CN103450154A - Double amide derivative containing sulfur ether and N-sulfur cyano (sulphone) imine structure and replacing pyrazolecarboxamide and preparing method and purpose thereof - Google Patents
Double amide derivative containing sulfur ether and N-sulfur cyano (sulphone) imine structure and replacing pyrazolecarboxamide and preparing method and purpose thereof Download PDFInfo
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- 0 Cc(cc(*)cc1C(N*)=O)c1NC(c1cc(CSC)n[n]1-c(nccc1)c1Cl)=O Chemical compound Cc(cc(*)cc1C(N*)=O)c1NC(c1cc(CSC)n[n]1-c(nccc1)c1Cl)=O 0.000 description 5
- BKRSNZAWNVEGTR-UHFFFAOYSA-N CSCc(cc1C(O)=O)n[n]1-c(nccc1)c1Cl Chemical compound CSCc(cc1C(O)=O)n[n]1-c(nccc1)c1Cl BKRSNZAWNVEGTR-UHFFFAOYSA-N 0.000 description 1
- WNAJXPYVTFYEST-UHFFFAOYSA-N Cc1cccc(C(O)=O)c1N Chemical compound Cc1cccc(C(O)=O)c1N WNAJXPYVTFYEST-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a double amide derivative containing a sulfur ether and N-sulfur cyano (sulphone) imine structure and replacing pyrazolecarboxamide and a preparing method and purpose thereof, and relates to double amide derivatives containing the pyrazolecarboxamide. The double amide derivative containing the pyrazolecarboxamide has a chemical structure general formula as shown in the map I. The structure general formula and the synthetic method of the double amide derivative and the purpose for being used as insecticides, antiseptics, a plant virus resistance agent and a plant activator are disclosed. The double amide derivative containing the sulfur ether and N-sulfur cayano (sulphone) imine structure and replacing the pyrazolecarboxamide can be mixed with auxiliaries or synergists which are acceptable in agriculture to form a processing technology to be used for preparing the insecticides, the antiseptics, the plant virus resistance agent and the plant activator. The invention further discloses the purpose and preparing method of the double amide derivative containing the sulfur ether and N-sulfur cyano (sulphone) imine structure and replacing the pyrazolecarboxamide combining with commodity insecticides, commodity antiseptics, commodity plant virus resistance agents and commodity plant activators to be used for preventing and curing plant diseases, insect pests, virus diseases in agriculture, forestry and horticulture.
Description
Technical field
Technical scheme of the present invention relates to pyrazole compound, specifically relates to as the diamide derivative containing pyrazole heterocycle.
Background technology
In recent years, the bisamide compounds is because of its novel structure, mechanism of action uniqueness, high reactivity, and Mammals is had to the higher characteristics such as security, developed into the novel efficient pesticides of a class, comprising the phthalic imidine insecticides, represent that medicine is the Flubendiamide (EP1006107) that Japanese agricultural chemicals company finds; The phthalic imidine insecticides, represent chlorantraniliprole (WO03015519) and cyanogen insect amide (WO2004067528) that medicine is the du pont company research and development.Two compounds structure differences; but mechanism of action is all the ryanodine receptor that acts on insect, cause the continuous release of calcium ion in muscle and nervous tissue cell, cause insect muscle constantly to shrink; finally cause death (Gerorge P. Lahm, the Bioorganic& of insect; Medicinal Chemistry, 2009,17:4127-4133).
Although the bisamide insecticides shows outstanding superiority aspect active, some areas are due to frequent excessively dispenser, and insect has showed resistance in various degree, and up to the present the commercial kind number of this insecticides is very limited.The pyridine of sulfone worm is that its mechanism of action is mainly the cholinocepter (Y. M.Zhu, J. Agric.FoodChem.2011,59:2950) that acts on insect by a class sulfimide class broad spectrum pesticide of The Dow Agrosciences, LLC.'s research and development.2012, Syngenta Co.,Ltd was incorporated into the sulfimide structure of sulfone worm pyridine in the structure of bisamide, found that the synthetic target compound of design has good insecticidal activity (Christian Gnamm, Bioorganic& Medicinal Chemistry Letters, 2012,22:3800-3806).Recently, seminar is incorporated into the active substructure unit of sulfimide class in the phthalic imidine skeleton, the bisamide analog derivative that a class has fine insecticidal activity has been synthesized in design, the activity of part of compounds with contrast medicament cyanogen insect amide quite (CN201310000509.1, CN201310000556.6).Experience according to the contriver, we think the characteristics of ryanodine receptor sterilant due to molecule self, its migration in plant materials is subject to certain restrictions, and sulfimide class substructure unit can improve, the activity of bisamide insecticides is considered to because the sulfoximide structure can improve the water-soluble of bisamide, reduced the logP of this analog derivative, make more easily and absorb, can well be evenly distributed in plant materials and soil.In order further to study the ryania compounds of high-efficiency low-toxicity, the present invention utilizes pesticide molecule active fragments splicing principle design to synthesize the substituted pyrazolecarboxylic benzamide type bisamide derivatives of novel Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure of a class, and carried out the bioactive screening of system, to improving the water-soluble of target molecule, improve its upper and lower and lateral migration in plant materials, for the initiative research of novel pesticide provides eco-friendly ultra-high efficiency novel candidate compound.
Summary of the invention
Technical problem to be solved by this invention is: the synthetic method that the substituted pyrazolecarboxylic benzamide type bisamide derivatives of new Sulfide-containing Hindered, sulphur (sulfone) cyanogen imine structure is provided, biological activity and the measuring method thereof of this compounds regulation and control agricultural, gardening and health and forestry plant insect and the phytopathy original are provided, the middle application of these compounds at agriculture field, gardening field, field of forestry and health field is provided simultaneously.
The present invention solves this technical problem adopted technical scheme: the chemical structure of general formula containing pyrazole ring diamide derivative with agriculture field, gardening field, forestry and health field insecticidal activity, fungicidal activity, anti-phytoviral activity, inducing plant generation anti-disease activity, insect growth regulator activity is shown in formula I
Wherein, X is selected from: methylthio group, N-cyano methyl sulfilimine base, N-cyano methyl sulfone imino-; Y is selected from: chlorine, bromine, cyano group; R
1be selected from: methyl, cyclopropyl, cyclohexyl, 5-methylthiazol-2-base.Specifically can be divided into following three kinds of forms:
Wherein, Y is selected from: chlorine, bromine, cyano group; R
1be selected from: methyl, cyclopropyl, cyclohexyl, 5-methylthiazol-2-base.
The pyrazole ring diamide compound IA of containing of the present invention, IB, IC press the method shown in Scheme-1 and synthesize:
X is selected from: methylthio group, N-cyano methyl sulfilimine base, N-cyano methyl sulfone imino-; Y is selected from: chlorine, bromine, cyano group;
R
1be selected from: methyl, cyclopropyl, cyclohexyl, 5-methylthiazol-2-base
Scheme-1 is containing pyrazole ring diamide compound I synthetic route
Specifically be divided into following steps:
A. replace the preparation of benzoxazine IV:
Add 15 milliliters of acetonitriles, 1.0 mmole 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-formic acid II, 5 mmole Methanesulfonyl chlorides in 50 milliliters of round-bottomed flasks, be abbreviated as MsCl, 5 mmole pyridines, be abbreviated as Py, be cooled to-5 degrees centigrade, stir after 30 minutes and add 1.0 mmoles to replace anthranilic acid III, slowly rise to after room temperature to stir and spend the night, add 10 ml waters, there is yellow mercury oxide IV to separate out, filter, the washing of gained solid, vacuum-drying, be directly used in next step reaction; Described replacement anthranilic acid III is selected from 3-methyl-5-chloro-2-benzaminic acid, the bromo-2-benzaminic acid of 3-methyl-5-, 3-methyl-5-cyano group-2-benzaminic acid; Described replacement benzoxazine IV is selected from 2-(1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-yl)-chloro-4-oxo of 8-methyl-6--4H-benzo [d] [1,3] oxazines, 2-(1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-yl)-bromo-4-oxo of 8-methyl-6--4H-benzo [d] [1,3] oxazines, 2-(1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-yl)-8-methyl-6-cyano group-4-oxo-4H-benzo [d] [1,3] oxazine.
B. contain the preparation of pyrazole ring diamide compound IA:
In 50 milliliters of round-bottomed flasks, add 1.0 mmoles to replace benzoxazine IV, 20 milliliters of tetrahydrofuran (THF)s, be abbreviated as the replacement amine of THF, 4.0 mmoles, reaction conditions is determined according to the character that replaces amine, under methylamine, cyclopropylamine, hexahydroaniline room temperature condition, about stirring reaction 2-4 hour, 5-methyl-2-amino-thiazole reacts about 4 hours under the reflux condition; After having reacted, concentrating under reduced pressure is except desolventizing, the gained resistates is through 200～300 order purification by silica gel column chromatography, the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate, volume ratio is 3: 1, obtains yellow or white solid, is containing pyrazole ring diamide compound IA, with gained sterling calculated yield, yield 75-90%; The amount of synthetic compound enlarges or dwindles by corresponding proportion; The volume of respective reaction container enlarges in proportion or dwindles.The described pyrazole ring diamide compound IA that contains is selected from:
1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-chloro-phenyl-)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-methyl-carbamoyl-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-cyclopropyl amino formyl radical-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-cyclohexylamino formyl radical-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-methyl-carbamoyl-4-cyano-phenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-cyclopropyl amino formyl radical-4-cyano-phenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-cyano-phenyl)-1H-pyrazoles-5-methane amide.
C. contain the preparation of pyrazole ring diamide compound IB:
In 50 milliliters of round-bottomed flasks, add 1.0 mmoles containing pyrazole ring diamide compound IA, 15 milliliters of tetrahydrofuran (THF)s, ice-water bath is cooled to 0 degree centigrade.Then add respectively 2.0 mmole cyanamides and 1.1 mmole acetic acid iodobenzenes, stir stirred overnight at room temperature after 3 hours at this temperature, the 2nd day by the direct removal of solvent under reduced pressure of reaction solution, resistates obtains faint yellow or white solid through 200～300 order purification by silica gel column chromatography, eluent is ethyl acetate: methyl alcohol, and volume ratio is 20: 1, is containing pyrazole ring diamide compound IB, with gained sterling calculated yield, yield 70-90%.The amount of synthetic compound enlarges or dwindles by corresponding proportion; The volume of respective reaction container enlarges in proportion or dwindles.The described pyrazole ring diamide compound IB that contains is selected from: 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-methyl-carbamoyl-4-chloro-phenyl-)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-cyclopropyl amino formyl radical-4-chloro-phenyl-)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-chloro-phenyl-)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-methyl-carbamoyl-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-cyclopropyl amino formyl radical-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-methyl-carbamoyl-4-cyano-phenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-cyclopropyl amino formyl radical-4-cyano-phenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-cyano-phenyl)-1H-pyrazoles-5-methane amide.
D. contain the preparation of pyrazole ring diamide compound IC:
Add 2.0 mmole metachloroperbenzoic acids in 50 milliliters of round-bottomed flasks, write a Chinese character in simplified form m-CPBA, 10 ml methanol, ice-water bath is cooled to 0 degree centigrade and stirs 10 minutes, then 10 ml water solution of 3.0 mmole Anhydrous potassium carbonates is splashed in reaction system, has a large amount of white solids to separate out.0 degree centigrade is stirred the 10 ml methanol solution that after 20 minutes, 1.0 mmoles contained to pyrazole ring diamide compound IB and dropwise adds, after dropwising, stir 2 hours, after the TLC monitoring reaction completes, removal of solvent under reduced pressure methyl alcohol, 60 milliliters of ethyl acetate extractions three times for residuum, merge organic layer, with saturated common salt water washing 2 times, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, resistates obtains white solid through 200～300 order purification by silica gel column chromatography, be containing the pyrazole ring diamide compound, the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate, difference according to product, volume ratio is between 1: 1～1: 3, obtain white solid IC, with gained sterling calculated yield, yield 50-80%.The amount of synthetic compound enlarges or dwindles by corresponding proportion; The volume of respective reaction container enlarges in proportion or dwindles.The described pyrazole ring diamide compound IC that contains is selected from: 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-methyl-carbamoyl-4-chloro-phenyl-)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-cyclopropyl amino formyl radical-4-chloro-phenyl-)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfone sulfilimine methylene)-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-chloro-phenyl-)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-methyl-carbamoyl-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-cyclopropyl amino formyl radical-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-methyl-carbamoyl-4-cyano-phenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-cyclopropyl amino formyl radical-4-cyano-phenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-cyano-phenyl)-1H-pyrazoles-5-methane amide.
It is synthetic that 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-formic acid II presses the method shown in Scheme-2:
The synthetic route of Scheme-2 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-formic acid II
E.2, the preparation of 2-dimethyl-4-chloromethyl-DOX V:
In 1000 milliliters of round-bottomed flasks, add successively 350 milliliters of acetone, 2.58 gram tosic acid, write a Chinese character in simplified form into p-TsO hour, after stirring and dissolving, splash into 37.82 milliliters of 1-glycerin chlorohydrins, dropwise rear stirring at room reaction 12 hours, add triethylamine to regulate pH to neutral, then acetone is removed in air distillation, the cut of 46-48 degree centigrade/1.7kPa is collected in underpressure distillation, obtain colourless transparent liquid, gained sterling calculated yield, obtain 65.36%.Synthetic 2,2-dimethyl-4-chloromethyl-1, the amount of 3-dioxolanes V enlarges or dwindles by corresponding proportion; The volume of respective reaction container enlarges in proportion or dwindles.
F.2, the preparation of 2-dimethyl-4-methylene radical-DOX VI:
In 500 milliliters of round-bottomed flasks; add successively 22.35 gram potassium tert.-butoxides, 300 milliliters of anhydrous tetrahydro furans; nitrogen protection drops to 0 degree centigrade, then splashes into 20 grams 2,2-dimethyl-4-chloromethyl-1; 3-dioxolane V; be warming up to stirring at room reaction 12 hours after dropwising, filter a small amount of washed with dichloromethane of filter cake; remove filter cake, filtrate is directly used in next step reaction.The amount of synthetic 2,2-dimethyl-4-methylene radical-DOX VI enlarges or dwindles by corresponding proportion; The volume of respective reaction container enlarges in proportion or dwindles.
