CN104031026B - O-formylamino benzamide derivatives containing N-cyano sulfone(sulfur)imine, preparation method thereof and uses thereof - Google Patents
O-formylamino benzamide derivatives containing N-cyano sulfone(sulfur)imine, preparation method thereof and uses thereof Download PDFInfo
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- CN104031026B CN104031026B CN201410081794.9A CN201410081794A CN104031026B CN 104031026 B CN104031026 B CN 104031026B CN 201410081794 A CN201410081794 A CN 201410081794A CN 104031026 B CN104031026 B CN 104031026B
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- 0 Cc(cc(*)cc1C(O)=O)c1N Chemical compound Cc(cc(*)cc1C(O)=O)c1N 0.000 description 3
- GPKMRCUVXVTKTC-UHFFFAOYSA-N CC(C)(C/S(/C)=N/C#N)NC(c1cc(Br)cc(C)c1NC(c1cc(Cl)n[n]1-c1ncccc1Cl)=O)=O Chemical compound CC(C)(C/S(/C)=N/C#N)NC(c1cc(Br)cc(C)c1NC(c1cc(Cl)n[n]1-c1ncccc1Cl)=O)=O GPKMRCUVXVTKTC-UHFFFAOYSA-N 0.000 description 1
- JRQKOOKATXODLT-UHFFFAOYSA-N CC(C)(C/S(/C)=N/C#N)NC(c1cc(Cl)cc(C)c1NC(c1cc(Br)n[n]1-c1ncccc1Cl)=O)=O Chemical compound CC(C)(C/S(/C)=N/C#N)NC(c1cc(Cl)cc(C)c1NC(c1cc(Br)n[n]1-c1ncccc1Cl)=O)=O JRQKOOKATXODLT-UHFFFAOYSA-N 0.000 description 1
- RADSORBPJSNIJM-UHFFFAOYSA-N CC(C)(C/S(/C)=N/C#N)NC(c1cc(Cl)cc(C)c1NC(c1cc(Cl)n[n]1-c1ncccc1Cl)=O)=O Chemical compound CC(C)(C/S(/C)=N/C#N)NC(c1cc(Cl)cc(C)c1NC(c1cc(Cl)n[n]1-c1ncccc1Cl)=O)=O RADSORBPJSNIJM-UHFFFAOYSA-N 0.000 description 1
- WNAJXPYVTFYEST-UHFFFAOYSA-N Cc(cccc1C(O)=O)c1N Chemical compound Cc(cccc1C(O)=O)c1N WNAJXPYVTFYEST-UHFFFAOYSA-N 0.000 description 1
- LJAGTZZWUILRAM-UHFFFAOYSA-N Cc1cc(Cl)cc(C(NCC/S(/C)=N/C#N)=O)c1NC(c1cc(Br)n[n]1-c1ncccc1Cl)=O Chemical compound Cc1cc(Cl)cc(C(NCC/S(/C)=N/C#N)=O)c1NC(c1cc(Br)n[n]1-c1ncccc1Cl)=O LJAGTZZWUILRAM-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
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- General Health & Medical Sciences (AREA)
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- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides o-formylamino benzamide derivatives containing N-cyano sulfone(sulfur)imine, a preparation method thereof and uses thereof. The invention relates to bisamide derivatives containing pyrazolecarboxamide, and the general chemical formula of the derivatives is shown as the formula I. The invention discloses a general structural formula and synthesis methods of the compounds, uses of the compounds serving as insecticides, bactericides, plant virus resisting agents and plant activators, and processing processes for the compounds in the preparation of the insecticides, the bactericides, the plant virus resisting agents and the plant activators in a manner of being mixed with agriculturally-acceptable assistants or synergists. The invention further discloses uses of combination of the compounds with the commercial insecticides, bactericides, plant virus resisting agents and plant activators in the prevention and treatment of the diseases, insect pests and viral diseases in agriculture, forestry and horticulture and a preparation method thereof.
Description
Technical field
Technical scheme is related to pyrazole compound, the specially adjacent formamido group benzene of the sulfone of cyano group containing n- (sulphur) imines
Carboxamides derivatives.
Background technology
Report a series of pyrazine diamide compounds since doctor tsuda found university in 1989 in Osaka, Japan
Since having certain insecticidal activity, diamide compound becomes to be studied for Ge great agricultural chemicals company in the world and R＆D institution
Focus.Until 1998, Japanese agricultural chemicals company was just found that first bisamide insecticides --- Flubendiamide
(ep1006107).This insecticides except according to there being excellent activity, and existing insecticide no interactions resistance, and lactation is moved
Beyond the advantages of thing is safe, also unique mechanism of action.Its particular mechanism of this bisamide insecticides is probably to suppress
The release of calcium ion and become ryanodine receptor activator.This unique mechanism of action has attracted the agricultural chemicals company in the whole world quickly
Research to ryanodine receptor activator insecticides.2000, du pont company was just found that second ryanodine receptor
Activator insecticides --- chlorantraniliprole (wo03015519), and successfully listed in 2007.Subsequently, du pont company pair
Chlorantraniliprole does further structure optimization it was found that second generation ryanodine receptor insecticides --- the cyanogen of desinsection more wide spectrum
Insect amide (wo2004067528).
Although bisamide insecticides show prominent superiority at active aspect, some areas are due to frequent mistake
Degree dispenser, the rendered different degrees of resistance to the action of a drug of insect, the kind number of up to the present this insecticides commercialization is very
Limited.In order to overcome this situation at present, find the ryanodine receptor insecticide of more high bioactivity and related agricultural chemicals, Zhejiang
Work research institute have studied fluorine-containing methoxyl group pyrazoles adjacent formamide benzene Carbox amide have more effectively, low toxicity, low cost,
Environmentally safe the advantages of (cn101967139a).Domestic Duo Jia research unit is all carrying out related innovative research work, mesh
The front report also not having activity to exceed target molecule parent active.Recently, Syngenta Co., Ltd is by n- cyano group sulfone (sulphur) imine structure
It is introduced in the structure of benzamide, find that the target compound of design synthesis has good insecticidal activity (christian
Gnamm, novel diamide insecticides:sulfoximines, sulfonimidamides and other new
Sulfonimidoyl derivatives, bioorganic ＆ medicinal chemistry letters, 2012,22:
3800-3806).
Due to molecule itself, its migration in plant body is subject to certain limiting to ryanodine receptor insecticides
System, in order to study the ryania class compound of high-efficiency low-toxicity further, the present invention utilize pesticide molecule design principle by other
Pesticide activity fragment is introduced in bisamide molecule, and design has synthesized the adjacent formamido group benzene first of class cyano group containing n- sulfone (sulphur) imines
Amide derivatives, and carried out the screening of the biologically active of system, to improving the water-soluble of target molecule, improve it and planting
Upper and lower and lateral migration in object, the innovative research for novel pesticide provides the new candidate compounds of eco-friendly ultra high efficiency.
Content of the invention
The technical problem to be solved is: provides the adjacent formamido group benzene first of new sulfone (sulphur) imines of cyano group containing n-
The synthetic method of amide derivatives, provides this kind of compound modulates agricultural, gardening and health and forestry plant insect and plant
The biologically active of pathogen and its assay method, provide simultaneously these compounds agriculture field, horticultural field, field of forestry and
The middle application of health field.
The present invention solve this technical problem be the technical scheme is that with agriculture field, horticultural field, forestry and
Health field insecticidal activity, bactericidal activity, anti-phytoviral activity, induction plant produce anti-disease activity, insect growth adjusts and lives
The chemical structure of general formula of the anthranilic diamides derivative of n- cyano group sulfone (sulphur) imines of property is shown in formula i
Wherein, x is selected from: halogen, cn, no2、nh2, replace alkyl, replace unsaturated alkyl；Y is selected from: halogen, cn, no2、
nh2, replace alkyl, replace unsaturated alkyl；r1It is selected from: replace alkyl, replace unsaturated alkyl, methyl mercapto replacement alkyl, first sulphur
Base replaces unsaturated alkyl, cyano group, substituted sulphonyl, substituted-amino formoxyl；X is preferred: chlorine, bromine；Y is preferred: chlorine, bromine；r1Excellent
Choosing: 2-methylmercaptoethyl, 2- ((n- cyano group) methyl sulfilimine base) ethyl, 2- ((n- cyano group) methyl sulfone imido grpup) ethyl, 2-
The methyl mercapto tert-butyl group, 2- ((n- cyano group) the methyl sulfilimine base) tert-butyl group, 2- ((n- cyano group) methyl sulfone imido grpup) tert-butyl group；Tool
Body can be divided into following 3 kinds of structure types:
Wherein, x is selected from: halogen, cn, no2、nh2, replace alkyl, replace unsaturated alkyl；Y is selected from: halogen, cn, no2、
nh2, replace alkyl, replace unsaturated alkyl；r2It is selected from: h, replacement alkyl, replacement unsaturated alkyl, substituted aryl；X is preferred:
cl、br；Y is preferred: c1, br；r2Preferably: h, ch3.
Anthranilic diamides derivative i, ia, ib, ic of sulfone (sulphur) imines of cyano group containing n- of the present invention press
Method synthesis shown in scheme-1:
Wherein, x is selected from: halogen, cn, no2、nh2, replace alkyl, replace unsaturated alkyl；Y is selected from: halogen, cn, no2、
nh2, replace alkyl, replace unsaturated alkyl；r2It is selected from: h, replacement alkyl, replacement unsaturated alkyl, substituted aryl；X is preferred:
cl、br；Y is preferred: cl, br；r2Preferably: h, ch3.
