CN101935291A - Cyano phthalic diamide compounds, preparation method thereof and use thereof as agricultural chemical pesticide - Google Patents
Cyano phthalic diamide compounds, preparation method thereof and use thereof as agricultural chemical pesticide Download PDFInfo
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- CN101935291A CN101935291A CN 201010279790 CN201010279790A CN101935291A CN 101935291 A CN101935291 A CN 101935291A CN 201010279790 CN201010279790 CN 201010279790 CN 201010279790 A CN201010279790 A CN 201010279790A CN 101935291 A CN101935291 A CN 101935291A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/34—Nitriles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/10—Sulfones; Sulfoxides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton
- C07C255/29—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton containing cyano groups and acylated amino groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
- C07C317/48—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/60—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton with the carbon atom of at least one of the carboxyl groups bound to nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/90—Benzo [c] furans; Hydrogenated benzo [c] furans with an oxygen atom in position 1 and a nitrogen atom in position 3, or vice versa
Abstract
The invention discloses cyano phthalic diamide compounds, a preparation method thereof and use thereof as an agricultural chemical pesticide. The compounds are represented by a structural formula (1), wherein the substituent groups are defined in the description. The phthalic diamide compounds of the invention have wide spectrum pesticidal activities and are effective for epidoptera; particularly, the compounds have high activities for plutella xylostella, cotton bollworm, prodenia litura and the like, and a better effect can be achieved with a small dose of the phthalic diamide compounds.
Description
Technical field
The present invention relates to a kind of phthalyl aminated compounds, preparation method and as the purposes of agrochemicals sterilant.
Background technology
At present to disease and pest-controlling agent on ecology and requirement economically improve constantly, particularly the requirement for composition, selectivity, toxicity and the production method of amount of application, residue improves constantly.Because sterilant, sterilant are in use for some time, insect, germ can produce resistance to it, therefore, need exploitation novel compound with desinsection, fungicidal activity and composition.
Known multiple phthalyl aminated compounds (ryania acceptor inhibitor class) has insecticidal activity (referring to EP0919542A2, WO2004/018410A1, WO2010/012442A2), wherein the phthalyl aminated compounds Flubendiamide of being developed jointly by Japanese agricultural chemicals company and Beyer Co., Ltd (flubendiamide) has excellent insecticidal activity (J.Pesticide Sci. to various agricultural and gardening lepidoptera pest, 2005,30 (4): 354-360).At present, the phthalyl aminated compounds of replacement has caused agricultural chemicals initiative scientific research personnel's common concern as agricultural chemicals, becomes the focus of new pesticides initiative research.
In the prior art, do not see open as the preparation and the insecticidal activity thereof of the phthalyl aminated compounds of cyano-containing shown in the present.
Summary of the invention
The object of the present invention is to provide a kind of phthalyl aminated compounds that just can control the cyano-containing of various disease and pests under very little dosage, it can be applicable to agricultural and goes up to prevent and treat disease and the insect pest of crop.
For achieving the above object, the invention provides following technical scheme:
The phthalyl aminated compounds of the cyano-containing of a kind of formula (I) expression or its agricultural go up the salt that is suitable for,
Wherein:
R
1, R
2Be independently selected from hydrogen, C
1-C
6Alkyl, C
3-C
6Cycloalkyl, C
2-C
6Alkenyl or C
2-C
6Alkynyl, the hydrogen on the described group can also be by halogen, cyano group, nitro, C
1-C
6The phenoxy group of the phenyl of alkoxyl group, phenyl, replacement, phenoxy group, replacement, alkylthio, alkyl sulphinyl or alkyl sulphonyl further replace;
Perhaps R
1And R
2Form cycloalkyl together with the carbon that is connected;
R
3Be selected from hydrogen, halogen, cyano group, nitro, aryl, ester group, C
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
6Alkoxyl group or halo C
1-C
6Alkoxyl group;
R
4Be selected from hydrogen or C
1-C
6Alkyl;
X is selected from methylene radical, C
1-C
6Methylene radical that alkyl, cyano group replace or direct key;
Perhaps X and R
4Form triatomic ring, tetra-atomic ring, five-ring, six-ring, five-membered ring or hexa-member heterocycle with the N that is connected;
Y is selected from hydrogen, halogen, cyano group, nitro, hydroxyl, C
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
3Alkoxyl group, halo C
1-C
3The heterocyclic aryl of the phenyl of alkoxyl group, phenyl, replacement, heterocyclic aryl or replacement;
A is CH or N;
M is 0～4 integer.
As preferred embodiment, in the phthalyl aminated compounds of the cyano-containing of above-mentioned (I) expression:
R
1, R
2Be independently selected from hydrogen, C
1-C
3Alkyl, C
3-C
6Cycloalkyl or C
2-C
3Alkenyl, the hydrogen on the described group can also substituted phenyl, phenoxy group, alkylthio, alkyl sulphinyl or the alkyl sulphonyl of replacement further replace;
Perhaps R
1And R
2Form cyclohexyl together with the carbon that is connected;
R
3Be selected from hydrogen or halogen;
R
4Be selected from hydrogen or C
1-C
3Alkyl;
Perhaps X and R
4Form five-membered ring or hexa-member heterocycle with the N that is connected;
Y is selected from hydrogen, halogen atom, nitro, hydroxyl, C
1-C
3Alkyl, fluoro C
1-C
3Alkyl, C
1-C
3Alkoxyl group or fluoro C
1-C
3Alkoxyl group;
M is 1～3 integer.
As further preferred embodiment, in the phthalyl aminated compounds of the cyano-containing of above-mentioned (I) expression:
R
1, R
2Be independently selected from hydrogen, methyl, ethyl, sec.-propyl, cyclopropyl or allyl group, group such as the hydrogen on the described group can also substituted phenyl, the phenoxy group of replacement, methylthio group, methylsulfinyl, methyl sulphonyl further replaces;
R
3Be selected from fluorine, chlorine, bromine or iodine, R
3Be positioned at 3 or 4 of phenyl ring;
R
4Be hydrogen or methyl;
X is the methylene radical or the direct key of methylene radical, methyl, cyano group replacement;
Perhaps X and R
4Contain the oxygen hexa-member heterocycle with the N composition that is connected;
Y is selected from hydrogen, fluorine, chlorine, nitro, hydroxyl, methyl, methoxyl group, trifluoromethyl, trifluoromethoxy or seven fluorine sec.-propyls.