G.3-(2,2-dimethyl-1,3-dioxy cyclopentyl-4-thiazolinyl)-ethyl 2-oxopropanoate VII's is synthetic
In 1000 milliliters of round-bottomed flasks, add previous step gained filtrate, then add 23.14 gram pyridines, condition of ice bath drops to 0 degree centigrade, then slowly drip the dichloromethane solution of 36.32 gram ethyl oxalyl chlorides, after dropwising, continue stirring reaction 4 hours under ice bath, after the TLC monitoring reaction completes, splash into 20 ml waters, then use 150 milliliters of dichloromethane extractions three times, merge organic layer, with saturated sodium-chloride, wash, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, resistates is through 200～300 order purification by silica gel column chromatography, obtain the reddish-brown thick liquid, eluent is sherwood oil: the ethyl acetate volume ratio is 10: 1.By gained sterling calculated yield, two step total recoverys 85.76%; The amount of synthetic 3-(2,2-dimethyl-1,3-dioxy cyclopentyl-4-thiazolinyl)-ethyl 2-oxopropanoate VII enlarges or dwindles by corresponding proportion; The volume of respective reaction container enlarges in proportion or dwindles.
H.1-(3-chloropyridine-2-yl)-3-methylol-1H-pyrazole-5-ethyl formate VIII's is synthetic
In 500 milliliters of round-bottomed flasks, add successively 12.95 gram 3-(2, 2-dimethyl-1, 3-dioxy cyclopentyl-4-thiazolinyl)-ethyl 2-oxopropanoate VII, 250 milliliters of ethanol, add 8.68 gram 3-chloride-2-hydrazinopyridines after stirring and dissolving, stirring at room reaction 6 hours, after the TLC monitoring reaction completes, drip 36.5% concentrated hydrochloric acid in system, regulate the pH=3 left and right, then removal of solvent under reduced pressure ethanol, residuum adds ethyl acetate and water, get ethyl acetate layer, 150 milliliters of ethyl acetate extractions three times for water layer, merge organic layer, with saturated nacl aqueous solution, wash, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, resistates is through 200～300 order purification by silica gel column chromatography, obtain white solid, eluent is sherwood oil: the ethyl acetate volume ratio is 2: 1.With gained sterling calculated yield, yield 57.83%.The amount of synthetic 1-(3-chloropyridine-2-yl)-3-methylol-1H-pyrazole-5-ethyl formate VIII compound enlarges or dwindles by corresponding proportion; The volume of respective reaction container enlarges in proportion or dwindles.
I.1-(3-chloropyridine-2-yl)-3-methanesulfonates methylene radical-1H-pyrazole-5-ethyl formate IX's is synthetic
In 100 milliliters of round-bottomed flasks, add successively 5.13 gram 1-(3-chloropyridine-2-yl)-3-methylol-1H-pyrazole-5-ethyl formate VIII, 2.76 gram triethylamine, 50 milliliters of anhydrous tetrahydro furans, nitrogen protection drops to 0 degree centigrade, then slowly drip 10 milliliters of tetrahydrofuran solutions of 2.50 gram Methanesulfonyl chlorides (writing a Chinese character in simplified form MsCl), dropwise under rear condition of ice bath and continue stirring reaction 2 hours, after the TLC monitoring reaction completes, splash into 20 ml waters, then with 150 milliliters of ethyl acetate extractions three times, merge organic layer, use the saturated nacl aqueous solution washed twice, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, residuum directly drops into next step reaction according to theoretical yield.The amount of synthetic 1-(3-chloropyridine-2-yl)-3-methanesulfonates methylene radical-1H-pyrazole-5-ethyl formate IX enlarges or dwindles by corresponding proportion; The volume of respective reaction container enlarges in proportion or dwindles.
J.1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-IH-pyrazole-5-ethyl formate X's is synthetic
In 100 milliliters of round-bottomed flasks, the residuum of previous step gained is molten in 50 milliliters of acetonitriles, condition of ice bath drops to 0 degree centigrade, then dropwise splash into the 20% sodium methyl mercaptide solution with respect to 1-(3-chloropyridine-2-yl)-3-methanesulfonates methylene radical-1H-pyrazole-5-ethyl formate IX theoretical yield molar weight 1.5 equivalents under condition of ice bath, rise to stirring at room reaction 3h after dropwising.After the TLC monitoring reaction completes, removal of solvent under reduced pressure acetonitrile, ethyl acetate and water dissolution for residuum, get ethyl acetate layer, 120 milliliters of ethyl acetate extractions three times for water layer, merge organic phase, uses the saturated nacl aqueous solution washed twice, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, resistates, through 200～300 order purification by silica gel column chromatography, obtains faint yellow thick liquid, obtain faint yellow solid after static, eluent is sherwood oil: the ethyl acetate volume ratio is 3: 1.By gained sterling calculated yield, two step total recoverys 77.82%.The amount of synthetic 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazole-5-ethyl formate X compound enlarges or dwindles by corresponding proportion; The volume of respective reaction container enlarges in proportion or dwindles.
K.1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-formic acid II's is synthetic
In 100 milliliters of round-bottomed flasks, by 3.85 gram 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazole-5-ethyl formate X is molten in 20 ml methanol, then 0.74 gram sodium hydrate solid particle is molten in 10 ml methanol, at ambient temperature, by the methanol solution of sodium hydroxide, dropwise splash in reaction system, after dropwising, stirring at room reaction 6 hours, after the TLC monitoring reaction completes, removal of solvent under reduced pressure methyl alcohol, the a small amount of water dissolution of residuum, then with 60 milliliters of ether washings three times, the water intaking layer, regulate the pH=4 left and right with dilute hydrochloric acid, there is solid to wash out, filter, the filter cake washing, the dry product that obtains.With gained sterling calculated yield, yield 89.07%.The amount of synthetic 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-formic acid II compound enlarges or dwindles by corresponding proportion; The volume of respective reaction container enlarges in proportion or dwindles.
It is synthetic that the 3-chloride-2-hydrazinopyridine is pressed the method shown in Scheme-3:
The synthetic method of Scheme-3 3-chloride-2-hydrazinopyridine
L.3-the preparation of chloride-2-hydrazinopyridine:
In 500 milliliters of round-bottomed flasks, add successively 50 grams 2, the hydrazine hydrate of 3-dichloropyridine, 150 milliliters of ethanol, 127 grams 80%, reflux stirs 26 hours, after the TLC monitoring reaction is complete, reaction system is down to room temperature, filter filter cake washing, the dry needle-like white crystal that obtains.With gained sterling calculated yield, yield 90.13%.The amount of synthetic 3-chloride-2-hydrazinopyridine compound enlarges or dwindles by corresponding proportion; The volume of respective reaction container enlarges in proportion or dwindles.
Replacing the anthranilic acid III method shown in Scheme-4 of pressing synthesizes:
Scheme-4 replaces anthranilic acid III synthetic method
Concrete operations are:
M.3-the preparation of methyl-5-chloro (bromine)-2-benzaminic acid:
Add 20 mmole 3-methyl-2-amino phenylformic acid, 50 milliliters of DMF, 30 mmole N-chlorosuccinimides (or N-bromosuccinimide) in 100 milliliters of round-bottomed flasks, after return stirring 3 hours, reaction solution is poured in frozen water, dilute hydrochloric acid is acidified to pH=6, filter, a small amount of ethanol of gained solid is washed, and obtains gray solid chloro or bromo anthranilic acid III, with gained sterling calculated yield, yield 83%; The amount of synthetic chloro or bromo anthranilic acid III enlarges or dwindles by corresponding proportion; The volume of respective reaction container enlarges in proportion or dwindles.Y is selected from: chlorine, bromine.
N.3-the preparation of methyl-5-cyano group-2-benzaminic acid:
In 250 milliliters of round-bottomed flasks, add successively the bromo-2-benzaminic acid of 15 gram 3-methyl-5-, 1.08 gram potassiumiodides, 8.76 gram cuprous cyanides, 100 milliliters of DMF, reflux stirs 12 hours, after the TLC monitoring reaction completes, reaction system is poured in 500 milliliters of frozen water, added 15 milliliters of quadrols, stir after 10 minutes and filter, remove filter cake, filtrate is acidified to the pH=4 left and right with dilute hydrochloric acid, has solid to separate out, and filters, the filter cake washing, the dry product that obtains.With gained sterling calculated yield, yield 52.24%; The amount of synthetic 3-methyl-5-cyano group anthranilic acid III enlarges or dwindles by corresponding proportion; The volume of respective reaction container enlarges in proportion or dwindles.
O. the mensuration of the substituted pyrazolecarboxylic benzamide type bisamide derivatives I of Sulfide-containing Hindered of the present invention, N-cyano group sulphur or sulfoximide structure to the mythimna separata insecticidal activity:
The substituted pyrazolecarboxylic benzamide type bisamide derivatives I of Sulfide-containing Hindered of the present invention, N-cyano group sulphur or sulfoximide structure is as follows to the screening method of mythimna separata insecticidal activity: adopt the blade medicine embrane method; The solution that sample to be tested is mixed with 5 ug/ml carries out, get former medicine sample and first use a small amount of acetone solution, then, with 0.5 ‰ Triton-100 aqueous solution dilutions, the 0.5%Triton-100 aqueous solution is contrast, each concentration repeats for 2 times, 10 examination worms of each re-treatment; Get fresh free of contamination maize leaf, soaked for 10 seconds in liquid, after indoor drying (approximately 2 hours), put into the culture dish of 9 centimetres of diameters, mythimna separata 3 instar larvaes that access size respectively is basically identical, tighten and be placed in mythimna separata constant temperature insectary with bungee, check result after 72 hours, touch polypide with little writing brush or tweezers, can not coordinated movement as death; With cyanogen insect amide, the positive contrast of Provado.
P. the mensuration of the substituted pyrazolecarboxylic benzamide type bisamide derivatives I of Sulfide-containing Hindered of the present invention, N-cyano group sulphur or sulfoximide structure to the pathogenic fungi fungicidal activity:
Sulfide-containing Hindered of the present invention, the substituted pyrazolecarboxylic benzamide type bisamide derivatives I sterilization of N-cyano group sulphur or sulfoximide structure or bacteriostatic activity adopt thalli growth rate assay method, detailed process is: get 5 milligrams of sample dissolution in appropriate dimethyl formamide, then with containing the medicament that a certain amount of polysorbas20 emulsifier aqueous solution is diluted to 500 ug/ml, reagent agent is respectively drawn under aseptic condition in 1 milliliter of injection culture dish, add respectively again 9 milliliters of substratum, make 50 ug/ml pastille flat boards after shaking up, do blank with the flat board that adds 1 milliliter of aqua sterilisa, cut the bacterium dish with the punch tool of 4 millimeters of diameters along the mycelia outer rim, move on the pastille flat board, being equilateral triangle puts, every processing repeats 3 times, culture dish is placed in 24 ± 1 degrees centigrade of constant incubators and cultivates, colony diameter to be contrasted expands to 2-3 centimetre of " Invest, Then Investigate " and respectively processes bacterium dish expansion diameter, average, relatively calculate relative bacteriostasis rate with blank, the kind that comprises multiple representative majority of plant pathogenic bacteria of the actual generation in field in China's agriculture production for the examination bacterial classification, its title and code name comprise AS: tomato early blight bacterium (Alternaria solani), BC: botrytis cinerea pers (Botrytis cinerea), CA: peanut Cercospora bacteria (Cercospora arachidicola), GZ: fusarium graminearum (Gibberella zeae), PI: phytophthora infestans (Phytophthora infestans (Mont.) de Bary), PP: Botryosphaeria berengeriana f. sp (Physalospora piricola), PS: Rhizoctonia solani Kuhn (Pellicularia sasakii), RC: Rhizoctonia cerealis (Rhizoctonia cerealis), SS: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum).
The invention has the beneficial effects as follows: the present invention has carried out the optimization of guide structure to substituted pyrazolecarboxylic benzamide type bisamide derivatives IA, IB, the IC of Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure, and synthetic new compound has been carried out to desinsection, antibacterial and the mensuration of inducing anti-disease activity and the research that mixes use, this compounds can be used for disease, insect pest and the virus disease control in agriculture field, field of forestry, gardening field.
The present invention will be by specific preparation and biological activity determination and be the embodiment substituted pyrazolecarboxylic benzamide type bisamide derivatives I that more specifically describes Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure with formulation that commercially available agricultural chemical is used in combination complete processing and selection synthetic and biological activity and application thereof, but described embodiment is unrestricted the present invention for specific description the present invention only, especially its biological activity and complete processing only illustrate, and unrestricted this patent, embodiment is as follows:
Embodiment 13-methyl-5-replacement-2-benzaminic acid III's is synthetic:
(1) 3-methyl-5-chloro (bromine)-2-benzaminic acid is synthetic
Add 20 mmole 3-methyl-2-amino phenylformic acid, 50 milliliters of DMF, 30 mmole N-chlorosuccinimides (or N-bromosuccinimide) in 100 milliliters of round-bottomed flasks, after return stirring 3 hours, reaction solution is poured in frozen water, dilute hydrochloric acid is acidified to pH=6, filter, the a small amount of ethanol of gained solid is washed, and obtains gray solid chloro or bromo anthranilic acid III, yield 83%.Y is selected from: chlorine, bromine.Wherein, 3-methyl-5-chloro-2-benzaminic acid
1h NMR (400MHz, DMS0-d
6): δ: 7.56 (d, 1H), 7.23 (d, 1H), 2.11 (s, 3H); The bromo-2-benzaminic acid of 3-methyl-5-
1h NMR (400MHz, DMSO-d
6): δ: 7.88 (s, 1H), 7.45 (s, 1H), 2.08 (s, 3H).
(2) 3-methyl-5-cyano group-2-benzaminic acid is synthetic
In 250 milliliters of round-bottomed flasks, add successively the bromo-2-benzaminic acid of 15 gram 3-methyl-5-, 1.08 gram potassiumiodides, 8.76 gram cuprous cyanides, 100 milliliters of DMF, reflux stirs 12 hours, after the TLC monitoring reaction completes, reaction system is poured in 500 milliliters of frozen water, added 15 milliliters of quadrols, stir after 10 minutes and filter, remove filter cake, filtrate is acidified to the pH=4 left and right with dilute hydrochloric acid, has solid to separate out, filter, the filter cake washing, dry product, the yield 52.24% of obtaining.
