CN103601718A - O-formammidotiazol-benzamide derivatives based on ryanodine receptor, and preparation method and applications thereof - Google Patents

Abstract

The invention provides o-formammidotiazol-benzamide derivatives, and a preparation method and applications thereof. The o-formammidotiazol-benzamide derivatives have the chemical structure general formula represented by the formula I or the formula II. The invention discloses the structure general formula of the compounds, the synthesis method and the applications of the compounds as insecticides, acaricides and bactericides; the compounds are mixed with agriculturally acceptable auxiliary agents or synergistic agents for use in processing crafts of preparing the insecticides, the acaricides and the bactericides. The invention also discloses the applications of the compounds in combination with the commercial insecticides, the acaricides, the bactericides, anti-plant virus agents and plant activators for prevention and treatment of agriculture, forestry, horticulture plant diseases, insect attacks, acarus attacks and virus diseases, and the preparation method of the compounds.

Description

One class anthranilic diamides derivative based on fish mud fourth acceptor and its production and use

Technical field

The present invention relates to some anthranilic diamides derivative, relate to for preparing their method, relate to them and be used as the purposes of sterilant, miticide and fungicidal activity reagent, and use the methods and applications in these compounds and the pest control in agricultural, forestry, gardening environment of their composition, mite evil, disease, virus disease.

Background technology

Insect can cause yield showing to the infringement of the farm crop in growth and the farm crop of storage reducing, and then causes production cost to increase.Pest control is very important aspect the food of forestry, chamber crop, ornamental plant, crop nursery stock, storage and fibre product, livestock industry, family, lawn, woodwork and health.Novel ultra-high efficiency sterilant biamide structure is novel, and mechanism of action is unique, to mammalian safe, mainly contains phthalic imidine insecticides Flubendiamide (EP1006107); Phthalic imidine insecticides chlorantraniliprole (WO03015519) and cyanogen insect amide (WO2004067528).Two compounds structures are different, but mechanism of action is all the ryanodine receptor that acts on insect, cause the continuous release of calcium ion in muscle and nervous tissue cell, cause insect muscle constantly to shrink, finally cause death (Gerorge P.Lahm, the New and selective ryanodine receptor activators for insect control of insect, Bioorganic & Medicinal Chemistry, 2009,17,4127-4133).

Although bisamide insecticides shows outstanding superiority aspect active, some areas are due to frequent excessively dispenser, and insect has showed resistance in various degree, and up to the present the commercial kind number of this insecticides is very limited.In order further to study the ryania compounds of high-efficiency low-toxicity, the present invention utilizes pesticide molecule active fragments splicing principle design to synthesize the anthranilic diamides derivative of a class based on fish mud fourth acceptor, for the initiative research of novel pesticide provides eco-friendly ultra-high efficiency novel candidate compound.

Summary of the invention

Technical problem to be solved by this invention is: the synthetic method that a class anthranilic diamides derivative is provided, biological activity and measuring method thereof that this compounds regulation and control agricultural, gardening and health and forestry plant insect and the phytopathy original are provided provide the middle application of these compounds at agriculture field, gardening field, field of forestry and health field simultaneously.

The chemical structure of general formula with the anthranilic diamides derivative of agriculture field, gardening field, forestry and health field insecticidal activity, fungicidal activity, anti-phytoviral activity, inducing plant generation anti-disease activity, insect growth regulator activity is shown in formula I or II:

Wherein: R ¹and R ²be selected from hydrogen, the alkyl that contains 1-10 carbon atom, have by 1-4 F, the alkyl that contains 1-10 carbon atom that Cl replaces, the cycloalkyl that contains 3-7 carbon atom, contain 3-6 carbon atom and O, N, S, the heterocyclic group of 1-2 atom in P, aryl, hydroxyl, the alkoxyl group that contains 1-10 carbon atom, aryloxy, trifluoromethoxy, cyano group, nitro, amino, the alkylamino that contains 1-10 carbon atom, the dialkyl amido that contains 1-10 carbon atom, sulfydryl, the alkylthio that contains 1-10 carbon atom, arylthio, formyl radical, the alkyl-carbonyl that contains 1-10 carbon atom, aryl carbonyl, manthanoate, the alkyl carboxyl that contains 1-10 carbon atom, aryl carboxyl, the alkoxyl group carboxyl that contains 1-10 carbon atom, aryloxy carboxyl, formamido group, the alkyl amido that contains 1-10 carbon atom, aryl-amino-carbonyl, urea groups, the alkyl urea groups that contains 1-10 carbon atom, aryl-ureido, amino carboxyl, the alkylamino carboxyl that contains 1-10 carbon atom, arylamino carboxyl, trifluoroacetyl group, F, Cl, Br, I, hydroxycarbonyl group, the alkoxy carbonyl that contains 1-10 carbon atom, aryloxycarbonyl, sulfinyl, the alkyl sulphinyl that contains 1-10 carbon atom, aryl sulfonyl kia, alkylsulfonyl, the alkyl sulphonyl that contains 1-10 carbon atom, aryl sulfonyl, sulfonamido, the alkyl sulfonyl that contains 1-10 carbon atom is amino, Arenesulfonyl amino functional group,

R ³the alkyl that is selected from hydrogen, contains 1-10 carbon atom, there is the alkyl that contains 1-10 carbon atom, the cycloalkyl that contains 3-7 carbon atom that are replaced by 1-4 F, Cl, contain 3-6 carbon atom and O, N, heterocyclic group, the aryl of 1-2 atom in S, P;

R ⁴be selected from hydrogen, the alkyl that contains 1-10 carbon atom, there is the alkyl that contains 1-10 carbon atom being replaced by 1-4 fluorine or chlorine, the cycloalkyl that contains 3-7 carbon atom, contain 3-6 carbon atom and O, N, S, the heterocyclic group of 1-2 atom in P, aryl, hydroxyl, the alkoxyl group that contains 1-10 carbon atom, aryloxy, trifluoromethoxy, cyano group, nitro, amino, the alkylamino that contains 1-10 carbon atom, the dialkyl amido that contains 1-10 carbon atom, sulfydryl, the alkylthio that contains 1-10 carbon atom, arylthio, formyl radical, the alkyl-carbonyl that contains 1-10 carbon atom, aryl carbonyl, formamido group, the alkyl amido that contains 1-10 carbon atom, aryl-amino-carbonyl, urea groups, the alkyl urea groups that contains 1-10 carbon atom, aryl-ureido, amino carboxyl, the alkylamino carboxyl that contains 1-10 carbon atom, arylamino carboxyl, trifluoroacetyl group, the alkoxy carbonyl that contains 1-10 carbon atom, aryloxycarbonyl, sulfinyl, the alkyl sulphinyl that contains 1-10 carbon atom, aryl sulfonyl kia, alkylsulfonyl, the alkyl sulphonyl that contains 1-10 carbon atom, aryl sulfonyl, sulfonamido, the alkyl sulfonyl that contains 1-10 carbon atom is amino, Arenesulfonyl amino functional group,

X, Y and Z are selected from CR ⁵r ⁶, NR ₃, O, S, CO, SO, SO ₂; Y can be CR ⁵r ⁶-CR ⁵r ⁶, or do not exist; R ⁵, R ⁶the alkyl that is selected from hydrogen, contains 1-10 carbon atom, there is the alkyl that contains 1-10 carbon atom being replaced by 1-4 F, Cl;

m＝1，2。

The compound of general formula (I)-(II) can have asymmetric center.Contain by the compound of the formula of the atom of Asymmetrical substitute (I)-(II) and also can obtain with optically active form or racemic isolated in form.All optical isomers shown or described compound are all regarded as a part of the present invention.All tautomers, salt, hydrate, solvation form shown or described compound are also regarded as a part of the present invention.

The compound of general formula (I)-(II) can form metabolite after administration, N-oxide compound and other oxidation products of for example by the endogenous enzyme of insect and plant, being formed.Some in described metabolite may have insecticidal activity.All metabolites shown or described compound comprise that N-oxide compound is all considered to be a part of the present invention.All prodrugs shown or described compound are also considered to be a part of the present invention.

Term " alkyl " refers to the straight or branched of carbon atom, and " low alkyl group " refers to alkyl chain straight chain or side chain of 1-10 carbon atom, except as otherwise noted.Straight chain be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, amyl group, hexyl and heptyl, heptyl, octyl group, nonyl, decyl with low-grade alkyl group side chain.This alkyl group is included in the substituted radical in carbochain.

Term " aryl " refers to the carbocyclic aromatic group optionally replacing, as phenyl and naphthyl.Suitable substituting group on aryl can include but not limited to, for example, and alkyl, halogen, cyano group, hydroxyl, carboxyl, alkoxyl group, amino, alkylamino and dialkyl amido.Aromatic yl group can comprise one or more heteroatomss on ring, as nitrogen, oxygen or sulphur." salt " refers to a kind of salt of organic or inorganic, and it, can be directly or compound of the present invention is provided indirectly when being administered to environment, plant or insect.The embodiment of salt includes, but not limited to inorganic acid salt or the organic acid salt of alkaline residue.Salt can comprise, for example, and the salt of the conventional quaternary ammonium of the parent compound being formed by mineral acid or organic acid.For example, such salt can include, but not limited to those derived from following mineral acid and organic acid salt: 1,2-ethionic acid, Aspirin, 2-ethylenehydrinsulfonic acid, acetic acid, xitix, Phenylsulfonic acid, phenylformic acid, heavy carbonic, carbonic acid, citric acid, ethylenediamine tetraacetic acid (EDTA), ethane disulfonic acid, ethane sulfonic acid, fumaric acid, glucoheptonic acid, glyconic acid, L-glutamic acid, oxyacetic acid, glycoloyl Pro-gen 90 (glycollyarsanilic), Sucrets formic acid (hexylresorcinic), hydration A Bamei acid (hydrabamic), Hydrogen bromide, hydrochloric acid, hydroiodic acid HI, hydroxymaleic acid (hydroxymaleic), hydroxynaphthoic acid, ethylenehydrinsulfonic acid, lactic acid, lactobionic acid, lauryl sulfonic acid, toxilic acid, oxysuccinic acid, amygdalic acid, methylsulfonic acid, naphthene sulfonic acid (napsylic acid), nitric acid, oxalic acid, pamoic acid, pantothenic acid, toluylic acid, phosphoric acid, polygalacturonic acid, propionic acid, Whitfield's ointment, stearic acid, subacetate (subacetic), succsinic acid, thionamic acid, Sulphanilic Acid (sulfanilic), sulfuric acid, Weibull, tartrate, toluenesulphonic acids, naphthene sulfonic acid, amygdalic acid and other acid.Preferred hydrochloric acid, Hydrogen bromide, sulfuric acid, phosphoric acid or nitric acid.

" prodrug " refers to non-active compound, the interim derivative of the functional group of active compound, and it can change into active compound after administration, can produce the non-active compound of active compound in environment, when plant and insect body intracellular metabolite; Document sees reference: A.L.Simplicio etc., Prodrugs for Amines, Molecules, 2008,13:519-547.

Term: mol is mole; Mmol is mmole; ML is milliliter; ℃ be degree Celsius; N is equivalent concentration; UL is microlitre; L rises; MM is every liter of mmole.

The invention still further relates to the composition that contains compound, said composition is in pure state or have suitable carrier, adjuvant and vehicle, as extender, solvent or solid carrier or tensio-active agent.Composition can be prepared as agricultural chemicals and use.

The composition the present invention relates to: emulsifiable concentrate, suspension-concentrates, can directly spray or dilutable solution, the paste that can smear, dilution emulsion, soluble powder, dispersible pulvis, wettable powder, pulvis, granule, pill, tablet, film and comprise seed pelleting or polymeric material encapsulant, it comprises at least one in activeconstituents of the present invention.

The example of suitable solvent comprises not hydrogenation or partially hydrogenated aromatic hydrocarbons, as xylene mixture, alkylated naphthalene or tetraline; Aliphatic series or clicyclic hydrocarbon, as paraffin or hexanaphthene; Alcohols, as ethanol, propyl alcohol or butanols, glycols and ethers thereof and ester class, as propylene glycol, dipropylene glycol, ethylene glycol or ethylene glycol monomethyl ether or ethylene glycol monomethyl ether; Ketone, as pimelinketone, isophorone or Pyranton; Intensive polar solvent, as NMP, methyl-sulphoxide or DMF; Water; Not epoxidation or epoxidized vegetable oil, as not epoxidation or epoxidized oil rapeseed oil, Viscotrol C, Oleum Cocois or soya-bean oil, and silicone oil.

The carrier of suitable pulvis solid is calcite, talcum, kaolin, float stone, brick gravel, sepiolite or wilkinite or sand for example; In addition, can use the granulated material, particularly rhombspar of a large amount of inorganic or organic natures or the plant residue of pulverizing.

Suitable tensio-active agent comprise there is the non-ionic type of well emulsify characteristic, dispersing characteristic and wetting property, the mixture of cationic and/or anion surfactant or tensio-active agent.Suitable ionic surfactant pack is drawn together the water miscible polyethylene oxide adducts of polyglycol ether derivative, polypropylene glycol, ethene diamino polypropylene glycol or the alkyl polypropylene glycol of aliphatic series or alicyclic alcohol, saturated or unsaturated fatty acids or alkylbenzene phenols.Suitable cats product comprises quaternary ammonium salt.Suitable anion surfactant comprises an alkali metal salt, alkaline earth salt or (unsubstituted or replacement) ammonium salt of lipid acid, as oleic acid or stearic sodium salt or sylvite, and the salt of sulfonic acid, phosphoric acid salt, the salt of phosphoric acid ester or the salt of phosphatide.

Said composition can further include solid or liquid adjuvants, as stablizer, and for example not epoxidation or epoxidised vegetables oil (for example epoxidation Oleum Cocois, rape seed oil or soya-bean oil); Defoamer, for example silicone oil; Sanitas; Viscosity modifier; Tackiness agent and/or tackifier, fertilizer or for realizing other activeconstituents of certain effects, for example, sterilant, mycocide, nematocides, plant activator, invertebrate poison or weedicide.

The present invention also provides a kind of method, the method is by apply one or more pest controls in the compound of the present invention of effective quantity under agricultural and non-agricultural environment, and described method comprises and compound of the present invention contacted to insect or its environment with composition.The enough compounds of the present invention of energy and composition are for control (take precautions against or eliminate) insect, this insect occurs on crop, plant (especially useful plant) and the ornamental plant in agricultural, gardening and forestry especially, or on the organs such as fruit, flower, leaf, stem, stem tuber or root of these plants.Compound of the present invention is also suitable for preventing that infest is as materials such as timber, textiles, plastics, tackiness agent, glue, coating, paper and card, leather, floor covering and material of construction.

The invention still further relates to the application method of compound and composition, this application method is the method for pest control, as sprinkling, atomization, dusting, brushing, dressing, disseminate or pour into (application method that select to be applicable to re-set target according to general status), and for the purposes of the composition of pest control.

The present invention can, in the situation that not departing from its spirit or essential characteristic, realize with other particular forms.Should be understood that any and all embodiments of the present invention can be in conjunction with any other embodiment to describe other preferred embodiment.Also in should be understood that preferred embodiment, each independent element is intended to be regarded as individually the independently preferred implementation of himself.In addition, any element in an embodiment means by being combined with other any and all elements from any embodiment, to describe other embodiment.

The synthetic method of anthranilic diamides derivative I of the present invention or II is as follows:

Wherein: R ¹and R ²be selected from hydrogen, the alkyl that contains 1-10 carbon atom, have by 1-4 F, the alkyl that contains 1-10 carbon atom that Cl replaces, the cycloalkyl that contains 3-7 carbon atom, contain 3-6 carbon atom and O, N, S, the heterocyclic group of 1-2 atom in P, aryl, hydroxyl, the alkoxyl group that contains 1-10 carbon atom, aryloxy, trifluoromethoxy, cyano group, nitro, amino, the alkylamino that contains 1-10 carbon atom, the dialkyl amido that contains 1-10 carbon atom, sulfydryl, the alkylthio that contains 1-10 carbon atom, arylthio, formyl radical, the alkyl-carbonyl that contains 1-10 carbon atom, aryl carbonyl, manthanoate, the alkyl carboxyl that contains 1-10 carbon atom, aryl carboxyl, the alkoxyl group carboxyl that contains 1-10 carbon atom, aryloxy carboxyl, formamido group, the alkyl amido that contains 1-10 carbon atom, aryl-amino-carbonyl, urea groups, the alkyl urea groups that contains 1-10 carbon atom, aryl-ureido, amino carboxyl, the alkylamino carboxyl that contains 1-10 carbon atom, arylamino carboxyl, trifluoroacetyl group, F, Cl, Br, I, hydroxycarbonyl group, the alkoxy carbonyl that contains 1-10 carbon atom, aryloxycarbonyl, sulfinyl, the alkyl sulphinyl that contains 1-10 carbon atom, aryl sulfonyl kia, alkylsulfonyl, the alkyl sulphonyl that contains 1-10 carbon atom, aryl sulfonyl, sulfonamido, the alkyl sulfonyl that contains 1-10 carbon atom is amino, Arenesulfonyl amino functional group,

R ³the alkyl that is selected from hydrogen, contains 1-10 carbon atom, there is the alkyl that contains 1-10 carbon atom, the cycloalkyl that contains 3-7 carbon atom that are replaced by 1-4 F, Cl, contain 3-6 carbon atom and O, N, heterocyclic group, the aryl of 1-2 atom in S, P;

R ⁴be selected from hydrogen, the alkyl that contains 1-10 carbon atom, there is the alkyl that contains 1-10 carbon atom being replaced by 1-4 fluorine or chlorine, the cycloalkyl that contains 3-7 carbon atom, contain 3-6 carbon atom and O, N, S, the heterocyclic group of 1-2 atom in P, aryl, hydroxyl, the alkoxyl group that contains 1-10 carbon atom, aryloxy, trifluoromethoxy, cyano group, nitro, amino, the alkylamino that contains 1-10 carbon atom, the dialkyl amido that contains 1-10 carbon atom, sulfydryl, the alkylthio that contains 1-10 carbon atom, arylthio, formyl radical, the alkyl-carbonyl that contains 1-10 carbon atom, aryl carbonyl, formamido group, the alkyl amido that contains 1-10 carbon atom, aryl-amino-carbonyl, urea groups, the alkyl urea groups that contains 1-10 carbon atom, aryl-ureido, amino carboxyl, the alkylamino carboxyl that contains 1-10 carbon atom, arylamino carboxyl, trifluoroacetyl group, the alkoxy carbonyl that contains 1-10 carbon atom, aryloxycarbonyl, sulfinyl, the alkyl sulphinyl that contains 1-10 carbon atom, aryl sulfonyl kia, alkylsulfonyl, the alkyl sulphonyl that contains 1-10 carbon atom, aryl sulfonyl, sulfonamido, the alkyl sulfonyl that contains 1-10 carbon atom is amino, Arenesulfonyl amino functional group,

X, Y and Z are selected from CR ⁵r ⁶, NR ₃, O, S, CO, SO, SO ₂; Y can be CR ⁵r ⁶-CR ⁵r ⁶, or do not exist; R ⁵, R ⁶the alkyl that is selected from hydrogen, contains 1-10 carbon atom, there is the alkyl that contains 1-10 carbon atom being replaced by 1-4 F, Cl;

Intermediate III can be prepared by the following method.