As highly preferred embodiment, the structural formula of the phthalyl aminated compounds of the cyano-containing of above-mentioned (I) expression is:
Or its salt.
R in the phthalyl aminated compounds of the cyano-containing of above-mentioned formula (I) expression
1, R
2, R
3, R
4, in A, X, Y and the m definition:
Alkyl is meant the straight or branched form, for example groups such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, tertiary butyl, n-pentyl, isopentyl, n-hexyl.Cycloalkyl is meant and comprises the closed chain form, for example groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.Alkenyl is meant the straight or branched form, for example groups such as vinyl, 1-propenyl, allyl group, pseudoallyl, 1-butylene base, 1,3-butadiene base, 1-hexenyl.Alkynyl is meant the straight or branched form, for example groups such as ethynyl, 2-butyne base, valerylene base, 3-hexin base.Haloalkyl is meant the group that alkyl is replaced by one or more halogen atoms.Alkoxyl group is meant that the alkyl end is connected with the group of Sauerstoffatom, for example methoxyl group, oxyethyl group, positive propoxy, isopropoxy, tert-butoxy etc.Halogenated alkoxy is meant that alkyl is replaced by one or more halogen atoms, and end is connected with the group of Sauerstoffatom.Alkylthio is meant that the alkyl end is connected with the group of sulphur atom, as methylthio group, ethylmercapto group etc.Alkyl sulphinyl is meant the terminal group for (SO-) of alkyl, as methylsulfinyl.Alkyl sulphonyl is meant the terminal (SO of being of alkyl
2-) group, as methyl sulphonyl.Halogen is meant fluorine, chlorine, bromine, iodine.
The phthalyl aminated compounds of the cyano-containing of formula of the present invention (I) expression has two or more optically active isomers and diastereomer in some cases contain one or more asymmetric centers in some cases in its structural formula.The present invention also comprises optically active isomer that all are independent and the mixture of being made up of by arbitrary proportion these isomer.
The present invention also is provided for the intermediate of phthalyl aminated compounds of the cyano-containing of preparation formula (I) expression, has as shown in the formula (II) or (III) structural formula:
Wherein:
R
1, R
2Be independently selected from hydrogen, C
1-C
6Alkyl, C
3-C
6Cycloalkyl, C
2-C
6Alkenyl or C
2-C
6Alkynyl, the hydrogen on the described group can also be by halogen, cyano group, nitro, C
1-C
6The phenoxy group of the phenyl of alkoxyl group, phenyl, replacement, phenoxy group, replacement, alkylthio, alkyl sulphinyl or alkyl sulphonyl further replace;
Perhaps R
1And R
2Form cycloalkyl together with the carbon that is connected;
R
3Be selected from hydrogen, halogen, cyano group, nitro, aryl, ester group, C
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
6Alkoxyl group or halo C
1-C
6Alkoxyl group.
As preferred embodiment, above-mentioned formula (II) or (III) expression structural formula of compound in:
R
1, R
2Be independently selected from hydrogen, C
1-C
3Alkyl, C
3-C
6Cycloalkyl or C
2-C
3Alkenyl, the hydrogen on the described group can also substituted phenyl, phenoxy group, alkylthio, alkyl sulphinyl or the alkyl sulphonyl of replacement further replace;
Perhaps R
1And R
2Form cyclohexyl together with the carbon that is connected;
R
3Be selected from hydrogen or halogen.
As further preferred embodiment, above-mentioned formula (II) or (III) expression structural formula of compound in:
R
1, R
2Be independently selected from hydrogen, methyl, ethyl, sec.-propyl, cyclopropyl or allyl group, group such as the hydrogen on the described group can also substituted phenyl, the phenoxy group of replacement, methylthio group, methylsulfinyl, methyl sulphonyl further replaces;
R
3Be selected from fluorine, chlorine, bromine or iodine, R
3Be positioned at 3 or 4 of phenyl ring.
The phthalyl aminated compounds of the cyano-containing of (I) of the present invention expression can prepare by the following method:
Promptly comprise the steps:
(1) at inert solvent, exist or do not exist under the situation of alkali, the Tetra hydro Phthalic anhydride of the replacement of structural formula (VI) expression and the aminoacetonitriles of the replacement that the structure formula V is represented advance the replacement mebenil yl benzoic acid that the N-acylation reaction obtains structural formula (III) expression;
(2) at inert solvent, the replacement mebenil yl benzoic acid of structural formula (III) expression and acylating reagent reaction obtain the different imide of phthalyl of the replacement of structural formula (II) expression;
(3) in inert solvent, exist or do not exist under the situation of acid, the amine reaction of the replacement of the different imide of phthalyl of the replacement of structural formula (II) expression and structural formula (IV) expression obtains the phthalyl aminated compounds of the cyano-containing of structural formula (I) expression;
R in the compound of structural formula (IV) to (VI) expression wherein
1, R
2, R
3, R
4,, the phthalyl aminated compounds of the cyano-containing of Y and m definition as above-mentioned structural formula (I) expression.