Synthesizing of embodiment 23-chloride-2-hydrazinopyridine
In 500 milliliters of round-bottomed flasks, add successively 50 grams 2, the hydrazine hydrate of 3-dichloropyridine, 150 milliliters of ethanol, 127 grams 80%, reflux stirs 26 hours, the TLC monitoring reaction fully after, reaction system is down to room temperature, there is solid to separate out, filter, the filter cake washing, dry needle-like white crystal, the yield 90.13% of obtaining.
The preparation of embodiment 31-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-substituted-amino formyl radical-4-substituted-phenyl)-1H-pyrazoles-5-methane amide
(1) 2,2-dimethyl-4-chloromethyl-DOX V's is synthetic
In 1000 milliliters of round-bottomed flasks, add successively 350 milliliters of acetone, 2.58 gram tosic acid, write a Chinese character in simplified form into p-TsO hour, after stirring and dissolving, splash into 37.82 milliliters of 1-glycerin chlorohydrins, dropwise rear stirring at room reaction 12 hours, add triethylamine to regulate pH to neutral, then acetone is removed in air distillation, and the cut of 46-48 degree centigrade/1.7kPa is collected in underpressure distillation, obtain colourless transparent liquid, yield 65.36%;
1h NMR (400MHz, CDCl
3) δ 4.27-4.32 (m, 1H), 4.08-4.13 (m, 1H), 3.86-3.90 (m, 1H), 3.55-3.60 (m, 1H), 3.43-3.49 (m, 1H), 1.43 (s, 1H), 1.35 (s, 1H).
(2) 2,2-dimethyl-4-methylene radical-DOX VI's is synthetic
In 500 milliliters of round-bottomed flasks; add successively 22.35 gram potassium tert.-butoxides, 300 milliliters of anhydrous tetrahydro furans; nitrogen protection drops to 0 degree centigrade, then splashes into 20 grams 2,2-dimethyl-4-chloromethyl-1; 3-dioxolane V; be warming up to stirring at room reaction 12 hours after dropwising, filter a small amount of washed with dichloromethane of filter cake; remove filter cake, filtrate is directly used in next step reaction.
(3) 3-(2,2-dimethyl-1,3-dioxy cyclopentyl-4-thiazolinyl)-ethyl 2-oxopropanoate VII's is synthetic
In 1000 milliliters of round-bottomed flasks, add previous step gained filtrate, then add with respect to previous step compound VI theoretical yield molar weight 2.2 equivalents, i.e. 23.14 gram pyridines, condition of ice bath drops to 0 degree centigrade, then slowly drip with respect to previous step compound VI theoretical yield molar weight 2 equivalents, the i.e. dichloromethane solution of 36.32 gram ethyl oxalyl chlorides, after dropwising, continue stirring reaction 4 hours under condition of ice bath, after the TLC monitoring reaction completes, splash into 20 ml waters, then use 150 milliliters of dichloromethane extractions three times, merge organic layer, with saturated sodium-chloride, wash, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, resistates is through 200～300 order purification by silica gel column chromatography, obtain the reddish-brown thick liquid, eluent is sherwood oil: the ethyl acetate volume ratio is 10: 1, two step total recoverys 85.76%, 3-(2,2-dimethyl-1,3-dioxy cyclopentyl-4-thiazolinyl)-ethyl 2-oxopropanoate VII wherein
1h NMR (400MHz, CDCl3) δ: 6.40 (s, 1H), 5.02 (s, 2H), 4.24 (q, 2H), 1.48 (s, 6H), 1.29 (t, 3H).
(4) 1-(3-chloropyridine-2-yl)-3-hydroxy methylene-1H-pyrazole-5-ethyl formate VIII's is synthetic
In 500 milliliters of round-bottomed flasks, add successively 12.95 gram 3-(2, 2-dimethyl-1, 3-dioxy cyclopentyl-4-thiazolinyl)-ethyl 2-oxopropanoate VII, 250 milliliters of ethanol, add 8.68 gram 3-chloride-2-hydrazinopyridines after stirring and dissolving, stirring at room reaction 6 hours, after the TLC monitoring reaction completes, drip 36.5% concentrated hydrochloric acid in system, regulate the pH=3 left and right, then removal of solvent under reduced pressure ethanol, residuum adds ethyl acetate and water, get ethyl acetate layer, 150 milliliters of ethyl acetate extractions three times for water layer, merge organic layer, use the saturated nacl aqueous solution washed twice, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, resistates is through 200～300 order purification by silica gel column chromatography, obtain white solid, eluent is sherwood oil: the ethyl acetate volume ratio is 2: 1, total recovery 57.83%, its nuclear magnetic data
1h NMR (400MHz, CDCl3) δ: 8.51 (dd, 1H), 7.91 (dd, 1H), 7.43 (dd, 1H), 7.06 (s, 1H), 4.77 (s, 2H), 4.22 (q, 2H), 2.70 (br, 1H), 1.21 (t, 3H).
(5) 1-(3-chloropyridine-2-yl)-3-methanesulfonate ester methylene radical-1H-pyrazole-5-ethyl formate IX's is synthetic
In 100 milliliters of round-bottomed flasks, add successively 5.13 gram 1-(3-chloropyridine-2-yl)-3-hydroxy methylene-1H-pyrazole-5-ethyl formate VIII, 2.76 gram triethylamine, 50 milliliters of anhydrous tetrahydro furans, nitrogen protection drops to 0 degree centigrade, then slowly drip 10 milliliters of tetrahydrofuran solutions of 2.50 gram Methanesulfonyl chlorides (writing a Chinese character in simplified form MsCl), dropwise under rear condition of ice bath and continue stirring reaction 2 hours, after the TLC monitoring reaction completes, splash into 20 ml waters, then with 150 milliliters of ethyl acetate extractions three times, merge organic layer, use the saturated nacl aqueous solution washed twice, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, residuum directly drops into next step reaction according to theoretical yield.
(6) 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazole-5-ethyl formate X's is synthetic
In 100 milliliters of round-bottomed flasks, the residuum of previous step gained is molten in 50 milliliters of acetonitriles, condition of ice bath drops to 0 degree centigrade, then dropwise splash into the 20% sodium methyl mercaptide solution with respect to 1-(3-chloropyridine-2-yl)-3-methanesulfonate ester methylene radical-1H-pyrazole-5-ethyl formate IX theoretical yield molar weight 1.5 equivalents under condition of ice bath, rise to stirring at room reaction 3h after dropwising.After the TLC monitoring reaction completes, removal of solvent under reduced pressure acetonitrile, ethyl acetate and water dissolution for residuum, get ethyl acetate layer, 120 milliliters of ethyl acetate extractions three times for water layer, merge organic phase, use the saturated nacl aqueous solution washed twice, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, resistates is through 200～300 order purification by silica gel column chromatography, obtain faint yellow thick liquid, obtain faint yellow solid after static, eluent is sherwood oil: the ethyl acetate volume ratio is 3: 1, two step total recoverys 77.82%; 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazole-5-ethyl formate X wherein
1h NMR (400MHz, CDCl3) δ: 8.52 (dd, 1H), 7.90 (dd, 1H), 7.43 (dd, 1H), 7.06 (s, 1H), 4.22 (q, 2H), 3.77 (s, 2H), 2.09 (s, 3H), 1.22 (t, 3H).
(7) 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-formic acid II's is synthetic
In 100 milliliters of round-bottomed flasks, by 3.85 gram 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazole-5-ethyl formate X is molten in 20 ml methanol, 0.74 gram sodium hydrate solid particle is molten in 10 ml methanol, at room temperature the methanol solution of sodium hydroxide is dropwise splashed into to reaction system, after dropwising, stirring at room reaction 6 hours, after the TLC monitoring reaction is complete, methyl alcohol is removed in decompression, the a small amount of water dissolution of residuum, then with 60 milliliters of ether washings three times, the water intaking layer, regulate the pH=4 left and right with dilute hydrochloric acid, there is solid to wash out, filter, the filter cake washing, the dry product that obtains, yield 89.07%.1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-formic acid II wherein
1h NMR (400MHz, CDCl3) δ: 10.56 (br, 1H), 8.49 (dd, 1H), 7.89 (dd, 1H), 7.41 (dd, 1H), 7.05 (s, 1H), 3.75 (s, 2H), 2.06 (s, 3H).
(8) [1,3] oxazine IV's is synthetic for 2-(1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-yl)-8-methyl-6-replacement-4-oxo-4H-benzo [d]
Add 15 milliliters of acetonitriles, 1.0 mmole 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-formic acid II, 5 mmole Methanesulfonyl chlorides in 50 milliliters of round-bottomed flasks, be abbreviated as MsCl, 5 mmole pyridines, be abbreviated as Py, be cooled to-5 degrees centigrade, stir after 30 minutes and add 1.0 mmoles to replace anthranilic acid III, slowly rise to after room temperature to stir and spend the night, after the TLC monitoring reaction is complete, add 10 ml waters, there is yellow mercury oxide IV to separate out, filter gained solid washing and drying, be directly used in next step reaction; Described replacement anthranilic acid III is selected from 3-methyl-5-chloro-2-benzaminic acid, the bromo-2-benzaminic acid of 3-methyl-5-, 3-methyl-5-cyano group-2-benzaminic acid; Described replacement benzoxazine IV is selected from 2-(1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-yl)-chloro-4-oxo of 8-methyl-6--4H-benzo [d] [1,3] oxazines, 2-(1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-yl)-bromo-4-oxo of 8-methyl-6--4H-benzo [d] [1,3] oxazines, 2-(1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-yl)-8-methyl-6-cyano group-4-oxo-4H-benzo [d] [1,3] oxazine.Wherein, 2-(1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-yl)-chloro-4-oxo of 8-methyl-6--4H-benzo [d] [1,3] oxazine
1h NMR (400MHz, CDCl
3) δ: 8.57 (dd, 1H), 7.95-7.98 (m, 2H), 7.46-7.50 (m, 2H), 7.29 (s, 1H), 3.82 (s, 2H), 2.12 (s, 3H), 1.81 (s, 3H); 2-(1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-yl)-bromo-4-oxo of 8-methyl-6--4H-benzo [d] [1,3] oxazine
1h NMR (400MHz, CDCl
3) δ: 8.57 (dd, 1H), 8.13 (d, 1H), 7.96 (dd, 1H), 7.63 (d, 1H), 7.48 (dd, 1H), 7.29 (s, 1H), 3.82 (s, 2H), 2.12 (s, 3H), 1.80 (s, 3H); 2-(1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-yl)-8-methyl-6-cyano group-4-oxo-4H-benzo [d] [1,3] oxazine
1h NMR (400MHz, DMSO) δ: 8.62 (dd, 1H), 8.36 (d, 1H), 8.33 (dd, 1H), (8.08 d, 1H), 7.74 (dd, 1H), 7.30 (s, 1H), (3.83 s, 2H), 2.08 (s, 3H), 1.73 (s, 3H).
(9) 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-substituted-amino formyl radical-4-substituted-phenyl)-1H-pyrazoles-5-methane amide IA's is synthetic
Add 1.0 mmole 2-(1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-yl)-8-methyl-6-replacement-4-oxo-4H-benzo [d] [1 in 50 milliliters of round-bottomed flasks, 3] oxazine IV, 20 milliliters of tetrahydrofuran (THF)s, be abbreviated as the replacement amine of THF, 4.0 mmoles, reaction conditions is determined according to the character that replaces amine, under methylamine, cyclopropylamine, hexahydroaniline room temperature condition, about stirring reaction 2-4 hour, 5-methyl-2-amino-thiazole reacts about 4 hours under the reflux condition; After having reacted, concentrating under reduced pressure is except desolventizing, and the gained resistates is through 200～300 order purification by silica gel column chromatography, the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate, volume ratio is 3: 1, obtains white solid IA, concrete physical parameter is in Table 1, yield 75-90%; described 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-substituted-amino formyl radical-4-substituted-phenyl)-1H-pyrazoles-5-methane amide IA is selected from: 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-chloro-phenyl-)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-methyl-carbamoyl-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-cyclopropyl amino formyl radical-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-cyclohexylamino formyl radical-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-methyl-carbamoyl-4-cyano-phenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-cyclopropyl amino formyl radical-4-cyano-phenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-cyano-phenyl)-1H-pyrazoles-5-methane amide.The physical and chemical parameter of compound is in Table 1
Embodiment 41-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-substituted-amino formyl radical-4-substituted-phenyl)-1H-pyrazoles-5-methane amide IB's is synthetic
Add 1.0 mmole 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-substituted-amino formyl radical-4-substituted-phenyl)-1H-pyrazoles-5-methane amide IA, 15 milliliters of tetrahydrofuran (THF)s in 50 milliliters of round-bottomed flasks, ice-water bath is cooled to 0 degree centigrade.Then add respectively 2.0 mmole cyanamides and 1.1 mmole acetic acid iodobenzenes, stir stirred overnight at room temperature after 3 hours at this temperature, after the TLC monitoring reaction completes, by the direct removal of solvent under reduced pressure of reaction solution, resistates obtains white solid IB through 200～300 order purification by silica gel column chromatography, and eluent is ethyl acetate: methyl alcohol, and volume ratio is 20: 1, concrete physical parameter is in Table 1, yield 70-90%.Described 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-substituted-amino formyl radical-4-substituted-phenyl)-1H-pyrazoles-5-methane amide IB is selected from: 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-methyl-carbamoyl-4-chloro-phenyl-)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-cyclopropyl amino formyl radical-4-chloro-phenyl-)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-chloro-phenyl-)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-methyl-carbamoyl-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-cyclopropyl amino formyl radical-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-methyl-carbamoyl-4-cyano-phenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-cyclopropyl amino formyl radical-4-cyano-phenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-cyano-phenyl)-1H-pyrazoles-5-methane amide.The physical and chemical parameter of compound is in Table 1
Embodiment 51-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-substituted-amino formyl radical-4-substituted-phenyl)-1H-pyrazoles-5-methane amide IC's is synthetic
Add 2.0 mmole metachloroperbenzoic acids in 50 milliliters of round-bottomed flasks, write a Chinese character in simplified form m-CPBA, 10 ml methanol, ice-water bath is cooled to 0 degree centigrade and stirs 10 minutes, then 10 ml water solution of 3.0 mmole Anhydrous potassium carbonates is splashed in reaction system, has a large amount of white solids to separate out.0 degree centigrade of stirring dropwise added the 10 ml methanol solution of 1.0 mmole 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-substituted-amino formyl radical-4-substituted-phenyl)-1H-pyrazoles-5-methane amide IB after 20 minutes, after dropwising, stir 2 hours, after the TLC monitoring reaction completes, removal of solvent under reduced pressure methyl alcohol, 60 milliliters of ethyl acetate extractions three times for residuum, merge organic layer, with saturated common salt water washing 2 times, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, resistates obtains white solid IC through 200～300 order purification by silica gel column chromatography, the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate, difference according to product, volume ratio is between 1: 1～1: 3, obtain white solid IC, concrete physical parameter is in Table 1, yield 50-80%.Described 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-substituted-amino formyl radical-4-substituted-phenyl)-1H-pyrazoles-5-methane amide IC is selected from: 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-methyl-carbamoyl-4-chloro-phenyl-)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-cyclopropyl amino formyl radical-4-chloro-phenyl-)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfone sulfilimine methylene)-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-chloro-phenyl-)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-methyl-carbamoyl-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-cyclopropyl amino formyl radical-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-methyl-carbamoyl-4-cyano-phenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-cyclopropyl amino formyl radical-4-cyano-phenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-cyano-phenyl)-1H-pyrazoles-5-methane amide.The physical and chemical parameter of compound is in Table 1
Embodiment 6
The substituted pyrazolecarboxylic benzamide type bisamide derivatives I of Sulfide-containing Hindered of the present invention, N-cyano group sulphur or sulfoximide structure and complete processing and the stability of commercially available agricultural chemical compound preparation
Sulfide-containing Hindered of the present invention, the substituted pyrazolecarboxylic benzamide type bisamide derivatives I of N-cyano group sulphur or sulfoximide structure and the mixture complete processing of commercially available agricultural chemical are in Table 2, from table 2, most medicament all can be processed according to the method for statement, the main component of liquid preparation is effective constituent and solubility promoter and tensio-active agent, synergistic agent, antifreezing agent, stablizer, other the component etc. such as thickening material or permeate agent, the composition of solid preparation mainly includes the effect composition, the upper acceptable adjuvant component of other agriculturals such as tensio-active agent and filler, the cold storage test of process preparation, liquid preparation is placed 1 week without Precipitation at 0 ± 2 degree centigrade, solid preparation is placed 2 weeks at 54 ± 2 degrees centigrade, caking phenomenon does not appear in medicament, all preparations store the medicament drug effect of placement front and back without significant difference, the rate of decomposition of composition effective constituent is in 5%, the composite preparation qualified stability.
