CN103172613B - One class contains anthranilic diamides derivative of N-cyano group sulfone (sulphur) imines and its production and use - Google Patents

One class contains anthranilic diamides derivative of N-cyano group sulfone (sulphur) imines and its production and use Download PDF

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CN103172613B
CN103172613B CN201310000509.1A CN201310000509A CN103172613B CN 103172613 B CN103172613 B CN 103172613B CN 201310000509 A CN201310000509 A CN 201310000509A CN 103172613 B CN103172613 B CN 103172613B
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methyl
chloropyridine
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pyrazoles
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CN103172613A (en
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范志金
华学文
陈旭艳
毛武涛
陈晓燕
梁小文
刘细平
姬晓恬
李娟娟
宗广宁
李凤云
李岳东
房震
王曙华
周立峰
黄亮文
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JIANGXI TIANREN ECOLOGY CO Ltd
Nankai University
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JIANGXI TIANREN ECOLOGY CO Ltd
Nankai University
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Abstract

The invention provides a class and contain anthranilic diamides derivative of N-cyano group sulfone (sulphur) imines and its production and use, the present invention relates to containing pyrazole carboxamides bisamide derivatives, there is the chemical structure of general formula as shown in I.

Description

One class contains anthranilic diamides derivative of N-cyano group sulfone (sulphur) imines and its production and use
Technical field
Technical scheme of the present invention relates to pyrazole compound, is specially the anthranilic diamides derivative containing N-cyano group sulfone (sulphur) imines.
Background technology
Reported since a series of pyrazine diamide compound has certain insecticidal activity since doctor Tsuda found university in 1989 at Osaka, Japan, diamide compound just becomes the focus of Ge great agricultural chemicals company and R&D institution's research in the world.Until 1998, Japanese agricultural chemicals company has just found first bisamide insecticides---Flubendiamide (EP1006107).This insecticides, except according to there being excellent activity, with existing sterilant without cross resistance, and to beyond the advantages such as mammalian safe, also has unique mechanism of action.Its particular mechanism of this bisamide insecticides may be suppress the release of calcium ion and become ryanodine receptor activator.The mechanism of action of this uniqueness attracts global agricultural chemicals company to the research of ryanodine receptor activator insecticides very soon.2000, du pont company just found second ryanodine receptor activator insecticides---chlorantraniliprole (WO03015519), and successfully went on the market in 2007.Subsequently, further composition optimizes is done to chlorantraniliprole by du pont company, has found s-generation ryanodine receptor insecticides---the cyanogen insect amide (WO2004067528) of desinsection more wide spectrum.
Although bisamide insecticides shows outstanding superiority in active, some areas are due to frequent excessively dispenser, and insect has showed resistance in various degree, and up to the present this insecticides commercial kind number is very limited.In order to overcome current this situation, find the ryanodine receptor sterilant of more high biological activity and relevant agricultural chemicals, the adjacent formamide benzene Carbox amide that Zhejiang chemical research institute have studied fluorine-containing methoxyl group pyrazoles have more effectively, low toxicity, low cost, the advantage (CN101967139A) such as environmentally safe.Domestic Duo Jia research unit is all carrying out relevant innovative research work, does not also have activity to exceed the report of target molecule parent active at present.Recently, N-cyano group sulfone (sulphur) imine structure is introduced in the structure of benzamide by Syngenta Co., Ltd, find that the target compound of design and synthesis has good insecticidal activity (Christian Gnamm, Novel diamide insecticides:sulfoximines, sulfonimidamides and other new sulfonimidoylderivatives, Bioorganic & Medicinal Chemistry Letters, 2012,22:3800-3806).
Ryanodine receptor insecticides is due to the feature of molecule self, its migration in plant materials is subject to certain restrictions, in order to study the ryania compounds of high-efficiency low-toxicity further, other pesticide activity fragments are introduced in bisamide molecule by the principle that the present invention utilizes pesticide molecule to design, design and synthesis one class is containing the anthranilic diamides derivative of N-cyano group sulfone (sulphur) imines, and carried out the bioactive screening of system, to improving the water-soluble of target molecule, improve its in plant materials up and down and lateral migration, innovative research for novel pesticide provides eco-friendly ultra-high efficiency novel candidate compounds.
Summary of the invention
Technical problem to be solved by this invention is: the synthetic method providing the new anthranilic diamides derivative containing N-cyano group sulfone (sulphur) imines, this kind of compound modulates agricultural, the biological activity of gardening and health and forestry plant insect and the phytopathy original and measuring method thereof are provided, provide these compounds to apply in agriculture field, horticultural field, field of forestry and health field simultaneously.
The present invention solves this technical problem adopted technical scheme: have agriculture field, horticultural field, forestry and health field insecticidal activity, fungicidal activity, anti-phytoviral activity, inducing plant produce anti-disease activity, the chemical structure of general formula of the anthranilic diamides derivative of N-cyano group sulfone (sulphur) imines of insect growth regulator activity is shown in formula I
General formula I:
Wherein, X is selected from: halogen, CN, NO 2, NH 2, substituted alkyl, replacement unsaturated alkyl; Y is selected from: halogen, CN, NO 2, NH 2, substituted alkyl, replacement unsaturated alkyl; R 1be selected from: substituted alkyl, replacement unsaturated alkyl, methylthio group substituted alkyl, methylthio group replace unsaturated alkyl, cyano group, substituted sulphonyl, substituted-amino formyl radical; X is preferred: chlorine, bromine; Y is preferred: chlorine, bromine; R 1preferred: 2-methylmercaptoethyl, 2-((N-cyano group) methyl sulfilimine base) ethyl, 2-((N-cyano group) methyl sulfone imido grpup) ethyl, the 2-methylthio group tertiary butyl, 2-((N-cyano group) the methyl sulfilimine base) tertiary butyl, 2-((N-cyano group) methyl sulfone imido grpup) tertiary butyl; Specifically can be divided into following 3 kinds of structure types:
Wherein, X is selected from: halogen, CN, NO 2, NH 2, substituted alkyl, replacement unsaturated alkyl; Y is selected from: halogen, CN, NO 2, NH 2, substituted alkyl, replacement unsaturated alkyl; R 2be selected from: H, substituted alkyl, replacement unsaturated alkyl, substituted aryl; X is preferred: Cl, Br; Y is preferred: Cl, Br; R 2preferred: H, CH 3.
Anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC press the method synthesis shown in Scheme-1:
Wherein, X is selected from: halogen, CN, NO 2, NH 2, substituted alkyl, replacement unsaturated alkyl; Y is selected from: halogen, CN, NO 2, NH 2, substituted alkyl, replacement unsaturated alkyl; R 2be selected from: H, substituted alkyl, replacement unsaturated alkyl, substituted aryl; X is preferred: Cl, Br; Y is preferred: Cl, Br; R 2preferred: H, CH 3.
Scheme-1 is containing anthranilic diamides derivative I, IA, IB, IC synthetic route of N-cyano group sulfone (sulphur) imines
Specifically be divided into following steps:
A. the preparation of benzoxazine IV is replaced:
In 50 milliliters of round-bottomed flasks, add 15 milliliters of acetonitriles, 1.0 mmole 3-replace-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-formic acid II, 5 mmole Methanesulfonyl chlorides, be abbreviated as MsCl, 0.4 gram of i.e. 5 mmole pyridine, be abbreviated as Py, be cooled to-5 degrees Celsius, stir after 30 minutes and add 1.0 mmoles replacement anthranilic acids, stir after slowly rising to room temperature and spend the night, have yellow solid to replace benzoxazine IV to separate out, filter, washing, vacuum-drying, is directly used in next step reaction, described 3-replaces-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-formic acid II and is selected from the chloro-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-formic acid, the bromo-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-formic acid, described replacement benzoxazine IV is selected from 2-(the chloro-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-base) the chloro-4-oxo of-8-methyl-6--4H-benzo-[d] [1, 3]-oxazines, 2-(the chloro-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-base) the bromo-4-oxo of-8-methyl-6--4H-benzo-[d] [1, 3]-oxazines, 2-(the bromo-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-base) the chloro-4-oxo of-8-methyl-6--4H-benzo-[d] [1, 3]-oxazines, 2-(the bromo-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-base) the bromo-4-oxo of-8-methyl-6--4H-benzo-[d] 1, 3]-oxazines.