Hal is Cl, Br orI; A NH ₂-NH ₂; Ethyl maleate and sodium ethylate for b reflux in ethanol; C phosphoryl chloride refluxes in second cyanogen; Potassium Persulphate and sulfuric acid for d reflux in second cyanogen; Alkali catalyzed hydrolysis reaction (sodium hydroxide, methyl alcohol, water) for e;

A K wherein ₂cO ₃/ DMPF; B LDA/THF/CO ₂reaction;

Compound IV can be prepared by the following method:

Wherein a is that aromatic nucleus replaces reagent, and for example N-N-iodosuccinimide is prepared iodo IV, and N-bromo-succinimide is prepared bromo IV, and N-chlorosuccinimide is prepared chloro IV, HNO ₃/ H ₂sO ₄or HNO ₃/ diacetyl oxide is prepared nitrated IV;

Compound IV also can be prepared by the following method:

Sub can be that iodine replaces, for example, with N-N-iodosuccinimide, in reaction step a, by initiator, prepared; With suitable b, can prepare a series of IV; For example with CuCN, can prepare R ¹the product IV of=CN;

Intermediate X) can prepare by the following method:

Wherein a is chloral hydrate and oxammonium sulfate, and b is methylsulfonic acid, and c is sodium hydroxide and aqueous hydrogen peroxide solution, d is that aromatic nucleus replaces reagent, and for example N-N-iodosuccinimide is prepared iodo IV, and N-bromo-succinimide is prepared bromo IV, N-chlorosuccinimide is prepared chloro IV, HNO ₃/ H ₂sO ₄or HNO ₃/ diacetyl oxide is prepared nitrated IV;

Intermediate X also can be prepared by the following method:

Sub can be that iodine replaces, for example, with N-N-iodosuccinimide, in reaction step a, by initiator, prepare iodo product.With suitable reagent b, can prepare a series of X.For example with CuCN, can prepare R ¹the product X of=CN;

Intermediate X also can be prepared by the following method:

A is methyl esterification reagent, methyl-sulfate for example, and b is that suitable aromatic ring replaces reagent, and for example N-N-iodosuccinimide is prepared iodo product, and N-bromo-succinimide is prepared bromination product, and N-chlorosuccinimide is prepared chloro-product, HNO ₃/ H ₂sO ₄or HNO ₃/ diacetyl oxide is prepared nitration product; C is NaOH/HCl.The method is applicable to replace and under reagent b reaction conditions, to be unsuitable for the situation that carboxyl exists and to prepare compounds X at aromatic ring.

Intermediate X also can be prepared by the following method:

A is nitrating agent, for example the mixture of the vitriol oil and concentrated nitric acid; B is reductive agent, for example zinc dichloride; C is hydrolysis reaction, for example sodium hydroxide/ethyl alcohol/water.

The invention has the beneficial effects as follows: anthranilic diamides derivative I or II have carried out guide's optimization, and synthetic new compound has been carried out to the screening of desinsection, acaricidal activity and bacteriostatic activity and antiviral activity, carried out it simultaneously and mixed the research of using with common agricultural chemicals, this compounds can be for control agriculture field and field of forestry and the plant pest in gardening field and the control of virus disease.

The present invention illustrates synthetic and biological activity and the application of anthranilic diamides derivative I or II more by specific preparation and biological activity determination embodiment, described embodiment is unrestricted the present invention for illustrating the present invention only, especially biological activity only illustrates, and unrestricted the present invention, embodiment is as follows:

The preparation of the bromo-1-of embodiment 1:3-(3-chloropyridine-2-yl)-N-(4-cyano group-2-(methoxyl group formamyl)-6-aminomethyl phenyl)-1H-pyrazoles-5-methane amide (Compound I-10)

Compound I-10 can be prepared with the following method, and concrete steps are as follows:

The preparation of the bromo-1-of intermediate 3-(the chloro-pyridyl of 3-)-1H-pyrazoles-5-formic acid III-1

The preparation of 2-(the bromo-pyrazol-1-yl of 3-)-3-chloropyridine:

The bromo-1H-pyrazoles of 3-is dissolved in to DMF (80mL), adds the chloro-pyridine of 2,3-bis-(13.8 grams) and salt of wormwood (57.3 grams), and mixture is stirred 8 hours at 100 ℃.Add after water, by ethylamine extraction 2 times for mixture, the organic layer that water, salt water washing merge 2 times, uses Na ₂sO ₄dry, and concentrated in a vacuum.By column chromatography for resistates (propyl group amine/ethylamine 6:1) purifying, obtain 7 grams for the title compound 2-of white solid (the bromo-pyrazol-1-yl of 3-)-3-chloropyridine.

The preparation of the bromo-1-of 3-(the chloro-pyridyl of 3-)-1H-pyrazoles-5-formic acid III-1:

-78 ℃ to 2-(the bromo-1H-pyrazol-1-yl of 3-) the chloro-pyridine of-3-(3.04 grams, 11.8mmol) in the solution in anhydrous THF (25mL) can keep temperature to drip LDA solution (6mL, 2M) lower than the speed of-71 ℃.At-78 ℃, stir this mixture 15 minutes, and then with carbonic acid gas bubbling, pass into 10 minutes, make it be warming up to-57 ℃, reaction mixture is warmed to-20 ℃, and water cancellation.Reaction mixture is concentrated, then, in water-soluble (100ml) and ether (80mL), then, add the NaOH aqueous solution (1N, 2mL).Water solution extract is washed with ether, and with the HCl aqueous solution (2N) acidifying.The solids that filtration is separated out, washes with water, and dry, obtains 2 grams for the title compound of brown solid, yield: 59%.The preparation process of intermediate 2-amino-5-cyano group-3-tolyl acid IV-1 is as follows:

Wherein: a application N-N-iodosuccinimide, b application cupric cyanide (CuCN)

The preparation of the iodo-3-tolyl acid of 2-amino-5-:

To 2-amino-3-tolyl acid (2.6 grams, 16.2mmol) be dissolved in solution in DMF (100mL) and add N-N-iodosuccinimide (3.65 grams, 16.2mmol), at room temperature stir 10 hours.Add elutriation and go out solid reaction product, by solid filtering, solvent is washed, obtain into colorless solid (1.7 grams, yield: 36%).

The preparation of 2-amino-5-cyano-3-tolyl acid IV-1:

By the iodo-3-tolyl acid of 2-amino-5-(1.4 grams, 5.0mmol) and cupric cyanide (0.47 gram, mixture 5.0mmol) being dissolved in DMF (10mL) stirs 9 hours at 150 ℃.By reaction product vacuum concentration, add 20mL water and 2mL hexanediamine, at room temperature stir 1 hour.Solid filtering is removed, to liquid, added 2N hydrochloric acid and be adjusted to pH value 5, be extracted with ethyl acetate 3 times.The extraction liquid merging together is concentrated, with dried over sodium sulfate obtain into colorless solid (0.7 gram, yield: 72%).

2-(the bromo-1-of 3-(the chloro-pyridine-2-of 3-yl)-1H-pyrazoles-5-yl)-8-methyl-4-oxo-4H-benzo [d] [preparation of 1,3] oxazine-6-formonitrile HCN V-1:

To the bromo-1-of 3-(the chloro-4-pyridine-2-of 3-yl)-1H-pyrazoles-5-carboxylic acid III-1, (3.0 grams, 0.01mol) (1.8 grams, 0.01mol) be dissolved in CH with 2-amino-5-cyano-3-tolyl acid (IV-1) ₃solution in CN (50mL) adds pyridine (5mL) and CH ₃sO ₂cl (3mL), then stirs 2 hours.After completing, reaction mixture is concentrated to remove most of solvent, and filter out yellow solid product V-1 (1.9 grams, yield: 41%).

The preparation of Compound I-10:

To 2-(the bromo-1-of 3-(3-chloropyridine-2-yl)-1H-pyrazoles-5-yl)-8-methyl-4-oxo-4H-benzo [d] [1,3] oxazine-6-formonitrile HCN (V-1) (50 milligrams, 0.11mmol) be dissolved in CH ₃solution in CN (5mL) adds NH ₂oCH ₃hCl (192.1 milligrams, 2.3mmol) and Et ₃n (319.3uL, 2.3mmol), at room temperature stirs 1 hour.Reaction mixture is filtered, and by filtrate vacuum concentration and carry out flash chromatography (methylene dichloride: methyl alcohol=10:1), obtain into colorless solid product (20 milligrams, yield: 36%); 1H NMR (DMSO-d ₆, 300MHz), δ: 2.24 (s, 3H), 3.53 (s, 3H), 7.41 (s, 1H), 7.60 (dd, 1H, J=7.8Hz, J=4.5Hz), 7.73 (s, 1H), 7.93 (s, 1H), 8.16 (d, 1H, J=7.8Hz), 8.47 (d, 1H, J=4.5Hz), 10.51 (s, 1H), 11.57 (s, 1H); LC-MS:m/z=489.0062, m/z (calculated value)=489.0072.

The preparation of the bromo-N-of embodiment 2:3-(4-chloro-2-methyl-6-(carboxyamino formyl radical) phenyl)-1-(3,5-dichloropyridine-2-yl)-1H-pyrazoles-5-methane amide (Compound I-2)

Compound I-2 can be prepared with the following method, and concrete steps are as follows:

2-(the bromo-1H-pyrazol-1-yl of 3-)-3, the preparation of 5-dichloropyridine:

This compound adopts and prepares 2-(the bromo-1H-pyrazol-1-yl of the 3-) method that-3-chloropyridine is identical and carry out, and by the bromo-1H-pyrazoles of 3-and 2,3,5-trichloropyridine, is prepared.

The preparation of the bromo-1-of 3-(3,5-dichloropyridine-2-yl)-1H-pyrazoles-5-formic acid (III-2):

The method identical with preparing III-1 used in compound III-2, and by 2-(the bromo-1H-pyrazol-1-yl of 3-)-3, prepared by 5-dichloropyridine and carbonic acid gas.

The preparation of the chloro-3-tolyl acid of 2-amino-5-(compound IV-2):

Adopt and prepare the identical method of the iodo-3-tolyl acid of 2-amino-5-and carry out, wherein with the alternative N-N-iodosuccinimide reagent of N-chlorosuccinimide reagent.

2-(the bromo-1-of 3-(3,5-dichloropyridine-2-yl)-1H-pyrazoles-5-yl)-6-chloro-8-methyl-4H-benzo [d] [preparation of 1,3] oxazine-4-ketone (V-2):

To the bromo-1-of 3-(3,5-dichloropyridine-2-yl)-1H-pyrazoles-5-formic acid (III-2), (3.4 grams, 10mmol) (1.9 grams, 10mmol) be dissolved in CH with the chloro-3-tolyl acid of 2-amino-5-(IV-2) ₃solution in CN (50mL) adds pyridine (5mL) and CH ₃sO ₂cl (3mL), then stirs 2 hours.After completing, reaction mixture is concentrated to remove most of solvent, and filter out yellow solid (2.2 grams, yield: 45%).

The preparation of the bromo-N-of 3-(4-chloro-2-methyl-6-(methylamino formyl radical) phenyl)-1-(3,5-dichloropyridine-2-yl)-1H-pyrazoles-5-methane amide (Compound I-2):

To 2-(the bromo-1-of 3-(3,5-dichloropyridine-2-yl)-1H-pyrazoles-5-yl), [(54 milligrams, 0.11mmol) be dissolved in CH to 1,3] oxazine-4-ketone (III-6) to-6-chloro-8-methyl-4H-benzo [d] ₃solution in CN (5mL) adds NH ₂oHHCl (158.9 milligrams, 2.3mmol) and Et3N (319.3uL, 2.3mmol), at room temperature stir 1 hour.Reaction mixture is filtered, and by filtrate vacuum concentration and carry out flash chromatography (methylene dichloride: methyl alcohol=10:1), obtain colorless solid (23 milligrams, yield: 40%); 1H NMR (DMSO-d ₆, 300MHz), δ: 2.30 (s, 3H), 7.31 (s, 1H), 7.55 (s, 1H), 7.65 (s, 1H), 8.27 (s, 1H), 8.65 (s, 1H), 10.67 (s, 1H); LC-MS:m/z=517.9181, m/z (calculated value)=517.9184.

The preparation of the bromo-1-of embodiment 3:3-(3-chloropyridine-2-yl)-N-(4-cyano group-2-(hydroxyl amino formyl radical)-6-aminomethyl phenyl)-1H-pyrazoles-5-methane amide (Compound I-9):

Compound I-9 adopt the step identical with Preparation Example 1 by above-mentioned route from intermediate V-1) prepare reagent compound VI wherein) use NH ₂oHHCl replaces CH ₃oNH ₂hCl.

To 2-(the bromo-1-of 3-(3-chloropyridine-2-yl)-1H-pyrazoles-5-yl), [(50 milligrams, 0.11mmol) be dissolved in CH to 1,3] oxazine-6-formonitrile HCN (V-1) to-8-methyl-4-oxo-4H-benzo [d] ₃solution in CN (5mL) adds NH ₂oHHCl (159.8 milligrams, 2.3mmol) and Et ₃n (319.3uL, 2.3mmol), at room temperature stirs 1 hour.Reaction mixture is filtered, and by filtrate vacuum concentration and carry out flash chromatography (methylene dichloride: methyl alcohol=10:1), obtain into colorless solid (15 milligrams, yield: 28%); ¹h NMR (DMSO-d ₆, 300MHz), δ: 2.14 (s, 3H), (7.36 s, 1H), 7.61-7.65 (dd, 1H, J=7.8Hz, J=4.8Hz), 7.75 (s, 1H), (8.04 s, 1H), 8.18-8.21 (d, 1H, J=7.8Hz), 8.51-8.52 (d, 1H, J=4.8Hz), 10.33-10.37 (brs, 2H); LC-MS:m/z=474.9907, m/z (calculated value)=474.9916.

The preparation of the bromo-1-of embodiment 4:3-(3-chloropyridine-2-yl) N-(the chloro-2-of 4-(oxyethyl group formamyl)-6-aminomethyl phenyl)-1H-pyrazoles-5-methane amide (Compound I-6):

Compound I-6 adopt the step identical with Preparation Example 1 synthetic, and reagent compound IV wherein replaces IV-1 to obtain intermediate V-3 with IV-2.

2-(the bromo-1-of 3-(3-chloropyridine-2-yl)-1H-pyrazoles-5-yl)-8-methyl-4-oxo-4H-benzo [d] [preparation of 1,3] oxazine-6-formonitrile HCN V-3:

To the bromo-1-of 3-(3-chloropyridine-2-yl)-1H-pyrazoles-5-carboxylic acid, (3.2 grams, 0.01mol) (1.9 grams, 0.01mol) be dissolved in CH with 2-amino-5-cyano-3-tolyl acid ₃solution in CN (50mL) adds pyridine (5mL) and CH ₃sO ₂cl (3mL), then stirs 2 hours.After completing, reaction mixture is concentrated to remove most of solvent, and filter out yellow solid (1.9 grams, yield: 40%).

By the identical step of Preparation Example 1, intermediate V-3 is changed into product I-6, reagent compound VI CH wherein ₃cH ₂oNH ₂hCl replaces CH ₃oNH ₂hCl prepares I-6.

To 2-(the bromo-1-of 3-(3-chloropyridine-2-yl)-1H-pyrazoles-5-yl), [(52 milligrams, 0.11mmol) be dissolved in CH to 1,3] oxazine-4-ketone V-3 to-6-chloro-8-methyl-4H-benzo [d] ₃solution in CN (5mL) adds CH ₃cH ₂oNH ₂hCl (225 milligrams, 2.3mmol) and Et ₃n (319.3uL, 2.3mmol), at room temperature stirs 1 hour.Reaction mixture is filtered, and by filtrate vacuum concentration and carry out flash chromatography (methylene dichloride: methyl alcohol=10:1), obtain colorless solid (22 milligrams, yield: 38%); ¹hNMR (DMSO-d ₆, 300MHz), δ: 1.24 (t, 3H), 2.23 (s, 3H), 3.53 (q, 2H), 7.30 (s, 1H), (7.52 s, 1H), 7.61 (dd, 1H, J=8.0Hz, J=4.8Hz), 7.70 (s, 1H), (8.17 d, 1H, J=8.0Hz), 8.49 (d, 1H, J=4.8Hz), 10.45 (s, 1H); LC-MS:m/z=511.9880, m/z (calculated value)=511.9887.