Embodiment 7
The insecticidal activity of the substituted pyrazolecarboxylic benzamide type bisamide derivatives I of Sulfide-containing Hindered of the present invention, N-cyano group sulphur or sulfoximide structure
The substituted pyrazolecarboxylic benzamide type bisamide derivatives I of Sulfide-containing Hindered of the present invention, N-cyano group sulphur or sulfoximide structure the results are shown in Table 3 to the insecticidal activity assay of mythimna separata, data show when 5 ug/ml, Hxw005-16 of the present invention, Hxw005-10, Hxw005-14, Hxw005-11, Hxw005-23, Hxw005-25, Hxw005-46, Hxw005-44 have shown mythimna separate preferably, but insecticidal effect is not remarkable.
Embodiment 8
Antibacterial or the fungicidal activity of the substituted pyrazolecarboxylic benzamide type bisamide derivatives I of Sulfide-containing Hindered of the present invention, N-cyano group sulphur or sulfoximide structure
Title and the code name of the frequently seen plants pathogenic fungi of the present invention's test comprise AS: tomato early blight bacterium (Alternaria solani); BC: botrytis cinerea pers (Botrytis cinerea); CA: peanut Cercospora bacteria (Cercospora arachidicola); GZ: fusarium graminearum (Gibberella zeae); PI: phytophthora infestans (Phytophthora infestans (Mont.) de Bary); PP: Botryosphaeria berengeriana f. sp (Physalospora piricola); PS: Rhizoctonia solani Kuhn (Pellicularia sasakii); RC: Rhizoctonia cerealis (Rhizoctonia cerealis); SS: Sclerotinia sclerotiorum (sclerotinia sclerotiorum), these bacterial classifications have good representativeness, can represent the kind of most of pathogenic bacteria that in agriculture production, field occurs.Thalli growth rate method measurement result is in Table 4, and table 4 shows, when 50 ug/ml, all compounds that the present invention synthesizes all have fungicidal activity in various degree, hxw006-6 to the fungicidal activity of AS higher than 40%, Hxw005-14 to the fungicidal activity of GZ higher than 40%, Hxw005-18, Hxw006-10, Hxw006-12, Hxw006-16, Hxw005-10, Hxw005-14, Hxw005-11, Hxw005-17, lfy002-14, lfy002-18, lfy002-20, Hxw005-23, Hxw005-25, Hxw005-26, Hxw005-43, Hxw006-9, Hxw005-44, Hxw006-6 to the fungicidal activity of PP higher than 40%, Hxw005-13, Hxw005-18, Hxw005-16, Hxw005-20, Hxw005-10, Hxw005-14, Hxw005-19, Hxw005-1l, Hxw005-17, Hxw005-21, Hxw005-23, Hxw005-25, Hxw005-26, Hxw005-43, Hxw005-46, Hxw005-44, Hxw005-47 to the fungicidal activity of BC higher than 40%, Hxw005-13, Hxw005-18, Hxw005-16, Hxw005-20, Hxw006-10, Hxw006-12, Hxw006-16, Hxw005-10, Hxw005-14, Hxw005-19, Hxw005-11, Hxw005-17, Hxw005-21, lfy002-14, lfy002-20, lfy002-18, Hxw005-23, Hxw005-25, Hxw005-26, Hxw005-43, Hxw005-46, Hxw006-9, Hxw005-44, Hxw005-47, Hxw006-6 to the fungicidal activity of SS higher than 70%, Hxw005-18 wherein, Hxw005-16, Hxw005-20, Hxw006-16, Hxw005-19, Hxw005-17, lfy002-20, lfy002-18, Hxw005-23, Hxw005-25, Hxw005-26, Hxw005-43, Hxw005-44 to the fungicidal activity of SS higher than 90%, Hxw005-13, Hxw005-18, Hxw005-16, Hxw005-20, Hxw006-10, Hxw006-12, Hxw006-16, Hxw005-10, Hxw005-14, Hxw005-19, Hxw005-11, Hxw005-17, Hxw005-21, lfy002-14, lfy002-20, lfy002-18, Hxw005-23, Hxw005-25, Hxw005-26, Hxw005-43, Hxw005-46, Hxw006-9, Hxw005-44, Hxw005-47, Hxw006-6 to the fungicidal activity of RC higher than 50%, Hxw005-13, Hxw005-18, Hxw005-16, Hxw005-20, Hxw006-10, Hxw006-12, Hxw005-10, Hxw005-14, Hxw005-19, Hxw005-11, Hxw005-17, Hxw005-21, lfy002-14, lfy002-20, Hxw005-23, Hxw005-25, Hxw005-26, Hxw005-43, Hxw005-46, Hxw006-9, Hxw005-44, Hxw005-47 to the fungicidal activity of PS higher than 50%.
Embodiment 9
The substituted pyrazolecarboxylic benzamide type bisamide derivatives I of Sulfide-containing Hindered of the present invention, N-cyano group sulphur or sulfoximide structure and insecticide composition are prevented and treated the application in agricultural and forestry and gardening plant insect pest
All Sulfide-containing Hindereds of the present invention of the present invention, substituted pyrazolecarboxylic benzamide type bisamide derivatives I and the existing sterilant of N-cyano group sulphur or sulfoximide structure: Chlorpyrifos 94, the inferior Nong in ground, acetamiprid, Affirm (Merck Co.), milbemectin, Avrmectin, pleocidin, fenvalerate, efficient fenvalerate, Cypermethrin, effective cypermethrin, lambda-cyhalothrin, Deltamethrin, Fenvalerate, the Beta-cyfloxylate, cyfloxylate, the Lambda-lambda-cyhalothrin, Permanone, permethrin, esbiothrin, cyhalothrin, bifenthrin, permethrin, ether chrysanthemum ester, flumethrin, fluvalinate, Provado, acetamiprid, Ti304, imidaclothiz, thiacloprid, Diacloden, clothianidin, MTI-446, clothianadin, Da Tenan, diflubenzuron, young urea goes out, Teflubenzuron, deinsectization is grand, HEXAFLUMURON, flufenoxuron, the pyridine worm is grand, lufenuron, the poisonous insect urea, penfluron, Noviflumuron is noviflumuron, and it is for No. CAS 121451-02-3, flucycloxuron, Novaluron is Rimon, fluorine pyridine urea, Bay sir6874 i.e. { 1-[(3.5-bis-chloro-4) 4-nitrophenoxy phenyl 3-3-(2-chlorobenzene)-urea }, Bay SIR-8514 i.e. [1-(4-Trifluoromethoxyphen-l)-3-(2-chlorobenzene)-urea], piperazine worm urea, Bistrifluron is bistrifluron, furan tebufenozide, the worm hydrazides, chlorine worm hydrazides, methoxyfenozide, ring worm hydrazides, Rogor, omethoate, SD-1750, acephate, triazophos, Resitox, pyridaphenthione, isazofos, Ro 7-5050, SevinCarbaryl, Aphox, meta-tolyl-N-methylcarbamate (MTMC), isoprocarb, cartap, fenobucarb, leaf disperses, carbaryl, benfuracarb, carbosulfan, cartap, bromopropylate, hexythiazox, fenpyroximate, pyridaben, clofentezine, propargite, diafenthiuron, benfuracarb, pymetrozine, spiral shell mite ester, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azocyclotin, Buprofezin, ethoprophos, ethiprole, the desinsection list, disosultap, chlorantraniliprole, Flubendiamide, the fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, tebufenpyrad, bromothalonil, pyrazinones, second mite azoles, tebufenpyrad, the young ketone of rattling away, Nylar, any one in emaricin etc. or two kinds are used in combination, the quality percentage composition of substituted pyrazolecarboxylic benzamide type bisamide derivatives I in composition of Sulfide-containing Hindered of the present invention, N-cyano group sulphur or sulfoximide structure is 1%-90%, and the substituted pyrazolecarboxylic benzamide type bisamide derivatives I of Sulfide-containing Hindered of the present invention, N-cyano group sulphur or sulfoximide structure and the ratio of commercially available agricultural chemical are mass percent 1%: 99% to 99%: 1%, can directly be watered rear spraying, comprise the upper acceptable solvent of agricultural and emulsifying agent and solubility promoter and synergistic agent etc. in its preparation, the formulation of composition processing is selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, the dispersible body preparation, the dispersible solid preparation, seed treatment emulsion, aqueous emulsion, large granula, granule, microemulsion, oil-suspending agent, finish, seed with coated pesticidal, suspended emulsion agent, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, CG/Encapsulated granule, capsule suspension, can disperse dense dose, pulvis, the Waterless Seed Dressing pulvis, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the seed treatment suspension agent, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, large granula, the drift pulvis, granula, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix filling agent, the medicine paint, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, soluble powder, the seed treatment water solube powder, the ultra-low volume suspension agent, tablet, follow the trail of pulvis, ultra low volume liquids, the steam releasing agent, water-dispersible granules, wettable powder, any one in wet-mixing kind water-dispersible powder, the insect pest that can prevent and treat mainly contains red spider, Asiatic migrotory locust, clouding car locust, Chinese rice grasshopper, Patanga japonica (l.Bol.), single thorn mole cricket, the east mole cricket, rice thrips, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian manages thrips, Trialeurodes vaporariorum Westwood, Bemisia tabaci, rice green leafhopper, green leaf hopper, chlorita biguttula, spot clothing plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, the flat angle of sugarcane plant hopper, cotten aphid, green bugs, grain aphid, black peach aphid, kaoliang aphid, radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, san jose scale, wax insect, ceroplastes rubens, Didesmococcus koreanus Borchs, pear lace bug, the banana lace bug, thin corner piece stinkbug, Orius minutus, slender rice bug, paddy fly, niphe elongata, scotinophora lurida, Nezara viridula smaragdula Fabricius., green plant bug, alfalfa plant bug, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, cnidocampa flavescens walker, brown slug moth, thosea siensis, gelechiid, pink bollworm, brachmia triannuella, small cabbage moth, small heart-eating peach worm, eating-core bean worm, small heart-eating peach worm, the apple Spilonota lechriaspis, brown belt length leaf roller, Adoxophyes cyrtosema, striped rice borer, bean-pod borer, Pyrausta nubilalis (Hubern)., yellow rice borer, Oeobia undalis, Cnaphalocrocis medinali(rice leaf roller), the bar snout moth's larva, the wild snout moth's larva of lap leaf, dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, pink rice borer, bollworm, ancient cooking vessel point diamond drill, black cutworm, large cutworm, yellow cutworm, steal poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, the straight burr rice hesperiidae, pelopidas mathias, the oranges and tangerines swallowtail butterfly, Common Mormon, small white, pyrameis indica, the yellow a kind of butterfly harmful to crop plants of ramie, the beans blister beetle, the Venus ground beetle, wrinkle sheath ground beetle, wheat head ground beetle, pleonomus canaliculatus, Agriotes subrittatus Motschulsky, khapra beetle, attagenus piceus, the little buprestid beetle of oranges and tangerines, gold edge buprestid beetle, tenebrio molitor, dark mealworm, red flour beetle, confused flour beetle, the verdigris different beetle, H. parallela, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori, pink neck longicorn, large daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, Phyllotreta striolata, Callosobruchus chinensis, pea weevil, broad bean weevil, sitophilus zea-mais, rice weevil, dolerus tritici, pear fruit sawfly, the yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm is hanged the cocoon ichneumon wasp, bollworm tooth lip ichneumon wasp, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, contarinia tritici, pachydiplosis oryzae, citrus fruit fly, the melon trypetid, the latent fly of wheat leaf ash, Americal rice leaf miner, the black fly of diving of beans stalk, frit fly, plant fly, onion fly, the radish fly, full skirt chases after posts fly, Pyrausta nubilalis (Hubern). is strict posts fly, armyworm lacks Agricultural pests such as must posting fly, forestry pest, gardening pest insect and sanitary insect pest, controlling mode also comprises double controlling simultaneously, the prevention effect of composition is good, and drug effect plays stably, and has certain synergism and summation action, finds not have the composition of antagonistic action, the applicable crop of these compositions comprises paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape.Composition has improved the defence capability of plant in desinsection, makes plant produce the defence capability to pathogenic fungi, bacterium and virus infection.