B.1-the preparation of (3-chloropyridine-2-base)-3-halo-1H-pyrazoles-5-formyl-2-methyl-4-halo-6-(2-(methylthio group alkyl) amido formacyl) aniline IA:
In 50 milliliters of round-bottomed flasks, add 0.5 mmole replace benzoxazine IV, 20 milliliters of tetrahydrofuran (THF)s, be abbreviated as the replacement methylmercaptan ethyl ammonia of THF, 5.0 mmoles, reaction mixture stirring at room temperature 7 hours; Concentrating under reduced pressure is except desolventizing, gained resistates obtains yellow or white solid 1-(3-chloropyridine-2-base)-3-halo-1H-pyrazoles-5-formyl-2-methyl-4-halo-6-(2-(methylthio group alkyl) amido formacyl) aniline IA through 200 ~ 300 order purification by silica gel column chromatography, eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, and volume ratio is 3: 1; By gained sterling calculated yield, yield 40-70%; The amount of synthetic compound expands by corresponding proportion or reduces; The volume scale of respective reaction container or reduce.Described 1-(3-chloropyridine-2-base)-3-halo-1H-pyrazoles-5-formyl-2-methyl-4-halo-6-(2-(methylthio group alkyl) amido formacyl) aniline IA is selected from 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-chloro-6-(2-(methylmercaptoethyl) amido formacyl) aniline, 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-chloro-6-(2-(the methylthio group tertiary butyl) amido formacyl) aniline, 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-bromo-6-(2-(methylmercaptoethyl) amido formacyl) aniline, 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-bromo-6-(2-(the methylthio group tertiary butyl) amido formacyl) aniline, 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-chloro-6-(2-(methylmercaptoethyl) amido formacyl) aniline, 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-chloro-6-(2-(the methylthio group tertiary butyl) amido formacyl) aniline, 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-bromo-6-(2-(methylmercaptoethyl) amido formacyl) aniline, 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-bromo-6-(2-(the methylthio group tertiary butyl) amido formacyl) aniline.
C.1-the preparation of (3-chloropyridine-2-base)-3-halo-1H-pyrazoles-5-formyl-2-methyl-4-halo-6-(2-((N-cyano methyl sulfilimine base) alkyl) amido formacyl) aniline IB:
In 50 milliliters of round-bottomed flasks, add 0.5 mmole 1-(3-chloropyridine-2-base)-3-halo-1H-pyrazoles-5-formyl-2-methyl-4-halo-6-(2-(methylthio group alkyl) amido formacyl) aniline IA, 15 milliliters of dry methylene dichloride, ice-water bath is cooled to 0 degree Celsius.Then 1.0 mmole cyanamides and 0.5 mmole acetic acid iodobenzene is added respectively; stirred overnight at room temperature after 3 hours is stirred at this temperature; 2nd day by direct for reaction solution removal of solvent under reduced pressure; resistates obtains faint yellow or white solid 1-(3-chloropyridine-2-base)-3-halo-1H-pyrazoles-5-formyl-2-methyl-4-halo-6-(2-((N-cyano methyl sulfilimine base) alkyl) amido formacyl) aniline IB through 200 ~ 300 order purification by silica gel column chromatography; eluent is ethyl acetate; by gained sterling calculated yield, yield 40-60%.The amount of synthetic compound expands by corresponding proportion or reduces; The volume scale of respective reaction container or reduce.Described 1-(3-chloropyridine-2-base)-3-halo-1H-pyrazoles-5-formyl-2-methyl-4-halo-6-(2-((N-cyano methyl sulfilimine base) alkyl) amido formacyl) aniline IB is selected from the chloro-6-of 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-(2-((N-cyano methyl sulfilimine base) ethyl) amido formacyl) aniline, the chloro-6-of 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-(2-((the N-cyano methyl sulfilimine base) tertiary butyl) amido formacyl) aniline, the bromo-6-of 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-(2-((N-cyano methyl sulfilimine base) ethyl) amido formacyl) aniline, the bromo-6-of 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-(2-((the N-cyano methyl sulfilimine base) tertiary butyl) amido formacyl) aniline, the chloro-6-of 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-(2-((N-cyano methyl sulfilimine base) ethyl) amido formacyl) aniline, the chloro-6-of 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-(2-((the N-cyano methyl sulfilimine base) tertiary butyl) amido formacyl) aniline, the bromo-6-of 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-(2-((N-cyano methyl sulfilimine base) ethyl) amido formacyl) aniline, the bromo-6-of 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-(2-((the N-cyano methyl sulfilimine base) tertiary butyl) amido formacyl) aniline.
D.1-the preparation of (3-chloropyridine-2-base)-3-halo-1H-pyrazoles-5-formyl-2-methyl-4-halo-6-(2-((N-cyano methyl sulfoximide base) alkyl) amido formacyl) aniline IC:
1.0 mmole metachloroperbenzoic acids are added in 50 milliliters of three mouthfuls of round-bottomed flasks, write a Chinese character in simplified form m-CPBA, 8 milliliters of ethanol, ice-water bath is cooled to 0 degree Celsius and stirs 10 minutes, then adds disposable for 7 ml water solution of 1.5 mmole Anhydrous potassium carbonates, has a large amount of white solid to separate out.8 milliliters of ethanolic solns of 0.5 mmole 1-(3-chloropyridine-2-base)-3-halo-1H-pyrazoles-5-formyl-2-methyl-4-halo-6-(2-((N-cyano methyl sulfilimine base) alkyl) amido formacyl) aniline IB dropwise added after 20 minutes by 0 degree Celsius of stirring, stirred and quenched in water by reaction solution after 1 hour; Then 50 milliliters of extraction into ethyl acetate three times are used, organic layer saturated common salt water washing 2 times, anhydrous magnesium sulfate drying, removal of solvent under reduced pressure, resistates obtains faint yellow or white solid 1-(3-chloropyridine-2-base)-3-halo-1H-pyrazoles-5-formyl-2-methyl-4-halo-6-(2-((N-cyano methyl sulfoximide base) alkyl) amido formacyl) aniline IC through 200 ~ 300 order purification by silica gel column chromatography, eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, according to the difference of product, volume ratio is between 1: 1 ~ 1: 3; By gained sterling calculated yield, yield 50-70%.The amount of synthetic compound expands by corresponding proportion or reduces; The volume scale of respective reaction container or reduce.Described 1-(3-chloropyridine-2-base)-3-halo-1H-pyrazoles-5-formyl-2-methyl-4-halo-6-(2-((N-cyano methyl sulfoximide base) alkyl) amido formacyl) aniline IC is selected from the chloro-6-of 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-(2-((N-cyano methyl sulfoximide base) ethyl) amido formacyl) aniline, the chloro-6-of 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-(2-((the N-cyano methyl sulfoximide base) tertiary butyl) amido formacyl) aniline, the bromo-6-of 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-(2-((N-cyano methyl sulfoximide base) ethyl) amido formacyl) aniline, the bromo-6-of 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-(2-((the N-cyano methyl sulfoximide base) tertiary butyl) amido formacyl) aniline, the chloro-6-of 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-(2-((N-cyano methyl sulfoximide base) ethyl) amido formacyl) aniline, the chloro-6-of 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-(2-((the N-cyano methyl sulfoximide base) tertiary butyl) amido formacyl) aniline, the bromo-6-of 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-(2-((N-cyano methyl sulfoximide base) ethyl) amido formacyl) aniline, the bromo-6-of 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-(2-((the N-cyano methyl sulfoximide base) tertiary butyl) amido formacyl) aniline.