As preferred embodiment, inert solvent is selected from tetrahydrofuran (THF), acetonitrile, 1 described in the above-mentioned steps (1), 4-dioxane, N, dinethylformamide, N, one or more combinations in N-N,N-DIMETHYLACETAMIDE, toluene or the methylene dichloride, described alkali comprises organic bases and mineral alkali, and described organic bases is selected from triethylamine, pyridine or 3-picoline, and described mineral alkali is selected from salt of wormwood, sodium bicarbonate, sodium hydroxide or anhydrous sodium acetate; Inert solvent is selected from toluene, 1 described in the above-mentioned steps (2), 2-ethylene dichloride, ethyl acetate, tetrahydrofuran (THF), acetonitrile, 1, one or more combinations in 4-dioxane or the methylene dichloride, described acylating reagent is methyl-chloroformate, diacetyl oxide or trifluoroacetic anhydride, for the mebenil yl benzoic acid of every mole of formula (III), the usage quantity of acylating reagent can be counted in the scope suitably to molar excess at 1 mole and be selected; Inert solvent is selected from tetrahydrofuran (THF), methylene dichloride, 1 described in the above-mentioned steps (3), 2-ethylene dichloride, ether, 1, one or more combinations in 4-dioxane, acetonitrile or the toluene, described acid comprises organic acid and mineral acid, described organic acid is selected from acetate, trifluoroacetic acid or p-methyl benzenesulfonic acid, and described mineral acid is hydrochloric acid or sulfuric acid; Temperature of reaction is between the boiling point of used inert solvent at 0 ℃.
Reaction times is preferably 2～12h with reaction scale and temperature of reaction and different.
After reaction finishes, can the described product of formula (I) be separated from reaction mixture, if desired, can use separation means such as recrystallization, column chromatography with conventional methods such as filtration.
Product has solid through acidifying, extraction, after concentrating and separates out in the above-mentioned steps (1), with solvent wash, filter after with its separation.
The Tetra hydro Phthalic anhydride of the replacement of the formula of using among the above-mentioned preparation method (VI) expression is a kind of known compound, can be prepared by many currently known methodss.
The typical compound of formula of the present invention (I) expression is listed in concordance list 1 and the concordance list 2, but they never limit the scope of the invention.In concordance list 1, the typical compound of formula (I) expression is worked as R
4Be hydrogen, when X was direct key, typical compound was suc as formula shown in (Ia):
Concordance list 1
The typical compound of concordance list 2 Chinese styles (I) expressions, when A is CH, X is methylene radical or the N XR that methylene radical, methyl, cyano group replace
4When becoming ring, typical compound is suc as formula shown in (Ib):
Concordance list 2
Following table 3 is the nuclear magnetic data of part of compounds described in concordance list 1 and the concordance list 2.
Annotate: compound number described in the table 3 is corresponding with compound number described in table 1 and the table 2.Wherein s is unimodal, and brs is wide unimodal, and d is bimodal, and dd is a double doublet, and t is a triplet, and q is a quartet, and m is a multiplet.
Table 3 compound nuclear magnetic data
With the pest control agent of the phthalyl aminated compounds shown in the above-mentioned formula (I), under low dose, harmful organism had the prevention effect of superelevation as effective constituent.
The phthalyl aminated compounds of the cyano-containing of formula of the present invention (I) expression or its agricultural go up the salt that is suitable for, and can be used for agricultural chemical insecticide.
Specifically, for Agricultural pests classes such as control small cabbage moth, lopper worm, prodenia litura, beet armyworm, the greedy noctuid in meadow, bollworm, oriental armyworm, tobacco budworm, cigarette poison moth, cnaphalocrocis medinalls guenee, rice Adoxophyes spp, codling moth, the little solid moth of peach, oriental fruit months, black cutworm, colorado potato beetles, aulacophora femoralis, Phytophthira, aleyrodid class, thrips class, locustamigratoria, liriomyza bryoniae classes.Wherein, contain the agriculture and garden pest control agent of The compounds of this invention, effective especially for Agricultural pests class etc.In addition, the agriculture and garden pest control agent of phthalyl aminated compounds that contains the cyano-containing of formula of the present invention (I) expression, that organic phosphates, amino formate, pyrethroids, benzoyl area kind etc. have been produced the insect of resistance is effective for preventing and treating.And then, the phthalyl aminated compounds of the cyano-containing of formula of the present invention (I) expression is because have the excellent permeation transitivity, handle soil so contain the agriculture and garden of phthalyl aminated compounds of the cyano-containing of formula of the present invention (I) expression by use with pest control agent, in classes such as control soil harmful insect class, mite class, also can prevent and treat the insect of leaves and stems.
As other preferred configuration of the pest control agent of the phthalyl aminated compounds of the cyano-containing that contains formula of the present invention (I) expression, can list the agriculture and garden pest control agent of the above-mentioned phytotrophy mite of integrated control class, Agricultural pests class, soil pests class etc.
The phthalyl aminated compounds of the cyano-containing of formula of the present invention (I) expression can be used as the active constituent of chemistry of pesticide sterilant, be mixed with various liquors, missible oil, suspension agent, aqueous suspension, microemulsion, (water) emulsion, pulvis, wettable powder, soluble powder, (water dispersible) granule or capsule etc., be used for the pest control of farm crop such as paddy rice, soybean, wheat, cotton, corn, vegetables and rape.
When being configured to the chemistry of pesticide sterilant, the weight percentage of active ingredient is that the weight percentage of phthalyl aminated compounds of the cyano-containing of formula of the present invention (I) expression is preferably 0.001%-99.99% (weight), and all the other be acceptable carrier on the agricultural.
Carrier can be solid or liquid.Suitable solid carrier comprises natural or synthetic clay and silicate, for example natural silica and diatomite; Magnesium Silicate q-agent is talcum for example; Magnesium aluminum silicate is kaolinite, kaolin, polynite and mica for example; White carbon black, lime carbonate, light calcium carbonate; Calcium sulfate; Wingdale; Sodium sulfate; Amine salt such as ammonium sulfate, hexamethylene diamine.Liquid vehicle comprises water and organic solvent, and when water was cooked solvent or thinner, organic solvent also can be used as auxiliary or antifreeze additive.Appropriate organic solvent comprises aromatic hydrocarbons for example benzene, dimethylbenzene, toluene etc.; Hydrochloric ether, for example chlorinated benzene, vinylchlorid, trichloromethane, methylene dichloride etc.; Aliphatic hydrocarbon, for example petroleum fractions, hexanaphthene, light mineral oil; Alcohols, for example Virahol, butanols, ethylene glycol, glycerol and hexalin etc.; And their ether and ester; Also have ketone, for example acetone, pimelinketone and dimethyl formamide and N-methyl-pyrrolidone.