Embodiment 10
The substituted pyrazolecarboxylic benzamide type bisamide derivatives I of Sulfide-containing Hindered of the present invention, N-cyano group sulphur or sulfoximide structure and sterilant combination prevent and treat the application in agricultural and forestry and gardening plant disease
All Sulfide-containing Hindereds of the present invention of the present invention, the substituted pyrazolecarboxylic benzamide type bisamide derivatives I of N-cyano group sulphur or sulfoximide structure and existing sterilant are as diazosulfide, tiadinil, tisocromide, the first thiophene lures amine, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-sodium formiate, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, the DL-beta-aminobutyric acid, isotianil (isotianil), 3,4-, bis-chloroisothiazoles-5-formic acid, 3,4-, bis-chloroisothiazoles-5-sodium formiate, 3,4-, bis-chloroisothiazoles-5-ethyl formate, virazole, antofine, Ningnanmycin or Whitfield's ointment, frost urea cyanogen, thiram, ziram, zinc manganese ethylenebisdithiocarbamate, phosethyl Al, thiophanate_methyl, m-tetrachlorophthalodinitrile, the enemy can be loose, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, Whitfield's ointment, flumorph, dimethomorph, efficient metaxanin, efficient M 9834, two chlorine zarilamids, flusulfamide, the first flusulfamide, thiophene fluorine bacterium amine, fultolanil, tecloftalam, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, the pyrrole metsulfovax, mandipropamid, zoxamide, fenfuram, carboxin, chlozolinate, RP-26019, Azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, SSF 126, orysastrobin, ZEN 90160, Strobilurin, oxime bacterium ester, enostroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, SN-108266, difenoconazole, alkene azoles alcohol, efficient alkene azoles alcohol, epoxiconazole, RH-7592, fluquinconazole, fluzilazol, flutriafol, own azoles alcohol, imibenconazole, plant the bacterium azoles, metconazole, nitrile bacterium azoles, Topaze, Wocosin 50TK, prothioconazoles, simeconazoles, tebuconazole, tertraconazole, triadimenol, triticonazole, bitertanol, thiabendazole, fuberidazole, imazalil, efficient imazalil, prochloraz, fluorine bacterium azoles, cyazofamid, fenamidone, the Evil imidazoles, pefurazoate, famoxadone, SYP-Z048, hymexazo, the spirit of Evil frost, Guardian, etridiazole, octhilinone, benthiozole, dodemorph, fenpropimorph, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium amine, boscalid amine, fluopicolide, pyridine bacterium amine, cyprodinil, the fluorine mepanipyrim, ferimzone, mepanipyrim, phonetic mould amine, fenarimol, nuarimol, chinomethionate, dithianon, ethoxyquin, hydroxyquinoline, the third oxygen quinoline, benzene oxygen quinoline, the mould prestige of second, iprovalicarb, the benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, iprobenfos, pyrazophos, tolclofosmethyl, miewensu, kasugamycin, polyoxin, Polyoxin, validamycin, jingganmycin, Streptomycin sulphate, metaxanin, furalaxyl, M 9834, ofurace, mebenil, derosal, F-1991, thiophanate_methyl, triazolone, bupirimate, dimethirimol, the phonetic phenol of second, Difolatan, Vancide 89, Phaltan, Vinclozoline, fluoromide, dimetachlone, m-tetrachlorophthalodinitrile, isoprothiolane, Kitazine, bismerthiazol, quintozene, zinc manganese ethylenebisdithiocarbamate, zinc 1,2-propylene bisdithiocarbamate, fosetylaluminium, sulphur, Bordeaux mixture, copper sulfate, copper oxychloride, Red copper oxide, copper hydroxide, metrafenone, pencycuron, diclomezin, phthalide, pyroquilon, volution bacterium amine, tricyclazole, triforine, the pyridine of many fruits, the hot salt of biguanides, iminoctadine, dicloran, the benzene flusulfamide, the toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, methyl iodide, metamsodium, enemy's line ester, dazomet, dichloroisopropyl ether, lythidathion, cadusafos, fensulfothion, thionazin, fenamiphos, ethoprophos, dichlofenthion, isazofos, fosthietan, oxamyl, aldicarb, carbofuran, sulfuryl fluoride, dichloropropylene, dichloro-isonicotinic acid, other known any any one or two kinds that can be used as in sterilant such as allyl isothiazole are used in combination, the total quality percentage composition of substituted pyrazolecarboxylic benzamide type bisamide derivatives I in composition of Sulfide-containing Hindered of the present invention, N-cyano group sulphur or sulfoximide structure is 1%-90%, and the substituted pyrazolecarboxylic benzamide type bisamide derivatives I of Sulfide-containing Hindered of the present invention, N-cyano group sulphur or sulfoximide structure and the ratio of commercially available agricultural chemical are mass percent 1%: 99% to 99%: 1%, the prevention effect of composition is good, and these compositions have certain synergism and summation action, does not find to have the composition of antagonistic action, above-mentioned composition can be for the control of agricultural plants disease and gardening plant disease, controlling object comprises that more than 20 of the Achylas, Aphanomyces, pythium, phytophthora, Sclerospora, Plasmopara, Pseudoperonospora, Peronospora of Oomycete etc. belong to the diseases that produce, as other diseases of plurality of cereals crop, cash crop, gardening plant and the forestry plants such as seedling blight of rice, tomato root maize ear rot, the late blight of potato, black shank, millet Powdery Mildew, downy mildew of garpe, downy mildew of lettuce, cucumber downy mildew, cucumber anthracnose etc., the formulation of composition processing is selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, the dispersible body preparation, the dispersible solid preparation, seed treatment emulsion, aqueous emulsion, large granula, granule, microemulsion, oil-suspending agent, finish, seed with coated pesticidal, suspended emulsion agent, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, CG/Encapsulated granule, capsule suspension, can disperse dense dose, pulvis, the Waterless Seed Dressing pulvis, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the seed treatment suspension agent, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, large granula, the drift pulvis, granula, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix filling agent, the medicine paint, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, soluble powder, the seed treatment water solube powder, the ultra-low volume suspension agent, tablet, follow the trail of pulvis, ultra low volume liquids, the steam releasing agent, water-dispersible granules, wettable powder, any one in wet-mixing kind water-dispersible powder.The applicable crop of these compositions comprises that cereal (comprises paddy, wheat, barley, oat, corn, millet, Chinese sorghum etc.), tuber crops (comprise sweet potato, potato, cassava etc.), beans (comprises soybean, broad bean, pea, mung bean, red bean etc.) and fiber (cotton, crudefiber crop, silkworm and mulberry etc.), oil plant (peanut, rape, sesame, soybean, Sunflower Receptacle etc.), sugar material (beet, sugarcane etc.), beverage (tealeaves, coffee, cocoa etc.), hobby (tobacco leaf etc.), medicinal (ginseng, the bulb of fritillary etc.), the torrid zone (rubber, coconut, oil palm, sisal hemp etc.) food crop and the fruit such as, flowers, oil plant, sugar material and cotton, fiber crops, tea, tobacco, cash crop and the plantation melons such as Chinese medicinal materials, really, tea, silkworm and mulberry, vegetables (containing various wild vegetable etc.), bamboo shoots, flowers and ornamental plant, hops, medicinal material, pepper, the garden crops such as seedling and other garden crops are 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 etc.), melon (watermelon, muskmelon, hami melon, pawpaw etc.), beans (soybean, broad bean, pea-pods etc.), potato, wheat, corn, paddy rice, peanut, fruit tree, (apple, banana, citrus, peach, papaya), flowers (as orchid), potted landscape etc.Composition has improved the defence capability of plant in sterilization, makes plant produce the defence capability to pathogenic fungi, bacterium and virus infection.
Table 2 is of the present invention containing the pyrazole ring diamide derivative I working method mixed with commercially available agricultural chemical
The mythimna separate of the substituted pyrazolecarboxylic benzamide type bisamide derivatives I of table 3 Sulfide-containing Hindered of the present invention, N-cyano group sulphur or sulfoximide structure
| Sequence number | Numbering and concentration 5mg/L | 72h mortality ratio (%) | Sequence number | Numbering and concentration 5mg/L | 72h mortality ratio (%) |
| 1 | Hxw005-13 | 5 | 15 | lfl002-20 | 0 |
| 2 | Hxw005-18 | 0 | 16 | lfy002-18 | 0 |
| 3 | Hxw005-16 | 10 | 17 | Hxw005-23 | 30 |
| 4 | Hxw005-20 | 0 | 18 | Hxw005-25 | 10 |
| 5 | Hxw006-10 | 0 | 19 | Hxw005-26 | 0 |
| 6 | Hxw006-12 | 0 | 20 | Hxw005-43 | 0 |
| 7 | Hxw006-16 | 0 | 21 | Hxw005-46 | 10 |
| 8 | Hxw005-10 | 25 | 22 | Hxw006-9 | 0 |
| 9 | Hxw005-14 | 30 | 23 | Hxw005-44 | 15 |
| 10 | Hxw005-19 | 0 | 24 | Hxw005-47 | 0 |
| 11 | Hxw005-11 | 15 | 25 | Hxw006-6 | 0 |
| 12 | Hxw005-17 | 0 | 26 | Cyanogen insect amide | 100 |
| 13 | Hxw005-21 | 0 | 27 | Provado | 0 |
| 14 | lfy002-14 | 0 | ? | ? | ? |
[0129]the fungicidal activity (/ %) of the substituted pyrazolecarboxylic benzamide type bisamide derivatives I of table 4 Sulfide-containing Hindered of the present invention, N-cyano group sulphur or sulfoximide structure
| Compound number | AS | CA | GZ | PP | BC | SS | RC | PS | PI |
| Hxw005-13 | 24.14 | 12.00 | 11.76 | 37.74 | 64.58 | 84.00 | 67.44 | 56.25 | 29.63 |
| Hxw005-18 | 13.79 | 8.00 | 0 | 45.28 | 56.25 | 94.67 | 60.47 | 54.69 | 25.93 |
| Hxw005-16 | 13.79 | 4.00 | 0 | 30.19 | 54.17 | 90.67 | 60.47 | 54.69 | 25.93 |
| Hxw005-20 | 13.79 | 12.00 | 20.59 | 33.96 | 62.50 | 93.33 | 65.12 | 59.38 | 29.63 |
| Hxw006-10 | 9.52 | 22.22 | 18.18 | 45.45 | 27.59 | 86.57 | 51.72 | 59.04 | 14.81 |
| Hxw006-12 | 19.05 | 22.22 | 21.21 | 49.09 | 34.48 | 88.06 | 65.52 | 57.83 | 22.22 |
| Hxw006-16 | 19.05 | 11.11 | 15.15 | 40.00 | 24.14 | 92.54 | 56.90 | 34.94 | 14.81 |
| Hxw005-10 | 17.24 | 4.00 | 32.35 | 45.28 | 56.25 | 85.33 | 62.79 | 56.25 | 25.93 |
| Hxw005-14 | 13.79 | 4.00 | 58.82 | 49.06 | 52.08 | 69.33 | 65.12 | 57.81 | 29.63 |
| Hxw005-19 | 13.79 | 12.00 | 8.82 | 39.62 | 52.08 | 94.67 | 62.79 | 54.69 | 25.93 |
| Hxw005-11 | 17.24 | 12.00 | 17.65 | 43.40 | 56.25 | 73.33 | 58.14 | 54.69 | 25.93 |
| Hxw005-17 | 17.24 | 16.00 | 14.71 | 41.51 | 54.17 | 97.33 | 60.47 | 56.25 | 29.63 |
| Hxw005-21 | 13.79 | 8.00 | 0 | 39.62 | 56.25 | 88.00 | 58.14 | 53.13 | 25.93 |
| lfy002-14 | 14.29 | 33.33 | 24.24 | 54.55 | 20.69 | 85.07 | 62.07 | 72.29 | 22.22 |
| lfy002-20 | 9.52 | 16.67 | 3.03 | 47.27 | 20.69 | 91.04 | 53.45 | 55.42 | 14.81 |
| lfy002-18 | 14.29 | 11.11 | 12.12 | 43.64 | 31.03 | 94.03 | 63.79 | 49.40 | 18.52 |
| Hxw005-23 | 17.24 | 8.00 | 14.71 | 49.06 | 52.08 | 96.00 | 60.47 | 51.56 | 33.33 |
| Hxw005-25 | 17.24 | 8.00 | 11.76 | 45.28 | 54.17 | 93.33 | 60.47 | 54.69 | 25.93 |
| Hxw005-26 | 13.79 | 12.00 | 0 | 49.06 | 58.33 | 93.33 | 62.79 | 56.25 | 25.93 |
| Hxw005-43 | 10.34 | 8.00 | 23.53 | 47.17 | 54.17 | 92.00 | 67.44 | 57.81 | 22.22 |
| Hxw005-46 | 13.79 | 8.00 | 14.71 | 35.85 | 56.25 | 89.33 | 58.14 | 54.69 | 22.22 |
| Hxw006-9 | 19.05 | 22.22 | 24.24 | 43.64 | 34.48 | 86.57 | 60.34 | 53.01 | 14.81 |
| Hxw005-44 | 17.24 | 4.00 | 0 | 45.28 | 52.08 | 94.67 | 62.79 | 56.25 | 25.93 |
| Hxw005-47 | 31.03 | 12.00 | 2.94 | 39.62 | 52.08 | 82.67 | 69.77 | 64.06 | 29.63 |
| Hxw006-6 | 52.38 | 16.67 | 12.12 | 47.27 | 20.69 | 82.09 | 60.34 | 48.19 | 18.52 |
| Cyanogen insect amide | 24.14 | 24.00 | 11.76 | 45.28 | 70.83 | 86.67 | 62.79 | 62.50 | 29.63 |
| Provado | 20.69 | 8.00 | 29.41 | 35.85 | 54.17 | 84.00 | 60.47 | 59.38 | 25.93 |
The measurement result that data are 50 ug/ml; 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 (Physalosporapiricola); PS: Rhizoctonia solani Kuhn (Pellicularia sasakii); RC: Rhizoctonia cerealis (Rhizoctonia cerealis); SS: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum); ND: undetermined.