When X=halogen, substituted pyrazolecarboxylic-5-formic acid II presses the method synthesis shown in Scheme-2:
The synthetic route of Scheme-23-halo-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-formic acid II
E.2-the preparation of diazanyl substituted pyridines VI:
By 50 mmoles 2, hydrazine hydrate, 50 milliliters of ethanol of 3-chloropyridine V, 100 mmoles join in 100 milliliters of three mouthfuls of round-bottomed flasks, 80 degrees Celsius of lower reflux 20 hours, remove solvent under reduced pressure, gained solid ethyl alcohol recrystallization obtains intermediate 2-diazanyl substituted pyridines VI, by gained sterling calculated yield, yield 91%.The amount of synthesis 2-diazanyl substituted pyridines VI expands by corresponding proportion or reduces; The volume scale of respective reaction container or reduce.
F.2-the preparation of (3-chloropyridine-2-base)-5-oxopyrazoline alkane-3-ethyl formate VII:
50 milliliters of ethanol are added in 100 milliliters of reaction flasks, slowly add the sodium Metal 99.5 of 55 mmoles, back flow reaction makes alcohol sodium solution. add the ethyl maleate of 50 mmole 2-diazanyl substituted pyridines VI, 60 mmoles at reflux, continue backflow 30 minutes, then lower the temperature, filter, the cold washing with alcohol of gained solid obtains yellow solid 2-(3-chloropyridine-2-base)-5-oxopyrazoline-3-ethyl formate VII, by gained sterling calculated yield, yield 70%.The amount of synthesis 2-(3-chloropyridine-2-base)-5-oxopyrazoline-3-ethyl formate VII expands by corresponding proportion or reduces; The volume scale of respective reaction container or reduce.
G.3-the synthesis of halo-1-(3-chloropyridine-2-base)-4,5-dihydro-1 h-pyrazole-5-ethyl formate VIII
5.4 grams of i.e. 20 mmole 2-(3-chloropyridine-2-base)-5-oxopyrazoline-3-ethyl formate VII, 50 milliliters of acetonitriles, 30 mmole three oxyhalogen phosphorus are added, stirring and refluxing 3 hours in 100 milliliters of single necked round bottom flask; The most of solvent of concentrated removing, resistates is dissolved in methylene dichloride, use saturated sodium bicarbonate aqueous solution and saturated common salt water washing successively, anhydrous sodium sulfate drying concentrates, thick product obtains yellow oil VIII through 200 ~ 300 order purification by silica gel column chromatography, eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, and volume ratio is 3: 1; By gained sterling calculated yield, yield 80-90%; The amount of synthesis 3-halo-1-(3-chloropyridine-2-base)-4,5-dihydro-1 h-pyrazole-5-ethyl formate VIII expands by corresponding proportion or reduces; The volume scale of respective reaction container or reduce; Described three oxyhalogen phosphorus are selected from phosphorus oxychloride, tribromo oxygen phosphorus; Described 3-halo-1-(3-chloropyridine-2-base)-4, the VIII of 5-dihydro-1 h-pyrazole-5-ethyl formate is selected from the chloro-1-of 3-(3-chloropyridine-2-base)-4,5-dihydro-1 h-pyrazole-5-ethyl formate, the bromo-1-of 3-(3-chloropyridine-2-base)-4,5-dihydro-1 h-pyrazole-5-ethyl formates.
H.3-the synthesis of halo-1-(3-chloropyridine-2-base)-1H-pyrazole-5-ethyl formate IX
3-halo-the 1-(3-chloropyridine-2-base)-4 of 30 mmoles of above-mentioned preparation is added in 100 milliliters of reaction flasks, 5-dihydro-1 h-pyrazole-5-ethyl formate VIII, 50 milliliters of acetonitriles, slowly add 3 milliliters of vitriol oils, then the Potassium Persulphate of 40 mmoles is added, reflux 3 hours, then lower the temperature, pour in frozen water and filter to obtain yellow solid 3-halo-1-(3-chloropyridine-2-base)-1H-pyrazole-5-ethyl formate IX, by gained sterling calculated yield, yield 65-75%.The amount of synthetic compound expands by corresponding proportion or reduces; The volume scale of respective reaction container or reduce; Described 3-halo-1-(3-chloropyridine-2-base)-1H-pyrazole-5-ethyl formate IX is selected from the chloro-1-of 3-(3-chloropyridine-2-base)-1H-pyrazole-5-ethyl formate, the bromo-1-of 3-(3-chloropyridine-2-base)-1H-pyrazole-5-ethyl formate.
I.3-the synthesis of halo-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-formic acid II
1.0 grams of i.e. 3.0 mmole 3-halo-1-(3-chloropyridine-2-base)-1H-pyrazole-5-ethyl formate, 10 ml methanol, 0.2 gram of i.e. 5.0 mmole sodium hydroxide are added successively, stirring at room temperature 8 hours in 50 milliliters of single necked round bottom flask.After TLC monitoring reaction terminates, the most of solvent of concentrated removing, adds 20 milliliters of frozen water, and aqueous solution ethyl acetate is washed once, is acidified to pH=4 with 2 mol/L dilute hydrochloric acid, and adularescent solid generates, filtration, and filter cake is washed, and vacuum-drying, obtains faint yellow solid II.The amount of synthesis 3-halo-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-formic acid II expands by corresponding proportion or reduces; The volume scale of respective reaction container or reduce; Described 3-halo-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-formic acid II is selected from the chloro-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-formic acid, the bromo-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-formic acid.
Replace anthranilic acid III and press the method synthesis shown in Scheme-3:
y is selected from: chlorine, bromine
Scheme-3 replaces o-amino benzoyl III synthetic method
Concrete operations are:
J. the preparation of anthranilic acid III is replaced:
20 mmole 3-methyl-2-amino phenylformic acid X, 50 milliliters of DMF, 30 mmole N-chlorosuccinimides (or N-bromosuccinimide) are added in 100 milliliters of round-bottomed flasks, return stirring is after 3 hours, reaction solution is poured in frozen water, dilute hydrochloric acid is acidified to pH=6, filter, gained precipitation obtains gray solid by a small amount of washing with alcohol and replaces anthranilic acid III, and by gained sterling calculated yield, yield is greater than 83%; The amount that synthesis replaces anthranilic acid III expands by corresponding proportion or reduces; The volume scale of respective reaction container or reduce.Described replacement anthranilic acid III is selected from 2-amido-3-methyl-5-chloro phenylformic acid, 2-amido-3-methyl-5-bromo-benzoic acid.
K. the anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC are to the mensuration of aphid cytotoxicity:
Anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC insecticidal activity screening method to aphid larva are as follows: adopt pickling process, black bean aphid (Aphis laburni Kaltenbach) (ALK), the normal population of indoor feeding; Take test compound 2.5 milligrams in beaker, drip 1 DMF (DMF), add 5 milliliters of acetone vibrations and dissolve sample, then add the solution to be measured having the water of tween 80 to be mixed with 200 mcg/ml; By cutting from basin for examination bean plant with at least 60 black bean aphids, flooded for 5 seconds in each liquid to be measured, take out and get rid of unnecessary liquid gently, be inserted in by moisturizing on water saturated sponge, with on lens cover after liquid is dry, the opening of lens upper end is with gauze sealing in case aphid escapes, and raise placement and check aphid death state after 24 hours, standard is: with try worm can creep maybe can stand or six Tiao Tuineng strenuous exercises be worm alive; Take clear water as contrast, Provado is positive control, calculation correction mortality ratio;
L. the anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC are to the mensuration of mythimna separata insecticidal activity:
Anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC adopt leaf dipping method to the screening of mythimna separata insecticidal activity: on analytical balance, take 2 milligrams of medicine samples in 10 ml penicillin vials, add 10 milliliters of acetone, become the mother liquor of 200 mcg/ml, cover plug vibration to dissolve, then liquid acetone diluted is become the working fluid of 5 mcg/ml, with straight peen ophthalmology tweezers soaking maize blade, 2 ~ 3 seconds time, get rid of remaining liquid.Each 1, totally 8, each sample; Be successively placed in treatment paper by sample flag sequence, the culture dish of the markd 10cm of tool is put into after liquid is done, access at the beginning of 10 3 ages with elbow ophthalmology tweezers and incubate armyworm larvae, test process is placed in constant temperature standard insectary and cultivates check result after 24 hours or 48 hours, larva body is touched with little writing brush or tweezers, completely motionless for death standard with larva; Taking cyanogen insect amide as positive control, is blank by the leaf of Semen Maydis of acetone soln dipping.Carry out the determination of activity of compound 1.0 mcg/ml and 0.1 mcg/ml concentration simultaneously.