The preparation of the bromo-1-of embodiment 5:3-(3-chloropyridine-2-yl)-N-(4-cyano group-2-(oxyethyl group formamyl)-6-aminomethyl phenyl)-1H-pyrazoles-5-methane amide (Compound I-11):

To 2-(the bromo-1-of 3-(3-chloropyridine-2-yl)-1H-pyrazoles-5-yl)-8-methyl-4-oxo-4H-benzo [d] [1,3 (30 milligrams of] oxazine-6-formonitrile HCNs (V-1), 0.07mmol) and triethylamine (143 milligrams, 1.4mmol) be dissolved in 3 milliliters of CH ₃solution in CN adds CH ₃cH ₂oNH ₂hCl (138 milligrams, 1.4mmol), at room temperature stir and spend the night.Reaction mixture is filtered, and by filtrate vacuum concentration and carry out rapid column chromatography (methylene dichloride: methyl alcohol=10:1), obtain white solid (6 milligrams, yield: 18%); 1H NMR (DMSO-d ₆, 300MHz), δ: 1.21 (t, 3H), 2.22 (s, 3H), 3.91 (q, 2H), 7.40 (s, 1H), (7.63 dd, 1H, J=7.9Hz, J=4.8Hz), 7.75 (s, 1H), 7.91 (s, 1H), 8.18 (d, 1H, J=7.9Hz), 8.48 (d, 1H, J=4.8Hz), 10.48 (s, 1H), 11.45 (s, 1H); LC-MS:m/z=503.0225, m/z (calculated value)=503.0229.

The preparation of the bromo-1-of embodiment 6:3-(3-chloropyridine-2-yl)-N-(the chloro-2-of 4-(methoxyl group formamyl)-6-aminomethyl phenyl)-1H-pyrazoles-5-methane amide (Compound I-5):

This compound adopts the step identical with Preparation Example 1 synthetic, uses CH ₃oNH ₂hCl with by intermediate V-3) react, convert it into product (I-5).

To 2-(the bromo-1-of 3-(3-chloropyridine-2-yl)-1H-pyrazoles-5-yl), [(49.7 milligrams, 0.11mmol) be dissolved in CH to 1,3] oxazine-4-ketone (V-3) to-6-chloro-8-methyl-4H-benzo [d] ₃solution in CN (5mL) adds CH ₃oNH ₂hCl (192.1 milligrams, 2.3mmol) and Et ₃n (319.3uL, 2.3mmol), at room temperature stirs 1 hour.Reaction mixture is filtered, and by filtrate vacuum concentration and carry out flash chromatography (methylene dichloride: methyl alcohol=10:1), obtain colorless solid (23 milligrams, yield: 40%); 1HNMR (DMSO-d ₆, 300MHz), δ: 2.22 (s, 3H), 3.45 (s, 3H), 7.32 (s, 1H), (7.51 s, 1H), 7.61 (dd, 1H, J=7.8Hz, J=4.8Hz), 7.69 (s, 1H), (8.19 d, 1H, J=7.8Hz), 8.49 (d, 1H, J=4.8Hz), 10.87 (s, 1); LC-MS:m/z=497.9721, m/z (calculated value)=497.9730.

Table 1 has been listed and has been prepared the concrete structure that I-18 is arrived in general formula (I) Compound I-1: R in table ¹, R ², R ³with defined R in above-mentioned general formula (I) ¹, R ², R ³there is identical implication.

The bromo-1-of embodiment 7:3-(3-chloropyridine-2-yl)-N-(4-cyano group-2-(isopropoxy formamyl)-6-aminomethyl phenyl)-1H-pyrazoles-5, the preparation of methane amide (I-27)

Compound I-27 adopt following method preparation, and concrete steps are as follows.

The preparation of 2-amino-5-cyano-N-isopropoxy-3-methyl benzamide VIII-1:

To (200 milligrams of 2-amino-5-cyano-3-tolyl acid IV-1,1.14mmol) with (127 milligrams of O-sec.-propyl oxyammonias, 1.14mmol) be dissolved in the mixing solutions of 10 milliliters of methylene dichloride and add 2-(7-azo benzotriazole)-N, N, N ', (649 milligrams of N '-tetramethyl-urea phosphofluoric acid esters (HATU), 1.71mmol) and N, N-diisopropylethylamine (DIPEA) (441 milligrams, 3.42mmol), stir and spend the night under room temperature.Solvent vacuum is drained, remaining solid is obtained to yellow oil product (120 milligrams, yield 42%) with separated (petroleum ether/ethyl ether=3/1) purifying of silicagel column.

The preparation of the bromo-1-of 3-(3-chloropyridine-2-yl)-N-(4-cyano group-2-(isopropoxy formamyl)-6-aminomethyl phenyl)-1H-pyrazoles-5-methane amide (I-27):

To (50 milligrams of the bromo-1-of 3-(the chloro-pyridyl of 3-)-1H-pyrazoles-5-formic acid III-1,0.17mmol) be dissolved in the solution of 10 milliliters of methylene dichloride and splash into (63 milligrams of oxalyl chlorides, 0.495mmol) He DMF, under room temperature, stir 2 hours, solvent vacuum is drained and obtained the bromo-1-of acyl chlorides intermediate 3-(3-chloropyridine-2-yl)-1H-pyrazoles-5-formyl chloride IX-1.Intermediate compound I X-1 is dissolved in to 1 milliliter of pyridine, add 2-amino-5-cyano-N-isopropoxy-3-methyl benzamide VIII-1 (41 milligrams, 0.17mmol), be heated to 60 ℃, keep 30 minutes, add 10 ml waters and mix, be extracted with ethyl acetate 3 times, each 10 milliliters, add 10 mL of saline, dry with potassium sulfate, concentrated, by Preparative TLC chromatographic purification, obtain white solid product (15 milligrams, 17%). ¹h NMR (DMSO-d ₆, 300MHz), δ: 1.25 (d, 6H), 3.95 (m, 1H), 7.40 (s, 1H), 7.60 (dd, 1H, J=7.8Hz, J=4.7Hz), 7.72 (s, 1H), 7.90 (s, 1H), 8.16 (d, 1H, J=7.8Hz), 8.45 (d, 1H, J=4.7Hz), 10.39 (s, 1H), 11.45 (s, 1H); LC-MS:m/z=517.0386, m/z (calculated value)=517.0385.

The preparation of the bromo-N-of embodiment 8:3-(the chloro-6-aminomethyl phenyl of 2-(tert.-butoxy formamyl)-4-)-1-(3-chloropyridine-2-yl)-1H-pyrazoles-5-methane amide I-20:

Compound I-20 adopt the step preparation identical with Preparation Example 7, and wherein O-sec.-propyl oxyammonia replaces with O-tertiary butyl oxyammonia, and 2-amino-5-cyano-3-tolyl acid IV-1 replaces with the chloro-3-tolyl acid of 2-amino-5-IV-2, obtains product I-20. ¹h NMR (DMSO-d ₆, 300MHz) δ: 1.15 (s, 9H), 2.21 (s, 3H), 7.32 (s, 1H), 7.52 (s, 1H), 7.60 (dd, 1H, J=7.8Hz, J=4.8Hz), 7.66 (s, 1H), 8.17 (d, 1H, J=7.8Hz), 8.50 (d, 1H, J=4.8Hz), 10.53 (s, 1H); LC-MS:m/z=540.0185, m/z (calculated value)=540.0200.

The preparation of the bromo-N-of embodiment 9:3-(2-(tert.-butoxy formamyl)-4-cyano group-6-aminomethyl phenyl)-1-(3-chloropyridine-2-yl)-1H-pyrazoles-5-methane amide I-28:

Compound I-28 adopt the step preparation identical with Preparation Example 7, and wherein O-sec.-propyl oxyammonia replaces with O-tertiary butyl oxyammonia, obtains product I-28. ¹h NMR (DMSO-d ₆, 300MHz) δ: 1.22 (s, 9H), 2.22 (s, 3H), (7.38 s, 1H), 7.58 (dd, 1H, J=7.8Hz, J=4.8Hz), 7.69 (s, 1H), (7.86 s, 1H), 8.11 (d, 1H, J=7.8Hz), 8.40 (d, 1H, J=4.8Hz), 10.43 (s, 1H), 11.55 (s, 1H); LC-MS:m/z=531.0538, m/z (calculated value)=531.0542.

The bromo-1-of embodiment 10:3-(3-chloropyridine-2-yl)-N-(preparation of 4-cyano group-2-(((1,1-dioxy-tetrahydrochysene-2H-thiapyran-4-yl) formamyl) 6-aminomethyl phenyl)-1H-pyrazoles-5-methane amide I-32:

Compound I-32 adopt the step identical with Preparation Example 7 to prepare, O-sec.-propyl 4-(amino oxygen base) tetrahydrochysene-2H-thiapyran-1 for oxyammonia wherein, and 1-dioxide replaces obtaining product I-32. ¹h NMR (DMSO-d ₆, 300MHz), δ: 1.35-1.48 (m, 4H), 1.75-1.81 (m, 4H), 2.24 (s, 3H), 3.61 (m, 1H), (7.41 s, 1H), 7.60 (dd, 1H, J=7.8Hz, J=4.5Hz), 7.78 (s, 1H), 7.89 (s, 1H), (8.17 d, 1H, J=7.8Hz), 8.47 (d, 1H, J=4.5Hz), 10.65 (s, 1H); LC-MS:m/z=607.0151, m/z (calculated value)=607.0161.

The preparation of the bromo-1-of embodiment 11:3-(3-chloropyridine-2-yl)-N-(4-chloro-2-methyl-6-(((1-methyl isophthalic acid-oxidation phosphine heterocyclic hexane-4-yl) oxygen base) formamyl) phenyl)-1H-pyrazoles-5-methane amide I-23:

Compound I-23 adopt the step preparation identical with Preparation Example 8, O-tertiary butyl 4-(amino oxygen base) tetrahydrochysene-2H-thiapyran-1 for oxyammonia wherein, and the replacement of 1-dioxide, obtains product (I-23).1H NMR (DMSO-d ₆, 300MHz), δ: 1.34-1.48 (m, 4H), 1.76-1.83 (m, 4H), 2.22 (s, 3H), 3.62 (m, 1H), 7.38 (s, 1H), 7.60 (m, 2H), 7.55 (s, 1H), 7.62, (8.17 d, 1H, J=8.1Hz), 8.49 (d, 1H, J=4.5Hz), 10.10 (s, 1H); LC-MS:m/z=615.9810, m/z (calculated value)=615.9819.

Table 1 has been listed the concrete structure to I-32 with the I-19 of the general formula compound I of above-mentioned preparation.R in table ¹, R ², R ³with defined R in above-mentioned general formula (I) ¹, R ², R ³there is identical implication.

The preparation of the bromo-1-of embodiment 12:3-(3-chloropyridine-2-yl)-N-(7-cyano group-5-(methylamino formyl radical)-2,3-dihydro-1H-indenes-4-yl)-1H-pyrazoles-5-methane amide II-15

Compound I I-15 adopts following method to prepare, and concrete steps are as follows:

Intermediate 4-amino-7-cyano group-2, the preparation of 3-dihydro-1H-indenes-5-carboxylic acid X-1:

The preparation of 2-hydroxyl imide base-N-indane-4-base-ethanamide:

To (5.46 grams of chloral hydrates, 33mmol) and anhydrous sodium sulphate (25.6 grams, 92 ml water solution 180mmol) add oxammonium sulfate (25.6 grams, 156mmol), 4-amino indole (4 grams, the solution of 30.8 ml waters of 30mmol) He 3.1 milliliters of vitriol oils.Be heated to 45 ℃, 90 minutes, reheat to 52 ℃, 45 minutes, reheat to 75 ℃ 60 minutes.Be cooled to room temperature, cross leaching solid, water and hexane are washed, and solid vacuum-drying is obtained to gray solid product (5.54 grams, 90% productive rate).1,6,7,8-tetrahydrochysene-1-azepine-as-indenes alkene-2, the preparation of 3-diketone (as-indenes alkene=asymmetric indacene):

To the methylsulfonic acids of 80 ℃ (21 milliliters) add on a small quantity gradually 2-hydroxyl imide base-N-indane-4-base-ethanamide (5.54 grams, 27.1mmol), stir 25 minutes at 80 ℃, be cooled to room temperature, by reaction product to entering in frozen water, by solid filtering, be dissolved in 1N sodium hydroxide solution, with acetic acid neutralization, just solid filtering is removed, by remaining liq concentrated hydrochloric acid acidifying, by solid filtering, wash with water, dry, obtain orange solids product (1.2 grams, 24% productive rate).

The preparation of 4-amino-indane-5-carboxylate methyl ester:

In 30 minutes to 1,6,7,8-tetrahydrochysene-1-azepine-as-indenes alkene-2,3-diketone (1.2 grams, 6.4mmol) be dissolved in the solution of 30 milliliters of 1N sodium hydroxide and add 15 milliliter of 3% aqueous hydrogen peroxide solution, at room temperature stir 1 hour, use 1N hcl acidifying, solid is collected in filtration, washes with water, dry, obtain solid product 4-amino-indane-5-carboxylic acid (500 milligrams, 44% productive rate).By (500 milligrams of 4-amino-indenes-5-carboxylic acids, 2.82mmol) be dissolved in 10 milliliters of ethyl acetate and 10 milliliters of ethanol, to this solution, add trimethyl silicon based triazonmethane (2.82 milliliters, 5.64mmol, 2mmol/L hexane solution), under room temperature, stir 1 hour, vacuum-evaporation, except desolventizing, uses column chromatography purifying (petroleum ether/ethyl ether=5/1, silica gel by residuum, ultraviolet detection) obtain white solid product (390 milligrams, 72% productive rate).

4-amino-7-is iodo-2, the preparation of 3-dihydro-1H-indenes-5-carboxylate methyl ester:

To 4-amino-indane-5-carboxylate methyl ester (228 milligrams, 1.18mmol) be dissolved in the solution of 2 milliliters of acetic acid, add N-N-iodosuccinimide (267 milligrams, 1.18mmol).At room temperature stir and spend the night.Product is poured in 10 ml waters, be extracted with ethyl acetate 3 times, each 20 milliliters, combining extraction liquid, with sodium bicarbonate aqueous solution and salt washing, by dried over sodium sulfate, filter, concentrated, concentrated product is used column chromatography to purifying (petroleum ether/ethyl ether=5/1, silica gel, ultraviolet detection) obtain yellow solid product (360 milligrams, 95% productive rate).

4-amino-7-cyano group-2, the preparation of 3-dihydro-1H-indenes-5-carboxylate methyl ester:

By 4-amino-7-iodo-2, (340 milligrams of 3-dihydro-1H-indenes-5-carboxylate methyl esters, 1.06mmol) and cupric cyanide (114 milligrams, 1.27mmol) mixing solutions at 3 milliliters of DMF is heated to 135 ℃, keeps 18 hours, then reaction product is poured in 20 ml waters, solid product is collected in filtration, uses column chromatography purifying (petroleum ether/ethyl ether=4/1, silica gel, ultraviolet detection) obtain faint yellow solid product (136 milligrams, 58% productive rate).

4-amino-7-cyano group-2, the preparation of 3-dihydro-1H-indenes-5-carboxylic acid (X-1)

By 4-amino-7-cyano group-2, and 3-dihydro-1H-indenes-5-carboxylate methyl ester (120 milligrams, 0.5mmol) and LiOHH ₂(112 milligrams of O, 2.8mmol) mixing solutions at 5 ml methanol and 5 ml waters at room temperature stirs and spends the night, then underpressure distillation is except desolventizing, add 10 ml water dilutions, with 1N hydrochloric acid adjust pH to 6, filter and collect solid product, with 5 milliliters of washings, dry, obtain white solid product (110 milligrams, 96% productive rate).

2-(the bromo-1-of 3-(3-chloropyridine-2-yl)-1H-pyrazoles-5-yl)-4-oxygen-4,7,8,9-tetrahydroindene [4,5-d] [preparation of 1,3] oxazine-6-formonitrile HCN (XI-1):

To the bromo-1-of 3-(3-chloropyridine-2-yl)-1H-pyrazoles-5-carboxylic acid (III-1), (3.02 grams, 0.01mol), with 4-amino-7-cyano group-2, (2.02 grams, 0.01mol) be dissolved in CH to 3-dihydro-1H-indenes-5-carboxylic acid (X-1) ₃in solution in CN (50mL), add pyridine (5mL) and CH ₃sO ₂cl (3mL), then stirs 2 hours.After completing, reaction mixture is concentrated to remove most solvent and to filter out the solid (1.9 grams, yield 38%) in Baise; LC-MS:m/z=467.9845, m/z (calculated value)=467.9858.

The preparation of the bromo-1-of 3-(3-chloropyridine-2-yl)-N-(7-cyano group-5-(methylamino formyl radical)-2,3-dihydro-1H-indenes-4-yl)-1H-pyrazoles-5-methane amide (Compound I I-15):

To 2-(the bromo-1-of 3-(3-chloropyridine-2-yl)-1H-pyrazoles-5-yl)-4-oxygen-4, [(52 milligrams, 0.11mmol) be dissolved in CH to 1,3] oxazine-6-formonitrile HCN (XI-1) to 7,8,9-tetrahydroindene [4,5-d] ₃in solution in CN (5mL), add CH ₃nH ₂hCl (154 milligrams, 2.3mmol) and Et ₃n (319.3uL, 2.3mmol), at room temperature stirs 1 hour.Reaction mixture is filtered, by filtrate vacuum concentration and carry out flash chromatography (methylene dichloride: methyl alcohol=10:1), obtain white solid (23 milligrams, yield 39%; 1HNMR (DMSO-d ₆, 300MHz), δ: 2.01-2.06 (m, 2H), 2.69-2.76 (m, 5H), 3.02-3.07 (t, 2H), 7.41 (s, 1H), 7.62 (dd, 1H, J=4.8Hz, J=4.8Hz), 7.79 (s, 1H), 8.19 (dd, 1H, J=1.5Hz, J=1.5Hz), 8.50 (m, 2H), 10.88 (s, 1H) .LC-MS:m/z=499.0268, m/z (calculated value)=499.0280.

The bromo-1-of embodiment 13:3-(3-chloropyridine-2-yl)-N-(the chloro-5-of 7-(methylamino formyl radical)-2,3-dihydro-1H-indenes-4-yl)-1H-pyrazoles-5-methane amide (Compound I I-5)

Compound I I-5 adopts the step preparation identical with Preparation Example 12, and wherein use intermediate X-2 in intermediate X-1 replace obtaining product II-5.

4-amino-7-is chloro-2, the preparation of 3-dihydro-1H-indenes-5-carboxylic acid X-2:

This intermediate adopts the step identical with intermediate X-1 in Preparation Example 12 to prepare by synthetic schemes, wherein prepare 4-amino-7-iodo-2, that step of 3-dihydro-1H-indenes-5-carboxylic acid replaces N-N-iodosuccinimide to obtain intermediate X-2 with N-chlorosuccinimide.