Anthranilic diamides derivative i, ia, ib, ic synthesis road of scheme-1 cyano group containing n- sulfone (sulphur) imines
Line
It is specifically divided into following steps:
A. the preparation of replacement Benzoxazine iv:
50 milliliters of round-bottomed flasks add 15 milliliters of acetonitriles, 1.0 mMs of 3- replace -1- (3- chloropyridine -2- base) -
1h- pyrazoles -5- formic acid ii, 5 mMs of methylsufonyl chlorides, are abbreviated as mscl, 0.4 gram i.e. 5 mMs of pyridines, are abbreviated as py, cold
But to -5 degrees Celsius, stirring adds 1.0 mMs of replacement ortho-aminobenzoic acids after 30 minutes, is slowly increased to stirred after room temperature
At night, there is yellow solid to replace Benzoxazine iv and separate out, filter, washing, vacuum drying, be directly used in next step reaction；Described 3-
Replace -1- (3- chloropyridine -2- base) -1h- pyrazoles -5- formic acid ii and be selected from the chloro- 1- of 3- (3- chloropyridine -2- base) -1h- pyrazoles -5-
The bromo- 1- of formic acid, 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) -8- methyl -6- chloro- 4- oxo -4h- benzo-[d] [1,3]-piperazine, 2- (3-
Chloro- 1- (3- chloropyridine -2- base) -1h- pyrazoles -5- base) -8- methyl -6- bromo- 4- oxo -4h- benzo-[d] [1,3]-piperazine,
2- (the bromo- 1- of 3- (3- chloropyridine -2- base) -1h- pyrazoles -5- base) -8- methyl -6- chloro- 4- oxo -4h- benzo-[d] [1,3] -
Piperazine, 2- (the bromo- 1- of 3- (3- chloropyridine -2- base) -1h- pyrazoles -5- base) -8- methyl -6- bromo- 4- oxo -4h- benzo-[d]
[1,3]-piperazine.
B.1- (3- chloropyridine -2- base) -3- halo -1h- pyrazoles -5- formyl -2- methyl -4- halo -6- (2- (methyl mercapto
Alkyl) amido formacyl) aniline ia preparation:
Add 0.5 mM and replace Benzoxazine iv, 20 milliliters of oxolanes in 50 milliliters of round-bottomed flasks, be abbreviated as
Thf, 5.0 mMs of replacement methylmercaptan ethyl ammonia, reactant mixture is stirred at room temperature 7 hours；Reduced pressure concentration removes solvent, and gained is residual
Excess purifies to obtain yellow or white solid 1- (3- chloropyridine -2- base) -3- halo -1h- pyrrole through 200～300 mesh silica gel column chromatographies
Azoles -5- formyl -2- methyl -4- halo -6- (2- (methyl mercapto alkyl) amido formacyl) aniline ia, eluant, eluent is Celsius for 60～90
The petroleum ether of degree: ethyl acetate, volume ratio is 3: 1；With gained sterling calculated yield, yield 40-70%；The amount of synthesis compound
Expand or shrink by corresponding proportion；The volume of respective reaction container is scaled up or reduces.Described 1- (3- chloropyridine -2-
Base) -3- halo -1h- pyrazoles -5- formyl -2- methyl -4- halo -6- (2- (methyl mercapto alkyl) amido formacyl) aniline ia choosing
From chloro- 6- (2- (methylmercaptoethyl) carbamoyl of 1- (3- chloropyridine -2- base) -3- chloro- 1h- pyrazoles -5- formyl -2- methyl -4-
Base) aniline, the chloro- 6- (2- (the methyl mercapto tert-butyl group) of 1- (3- chloropyridine -2- base) -3- chloro- 1h- pyrazoles -5- formyl -2- methyl -4-
Amido formacyl) aniline, bromo- 6- (2- (the first sulphur of 1- (3- chloropyridine -2- base) -3- chloro- 1h- pyrazoles -5- formyl -2- methyl -4-
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 methyl mercapto tert-butyl group) amido formacyl) aniline, 1- (3- chloropyridine -2- base) -3- bromo- 1h- pyrazoles -5- formyl -2- first
The chloro- 6- of base -4- (2- (methylmercaptoethyl) amido formacyl) aniline, 1- (3- chloropyridine -2- base) -3- bromo- 1h- pyrazoles -5- first
The chloro- 6- of acyl -2- methyl -4- (2- (the methyl mercapto tert-butyl group) amido formacyl) aniline, 1- (3- chloropyridine -2- base) the bromo- 1h- of -3-
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 methyl mercapto tert-butyl group) amido formacyl) aniline.
C.1- (3- chloropyridine -2- base) -3- halo -1h- pyrazoles -5- formyl -2- methyl -4- halo -6- (2- ((n- cyano group
Methyl sulfilimine base) alkyl) amido formacyl) and aniline ib preparation:
0.5 mM of 1- (3- chloropyridine -2- base) -3- halo -1h- pyrazoles -5- first is added in 50 milliliters of round-bottomed flasks
Acyl -2- methyl -4- halo -6- (2- (methyl mercapto alkyl) amido formacyl) aniline ia, the dichloromethane of 15 milliliters of dryings, frozen water
Bath is cooled to 0 degree Celsius.It is then respectively adding 1.0 mMs of cyanamides and 0.5 mM of iodobenzene acetate, at a temperature of this, stirring 3 is little
When after be stirred overnight at room temperature, by direct for reactant liquor removal of solvent under reduced pressure, residue is pure through 200～300 mesh silica gel column chromatographies within the 2nd day
Change 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, eluant, eluent is ethyl acetate, with gained sterling meter
Calculate yield, yield 40-60%.The amount of synthesis compound is expanded or shunk by corresponding proportion；The volume of respective reaction container press than
Example expands or shrinks.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 be selected from 1- (3- chloropyridine -2- base) -3- chloro- 1h- pyrrole
The chloro- 6- of azoles -5- formyl -2- methyl -4- (2- ((n- cyano methyl sulfilimine base) ethyl) amido formacyl) aniline, 1- (3- chlorine
Pyridine -2- base) the chloro- 6- of -3- chloro- 1h- pyrazoles -5- formyl -2- methyl -4- (2- ((the n- cyano methyl sulfilimine base) tert-butyl group)
Amido formacyl) aniline, bromo- 6- (2- ((the n- cyanogen of 1- (3- chloropyridine -2- base) -3- chloro- 1h- pyrazoles -5- formyl -2- methyl -4-
Ylmethyl sulfilimine base) ethyl) amido formacyl) aniline, 1- (3- chloropyridine -2- base) -3- chloro- 1h- pyrazoles -5- formyl -2-
The bromo- 6- of methyl -4- (2- ((the n- cyano methyl sulfilimine base) tert-butyl group) amido formacyl) aniline, 1- (3- chloropyridine -2-
Base) the chloro- 6- of -3- bromo- 1h- pyrazoles -5- formyl -2- methyl -4- (2- ((n- cyano methyl sulfilimine base) ethyl) carbamoyl
Base) aniline, chloro- 6- (2- ((the n- cyano methyl sulphur of 1- (3- chloropyridine -2- base) -3- bromo- 1h- pyrazoles -5- formyl -2- methyl -4-
Imido grpup) tert-butyl group) amido formacyl) aniline, 1- (3- chloropyridine -2- base) -3- bromo- 1h- pyrazoles -5- formyl -2- methyl -4-
Bromo- 6- (2- ((n- cyano methyl sulfilimine base) ethyl) amido formacyl) aniline, 1- (3- chloropyridine -2- base) the bromo- 1h- of -3-
The bromo- 6- of pyrazoles -5- formyl -2- methyl -4- (2- ((the n- cyano methyl sulfilimine base) tert-butyl group) amido formacyl) aniline.
D.1- (3- chloropyridine -2- base) -3- halo -1h- pyrazoles -5- formyl -2- methyl -4- halo -6- (2- ((n- cyano group
Methyl sulfone imido grpup) alkyl) amido formacyl) and aniline ic preparation:
Add 1.0 mMs of metachloroperbenzoic acids in 50 milliliters of three neck round bottom flasks, write a Chinese character in simplified form m-cpba, 8 milliliters of second
Alcohol, ice-water bath is cooled to 0 degree Celsius and stirs 10 minutes, then will be disposable for 7 milliliters of aqueous solution of 1.5 mMs of Anhydrous potassium carbonates
Add, have a large amount of white solids to separate out.By 0.5 mM of 1- (3- chloropyridine -2- base) -3- halogen after 0 degree Celsius of stirring 20 minutes
Generation -1h- pyrazoles -5- formyl -2- methyl -4- halo -6- (2- ((n- cyano methyl sulfilimine base) alkyl) amido formacyl) benzene
8 milliliters of ethanol solutions of amine ib are added dropwise over, and stirring after 1 hour is quenched reactant liquor in water；Then with 50 milliliters of ethyl acetate
Extraction three times, organic layer saturated common salt water washing 2 times, anhydrous magnesium sulfate is dried, removal of solvent under reduced pressure, residue through 200～
300 mesh silica gel column chromatographies purify 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, eluant, eluent is 60～90
Degree Celsius petroleum ether: ethyl acetate, according to the difference of product, volume ratio is between 1: 1～1: 3；Calculated with gained sterling and receive
Rate, yield 50-70%.The amount of synthesis compound is expanded or shunk by corresponding proportion；The volume of respective reaction container expands in proportion
Big 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) and aniline ic be selected from 1- (3- chloropyridine -2- base) -3- chloro- 1h- pyrazoles -5-
The chloro- 6- of formyl -2- methyl -4- (2- ((n- cyano methyl sulfoximide base) ethyl) amido formacyl) aniline, 1- (3- chloropyridine -
2- yl) the chloro- 6- of -3- chloro- 1h- pyrazoles -5- formyl -2- methyl -4- (2- ((the n- cyano methyl sulfoximide base) tert-butyl group) amido first
Acyl group) aniline, bromo- 6- (2- ((the n- cyano methyl of 1- (3- chloropyridine -2- base) -3- chloro- 1h- pyrazoles -5- formyl -2- methyl -4-
Sulfoximide base) ethyl) amido formacyl) aniline, 1- (3- chloropyridine -2- base) -3- chloro- 1h- pyrazoles -5- formyl -2- methyl -4-
Bromo- 6- (2- ((the n- cyano methyl sulfoximide base) tert-butyl group) amido formacyl) aniline, 1- (3- chloropyridine -2- base) -3- are bromo-
The chloro- 6- of 1h- pyrazoles -5- formyl -2- methyl -4- (2- ((n- cyano methyl sulfoximide base) ethyl) amido formacyl) aniline, 1-
(3- chloropyridine -2- base) -3- bromo- 1h- pyrazoles -5- formyl -2- methyl -4- chloro- 6- (2- ((n- cyano methyl sulfoximide base) uncle
Butyl) amido formacyl) aniline, the bromo- 6- (2- of 1- (3- chloropyridine -2- base) -3- bromo- 1h- pyrazoles -5- formyl -2- methyl -4-
((n- cyano methyl sulfoximide base) ethyl) amido formacyl) aniline, 1- (3- chloropyridine -2- base) -3- bromo- 1h- pyrazoles -5- first
The bromo- 6- of acyl -2- methyl -4- (2- ((the n- cyano methyl sulfoximide base) tert-butyl group) amido formacyl) aniline.