Carrier also can be a tensio-active agent.Suitable tensio-active agent can be emulsifying agent, dispersion agent or wetting agent; Can be ionic or non-ionic type.Nonionic emulsifier is polyoxyethylene fatty acid fat, polyoxyethylene aliphatic alcohol ether, polyoxyethylene fatty amine for example, and commercially available emulsifying agent: agricultural newborn 2201B, agricultural newborn 0203B, farming breast 100
#, farming breast 500
#, farming breast 600
#, agricultural newborn 600-2
#, farming breast 1601, farming breast 2201, agricultural newborn NP-10, agricultural newborn NP-15, farming breast 507
#, agricultural newborn OX-635, agricultural newborn OX-622, agricultural newborn OX-653, agricultural newborn OX-667, peaceful breast 36
#Dispersion agent comprises sodium lignosulfonate, draws back powder, calcium lignin sulphonate, condensation compound of methyl naphthalene sulfonic acid and formaldehyde etc.Wetting agent is: sodium laurylsulfate, Sodium dodecylbenzene sulfonate, sodium alkyl naphthalene sulfonate etc.
Above-mentioned chemistry of pesticide sterilant can be prepared by method in common.For example, active substance is mixed with liquid solvent and/or solid carrier, add tensio-active agent such as emulsifying agent, dispersion agent, stablizer, wetting agent simultaneously, can also add other auxiliary agent as tackiness agent, defoamer, oxygenant etc.
The phthalyl aminated compounds of cyano-containing of the present invention can also with weedicide, sterilant, nematocides, plant-growth regulator, fertilizer, and other sterilant or other agrochemicals use that is mixed.
When the control harmful organism, on the medium that pesticide preparation of the present invention is imposed on the harmful organism that needs control or its growth, wherein active ingredient is that the significant quantity of phthalyl aminated compounds of the cyano-containing of formula (I) expression is that per hectare 10 restrains 1000 grams.
The phthalyl aminated compounds of the cyano-containing of formula of the present invention (I) expression or its agricultural go up salt and the preparation thereof that is suitable for, and have the following advantages compared to existing technology:
(1) the present invention introduces alpha-aminonitriles functional group first in the phthalyl amine structure, and compound structure has novelty;
(2) compound of the present invention and preparation thereof have the insecticidal activity of superelevation: under 0.16mg/L dosage lepidoptera pest is shown good effect;
(3) compound of the present invention and preparation thereof have good security, and be good to securities such as part crop such as wheat, soybean, cotton, corn, paddy rice, and to having property of environment.
(4) compound of the present invention and preparation thereof have rational toxicity, eco-toxicity and Environmental compatibility, belong to the environmentally friendly agricultural chemicals of low toxicity.
Embodiment
Following specific embodiment is used for further specifying the present invention, but the present invention is not limited to this.
Synthetic embodiment
Embodiment 1
3-iodo-N
1-(2-methyl-4-sevoflurane isopropyl base)-N
2The preparation (compound 24) of-(1-methyl isophthalic acid-cyano ethyl) phthalic diamide
Step 1: synthetic 3-iodo-N-(1-methyl isophthalic acid-cyano ethyl) mebenil yl benzoic acid
2-amino-2-dimethyl propionitrile (0.84g, 10mmol) and triethylamine (0.20g, mixture 2mmol) is dissolved in N, N-N,N-DIMETHYLACETAMIDE (DMA, 3mL), (2.74g is in DMA 10mmol) (8mL) solution at room temperature slowly to join 3-iodo Tetra hydro Phthalic anhydride.Reaction mixture stirs 1h, pours in the water, uses the dilute hydrochloric acid acidifying.The water ethyl acetate extraction is used anhydrous magnesium sulfate drying.Under reduced pressure obtain orange oily product except that desolvating, thing is separated out solid in a few hours, with the mixture washing of ether and normal hexane.Get white solid product 1.80g (50%), 141～143 ℃ of fusing points, nuclear magnetic data is:
1HNMR (400MHz, DMSO-d
6): δ=13.23 (1H, brs), 8.77 (1H, s), 8.09-8.07 (1H, d), 7.93-7.91 (1H, d), 7.28-7.24 (1H, t), 1.64 (6H, s).
Step 2: the synthetic different imide of 3-iodo-N-(1-methyl isophthalic acid-cyano ethyl) adjacent benzene
(0.76g, (1.07g, 3mmol) in the suspension of 10ml toluene, reaction mixture at room temperature stirs 30min 3.6mmol) to join 3-iodo-N-(1-methyl isophthalic acid-cyano ethyl) mebenil yl benzoic acid with trifluoroacetic anhydride.Decompression removes to desolvate down and obtains the 1.02g crude product, and this crude product can directly enter next step reaction without purifying.148～150 ℃ of melting point compounds, nuclear magnetic data is:
1H NMR (400MHz, CDCl
3): δ=8.30-8.28 (1H, d), 7.98-7.96 (1H, d), 7.45-7.41 (1H, t), 1.85 (6H, s).
Step 3: synthetic 3-iodo-N
1-(2-methyl-4-sevoflurane isopropyl base)-N
2-(1-methyl isophthalic acid-cyano ethyl) phthalic diamide
The different imide of 3-iodo-N-(1-methyl isophthalic acid-cyano ethyl) adjacent benzene (1.02g, in acetonitrile solution 3mmol) (10mL), add 2-methyl-4-sevoflurane isopropyl amine (0.80g, 2.90mmol) and trifluoroacetic acid (0.01g), reaction mixture stirring 3h.Filter, the collecting precipitation thing with a small amount of low temperature acetonitrile washing, obtains first product; Behind the filtrate steaming removal solvent, (eluent: n-hexane/ethyl acetate=2/1-1/1), get second batch of product with two batches of products merging, obtains 3-iodo-N by silica gel chromatography with the gained resistates
1-(2-methyl-4-sevoflurane isopropyl base)-N
2-(1-methyl isophthalic acid-cyano ethyl) phthalic diamide 1.04g (60%), 243～245 ℃ of fusing points, nuclear magnetic data is:
1H NMR (400MHz, DMSO-d
6): δ=9.85 (1H, s), 8.99 (1H, s), 8.05-8.03 (1H, d), 7.79-7.77 (2H, d), 7.53-7.49 (2H, t), 7.33-7.29 (1H, t), 2.36 (3H, s), 1.61 (6H, s).