2-(the bromo-1-of 3-(3-chloropyridine-2-yl)-1H-pyrazoles-5-yl)-6-is chloro-8,9-indane [4,5-d] [preparation of 1,3] oxazine-4 (7H)-one XI-2:

To the bromo-1-of 3-(3-chloropyridine-2-yl)-1H-pyrazoles-5-carboxylic acid III-1 (3.02 grams, 0.01mol) and 4-amino-7-chloro-2, (2.12 grams, 0.01mol) be dissolved in CH to 3-dihydro-1H-indenes-5-carboxylic acid (X-2) ₃in solution in CN (50mL), add pyridine (5mL) and CH ₃sO ₂cl (3mL), then at room temperature stirs 2 hours.After completing, reaction mixture is concentrated to remove most solvent and to filter out the solid (2.1 grams, yield 41%) in Baise.

The preparation of the bromo-1-of 3-(3-chloropyridine-2-yl)-N-(the chloro-5-of 7-(methylamino formyl radical)-2,3-dihydro-1H-indenes-4-yl)-1H-pyrazoles-5-methane amide II-5:

Chloro-8 to 2-(the bromo-1-of 3-(3-chloropyridine-2-yl)-1H-pyrazoles-5-yl)-6-, [(54 milligrams, 0.11mmol) be dissolved in CH to 1,3] oxazine-4 (7H)-one (XI-2) to 9-indane [4,5-d] ₃in solution in CN (5mL), add CH ₃nH ₂hCl (154 milligrams, 2.3mmol) and Et3N (319.3uL, 2.3mmol), at room temperature stir 1 hour.Reaction mixture is filtered, by filtrate vacuum concentration, with cold methanol, wash, obtain micro-yellow solid (22 milligrams, yield 35%); 1H NMR (DMSO-d ₆, 300MHz) δ: 10.59 (s, 1H), 8.47 (d, J=4.6Hz, 1H), 8.09 (q, J=7.5Hz, 1H), 8.21 (d, J=7.8Hz, 1H), 7.61 (dd, J=7.8Hz, 4.6Hz, 1H), 7.43 (s, 1H), 7.40 (s, 1H), (2.98 m, J=7.6Hz, 4H), 2.73 (d, J=7.5Hz, 3H), 2.06 (m, J=7.4Hz, 2H).; LC-MS:m/z=507.9930, m/z (calculated value)=507.9937.

The preparation of the bromo-1-of embodiment 14:3-(3,5-dichloropyridine-2-yl)-N-(7-cyano group-5-(methyl base formamyl)-2,3-dihydro-1H-indenes-4-yl)-1H-pyrazoles-5-methane amide II-17:

This compound adopts the step identical with Preparation Example 12 to prepare by synthetic schemes, wherein with replacement intermediate III-1, intermediate III-2, finally obtains the Compound I I-17 of this Preparation Example). ¹h NMR (DMSO-d ₆, 300MHz) δ: 11.19 (s, 1H), 8.43 (d, J=2.4Hz, 1H), 7.91 (d, J=2.1Hz, 1H), 7.59 (s, 1H), 7.07 (s, 1H), 6.25 (d, J=4.6Hz, 1H), 3.13 (t, J=7.5Hz, 2H), 3.04 (d, J=4.8Hz, 3H), 2.85 (t, J=7.4Hz, 2H), 2.14 (m, J=7.5Hz, 2H); LC-MS:m/z=532.9878, m/z (calculated value)=532.9890.

The preparation of the bromo-1-of embodiment 15:3-(3-chloropyridine-2-yl)-N-(4-cyano group-2-(methylamino formyl radical)-5,6,7,8-naphthane-1-yl)-1H-pyrazoles-5-methane amide II-16:

This compound adopts the step identical with Preparation Example 12 synthetic, wherein uses intermediate X-3) replacement intermediate X-1) and finally obtain the Compound I I-16 of this Preparation Example.Prepared by intermediate X-3 use the following step.

Intermediate 1-amino-4-cyano group-5, the preparation of 6,7,8-naphthane-2-carboxylic acid X-3:

This compound adopts the step preparation identical with intermediate X-1 of Preparation Example 12, wherein uses initial compounds 5,6,7, and 8-naphthane-1-amine replaces 4-amino indole and finally obtains X-3.

1-amino-4-cyano group-5,6,7,8-naphthane-2-carboxylic acid X-3

2-(the bromo-1-of 3-(3-chloropyridine-2-yl)-1H-pyrazoles-5-yl)-4-oxygen-7,8,9,10-naphthane [1, the 2-d] [preparation of 1,3] oxazine-6-formonitrile HCN (XI-3).To (50 milligrams of the bromo-1-of 3-(3-chloropyridine-2-yl)-1H-pyrazoles-5-carboxylic acids (III-1), 0.17mmol) and (17 milligrams of triethylamines, in 5 milliliters of second cyanogen solution 0.17mmol) 0 ℃ splash into Methanesulfonyl chloride (21 milligrams, 0.18mmol) and at 0 ℃ stir 15 minutes.Add 1-amino-4-cyano group-5,6,7,8-naphthane-2-carboxylic acid (X-3) (36 milligrams, 0.17mmol) and at 0 ℃ stir 15 minutes.At 0 ℃ of dropping triethylamine, (34 milligrams, 0.34mmol) and at 0 ℃ stir 40 minutes.Then 0 ℃ splash into Methanesulfonyl chloride (21 milligrams, 0.18mmol).Reactor is heated to room temperature, and stirring is spent the night.Add 20 ml water dilutions, be extracted with ethyl acetate each 30 milliliters 3 times.Extraction liquid is merged, with 10 milliliter of 10% sodium bicarbonate and 10 mL of saline, wash, by dried over mgso, concentrated, obtain light yellow solid product (60 milligrams, productive rate 76%).

The preparation of the bromo-1-of 3-(3-chloropyridine-2-yl)-N-(4-cyano group-2-(methylamino formyl radical)-5,6,7,8-naphthane-1-yl)-1H-pyrazoles-5-methane amide II-16:

To 2-(the bromo-1-of 3-(3-chloropyridine-2-yl)-1H-pyrazoles-5-yl)-4-oxygen-7, [(60 milligrams, 0.13mmol) be dissolved in CH to 1,3] oxazine-6-formonitrile HCN XI-3 to 8,9,10-naphthane [1,2-d] ₃in solution in CN (5mL), drip 25% aqueous methylamine solution (0.5mmol), at room temperature stir 1 hour.By reaction product vacuum concentration, solid is washed with cold methanol, obtains white solid (34 milligrams, yield 39%); ¹h NMR (DMSO-d ₆, 300MHz), δ: 1.80-1.85 (m, 4H), 2.71 (d, 3H, J=7.2Hz), 2.79-2.88 (m, 4H), 7.41 (s, 1H), 7.61 (dd, 1H, J=7.8Hz, J=4.8Hz), (7.78 s, 1H), 8.17 (d, 1H, J=4.8Hz), 8.21 (br.s, 1H), 8.48 (d, 1H, J=7.8Hz), 10.88 (s, 1H); LC-MS:m/z=513.0428, m/z (calculated value)=513.0436.

The preparation of the bromo-1-of embodiment 16:3-(3-chloropyridine-2-yl)-N-(the chloro-2-of 4-(methylamino formyl radical)-5,6,7,8-naphthane-1-yl)-1H-pyrazoles-5-methane amide II-3

This compound adopts the step identical with Preparation Example 15 to prepare by synthetic schemes.The preparation of intermediate X-4:

1-amino-4-is chloro-5,6,7,8-naphthane-2-carboxylic acid X-4

Intermediate X-4 can be used and intermediate X-3 in Preparation Example 14) identical step is from 7, the amine-initiated compound preparation of 8-naphthane-1-, wherein prepare 1-amino-4-iodo-5,6, that step of 7,8-naphthane-2-carboxylic acid replaces N-N-iodosuccinimide to obtain intermediate X-4 with N-chlorosuccinimide.By intermediate X-4) with preparing the same method of II-15, obtain object product (II-3); ¹h NMR (DMSO-d ₆, 300MHz), δ: 1.85-1.90 (m, 4H), 2.73 (d, J=7.3Hz, 3H), 2.85-2.92 (m, 4H), 7.42 (s, 1H), 7.51 (s, 1H), 7.63 (dd, 1H, J=7.8Hz, J=4.6Hz), 8.17 (d, 1H, J=7.8Hz), 8.35 (Br.s, 1H), 8.47 (d, 1H, J=4.6Hz), 10.87 (s, 1H); LC-MS:m/z=522.0088, m/z (calculated value)=522.0094.

The preparation of the bromo-1-of embodiment 17:3-(3-chloropyridine-2-yl)-N-(7-cyano group-5-(sec.-propyl base formamyl)-2,3-dihydro-1H-indenes-4-yl)-1H-pyrazoles-5-methane amide II-24:

Compound I I-24 can use the step identical with Preparation Example 12 Compound I I-15 synthetic, wherein isopropylamine (iPrNH for final step ₂) react and obtain Compound I I-24 with intermediate X I-1). ¹h NMR (DMSO-d ₆) δ: 1.14 (d, J=6.7Hz, 6H), 2.09 (m, J=7.5Hz, 2H), 2.97 (t, J=7.4Hz, 2H), 3.11 (t, J=7.5Hz, 2H), 3.98 (m, 1H), 7.38 (s, 1H), 7.61 (dd, J=8.1,4.5Hz, 1H), (7.75 s, 1H), 8.13-8.17 (m, 2H), 8.43 (d, J=4.5Hz, 1H), 10.85 (s, 1H); LC-MS:m/z=527.0578, m/z (calculated value)=527.0593

The preparation of the bromo-N-of embodiment 18:3-(the chloro-5-of 7-(sec.-propyl base formamyl)-2,3-dihydro-1H-indenes-4-yl)-1-(3-chloropyridine-2-yl)-1H-pyrazoles-5-methane amide II-11:

Compound I I-11 can use the step identical with Preparation Example 17II-24 synthetic, wherein with intermediate X-2, replaces intermediate X-1 can obtain Compound I I-11). ¹h NMR (DMSO-d ₆, 300MHz) δ: 1.10 (d, J=6.7Hz, 6H), 2.08 (t, J=7.5Hz, 2H), 2.95 (t, J=7.4Hz, 2H), 3.08 (t, J=7.5Hz, 2H), 3.90 (m, 1H), 7.35 (s, 1H), 7.45 (s, 1H), 7.60 (dd, J=7.8,4.5Hz, 1H), 8.12 (d, J=7.8Hz, 1H), 8.26 (d, J=7.8Hz, 1H), (8.43 d, J=4.5Hz, 1H), 10.88 (s, 1H); LC-MS:m/z=536.0245, m/z (calculated value)=536.0250.

Table 2 has been listed the concrete structure to II-29 with the II-1 of above-mentioned synthetic general formula compound II.R in table ¹, R ², R ⁴and defined R in X, Y, Z and above-mentioned general formula (II) ¹, R ², R ⁴and X, Y, Z have identical implication.

The preparation of the bromo-1-of embodiment 19:3-(3-chloropyridine-2-yl)-N-(7-cyano group-5-(isopropoxy base formamyl)-2,3-dihydro-1H-indenes-4-yl)-1H-pyrazoles-5-methane amide II-34:

Compound I I-34) adopt following method to prepare, concrete steps are as follows:

4-amino-7-cyano group-2, the preparation of 3-dihydro-1H-indenes-5-isopropoxy acid amides XIII-1

To 4-amino-7-cyano group-2, (240 milligrams of 3-dihydro-1H-indenes-5-carboxylic acids (X-1), 1.2mmol) and O-sec.-propyl oxyammonia (134 milligrams, 1.2mmol) be dissolved in the mixing solutions of 10 milliliters of methylene dichloride and add 2-(7-azo benzotriazole)-N, N, N ', N '-tetramethyl-urea phosphofluoric acid ester (HATU) (649 milligrams, 1.71mmol) and (441 milligrams of DIPEAs (DIPEA), 3.42mmol), under room temperature, stir and spend the night.Solvent vacuum is drained, by remaining solid with separated (petroleum ether/ethyl ether=3/1) purifying of silicagel column obtain yellow oil product (130 milligrams, productive rate: 40%).

The preparation of the bromo-1-of 3-(3-chloropyridine-2-yl)-N-(7-cyano group-5-(isopropoxy base formamyl)-2,3-dihydro-1H-indenes-4-yl)-1H-pyrazoles-5-methane amide II-34:

To (75 milligrams of the bromo-1-of 3-(the chloro-pyridyl of 3-)-1H-pyrazoles-5-formic acid III-1,0.25mmol) be dissolved in the solution of 15 milliliters of methylene dichloride and splash into (95 milligrams of oxalyl chlorides, 0.75mmol) He DMF, under room temperature, stir 2 hours, solvent vacuum is drained and obtained the bromo-1-of acyl chlorides intermediate 3-(3-chloropyridine-2-yl)-1H-pyrazoles-5-formyl chloride IX-1.Intermediate compound I X-1 is dissolved in to 2 milliliters of pyridines, adds 4-amino-7-cyano group-2, (64 milligrams of 3-dihydro-1H-indenes-5-methane amides (XIII-1), 0.25mmol), be heated to 60 ℃, keep 30 minutes, adding 10 ml waters mixes, be extracted with ethyl acetate 3 times, each 10 milliliters, add 10 mL of saline, dry with potassium sulfate, concentrated, with Preparative TLC chromatographic purification obtain white solid product (27 milligrams, productive rate: 20%). ¹h NMR (DMSO-d ₆, 300MHz) δ: 10.78 (s, 1H), 8.42 (d, J=4.1Hz, 1H), 8.21 (d, J=7.6Hz, 1H), 7.68 (dd, J=7.6Hz, 4.1Hz, 1H), 7.75 (s, 1H), (7.40 s, 1H), 4.15 (m, 1H), 3.02 (m, 2H), 2.76 (m, 2H), 2.03 (m, 2H), 1.32 (d, J=7.8Hz, 6H); LC-MS:m/z=543.0528, m/z (calculated value)=543.0542.

The preparation of the bromo-N-of embodiment 20:3-(the chloro-5-of 7-(isopropoxy base formamyl)-2,3-dihydro-1H-indenes-4-yl)-1-(3-chloropyridine-2-yl)-1H-pyrazoles-5-methane amide II-32:

Compound I I-32) the available step identical with Preparation Example 19 (II-34) preparation, wherein uses intermediate X-2) replacement intermediate X-1) can obtain Compound I I-32). ¹h NMR (DMSO-d ₆, 300MHz) δ: 10.55 (s, 1H), 8.41 (d, J=4.2Hz, 1H), 8.20 (d, J=7.5Hz, 1H), 7.65 (dd, J=7.6Hz, 4.1Hz, 1H), 7.58 (s, 1H), (7.38 s, 1H), 4.15 (m, 1H), 3.03 (m, 2H), 2.74 (m, 2H), 2.02 (m, 2H), 1.32 (d, J=7.8Hz, 6H); LC-MS:m/z=552.0188, m/z (calculated value)=552.0200

Table 2 has been listed the concrete structure to II-40 with the II-30 of above-mentioned synthetic compound.R in table ¹, R ², R ⁴and defined R in X, Y, Z and above-mentioned general formula I I ¹, R ², R ⁴and X, Y, Z have identical implication.

O-formammidotiazol-benzamide compounds is ryania (ryanodine) receptor stimulant, and its insecticidal action can be measured by clone's insect ryanodine receptor clone.Referring to George P.Lahm, Deng Rynaxypyre:A new insecticidal anthranilic diamide that acts as a potent and selective ryanodine receptor activator, Bioorganic & Medicinal Chemistry Letters17 (2007) 6274-6279.George?P.Lahm，Daniel?Cordova，James?D.Barry,New?and?selective?ryanodine?receptor?activators?for?insect?control，Bioorganic&Medicinal?Chemistry17(2009)4127-4133。

The method of setting up the insect ryanodine receptor clone of cloning is as follows:

Embodiment 21: the clone of insect ryanodine receptor gene:

Will be from the insect ryanodine receptor gene clone of Heliothis virescens (Heliothis virescens) and drosophila melanogaster (Drosophila melanogaster) in sf9 clone, make to test compound biological activity, to obtain about it based on the information of the killing ability of described ryanodine receptor (RYR) agonist activity below.Drosophila melanogaster gene order is from http://www.ncbi.nlm.nih.gov/protein/Q24498.3, RecName:Full=Ryanodine receptor44F, Swiss-Prot:Q24498.3 (residues1to5127), referring to: Takeshima, H., Nishi, M., Iwabe, N., Miyata, T., Hosoya, T., Masai, I.and Hotta, Y., Isolation and characterization of a gene for a ryanodine receptor/calcium release channel in Drosophila melanogaster, FEBS Lett.337 (1): 81-87 (1994).Heliothis virescens gene order is from http://www.ncbi.nlm.nih.gov/protein/294518427, GenBank:ADE98194.1, Residues1to5128.DNA sequence dna improves protein expression degree with following method optimization: by improving CAI value to 0.88 increase codon usage bias, optimize GC content and unfavorable peak to increase the stability of mRNA, by loop-stem structure smash to increase mRNA stability and with rrna bonding force, screening has changed some negative cis acting sites.DNA is put in pUC57 plasmid vector.With pIB/V5-His plasmid vector (Invitrogen), make subclone, cloning site is BamHI-XhoI, Qiagen removes intracellular toxin plasmid extraction test kit, TE damping fluid (10mM Tris-Cl, pH8.0,1mM EDTA), adopt the step (http://invitrogen.com) of the large upgrading grain of Qiagen.The length of clone's drosophila melanogaster gene DNA is 15398 base pairs, and the length of Heliothis virescens gene DNA is 15401 base pairs.The reference of clone gene method: C.L.Patten, et al. (2009) .Molecular Biotechnology:Principles and Applications of Recombinant DNA.Washington, D.C:ASM Press.ISBN1-55581-498-0; Brown, T. (2006) .Gene cloning and DNA analysis:an introduction.Cambridge, MA:Blackwell Pub.ISBN1-4051-1121-6.