When x=halogen, method synthesis as shown in scheme-2 for the substituted pyrazolecarboxylic -5- formic acid ii:
E.2- the preparation of diazanyl substituted pyridines vi:
50 mMs of 2,3- chloropyridine v, 100 mMs of hydrazine hydrate, 50 milliliters of ethanol are added to 100 milliliters of three mouthfuls of circles
In the flask of bottom, it is heated to reflux under 80 degrees Celsius 20 hours, removes solvent under reduced pressure, gained solid ethyl alcohol recrystallization obtains intermediate 2-
Diazanyl substituted pyridines vi, with gained sterling calculated yield, yield 91%.The amount of synthesis 2- diazanyl substituted pyridines vi presses corresponding proportion
Expand or shrink；The volume of respective reaction container is scaled up or reduces.
F.2- the preparation of (3- chloropyridine -2- base) -5- oxopyrazoline alkane -3- Ethyl formate vii:
Add 50 milliliters of ethanol in 100 milliliters of reaction bulbs, be slowly added into 55 mMs of metallic sodium, back flow reaction is made
Alcohol sodium solution. add 50 mMs of 2- diazanyl substituted pyridines vi, 60 mMs of diethyl maleates at reflux, continue
Continuous backflow 30 minutes, then lowers the temperature, and filters, the cold ethanol of gained solid wash yellow solid 2- (3- chloropyridine -2- base) -
5- oxopyrazoline -3- Ethyl formate vii, with gained sterling calculated yield, yield 70%.Synthesis 2- (3- chloropyridine -2- base) -
The amount of 5- oxopyrazoline -3- Ethyl formate vii is expanded or shunk by corresponding proportion；The volume of respective reaction container expands in proportion
Big or reduce.
G.3- the synthesis of halo -1- (3- chloropyridine -2- base) -4,5- dihydro -1h- pyrazole-5-ethyl formate viii
5.4 grams i.e. 20 mMs of 2- (3- chloropyridine -2- base) -5- oxo pyrroles are added in 100 milliliters of single necked round bottom flask
Oxazoline -3- Ethyl formate vii, 50 milliliters of acetonitriles, 30 mM of three oxyhalogen phosphorus, are stirred at reflux 3 hours；Concentrate removing most of molten
Agent, residue is dissolved in dichloromethane, uses saturated sodium bicarbonate aqueous solution and saturated common salt water washing, anhydrous sodium sulfate drying successively
Concentrate, crude product purifies to obtain yellow oil viii through 200～300 mesh silica gel column chromatographies, and eluant, eluent is 60～90 degrees Celsius
Petroleum ether: ethyl acetate, volume ratio is 3: 1；With gained sterling calculated yield, yield 80-90%；Synthesis 3- halo -1- (3- chlorine
Pyridine -2- base) amount of -4,5- dihydro -1h- pyrazole-5-ethyl formate viii expands or shrinks by corresponding proportion；Respective reaction is held
The volume of device is scaled up or reduces；Described three oxyhalogen phosphorus are selected from POCl3, tribromo oxygen phosphorus；Described 3- halo -1- (3- chlorine
Pyridine -2- base) -4,5- dihydro -1h- pyrazole-5-ethyl formate viii be selected from the chloro- 1- of 3- (3- chloropyridine -2- base) -4,5- bis-
Hydrogen -1h- pyrazole-5-ethyl formate, the bromo- 1- of 3- (3- chloropyridine -2- base) -4,5- dihydro -1h- pyrazole-5-ethyl formate.
H.3- the synthesis of halo -1- (3- chloropyridine -2- base) -1h- pyrazole-5-ethyl formate ix
30 mMs of above-mentioned preparation of 3- halo -1- (3- chloropyridine -2- base) -4 is added in 100 milliliters of reaction bulbs,
5- dihydro -1h- pyrazole-5-ethyl formate viii, 50 milliliters of acetonitriles, are slowly added into 3 milliliters of concentrated sulfuric acids, are subsequently adding 40 mMs
Potassium peroxydisulfate, flow back 3 hours, then lower the temperature, pour into and in frozen water, filter to obtain yellow solid 3- halo -1- (3- chloropyridine -2-
Base) -1h- pyrazole-5-ethyl formate ix, with gained sterling calculated yield, yield 65-75%.The amount of synthesis compound is pressed corresponding
Ratio expands or shrinks；The volume of respective reaction container is scaled up or reduces；Described 3- halo -1- (3- chloropyridine -2-
Base) -1h- pyrazole-5-ethyl formate ix be 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 i.e. 3.0 mMs of 3- halo -1- (3- chloropyridine -2- are sequentially added in 50 milliliters of single necked round bottom flask
Base) -1h- pyrazole-5-ethyl formate, 10 ml methanol, 0.2 gram i.e. 5.0 mMs of NaOH, be stirred at room temperature 8 hours.tlc
After monitoring reaction terminates, concentrate and remove most of solvent, add 20 milliliters of frozen water, aqueous solution ethyl acetate washed once, and uses 2
Mol/L watery hydrochloric acid is acidified to ph=4, has white solid to generate, filters, 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 is expanded or shunk by corresponding proportion；Accordingly
The volume of reaction vessel is scaled up or reduces；Described 3- halo -1- (3- chloropyridine -2- base) -1h- pyrazoles -5- formic acid ii
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- first
Acid.
Replace method as shown in scheme-3 for the ortho-aminobenzoic acid iii to synthesize:
Concrete operations are:
J. the preparation of replacement ortho-aminobenzoic acid iii:
20 mMs of 3- methyl-2-amino benzoic acid x, 50 milliliters of dmf, 30 mmoles are added in 100 milliliters of round-bottomed flasks
That n- chlorosuccinimide (or n- NBS), return stirring, after 3 hours, reactant liquor is poured in frozen water, dilute
Hydrochloric acid is acidified to ph=6, filters, and gained precipitation washs to obtain gray solid replacement ortho-aminobenzoic acid iii with a small amount of ethanol, uses institute
Obtain sterling calculated yield, yield is more than 83%；The amount that synthesis replaces ortho-aminobenzoic acid iii is expanded or shunk by corresponding proportion；
The volume of respective reaction container is scaled up or reduces.Described replacement ortho-aminobenzoic acid iii be selected from 2- amido -3- methyl -
5- chlorobenzoic acid, 2- amido -3- methyl -5- bromobenzoic acid.
K. anthranilic diamides derivative i, ia, ib, ic of sulfone (sulphur) imines of cyano group containing n- of the present invention is to aphid
The mensure of worm cytotoxicity:
Anthranilic diamides derivative i, ia, ib, ic of sulfone (sulphur) imines of cyano group containing n- of the present invention is to aphid children
The insecticidal activity screening technique of worm is as follows: adopts infusion process, black bean aphid (aphis laburni kaltenbach) (alk), room
The normal population of interior raising；Weigh 2.5 milligrams of test compound in beaker, 1 n of dropping, n- dimethylformamide (dmf),
Plus 5 milliliters of acetone vibrate dissolving samples, the water adding Tween 80 is configured to the solution to be measured of 200 mcg/ml；To carry
Cutting from basin for examination bean plant of at least 60 black bean aphids, impregnates 5 seconds, taking-up is gently got rid of many in each liquid to be measured
Remaining liquid, is inserted in by moisturizing on water saturated sponge, with cloche cover after liquid is done, the opening of cloche upper end
With gauze sealing in case aphid escape, raise place 24 hours after check aphid death state, standard is: can be creeped with test worm or
Can stand or six Tiao Tuineng strenuous exercises be worm alive；With clear water for comparison, imidacloprid is positive control, calculates correction dead
Rate；
L. anthranilic diamides derivative i, ia, ib, ic of sulfone (sulphur) imines of cyano group containing n- of the present invention is to viscous
The mensure of worm insecticidal activity:
Anthranilic diamides derivative i, ia, ib, ic of sulfone (sulphur) imines of cyano group containing n- of the present invention are to mythimna separata
The screening of insecticidal activity adopts leaf dipping method: weighs 2 milligrams of medicine samples on assay balance in 10 milliliters of penicillin vials, plus 10
Milliliter acetone, becomes the mother liquor of 200 mcg/ml, covers plug vibration dissolving, then liquid acetone is diluted to 5 micrograms/in the least
The working solution rising, with straight peen ophthalmology tweezers soaking maize blade, 2～3 seconds time, gets rid of extraction raffinate.1 tablet once, each sample totally 8
Piece；It is successively placed on process paper by sample flag sequence, put in the culture dish having markd 10cm after liquid is done, with curved
Head ophthalmology tweezers access incubates armyworm larvae at the beginning of 10 3 ages, by test process be placed in constant temperature standard insectary culture 24 hours or
Inspection result after 48 hours, touches larva body with little writing brush or tweezers, with larva completely motionless as death standard；With cyanogen insect amide
For positive control, the maize leaves with acetone soln dipping are blank.Carry out compound 1.0 mcg/ml and 0.1 micro- simultaneously
The determination of activity of grams per milliliter concentration.
M. anthranilic diamides derivative i, ia, ib, ic of sulfone (sulphur) imines of cyano group containing n- of the present invention is to little
The mensure of diamond-back moth insecticidal activity:
Anthranilic diamides derivative i, ia, ib, ic of sulfone (sulphur) imines of cyano group containing n- of the present invention are to pickles
The screening of moth insecticidal activity adopts blade medicine embrane method: sample to be tested is configured to the solution of 200 mcg/ml, takes active compound sample first
Use a small amount of acetone solution, then diluted with the 0.5 ‰ triton-100 aqueous solution, the 0.5 ‰ triton-100 aqueous solution are comparison, often
Individual 3 repetitions of concentration, each repeats to process 10 test worms；Take fresh free of contamination cabbage leaves, soak 10 seconds in liquid, in
After (about 2 hours) are dried in interior, put in the culture dish of 9 centimetres of diameter, be respectively connected to the basically identical diamondback moth of size 2 age children
Worm, is placed in after being tightened with rubber band in diamondback moth constant temperature insectary, inspection result after 96 hours or 120 hours, with little writing brush or
Tweezers touch polypide it is impossible to the coordinated movement of various economic factors is as death；With cyanogen insect amide as positive control.Carry out simultaneously compound 5.0 microgram/
Milliliter and the determination of activity of 1.0 mcg/ml concentration.