Embodiment 2
4-chloro-N
1-(2,4 dichloro benzene base)-N
2The preparation of-(1-methyl isophthalic acid-cyano ethyl) phthalic diamide
(compound 48)
Step 1: synthetic 4-chloro-N-(1-methyl isophthalic acid-cyano ethyl) mebenil yl benzoic acid
2-amino-2-dimethyl propionitrile (0.84g, 10mmol) and triethylamine (0.20g, mixture 2mmol) is dissolved in N, N-N,N-DIMETHYLACETAMIDE (DMA, 3mL), (2.74g is in DMA 10mmol) (8mL) solution at room temperature slowly to join the 4-chloro-phthalic anhydride.Reaction mixture stirs 1h, pours in the water, uses the dilute hydrochloric acid acidifying.The water ethyl acetate extraction is used anhydrous magnesium sulfate drying.Under reduced pressure obtain transparent oily product except that desolvating, thing is separated out solid in a few hours, with the mixture washing of ether and normal hexane.Get product 1.73g (65%), 127～130 ℃ of fusing points.
Step 2: the synthetic different imide of 4-chloro-N-(1-methyl isophthalic acid-cyano ethyl) adjacent benzene
(1.01g, (1.06g, 4mmol) in the suspension of 12ml toluene, reaction mixture at room temperature stirs 30min 4.8mmol) to join 4-chloro-N-(1-methyl isophthalic acid-cyano ethyl) mebenil yl benzoic acid with trifluoroacetic anhydride.Decompression removes to desolvate down and obtains the 0.99g crude product, and this crude product can directly enter next step reaction without purifying.
Step 3: synthetic 4-chloro-N
1-(2,4 dichloro benzene base)-N
2-(1-methyl isophthalic acid-cyano ethyl) phthalic diamide
The different imide of 4-chloro-N-(1-methyl isophthalic acid-cyano ethyl) adjacent benzene (0.99g, in acetonitrile solution 4mmol) (12mL), add 2,4 dichloro aniline (0.63g, 3.9mmol) and trifluoroacetic acid (0.01g), reaction mixture stirring 3h.Filter, the collecting precipitation thing with a small amount of low temperature acetonitrile washing, obtains first product; Behind the filtrate steaming removal solvent, (eluent: n-hexane/ethyl acetate=2/1-1/1), get second batch of product with two batches of products merging, obtains 4-chloro-N by silica gel chromatography with the gained resistates
1-(2,4 dichloro benzene base)-N
2-(1-methyl isophthalic acid-cyano ethyl) phthalic diamide 1.13g (71%), 176～178 ℃ of fusing points, nuclear magnetic data is:
1H NMR (400MHz, DMSO-d
6): δ=9.96 (1H, s), 9.08 (1H, s), 7.85-7.70 (4H, m), 7.67-7.55 (1H, m), 7.49-7.41 (1H, m), 1.61 (6H, s).
The The compounds of this invention of enumerating in concordance list 1, concordance list 2 and the table 3 (I) all can synthesize according to the described preparation method of above-mentioned synthetic embodiment 1-2.
Following examples 3 to embodiment 5 provide with compound of the present invention (I) as the active substance component, and the concrete instance of several sterilant formulations of processing preparation it is to be noted that the present invention not merely is confined in the scope of following example.In these prescription examples, all " % " all refer to weight percent.
Embodiment 3 wettable powder agent prescriptions
Compound with 15% (24) (table 1), 5% sulfonated lignin (M
q), 1% ethoxylated dodecyl alcohol (JFC), 40% diatomite and 44% light calcium carbonate mix equably, pulverizes, and promptly gets wettable powder.
Embodiment 4 emulsifiable concentrate formulations
(No. 602, table 1,5% farming breast No. 500 (calcium salts), 5% farming breast, 5% N-N-methyl-2-2-pyrrolidone N-and 75% dimethylbenzene heated and stirred are even, promptly get missible oil for compound with 10% (24).
Embodiment 5 granula prescriptions
Compound with 5% (24) (table 1), 1% polyvinyl alcohol (PVA), 4% naphthalenesulfonic acid-formaldehyde condensate (NMO) and 90% clay mix equably; pulverize; add 20 parts of water to these 100 parts of mixtures then; mediate; with the extruding granulator; make 14-32 purpose particle, drying promptly gets granule.
Provide below and use compound of the present invention to carry out the example of biological activity determination, it is to be noted that the present invention not merely is confined in the scope of following example.
The insecticidal activity evaluation test is carried out according to following method:
Take by weighing the certain mass preparation, the adding distil water dilution is mixed with measures the desired concn soup.Screening concentration be from 500,100,20,4,0.8,0.16,0.032mg/L, chemicals treatment amount of liquid medicine 10mL.Test target is designated as oriental armyworm (Mythima separata), bollworm (Helicothis armigera), aphis craccivora (Aphis medicagini), small cabbage moth (Plutella xylostella), prodenia litura (Prodenia litura), the greedy noctuid (Spodop terafrugiperda) in meadow etc.
(1) oriental armyworm screening---soak the seedling feeding method
Leaf of Semen Maydis is fully soaked into the back dry in the shade naturally in soup, put into culture dish, connect 3 mid-term in age larva, add a cover mark and be placed in the observation ward.Test repeats 4 times.Check result behind the 72h.Touch polypide with writing brush, reactionlessly be considered as dead worm.