Embodiment 22: the gene transfection of insect ryanodine receptor:

By the plasmid DNA that contains genes involved and

reagent (Invitrogen) is mixed together in SF900II (SFM, Gibco), and cultivates with the fresh insect cell going down to posterity.Typical condition is as follows: Sf9 cell density is 1.0 * 10^6/mL, (suspension cell) of cell volume 10ml, 10 μ g plasmids, 30mL

reagent, incubation time is 30 minutes, the transient expression time is 48-72 hour.Following reagent is added together in 1.5mL micro-centrifuge tube and prepares transfection mixture: 1ml SF900II (SFM, Gibco), and 10 μ g pIB/V5-His plasmids are (in TE damping fluid, 10mM Tris-Cl, 1mM EDTA, 1 μ g/ μ L, pH8.0) and 30 μ L

reagent (Invitrogen) (stir before use, add afterwards always).Stir gently transfection mixture 10 seconds, at room temperature cultivate 30 minutes.In SF900II (SFM, Gibco), with Biocolor China shaking table, under 110rpm, at 27 ℃, cultivate Sf9 cell (being greater than the logarithmic phase cell of 95% survival rate).By 10mL sf9 cell with 1 * 10 ⁶the concentration of individual cell/ml is seeded in the shaking flask of 50ml volume.Whole transfection mixture is joined in 10mL sf9 cell, and in shaking table, under 110rpm, at 27 ℃, cultivate 48-72 hour, then results.Cell after transfection confirms transfection success with positive compound cyanogen insect amide and Rynaxypyr test.Table 3 is listed test result, and testing method is shown in embodiment 23.Document: George P.Lahm, Deng Rynaxypyre:A new insecticidal anthranilic diamide that acts as a potent and selective ryanodine receptor activator, Bioorganic & Medicinal Chemistry Letters17 (2007) 6274-6279.George?P.Lahm，Daniel?Cordova，James?D.Barry，New?and?selective?ryanodine?receptor?activators?for?insect?control，Bioorganic&Medicinal?Chemistry17(2009)4127-4133。

Embodiment 23: with Sf9 cell carry out calcium Transfer Experiment (Calcium MobilizationAssay) with detection compound to activating the activity of ryanodine receptor:

It is relevant with compound insecticidal effect that this activity is proved to be, referring to George P.Lahm, Deng Rynaxypyre:A new insecticidal anthranilic diamide that acts as a potent and selective ryanodine receptor activator, Bioorganic & Medicinal Chemistry Letters17 (2007) 6274-6279.George?P.Lahm，Daniel?Cordova，James?D.Barry，New?and?selective?ryanodine?receptor?activators?for?insect?control，Bioorganic&Medicinal?Chemistry17(2009)4127-4133。By wild-type and transfection Sf9 cell dilution to 1.4 * 10 ⁶individual cell/ml and suspension are used in Fluo-4AM (2 μ M) load in SF-900SFM substratum 45 minutes in room temperature.After load, by cell with 1000rpm centrifugal 2 minutes, then be suspended in fresh substratum and remove dyestuff, repeated centrifugation process.Then by cell Eddy diffusion in physiological saline.The cell (1.4 * 10 of dye load ⁵individual cells/well) be inoculated into 96 orifice plates (Corning, 3603), and before the test of Flexstation plate reader, make its painted 30 minutes.Xiang Kongzhong adds the test compound being prepared in physiological saline.The fluorescence that monitoring excites at 485nm, launches at 525nm.2 samples for each data point, calculate the activity (EC that each compound activates ryanodine receptor ₅₀) numerical value.Table 4 has been listed in activating the process of insect ryanodine receptor, compares with bromine cyanogen insect amide and Rynaxypyr, utilizes the ryanodine receptor agonist activity (EC of some the compounds of this invention of insect ryanodine receptor transfection Sf9 clone mensuration ₅₀value).

Embodiment 24: express the insect of ryanodine receptor and the preparation of mammal cell line:

In mammal cell line, ryanodine receptor agonist activity represents the potential effect of compound to Mammals and the mankind, and can be used as the indication of the genotoxic potential effect of compound.Can come with the mammalian cell of suitable expression ryanodine receptor test compounds to assess their selectivity to the activity of mammiferous ryanodine receptor and relative insect cell line.Referring to Ebbinghaus-Kintscher, U., Flubendiamide, the first insecticide with a novel mode of action on insect ryanodine receptors, Pflanzenschutz-Nachrichten Bayer60/2007,2117-140.From Invitrogen Life Technologies, obtain Sf9 clone and Sf-900II SFM substratum.In shaking flask, on Sf-900IISFM substratum, grow at 27 ℃ wild-type and transfection Sf9 cell.From American type culture collection (ATCC), obtain PC-12 clone (pheochromocytoma clone) and it is grown the RPMI-1640 substratum of ATCC preparation.By adding heat-inactivated horse serum to basic medium to final concentration 10%, adding foetal calf serum to final concentration is 5%, to manufacture growth medium.By cell at 37 ℃, 5%CO ₂lower cultivation.From ATCC, obtain C2C12 clone (mouse muscle-forming cell system), and it is grown in Dulbecco's Modified Eagle ' the s substratum of ATCC preparation.To adding fetal bovine serum in basic medium to being 10% to prepare growth medium to final concentration.At 37 ℃, 5%CO ₂lower cultivation cell.From ATCC, obtain IMR-32 clone (human neuroblastoma clone), and it is grown in Eagle ' the sMinimum Essential substratum of ATCC preparation.To adding fetal bovine serum in basic medium, to final concentration, be 10% to prepare growth medium.In 37 ℃, 5%CO ₂lower cultivation cell.

Embodiment 25: by C2C12 and IMR32 clone, carry out calcium Transfer Experiment:

In experiment the day before yesterday, with the density of 30000 cell/100uL, C2C12 and IMR32 cell are laid on 96 hole black walls of dianegative, then at 5%CO ₂, overnight incubation in 37 ℃ of incubators.Before measuring, cell monolayer reaches 80-90% and converges.Remove substratum, and with the HBSS damping fluid that contains Fluo-4AM (2 μ M) load cells 45 minutes at 37 ℃.After load, with HBSS damping fluid by twice of cell washing.Then with Flexstation plate reader, carry out calcium Transfer Experiment.Xiang Kongzhong adds the test compound being prepared in HBSS, and concentration is 0uM, 1uM, 10uM, 100uM, 1mM.The fluorescence that monitoring excites at 485nm, launches at 525nm.Calculate each compound and activate the active numerical value that calcium shifts.

Embodiment 26: by PC12 clone, carry out calcium Transfer Experiment:

PC12 cell is suspension cell, by cell dilution to 1.0 * 10 ⁶individual cell/ml, and suspension is at 37 ℃, is used in Fluo-4AM (2 μ M) load in HBSS damping fluid 45 minutes.After load, by cell with 1000rpm centrifugal 2 minutes, then be suspended in HBSS damping fluid to remove dyestuff, repeated centrifugation process.Then by cell Eddy diffusion in HBSS.By the cell of dye load (1.0 * 10 ⁵individual cells/well) be inoculated into 96 orifice plates (Corning, 3603), and before the test of Flexstation plate reader, make its painted 30 minutes.Xiang Kongzhong adds the test compound being prepared in HBSS, and concentration is 0uM, 1uM, 10uM, 100uM, 1mM.The fluorescence in 525nm transmitting that monitoring excites at 485nm, calculates each compound and activates the active numerical value that calcium shifts.

Table 5 has been listed with bromine cyanogen insect amide and has been compared with Rynaxypyr, part of compounds of the present invention activates the activity that mammalian cell calcium shifts, comprise PC-12 cell (pheochromocytoma cell), C2C12 cell (mouse muscle-forming cell), IMR-32 cell (human neuroblastoma cell).

Embodiment 27: the desinsection of anthranilic diamides derivative I of the present invention or II, acaricidal activity measurement result.

Utilize greenhouse insect and insect larvae to carry out pesticidal measurement.The desinsection of compound of the present invention, the evaluation of acaricidal activity are undertaken by greenhouse insecticidal test, and table 6 has been listed the Insecticiding-miticiding result of compound.Table 6 is visible: part anthranilic diamides derivative of the present invention sees the above table the insecticidal activity assay result of mythimna separata, data show, when 1 mcg/ml, I-1 of the present invention, I-3, I-4, I-7, I-10, I-12, I-15, II-10, II-23, II-31, II-32, II-34, II-35, II-36, II-37, II-39, II-40 have all shown excellent mythimna separate, in administration after 48 hours, mortality ratio all reaches more than 85%, apparently higher than the activity of positive control medicament cyanogen insect amide.Other compounds to the insecticidal activity of mythimna separata also more than 60%.Measured the activity of citrus red mite simultaneously, the results are shown in Table 6, when 1 mcg/ml, acaricidal activity result to citrus red mite shows, I-1 of the present invention, I-2, I-4, I-7, I-9, I-10, II-23, II-24, II-31, II-32, II-35, II-36, II-37, II-39 have all shown the excellent red spider activity of killing, in administration, after 48 hours, mortality ratio all reaches more than 85%, apparently higher than the activity of positive control medicament cyanogen insect amide.Other compounds to the insecticidal activity of citrus red mite also more than 60%.

Part anthranilic diamides derivative of the present invention the results are shown in Table 6 to the insecticidal activity assay of small cabbage moth, data show, when 1 mcg/ml, I-1 of the present invention, I-5, I-8, I-9, I-17, I-18, I-25, I-30, II-2, II-10, II-11, II-25, II-28, II-37, II-39 have all shown the excellent small cabbage moth activity of killing, in administration after 48 hours, mortality ratio all reaches more than 85%, apparently higher than the activity of positive control medicament cyanogen insect amide.Other each compounds to the insecticidal activity of small cabbage moth also more than 60%.

Done the determination of activity to grub simultaneously, the results are shown in Table 6, when 1 mcg/ml, insecticidal activity result to grub shows, I-2 of the present invention, I-5, I-9, I-17, I-18, I-25, I-30, II-11, II-18, II-25 have all shown the excellent grub activity of killing, in administration, after 48 hours, mortality ratio all reaches more than 85%, apparently higher than the activity of positive control medicament cyanogen insect amide.Other each compounds to the insecticidal activity of grub also more than 60%.

Therefore, compound of the present invention has good desinsection, an acaricidal activity.

Embodiment 28: the fungicidal activity of anthranilic diamides derivative I of the present invention or II is measured:

Anthranilic diamides derivative I of the present invention or II sterilization or bacteriostatic activity adopt thalli growth rate assay method, detailed process is: get 5 milligrams of sample dissolution in appropriate dimethyl formamide, then with containing the medicament that a certain amount of polysorbas20 emulsifier aqueous solution is diluted to 500 mcg/ml, reagent agent is respectively drawn under aseptic condition in 1 milliliter of injection culture dish, add respectively again 9 milliliters of substratum, after shaking up, make 50 mcg/ml pastilles dull and stereotyped, to add the flat board of 1 milliliter of aqua sterilisa, do blank, with the punch tool of 4 millimeters of diameters, along mycelia outer rim, cut bacterium dish, move on pastille flat board, being equilateral triangle puts, every processing repeats 3 times, culture dish is placed in 24 ± 1 degrees Celsius of constant incubators and is cultivated, colony diameter to be contrasted expands to 2-3 centimetre of " Invest, Then Investigate " and respectively processes bacterium dish expansion diameter, average, relatively calculate relative bacteriostasis rate with blank, the kind that comprises multiple representative majority of plant pathogenic bacteria of the actual generation in field in China's agriculture production for examination bacterial classification, its title and code name comprise AS: tomato early blight bacterium (Alternaria solani), BC: botrytis cinerea pers (Botrytis cinerea), CA: peanut Cercospora bacteria (Cercospora arachidicola), GZ: fusarium graminearum (Gibberella zeae), PI: phytophthora infestans (Phytophthora infestans (Mont.) de Bary), PP: Botryosphaeria berengeriana f. sp (Physalospora piricola), PS: Rhizoctonia solani Kuhn (Pellicularia sasakii), RC: Rhizoctonia cerealis (Rhizoctonia cerealis), SS: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum).Thalli growth rate method measurement result is in Table 7, and table 7 shows, when 50 mcg/ml, all compounds that the present invention synthesizes all have fungicidal activity in various degree, I-1 to the fungicidal activity of GZ, AS bacterium higher than 40%; I-2 to the fungicidal activity of PI, AS bacterium higher than 40%; I-3 to the fungicidal activity of GZ bacterium higher than 40%; I-6 to the fungicidal activity of AS bacterium higher than 40%; I-10 to the fungicidal activity of GZ, PI bacterium higher than 40%; I-13 to the fungicidal activity of PI bacterium higher than 40%; I-16 to the fungicidal activity of GZ bacterium higher than 40%; I-20 to the fungicidal activity of GZ, PI bacterium higher than 40%; I-23 to the fungicidal activity of SS, RC bacterium higher than 40%; I-29 to the fungicidal activity of PS, GZ, PI, AS, SS, RC bacterium higher than 40%; II-3 to the fungicidal activity of GZ, SS bacterium higher than 40%; II-8 to GZ fungicidal activity higher than 40%; II-11 to GZ, AS, SS fungicidal activity higher than 40%; II-18 to GZ fungicidal activity higher than 40%; II-24 to AS fungicidal activity higher than 40%; II-28 to SS, RC fungicidal activity higher than 40%; II-28 to PI, AS fungicidal activity higher than 40%; II-35 to GZ, PI, AS, SS, RC fungicidal activity higher than 40%; II-39 to PI, AS, SS, RC fungicidal activity higher than 40%; II-40 to CA, PS, GZ, RC fungicidal activity higher than 40%; Therefore this compounds has shown good fungicidal activity.

Embodiment 29: the application in anthranilic diamides derivative I of the present invention or II and insecticide composition control agricultural and forestry and gardening plant insect pest

All anthranilic diamides derivative Is of the present invention or II and existing sterilant: Chlorpyrifos 94, the sub-Nong in ground, acetamiprid, Affirm (Merck Co.), milbemectin, Avrmectin, pleocidin, fenvalerate, efficient fenvalerate, Cypermethrin, effective cypermethrin, lambda-cyhalothrin, Deltamethrin, Fenvalerate, Beta-cyfloxylate, cyfloxylate, Lambda-lambda-cyhalothrin, Permanone, permethrin, esbiothrin, cyhalothrin, bifenthrin, permethrin, ether chrysanthemum ester, flumethrin, fluvalinate, Provado, acetamiprid, Ti304, imidaclothiz, thiacloprid, Diacloden, clothianidin, MTI-446, clothianadin, Da Tenan, diflubenzuron, young urea goes out, Teflubenzuron, deinsectization is grand, HEXAFLUMURON, flufenoxuron, pyridine worm is grand, lufenuron, poisonous insect urea, penfluron, Noviflumuron is noviflumuron, and it is for No. CAS 121451-02-3, flucycloxuron, Novaluron is Rimon, fluorine pyridine urea, Bay sir6874 i.e. { 1-[(3.5-bis-chloro-4) 4-nitrophenoxy phenyl 3-3-(2-chlorobenzene)-urea }, Bay SIR-8514 i.e. [1-(4-Trifluoromethoxyphen-l)-3-(2-chlorobenzene)-urea], piperazine worm urea, Bistrifluron is bistrifluron, furan tebufenozide, worm hydrazides, chlorine worm hydrazides, methoxyfenozide, ring worm hydrazides, Rogor, omethoate, SD-1750, acephate, triazophos, Resitox, pyridaphenthione, isazofos, Ro 7-5050, SevinCarbaryl, Aphox, meta-tolyl-N-methylcarbamate (MTMC), isoprocarb, cartap, fenobucarb, leaf disperses, carbaryl, benfuracarb, carbosulfan, cartap, bromopropylate, hexythiazox, fenpyroximate, pyridaben, clofentezine, propargite, diafenthiuron, benfuracarb, pymetrozine, spiral shell mite ester, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azocyclotin, Buprofezin, ethoprophos, ethiprole, desinsection list, disosultap, chlorantraniliprole, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, tebufenpyrad, bromothalonil, pyrazinones, second mite azoles, tebufenpyrad, the young ketone of rattling away, Nylar, any one in emaricin etc. or two kinds are used in combination for preventing and treating agricultural and forestry and gardening plant insect pest, anthranilic diamides derivative I of the present invention or the II quality percentage composition in composition is 1%-90%, and the ratio of anthranilic diamides derivative I of the present invention or II and above-mentioned sterilant is that mass percent 1%:99% is to 99%:1%, can directly be watered rear spraying, comprise the upper acceptable solvent of agricultural and emulsifying agent and solubility promoter and synergistic agent etc. in the preparation of composition, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, dispersible dense dose, missible oil, electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes dress agent, liquid/liquid mixes dress agent, cold mist agent, Gu Gu/mix filling agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent, the insect pest that can prevent and treat mainly contains red spider, Asiatic migrotory locust, clouding car locust, Chinese rice grasshopper, Patanga japonica (l.Bol.), single thorn mole cricket, east mole cricket, rice thrips, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian manages thrips, Trialeurodes vaporariorum Westwood, Bemisia tabaci, rice green leafhopper, green leaf hopper, chlorita biguttula, spot clothing plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, the flat angle of sugarcane plant hopper, cotten aphid, green bugs, grain aphid, black peach aphid, kaoliang aphid, radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, san jose scale, wax insect, ceroplastes rubens, Didesmococcus koreanus Borchs, pear lace bug, banana lace bug, thin corner piece stinkbug, Orius minutus, slender rice bug, paddy fly, niphe elongata, scotinophora lurida, Nezara viridula smaragdula Fabricius., green plant bug, alfalfa plant bug, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, cnidocampa flavescens walker, brown slug moth, thosea siensis, gelechiid, pink bollworm, brachmia triannuella, small cabbage moth, small heart-eating peach worm, eating-core bean worm, small heart-eating peach worm, apple Spilonota lechriaspis, brown belt length leaf roller, Adoxophyes cyrtosema, striped rice borer, bean-pod borer, Pyrausta nubilalis (Hubern)., yellow rice borer, Oeobia undalis, Cnaphalocrocis medinali(rice leaf roller), bar snout moth's larva, the wild snout moth's larva of lap leaf, dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, pink rice borer, bollworm, ancient cooking vessel point diamond drill, black cutworm, large cutworm, yellow cutworm, steal poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, straight burr rice hesperiidae, pelopidas mathias, oranges and tangerines swallowtail butterfly, Common Mormon, small white, pyrameis indica, the yellow a kind of butterfly harmful to crop plants of ramie, beans blister beetle, Venus ground beetle, wrinkle sheath ground beetle, wheat head ground beetle, pleonomus canaliculatus, Agriotes subrittatus Motschulsky, khapra beetle, attagenus piceus, the little buprestid beetle of oranges and tangerines, gold edge buprestid beetle, tenebrio molitor, dark mealworm, red flour beetle, confused flour beetle, verdigris different beetle, H. parallela, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori, pink neck longicorn, large daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, Phyllotreta striolata, Callosobruchus chinensis, pea weevil, broad bean weevil, sitophilus zea-mais, rice weevil, dolerus tritici, pear fruit sawfly, yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm is hanged cocoon ichneumon wasp, bollworm tooth lip ichneumon wasp, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, contarinia tritici, pachydiplosis oryzae, citrus fruit fly, melon trypetid, the latent fly of wheat leaf ash, Americal rice leaf miner, the black latent fly of beans stalk, frit fly, plant fly, onion fly, radish fly, full skirt chases after posts fly, Pyrausta nubilalis (Hubern). is strict posts fly, armyworm lacks must post the Agricultural pests such as fly, forestry pest, plant in control agricultural and forestry and gardening plant insect pest comprises paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape.Composition has improved the defence capability of plant in desinsection, makes plant produce the defence capability to pathogenic fungi, bacterium and virus infection.