Claims (10)
1. the substituted pyrazolecarboxylic benzamide type bisamide of a class Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure is characterized in that having the chemical structure of general formula suc as formula shown in I:
Wherein, X is selected from: methylthio group, N-cyano methyl sulfilimine base, N-cyano methyl sulfone imino-; Y is selected from: chlorine, bromine, cyano group; R
1be selected from: methyl, cyclopropyl, cyclohexyl, 5-methylthiazol-2-base.
2. the substituted pyrazolecarboxylic benzamide type bisamide of a class Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure is characterized in that having the chemical structure of general formula suc as formula shown in IA:
Y is selected from: chlorine, bromine, cyano group; R
1be selected from: methyl, cyclopropyl, cyclohexyl, 5-methylthiazol-2-base.
3. the substituted pyrazolecarboxylic benzamide type bisamide of a class Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure is characterized in that having the chemical structure of general formula suc as formula shown in IB:
Y is selected from: chlorine, bromine, cyano group; R
1be selected from: methyl, cyclopropyl, cyclohexyl, 5-methylthiazol-2-base.
4. the substituted pyrazolecarboxylic benzamide type bisamide of a class Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure is characterized in that having the chemical structure of general formula suc as formula shown in IC:
Y is selected from: chlorine, bromine, cyano group; R
1be selected from: methyl, cyclopropyl, cyclohexyl, 5-methylthiazol-2-base.
5. claim 1,2,3,4 described classes are containing the synthetic method of the substituted pyrazolecarboxylic benzamide type bisamide I of Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure, IA, IB, IC, and concrete synthetic route is as follows:
Wherein, X is selected from: methylthio group, N-cyano methyl sulfilimine base, N-cyano methyl sulfone imino-; Y is selected from: chlorine, bromine, cyano group; R
1be selected from: methyl, cyclopropyl, cyclohexyl, 5-methylthiazol-2-base;
Specifically be divided into following steps:
A. replace the preparation of benzoxazine IV:
Add 15 milliliters of acetonitriles, 1.0 mmole 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-formic acid II, 5 mmole Methanesulfonyl chlorides in 50 milliliters of round-bottomed flasks, be abbreviated as MsCl, 5 mmole pyridines, be abbreviated as Py, be cooled to-5 degrees centigrade, stir after 30 minutes and add 1.0 mmoles to replace anthranilic acid III, slowly rise to after room temperature to stir and spend the night, add 10 ml waters, there is yellow mercury oxide IV to separate out, filter, the washing of gained solid, vacuum-drying, be directly used in next step reaction; Described replacement anthranilic acid III is selected from 3-methyl-5-chloro-2-benzaminic acid, the bromo-2-benzaminic acid of 3-methyl-5-, 3-methyl-5-cyano group-2-benzaminic acid; Described replacement benzoxazine IV is selected from 2-(1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-yl)-chloro-4-oxo of 8-methyl-6--4H-benzo [d] [1,3] oxazines, 2-(1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-yl)-bromo-4-oxo of 8-methyl-6--4H-benzo [d] [1,3] oxazines, 2-(1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-yl)-8-methyl-6-cyano group-4-oxo-4H-benzo [d] [1,3] oxazine;
B. contain the preparation of pyrazole ring diamide compound IA:
In 50 milliliters of round-bottomed flasks, add 1.0 mmoles to replace benzoxazine IV, 20 milliliters of tetrahydrofuran (THF)s, be abbreviated as the replacement amine of THF, 4.0 mmoles, reaction conditions is determined according to the character that replaces amine, under methylamine, cyclopropylamine, hexahydroaniline room temperature condition, about stirring reaction 2-4 hour, 5-methyl-2-amino-thiazole reacts about 4 hours under the reflux condition; After having reacted, concentrating under reduced pressure is except desolventizing, the gained resistates is through 200～300 order purification by silica gel column chromatography, the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate, volume ratio is 3: 1, obtains yellow or white solid, is containing pyrazole ring diamide compound IA, with gained sterling calculated yield, yield 75-90%; The amount of synthetic compound enlarges or dwindles by corresponding proportion; The volume of respective reaction container enlarges in proportion or dwindles; the described pyrazole ring diamide compound IA that contains is selected from: 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-chloro-phenyl-)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-methyl-carbamoyl-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-cyclopropyl amino formyl radical-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-cyclohexylamino formyl radical-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-methyl-carbamoyl-4-cyano-phenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-cyclopropyl amino formyl radical-4-cyano-phenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-cyano-phenyl)-1H-pyrazoles-5-methane amide,
C. contain the preparation of pyrazole ring diamide compound IB:
In 50 milliliters of round-bottomed flasks, add 1.0 mmoles containing pyrazole ring diamide compound IA, 15 milliliters of tetrahydrofuran (THF)s, ice-water bath is cooled to 0 degree centigrade; Then add respectively 2.0 mmole cyanamides and 1.1 mmole acetic acid iodobenzenes, stir stirred overnight at room temperature after 3 hours at this temperature, the 2nd day by the direct removal of solvent under reduced pressure of reaction solution, resistates obtains faint yellow or white solid through 200～300 order purification by silica gel column chromatography, eluent is ethyl acetate: methyl alcohol, and volume ratio is 20: 1, is containing pyrazole ring diamide compound IB, with gained sterling calculated yield, yield 70-90%; The amount of synthetic compound enlarges or dwindles by corresponding proportion; The volume of respective reaction container enlarges in proportion or dwindles; the described pyrazole ring diamide compound IB that contains is selected from: 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-methyl-carbamoyl-4-chloro-phenyl-)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-cyclopropyl amino formyl radical-4-chloro-phenyl-)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-chloro-phenyl-)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-methyl-carbamoyl-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-cyclopropyl amino formyl radical-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-methyl-carbamoyl-4-cyano-phenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-cyclopropyl amino formyl radical-4-cyano-phenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfilimine methylene)-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-cyano-phenyl)-1H-pyrazoles-5-methane amide,
D. contain the preparation of pyrazole ring diamide compound IC:
Add 2.0 mmole metachloroperbenzoic acids in 50 milliliters of round-bottomed flasks, write a Chinese character in simplified form m-CPBA, 10 ml methanol, ice-water bath is cooled to 0 degree centigrade and stirs 10 minutes, then 10 ml water solution of 3.0 mmole Anhydrous potassium carbonates is splashed in reaction system, has a large amount of white solids to separate out, 0 degree centigrade is stirred the 10 ml methanol solution that after 20 minutes, 1.0 mmoles contained to pyrazole ring diamide compound IB and dropwise adds, after dropwising, stir 2 hours, after the TLC monitoring reaction completes, removal of solvent under reduced pressure methyl alcohol, 60 milliliters of ethyl acetate extractions three times for residuum, merge organic layer, with saturated common salt water washing 2 times, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, resistates obtains white solid through 200～300 order purification by silica gel column chromatography, be containing the pyrazole ring diamide compound, the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate, difference according to product, volume ratio is between 1: 1～1: 3, obtain white solid IC, with gained sterling calculated yield, yield 50-80%, the amount of synthetic compound enlarges or dwindles by corresponding proportion, the volume of respective reaction container enlarges in proportion or dwindles, the described pyrazole ring diamide compound IC that contains is selected from: 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-methyl-carbamoyl-4-chloro-phenyl-)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-cyclopropyl amino formyl radical-4-chloro-phenyl-)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfone sulfilimine methylene)-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-chloro-phenyl-)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-methyl-carbamoyl-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-cyclopropyl amino formyl radical-4-bromophenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-methyl-carbamoyl-4-cyano-phenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-cyclopropyl amino formyl radical-4-cyano-phenyl)-1H-pyrazoles-5-methane amide, 1-(3-chloropyridine-2-yl)-3-(N-cyano methyl sulfoximide methylene)-N-(6-methyl-2-(5-methylthiazol-2-formamyl)-4-cyano-phenyl)-1H-pyrazoles-5-methane amide,
It is synthetic that 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-formic acid II presses the method shown in Scheme-2:
The synthetic route of Scheme-2 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-formic acid II
E.2, the preparation of 2-dimethyl-4-chloromethyl-DOX V:
In 1000 milliliters of round-bottomed flasks, add successively 350 milliliters of acetone, 2.58 gram tosic acid, write a Chinese character in simplified form into p-TsO hour, after stirring and dissolving, splash into 37.82 milliliters of 1-glycerin chlorohydrins, dropwise rear stirring at room reaction 12 hours, add triethylamine to regulate pH to neutral, then acetone is removed in air distillation, the cut of 46-48 degree centigrade/1.7kPa is collected in underpressure distillation, obtain colourless transparent liquid, gained sterling calculated yield, obtain 65.36%; Synthetic 2,2-dimethyl-4-chloromethyl-1, the amount of 3-dioxolanes V enlarges or dwindles by corresponding proportion; The volume of respective reaction container enlarges in proportion or dwindles;
F.2, the preparation of 2-dimethyl-4-methylene radical-DOX VI:
In 500 milliliters of round-bottomed flasks, add successively 22.35 gram potassium tert.-butoxides, 300 milliliters of anhydrous tetrahydro furans, nitrogen protection drops to 0 degree centigrade, then splashes into 20 grams 2,2-dimethyl-4-chloromethyl-1,3-dioxolane V, be warming up to stirring at room reaction 12 hours after dropwising, filter a small amount of washed with dichloromethane of filter cake, remove filter cake, filtrate is directly used in next step reaction; The amount of synthetic 2,2-dimethyl-4-methylene radical-DOX VI enlarges or dwindles by corresponding proportion; The volume of respective reaction container enlarges in proportion or dwindles;
G.3-(2,2-dimethyl-1,3-dioxy cyclopentyl-4-thiazolinyl)-ethyl 2-oxopropanoate VII's is synthetic
In 1000 milliliters of round-bottomed flasks, add previous step gained filtrate, then add 23.14 gram pyridines, condition of ice bath drops to 0 degree centigrade, then slowly drip the dichloromethane solution of 36.32 gram ethyl oxalyl chlorides, after dropwising, continue stirring reaction 4 hours under condition of ice bath, after the TLC monitoring reaction completes, splash into 20 ml waters, then use 150 milliliters of dichloromethane extractions three times, merge organic layer, with saturated sodium-chloride, wash, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, resistates is through 200～300 order purification by silica gel column chromatography, obtain the reddish-brown thick liquid, eluent is sherwood oil: the ethyl acetate volume ratio is 10: 1, by gained sterling calculated yield, two step total recoverys 85.76%, the amount of synthetic 3-(2,2-dimethyl-1,3-dioxy cyclopentyl-4-thiazolinyl)-ethyl 2-oxopropanoate VII enlarges or dwindles by corresponding proportion, the volume of respective reaction container enlarges in proportion or dwindles,
H.1-(3-chloropyridine-2-yl)-3-methylol-1H-pyrazole-5-ethyl formate VIII's is synthetic
In 500 milliliters of round-bottomed flasks, add successively 12.95 gram 3-(2, 2-dimethyl-1, 3-dioxy cyclopentyl-4-thiazolinyl)-ethyl 2-oxopropanoate VII, 250 milliliters of ethanol, add 8.68 gram 3-chloride-2-hydrazinopyridines after stirring and dissolving, stirring at room reaction 6 hours, after the TLC monitoring reaction completes, drip 36.5% concentrated hydrochloric acid in system, regulate the pH=3 left and right, then removal of solvent under reduced pressure ethanol, residuum adds ethyl acetate and water, get ethyl acetate layer, 150 milliliters of ethyl acetate extractions three times for water layer, merge organic layer, with saturated nacl aqueous solution, wash, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, resistates is through 200～300 order purification by silica gel column chromatography, obtain white solid, eluent is sherwood oil: the ethyl acetate volume ratio is 2: 1, with gained sterling calculated yield, yield 57.83%, the amount of synthetic 1-(3-chloropyridine-2-yl)-3-methylol-1H-pyrazole-5-ethyl formate VIII compound enlarges or dwindles by corresponding proportion, the volume of respective reaction container enlarges in proportion or dwindles,
I.1-(3-chloropyridine-2-yl)-3-methanesulfonates methylene radical-1H-pyrazole-5-ethyl formate IX's is synthetic
In 100 milliliters of round-bottomed flasks, add successively 5.13 gram 1-(3-chloropyridine-2-yl)-3-methylol-1H-pyrazole-5-ethyl formate VIII, 2.76 gram triethylamine, 50 milliliters of anhydrous tetrahydro furans, nitrogen protection drops to 0 degree centigrade, then slowly drip 2.50 gram Methanesulfonyl chlorides, write a Chinese character in simplified form MsCl, 10 milliliters of tetrahydrofuran solutions, dropwise under rear condition of ice bath and continue stirring reaction 2 hours, after the TLC monitoring reaction completes, splash into 20 ml waters, then with 150 milliliters of ethyl acetate extractions three times, merge organic layer, use the saturated nacl aqueous solution washed twice, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, residuum directly drops into next step reaction according to theoretical yield, the amount of synthetic 1-(3-chloropyridine-2-yl)-3-methanesulfonates methylene radical-1H-pyrazole-5-ethyl formate IX enlarges or dwindles by corresponding proportion, the volume of respective reaction container enlarges in proportion or dwindles,
J.1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazole-5-ethyl formate X's is synthetic
In 100 milliliters of round-bottomed flasks, the residuum of previous step gained is molten in 50 milliliters of acetonitriles, condition of ice bath drops to 0 degree centigrade, then dropwise splash into the 20% sodium methyl mercaptide solution with respect to 1-(3-chloropyridine-2-yl)-3-methanesulfonates methylene radical-1H-pyrazole-5-ethyl formate IX theoretical yield molar weight 1.5 equivalents under condition of ice bath, rise to stirring at room reaction 3h after dropwising; After the TLC monitoring reaction completes, removal of solvent under reduced pressure acetonitrile, ethyl acetate and water dissolution for residuum, get ethyl acetate layer, 120 milliliters of ethyl acetate extractions three times for water layer, merge organic phase, uses the saturated nacl aqueous solution washed twice, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, resistates, through 200～300 order purification by silica gel column chromatography, obtains faint yellow thick liquid, obtain faint yellow solid after static, eluent is sherwood oil: the ethyl acetate volume ratio is 3: 1; By gained sterling calculated yield, two step total recoverys 77.82%; The amount of synthetic 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazole-5-ethyl formate X compound enlarges or dwindles by corresponding proportion; The volume of respective reaction container enlarges in proportion or dwindles;
K.1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-formic acid II's is synthetic
In 100 milliliters of round-bottomed flasks, by 3.85 gram 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazole-5-ethyl formate X is molten in 20 ml methanol, then 0.74 gram sodium hydrate solid particle is molten in 10 ml methanol, at ambient temperature, by the methanol solution of sodium hydroxide, dropwise splash in reaction system, after dropwising, stirring at room reaction 6 hours, after the TLC monitoring reaction completes, removal of solvent under reduced pressure methyl alcohol, the a small amount of water dissolution of residuum, then with 60 milliliters of ether washings three times, the water intaking layer, regulate the pH=4 left and right with dilute hydrochloric acid, there is solid to wash out, filter, the filter cake washing, the dry product that obtains, with gained sterling calculated yield, yield 89.07%, the amount of synthetic 1-(3-chloropyridine-2-yl)-3-methylthio group methylene radical-1H-pyrazoles-5-formic acid II compound enlarges or dwindles by corresponding proportion, the volume of respective reaction container enlarges in proportion or dwindles,
It is synthetic that the 3-chloride-2-hydrazinopyridine is pressed the method shown in Scheme-3:
The synthetic method of Scheme-3 3-chloride-2-hydrazinopyridine
L.3-the preparation of chloride-2-hydrazinopyridine:
In 500 milliliters of round-bottomed flasks, add successively 50 grams 2, the hydrazine hydrate of 3-dichloropyridine, 150 milliliters of ethanol, 127 grams 80%, reflux stirs 26 hours, after the TLC monitoring reaction is complete, reaction system is down to room temperature, filter filter cake washing, the dry needle-like white crystal that obtains; With gained sterling calculated yield, yield 90.13%; The amount of synthetic 3-chloride-2-hydrazinopyridine compound enlarges or dwindles by corresponding proportion; The volume of respective reaction container enlarges in proportion or dwindles;
Replacing the anthranilic acid III method shown in Scheme-4 of pressing synthesizes:
Scheme-4 replaces anthranilic acid III synthetic method
Concrete operations are:
M.3-the preparation of methyl-5-chloro (bromine)-2-benzaminic acid:
Add 20 mmole 3-methyl-2-amino phenylformic acid, 50 milliliters of DMF, 30 mmole N-chlorosuccinimide or N-bromosuccinimides in 100 milliliters of round-bottomed flasks, after return stirring 3 hours, reaction solution is poured in frozen water, dilute hydrochloric acid is acidified to pH=6, filter, a small amount of ethanol of gained solid is washed, and obtains gray solid chloro or bromo anthranilic acid III, with gained sterling calculated yield, yield 83%; The amount of synthetic chloro or bromo anthranilic acid III enlarges or dwindles by corresponding proportion; The volume of respective reaction container enlarges in proportion or dwindles; Y is selected from: chlorine, bromine;
N.3-the preparation of methyl-5-cyano group-2-benzaminic acid:
In 250 milliliters of round-bottomed flasks, add successively the bromo-2-benzaminic acid of 15 gram 3-methyl-5-, 1.08 gram potassiumiodides, 8.76 gram cuprous cyanides, 100 milliliters of DMF, reflux stirs 12 hours, after the TLC monitoring reaction completes, reaction system is poured in 500 milliliters of frozen water, added 15 milliliters of quadrols, stir after 10 minutes and filter, remove filter cake, filtrate is acidified to the pH=4 left and right with dilute hydrochloric acid, has solid to separate out, and filters, the filter cake washing, the dry product that obtains; With gained sterling calculated yield, yield 52.24%; The amount of synthetic 3-methyl-5-cyano group anthranilic acid III enlarges or dwindles by corresponding proportion; The volume of respective reaction container enlarges in proportion or dwindles.