M. the anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC are to the mensuration of small cabbage moth insecticidal activity:
Anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC adopt blade medicine embrane method to the screening of small cabbage moth insecticidal activity: sample to be tested is mixed with the solution of 200 mcg/ml, get former medicine sample and first use a small amount of acetone solution, then with 0.5 ‰ Triton-100 aqueous solution dilutions, the 0.5 ‰ Triton-100 aqueous solution are contrast, each concentration repeats for 3 times, each re-treatment 10 examination worm; Get fresh free of contamination cabbage leaves, soaked for 10 seconds in liquid, after (about 2 hours) are dried in indoor, put into the culture dish of diameter 9 centimetres, access basically identical small cabbage moth 2 instar larvae of size respectively, tighten with bungee and be placed in small cabbage moth constant temperature insectary, check result after 96 hours or 120 hours, touch polypide with little writing brush or tweezers, can not coordinated movement as death; Take cyanogen insect amide as positive control.Carry out the determination of activity of compound 5.0 mcg/ml and 1.0 mcg/ml concentration simultaneously.
N. the anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC are to the mensuration of pathogenic fungi fungicidal activity:
Anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC 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 the medicament being diluted to 500 mcg/ml containing a certain amount of polysorbas20 emulsifier aqueous solution, reagent agent is aseptically respectively drawn in 1 milliliter of injection culture dish, add 9 milliliters of substratum more respectively, 50 mcg/ml pastilles are made dull and stereotyped after shaking up, blank is done with the flat board adding 1 milliliter of aqua sterilisa, bacterium dish is cut along mycelia outer rim with the punch tool of diameter 4 millimeters, move on pastille flat board, put in equilateral triangle, often process repetition 3 times, culture dish is placed in 24 ± 1 degrees Celsius of constant incubators and cultivates, treat that contrast colony diameter expands to 2-3 centimetre of " Invest, Then Investigate " and respectively processes bacterium dish expansion diameter, average, compare with blank and calculate relative bacteriostasis rate, the kind of the majority of plant pathogenic bacteria of the actual generation in multiple representative field in China's agriculture production is comprised 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).
The invention has the beneficial effects as follows: the present invention has carried out the optimization of guide structure to containing the anthranilic diamides derivative I of N-cyano group sulfone (sulphur) imines, IA, IB, IC, and desinsection, antibacterial and inducing anti-disease activity, the mensuration of anti-phytoviral activity and research used in combination have been carried out to the new compound of synthesis, this compounds can be used for agriculture field, field of forestry, the disease of horticultural field, insect pest and virus disease control.
The present invention will be that embodiment more specifically describes containing the anthranilic diamides derivative I of N-cyano group sulfone (sulphur) imines, the synthesis of IA, IB, IC and biological activity and application thereof by specific preparation and biological activity determination and with the formulation that commercially available agricultural chemical combinationally uses complete processing and selection, but described embodiment is unrestricted the present invention for specific description the present invention only, especially its biological activity and complete processing only illustrate, and unrestricted this patent, embodiment is as follows:
Embodiment 1
The synthesis of 3-methyl-5-halo-2-benzaminic acid III:
3.0 grams of i.e. 20 mmole 3-methyl-2-amino phenylformic acid X, 30 milliliters of DMF, 6.7 grams of i.e. 30 mmole NCS (or 30 mmole NBS) are added in 100 milliliters of round-bottomed flasks, return stirring is after 3 hours, reaction solution is poured in frozen water, dilute hydrochloric acid is acidified to pH=6, filter, a small amount of washing with alcohol of gained solid obtains 2-amino-3-methyl-5-halo-phenylformic acid III, gray solid, more than 4.6 grams, yield is greater than 83%.Y is selected from: chlorine, bromine, and described 2-amino-3-methyl-5-halo-phenylformic acid III is selected from-2-amino-3-methyl-5-chloro phenylformic acid, the bromo-phenylformic acid of 2-amino-3-methyl-5-; Wherein, 2-amino-3-methyl-5-chloro phenylformic acid 1h NMR (400MHz, DMSO-d 6): δ: 7.96 (s, 1H), 7.56 (d, 1H), 7.23 (d, 1H), 2.11 (s, 3H); 2-amino-3-methyl-5-bromo-benzoic acid 1h NMR (300MHz, DMSO-d 6): δ: 7.70 (s, 1H), 7.31 (s, 1H), 2.10 (s, 3H).
Embodiment 2
The preparation of 3-halo-1-(3-chloropyridine-2-base)-N-(4-halo-2-methyl-6-((2-(methylthio group) alkyl) formamyl) phenyl)-1H-pyrazoles-5-methane amide
(1) synthesis of 3-chloride-2-hydrazinopyridine VI:
By 50 mmoles 2, hydrazine hydrate, 50 milliliters of ethanol of 3-pyridine V, 100 mmoles join in 100 milliliters of three mouthfuls of round-bottomed flasks, 80 degrees Celsius of lower reflux 20 hours, remove solvent under reduced pressure, gained solid ethyl alcohol recrystallization obtains needle-like crystal 3-chloride-2-hydrazinopyridine VI 6.5 grams, yield 90%.
(2) synthesis of 5-oxo-2-(3-chloropyridine-2-base) pyrazoline-3-ethyl formate VII:
In 250 milliliters of single necked round bottom flask, add 100 milliliters of absolute ethanol, add 1.77 grams of i.e. 55 mmole sodium Metal 99.5s, temperature slightly rises, and stirs and forms transparent and homogeneous solution after 10 minutes in batches; Add 7.1 grams of i.e. 50 mmole 3-chloride-2-hydrazinopyridine VI formation yellow suspension, be heated to backflow, drip 11.2 grams of i.e. 65 mmole ethyl maleates under reflux state, drip complete, continue backflow 1 hour; After TLC monitoring reaction terminates, be cooled to 40 degrees Celsius, add 3.5 milliliters of glacial acetic acids; Reaction mixture is concentrated near dry, and thick product ethyl alcohol recrystallization obtains 7.9g yellow solid VII, yield 59%; 1h NMR (300MHz, CDCl 3) δ 8.26 (dd, 1H), 7.89 (dd, 1H), 7.19 (dd, 1H), 4.80 (dd, 1H), 4.20 (q, 2H), 2.90 (dd, 1H,), 2.35 (dd, 1H), 1.24 (t, 3H, CH 3).