N. anthranilic diamides derivative i, ia, ib, ic of sulfone (sulphur) imines of cyano group containing n- of the present invention is to disease
The mensure of fungal pathogenses bactericidal activity:
Anthranilic diamides derivative i, ia, ib, ic of sulfone (sulphur) imines of cyano group containing n- of the present invention sterilized or
Bacteriostatic activity adopts thalli growth rate determination method, and detailed process is: take 5 milligrams of samples to be dissolved in appropriate dimethylformamide,
Then with being diluted to the medicament of 500 mcg/ml containing a certain amount of polysorbas20 emulsifier aqueous solution, by reagent agent in aseptic bar
Respectively draw in 1 milliliter of injection culture dish under part, then be separately added into 9 milliliters of culture mediums, make 50 mcg/ml pastilles after shaking up and put down
Plate, does blank with the flat board adding 1 milliliter of aqua sterilisa, cuts bacterium disk with 4 millimeters of card punch of diameter along mycelia outer rim, moves
To pastille flat board, put in equilateral triangle, often process and be repeated 3 times, culture dish is placed on 24 ± 1 degrees Celsius of constant incubators
Interior culture, investigates each process bacterium disk extension diameter after comparison colony diameter expands to 2-3 centimetre, averages, right with blank
Calculate bacteriostasis rate relatively according to comparing, include multiple representative major parts that field actually occurs in China's agricultural production for examination bacterial classification
The kind of phytopathogen, its title and code name include as: tomato early blight bacterium (alternaria solani)；Bc: cucumber ash
Mould germ (botrytis cinerea)；Ca: peanut Cercospora bacteria (cercospora arachidicola)；Gz: gibberella saubinetii
Germ (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 derives to the anthranilic diamides of sulfone (sulphur) imines of cyano group containing n-
Thing i, ia, ib, ic have carried out the optimization of guide structure, and it is disease-resistant that the noval chemical compound of synthesis has been carried out with desinsection, antibacterial and induction
Activity, the mensure of anti-phytoviral activity and the research being used in mixed way, this kind of compound can be used for agriculture field, forestry neck
Domain, the disease of horticultural field, insect pest and virus disease preventing and treating.
The present invention will be applied in combination processing technology and choosing by specific preparation and biological activity determination and with commercially available agricultural chemical
The formulation selected for embodiment more specifically describe the anthranilic diamides derivative i of sulfone (sulphur) imines of cyano group containing n-,
The synthesis of ia, ib, ic and biologically active and its application, but described embodiment is only used for the specific description present invention and unrestricted
Invention, especially its biologically active and processing technology are merely illustrative, and unrestricted this patent, specific embodiment is such as
Under:
Embodiment 1
The synthesis of 3- methyl -5- halo -2- aminobenzoic acid iii:
100 milliliters of round-bottomed flasks add 3.0 grams i.e. 20 mMs of 3- methyl-2-amino benzoic acid x, 30 milliliters of dmf,
6.7 grams i.e. 30 mMs of ncs (or 30 mMs of nbs), return stirring, after 3 hours, reactant liquor is poured in frozen water, watery hydrochloric acid acid
Change to ph=6, filter, a small amount of ethanol of gained solid washs to obtain 2- amino -3- methyl -5- halo-benzoic acid iii, and grey is solid
Body, more than 4.6 grams, yield is more than 83%.Y is selected from: chlorine, bromine, described 2- amino -3- methyl -5- halo-benzoic acid iii choosing
From -2- amino -3- methyl-5-chloro benzoic acid, the bromo- benzoic acid of 2- amino -3- methyl -5-；Wherein, 2- amino -3- methyl-5-chloro
Benzoic acid1H nmr (400mhz, dmso-d6): δ: 7.96 (s, 1h), 7.56 (d, 1h), 7.23 (d, 1h), 2.11 (s, 3h)；2-
Amino -3- methyl -5- bromobenzoic acid1Hnmr (300mhz, dmso-d6): δ: 7.70 (s, 1h), 7.31 (s, 1h), 2.10 (s,
3h).
Embodiment 2
3- halo -1- (3- chloropyridine -2- base)-n- (4- halo -2- methyl -6- ((2- (methyl mercapto) alkyl) carbamyl
Base) phenyl) -1h- pyrazoles -5- formamide preparation
(1) synthesis of 3- chloride-2-hydrazinopyridine vi:
50 mMs of 2,3- pyridine v, 100 mMs of hydrazine hydrate, 50 milliliters of ethanol are added to 100 milliliters of three mouthfuls of round bottoms
In flask, it is heated to reflux under 80 degrees Celsius 20 hours, removes solvent under reduced pressure, gained solid ethyl alcohol recrystallization obtains acicular crystal 3-
Vi6.5 gram of chloride-2-hydrazinopyridine, yield 90%.
(2) synthesis of 5- oxo -2- (3- chloropyridine -2- base) pyrazoline -3- Ethyl formate vii:
Add 100 milliliters of absolute ethanol in 250 milliliters of single necked round bottom flask, be dividedly in some parts 1.77 grams i.e. 55 mMs of gold
Belong to sodium, temperature slightly rises, stirring formed transparent and homogeneous solution after 10 minutes；Add the chloro- 2- diazanyl of 7.1 grams i.e. 50 mMs of 3-
Pyridine vi forms yellow suspension, is heated to flowing back, and under reflux state, 11.2 grams of dropping i.e. 65 mMs of diethyl maleates, drip
Finish, continue backflow 1 hour；After tlc monitoring reaction terminates, it is cooled to 40 degrees Celsius, adds 3.5 milliliters of glacial acetic acids；Reaction mixing
Thing is concentrated into closely dry, and crude product ethyl alcohol recrystallization obtains 7.9g yellow solid vii, yield 59%；1H nmr (300mhz,
cdcl3) 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, ch3).
(3) synthesis of 3- halo -1- (3- chloropyridine -2- base) -4,5- dihydro -1ii- pyrazole-5-ethyl formate viii
5.4 grams i.e. 20 mMs of 5- oxo -2- (3- chloropyridine -2- base) pyrroles are added in 100 milliliters of single necked round bottom flask
Oxazoline -3- Ethyl formate vii, 50 milliliters of acetonitriles, 30 mM of three halo oxygen phosphorus, are abbreviated as p (0) x3, x is cl, br, stirs back
Stream 3 hours；Concentrate and remove most of solvent, residue is dissolved in dichloromethane, use saturated sodium bicarbonate aqueous solution and saturation successively
Brine It, anhydrous sodium sulfate drying, concentrate, crude product purifies to obtain yellow oil 3- through 200～300 mesh silica gel column chromatographies
Halo -1- (3- chloropyridine -2- base) -4,5- dihydro -1h- pyrazole-5-ethyl formate viii, eluant, eluent is 60～90 degrees Celsius
Petroleum ether: ethyl acetate, volume ratio is 3: 1；With gained sterling calculated yield, yield 80-90%.Three described halo oxygen phosphorus choosings
From POCl3, tribromo oxygen phosphorus；Described 3- halo -1- (3- chloropyridine -2- base) -4,5- dihydro -1h- pyrazoles -5- formic acid second
Ester viii is selected from the chloro- 1- of 3- (3- chloropyridine -2- base) -4,5- dihydro -1h- pyrazole-5-ethyl formate, the bromo- 1- of 3- (3- chlorine pyrrole
Pyridine -2- base) -4,5- dihydro -1h- pyrazole-5-ethyl formate；The chloro- 1- of wherein 3- (3- chloropyridine -2- base) -4,5- dihydro -1h-
Pyrazole-5-ethyl formate1Hnmr (400mhz, cdcl3) 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 (, 3h)；The bromo- 1- of 3- (3- chloropyridine -2- base) -4,5- dihydro -
1h- pyrazole-5-ethyl formate1Hnmr (300mhz, cdcl3) 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)-ih- pyrazole-5-ethyl formate ix
Add in 100 milliliters of single necked round bottom flask 10 mMs of 3- halo -1- (3- chloropyridine -2- base) -4,5- dihydros -
1h- pyrazole-5-ethyl formate viii, 30 milliliters of acetonitriles, 1.1 milliliter of 98% concentrated sulfuric acid, stir 5 minutes, add 3.3 grams i.e. 15 milli
Mole potassium persulfate, is stirred at reflux 3 hours；Reactant mixture is poured into after being cooled to room temperature in 300 milliliters of frozen water, filters, institute
Obtain solid ethyl alcohol recrystallization and obtain yellow crystals 3- halo -1- (3- chloropyridine -2- base) -1h- pyrazole-5-ethyl formate ix, use
Gained sterling calculated yield, yield 64-70%；Described 3- halo -1- (3- chloropyridine -2- base) -1h- pyrazoles -5- formic acid second
Ester 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 chloro- 1- of wherein 3- (3- chloropyridine -2- base) -1h- pyrazole-5-ethyl formate1h nmr(400mhz
cdcl3) 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 formate1h nmr(300mhz cdcl3) 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 mMs of 3- halo -1- (3- chloropyridine -2- base) -1h- pyrrole is sequentially added in 50 milliliters of single necked round bottom flask
Azoles -5- Ethyl formate ix, 10 ml methanol, 0.2 gram i.e. 5.0 mMs of NaOH, are stirred at room temperature 8 hours, tlc monitoring reaction
After end, concentrate and remove most of solvent, add 20 milliliters of frozen water, aqueous solution ethyl acetate washed once, and 2 mol/L are dilute
Hydrochloric acid is acidified to ph=4, has white solid to generate, filters, filter cake is washed, and vacuum drying obtains faint yellow solid 3- halo -1-
(3- chloropyridine -2- base) -1h- pyrazoles -5- formic acid ii0.63g, yield 70%；Described 3- halo -1- (3- chloropyridine -2-