6. claim 1,2,3, the 4 described substituted pyrazolecarboxylic benzamide type bisamide I containing Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure, IA, IB, IC and agricultural go up the purposes of acceptable auxiliary agent in preparing sterilant.
7. claim 1,2,3, the 4 described substituted pyrazolecarboxylic benzamide type bisamide I containing Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure, IA, IB, IC and agricultural go up the purposes of acceptable auxiliary agent in preparing sterilant.
8. claim 1,2,3, the 4 described substituted pyrazolecarboxylic benzamide type bisamide I containing Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure, IA, IB, IC and agricultural go up the purposes of acceptable auxiliary agent in preparing anti-plant virus agent.
9. claim 1,2,3,4 described substituted pyrazolecarboxylic benzamide type bisamide I containing Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure, IA, IB, IC and Insecticidal and acaricidal agents combination prevent and treat the application in doing harm to of agricultural and forestry and gardening plant insect pest, mite:
Substituted pyrazolecarboxylic benzamide type bisamide I, IA, IB, IC and insecticide composition containing Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure of the present invention prevented and treated the application in agricultural and forestry and gardening plant insect pest:
Of the present invention all containing Sulfide-containing Hindered, the substituted pyrazolecarboxylic benzamide type bisamide I of N-cyano group sulphur or sulfoximide structure, IA, IB, IC and existing sterilant: Chlorpyrifos 94, the inferior Nong in ground, acetamiprid, Affirm (Merck Co.), milbemectin, Avrmectin, pleocidin, fenvalerate, efficient fenvalerate, Cypermethrin, effective cypermethrin, lambda-cyhalothrin, Deltamethrin, Fenvalerate, the Bea-cyfloxylate, cyfloxylate, the Lambda-lambda-cyhalothrin, Permanone, permethrin, esbiothrin, cyhalothrin, bifenthrin, permethrin, ether chrysanthemum ester, flumethrin, fluvalinate, Provado, acetamiprid, Ti304, imidaclothiz, thiacloprid, Diacloden, clothianidin, MTI-446, clothianadin, Da Tenan, diflubenzuron, young urea goes out, Teflubenzuron, deinsectization is grand, HEXAFLUMURON, flufenoxuron, the pyridine worm is grand, lufenuron, the poisonous insect urea, penfluron, Noviflumuron is noviflumuron, and it is for No. CAS 121451-02-3, flucycloxuron, Novaluron is Rimon, fluorine pyridine urea, Bay sir6874 i.e. { 1-[(3.5-bis-chloro-4) 4-nitrophenoxy phenyl 3-3-(2-chlorobenzene)-urea }, Bay SIR-8514 i.e. [1-(4-Trifluoromethoxyphen-l)-3-(2-chlorobenzene)-urea], piperazine worm urea, Bistrifluron is bistrifluron, furan tebufenozide, the worm hydrazides, chlorine worm hydrazides, methoxyfenozide, ring worm hydrazides, Rogor, omethoate, SD-1750, acephate, triazophos, Resitox, pyridaphenthione, isazofos, Ro 7-5050, SevinCarbaryl, Aphox, meta-tolyl-N-methylcarbamate (MTMC), isoprocarb, cartap, fenobucarb, leaf disperses, carbaryl, benfuracarb, carbosulfan, cartap, bromopropylate, hexythiazox, fenpyroximate, pyridaben, clofentezine, propargite, diafenthiuron, benfuracarb, pymetrozine, spiral shell mite ester, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azocyclotin, Buprofezin, ethoprophos, ethiprole, the desinsection list, disosultap, chlorantraniliprole, Flubendiamide, the fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, tebufenpyrad, bromothalonil, pyrazinones, second mite azoles, tebufenpyrad, the young ketone of rattling away, Nylar, any one in emaricin or two kinds are used in combination for preventing and treating agricultural and forestry and gardening plant insect pest, substituted pyrazolecarboxylic benzamide type bisamide I, IA, IB, the quality percentage composition of IC in composition containing Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure of the present invention is 1%-90%, and the ratio of substituted pyrazolecarboxylic benzamide type bisamide I, IA, IB, IC and aforementioned sterilant containing Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure of the present invention is mass percent 1%: 99% to 99%: 1%, can directly be watered rear spraying, comprise the upper acceptable solvent of agricultural and emulsifying agent and solubility promoter and synergistic agent in the preparation of composition, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, the dispersible body preparation, the dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, can disperse dense dose, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix filling agent, the medicine paint, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in the steam releasing agent, the insect pest that can prevent and treat mainly contains red spider, Asiatic migrotory locust, clouding car locust, Chinese rice grasshopper, Patanga japonica (l.Bol.), single thorn mole cricket, the east mole cricket, rice thrips, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian manages thrips, Trialeurodes vaporariorum Westwood, Bemisia tabaci, rice green leafhopper, green leaf hopper, chlorita biguttula, spot clothing plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, the flat angle of sugarcane plant hopper, cotten aphid, green bugs, grain aphid, black peach aphid, kaoliang aphid, radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, san jose scale, wax insect, ceroplastes rubens, Didesmococcus koreanus Borchs, pear lace bug, the banana lace bug, thin corner piece stinkbug, Orius minutus, slender rice bug, paddy fly, niphe elongata, scotinophora lurida, Nezara viridula smaragdula Fabricius., green plant bug, alfalfa plant bug, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, cnidocampa flavescens walker, brown slug moth, thosea siensis, gelechiid, pink bollworm, brachmia triannuella, small cabbage moth, small heart-eating peach worm, eating-core bean worm, small heart-eating peach worm, the apple Spilonota lechriaspis, brown belt length leaf roller, Adoxophyes cyrtosema, striped rice borer, bean-pod borer, Pyrausta nubilalis (Hubern)., yellow rice borer, Oeobia undalis, Cnaphalocrocis medinali(rice leaf roller), the bar snout moth's larva, the wild snout moth's larva of lap leaf, dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, pink rice borer, bollworm, ancient cooking vessel point diamond drill, black cutworm, large cutworm, yellow cutworm, steal poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, the straight burr rice hesperiidae, pelopidas mathias, the oranges and tangerines swallowtail butterfly, Common Mormon, small white, pyrameis indica, the yellow a kind of butterfly harmful to crop plants of ramie, the beans blister beetle, the Venus ground beetle, wrinkle sheath ground beetle, wheat head ground beetle, pleonomus canaliculatus, Agriotes subrittatus Motschulsky, khapra beetle, attagenus piceus, the little buprestid beetle of oranges and tangerines, gold edge buprestid beetle, tenebrio molitor, dark mealworm, red flour beetle, confused flour beetle, the verdigris different beetle, H. parallela, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori, pink neck longicorn, large daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, Phyllotreta striolata, Callosobruchus chinensis, pea weevil, broad bean weevil, sitophilus zea-mais, rice weevil, dolerus tritici, pear fruit sawfly, the yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm is hanged the cocoon ichneumon wasp, bollworm tooth lip ichneumon wasp, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, contarinia tritici, pachydiplosis oryzae, citrus fruit fly, the melon trypetid, the latent fly of wheat leaf ash, Americal rice leaf miner, the black fly of diving of beans stalk, frit fly, plant fly, onion fly, the radish fly, full skirt chases after posts fly, Pyrausta nubilalis (Hubern). is strict posts fly, armyworm lacks must post the fly Agricultural pests, forestry pest, gardening pest insect and sanitary insect pest, controlling mode also comprises double controlling simultaneously, the prevention effect of composition is good, and drug effect plays stably, and has certain synergism and summation action, finds not have the composition of antagonistic action, comprise paddy in these composition for preventing and controlling agricultural and forestry and gardening plant insect pest, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape, composition has improved the defence capability of plant in desinsection, makes plant produce the defence capability to pathogenic fungi, bacterium and virus infection,
Substituted pyrazolecarboxylic benzamide type bisamide I containing Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure of the present invention, IA, IB, the combination of IC miticide prevent and treat the application in agricultural and forestry and gardening plant mite evil:
Of the present invention containing Sulfide-containing Hindered, the substituted pyrazolecarboxylic benzamide type bisamide I of N-cyano group sulphur or sulfoximide structure, IA, IB, IC and the upper acceptable auxiliary agent of agricultural and be selected from azocyclotin, cyhexatin, fenbutatin oxide, three phosphor tins, Zaprawa enolofos, dimethylvinphos, crotoxyphos, SD-1750, heptenopos, Phosdrin, monocrotophos, naled, Chlorpyrifos 94, Pyrimithate, imino-formyl chloride sulphur phosphorus, omethoate, dioxathion, Nialate, Malathion, methacrifos, Phosalone, Volaton, methylpyrimidine sulphur phosphorus, Resitox, sulfotep, triazophos, vamidothion, isocarbophos, acephatemet, propetamphos, dialifos, R-1504, acrinathrin, bifenthrin, cyhalothrin, the essence lambda-cyhalothrin, Fenvalerate, flucythrinate, flumethrin, taufluvalinate, brofluthrinate, Bifenazate, fenothiocarb, aldicarb, butocarboxim, oxamyl, Talcord, thiofanox, F-1991, sok, carbofuran, carbosulfan, meta-tolyl-N-methylcarbamate (MTMC), promacyl, formetanate, single carbonamidine, medimeform, amitraz, chlordimeform, peruscabin, bromopropylate, cyflumetofen, acequinocyl, Nissol, flufenoxuron, macro tetrolide, piericidin, thuringiensin, tetranactin, macro tetrolide, Avrmectin, doractin, eprinomectin, ivermectin, selamectin, moxidectin, pyrethrin, nicotine, matrine, nimbin, tubatoxin, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, hexythiazox, spiral shell mite ester, Fluacrypyrim, Ovotran, propargite, any one in pyridaben or two kinds of medicament combinations are prepared into miticide for preventing and treating agricultural and forestry and gardening plant mite evil, substituted pyrazolecarboxylic benzamide type bisamide I, IA, IB, the total quality percentage composition of IC in composition containing Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure of the present invention is 1%-90%, and the ratio of substituted pyrazolecarboxylic benzamide type bisamide I, IA, IB, IC and above-mentioned medicament containing Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure of the present invention is mass percent 1%: 99% to 99%: 1%, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, the dispersible body preparation, the dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, can disperse dense dose, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix filling agent, the medicine paint, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in the steam releasing agent, plant in composition for preventing and controlling agricultural and forestry and gardening plant mite evil is selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape, the applicable mite of composition evil is phytophagy evil mite, and the harmful mite that is selected from tetranychid and is Tetranychidae, Tenuipalpidae, furan line mite, Eriophyidae is that Panonychus citri belongs to, tetranychus telarius belongs to and these global Agricultural Mites of itch mite of Eriophyidae, forestry harmful mites, the harmful mite of gardening and the harmful mite of health.