(3) synthesis of 3-halo-1-(3-chloropyridine-2-base)-4,5-dihydro-1 h-pyrazole-5-ethyl formate VIII
In 100 milliliters of single necked round bottom flask, add 5.4 grams of i.e. 20 mmole 5-oxo-2-(3-chloropyridine-2-base) pyrazoline-3-ethyl formate VII, 50 milliliters of acetonitriles, 30 mmole three halo oxygen phosphorus, be abbreviated as P (O) X 3, X is Cl, Br, stirring and refluxing 3 hours; The most of solvent of concentrated removing, resistates is dissolved in methylene dichloride, use saturated sodium bicarbonate aqueous solution and saturated common salt water washing successively, anhydrous sodium sulfate drying, concentrated, thick product obtains yellow oil 3-halo-1-(3-chloropyridine-2-base)-4,5-dihydro-1 h-pyrazole-5-ethyl formate VIII through 200 ~ 300 order purification by silica gel column chromatography, eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, and volume ratio is 3: 1; By gained sterling calculated yield, yield 80-90%.Three described halo oxygen phosphorus are selected from phosphorus oxychloride, tribromo oxygen phosphorus; Described 3-halo-1-(3-chloropyridine-2-base)-4,5-dihydro-1 h-pyrazole-5-ethyl formate VIII is selected from the chloro-1-of 3-(3-chloropyridine-2-base)-4,5-dihydro-1 h-pyrazole-5-ethyl formate, the bromo-1-of 3-(3-chloropyridine-2-base)-4,5-dihydro-1 h-pyrazole-5-ethyl formates; The wherein chloro-1-of 3-(3-chloropyridine-2-base)-4,5-dihydro-1 h-pyrazole-5-ethyl formates 1hNMR (400MHz, CDCl 3) δ: 8.08 (dd, 1H), 7.65 (dd, 1H), 6.86 (dd, 1H), 5.30 (dd, 1H), 4.18 (q, 2H), 3.42-3.15 (m, 2H), 1.20 (t, 3H); The bromo-1-of 3-(3-chloropyridine-2-base)-4,5-dihydro-1 h-pyrazole-5-ethyl formates 1hNMR (300MHz, CDCl 3) δ: 8.07 (dd, 1H), 7.66 (dd, 1H), 6.85 (dd, 1H), 5.30 (dd, 1H), 4.18 (q, 2H), 3.43-3.14 (m, 2H), 1.20 (t, 3H).
(4) synthesis of 3-halo-1-(3-chloropyridine-2-base)-1H-pyrazole-5-ethyl formate IX
10 mmole 3-halo-1-(3-chloropyridine-2-base)-4 are added in 100 milliliters of single necked round bottom flask, 5-dihydro-1 h-pyrazole-5-ethyl formate VIII, 30 milliliters of acetonitriles, 1.1 milliliter of 98% vitriol oil, stir 5 minutes, add 3.3 grams of i.e. 15 mmole Potassium Persulfates, stirring and refluxing 3 hours; Reaction mixture is poured in 300 milliliters of frozen water after being cooled to room temperature, filter, gained solid ethyl alcohol recrystallization obtains yellow crystals 3-halo-1-(3-chloropyridine-2-base)-1H-pyrazole-5-ethyl formate IX, by gained sterling calculated yield, and yield 64-70%; Described 3-halo-1-(3-chloropyridine-2-base)-1H-pyrazole-5-ethyl formate IX is selected from the chloro-1-of 3-(3-chloropyridine-2-base)-1H-pyrazole-5-ethyl formate, the bromo-1-of 3-(3-chloropyridine-2-base)-1H-pyrazole-5-ethyl formate; The wherein chloro-1-of 3-(3-chloropyridine-2-base)-1H-pyrazole-5-ethyl formate 1h NMR (400MHz CDCl 3) δ: 8.51 (dd, 1H), 7.91 (dd, 1H), 7.45 (dd, 1H), 6.95 (s, 1H), 4.23 (q, 2H), 1.22 (t, 3H); The bromo-1-of 3-(3-chloropyridine-2-base)-1H-pyrazole-5-ethyl formate 1h NMR (300MHz CDCl 3) δ: 8.50 (dd, 1H), 7.89 (dd, 1H), 7.44 (dd, 1H), 6.95 (s, 1H), 4.23 (q, 2H), 1.20 (t, 3H).
(5) synthesis of 3-halo-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-formic acid II
3.0 mmole 3-halo-1-(3-chloropyridine-2-base)-1H-pyrazole-5-ethyl formate IX is added successively in 50 milliliters of single necked round bottom flask, 10 ml methanol, 0.2 gram is 5.0 mmole sodium hydroxide, stirring at room temperature 8 hours, after TLC monitoring reaction terminates, the most of solvent of concentrated removing, add 20 milliliters of frozen water, aqueous solution ethyl acetate is washed once, 2 mol/L dilute hydrochloric acid are acidified to pH=4, adularescent solid generates, filter, filter cake is washed, vacuum-drying, obtain faint yellow solid 3-halo-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-formic acid II 0.63g, yield 70%, described 3-halo-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-formic acid II is selected from 3-chloro-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-formic acid, 3-bromo-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-formic acid, wherein 3-chloro-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-formic acid 1h NMR (400MHzDMSO-d6) δ: 14.32 (s, br, 1H), 8.56 (dd, 1H), 8.26 (dd, 1H), 7.69 (dd, 1H), 7.20 (s, 1H), 3-bromo-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-formic acid 1h NMR (400MHz DMSO-d6) δ: 13.94 (s, br, 1H), 8.54 (dd, 1H), 8.24 (dd, 1H), 7.66 (dd, 1H), 7.24 (s, 1H).
(6) synthesis of 6-halo-2-(3-halo-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-base)-8-methyl-4H-3,1-benzoxazine-4-ketone IV
10 milliliters of acetonitriles are added in 50 milliliters of round-bottomed flasks, 1.0 mmole 3-halo-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-formic acid II, 0.57 gram is 5 mmole Methanesulfonyl chlorides, 0.4 gram is 5 mmole pyridines, be cooled to-5 degrees Celsius, stir after 30 minutes and add 01.0 mmole 2-amino-3-methyl-5-halogenated benzoic acid III, stir after slowly rising to room temperature and spend the night, there is yellow solid 6-halo-2-(3-halo-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-base)-8-methyl-4H-3, 1-benzoxazine-4-ketone IV separates out, filter, washing, next step reaction is directly used in after vacuum-drying, described 3-methyl-5-halo-2-benzaminic acid II is selected from 3-methyl-5-chloro-2-benzaminic acid, the bromo-2-benzaminic acid of 3-methyl-5-, described 2-amino-3-methyl-5-halo-phenylformic acid III is selected from-2-amino-3-methyl-5-chloro phenylformic acid, the bromo-phenylformic acid of 2-amino-3-methyl-5-, described 6-halo-2-(3-halo-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-base)-8-methyl-4H-3, 1-benzoxazine-4-ketone IV is selected from the chloro-2-of 6-(the chloro-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-base)-8-methyl-4H-3, 1-benzoxazine-4-ketone, the chloro-2-of 6-(the bromo-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-base)-8-methyl-4H-3, 1-benzoxazine-4-ketone, the bromo-2-of 6-(the bromo-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-base)-8-methyl-4H-3, 1-benzoxazine-4-ketone, the bromo-2-of 6-(the chloro-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-base)-8-methyl-4H-3, 1-benzoxazine-4-ketone.
(7) preparation of 1-(3-chloropyridine-2-base)-3-halo-1H-pyrazoles-5-formyl-2-methyl-4-halo-6-(2-(methylthio group alkyl) amido formacyl) aniline IA
0.5 mmole 6-halo-2-(3-halo-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-base)-8-methyl-4H-3 is added successively in 50 milliliters of three mouthfuls of round-bottomed flasks, 1-benzoxazine-4-ketone IV, 10 milliliters of acetonitriles, drip 0.9 gram of i.e. 10.0 mmole methylthio group ethamine or 2-methylthio group TERTIARY BUTYL AMINE, drip complete stirring at room temperature 4 hours; After TLC monitoring reaction terminates, rotary evaporation is except desolventizing, add saturated sodium bicarbonate aqueous solution and stir 10 minutes, 20 milliliters of extraction into ethyl acetate three times, merge organic phase and use saturated common salt water washing, anhydrous sodium sulfate drying, concentrate to obtain resistates, obtain white solid IA through 200 ~ 300 order purification by silica gel column chromatography, eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, and volume ratio is 2: 1; By gained sterling calculated yield; The concrete physical parameter of IA is in table 1.Described 1-(3-chloropyridine-2-base)-3-halo-1H-pyrazoles-5-formyl-2-methyl-4-halo-6-(2-(methylthio group alkyl) amido formacyl) aniline IA is selected from 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-chloro-6-(2-(methylmercaptoethyl) amido formacyl) aniline, 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-chloro-6-(2-(the methylthio group tertiary butyl) amido formacyl) aniline, 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-bromo-6-(2-(methylmercaptoethyl) amido formacyl) aniline, 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-bromo-6-(2-(the methylthio group tertiary butyl) amido formacyl) aniline, 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-chloro-6-(2-(methylmercaptoethyl) amido formacyl) aniline, 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-chloro-6-(2-(the methylthio group tertiary butyl) amido formacyl) aniline, 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-bromo-6-(2-(methylmercaptoethyl) amido formacyl) aniline, 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-bromo-6-(2-(the methylthio group tertiary butyl) amido formacyl) aniline.