Base) -1h- pyrazoles -5- formic acid ii be 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 acid1h 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 acid1H 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) 6- halo -2- (3- halo -1- (3- chloropyridine -2- base) -1h- pyrazoles -5- base) -8- methyl -4h-3,1- benzene
And the synthesis of piperazine -4- ketone iv
50 milliliters of round-bottomed flasks add 10 milliliters of acetonitriles, 1.0 mMs of 3- halo -1- (3- chloropyridine -2- base) -
1h- pyrazoles -5- formic acid ii, 0.57 gram i.e. 5 mMs of methylsufonyl chlorides, 0.4 gram i.e. 5 mMs of pyridines, are cooled to -5 degrees Celsius,
Stirring added 01.0 mM of 2- amino -3- methyl -5- halogen benzoic acid iii after 30 minutes, was slowly increased to stirred after room temperature
At night, there are 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, and filters, washing, is directly used in next step reaction after vacuum drying；Described 3- methyl -5- halo -
2- aminobenzoic acid ii is selected from 3- methyl-5-chloro -2- aminobenzoic acid, 3- methyl -5- bromo- 2- aminobenzoic acid；Described 2- ammonia
Base -3- methyl -5- halo-benzoic acid iii is selected from -2- amino -3- methyl-5-chloro benzoic acid, the bromo- benzene of 2- amino -3- methyl -5-
Formic acid；Described 6- halo -2- (3- halo -1- (3- chloropyridine -2- base) -1h- pyrazoles -5- base) -8- methyl -4h-3,1- benzene
And piperazine -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- benzo
Piperazine -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- benzo
Piperazine -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) 1- (3- chloropyridine -2- base) -3- halo -1h- pyrazoles -5- formyl -2- methyl -4- halo -6- (2- (methyl mercapto
Alkyl) amido formacyl) aniline ia preparation
Sequentially add in 50 milliliters of three neck round bottom flasks 0.5 mM of 6- halo -2- (3- halo -1- (3- chloropyridine -
2- yl) -1h- pyrazoles -5- base) -8- methyl -4h-3,1- Benzoxazine -4- ketone iv, 10 milliliters of acetonitriles, 0.9 gram of dropping i.e. 10.0
MM methyl mercapto ethamine or 2- methyl mercapto tert-butylamine, drip to finish and are stirred at room temperature 4 hours；After tlc monitoring reaction terminates, rotation is steamed
Send out and remove solvent, add saturated sodium bicarbonate aqueous solution to stir 10 minutes, 20 milliliters of ethyl acetate extract three times, merge organic phase
And use saturated common salt water washing, anhydrous sodium sulfate drying, it is concentrated to give residue, purify in vain through 200～300 mesh silica gel column chromatographies
Color solid ia, eluant, eluent is 60～90 degrees Celsius of petroleum ether: ethyl acetate, and volume ratio is 2: 1；Calculated with gained sterling and receive
Rate；The concrete physical parameter of ia is shown in Table 1.Described 1- (3- chloropyridine -2- base) -3- halo -1h- pyrazoles -5- formyl -2- methyl -
4- halo -6- (2- (methyl mercapto alkyl) amido formacyl) aniline ia be 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- are chloro-
1h- pyrazoles -5- formyl -2- methyl -4- chloro- 6- (2- (the methyl mercapto tert-butyl group) 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- chlorine
Pyridine -2- base) -3- chloro- 1h- pyrazoles -5- formyl -2- methyl -4- bromo- 6- (2- (the methyl mercapto tert-butyl group) amido formacyl) benzene
Amine, chloro- 6- (2- (methylmercaptoethyl) the amido first of 1- (3- chloropyridine -2- base) -3- bromo- 1h- pyrazoles -5- formyl -2- methyl -4-
Acyl group) aniline, chloro- 6- (2- (the tertiary fourth of methyl mercapto of 1- (3- chloropyridine -2- base) -3- bromo- 1h- pyrazoles -5- formyl -2- methyl -4-
Base) amido formacyl) aniline, the bromo- 6- (2- (first of 1- (3- chloropyridine -2- base) -3- bromo- 1h- pyrazoles -5- formyl -2- methyl -4-
Sulfenyl ethyl) amido formacyl) aniline, the bromo- 6- of 1- (3- chloropyridine -2- base) -3- bromo- 1h- pyrazoles -5- formyl -2- methyl -4-
(2- (the methyl mercapto tert-butyl group) amido formacyl) aniline.
Embodiment 3
1- (3- chloropyridine -2- base) -3- halo -1h- pyrazoles -5- formyl -2- methyl -4- halo -6- (2- ((n- cyano group first
Base sulfilimine base) alkyl) amido formacyl) and aniline ib synthesis
50 milliliters of three neck round bottom flasks add 0.53 gram i.e. 1.0 mMs of 3- halo -1- (3- chloropyridine -2- base) -
N- (4- halo -2- methyl -6- (2- (methyl mercapto alkyl) carbamoyl) phenyl) -1h- pyrazoles -5- formamide ia, adds 30
The oxolane stirring that milliliter is dried, ice-water bath is cooled to 0 degree Celsius.Be then respectively adding 0.16 gram i.e. 4 mMs of cyanamides and
0.33 gram i.e. 1.0 mMs of iodobenzene acetates, stirring at a temperature of this was stirred overnight at room temperature after 3 hours, directly subtracted reactant liquor within the 2nd day
Pressure removes solvent, and residue purifies to obtain white solid ib through 200～300 mesh silica gel column chromatographies, and eluant, eluent is ethyl acetate, ib's
Physical and chemical parameter is shown 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 be selected from 1- (3- chloropyridine -2- base) -3- chloro- 1h- pyrrole
The chloro- 6- of azoles -5- formyl -2- methyl -4- (2- ((n- cyano methyl sulfilimine base) ethyl) amido formacyl) aniline, 1- (3- chlorine
Pyridine -2- base) the chloro- 6- of -3- chloro- 1h- pyrazoles -5- formyl -2- methyl -4- (2- ((the n- cyano methyl sulfilimine base) tert-butyl group)
Amido formacyl) aniline, bromo- 6- (2- ((the n- cyanogen of 1- (3- chloropyridine -2- base) -3- chloro- 1h- pyrazoles -5- formyl -2- methyl -4-
Ylmethyl sulfilimine base) ethyl) amido formacyl) aniline, 1- (3- chloropyridine -2- base) -3- chloro- 1h- pyrazoles -5- formyl -2-
The bromo- 6- of methyl -4- (2- ((the n- cyano methyl sulfilimine base) tert-butyl group) amido formacyl) aniline, 1- (3- chloropyridine -2- base) -
The chloro- 6- of 3- bromo- 1h- pyrazoles -5- formyl -2- methyl -4- (2- ((n- cyano methyl sulfilimine base) ethyl) amido formacyl) benzene
Amine, chloro- 6- (2- ((the n- cyano methyl sulfilimine of 1- (3- chloropyridine -2- base) -3- bromo- 1h- pyrazoles -5- formyl -2- methyl -4-
Base) tert-butyl group) amido formacyl) aniline, 1- (3- chloropyridine -2- base) -3- bromo- 1h- pyrazoles -5- formyl -2- methyl -4- be bromo-
6- (2- ((n- cyano methyl sulfilimine base) ethyl) amido formacyl) aniline, 1- (3- chloropyridine -2- base) -3- bromo- 1h- pyrrole
The bromo- 6- of azoles -5- formyl -2- methyl -4- (2- ((the n- cyano methyl sulfilimine base) tert-butyl group) amido formacyl) aniline.
Embodiment 4
1- (3- chloropyridine -2- base) -3- halo -1h- pyrazoles -5- formyl -2- methyl -4- halo -6- (2- ((n- cyano group first
Base sulfoximide base) alkyl) amido formacyl) and aniline ic synthesis
0.17 gram i.e. 1.0 mMs of metachloroperbenzoic acids, 8 milliliters of dmf, ice is added in 50 milliliters of three neck round bottom flasks
Water-bath is cooled to 0 degree Celsius and stirs 10 minutes, then by 0.27 gram i.e. 7 milliliters of aqueous solution one of 2.9 mMs of Anhydrous potassium carbonates
Secondary property adds, and has a large amount of white solids to separate out；By 0.28 gram i.e. 0.5 mM of 1- (3- chlorine pyrrole after 0 degree Celsius of stirring 20 minutes
Pyridine -2- base) -3- halo -1h- pyrazoles -5- formyl -2- methyl -4- halo -6- (2- ((n- cyano methyl sulfilimine base) alkyl)
Amido formacyl) 8 milliliters of dmf solution of aniline ib are added dropwise over, and stirring after 1 hour is quenched reactant liquor in water；Then with 50
Milliliter ethyl acetate extracts three times, organic layer saturated common salt water washing 2 times, and anhydrous magnesium sulfate is dried, and removal of solvent under reduced pressure is residual
Excess purifies to obtain white solid ic through 200～300 mesh silica gel column chromatographies, and eluant, eluent is ethyl acetate, the physical and chemical parameter of ic and knot
Structure parameter is shown 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 be selected from 1- (3- chloropyridine -2- base) -3- chloro- 1h- pyrrole
The chloro- 6- of azoles -5- formyl -2- methyl -4- (2- ((n- cyano methyl sulfoximide base) ethyl) amido formacyl) aniline, 1- (3- chlorine
Pyridine -2- base) the chloro- 6- of -3- chloro- 1h- pyrazoles -5- formyl -2- methyl -4- (2- ((the n- cyano methyl sulfoximide base) tert-butyl group)
Amido formacyl) aniline, bromo- 6- (2- ((the n- cyanogen of 1- (3- chloropyridine -2- base) -3- chloro- 1h- pyrazoles -5- formyl -2- methyl -4-
Ylmethyl sulfoximide base) ethyl) amido formacyl) aniline, 1- (3- chloropyridine -2- base) -3- chloro- 1h- pyrazoles -5- formyl -2-
The bromo- 6- of methyl -4- (2- ((the n- cyano methyl sulfoximide base) tert-butyl group) amido formacyl) aniline, 1- (3- chloropyridine -2- base) -
The chloro- 6- of 3- bromo- 1h- pyrazoles -5- formyl -2- methyl -4- (2- ((n- cyano methyl sulfoximide base) ethyl) amido formacyl) benzene
Amine, chloro- 6- (2- ((the n- cyano methyl sulfoximide of 1- (3- chloropyridine -2- base) -3- bromo- 1h- pyrazoles -5- formyl -2- methyl -4-
Base) tert-butyl group) amido formacyl) aniline, 1- (3- chloropyridine -2- base) -3- bromo- 1h- pyrazoles -5- formyl -2- methyl -4- be bromo-
6- (2- ((n- cyano methyl sulfoximide base) ethyl) amido formacyl) aniline, 1- (3- chloropyridine -2- base) -3- bromo- 1h- pyrrole
The bromo- 6- of azoles -5- formyl -2- methyl -4- (2- ((the n- cyano methyl sulfoximide base) tert-butyl group) amido formacyl) aniline.