Embodiment 30: the application in anthranilic diamides derivative I of the present invention or II and miticide combination control agricultural and forestry and gardening plant mite evil

Anthranilic diamides derivative I of the present invention or II and the upper acceptable auxiliary agent of agricultural and be selected from azocyclotin, cyhexatin, fenbutatin oxide, three phosphor tins, Zaprawa enolofos, dimethylvinphos, crotoxyphos, SD-1750, heptenopos, Phosdrin, monocrotophos, naled, Chlorpyrifos 94, Pyrimithate, imino-formyl chloride sulphur phosphorus, omethoate, dioxathion, Nialate, Malathion, methacrifos, Phosalone, Volaton, methylpyrimidine sulphur phosphorus, Resitox, sulfotep, triazophos, vamidothion, isocarbophos, acephatemet, propetamphos, dialifos, R-1504, acrinathrin, bifenthrin, cyhalothrin, essence lambda-cyhalothrin, Fenvalerate, flucythrinate, flumethrin, taufluvalinate, brofluthrinate, Bifenazate, fenothiocarb, aldicarb, butocarboxim, oxamyl, Talcord, thiofanox, F-1991, sok, carbofuran, carbosulfan, meta-tolyl-N-methylcarbamate (MTMC), promacyl, formetanate, single carbonamidine, medimeform, amitraz, chlordimeform, peruscabin, bromopropylate, cyflumetofen, acequinocyl, Nissol, flufenoxuron, macro tetrolide, piericidin, thuringiensin, tetranactin, macro tetrolide, Avrmectin, doractin, eprinomectin, ivermectin, selamectin, moxidectin, pyrethrin, nicotine, matrine, nimbin, tubatoxin, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, hexythiazox, spiral shell mite ester, Fluacrypyrim, Ovotran, propargite, any one in pyridaben or two kinds of medicament combinations are prepared into miticide for preventing and treating agricultural and forestry and gardening plant mite evil, anthranilic diamides derivative I of the present invention or the II total quality percentage composition in composition is 1%-90%, and the ratio of anthranilic diamides derivative I of the present invention or II and above-mentioned medicament is mass percent 1%: 99% to 99%: 1%, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, dispersible dense dose, missible oil, electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes dress agent, liquid/liquid mixes dress agent, cold mist agent, Gu Gu/mix filling agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent, plant in composition for preventing and controlling agricultural and forestry and gardening plant mite evil is selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape, the applicable mite of composition evil is phytophagy evil mite, and it is that the harmful mite of Tetranychidae, Tenuipalpidae, furan line mite, Eriophyidae is that Panonychus citri belongs to, tetranychus telarius belongs to and these global Agricultural Mites of itch mite of Eriophyidae, forestry harmful mites, the harmful mite of gardening and the harmful mite of health that phytophagy evil mite is selected from tetranychid.

Embodiment 31: the application in anthranilic diamides derivative I of the present invention or II and sterilant combination control agricultural and forestry and gardening plant disease

All anthranilic diamides derivative Is of the present invention or II and existing sterilant are as diazosulfide, tiadinil, is abbreviated as TDL, tisocromide, first thiophene lures amine, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-sodium formiate, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, DL-beta-aminobutyric acid, isotianil, it is English general by name: isotianil, 3,4-, bis-chloroisothiazoles-5-formic acid, 3,4-, bis-chloroisothiazoles-5-sodium formiate, 3,4-, bis-chloroisothiazoles-5-ethyl formate, virazole, antofine, Ningnanmycin or Whitfield's ointment, frost urea cyanogen, thiram, ziram, zinc manganese ethylenebisdithiocarbamate, phosethyl Al, thiophanate_methyl, m-tetrachlorophthalodinitrile, enemy can be loose, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, flumorph, dimethomorph, efficient metaxanin, efficient M 9834, two chlorine zarilamids, flusulfamide, first flusulfamide, thiophene fluorine bacterium amine, fultolanil, tecloftalam, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, pyrrole metsulfovax, mandipropamid, zoxamide, fenfuram, carboxin, chlozolinate, RP-26019, Azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, SSF 126, orysastrobin, ZEN 90160, Strobilurin, oxime bacterium ester, enostroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, SN-108266, difenoconazole, alkene azoles alcohol, efficient alkene azoles alcohol, epoxiconazole, RH-7592, fluquinconazole, fluzilazol, flutriafol, own azoles alcohol, imibenconazole, plant bacterium azoles, metconazole, nitrile bacterium azoles, Topaze, Wocosin 50TK, prothioconazoles, simeconazoles, tebuconazole, tertraconazole, triadimenol, triticonazole, bitertanol, thiabendazole, fuberidazole, imazalil, efficient imazalil, prochloraz, fluorine bacterium azoles, cyazofamid, fenamidone, Evil imidazoles, pefurazoate, famoxadone, SYP-Z048, hymexazo, the spirit of Evil frost, Guardian, etridiazole, octhilinone, benthiozole, dodemorph, fenpropimorph, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium amine, boscalid amine, fluopicolide, pyridine bacterium amine, cyprodinil, fluorine mepanipyrim, ferimzone, mepanipyrim, phonetic mould amine, fenarimol, nuarimol, chinomethionate, dithianon, ethoxyquin, hydroxyquinoline, the third oxygen quinoline, benzene oxygen quinoline, the mould prestige of second, iprovalicarb, benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, iprobenfos, pyrazophos, tolclofosmethyl, miewensu, kasugamycin, polyoxin, Polyoxin, validamycin, jingganmycin, Streptomycin sulphate, metaxanin, furalaxyl, M 9834, ofurace, mebenil, derosal, F-1991, thiophanate_methyl, triazolone, bupirimate, dimethirimol, the phonetic phenol of second, Difolatan, Vancide 89, Phaltan, Vinclozoline, fluoromide, dimetachlone, m-tetrachlorophthalodinitrile, isoprothiolane, Kitazine, bismerthiazol, quintozene, zinc 1,2-propylene bisdithiocarbamate, fosetylaluminium, sulphur, Bordeaux mixture, copper sulfate, copper oxychloride, Red copper oxide, copper hydroxide, metrafenone, pencycuron, diclomezin, phthalide, pyroquilon, volution bacterium amine, tricyclazole, triforine, the pyridine of many fruits, the pungent salt of biguanides, iminoctadine, dicloran, benzene flusulfamide, toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, methyl iodide, metamsodium, enemy's line ester, dazomet, dichloroisopropyl ether, lythidathion, cadusafos, fensulfothion, thionazin, fenamiphos, ethoprophos, dichlofenthion, isazofos, fosthietan, oxamyl, aldicarb, carbofuran, sulfuryl fluoride, dichloropropylene, dichloro-isonicotinic acid, other known any any one or two kinds that can be used as in sterilant such as allyl isothiazole are used in combination for preventing and treating agricultural and forestry and gardening plant disease, anthranilic diamides derivative I of the present invention or the II total quality percentage composition in composition is 1%-90%, and the ratio of anthranilic diamides derivative I of the present invention or II and aforementioned sterilant is that mass percent 1%:99% is to 99%:1%, the prevention effect of composition is good, and these compositions have certain synergism and summation action, does not find to have the composition of antagonistic action, above-mentioned composition can be for the control of agricultural plants disease and gardening plant disease, controlling object comprises that more than 20 of the Achylas, Aphanomyces, pythium, phytophthora, Sclerospora, Plasmopara, Pseudoperonospora, Peronospora of Oomycete etc. belong to the diseases that produce, as other diseases of plurality of cereals crop, cash crop, gardening plant and the forestry plants such as seedling blight of rice, tomato root maize ear rot, the late blight of potato, black shank, millet Powdery Mildew, downy mildew of garpe, downy mildew of lettuce, cucumber downy mildew, cucumber anthracnose etc., the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, dispersible dense dose, missible oil, electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes dress agent, liquid/liquid mixes dress agent, cold mist agent, Gu Gu/mix filling agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent.These compositions comprise cereal for preventing and treating agricultural and forestry and the applicable plant of gardening plant disease: paddy, wheat, barley, oat, corn, millet, Chinese sorghum; Tuber crops: sweet potato, potato, cassava; Beans: soybean, broad bean, pea, mung bean, red bean and fiber: cotton, crudefiber crop, silkworm and mulberry; Oil plant: peanut, rape, sesame, soybean, Sunflower Receptacle; Sugar material: beet, sugarcane; Beverage: tealeaves, coffee, cocoa; Hobby: tobacco leaf; Medicinal: ginseng, the bulb of fritillary; The torrid zone: rubber, coconut, oil palm, sisal hemp; Food crop and fruit, flowers, oil plant, sugar material and cotton, fiber crops, tea, tobacco, Chinese medicinal materials cash crop and plant melon, really, tea, silkworm and mulberry, vegetables, contain various wild vegetable, bamboo shoots, flowers and ornamental plant, hops, medicinal material, pepper, seedling and other garden crop garden crops as tobacco: flue-cured tobacco, air-curing of tobacco leaves, suncured tabacco; Vegetables, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, melon: watermelon, muskmelon, hami melon, pawpaw; Beans: soybean, broad bean, pea-pods; Potato, wheat, corn, paddy rice, peanut, fruit tree: apple, banana, citrus, peach, papaya; Flowers: orchid; Potted landscape; Composition has improved the defence capability of plant in sterilization, makes plant produce the defence capability to pathogenic fungi, bacterium and virus infection.

Embodiment 32: anthranilic diamides derivative I of the present invention or II and antiviral agent are combined in the application in control agricultural and forestry and gardening plant virus disease

Anthranilic diamides derivative I of the present invention or II and existing Antiphytoviral medicament diazosulfide, tiadinil, be abbreviated as TDL, isotianil, it is English general by name: isotianil, 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-formic acid, 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-sodium formiate, 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-ethyl formate, 3, 4-bis-chloroisothiazoles-5-formic acid, 3, 4-bis-chloroisothiazoles-5-sodium formiate, 3, 4-bis-chloroisothiazoles-5-ethyl formate, DL-beta-aminobutyric acid, virazole, antofine, Ningnanmycin, tisocromide, first thiophene lures amine or Whitfield's ointment, cytosintetidemycin, dichloro-isonicotinic acid, allyl isothiazole, well ridge azanol, in jingganmycin, any 1 or 2 compound combinations are used for preventing and treating agricultural and forestry and gardening plant virus disease, the disease of control agricultural and forestry and gardening plant virus disease is selected from tobacco mosaic virus disease, various melon virus diseases, various solanaceous vegetables virus diseases, beans virus disease, Cruciferae virus disease, grain and oil crop virus disease, any in cotton virus disease and various fruit tree virus disease, wherein endanger serious being selected from: tobacco virus, peppery pimento virus disease, tomato virus disease, Chinese cabbage virus disease, Virus Diseases of Rice comprises rice dwarf virus disease, yellow dwart, stripe virus disease, fern leaf of tomato viral disease, pepper mosaic virus disease viral disease and tobacco veinal necrosis virus are sick, maize dwarf mosaic, cauliflower mosaic virus, oranges and tangerines virus disease, cymbidium mosaic virus, any in cybidium ring spot virus.These compositions are selected from paddy for preventing and treating the plant of agricultural and forestry and gardening plant virus disease, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, the agriculturals such as potted landscape, gardening, economical, the plants such as forestry, the use of these compositions improves the immunizing power of crop self, when producing the control of insect especially infection insect, has induced plant to produce the defence capability to viral diseases of plants, also can produce the direct prevention effect of virus disease, therefore, these compositions can be for preparation and the purposes of Antiphytoviral medicament and inducing plant Antiphytoviral medicament.Anthranilic diamides derivative I of the present invention or the II total quality percentage composition in composition is 1%-90%, and the ratio of anthranilic diamides derivative I of the present invention or II and aforementioned Antiphytoviral medicament is that mass percent 1%:99% is to 99%:1%, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, dispersible dense dose, missible oil, electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes dress agent, liquid/liquid mixes dress agent, cold mist agent, Gu Gu/mix filling agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent, between these compositions, all show and be added or synergism, when keeping insecticidal activity, its antiviral activity is all greater than the effect that any one compound is used separately, find no the composition of antagonistic action, the drug effect lasting period of composition is long.

Embodiment 33: complete processing and the stability of anthranilic diamides derivative I of the present invention or II and commercially available agricultural chemical compound preparation

The mixture complete processing of anthranilic diamides derivative I of the present invention or II and commercially available agricultural chemical is in Table 9, from table 9, most medicament all can be processed according to the method for statement, the main component of liquid preparation is effective constituent and solubility promoter and tensio-active agent, synergistic agent, antifreezing agent, stablizer, other the component etc. such as thickening material or permeate agent, the composition of solid preparation mainly includes effect composition, the upper acceptable adjuvant component of other agriculturals such as tensio-active agent and filler, the cold storage test of process preparation, liquid preparation is placed 1 week without Precipitation at 0 ± 2 degree Celsius, solid preparation is placed 2 weeks at 54 ± 2 degrees Celsius, there is not caking phenomenon in medicament, all preparations store the medicament drug effect of placement front and back without significant difference, the rate of decomposition of composition effective constituent is in 5%, composite preparation qualified stability.

Chemical structure and the physical and chemical parameter of table 1 anthranilic diamides derivative I of the present invention

The chemical structure of table 1 anthranilic diamides derivative I of the present invention and physical and chemical parameter (continuing)

Table 2: chemical structure and the physical and chemical parameter of anthranilic diamides derivative I I of the present invention

Table 2: the chemical structure of anthranilic diamides derivative I I of the present invention and physical and chemical parameter (continuing)

Table 2: the chemical structure of anthranilic diamides derivative I I of the present invention and physical and chemical parameter (continuing)

The result of the different mechanism of action Drug Calcium of table 3 ion channel activity measuring method

Table 4: the compound of anthranilic diamides derivative I of the present invention and II is to ryanodine receptor agonist activity value

Table 5: the activity that the compound of anthranilic diamides derivative I of the present invention and II shifts cell calcium

+++=calcium transfer activity is better than chloro-3 methylphenols of 4-.++=calcium transfer activity approximates chloro-3 methylphenols of 4-.+=calcium transfer activity is weaker than chloro-3 methylphenols of 4-.-=without calcium transfer activity.