10. claim 1,2,3,4 described substituted pyrazolecarboxylic benzamide type bisamide I containing Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure, IA, IB, IC prevent and treat the application in agricultural and forestry and gardening plant disease, virus disease with sterilant, anti-plant virus agent combination respectively:
Substituted pyrazolecarboxylic benzamide type bisamide I containing Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure of the present invention, IA, IB, IC and sterilant combination prevent and treat the application in agricultural and forestry and gardening plant disease
Of the present invention all containing Sulfide-containing Hindered, the substituted pyrazolecarboxylic benzamide type bisamide I of N-cyano group sulphur or sulfoximide structure, IA, IB, IC and existing sterilant are as diazosulfide, tiadinil, be abbreviated as TDL, tisocromide, the first thiophene lures amine, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-sodium formiate, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, the DL-beta-aminobutyric acid, isotianil, it is English general by name: isotianil, 3,4-, bis-chloroisothiazoles-5-formic acid, 3,4-, bis-chloroisothiazoles-5-sodium formiate, 3,4-, bis-chloroisothiazoles-5-ethyl formate, virazole, antofine, Ningnanmycin or Whitfield's ointment, frost urea cyanogen, thiram, ziram, zinc manganese ethylenebisdithiocarbamate, phosethyl Al, thiophanate_methyl, m-tetrachlorophthalodinitrile, the enemy can be loose, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, Whitfield's ointment, flumorph, dimethomorph, efficient metaxanin, efficient M 9834, two chlorine zarilamids, flusulfamide, the first flusulfamide, thiophene fluorine bacterium amine, fultolanil, tecloftalam, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, the pyrrole metsulfovax, mandipropamid, zoxamide, fenfuram, carboxin, chlozolinate, RP-26019, Azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, SSF 126, orysastrobin, ZEN 90160, Strobilurin, oxime bacterium ester, enostroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, SN-108266, difenoconazole, alkene azoles alcohol, efficient alkene azoles alcohol, epoxiconazole, RH-7592, fluquinconazole, fluzilazol, flutriafol, own azoles alcohol, imibenconazole, plant the bacterium azoles, metconazole, nitrile bacterium azoles, Topaze, Wocosin 50TK, prothioconazoles, simeconazoles, tebuconazole, tertraconazole, triadimenol, triticonazole, bitertanol, thiabendazole, fuberidazole, imazalil, efficient imazalil, prochloraz, fluorine bacterium azoles, cyazofamid, fenamidone, the Evil imidazoles, pefurazoate, famoxadone, SYP-Z048, hymexazo, the spirit of Evil frost, Guardian, etridiazole, octhilinone, benthiozole, dodemorph, fenpropimorph, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium amine, boscalid amine, fluopicolide, pyridine bacterium amine, cyprodinil, the fluorine mepanipyrim, ferimzone, mepanipyrim, phonetic mould amine, fenarimol, nuarimol, chinomethionate, dithianon, ethoxyquin, hydroxyquinoline, the third oxygen quinoline, benzene oxygen quinoline, the mould prestige of second, iprovalicarb, the benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, iprobenfos, pyrazophos, tolclofosmethyl, miewensu, kasugamycin, polyoxin, Polyoxin, validamycin, jingganmycin, Streptomycin sulphate, metaxanin, furalaxyl, M 9834, ofurace, mebenil, derosal, F-1991, thiophanate_methyl, triazolone, bupirimate, dimethirimol, the phonetic phenol of second, Difolatan, Vancide 89, Phaltan, Vinclozoline, fluoromide, dimetachlone, m-tetrachlorophthalodinitrile, isoprothiolane, Kitazine, bismerthiazol, quintozene, zinc 1,2-propylene bisdithiocarbamate, fosetylaluminium, sulphur, Bordeaux mixture, copper sulfate, copper oxychloride, Red copper oxide, copper hydroxide, metrafenone, pencycuron, diclomezin, phthalide, pyroquilon, volution bacterium amine, tricyclazole, triforine, the pyridine of many fruits, the hot salt of biguanides, iminoctadine, dicloran, the benzene flusulfamide, the toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, methyl iodide, metamsodium, enemy's line ester, dazomet, dichloroisopropyl ether, lythidathion, cadusafos, fensulfothion, thionazin, fenamiphos, ethoprophos, dichlofenthion, isazofos, fosthietan, oxamyl, aldicarb, carbofuran, sulfuryl fluoride, dichloropropylene, dichloro-isonicotinic acid, other known any any one or two kinds that can be used as in sterilant of allyl isothiazole are used in combination for preventing and treating agricultural and forestry and gardening plant disease, substituted pyrazolecarboxylic benzamide type bisamide I, IA, IB, the total quality percentage composition of IC in composition containing Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure of the present invention is 1%-90%, and substituted pyrazolecarboxylic benzamide type bisamide I, IA, IB, IC and aforementioned sterilant containing Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure of the present invention, the ratio of anti-plant virus agent are mass percent 1%: 99% to 99%: 1%, the prevention effect of composition is good, and these compositions have certain synergism and summation action, does not find to have the composition of antagonistic action, above-mentioned composition can be for the control of agricultural plants disease and gardening plant disease, controlling object comprises that more than 20 of Achyla, Aphanomyces, pythium, phytophthora, Sclerospora, Plasmopara, Pseudoperonospora, the Peronosporas of Oomycete belong to the disease produced, as other diseases of seedling blight of rice, tomato root maize ear rot, the late blight of potato, black shank, millet Powdery Mildew, downy mildew of garpe, downy mildew of lettuce, cucumber downy mildew, cucumber anthracnose plurality of cereals crop, cash crop, gardening plant and forestry plant, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, the dispersible body preparation, the dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, can disperse dense dose, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix filling agent, the medicine paint, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in the steam releasing agent, these compositions comprise cereal for preventing and treating agricultural and forestry and the applicable plant of gardening plant disease: paddy, wheat, barley, oat, corn, millet, Chinese sorghum, tuber crops: sweet potato, potato, cassava, beans: soybean, broad bean, pea, mung bean, red bean and fiber: cotton, crudefiber crop, silkworm and mulberry, oil plant: peanut, rape, sesame, soybean, Sunflower Receptacle, sugar material: beet, sugarcane, beverage: tealeaves, coffee, cocoa, hobby: tobacco leaf, medicinal: ginseng, the bulb of fritillary, the torrid zone: rubber, coconut, oil palm, sisal hemp, food crop and fruit, flowers, oil plant, sugar material and cotton, fiber crops, tea, tobacco, Chinese medicinal materials cash crop and plant melon, really, tea, silkworm and mulberry, vegetables, contain various wild vegetable, bamboo shoots, flowers and ornamental plant, hops, medicinal material, pepper, seedling and other garden crop garden crops as tobacco: flue-cured tobacco, air-curing of tobacco leaves, suncured tabacco, vegetables, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, melon: watermelon, muskmelon, hami melon, pawpaw, beans: soybean, broad bean, pea-pods, potato, wheat, corn, paddy rice, peanut, fruit tree: apple, banana, citrus, peach, papaya, flowers: orchid, potted landscape, composition has improved the defence capability of plant in sterilization, makes plant produce the defence capability to pathogenic fungi, bacterium and virus infection,
Substituted pyrazolecarboxylic benzamide type bisamide I, IA, IB, IC and anti-plant virus agent containing Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure of the present invention is combined in the application prevented and treated in agricultural and forestry and gardening plant virus disease
Of the present invention containing Sulfide-containing Hindered, the substituted pyrazolecarboxylic benzamide type bisamide I of N-cyano group sulphur or sulfoximide structure, IA, IB, IC and existing antiviral agent diazosulfide, tiadinil, be abbreviated as TDL, isotianil, it is English general by name: isotianil, the 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-formic acid, the 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-sodium formiate, the 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-ethyl formate, 3, 4-bis-chloroisothiazoles-5-formic acid, 3, 4-bis-chloroisothiazoles-5-sodium formiate, 3, 4-bis-chloroisothiazoles-5-ethyl formate, the DL-beta-aminobutyric acid, virazole, antofine, Ningnanmycin, tisocromide, the first thiophene lures amine or Whitfield's ointment, cytosintetidemycin, dichloro-isonicotinic acid, allyl isothiazole, well ridge azanol, in jingganmycin, any 1 or 2 compound combinations are for preventing and treating agricultural and forestry and gardening plant virus disease, be selected from tobacco mosaic virus disease for the disease of preventing and treating agricultural and forestry and gardening plant virus disease, various melon virus diseases, various solanaceous vegetables virus diseases, the beans virus disease, the Cruciferae virus disease, the grain and oil crop virus disease, any in cotton virus disease and various fruit tree virus disease, wherein endanger serious being selected from: tobacco virus, peppery pimento virus disease, tomato virus disease, Chinese cabbage virus disease, Virus Diseases of Rice comprises rice dwarf virus disease, yellow dwart, stripe virus disease, the fern leaf of tomato viral disease, pepper mosaic virus disease viral disease and tobacco veinal necrosis virus disease, maize dwarf mosaic, cauliflower mosaic virus, the oranges and tangerines virus disease, cymbidium mosaic virus, any in cybidium ring spot virus, these compositions are selected from paddy for the plant that prevents and treats agricultural and forestry and gardening plant virus disease, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, the potted landscape agricultural, gardening, economical, forestry plant, the use of these compositions makes the immunizing power of crop self improve, and when producing the control of insect especially infection insect, has induced plant to produce the defence capability to viral diseases of plants, also can produce the direct prevention effect of virus disease, therefore, these compositions can be for preparation and the purposes of Antiphytoviral medicament and inducing plant Antiphytoviral medicament, substituted pyrazolecarboxylic benzamide type bisamide I, IA, IB, the total quality percentage composition of IC in composition containing Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure of the present invention is 1%-90%, and the ratio of substituted pyrazolecarboxylic benzamide type bisamide I, IA, IB, IC and aforementioned anti-plant virus agent containing Sulfide-containing Hindered, N-cyano group sulphur or sulfoximide structure of the present invention is mass percent 1%: 99% to 99%: 1%, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, the dispersible body preparation, the dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, can disperse dense dose, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix filling agent, the medicine paint, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in the steam releasing agent, all show addition or synergism between these compositions, when keeping insecticidal activity, its antiviral activity all is greater than the effect that any one compound is used separately, find no the composition of antagonistic action, the drug effect lasting period of composition is long.
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| CN103880836A (en) * | 2014-04-04 | 2014-06-25 | 贵州大学 | 1-substituted-5-amino-4-pyrazol di-1,3,4-diazole sulfur ether or 1,3,4-diazole sulfone derivatives and application thereof |
| CN105777713A (en) * | 2016-04-06 | 2016-07-20 | 武汉工程大学 | N-(2-pyridyl)-2-(2,4-dimethyl parazole formamido) benzamide as well as preparation thereof and use thereof |
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| WO2019123194A1 (en) | 2017-12-20 | 2019-06-27 | Pi Industries Ltd. | Anthranilamides, their use as insecticide and processes for preparing the same. |
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| CN110407831A (en) * | 2019-08-13 | 2019-11-05 | 南通大学 | - the 2- of chloropyridine containing N-(3- base) pyrrazole structure pyrazoles oxime ester derivative preparation and application |
| CN111072590A (en) * | 2018-10-18 | 2020-04-28 | 天津农学院 | (R) -2-aryl-4, 5-dihydrothiazole-4-carboxylic acid derivatives, and preparation method and application thereof |
| CN113105350A (en) * | 2021-04-06 | 2021-07-13 | 利尔化学股份有限公司 | Process for preparing 2-amino-3-alkyl-5-chlorobenzoic acid |
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| CN105777713A (en) * | 2016-04-06 | 2016-07-20 | 武汉工程大学 | N-(2-pyridyl)-2-(2,4-dimethyl parazole formamido) benzamide as well as preparation thereof and use thereof |
| WO2019123194A1 (en) | 2017-12-20 | 2019-06-27 | Pi Industries Ltd. | Anthranilamides, their use as insecticide and processes for preparing the same. |
| WO2019150220A1 (en) | 2018-01-30 | 2019-08-08 | Pi Industries Ltd. | Novel anthranilamides, their use as insecticide and processes for preparing the same. |
| CN108658999A (en) * | 2018-04-24 | 2018-10-16 | 温州大学 | The synthetic method of 2- phenyl heterocycles simultaneously [2,3-d] pyrimidine -4 (3H) -one class compound |
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| CN110092776B (en) * | 2019-04-30 | 2021-09-07 | 南通大学 | Pyrazole oxime ester compound containing pyridine-difluoride pyrazole structure and preparation method and application thereof |
| CN110092776A (en) * | 2019-04-30 | 2019-08-06 | 南通大学 | The pyrazoles oxime ester compound and its preparation method and application of the connection polyfluoro pyrrazole structure containing pyridine |
| CN110407831A (en) * | 2019-08-13 | 2019-11-05 | 南通大学 | - the 2- of chloropyridine containing N-(3- base) pyrrazole structure pyrazoles oxime ester derivative preparation and application |
| CN113105350A (en) * | 2021-04-06 | 2021-07-13 | 利尔化学股份有限公司 | Process for preparing 2-amino-3-alkyl-5-chlorobenzoic acid |
| CN113105350B (en) * | 2021-04-06 | 2023-11-24 | 利尔化学股份有限公司 | Process for preparing 2-amino-3-alkyl-5-chlorobenzoic acid |
| WO2024038436A1 (en) | 2022-08-16 | 2024-02-22 | Adama Makhteshim Ltd. | Process for preparing cyantraniliprole via amino-cyano-benzene derivative |
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