Embodiment 5
The desinsection of anthranilic diamides derivative i, ia, ib, ic of sulfone (sulphur) imines of cyano group containing n- of the present invention
Activity
Anthranilic diamides derivative i, ia, ib, ic of sulfone (sulphur) imines of cyano group containing n- of the present invention are to mythimna separata
Insecticidal activity assay the results are shown in Table 2, as shown by data, in 5 mcg/ml, the 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 show excellent mythimna separate, after administration 48 hours, extremely
Rate of dying all reaches 100%, suitable with the activity of positive control medicament cyanogen insect amide.hxw003-10、hxw003-15、mt007-
37-1, hxw003-25 are respectively 40%, 70%, 70%, 60% to the insecticidal activity of mythimna separata.It is significantly higher than other for activity
This 20 kinds of compounds of medicament, have carried out secondary screening with 1.0 mcg/ml and 0.1 mcg/ml to mythimna separata, result shows respectively,
Under 1.0 mcg/ml concentration, the mt007-46-1 of the present invention showed excellent mythimna separate, in administration 48 hours
Afterwards, the death rate reaches 100%, and hxw003-21, hxw003-20, lfy001-8-1, zgn001-14-1 also show preferably
Mythimna separate, administration 48 hours after, the death rate is all more than 40%；Hxw002-45, hxw003-9, hxw003-27 couple
The insecticidal activity of mythimna separata has also reached 20%.And its insecticidal activity of compound mt007-50-1 that cn replaces only has 80%.
Anthranilic diamides derivative i, ia, ib, ic of sulfone (sulphur) imines of cyano group containing n- of the present invention are to pickles
The insecticidal activity assay of moth the results are shown in Table 3, during 200 mcg/ml, all sulfide derivatives, sulfinilimine derivatives and sulfoximide
Derivative has all reached 100% to the activity of diamondback moth, suitable with the insecticidal activity of cyanogen insect amide, thioether, sulfilimine, sulfoximide
Introducing do not affect insecticidal activity；And the activity of the derivative mt007-50-1 that cn replaces only has 75%, therefore, the introducing of halogen
Be conducive to raising and the holding of activity.During 10 mcg/ml, 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.
Activity reach 100%, higher than the 90% of cyanogen insect amide；Therefore, it is equally that the activity of the derivative of halogen substiuted takes better than cn
The activity of the derivative in generation；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, in 200 mcg/ml, the insecticidal activity result of aphid is shown, thioether
Derivative, the derivative of sulfilimine and the derivative of sulfoximide replacing is respectively provided with good killing aphids activity, and cyanogen insect amide is several
There is no killing aphids activity；The compound of the halogen substiuted of the present invention is significantly higher than the methyl substituted chemical combination of fork to the activity of aphid
Thing mt007-50-1.
Systemic activity test result shows, the derivative that thioether replaces has certain systemic activity, the derivative of sulfilimine
There is preferable systemic activity, the derivative of sulfoximide has extraordinary systemic activity, and the systemic activity of all compounds is all high
In the systemic activity of cyanogen insect amide, cyanogen insect amide does not almost have systemic activity.
Embodiment 6
Anthranilic diamides derivative i, ia, ib, ic's of sulfone (sulphur) imines of cyano group containing n- of the present invention is antibacterial
Or bactericidal activity:
The title of frequently seen plants disease fungus of present invention test and code name include 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), these bacterial classifications have good representativeness,
The kind of most of pathogen that field occurs in agricultural production can be represented.Thalli growth rate method measurement result is shown in Table 3, table 3
Show, in 50 mcg/ml, all compounds of present invention synthesis all have different degrees of bactericidal activity, mt007-45-1
Bactericidal activity to as bacterium is higher than 40%；Mt007-45-1 is higher than 40% to the bactericidal activity of gz bacterium；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 are to pp's
Bactericidal activity is 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 are higher than 40% to the bactericidal activity of bc；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 are higher than 40% to the bactericidal activity of ss, and wherein hxw003-24 to the inhibitory activity of ss bacterium is higher than
80%；zgn001-14-1、mt007-44-1、hxw003-9、lfy001-8-1、mt007-46-1、mt007-47-1、mt007-
36-1, mt007-41-1 are higher than 40% to the bactericidal activity of rc；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 sterilization to ps bacterium
Activity is higher than 40%.Therefore this kind of compound shows preferable bactericidal activity.
Embodiment 7
The anthranilic diamides derivative i of sulfone (sulphur) imines of cyano group containing n- of the present invention is prevented and treated with insecticide composition
Application in agricultural and forestry and gardening plant insect pest
Anthranilic diamides derivative i, ia, ib, ic of all sulfone (sulphur) imines of cyano group containing n- of the present invention with
Existing insecticide: chlopyrifos, sub- Nong, Acetamiprid, Affirm (Merck Co.), milbemectin, AVM, pleocidin,
Fenvalerate, esfenvalerate, cypermethrin, effective cypermethrin, Cyhalothrin, decis, Fenpropathrin,
Beta- cyfloxylate, cyfloxylate, lambda- Cyhalothrin, Permanone, permethrin, propylene chrysanthemum
Ester, cyhalothrin, Biphenthrin, Permethrin, ethofenprox, flumethrin, fluvalinate, imidacloprid, Acetamiprid, alkene
Pyridine worm amine, imidaclothiz, thiacloprid, Diacloden, clothianidin, MTI-446, clothianadin, Da Tenan, diflubenzuron, d ichlorbenzuron, Teflubenzuron,
Deinsectization is grand, HEXAFLUMURON, flufenoxuron, pyridine worm are grand, lufenuron, poisonous insect urea, penfluron, noviflumuron are noviflumuron, its cas
Number for 121451-02-3, flucycloxuron, novaluron be Rimon, chlorfluazuron, i.e. { [(3.5- bis- is chloro- for 1- for bay sir6874
4) 4-nitrophenoxy phenyl 3-3- (2- chlorobenzene)-urea }, bay sir-8514 be [1- (4- Trifluoromethoxyphen-l) -3- (2-
Chlorobenzene)-urea], piperazine worm urea, bistrifluron be bistrifluron, furan tebufenozide, tebufenozide, chlorine tebufenozide, methoxy worm acyl
Hydrazine, ring tebufenozide, Rogor, flolimat, DDVP, orthene, Hostathion, quinalphos, pyridaphethione, isazofos, leaf
Cicada dissipates, sevin, Aphox, MTMC, Mobucin, cartap, Bassa, leaf disperse, carbaryl, Benfuracard micro, fourth sulphur
Carbofuran, cartap, fenisobromolate, Hexythiazox, fenpyroximate, pyridaben, clofentezine, propargite, diafenthiuron, Benfuracard micro, pyrrole
Aphid ketone, Envidor, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azacyclotin, Buprofezin, phonamiphos, ethiprole, Cupric sulfate, kill
Worm pair, chlorantraniliprole, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, tebufenpyrad, chlorfenapyr, pyrazinones, second mite
Azoles, tebufenpyrad, any one or two kinds rattled away in young ketone, Nylar, emaricin etc. are applied in combination for preventing and treating agricultural and woods
Industry and gardening plant insect pest；The anthranilic diamides derivative i of sulfone (sulphur) imines of cyano group containing n- of the present invention, ia,
Ib, ic weight/mass percentage composition in the composition is 1%-90%, the adjacent formyl ammonia of sulfone (sulphur) imines of cyano group containing n- of the present invention
The ratio of yl-benzamide derivatives i, ia, ib, ic and above-mentioned insecticide is mass percent 1%: 99% to 99%: 1%；Can
Spray after being directly watered, in the preparation of composition, comprise agriculturally acceptable solvent and emulsifying agent and cosolvent and synergy
Agent etc., the formulation of composition processing is selected from sustained release agent, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid system
Agent, Seed Treatment emulsion, aqueous emulsion, granule, microemulsion, finish, with the seed of coated pesticidal, suspension emulsion, 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, oil bag
Aqueous emulsion, seed treatment, oil in water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog piece, smog
Agent, smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixing dress agent, liquid liquid mixing dress agent, harl agent, solid/
Gu it is mixing dress agent, medicine paint, Seed Treatment liquor, fine granule, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense
Jelly, sprinkle and pour agent, stylus, seed coat agent, poison bait, liniment, fritter poison bait, suspending agent, suspended emulsion, water-soluble granule, solvable
Property dense dose, film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent；Can prevent and treat
Insect pest mainly has red spider, Asiatic migrotory locust, reading room management, Chinese rice grasshopper, Patanga japonica (l.Bol.), single thorn mole cricket, Oriental burmeister, rice Ji
Horse, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian pipe thrips, Trialeurodes vaporariorum Westwood, Bemisia tabaci, rice green leafhopper, green leaf hopper, cotton
Leafhopper, 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, peach
Aphid, kaoliang aphid, radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, san jose scale, wax insect, ceroplastes rubens, Didesmococcus koreanus Borchs, pears net
Stinkbug, banana lace bug, thin corner piece stinkbug, Orius minutus, slender rice bug, paddy fly, niphe elongata, scotinophora lurida, green rice bug, green plant bug, lucerne
Mu fleahopper, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, oriental moth, brown slug moth, thosea siensis, gelechiid, cotton
Pink bollworm, brachmia triannuella, diamondback 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, corn borer, yellow rice borer, Oeobia undalis, rice leaf roller, bar snout moth's larva, lap leaf are wild
Snout moth's larva, dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, pink rice borer, bollworm, ancient cooking vessel point spark, little
Cutworm, big cutworm, yellow cutworm, steal poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, straight burr rice hesperiidae, pelopidas mathias,
Papilio xuthus, Common Mormon, cabbage butterfly, pyrameis indica, a ramie Huang a kind of butterfly harmful to crop plants, beans blister beetle, Venus ground beetle, wrinkle sheath ground beetle, the wheat head
The little buprestid beetle of ground beetle, pleonomus canaliculatus, Agriotes subrittatus Motschulsky, khapra beetle, attagenus piceus, oranges and tangerines, golden edge buprestid beetle, yellow meal worm, black powder
Worm, red flour beetle, confused flour beetle, verdigris different beetle, H. parallela, holotrichia oblita, mulberry borer, longicorn beetle, tangerine are brown
Longicorn, pink neck longicorn, big daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, phyllotreta striolata, Callosobruchus chinensis, pea weevil, broad bean weevil, corn
As, rice weevil, dolerus tritici, pear fruit sawfly, yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm hang 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, melonfly, wheat leaf ash are latent
Fly, Americal rice leaf miner, Soybean stem borer, frit fly, Hylemyia Platura Meigen, onion fly, radish fly, full skirt Exorista civilis, corn borer are strict to post fly, armyworm
Scarce must post the agricultural pests such as fly, forestry pest；Plant in preventing and treating agricultural and forestry and gardening plant insect pest includes paddy, little
Wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, garden pea, broad bean, pea, mung bean, red bean, cotton,
Silkworm and mulberry, peanut, rape, sesame, sunflower, 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, wood
Melon, really, tea, wild vegetables, bamboo shoots, hops, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape.Group
Compound improves the defence capability of plant while desinsection, so that plant is created to disease fungus, bacterium and virus infection
Defence capability.