The insecticidal activity (mythimna separata and red spider) of table 6 anthranilic diamides derivative I of the present invention or II

The insecticidal activity (mythimna separata and red spider) (continuing) of table 6 anthranilic diamides derivative I of the present invention or II

The insecticidal activity (small cabbage moth and grub) (continuing) of table 6 anthranilic diamides derivative I of the present invention or II

The insecticidal activity (small cabbage moth and grub) (continuing) of table 6 anthranilic diamides derivative I of the present invention or II

The bacteriostatic activity (/ %) of table 7 anthranilic diamides derivative I of the present invention or II

Numbering	Compound number	CA	BC	PS	GZ	PI	AS	SS	RC	PP
											1	I-1	22.76	11.55	17.3	45.66	5.19	43.09	37.56	23.64	24.35
2	I-2	7.08	11.73	18.09	29.59	43.33	43.13	34.35	15.31	10.7
											3	I-3	31.45	27.34	14.97	42.09	26.02	21.71	39.48	16.5	7.69
4	I-4	31.45	22.07	14.97	31.02	38.52	18.26	39.1	20.07	11.02
											5	I-5	31.45	27.34	14.97	32.09	26.02	21.71	39.48	16.5	7.69
6	I-6	22.76	11.55	17.3	45.66	5.19	43.09	37.56	23.64	24.35
											7	I-7	7.08	18.88	10.78	22.09	32.56	24.18	30.84	16.5	13.92
8	I-8	13.14	11.73	13.22	27.81	8.71	38.91	34.35	10.54	13.92
											9	I-9	27.11	6.28	21.95	34.81	5.19	37.23	29.87	21.26	7.69
10	I-10	20.07	19.54	36.73	43.44	46.73	39.77	33.92	21.87	21.71
											11	I-11	4.35	1.02	13.28	15.31	11.02	24.7	27.02	13.52	22.76
12	I-12	15.31	4.72	16.73	17.38	9.59	27.27	67.15	10.4	21.71
											13	I-13	10.11	8.16	5.9	33.16	41.02	23.65	39.62	6.97	17.15
14	I-14	10.11	8.16	5.9	33.16	22.12	23.65	39.71	6.97	17.15
											15	I-15	7.08	15.31	15.65	29.59	35.64	24.18	20.32	9.35	13.92
16	I-16	31.45	27.34	14.97	42.09	26.02	21.71	39.48	16.5	7.69
											17	1-17	28.76	6.28	17.3	14.59	13.52	7.92	33.71	28.4	7.69
18	I-18	16.17	4.59	5.9	29.59	27.94	23.65	34.35	11.73	7.47
											19	I-19	18.26	13.52	26.02	21.12	16.81	34.55	15.08	24.68	24.7
20	I-20	7.69	5.37	26.83	41.02	44.35	23.62	15.32	25.08	22.76
											21	I-21	13.52	23.24	15.73	30.33	32.73	30.19	26.47	16.61	23.24
22	I-22	15.31	12.13	20.31	19.5	26.73	23.52	60.7	29.17	11.36
											23	I-23	10.54	15.83	18.88	37.38	11.92	34.15	44.15	41.64	25.16
24	I-24	21.02	9.72	22.96	32.45	21.02	19.44	33.02	19.46	27.11
											25	I-25	22.73	11.52	17.27	25.63	5.16	23.06	37.53	23.61	24.32
26	I-26	7.05	11.7	18.06	29.56	23.3	23.1	34.32	15.28	10.67
											27	I-27	31.42	27.31	14.94	22.06	25.99	21.68	39.45	16.47	7.66
28	I-28	13.49	23.21	15.7	30.3	32.7	30.16	26.44	26.51	23.21
											29	I-29	15.28	12.1	40.28	42.47	41.7	43.49	40.67	49.14	11.33
30	I-30	10.51	15.8	18.85	37.35	30.99	24.12	27.12	21.61	25.13
											31	I-31	30.99	9.69	32.93	22.42	20.99	19.41	32.99	19.43	27.08
32	I-32	22.7	11.49	17.24	25.6	5.13	23.03	37.5	23.58	24.29
											33	II-1	7.02	11.67	18.03	29.53	23.27	23.07	34.29	15.25	10.64
34	II-2	31.39	27.28	14.91	32.03	25.96	21.65	39.42	16.44	7.63
											35	II-3	30.36	22.01	14.91	40.96	38.46	18.2	49.04	20.01	10.96
36	II-4	31.22	6.25	17.27	34.56	13.49	7.89	33.68	28.37	7.66
											37	II-5	22.7	11.49	17.24	35.6	5.13	33.03	37.5	23.58	24.29
38	II-6	7.02	18.82	10.72	32.03	22.5	24.12	30.78	16.44	13.86
											39	II-7	7.05	15.28	15.62	29.56	35.61	24.15	20.29	9.32	13.89
40	II-8	31.42	27.31	14.94	42.06	25.99	21.68	39.45	16.47	7.66
											41	II-9	23.49	6.25	17.27	34.56	13.49	7.89	33.68	28.37	7.64
42	II-10	16.14	4.56	5.87	29.56	27.91	23.62	34.32	11.7	7.44
											43	II-11	18.23	13.49	25.99	40.99	46.78	54.52	45.05	34.65	24.67
44	II-12	7.66	5.34	26.8	30.2	24.32	23.62	24.99	25.05	22.73
											45	II-13	31.42	22.04	14.94	30.79	38.49	18.23	19.07	20.04	10.99
46	II-14	17.89	27.31	33.94	22.06	25.99	21.68	39.45	16.47	7.66
											47	II-15	22.73	11.52	17.27	25.63	5.16	23.06	37.53	23.61	24.32
48	II-16	7.05	18.85	10.75	22.06	32.53	34.15	30.81	16.47	13.89
											49	II-17	13.11	11.7	13.19	27.78	8.68	38.88	34.32	10.51	13.66
50	II-18	27.08	6.25	21.92	52.78	5.16	37.2	29.84	21.23	7.66
											51	II-19	20.04	19.51	36.7	23.41	26.7	39.74	23.89	22.84	21.68
52	II-20	4.32	2.99	33.25	35.28	30.92	24.67	36.99	33.49	22.73

The bacteriostatic activity (/ %) (continuing) of table 7 anthranilic diamides derivative I of the present invention or II

Numbering	Compound number	CA	BC	PS	GZ	PI	AS	SS	RC	PP
											53	II-21	15.28	4.69	36.7	37.35	9.56	37.24	37.12	30.37	21.68
54	II-22	11.08	9.13	8.87	34.13	30.99	33.92	34.59	9.94	23.12
											55	II-23	10.05	8.1	5.84	33.1	30.96	33.59	39.56	6.91	17.09
56	II-24	13.08	11.67	13.16	27.75	8.65	48.85	34.29	10.48	13.86
											57	II-25	27.05	6.22	21.89	32.75	5.13	37.17	29.81	21.2	7.63
58	II-26	20.01	19.48	36.67	33.38	36.67	39.71	33.86	32.81	21.65
											59	II-27	4.29	0.96	33.22	35.25	30.96	24.64	36.96	33.46	22.7
60	II-28	15.25	4.66	36.67	37.32	9.53	37.21	67.09	50.34	21.65
											61	II-29	10.05	8.1	5.84	33.1	30.96	33.59	39.56	6.91	17.09
62	II-30	10.06	8.10	6.87	34.13	37.99	31.42	34.59	7.94	19.12
											63	II-31	7.02	15.25	15.59	29.53	35.58	34.12	20.26	9.29	13.86
64	II-32	31.39	27.28	14.91	32.03	25.96	21.65	39.42	16.44	7.63
											65	II-33	30.22	6.22	17.24	34.53	13.46	7.86	33.65	28.34	7.43
66	II-34	16.11	4.53	5.84	29.53	27.88	33.59	34.29	11.67	7.41
											67	II-35	18.2	13.46	25.96	50.96	66.75	54.49	45.02	54.62	24.64
68	II-36	7.63	5.31	26.77	30.45	34.29	33.59	24.96	35.02	22.7
											69	II-37	13.46	23.18	15.67	30.27	32.67	30.13	36.41	36.55	23.18
70	II-38	15.25	12.07	30.25	39.44	36.67	33.46	30.64	39.11	11.3
											71	II-39	10.48	15.77	18.82	37.32	40.96	54.09	67.09	51.58	25.1
72	II-40	50.96	9.66	42.9	42.39	20.96	19.38	32.96	49.4	27.05

The working method that table 8 anthranilic diamides derivative I or II are mixed with commercially available agricultural chemical

Claims (10)

1. a class anthranilic diamides derivative, is characterized in that having the chemical structure of general formula suc as formula shown in I or II:

Wherein: R ¹and R ²be selected from hydrogen, the alkyl that contains 1-10 carbon atom, have by 1-4 F, the alkyl that contains 1-10 carbon atom that Cl replaces, the cycloalkyl that contains 3-7 carbon atom, contain 3-6 carbon atom and O, N, S, the heterocyclic group of 1-2 atom in P, aryl, hydroxyl, the alkoxyl group that contains 1-10 carbon atom, aryloxy, trifluoromethoxy, cyano group, nitro, amino, the alkylamino that contains 1-10 carbon atom, the dialkyl amido that contains 1-10 carbon atom, sulfydryl, the alkylthio that contains 1-10 carbon atom, arylthio, formyl radical, the alkyl-carbonyl that contains 1-10 carbon atom, aryl carbonyl, manthanoate, the alkyl carboxyl that contains 1-10 carbon atom, aryl carboxyl, the alkoxyl group carboxyl that contains 1-10 carbon atom, aryloxy carboxyl, formamido group, the alkyl amido that contains 1-10 carbon atom, aryl-amino-carbonyl, urea groups, the alkyl urea groups that contains 1-10 carbon atom, aryl-ureido, amino carboxyl, the alkylamino carboxyl that contains 1-10 carbon atom, arylamino carboxyl, trifluoroacetyl group, F, Cl, Br, I, hydroxycarbonyl group, the alkoxy carbonyl that contains 1-10 carbon atom, aryloxycarbonyl, sulfinyl, the alkyl sulphinyl that contains 1-10 carbon atom, aryl sulfonyl kia, alkylsulfonyl, the alkyl sulphonyl that contains 1-10 carbon atom, aryl sulfonyl, sulfonamido, the alkyl sulfonyl that contains 1-10 carbon atom is amino, Arenesulfonyl amino functional group,

R ³the alkyl that is selected from hydrogen, contains 1-10 carbon atom, there is the alkyl that contains 1-10 carbon atom, the cycloalkyl that contains 3-7 carbon atom that are replaced by 1-4 F, Cl, contain 3-6 carbon atom and O, N, heterocyclic group, the aryl of 1-2 atom in S, P;

R ⁴be selected from hydrogen, the alkyl that contains 1-10 carbon atom, there is the alkyl that contains 1-10 carbon atom being replaced by 1-4 fluorine or chlorine, the cycloalkyl that contains 3-7 carbon atom, contain 3-6 carbon atom and O, N, S, the heterocyclic group of 1-2 atom in P, aryl, hydroxyl, the alkoxyl group that contains 1-10 carbon atom, aryloxy, trifluoromethoxy, cyano group, nitro, amino, the alkylamino that contains 1-10 carbon atom, the dialkyl amido that contains 1-10 carbon atom, sulfydryl, the alkylthio that contains 1-10 carbon atom, arylthio, formyl radical, the alkyl-carbonyl that contains 1-10 carbon atom, aryl carbonyl, formamido group, the alkyl amido that contains 1-10 carbon atom, aryl-amino-carbonyl, urea groups, the alkyl urea groups that contains 1-10 carbon atom, aryl-ureido, amino carboxyl, the alkylamino carboxyl that contains 1-10 carbon atom, arylamino carboxyl, trifluoroacetyl group, the alkoxy carbonyl that contains 1-10 carbon atom, aryloxycarbonyl, sulfinyl, the alkyl sulphinyl that contains 1-10 carbon atom, aryl sulfonyl kia, alkylsulfonyl, the alkyl sulphonyl that contains 1-10 carbon atom, aryl sulfonyl, sulfonamido, the alkyl sulfonyl that contains 1-10 carbon atom is amino, Arenesulfonyl amino functional group,

X, Y and Z are selected from CR ⁵r ⁶, NR ₃, O, S, CO, SO, SO ₂; Y is CR also ⁵r ⁶-CR ⁵r ⁶, or do not exist; R ⁵, R ⁶the alkyl that is selected from hydrogen, contains 1-10 carbon atom, there is the alkyl that contains 1-10 carbon atom being replaced by 1-4 F, Cl;

m＝1，2。

2. compound according to claim 1, wherein R ¹represent methyl, trifluoromethyl, pentafluoroethyl group, F, Cl, Br, cyano group, nitro; R ²represent trifluoromethyl, pentafluoroethyl group, F, Cl, Br, cyano group, nitro; R ³represent methyl, ethyl, propyl group, sec.-propyl, butyl, 2-butyl, the tertiary butyl, trifluoromethyl; R ⁴represent the cycloalkyl containing 3-6 carbon of methyl, ethyl, propyl group, sec.-propyl, butyl, 2-butyl, the tertiary butyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, replacement, heterocyclic group, the aryl that contains 3-5 carbon and 1-2 heteroatoms (O, N, S, P); X, Y and Z represent CH ₂, O, SO, SO ₂; M=1,2.

3. according to the class anthranilic diamides derivative I described in claim 1-2 or the salt of II, N-oxide compound, metal complex, metalloid complex compound and optical activity are lived or geometrical isomer.

4. the synthetic method of a class anthranilic diamides derivative I or II described in claim 1-3, concrete synthetic route is as follows:

Wherein: R ¹and R ²be selected from hydrogen, the alkyl that contains 1-10 carbon atom, have by 1-4 F, the alkyl that contains 1-10 carbon atom that Cl replaces, the cycloalkyl that contains 3-7 carbon atom, contain 3-6 carbon atom and O, N, S, the heterocyclic group of 1-2 atom in P, aryl, hydroxyl, the alkoxyl group that contains 1-10 carbon atom, aryloxy, trifluoromethoxy, cyano group, nitro, amino, the alkylamino that contains 1-10 carbon atom, the dialkyl amido that contains 1-10 carbon atom, sulfydryl, the alkylthio that contains 1-10 carbon atom, arylthio, formyl radical, the alkyl-carbonyl that contains 1-10 carbon atom, aryl carbonyl, manthanoate, the alkyl carboxyl that contains 1-10 carbon atom, aryl carboxyl, the alkoxyl group carboxyl that contains 1-10 carbon atom, aryloxy carboxyl, formamido group, the alkyl amido that contains 1-10 carbon atom, aryl-amino-carbonyl, urea groups, the alkyl urea groups that contains 1-10 carbon atom, aryl-ureido, amino carboxyl, the alkylamino carboxyl that contains 1-10 carbon atom, arylamino carboxyl, trifluoroacetyl group, F, Cl, Br, I, hydroxycarbonyl group, the alkoxy carbonyl that contains 1-10 carbon atom, aryloxycarbonyl, sulfinyl, the alkyl sulphinyl that contains 1-10 carbon atom, aryl sulfonyl kia, alkylsulfonyl, the alkyl sulphonyl that contains 1-10 carbon atom, aryl sulfonyl, sulfonamido, the alkyl sulfonyl that contains 1-10 carbon atom is amino, Arenesulfonyl amino functional group,

R ³the alkyl that is selected from hydrogen, contains 1-10 carbon atom, there is the alkyl that contains 1-10 carbon atom, the cycloalkyl that contains 3-7 carbon atom that are replaced by 1-4 F, Cl, contain 3-6 carbon atom and O, N, heterocyclic group, the aryl of 1-2 atom in S, P;

R ⁴be selected from hydrogen, the alkyl that contains 1-10 carbon atom, there is the alkyl that contains 1-10 carbon atom being replaced by 1-4 fluorine or chlorine, the cycloalkyl that contains 3-7 carbon atom, contain 3-6 carbon atom and O, N, S, the heterocyclic group of 1-2 atom in P, aryl, hydroxyl, the alkoxyl group that contains 1-10 carbon atom, aryloxy, trifluoromethoxy, cyano group, nitro, amino, the alkylamino that contains 1-10 carbon atom, the dialkyl amido that contains 1-10 carbon atom, sulfydryl, the alkylthio that contains 1-10 carbon atom, arylthio, formyl radical, the alkyl-carbonyl that contains 1-10 carbon atom, aryl carbonyl, formamido group, the alkyl amido that contains 1-10 carbon atom, aryl-amino-carbonyl, urea groups, the alkyl urea groups that contains 1-10 carbon atom, aryl-ureido, amino carboxyl, the alkylamino carboxyl that contains 1-10 carbon atom, arylamino carboxyl, trifluoroacetyl group, the alkoxy carbonyl that contains 1-10 carbon atom, aryloxycarbonyl, sulfinyl, the alkyl sulphinyl that contains 1-10 carbon atom, aryl sulfonyl kia, alkylsulfonyl, the alkyl sulphonyl that contains 1-10 carbon atom, aryl sulfonyl, sulfonamido, the alkyl sulfonyl that contains 1-10 carbon atom is amino, Arenesulfonyl amino functional group,

X, Y and Z are selected from CR ⁵r ⁶, NR ₃, O, S, CO, SO, SO ₂; Y is CR also ⁵r ⁶-CR ⁵r ⁶, or do not exist; R ⁵, R ⁶the alkyl that is selected from hydrogen, contains 1-10 carbon atom, there is the alkyl that contains 1-10 carbon atom being replaced by 1-4 F, Cl;

Midbody compound (III) can be prepared by the following method;

Hal is Cl, Br orI; A H2N-NH2; Ethyl maleate and sodium ethylate for b reflux in ethanol; C phosphoryl chloride refluxes in second cyanogen; Potassium Persulphate and sulfuric acid for d reflux in second cyanogen; Alkali catalyzed hydrolysis reaction (sodium hydroxide, methyl alcohol, water) for e;

A K wherein ₂cO ₃/ DMPF; B LDA/THF/CO ₂reaction;

Compound (IV) can be prepared by the following method:

Wherein a is that aromatic nucleus replaces reagent, and for example N-N-iodosuccinimide is prepared iodo IV, and N-bromo-succinimide is prepared bromo (IV), and N-chlorosuccinimide is prepared chloro (IV), HNO ₃/ H ₂sO ₄or HNO ₃nitrated (IV) is prepared by/diacetyl oxide;

Compound (IV) also can be prepared by the following method:

Sub can be that iodine replaces, for example, with N-N-iodosuccinimide, in reaction step a, by initiator, prepared; With suitable b, can prepare a series of (IV); For example with CuCN, can prepare R ¹the product of=CN (IV);

Midbody compound (X) can be prepared by the following method:

Wherein a is chloral hydrate and oxammonium sulfate, b is methylsulfonic acid, c is sodium hydroxide and aqueous hydrogen peroxide solution, d is that aromatic nucleus replaces reagent, for example N-N-iodosuccinimide is prepared iodo (IV), N-bromo-succinimide is prepared bromo (IV), and N-chlorosuccinimide is prepared chloro IV, HNO ₃/ H ₂sO ₄or HNO ₃nitrated (IV) is prepared by/diacetyl oxide;

Midbody compound (X) also can be prepared by the following method:

Sub can be that iodine replaces, for example, with N-N-iodosuccinimide, in reaction step a, by initiator, prepare iodo product; With suitable reagent b, can prepare a series of (X); For example with CuCN, can prepare R ¹the product of=CN (X);

Midbody compound (X) also can be prepared by the following method:

A is methyl esterification reagent, and for example, b is that suitable aromatic ring replaces reagent, and for example N-N-iodosuccinimide is prepared iodo product, and N-bromo-succinimide is prepared bromination product, and N-chlorosuccinimide is prepared chloro-product, HNO ₃/ H ₂sO ₄or HNO ₃/ diacetyl oxide is prepared nitration product; C is NaOH/HCl; The method is applicable to replace and under reagent b reaction conditions, to be unsuitable for the situation that carboxyl exists and to prepare compound (X) at aromatic ring;

Midbody compound (X) also can be prepared by the following method:

A is nitrating agent, for example the mixture of the vitriol oil and concentrated nitric acid; B is reductive agent, for example zinc dichloride; C is hydrolysis reaction, for example sodium hydroxide/ethyl alcohol/water.

5. a class anthranilic diamides derivative I claimed in claim 1 or II and agricultural go up the purposes of acceptable auxiliary agent in preparing Insecticidal and acaricidal agent.

6. a class anthranilic diamides derivative I claimed in claim 1 or II and agricultural go up the purposes of acceptable auxiliary agent in preparing sterilant.