(2) bollworm screening---spray method
Potted plant cotton (2-3 opens leaf age) is carried out reagent spray handle, dry.Put into culturing room and continue normal the cultivation.Blade is cut with scissors 5,12, behind the 19d, be put in the Φ 9cm plastic culture dish, connect greedy noctuid in meadow or cotton bollworm larvae, put a filter paper, add a cover.Place in the observation ward check result behind the 6d.
(3) small cabbage moth screening---pickling process
The wild cabbage sheet is cut, punched into disk, be dipped in 20s in the soup then, be put in the Φ 9cm plastic culture dish (5/ware), connect 15/ware of small cabbage moth 2 instar larvaes, put a filter paper, add a cover.Place 26 ℃ of indoor cultivation.Test repeats 4 times.Check result behind the 72h.Touch polypide with the tip tweezers, reactionlessly be considered as dead worm.
(4) aphis craccivora screening---pickling process
If the broad bean blade is cut off two ends, and the back side is placed on the fritter cotton up, places in the plastic culture dish, adds less water, connects aphis craccivora and becomes aphid to produce aphid.Remove into aphid behind the 24h, continue behind the cultivation 2d blade behind the abundant 5s of infiltration, to be placed on the cotton natural airing again in soup.Check result behind the 24h.
(5) prodenia litura screening---pickling process
The wild cabbage sheet is cut, beaten with punch tool and get the wild cabbage roundleaf, in soup, soak 20s, dry.Put into the six hole plastics casings that have circular hole (Φ 2cm), 3 in every hole.Insert 1/hole of prodenia litura larva in 3 mid-term in age, put into observation ward.Test repeats 4 times.Check result behind the 72h.Touch polypide with the tip tweezers, reactionlessly be considered as dead worm.
(6) the greedy noctuid screening in meadow---spray method
Potted plant cotton (2-3 opens leaf age) is carried out reagent spray handle, dry.Put into culturing room and continue normal the cultivation.Blade is cut with scissors 5,12, behind the 19d, be put in the Φ 9cm plastic culture dish, connect greedy noctuid in meadow or cotton bollworm larvae, put a filter paper, add a cover.Place in the observation ward check result behind the 6d.
Annotate: the described numbering of biological activity determination embodiment is corresponding with concordance list 1, concordance list 2 and the described compound number of table 3.
Test statistics: add up the dead borer population of each processing and the borer population of living, calculate mortality ratio.
CK contrasts mortality ratio＜20%, and test-results is credible, and test-results is proofreaied and correct, and CK contrast mortality ratio＜5% o'clock can not proofreaied and correct.
Living test is tested the result and shown: The compounds of this invention has good insecticidal activity, particularly to lepidoptera pest, have the insecticidal activity of wide spectrum as oriental armyworm, bollworm, small cabbage moth, prodenia litura, the greedy noctuid in meadow etc., homoptera pest is also had certain insecticidal activity." mg/L " all refer to every milligram of actives/liter.
Under the 500mg/L concentration, the mortality ratio of 23,24 and 137 pairs of oriental armyworms of compound is 100%.
Under the 500mg/L concentration, the mortality ratio of 32,33 pairs of aphis craccivoras of compound is 100%.
Under the 500mg/L concentration, compound 23,24,32,33,34,40,46,47,48, the mortality ratio of 137 pairs of small cabbage moths is greater than 80%, under the 100mg/L concentration, compound 23,24,33,34,46,47,48, the mortality ratio of 137 pairs of small cabbage moths is greater than 80%, under the 20mg/L concentration, compound 23,24,34,46,47, the mortality ratio of 48 pairs of small cabbage moths is greater than 80%, under the 4mg/L concentration, compound 23,24,34,47, the mortality ratio of 48 pairs of small cabbage moths is greater than 80%, 0.8mg/L under the concentration, compound 23,24, the mortality ratio of 47 pairs of small cabbage moths is greater than 80%, under the 0.16mg/L concentration, and compound 24, the mortality ratio of 47 pairs of small cabbage moths is 100%.
0.8mg/L under the concentration, the mortality ratio of 23,24 pairs of bollworms of compound is 100%, under the 0.16mg/L concentration, the mortality ratio of 24 pairs of bollworms of compound is 100%.
0.8mg/L under the concentration, the mortality ratio of the greedy noctuid in 23,24 pairs of meadows of compound is greater than 80%, under the 0.16mg/L concentration, the mortality ratio of the greedy noctuid in 24 pairs of meadows of compound is 100%.
0.16mg/L under the concentration, the mortality ratio of 24 pairs of prodenia lituras of compound is 100%.
The insecticidal activity of The compounds of this invention and control compound Flubendiamide (flubendiamide) is compared, the results are shown in table 4.
Table 4 insecticidal activity relatively
Table 4 shows, compare with existing compound Flubendiamide, when concentration during greater than 0.16mg/L, The compounds of this invention is suitable substantially to the insecticidal activity of small cabbage moth, prodenia litura has been brought into play higher insecticidal action, particularly under low rate of application (0.032Mg/L), The compounds of this invention is higher than the activity of Chlorpyrifos 94 and Cypermethrin far away than existing compound excellence.Based on the similarity on these compound structures, the result of this raising is beat all.
Compound 24 is carried out greenhouse residual activity test, the results are shown in table 5.Test-results shows: when 0.8mg/L, to compound 24 19 days processing examination worms behind medicine, small cabbage moth, the greedy noctuid in meadow and bollworm mortality ratio still reach 100%; When 0.16mg/L, along with the prolongation in treatment time, drug effect reduces, and behind the medicine 12 days, still can reach 100%, behind the medicine 19 days, small cabbage moth, the greedy noctuid in meadow and bollworm mortality ratio reduced to 60%, 55% and 80% respectively; 0.032mg/L the time, all lower to the drug effect of 3 kinds of examination worms.Compound 24 had very high residual activity.