Embodiment 8
Anthranilic diamides derivative i, ia, ib, ic of sulfone (sulphur) imines of cyano group containing n- of the present invention and mite killing
Application in agent combination preventing and treating agricultural and forestry and gardening plant mite evil
Anthranilic diamides derivative i, ia, ib, ic of sulfone (sulphur) imines of cyano group containing n- of the present invention and agricultural
Upper acceptable auxiliary agent and with selected from azacyclotin, plictran, fenbutatin oxide, three phosphor tins, chlorfenviphos, dimethylvinphos, crotoxyphos,
DDVP, heptenophos, Menite, Azodrin, 2-dichloroethylk dimethyl phosphate, chlopyrifos, Diothyl, imino-formyl chloride sulphur phosphorus, omethoate, dioxathion,
Ethodan, malathion, methacrifos, Phosalone, phoxim, methylpyrimidine sulphur phosphorus, quinalphos, sulfotep, Hostathion, aphid are gone out
Many, isocarbophos, acephatemet, propetamphos, dialifos, phosmet, acrinathrin, Biphenthrin, lambda-cyhalothrin, essence
Gamma cyhalothrin, Fenpropathrin, flucythrinate, flumethrin, taufluvalinate, brofluthrinate, Bifenazate, benzene
Sulphur prestige, Aldicarb, butocarboxim, oxamyl, Talcord, thiofanox, benomyl, sok, carbofuran, carbosulfan, speed
Go out prestige, promacyl, Carzol, single carbonamidine, medimeform, Amitraz, Spanon, Ergol, fenisobromolate, cyflumetofen, go out
Mite quinone, Nissol, flufenoxuron, macro tetrolide, piericidin, thuringiensin, tetranactin, macro tetrolide, AVM, Doramectin
Element, eprinomectin, ivermectin, selamectin, moxidectin, pyrethrin, nicotine, matrine, nimbin, trifoliate jewelvine
Ketone, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, Hexythiazox, Envidor, fluacrypyrim, chlorfenizon, propargite, mite of rattling away
Any one or two kinds of pharmaceutical agent combinations in spirit are prepared into acaricide and are used for preventing and treating agricultural and forestry and gardening plant mite evil；This
Anthranilic diamides derivative i, ia, ib, ic in the composition total of sulfone (sulphur) imines of cyano group containing n- of invention
Weight/mass percentage composition is 1%-90%, the anthranilic diamides derivative i of sulfone (sulphur) imines of cyano group containing n- of the present invention,
The ratio of ia, ib, ic and above-mentioned medicament is mass percent 1%: 99% to 99%: 1%；The formulation of composition processing is selected from slow
Release agent, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, Seed Treatment emulsion, aqueous emulsion, particle
Agent, microemulsion, finish, the seed with coated pesticidal, suspension emulsion, 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, oil-in-water
Emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog piece, smoke agent, smog ball, granular poison bait, foaming agent,
Gu the mixing dress agent of ointment, thermal fog, solid-liquid, liquid liquid mixing dress agent, harl agent, solid/mixing dress agent, medicine paint, Seed Treatment liquid
Agent, fine granule, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle pour agent, stylus, seed coat agent, poison
Bait, liniment, fritter poison bait, suspending agent, suspended emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, tracking powder
Agent, ultra low volume liquids, any one in steam releasing agent；In composition for preventing and controlling agricultural and forestry and gardening plant mite evil
Plant be selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, garden pea, broad bean, pea
Beans, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber
Glue, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, west
Melon, muskmelon, "Hami" melon, pawpaw, really, tea, wild vegetables, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus,
Peach, papaya, orchid, potted landscape；The mite evil that composition is suitable for is phytophagous evil mite, and phytophagous evil mite is tetranychid selected from tetranychid
Section, Tenuipalpidae, furan line mite, the evil mite of Eriophyidae be Panonychus citri belong to, tetranychus telarius belong to and the itch mite of Eriophyidae these are global
Agricultural Mites, forestry harmful mites, gardening evil mite and health evil mite.
Embodiment 9
Anthranilic diamides derivative i, ia, ib, ic of sulfone (sulphur) imines of cyano group containing n- of the present invention and sterilization
Application in agent combination preventing and treating agricultural and forestry and gardening plant disease
Anthranilic diamides derivative i, ia, ib, ic of all sulfone (sulphur) imines of cyano group containing n- of the present invention with
Existing bactericide such as diazosulfide, tiadinil, are abbreviated as tdl, tisocromide, first thiophene lure amine, 4- methyl isophthalic acid, 2,3- thiophenes two
Azoles -5- formic acid, 4- methyl isophthalic acid, 2,3- thiadiazoles -5- sodium formates, 4- methyl isophthalic acid, 2,3- thiadiazoles -5- Ethyl formates, dl- β-ammonia
Base butyric acid, isotianil, its English is general entitled: isotianil, 3,4- bis- chloroisothiazole -5- formic acid, the different thiophene of 3,4- dichloro
Azoles -5- sodium formate, 3,4- bis- chloroisothiazole -5- Ethyl formate, virazole, antofine, Ningnanmycin or salicylic acid, cymoxanil,
Thiram, ziram, Mancozeb, aliette, thiophanate-methyl, Bravo, enemy can pine, procymidone, fenpropidin, methyl Tobe
Tianjin, thiophanate, Metalaxyl-M, flumorph, dimethomorph, mefenoxam, benalaxyl-M, double chlorine zarilamid, flusulfamide, first
Flusulfamide, thiophene fluorine bacterium amine, flutolanil, tecloftalam, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furan
Pyrrole bacterium amine, pyrrole metsulfovax, mandipropamid, zoxamide, fenfuram, carboxin, chlozolinate, iprodione, Fluoxastrobin, ether bacterium
Amine, fluoxastrobin, kresoxim-methyl, SSF 126, orysastrobin, ZEN 90160, pyraclostrobin, trifloxystrobin, Enestroburin, alkene oxime
Bacterium amine, oxygen ring azoles, bromuconazole, Cyproconazole, Difenoconazole, olefin conversion, efficient olefin conversion, epoxiconazole, RH-7592, fluorine quinoline
Azoles, Flusilazole, Flutriafol, hexaconazole, glyoxalin, kind bacterium azoles, metconazole, nitrile bacterium azoles, penconazole, propiconazole, prothioconazoles, silicon
Fluorine azoles, Tebuconazole, tetraconazole, Triadimenol, triticonazole, bitertanol, probenazole, furidazol, imazalil, efficient suppression are mould
Azoles, Prochloraz, fluorine bacterium azoles, cyazofamid, Fenamidone, imidazoles, pefurazoate, cycloheximide triazole, pyridine bacterium azoles, mould clever, white
Spirit, Guardian, Grandox fumigant, octhilinone, benthiozole, dodemorph, butadiene morpholine, tridemorph, fenpiclonil, cough up bacterium
Nitrile, fluazinam, pyrifenox, ring pyridine bacterium amine, Boscalid, fluopicolide, pyridine bacterium amine, cyprodinil, fluorine mepanipyrim, phonetic bacterium
Hydrazone, mepanipyrim, pyrimethanil, Fenarimol, nuarimol, chinomethionat, dithianon, ethoxyquin, oxyquinoline, the third oxygen
Quinoline, quinoxyfen, diethofencarb, iprovalicarb, benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, IBP, pyrazophos,
Tolelofos-methyl, blasticidin-S, kasugarnycin, polyoxin, Polyoxin, valida, jinggangmeisu, streptomysin, metalaxyl,
Furalaxyl, M 9834, ofurace, mebenil, carbendazim, benomyl, thiophanate-methyl, triazolone, bupirimate, diformazan
Phonetic phenol, ethirimol, difoltan, captan, folpet, vinclozolin, fluoromide, dimethachlon, Bravo, Isoprothiolane,
Kitazine, Yekuzuo, pentachloronitrobenzene, Propineb, phosethyl-Al, sulphur, Bordeaux mixture, copper sulphate, copper oxychloride, oxidation
Cuprous, Kocide SD, metrafenone, Pencycuron, diclomezin, Rabcide, pyroquilon, volution bacterium amine, tricyclazole, triforine, many
Fruit pyridine, the pungent salt of biguanides, iminoctadine, botran, benzene flusulfamide, toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, phenyl allyloxy
Thiazole, bronopol, iodomethane, metham-sodium, enemy line ester, dazomet, nemamort, lythidathion, cadusafos, fensulfothion, thionazin,
Fenamiphos, phonamiphos, dichlofenthion, isazofos, fosthietan, oxamyl, Aldicarb, carbofuran, vikane, dichloropropylene, two
Chloroisonicotinic acid, allyl isothiazole etc. are other known any can be applied in combination for preventing as any one in bactericide or two kinds
Control agricultural and forestry and gardening plant disease；The anthranilic diamides of sulfone (sulphur) imines of cyano group containing n- of the present invention spreads out
Biological i, ia, ib, ic total weight/mass percentage composition in the composition is 1%-90%, and the sulfone of the cyano group containing n- (sulphur) of the present invention is sub-
The ratio of anthranilic diamides derivative i, ia, ib, ic of amine and aforementioned bactericide is mass percent 1%: 99%
To 99%: 1%；The prevention effect of composition is good, and these compositions have certain synergistic effect and summation action, does not find have
There is the composition of antagonistic action；Above-mentioned composition can be used for agricultural plant disease and the preventing and treating of gardening plant disease, and preventing and treating is right
As including the Achyla of Oomycete, Aphanomyces, pythium, Phytophthora, Sclerospora, Plasmopara, Pseudoperonospora, Peronospora
Belong to the disease producing Deng more than 20, such as seedling blight of rice, tomato root rot, the late blight of potato, black shank, millet is white
Plurality of cereals crop, industrial crops, the gardening such as powder disease, downy mildew of garpe, downy mildew of lettuce, cucumber downy mildew, cucumber anthracnose
Other diseases of plant and forestry plant etc.；The formulation of composition processing is selected from sustained release agent, pulvis, micro-capsule suspension, can divide
Dispersion liquid body preparation, dispersible solid preparation, Seed Treatment emulsion, aqueous emulsion, granule, microemulsion, finish, with coated pesticidal
Seed, suspension emulsion, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, dispersible dense
Agent, missible oil, electrostatic spray agent, water-in-oil emulsion, seed treatment, oil in water emulsion, smoke candle, granula subtilis, smoke candle, smog
Cylinder, smog rod, smog piece, smoke agent, smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixing dress agent, liquid/
Gu liquid mixing dress agent, harl agent, solid/mixing dress agent, medicine paint, Seed Treatment liquor, fine granule, oil suspending agent, finish, oil-dispersing property
Pulvis, paste, sheet poison bait, dense jelly, sprinkle pour agent, stylus, seed coat agent, poison bait, liniment, fritter poison bait, suspending agent, suspension
In emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, tracking pulvis, ultra low volume liquids, steam releasing agent
Any one.These compositions include cereal for preventing and treating the plant being suitable in agricultural and forestry and gardening plant disease: rice
Paddy, wheat, barley, oat, corn, millet, Chinese sorghum；Tuber crops: sweet potato, potato, cassava；Beans: soybean, broad bean, pea
Beans, mung bean, red bean and fiber: cotton, crudefiber crop, silkworm and mulberry；Oil plant: peanut, rape, sesame, soybean, sunflower；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；Grain
Food crop and fruit, flowers, oil plant, sugar material and cotton, fiber crops, tea, tobacco, Chinese medicine industrial crops and plantation melon, really, tea, silkworm and mulberry,
Vegetables, containing various wild vegetables, bamboo shoots, flowers and ornamental plant, hops, medicinal material, pepper, seedling and other garden crop gardening
Crop such 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, garden pea；Potato, wheat, corn, paddy rice,
Peanut, fruit tree: apple, banana, citrus, peach, papaya；Flowers: orchid；Potted landscape；Composition improves while sterilization
The defence capability of plant, makes plant create the defence capability to disease fungus, bacterium and virus infection.