7. the application in a class anthranilic diamides derivative I claimed in claim 1 or II and insecticide composition control agricultural and forestry and gardening plant insect pest:

All class anthranilic diamides derivative Is of the present invention or II and existing sterilant: Chlorpyrifos 94, the sub-Nong in ground, acetamiprid, Affirm (Merck Co.), milbemectin, Avrmectin, pleocidin, fenvalerate, efficient fenvalerate, Cypermethrin, effective cypermethrin, lambda-cyhalothrin, Deltamethrin, Fenvalerate, Beta-cyfloxylate, cyfloxylate, Lambda-lambda-cyhalothrin, Permanone, permethrin, esbiothrin, cyhalothrin, bifenthrin, permethrin, ether chrysanthemum ester, flumethrin, fluvalinate, Provado, acetamiprid, Ti304, imidaclothiz, thiacloprid, Diacloden, clothianidin, MTI-446, clothianadin, Da Tenan, diflubenzuron, young urea goes out, Teflubenzuron, deinsectization is grand, HEXAFLUMURON, flufenoxuron, pyridine worm is grand, lufenuron, poisonous insect urea, penfluron, NoIiflumuron is noviflumuron, and it is for No. CAS 121451-02-3, flucycloxuron, NoIaluron is Rimon, fluorine pyridine urea, Bay sir6874 i.e. { 1-[(3.5-bis-chloro-4) 4-nitrophenoxy phenyl 3-3-(2-chlorobenzene)-urea }, Bay SIR-8514 i.e. [1-(4-Trifluoromethoxyphen-l)-3-(2-chlorobenzene)-urea], piperazine worm urea, Bistrifluron is bistrifluron, furan tebufenozide, worm hydrazides, chlorine worm hydrazides, methoxyfenozide, ring worm hydrazides, Rogor, omethoate, SD-1750, acephate, triazophos, Resitox, pyridaphenthione, isazofos, Ro 7-5050, SevinCarbaryl, Aphox, meta-tolyl-N-methylcarbamate (MTMC), isoprocarb, cartap, fenobucarb, leaf disperses, carbaryl, benfuracarb, carbosulfan, cartap, bromopropylate, hexythiazox, fenpyroximate, pyridaben, clofentezine, propargite, diafenthiuron, benfuracarb, pymetrozine, spiral shell mite ester, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azocyclotin, Buprofezin, ethoprophos, ethiprole, desinsection list, disosultap, chlorantraniliprole, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, tebufenpyrad, bromothalonil, pyrazinones, second mite azoles, tebufenpyrad, the young ketone of rattling away, Nylar, any one in emaricin etc. or two kinds are used in combination for preventing and treating agricultural and forestry and gardening plant insect pest, a class anthranilic diamides derivative I of the present invention or the quality percentage composition of II in composition are 1%-90%, and the ratio of a class anthranilic diamides derivative I of the present invention or II and above-mentioned sterilant is that mass percent 1%:99% is to 99%:1%, can directly be watered rear spraying, comprise the upper acceptable solvent of agricultural and emulsifying agent and solubility promoter and synergistic agent etc. in the preparation of composition, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, dispersible dense dose, missible oil, electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes dress agent, liquid/liquid mixes dress agent, cold mist agent, Gu Gu/mix filling agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent, the insect pest that can prevent and treat mainly contains red spider, Asiatic migrotory locust, clouding car locust, Chinese rice grasshopper, Patanga japonica (l.Bol.), single thorn mole cricket, east mole cricket, rice thrips, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian manages thrips, Trialeurodes vaporariorum Westwood, Bemisia tabaci, rice green leafhopper, green leaf hopper, chlorita biguttula, spot clothing plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, the flat angle of sugarcane plant hopper, cotten aphid, green bugs, grain aphid, black peach aphid, kaoliang aphid, radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, san jose scale, wax insect, ceroplastes rubens, Didesmococcus koreanus Borchs, pear lace bug, banana lace bug, thin corner piece stinkbug, Orius minutus, slender rice bug, paddy fly, niphe elongata, scotinophora lurida, Nezara viridula smaragdula Fabricius., green plant bug, alfalfa plant bug, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, cnidocampa flavescens walker, brown slug moth, thosea siensis, gelechiid, pink bollworm, brachmia triannuella, small cabbage moth, small heart-eating peach worm, eating-core bean worm, small heart-eating peach worm, apple Spilonota lechriaspis, brown belt length leaf roller, Adoxophyes cyrtosema, striped rice borer, bean-pod borer, Pyrausta nubilalis (Hubern)., yellow rice borer, Oeobia undalis, Cnaphalocrocis medinali(rice leaf roller), bar snout moth's larva, the wild snout moth's larva of lap leaf, dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, pink rice borer, bollworm, ancient cooking vessel point diamond drill, black cutworm, large cutworm, yellow cutworm, steal poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, straight burr rice hesperiidae, pelopidas mathias, oranges and tangerines swallowtail butterfly, Common Mormon, small white, pyrameis indica, the yellow a kind of butterfly harmful to crop plants of ramie, beans blister beetle, Venus ground beetle, wrinkle sheath ground beetle, wheat head ground beetle, pleonomus canaliculatus, Agriotes subrittatus Motschulsky, khapra beetle, attagenus piceus, the little buprestid beetle of oranges and tangerines, gold edge buprestid beetle, tenebrio molitor, dark mealworm, red flour beetle, confused flour beetle, verdigris different beetle, H. parallela, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori, pink neck longicorn, large daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, Phyllotreta striolata, Callosobruchus chinensis, pea weevil, broad bean weevil, sitophilus zea-mais, rice weevil, dolerus tritici, pear fruit sawfly, yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm is hanged cocoon ichneumon wasp, bollworm tooth lip ichneumon wasp, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, contarinia tritici, pachydiplosis oryzae, citrus fruit fly, melon trypetid, the latent fly of wheat leaf ash, Americal rice leaf miner, the black latent fly of beans stalk, frit fly, plant fly, onion fly, radish fly, full skirt chases after posts fly, Pyrausta nubilalis (Hubern). is strict posts fly, armyworm lacks must post the Agricultural pests such as fly, forestry pest, plant in control agricultural and forestry and gardening plant insect pest comprises paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape, composition has improved the defence capability of plant in desinsection, makes plant produce the defence capability to pathogenic fungi, bacterium and virus infection.

8. the application in a class anthranilic diamides derivative I claimed in claim 1 or II and miticide combination control agricultural and forestry and gardening plant mite evil:

A class anthranilic diamides derivative I of the present invention or II and the upper acceptable auxiliary agent of agricultural and be selected from azocyclotin, cyhexatin, fenbutatin oxide, three phosphor tins, Zaprawa enolofos, dimethylvinphos, crotoxyphos, SD-1750, heptenopos, Phosdrin, monocrotophos, naled, Chlorpyrifos 94, Pyrimithate, imino-formyl chloride sulphur phosphorus, omethoate, dioxathion, Nialate, Malathion, methacrifos, Phosalone, Volaton, methylpyrimidine sulphur phosphorus, Resitox, sulfotep, triazophos, vamidothion, isocarbophos, acephatemet, propetamphos, dialifos, R-1504, acrinathrin, bifenthrin, cyhalothrin, essence lambda-cyhalothrin, Fenvalerate, flucythrinate, flumethrin, taufluvalinate, brofluthrinate, Bifenazate, fenothiocarb, aldicarb, butocarboxim, oxamyl, Talcord, thiofanox, F-1991, sok, carbofuran, carbosulfan, meta-tolyl-N-methylcarbamate (MTMC), promacyl, formetanate, single carbonamidine, medimeform, amitraz, chlordimeform, peruscabin, bromopropylate, cyflumetofen, acequinocyl, Nissol, flufenoxuron, macro tetrolide, piericidin, thuringiensin, tetranactin, macro tetrolide, Avrmectin, doractin, eprinomectin, ivermectin, selamectin, moxidectin, pyrethrin, nicotine, matrine, nimbin, tubatoxin, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, hexythiazox, spiral shell mite ester, Fluacrypyrim, Ovotran, propargite, any one in pyridaben or two kinds of medicament combinations are prepared into miticide for preventing and treating agricultural and forestry and gardening plant mite evil, a class anthranilic diamides derivative I of the present invention or the II total quality percentage composition in composition is 1%-90%, and the ratio of a class anthranilic diamides derivative I of the present invention or II and above-mentioned medicament is that mass percent 1%:99% is to 99%:1%, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, dispersible dense dose, missible oil, electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes dress agent, liquid/liquid mixes dress agent, cold mist agent, Gu Gu/mix filling agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent, plant in composition for preventing and controlling agricultural and forestry and gardening plant mite evil is selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape, the applicable mite of composition evil is phytophagy evil mite, and it is that the harmful mite of Tetranychidae, Tenuipalpidae, furan line mite, Eriophyidae is that Panonychus citri belongs to, tetranychus telarius belongs to and these global Agricultural Mites of itch mite of Eriophyidae, forestry harmful mites, the harmful mite of gardening and the harmful mite of health that phytophagy evil mite is selected from tetranychid.

9. the application in a class anthranilic diamides derivative I claimed in claim 1 or II and sterilant combination control agricultural and forestry and gardening plant disease:

All class anthranilic diamides derivative Is of the present invention or II and existing sterilant are as diazosulfide, tiadinil, is abbreviated as TDL, tisocromide, first thiophene lures amine, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-sodium formiate, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, DL-beta-aminobutyric acid, isotianil, it is English general by name: isotianil, 3,4-, bis-chloroisothiazoles-5-formic acid, 3,4-, bis-chloroisothiazoles-5-sodium formiate, 3,4-, bis-chloroisothiazoles-5-ethyl formate, virazole, antofine, Ningnanmycin or Whitfield's ointment, frost urea cyanogen, thiram, ziram, zinc manganese ethylenebisdithiocarbamate, phosethyl Al, thiophanate_methyl, m-tetrachlorophthalodinitrile, enemy can be loose, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, flumorph, dimethomorph, efficient metaxanin, efficient M 9834, two chlorine zarilamids, flusulfamide, first flusulfamide, thiophene fluorine bacterium amine, fultolanil, tecloftalam, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, pyrrole metsulfovax, mandipropamid, zoxamide, fenfuram, carboxin, chlozolinate, RP-26019, Azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, SSF 126, orysastrobin, ZEN 90160, Strobilurin, oxime bacterium ester, enostroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, SN-108266, difenoconazole, alkene azoles alcohol, efficient alkene azoles alcohol, epoxiconazole, RH-7592, fluquinconazole, fluzilazol, flutriafol, own azoles alcohol, imibenconazole, plant bacterium azoles, metconazole, nitrile bacterium azoles, Topaze, Wocosin 50TK, prothioconazoles, simeconazoles, tebuconazole, tertraconazole, triadimenol, triticonazole, bitertanol, thiabendazole, fuberidazole, imazalil, efficient imazalil, prochloraz, fluorine bacterium azoles, cyazofamid, fenamidone, Evil imidazoles, pefurazoate, famoxadone, SYP-Z048, hymexazo, the spirit of Evil frost, Guardian, etridiazole, octhilinone, benthiozole, dodemorph, fenpropimorph, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium amine, boscalid amine, fluopicolide, pyridine bacterium amine, cyprodinil, fluorine mepanipyrim, ferimzone, mepanipyrim, phonetic mould amine, fenarimol, nuarimol, chinomethionate, dithianon, ethoxyquin, hydroxyquinoline, the third oxygen quinoline, benzene oxygen quinoline, the mould prestige of second, iprovalicarb, benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, iprobenfos, pyrazophos, tolclofosmethyl, miewensu, kasugamycin, polyoxin, Polyoxin, validamycin, jingganmycin, Streptomycin sulphate, metaxanin, furalaxyl, M 9834, ofurace, mebenil, derosal, F-1991, thiophanate_methyl, triazolone, bupirimate, dimethirimol, the phonetic phenol of second, Difolatan, Vancide 89, Phaltan, Vinclozoline, fluoromide, dimetachlone, m-tetrachlorophthalodinitrile, isoprothiolane, Kitazine, bismerthiazol, quintozene, zinc 1,2-propylene bisdithiocarbamate, fosetylaluminium, sulphur, Bordeaux mixture, copper sulfate, copper oxychloride, Red copper oxide, copper hydroxide, metrafenone, pencycuron, diclomezin, phthalide, pyroquilon, volution bacterium amine, tricyclazole, triforine, the pyridine of many fruits, the pungent salt of biguanides, iminoctadine, dicloran, benzene flusulfamide, toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, methyl iodide, metamsodium, enemy's line ester, dazomet, dichloroisopropyl ether, lythidathion, cadusafos, fensulfothion, thionazin, fenamiphos, ethoprophos, dichlofenthion, isazofos, fosthietan, oxamyl, aldicarb, carbofuran, sulfuryl fluoride, dichloropropylene, dichloro-isonicotinic acid, other known any any one or two kinds that can be used as in sterilant such as allyl isothiazole are used in combination for preventing and treating agricultural and forestry and gardening plant disease, a class anthranilic diamides derivative I of the present invention or the II total quality percentage composition in composition is 1%-90%, and the ratio of a class anthranilic diamides derivative I of the present invention or II and aforementioned sterilant is that mass percent 1%:99% is to 99%:1%, the prevention effect of composition is good, and these compositions have certain synergism and summation action, does not find to have the composition of antagonistic action, above-mentioned composition can be for the control of agricultural plants disease and gardening plant disease, controlling object comprises that more than 20 of the Achylas, Aphanomyces, pythium, phytophthora, Sclerospora, Plasmopara, Pseudoperonospora, Peronospora of Oomycete etc. belong to the diseases that produce, as other diseases of plurality of cereals crop, cash crop, gardening plant and the forestry plants such as seedling blight of rice, tomato root maize ear rot, the late blight of potato, black shank, millet Powdery Mildew, downy mildew of garpe, downy mildew of lettuce, cucumber downy mildew, cucumber anthracnose etc., the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, dispersible dense dose, missible oil, electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes dress agent, liquid/liquid mixes dress agent, cold mist agent, Gu Gu/mix filling agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent, these compositions comprise cereal for preventing and treating agricultural and forestry and the applicable plant of gardening plant disease: paddy, wheat, barley, oat, corn, millet, Chinese sorghum, tuber crops: sweet potato, potato, cassava, beans: soybean, broad bean, pea, mung bean, red bean and fiber: cotton, crudefiber crop, silkworm and mulberry, oil plant: peanut, rape, sesame, soybean, Sunflower Receptacle, sugar material: beet, sugarcane, beverage: tealeaves, coffee, cocoa, hobby: tobacco leaf, medicinal: ginseng, the bulb of fritillary, the torrid zone: rubber, coconut, oil palm, sisal hemp, food crop and fruit, flowers, oil plant, sugar material and cotton, fiber crops, tea, tobacco, Chinese medicinal materials cash crop and plant melon, really, tea, silkworm and mulberry, vegetables, contain various wild vegetable, bamboo shoots, flowers and ornamental plant, hops, medicinal material, pepper, seedling and other garden crops as tobacco: flue-cured tobacco, air-curing of tobacco leaves, suncured tabacco, vegetables, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, melon: watermelon, muskmelon, hami melon, pawpaw, beans: soybean, broad bean, pea-pods, potato, wheat, corn, paddy rice, peanut, fruit tree: apple, banana, citrus, peach, papaya, flowers: orchid, potted landscape, composition has improved the defence capability of plant in sterilization, makes plant produce the defence capability to pathogenic fungi, bacterium and virus infection.

10. the application in a class anthranilic diamides derivative I claimed in claim 1 or II and anti-plant virus agent combination control agricultural and forestry and gardening plant virus disease:

A class anthranilic diamides derivative I of the present invention or II and existing Antiphytoviral medicament diazosulfide, tiadinil, be abbreviated as TDL, isotianil, it is English general by name: isotianil, 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-formic acid, 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-sodium formiate, 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-ethyl formate, 3, 4-bis-chloroisothiazoles-5-formic acid, 3, 4-bis-chloroisothiazoles-5-sodium formiate, 3, 4-bis-chloroisothiazoles-5-ethyl formate, DL-beta-aminobutyric acid, virazole, antofine, Ningnanmycin, tisocromide, first thiophene lures amine or Whitfield's ointment, cytosintetidemycin, dichloro-isonicotinic acid, allyl isothiazole, well ridge azanol, in jingganmycin, any 1 or 2 compound combinations are used for preventing and treating agricultural and forestry and gardening plant virus disease, the disease of control agricultural and forestry and gardening plant virus disease is selected from tobacco mosaic virus disease, various melon virus diseases, various solanaceous vegetables virus diseases, beans virus disease, Cruciferae virus disease, grain and oil crop virus disease, any in cotton virus disease and various fruit tree virus disease, wherein endanger serious being selected from: tobacco virus, peppery pimento virus disease, tomato virus disease, Chinese cabbage virus disease, Virus Diseases of Rice comprises rice dwarf virus disease, yellow dwart, stripe virus disease, fern leaf of tomato viral disease, pepper mosaic virus disease viral disease and tobacco veinal necrosis virus are sick, maize dwarf mosaic, cauliflower mosaic virus, oranges and tangerines virus disease, cymbidium mosaic virus, any in cybidium ring spot virus, these compositions are selected from paddy for preventing and treating the plant of agricultural and forestry and gardening plant virus disease, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, the agriculturals such as potted landscape, gardening, economical, the plants such as forestry, the use of these compositions improves the immunizing power of crop self, when producing the control of insect especially infection insect, has induced plant to produce the defence capability to viral diseases of plants, also can produce the direct prevention effect of virus disease, therefore, these compositions can be for preparation and the purposes of Antiphytoviral medicament and inducing plant Antiphytoviral medicament, a class anthranilic diamides derivative I of the present invention or the II total quality percentage composition in composition is 1%-90%, and the ratio of a class anthranilic diamides derivative I of the present invention or II and aforementioned Antiphytoviral medicament is that mass percent 1%:99% is to 99%:1%, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, dispersible dense dose, missible oil, electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes dress agent, liquid/liquid mixes dress agent, cold mist agent, Gu Gu/mix filling agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent, between these compositions, all show and be added or synergism, when keeping insecticidal activity, its antiviral activity is all greater than the effect that any one compound is used separately, find no the composition of antagonistic action, the drug effect lasting period of composition is long.