Embodiment 3
The synthesis of 1-(3-chloropyridine-2-base)-3-halo-1H-pyrazoles-5-formyl-2-methyl-4-halo-6-(2-((N-cyano methyl sulfilimine base) alkyl) amido formacyl) aniline IB
0.53 gram of i.e. 1.0 mmole 3-halo-1-(3-chloropyridine-2-base)-N-(4-halo-2-methyl-6-(2-(methylthio group alkyl) formamyl) phenyl)-1H-pyrazoles-5-methane amide IA is added in 50 milliliters of three mouthfuls of round-bottomed flasks; add 30 milliliters of dry tetrahydrofuran (THF)s to stir, ice-water bath is cooled to 0 degree Celsius.Then 0.16 gram of i.e. 4 mmole cyanamides and 0.33 gram i.e. 1.0 mmole acetic acid iodobenzene is added respectively, stirred overnight at room temperature after 3 hours is stirred at this temperature, 2nd day by direct for reaction solution removal of solvent under reduced pressure, resistates obtains white solid IB through 200 ~ 300 order purification by silica gel column chromatography, eluent is ethyl acetate, and the physical and chemical parameter of IB is in table 1.Described 1-(3-chloropyridine-2-base)-3-halo-1H-pyrazoles-5-formyl-2-methyl-4-halo-6-(2-((N-cyano methyl sulfilimine base) alkyl) amido formacyl) aniline IB is selected from the chloro-6-of 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-(2-((N-cyano methyl sulfilimine base) ethyl) amido formacyl) aniline, the chloro-6-of 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-(2-((the N-cyano methyl sulfilimine base) tertiary butyl) amido formacyl) aniline, the bromo-6-of 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-(2-((N-cyano methyl sulfilimine base) ethyl) amido formacyl) aniline, the bromo-6-of 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-(2-((the N-cyano methyl sulfilimine base) tertiary butyl) amido formacyl) aniline, the chloro-6-of 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-(2-((N-cyano methyl sulfilimine base) ethyl) amido formacyl) aniline, the chloro-6-of 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-(2-((the N-cyano methyl sulfilimine base) tertiary butyl) amido formacyl) aniline, the bromo-6-of 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-(2-((N-cyano methyl sulfilimine base) ethyl) amido formacyl) aniline, the bromo-6-of 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-(2-((the N-cyano methyl sulfilimine base) tertiary butyl) amido formacyl) aniline.
Embodiment 4
The synthesis of 1-(3-chloropyridine-2-base)-3-halo-1H-pyrazoles-5-formyl-2-methyl-4-halo-6-(2-((N-cyano methyl sulfoximide base) alkyl) amido formacyl) aniline IC
0.17 gram of i.e. 1.0 mmole metachloroperbenzoic acids, 8 milliliters of DMF are added in 50 milliliters of three mouthfuls of round-bottomed flasks, ice-water bath is cooled to 0 degree Celsius and stirs 10 minutes, then add disposable for 7 ml water solution of 0.27 gram of i.e. 2.9 mmole Anhydrous potassium carbonate, have a large amount of white solid to separate out; 0 degree Celsius is stirred after 20 minutes and is added by 8 milliliters of DMF dropwise of 0.28 gram of i.e. 0.5 mmole 1-(3-chloropyridine-2-base)-3-halo-1H-pyrazoles-5-formyl-2-methyl-4-halo-6-(2-((N-cyano methyl sulfilimine base) alkyl) amido formacyl) aniline IB, stirs and quenches in water by reaction solution after 1 hour; Then 50 milliliters of extraction into ethyl acetate three times are used, organic layer saturated common salt water washing 2 times, anhydrous magnesium sulfate drying, removal of solvent under reduced pressure, resistates obtains white solid IC through 200 ~ 300 order purification by silica gel column chromatography, and eluent is ethyl acetate, and the physical and chemical parameter of IC and structural parameter are in table 1.Described 1-(3-chloropyridine-2-base)-3-halo-1H-pyrazoles-5-formyl-2-methyl-4-halo-6-(2-((N-cyano methyl sulfoximide base) alkyl) amido formacyl) aniline IC is selected from the chloro-6-of 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-(2-((N-cyano methyl sulfoximide base) ethyl) amido formacyl) aniline, the chloro-6-of 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-(2-((the N-cyano methyl sulfoximide base) tertiary butyl) amido formacyl) aniline, the bromo-6-of 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-(2-((N-cyano methyl sulfoximide base) ethyl) amido formacyl) aniline, the bromo-6-of 1-(3-chloropyridine-2-base)-3-chloro-1H-pyrazoles-5-formyl-2-methyl-4-(2-(the N-cyano methyl sulfoximide base) tertiary butyl) amido formacyl) aniline, the chloro-6-of 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-(2-((N-cyano methyl sulfoximide base) ethyl) amido formacyl) aniline, the chloro-6-of 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-(2-((the N-cyano methyl sulfoximide base) tertiary butyl) amido formacyl) aniline, the bromo-6-of 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-(2-((N-cyano methyl sulfoximide base) ethyl) amido formacyl) aniline, the bromo-6-of 1-(3-chloropyridine-2-base)-3-bromo-1H-pyrazoles-5-formyl-2-methyl-4-(2-((the N-cyano methyl sulfoximide base) tertiary butyl) amido formacyl) aniline.
Embodiment 5
Of the present invention containing the anthranilic diamides derivative I of N-cyano group sulfone (sulphur) imines, the insecticidal activity of IA, IB, IC
Anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, the insecticidal activity assay of IC to mythimna separata the results are shown in Table 2, data show, when 5 mcg/ml, Hxw002-45 of the present invention, Hxw003-5, Hxw003-8, Hxw003-9, Hxw003-18, Hxw003-21, Hxw003-24, Mt007-36-1, Mt007-41-1, Hxw003-20, Hxw003-23, Hxw003-26, Hxw003-22, Hxw003-27, Lfy001-8-1, Mt007-46-1, Mt007-47-1, Zgn001-14-1, Mt007-44-1, Mt007-45-1 all shows excellent mythimna separate, in administration after 48 hours, mortality ratio all reaches 100%, suitable with the activity of positive control medicament cyanogen insect amide.Hxw003-10, Hxw003-15, Mt007-37-1, Hxw003-25 insecticidal activity to mythimna separata is respectively 40%, 70%, 70%, 60%.These 20 kinds of compounds of other medicaments are significantly higher than for activity, with 1.0 mcg/ml and 0.1 mcg/ml, multiple sieve is carried out to mythimna separata respectively, result shows, under 1.0 mcg/ml concentration, Mt007-46-1 of the present invention shows excellent mythimna separate, in administration after 48 hours, mortality ratio reaches 100%, and Hxw003-21, Hxw003-20, Lfy001-8-1, Zgn001-14-1 also show good mythimna separate, in administration after 48 hours, mortality ratio is all more than 40%; Hxw002-45, Hxw003-9, Hxw003-27 insecticidal activity to mythimna separata also reaches 20%.And its insecticidal activity of compound Mt007-50-1 that CN replaces only has 80%.
Anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC insecticidal activity assay to small cabbage moth the results are shown in Table 3, during 200 mcg/ml, all sulfide derivatives, sulfinilimine derivatives and the activity of sulfoximide derivative to small cabbage moth all reach 100%, suitable with the insecticidal activity of cyanogen insect amide, the introducing of thioether, sulfilimine, sulfoximide does not affect insecticidal activity; And the activity of the derivative Mt007-50-1 that CN replaces only has 75%, therefore, the introducing of halogen is conducive to active raising and maintenance.During 10 mcg/ml, the activity of Hxw002-45, Hxw003-9, Hxw003-10, Hxw002-15, Hxw003-21, Mt007-36-1, Mt007-37-1, Hxw003-22, Hxw003-25, Lfy001-8-1, Zgn001-14-1 etc. reaches 100%, higher than 90% of cyanogen insect amide; Therefore, be the activity that the activity of derivative of halogen substiuted is better than the derivative that CN replaces equally; The activity of other compounds of the present invention is also more than 50%.
Aphid determination of activity the results are shown in Table 3, when 200 mcg/ml, show the insecticidal activity result of aphid, it is active that the derivative that thioether replaces, the derivative of sulfilimine and the derivative of sulfoximide all have good killing aphis, and cyanogen insect amide does not almost have killing aphis active; The activity of compound to aphid of halogen substiuted of the present invention is significantly higher than the methyl substituted compound Mt007-50-1 of fork.
Systemic activity test result shows, the derivative that thioether replaces has certain systemic activity, the derivative of sulfilimine has good systemic activity, the derivative of sulfoximide has extraordinary systemic activity, the systemic activity of all compounds is all higher than the systemic activity of cyanogen insect amide, and cyanogen insect amide does not almost have systemic activity.
Embodiment 6
Of the present invention containing the anthranilic diamides derivative I of N-cyano group sulfone (sulphur) imines, the antibacterial or fungicidal activity of IA, IB, IC:
Title and the code name of the frequently seen plants pathogenic fungi of the present invention's test comprise AS: tomato early blight bacterium (Alternariasolani); BC: botrytis cinerea pers (Botrytis cinerea); CA: peanut Cercospora bacteria (Cercospora arachidicola); GZ: fusarium graminearum (Gibberella zeae); PI: phytophthora infestans (Phytophthora infestans (Mont.) deBary); PP: Botryosphaeria berengeriana f. sp (Physalospora piricola); PS: Rhizoctonia solani Kuhn (Pellicularia sasakii); RC: Rhizoctonia cerealis (Rhizoctonia cerealis); SS: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum), these bacterial classifications have good representativeness, can represent the kind of most of pathogenic bacteria that field occurs in agriculture production.Thalli growth rate method measurement result is in table 3, and table 3 shows, when 50 mcg/ml, all compounds of the present invention's synthesis all have fungicidal activity in various degree, Mt007-45-1 to the fungicidal activity of AS bacterium higher than 40%; Mt007-45-1 to the fungicidal activity of GZ bacterium higher than 40%; Zgn001-14-1, Mt007-45-1, Hxw003-9, Hxw003-10, Hxw003-15, Lfy001-8-1, Mt007-46-1, Hxw002-45, Hxw003-8, Mt007-36-1, Mt007-37-1, Hxw003-22, Hxw003-25, Hxw003-18, Hxw003-24 to the fungicidal activity of PP higher than 40%; Zgn001-14-1, Mt007-44-1, Lfy001-8-1, Mt007-46-1, Hxw003-5, Mt007-36-1, Mt007-37-1, Hxw003-18, Hxw003-20, Hxw003-23 to the fungicidal activity of BC higher than 40%; Zgn001-14-1, Mt007-44-1, Hxw003-15, Lfy001-8-1, Mt007-46-1, Hxw002-45, Hxw003-5, Hxw003-5, Mt007-36-1, Mt007-41-1, Hxw002-27, Hxw003-18, Hxw003-21, Hxw003-24, Hxw003-20, Hxw003-23, Hxw003-26 to the fungicidal activity of SS higher than 40%, wherein Hxw003-24 to the inhibit activities of SS bacterium higher than 80%; Zgn001-14-1, Mt007-44-1, Hxw003-9, Lf001-8-1, Mt007-46-1, Mt007-47-1, Mt007-36-1, Mt007-41-1 to the fungicidal activity of RC higher than 40%; Zgn001-14-1, Mt007-44-1, Mt007-45-1, Lfy001-8-1, Mt007-46-1, Mt007-47-1, Mt007-36-1, Mt007-37-1, Mt007-41-1 to the fungicidal activity of PS bacterium higher than 40%.Therefore this compounds shows good fungicidal activity.
Embodiment 7
Anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention and insecticide composition prevent and treat the application in agriculture and forestry and gardening plant insect pest
All anthranilic diamides derivative Is containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC and existing sterilant: Chlorpyrifos 94, the sub-Nong in ground, acetamiprid, Affirm (Merck Co.), milbemectin, Avrmectin, pleocidin, fenvalerate, esfenvalerate, 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, d ichlorbenzuron, Teflubenzuron, deinsectization is grand, HEXAFLUMURON, flufenoxuron, pyridine worm is grand, lufenuron, poisonous insect urea, penfluron, Noviflumuron and noviflumuron, its No. CAS is 121451-02-3, flucycloxuron, Novaluron and Rimon, chlorfluazuron, Bay sir 6874 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 and 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, Cupric sulfate, disosultap, chlorantraniliprole, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, tebufenpyrad, bromothalonil, pyrazinones, second mite azoles, tebufenpyrad, to rattle away young ketone, Nylar, any one or two kinds in emaricins etc. combinationally use for preventing and treating agricultural and forestry and gardening plant insect pest, anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC mass percentage are in the composition 1%-90%, and the ratio of the anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC and above-mentioned sterilant is mass percent 1%: 99% to 99%: 1%, can directly be watered rear spraying, comprise agriculturally acceptable solvent 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, with the seed of 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, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress 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, reading room management, Chinese rice grasshopper, Patanga japonica (l.Bol.), singly sting mole cricket, Oriental burmeister, rice thrips, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian pipe 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, sugarcane flat angle 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, Papilio xuthus, 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 hangs cocoon ichneumon wasp, Campoletis chlorideae, 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, Soybean stem borer, 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 improves the defence capability of plant while desinsection, makes plant create defence capability to pathogenic fungi, bacterium and virus infection.
Embodiment 8
Anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC and miticide combine prevent and treat agriculture and forestry and gardening plant mite do harm in application
Anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC and agriculturally acceptable auxiliary agent 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 or two kinds of pharmaceutical agent combinations in pyridaben are prepared into miticide and do harm to for preventing and treating agricultural and forestry and gardening plant mite, anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC total mass percentage are in the composition 1%-90%, and the ratio of the anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC 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, with the seed of 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, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress 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 during composition for preventing and controlling agricultural and forestry and gardening plant mite do harm to 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 mite evil that composition is suitable for is phytophagy evil mite, phytophagy evil mite be selected from tetranychid and Tetranychidae, Tenuipalpidae, furan line mite, Eriophyidae harmful mite and 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.
Embodiment 9
Anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC and antimicrobial combination prevent and treat the application in agriculture and forestry and gardening plant disease
All anthranilic diamides derivative Is containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC 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-chloroisothiazole-5-formic acid, 3,4-chloroisothiazole-5-sodium formiate, 3,4-bis-chloroisothiazole-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, mefenoxam, benalaxyl-M, two chlorine zarilamid, 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, olefin conversion, efficient olefin conversion, 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, 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 combinationally use for preventing and treating agricultural and forestry and gardening plant disease, anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC total mass percentage are in the composition 1%-90%, and the ratio of the anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC and aforementioned sterilant is mass percent 1%: 99% to 99%: 1%, the prevention effect of composition is good, and these compositions have certain synergism and summation action, does not find the composition with antagonistic action, above-mentioned composition may be used for the control of agricultural plants disease and gardening plant disease, the Achyla, Aphanomyces, pythium, phytophthora, Sclerospora, Plasmopara, Pseudoperonospora, Peronospora etc. more than 20 that controlling object comprises Oomycete belongs to the disease produced, as other diseases etc. of the plurality of cereals crops 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, cash crop, gardening plant and forestry plant, 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, with the seed of 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, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress 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 plant applicable in agricultural and forestry and 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, containing 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 improves the defence capability of plant while sterilization, makes plant create defence capability to pathogenic fungi, bacterium and virus infection.