Embodiment 10
Anthranilic diamides derivative i, ia, ib, ic of sulfone (sulphur) imines of cyano group containing n- of the present invention with disease-resistant
Toxic agent group is combined in the application in preventing and treating agricultural and forestry and gardening plant virus disease
Anthranilic diamides derivative i, ia, ib, ic of sulfone (sulphur) imines of cyano group containing n- of the present invention with existing
Antiphytoviral medicament diazosulfide, tiadinil, be abbreviated as tdl, isotianil, its English general entitled:
Isotianil, 4- methyl isophthalic acid, 2,3- thiadiazoles -5- formic acid, 4- methyl isophthalic acid, 2,3- thiadiazoles -5- sodium formates, 4- methyl isophthalic acid, 2,
3- thiadiazoles -5- Ethyl formate, 3,4- bis- chloroisothiazole -5- formic acid, 3,4- bis- chloroisothiazole -5- sodium formate, 3,4- dichloro are different
Thiazole -5- Ethyl formate, dl- beta-aminobutyric acid, virazole, antofine, Ningnanmycin, tisocromide, first thiophene lure amine or salicylic acid,
In cytosintetidemycin, dichloro-isonicotinic acid, allyl isothiazole, well ridge azanol, jinggangmeisu any 1 or 2 compound groups share in
Preventing and treating agricultural and forestry and gardening plant virus disease；The disease choosing of preventing and treating agricultural and forestry and gardening plant virus disease
From tobacco mosaic virus disease, various melon virosis, various solanberry viroid disease, beans virosis, Cruciferae virosis, grain
Any one of oily crop virosis, cotton virosis and various fruit tree virus disease, wherein endanger serious being selected from: tobacco virus
Sick, peppery pimento virosis, tomato virus disease, Chinese cabbage virus disease, Virus Diseases of Rice include rice dwarf virus disease, BYDV, striped
Leaf blight, fern leaf of tomato viral disease, pepper mosaic virus disease viral disease and tobacco veinal necrosis virus disease, maize dwarf mosaic, cauliflower flower
Any one of mosaic virus, oranges and tangerines virosis, cymbidium mosaic virus, cybidium ring spot virus.These compositions are used for preventing and treating agricultural
It is selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, Ma Ling with the plant of forestry and gardening plant virus disease
Potato, cassava, soybean, garden pea, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower, sweet
Dish, 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 vegetables, bamboo shoots, hops, horse
Bell potato, paddy rice, pepper, apple, banana, citrus, the agricultural such as peach, papaya, orchid, potted landscape, gardening, economy, forestry etc. are planted
Thing；The use of these compositions makes the immunity of crop itself improve, and is producing to insect especially infection insect preventing and treating
Produce the defence capability to viral diseases of plants induction of plant simultaneously；Also direct prevention effect can be produced to virus disease；
Therefore, these compositions can be used for Antiphytoviral medicament and the preparation inducing plant Antiphytoviral medicament and purposes.This
Anthranilic diamides derivative i, ia, ib, ic in the composition total of sulfone (sulphur) imines of cyano group containing n- of invention
Weight/mass percentage composition is 1%-90%, the anthranilic diamides derivative i of sulfone (sulphur) imines of cyano group containing n- of the present invention,
The ratio of ia, ib, ic and aforementioned Antiphytoviral medicament is mass percent 1%: 99% to 99%: 1%；Composition processing
Formulation be selected from sustained release agent, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, Seed Treatment emulsion,
Aqueous emulsion, granule, microemulsion, finish, the seed with coated pesticidal, suspension emulsion, soluble thick agent, poison grain, aerosol, bulk
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 piece, smoke agent, smog ball, granular poison
Solid bait, foaming agent, ointment, thermal fog, solid-liquid mixing dress agent, liquid liquid mixing dress agent, harl agent, solid/mixing fill agent, medicine paint,
Seed Treatment liquor, fine granule, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle pour agent, rod
Agent, seed coat agent, poison bait, liniment, fritter poison bait, suspending agent, suspended emulsion, water-soluble granule, soluble thick agent, film forming oil
Agent, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent；Addition is all shown between these compositions
Or synergistic effect, while keeping insecticidal activity, its antiviral activity is all higher than the effect that any one compound is used alone
Really；Find no the composition of antagonistic action, the drug effect lasting period of composition is long.
Embodiment 11
Anthranilic diamides derivative i, ia, ib, ic of sulfone (sulphur) imines of cyano group containing n- of the present invention with aforementioned
Insecticide, the processing technology of bactericide, anti-plant virus agent and activating plants agent complex preparation and stability
Anthranilic diamides derivative i, ia, ib, ic of sulfone (sulphur) imines of cyano group containing n- of the present invention with aforementioned
Insecticide, the mixture processing technology of bactericide, anti-plant virus agent and activating plants agent are shown in Table 5, from table 5, most of
Medicament all can be processed according to the method for statement, and the main group of liquid preparation is divided into active ingredient and cosolvent and surface to live
Property agent, synergist, antifreeze, stabilizer, other groups such as thickener or bleeding agent grade, the composition of solid pharmaceutical preparation mainly includes
Other agriculturally acceptable adjuvant components such as active ingredient, surfactant and filler, the cold storage test of process preparation,
Liquid preparation places 1 week no Precipitation at 0 ± 2 degree Celsius, and solid pharmaceutical preparation is placed 2 weeks at 54 ± 2 degrees Celsius, and medicament occurs without
Caking phenomenon, all formulations storage place before and after medicament drug effect no significant difference, the resolution ratio of composition active ingredient is 5%
Within, composite preparation qualified stability.
Anthranilic diamides derivative i, ia, ib, ic of sulfone (sulphur) imines of cyano group containing n- of table 2 present invention kill
Worm activity (mythimna separata, the 48h death rate/%)
| 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 | Imidacloprid | 20 | 0 | 0 |
Nd: undetermined.
Anthranilic diamides derivative i, ia, ib, ic of sulfone (sulphur) imines of cyano group containing n- of table 3 present invention kill
Worm activity (the diamondback moth 72h death rate/%；The aphid 48h death rate/%)
The bactericidal activity of anthranilic diamides derivative i, ia, ib, ic of table 4 sulfone (sulphur) imines of cyano group containing n-
(/ %)
| 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 is the measurement result of 50 mcg/ml；As: tomato early blight bacterium (alternaria solani)；Bc: yellow
Melon ash arrhizus bacteria (botrytis cinerea)；Ca: peanut Cercospora bacteria (cercospora arachidicola)；Gz: wheat
Gibberellic hypha (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.
Anthranilic diamides derivative i, ia, ib, ic of n- cyano group sulfone (sulphur) imines of table 5 present invention with aforementioned
The processing method of Insecticidal and acaricidal agent, bactericide and Antiphytoviral pharmacy mix
.
Claims (6)
1. the anthranilic diamides derivative of a class n- cyano group sulfilimine is it is characterised in that have following test number
And chemical constitution:
.
2. the anthranilic diamides derivative i of the sulfilimine of cyano group containing n- described in claim 1 be agriculturally subjected to
Purposes in preparing bactericide for the auxiliary agent.
3. the anthranilic diamides derivative i of the sulfilimine of cyano group containing n- described in claim 1 be agriculturally subjected to
Purposes in preparing insecticide for the auxiliary agent.
4. the anthranilic diamides derivative i of the sulfilimine of cyano group containing n- described in claim 1 and insecticide composition exist
Application in preventing and treating agricultural and forestry and gardening plant insect pest.
5. the anthranilic diamides derivative i acaricide group of the sulfilimine of cyano group containing n- described in claim 1 be combined in anti-
Control the application in agricultural and forestry and gardening plant mite evil.
6. the anthranilic diamides derivative i of the sulfilimine of cyano group containing n- described in claim 1 and antimicrobial combination exist
Application in preventing and treating agricultural and forestry and gardening plant disease.
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| CN201310000509.1A CN103172613B (en) | 2013-01-05 | 2013-01-05 | One class contains anthranilic diamides derivative of N-cyano group sulfone (sulphur) imines and its production and use |
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| Title |
|---|
| Novel diamide insecticides: Sulfoximines, sulfonimidamides and other new sulfonimidoyl derivatives;Christian Gnamm, et al;《Bioorganic & Medicinal Chemistry Letters》;20120412;第22卷;第3800-3806页 * |
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