Table 5 compound 24 residual activity test-results
Claims (13)
1. the phthalyl aminated compounds of the cyano-containing of a formula (I) expression or its agricultural go up the salt that is suitable for,
Wherein:
R
1, R
2Be independently selected from hydrogen, C
1-C
6Alkyl, C
3-C
6Cycloalkyl, C
2-C
6Alkenyl or C
2-C
6Alkynyl, the hydrogen on the described group can also be by halogen, cyano group, nitro, C
1-C
6The phenoxy group of the phenyl of alkoxyl group, phenyl, replacement, phenoxy group, replacement, alkylthio, alkyl sulphinyl or alkyl sulphonyl further replace;
Perhaps R
1And R
2Form cycloalkyl together with the carbon that is connected;
R
3Be selected from hydrogen, halogen, cyano group, nitro, aryl, ester group, C
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
6Alkoxyl group or halo C
1-C
6Alkoxyl group;
R
4Be selected from hydrogen or C
1-C
6Alkyl;
X is selected from methylene radical, C
1-C
6Methylene radical that alkyl, cyano group replace or direct key;
Perhaps X and R
4Form triatomic ring, tetra-atomic ring, five-ring, six-ring, five-membered ring or hexa-member heterocycle with the N that is connected;
Y is selected from hydrogen, halogen, cyano group, nitro, hydroxyl, C
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
3Alkoxyl group, halo C
1-C
3The heterocyclic aryl of the phenyl of alkoxyl group, phenyl, replacement, heterocyclic aryl or replacement;
A is CH or N;
M is 0～4 integer.
2. according to the phthalyl aminated compounds of the described cyano-containing of claim 1, it is characterized in that:
R
1, R
2Be independently selected from hydrogen, C
1-C
3Alkyl, C
3-C
6Cycloalkyl or C
2-C
3Alkenyl, the hydrogen on the described group can also substituted phenyl, phenoxy group, alkylthio, alkyl sulphinyl or the alkyl sulphonyl of replacement further replace;
Perhaps R
1And R
2Form cyclohexyl together with the carbon that is connected;
R
3Be selected from hydrogen or halogen;
R
4Be selected from hydrogen or C
1-C
3Alkyl;
Perhaps X and R
4Form five-membered ring or hexa-member heterocycle with the N that is connected;
Y is selected from hydrogen, halogen atom, nitro, hydroxyl, C
1-C
3Alkyl, fluoro C
1-C
3Alkyl, C
1-C
3Alkoxyl group or fluoro C
1-C
3Alkoxyl group;
M is 1～3 integer.
3. according to the phthalyl aminated compounds of the described cyano-containing of claim 2, it is characterized in that:
R
1, R
2Be independently selected from hydrogen, methyl, ethyl, sec.-propyl, cyclopropyl or allyl group, group such as the hydrogen on the described group can also substituted phenyl, the phenoxy group of replacement, methylthio group, methylsulfinyl, methyl sulphonyl further replaces;
R
3Be selected from fluorine, chlorine, bromine or iodine, R
3Be positioned at 3 or 4 of phenyl ring;
R
4Be hydrogen or methyl;
X is the methylene radical or the direct key of methylene radical, methyl, cyano group replacement;
Perhaps X and R
4Contain the oxygen hexa-member heterocycle with the N composition that is connected;
Y is selected from hydrogen, fluorine, chlorine, nitro, hydroxyl, methyl, methoxyl group, trifluoromethyl, trifluoromethoxy or seven fluorine sec.-propyls.
4. according to the phthalyl aminated compounds of the described cyano-containing of claim 3, it is characterized in that described phthalyl aminated compounds is:
5. according to the phthalyl aminated compounds of the described cyano-containing of claim 1, it is characterized in that comprising the R and/or the S optically active isomer of arbitrary proportion.
6. an intermediate that is used to prepare according to the phthalyl aminated compounds of the described cyano-containing of claim 1 is characterized in that having as shown in the formula (II) or compound (III),
Wherein:
R
1, R
2Be independently selected from hydrogen, C
1-C
6Alkyl, C
3-C
6Cycloalkyl, C
2-C
6Alkenyl or C
2-C
6Alkynyl, the hydrogen on the described group can also be by halogen, cyano group, nitro, C
1-C
6The phenoxy group of the phenyl of alkoxyl group, phenyl, replacement, phenoxy group, replacement, alkylthio, alkyl sulphinyl or alkyl sulphonyl further replace;
Perhaps R
1And R
2Form cycloalkyl together with the carbon that is connected;
R
3Be selected from hydrogen, halogen, cyano group, nitro, aryl, ester group, C
1-C
6Alkyl, halo C
1-C
6Alkyl, C
1-C
6Alkoxyl group or halo C
1-C
6Alkoxyl group.
7. according to the described intermediate that is used to prepare according to the described phthalyl aminated compounds of claim 1 of claim 6, it is characterized in that:
R
1, R
2Be independently selected from hydrogen, C
1-C
3Alkyl, C
3-C
6Cycloalkyl or C
2-C
3Alkenyl, the hydrogen on the described group can also substituted phenyl, phenoxy group, alkylthio, alkyl sulphinyl or the alkyl sulphonyl of replacement further replace;
Perhaps R
1And R
2Form cyclohexyl together with the carbon that is connected;
R
3Be selected from hydrogen or halogen.
8. according to the described intermediate that is used to prepare according to the described phthalyl aminated compounds of claim 1 of claim 7, it is characterized in that:
R
1, R
2Be independently selected from hydrogen, methyl, ethyl, sec.-propyl, cyclopropyl or allyl group, group such as the hydrogen on the described group can also substituted phenyl, the phenoxy group of replacement, methylthio group, methylsulfinyl, methyl sulphonyl further replaces;
R
3Be selected from fluorine, chlorine, bromine or iodine, R
3Be positioned at 3 or 4 of phenyl ring.
9. the preparation method of the phthalyl aminated compounds of the described cyano-containing of claim 1 is characterized in that may further comprise the steps:
(1) at inert solvent, exist or do not exist under the situation of alkali, the Tetra hydro Phthalic anhydride of the replacement of structural formula (VI) expression and the aminoacetonitriles of the replacement that the structure formula V is represented advance the replacement mebenil yl benzoic acid that the N-acylation reaction obtains structural formula (III) expression;
(2) at inert solvent, the replacement mebenil yl benzoic acid of structural formula (III) expression and acylating reagent reaction obtain the different imide of phthalyl of the replacement of structural formula (II) expression;
(3) in inert solvent, exist or do not exist under the situation of acid, the amine reaction of the replacement of the different imide of phthalyl of the replacement of structural formula (II) expression and structural formula (IV) expression obtains the phthalyl aminated compounds of the cyano-containing of structural formula (I) expression;
Wherein: R
1, R
2, R
3, R
4, A, X, Y and m definition according to claim 1.