Embodiment 10
Anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC and antiviral agent are combined in the application prevented and treated in agriculture and forestry and gardening plant virus disease
Anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC 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-chloroisothiazole-5-formic acid, 3, 4-bis-chloroisothiazole-5-sodium formiate, 3, 4-bis-chloroisothiazole-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 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 disease, various solanaceous vegetables virus disease, beans virus disease, Cruciferae virus disease, grain and oil crop virus disease, any one 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 disease, maize dwarf mosaic, cauliflower mosaic virus, oranges and tangerines virus disease, cymbidium mosaic virus, any one in cybidium ring spot virus.These compositions are selected from paddy for the plant preventing and treating 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 makes the immunizing power of crop self improve, while producing the control of insect especially infection insect, produce the defence capability to viral diseases of plants induction of plant, also can produce the direct prevention effect of virus disease, therefore, these compositions may be used for preparation and the purposes of Antiphytoviral medicament and inducing plant Antiphytoviral medicament.Anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC total mass percentage are in the composition 1%-90%, and the ratio of the anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC and aforementioned Antiphytoviral 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, with the seed of 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, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress 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, all show addition or synergism between these compositions, while maintenance insecticidal activity, its antiviral activity is all greater than the effect that any one compound is used alone, find no the composition of antagonistic action, the drug effect lasting period of composition is long.
Embodiment 11
The complete processing of anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC and foregoing pesticidal agent, sterilant, anti-plant virus agent and activating plants agent compound preparation and stability
Anthranilic diamides derivative I containing N-cyano group sulfone (sulphur) imines of the present invention, IA, IB, IC and foregoing pesticidal agent, sterilant, the mixture complete processing of anti-plant virus agent and activating plants agent is in table 5, from table 5, 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, other agriculturally acceptable adjuvant components such as tensio-active agent and filler, the cold storage test of process preparation, liquid preparation places 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 formulation storage place the medicament drug effect of front and back without significant difference, the rate of decomposition of composition effective constituent is within 5%, composite preparation qualified stability.
Table 2 is of the present invention containing the anthranilic diamides derivative I of N-cyano group sulfone (sulphur) imines, the insecticidal activity (mythimna separata, 48h mortality ratio/%) of IA, IB, IC
Sequence number Compound 5.0 mcg/ml 1.0 mcg/ml 0.1 mcg/ml
1 Hxw002-45 100 20 0
2 Hxw003-5 100 0 0
3 Hxw003-8 100 0 0
4 Hxw003-9 100 20 0
5 Hxw003-10 40 ND ND
6 Hxw003-15 70 0 0
7 Hxw003-18 100 0 0
8 Hxw003-21 100 40 0
9 Hxw003-24 100 0 0
10 Mt007-36-1 100 0 0
11 Mt007-37-1 70 0 0
12 Mt007-41-1 100 0 0
13 Hxw003-20 100 50 0
14 Hxw003-23 100 0 0
15 Hxw003-26 100 0 0
16 Hxw003-22 100 0 0
17 Hxw003-25 60 ND ND
18 Hxw003-27 100 20 0
19 Lfy001-8-1 100 70 0
20 Mt007-46-1 100 100 0
21 Mt007-47-1 100 0 0
22 Zgn001-14-1 100 50 0
23 Mt007-44-1 100 0 0
24 Mt007-45-1 100 0 0
25 Mt007-50-1 80 0 ND
26 Cyanogen insect amide 100 100 0
27 Provado 20 0 0
ND: undetermined.
Table 3 is of the present invention containing the anthranilic diamides derivative I of N-cyano group sulfone (sulphur) imines, insecticidal activity (the small cabbage moth 72h mortality ratio/% of IA, IB, IC; Aphid 48h mortality ratio/%)
Table 4 is containing the anthranilic diamides derivative I of N-cyano group sulfone (sulphur) imines, the fungicidal activity (/ %) of IA, IB, IC
Numbering Compound number AS CA GZ PP BC SS RC PS PI
1 Hxw002-45 21.74 10.53 16.28 44.64 4.17 62.07 36.54 22.62 23.33
2 Hxw003-5 6.06 10.71 17.07 28.57 42.31 42.11 33.33 14.29 9.68
3 Hxw003-8 30.43 26.32 13.95 41.07 25.00 20.69 38.46 15.48 6.67
4 Hxw003-9 30.43 21.05 13.95 50.00 37.50 17.24 48.08 19.05 10.00
5 Hxw003-10 30.43 26.32 13.95 41.07 25.00 20.69 38.46 15.48 6.67
6 Hxw003-15 21.74 10.53 16.28 44.64 4.17 62.07 36.54 22.62 23.33
7 Hxw003-18 6.06 17.86 9.76 41.07 61.54 63.16 29.82 15.48 12.90
8 Hxw003-21 12.12 10.71 12.20 26.79 7.69 57.89 33.33 9.52 12.90
9 Hxw003-24 26.09 5.26 20.93 51.79 4.17 86.21 28.85 20.24 6.67
10 Mt007-36-1 19.05 18.52 35.71 42.42 45.71 68.75 62.90 51.85 20.69
11 Mt007-37-1 3.33 0.00 32.26 74.29 50.00 23.68 36.00 62.50 21.74
12 Mt007-41-1 14.29 3.70 35.71 36.36 8.57 56.25 66.13 49.38 20.69
13 Hxw003-20 9.09 7.14 4.88 32.14 50.00 52.63 38.60 5.95 16.13
14 Hxw003-23 9.09 7.14 4.88 32.14 50.00 52.63 38.60 5.95 16.13
15 Hxw003-26 6.06 14.29 14.63 28.57 34.62 63.16 19.30 8.33 12.90
16 Hxw003-22 30.43 26.32 13.95 41.07 25.00 20.69 38.46 15.48 6.67
17 Hxw003-25 30.43 5.26 16.28 53.57 12.50 6.90 32.69 27.38 6.67
18 Hxw003-27 15.15 3.57 4.88 28.57 26.92 52.63 33.33 10.71 6.45
19 Lfy001-8-1 17.24 12.50 25.00 50.00 65.79 73.53 64.06 53.66 23.68
20 Mt007-46-1 6.67 4.35 25.81 40.00 43.33 52.63 44.00 64.06 21.74
21 Mt007-47-1 12.50 22.22 14.71 29.31 31.71 29.17 45.45 45.59 22.22
22 Zgn001-14-1 14.29 11.11 39.29 48.48 45.71 62.50 59.68 48.15 10.34
23 Mt007-44-1 9.52 14.81 17.86 36.36 40.00 53.13 66.13 50.62 24.14
24 Mt007-45-1 50.00 8.70 41.94 41.43 20.00 18.42 32.00 48.44 26.09
Data are the measurement result of 50 mcg/ml; AS: tomato early blight bacterium (Alternaria solani); BC: botrytis cinerea pers (Botrytiscinerea); 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); ND: undetermined.
The working method of the anthranilic diamides derivative I of table 5 N-cyano group of the present invention sulfone (sulphur) imines, IA, IB, IC and foregoing pesticidal, miticide, sterilant and Antiphytoviral pharmacy mix

Claims (2)

1. the anthranilic diamides derivative of a class Sulfide-containing Hindered, is characterized in that having the chemical structure of general formula such as formula shown in IA:
X is selected from: Cl, Br; Y is selected from: Cl, Br; R 2for methyl.
2. the anthranilic diamides derivative I A of a class Sulfide-containing Hindered according to claim 1 is preparing the purposes in sterilant.
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