The southern root-knot nematode (Meloidogyne incognita) was used as the test object, cucumber seedlings were used as the test host, and the test was carried out using the test tube planting method.

[0206] Operation process: Prepare the sample to be tested into a liquid medicine according to the required concentration and prepare a sufficient amount of second-instar larvae of root-knot nematodes. After planting one-week-old cucumber seedlings in test tubes, add an appropriate amount of prepared liquid medicine to the test tubes, and inoculate about 2,000 larvae into each test tube. The test tubes are placed at 20-25°C and cultured under 10 hours of light. After 45 days, the results are investigated and the number of root knots on the roots of each plant is counted. Each sample is tested 3 times, and each sample is treated 4 times in each test.

[0207] Distilled water was used as blank control, distilled water plus root-knot nematodes was used as negative control, and avermectin solution was used as positive control.

[0208] Disease index grading calculation reference Figure 2 .

[0209] In vivo nematicidal activity of compounds:

[0210] Table 5: In vivo activity of compound II:

[0211]

[0212]

[0213]

[0214]

[0215] Table 6: In vivo activity of compounds I-II:

[0216]

[0217]

[0218]

[0219] Table 7: In vivo activity of compounds I-III:

[0220]

[0221]

[0222] Table 8: In vivo activity of compounds I-IV:

[0223]

[0224]

[0225] In vitro activity

[0226] In vitro experiments were conducted in 96-well plates using the southern root-knot nematode (Meloidogyne incognita) as the test object.

[0227] The compound to be tested is diluted with acetone to a solution of a certain concentration, and then diluted with a certain amount of water to the test concentration. The drug solution and a certain amount of second-instar larvae of southern root-knot nematodes are added to a 96-well plate, with no less than 50 larvae in each well. After the preparation is completed, the 96-well plate is placed in a 25°C incubator, and the death of nematodes is observed and recorded for 72 hours. In the test, each compound is measured twice in parallel, with an aqueous solution of acetone as a blank control and fluthiamethoxam as a positive control. The mortality rate is shown in the table below.

[0228] In vitro nematicidal activity of compounds:

[0229] Table 9: In vitro activity of compound II:

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236] Table 10: In vitro activity of compounds I-II:

[0237]

[0238]

[0239] Table 11: In vitro activity of compounds I-III

[0240]

[0241]

[0242] Table 12: In vitro activities of compounds I-IV:

[0243]

[0244]

[0245] It can be seen from the activities summarized in the above table that the compounds of the present invention have very good nematicidal activity and can show obvious nematicidal effects at a concentration as low as 40 ppm.

[0246] All documents mentioned in the present invention are cited as references in this application, just as each document is cited as reference individually. In addition, it should be understood that after reading the above teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims attached to this application.

Claims

1. The compound represented by formula II, or its optical isomers, cis-trans isomers or pesticide-acceptable salts: In the formula, n is 1; m is 0 or 1; A is an oxygen or sulfur atom; G is selected from the group consisting of H, unsubstituted C 1-6 alkyl; Q is a group selected from the following: Where p is an integer from 0 to 3; Wherein R1 is selected from the following group: unsubstituted C 1-6 Alkyl or alkoxy, halogen.

2. The compound according to claim 1, or its optical isomers, cis-trans isomers or pesticide-acceptable salts, characterized in that: The unsubstituted C 1-6 Alkyl or alkoxy is unsubstituted C 1-3 Alkyl or alkoxy.

3. A compound of formula II, or an optical isomer, a cis-trans isomer, or a pesticide-acceptable salt thereof, characterized in that: The compound is selected from the following compounds:

4. A pesticide composition comprising the compound according to any one of claims 1 to 3, or its optical isomers, cis-trans isomers or pesticide-acceptable salts, and optionally a pesticide-acceptable excipient.

5. Use of the compound according to any one of claims 1 to 3, or its optical isomers, cis-trans isomers or pesticide-acceptable salts thereof, for killing parasitic nematodes of agricultural and forestry plants or for preparing a pesticide composition for killing parasitic nematodes of agricultural and forestry plants.

6. Use of the pesticide composition according to claim 4 for killing parasitic nematodes of agricultural and forestry plants.

7. A method for controlling and eliminating parasitic nematodes of agricultural and forestry plants, characterized in that: The method comprises the step of administering an effective amount of the compound according to any one of claims 1 to 3, or its optical isomers, cis-trans isomers or pesticide-acceptable salts, or the pesticide composition according to claim 4 to plants or crops that need to control and eliminate agricultural and forestry plant parasitic nematodes.

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