10. according to the preparation method of the phthalyl aminated compounds of the described cyano-containing of claim 9, it is characterized in that:
Inert solvent is selected from tetrahydrofuran (THF), acetonitrile, 1 described in the step (1), 4-dioxane, N, dinethylformamide, N, one or more combinations in N-N,N-DIMETHYLACETAMIDE, toluene or the methylene dichloride, described alkali comprises organic bases and mineral alkali, described organic bases is selected from triethylamine, pyridine or 3-picoline, and described mineral alkali is selected from salt of wormwood, sodium bicarbonate, sodium hydroxide or anhydrous sodium acetate;
Inert solvent is selected from toluene, 1 described in the step (2), 2-ethylene dichloride, ethyl acetate, tetrahydrofuran (THF), acetonitrile, 1, one or more combinations in 4-dioxane or the methylene dichloride, described acylating reagent are methyl-chloroformate, diacetyl oxide or trifluoroacetic anhydride;
Inert solvent is selected from tetrahydrofuran (THF), methylene dichloride, 1 described in the step (3), 2-ethylene dichloride, ether, 1, one or more combinations in 4-dioxane, acetonitrile or the toluene, described acid comprises organic acid and mineral acid, described organic acid is selected from acetate, trifluoroacetic acid or p-methyl benzenesulfonic acid, and described mineral acid is hydrochloric acid or sulfuric acid;
Temperature of reaction is between the boiling point of used inert solvent at 0 ℃.
11. a purposes that goes up the salt that is suitable for according to phthalyl aminated compounds or its agricultural of the cyano-containing of the described structural formula of one of claim 1 to 10 (I) expression is characterized in that being used for agricultural chemical insecticide.
12. a pesticide preparation is characterized in that, phthalyl aminated compounds or its agricultural of cyano-containing that contains the described structural formula of claim 1 (I) expression of 0.001%-99.99% (weight) goes up the salt that is suitable for, and agricultural goes up acceptable carrier.
13. method of preventing and treating harmful organism, it is characterized in that: the described pesticide preparation of claim 12 is imposed on the medium of the harmful organism of needs control or its growth, wherein the significant quantity of the phthalyl aminated compounds of active ingredient cyano-containing is that per hectare 10 restrains 1000 grams.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1222506A (en) * | 1997-11-25 | 1999-07-14 | 日本农药株式会社 | Phthalic acid diamide derivatives, agricultural and horticultural insecticides, and method for application of insecticides |
| US20030055287A1 (en) * | 1997-11-25 | 2003-03-20 | Masanori Tohnishi | Phthalic acid diamide derivatives, fluorine-containing aniline compounds as starting material, agricultural and horticultural insecticides, and a method for application of the insecticides |
| CN1413187A (en) * | 1999-12-22 | 2003-04-23 | 日本农药株式会社 | Aromatic diamide derivatives, chemicals for agricultural or horticultural use and usage thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4041045A (en) * | 1975-11-12 | 1977-08-09 | American Cyanamid Company | Dihydroimidaz oisoindolediones and the use thereof as herbicidal agents |
| IL51139A (en) * | 1976-12-21 | 1979-10-31 | American Cyanamid Co | 3-substituted 3h-imidazo(2,1-a)isoindole-2,5-dione derivatives,their preparation and herbicidal methods employing them |
| US4719303A (en) * | 1983-11-21 | 1988-01-12 | American Cyanamid Company | Preparation of substituted and unsubstituted 2-[(1-carbamoyl-1,2-dimethylpropyl)-carbamoyl]-3-quinolinecarboxylic, nicotinic and benzoic acids |
| CZ20021074A3 (en) * | 1999-09-24 | 2002-08-14 | Nihon Nohyaku Co., Ltd. | Derivatives of aromatic diamides and salts thereof, agricultural and horticultural preparations and method for using them |
| JP2005272452A (en) * | 2004-02-23 | 2005-10-06 | Nissan Chem Ind Ltd | Substituted benzanilide compound and pesticide |
| JP2010030970A (en) * | 2008-07-31 | 2010-02-12 | Bayer Cropscience Ag | Insecticidal benzenedicarboxamide derivative |
| CN101935291B (en) * | 2010-09-13 | 2013-05-01 | 中化蓝天集团有限公司 | Cyano phthalic diamide compounds, preparation method thereof and use thereof as agricultural chemical pesticide |
-
2010
- 2010-09-13 CN CN 201010279790 patent/CN101935291B/en active Active
-
2011
- 2011-08-22 WO PCT/CN2011/078711 patent/WO2012034472A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1222506A (en) * | 1997-11-25 | 1999-07-14 | 日本农药株式会社 | Phthalic acid diamide derivatives, agricultural and horticultural insecticides, and method for application of insecticides |
| US20030055287A1 (en) * | 1997-11-25 | 2003-03-20 | Masanori Tohnishi | Phthalic acid diamide derivatives, fluorine-containing aniline compounds as starting material, agricultural and horticultural insecticides, and a method for application of the insecticides |
| CN1413187A (en) * | 1999-12-22 | 2003-04-23 | 日本农药株式会社 | Aromatic diamide derivatives, chemicals for agricultural or horticultural use and usage thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《J.Pestic.Sci.》 20051231 Masanori Tohnishi等人 Flubendiamide,a Novel Insecticide Highly Active against Lepidopterous Insect Pests 354-360 1－13 第30卷, 第4期 * |
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| WO2012034472A1 (en) | 2012-03-22 |
| CN101935291B (en) | 2013-05-01 |
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Inventor after: Zhu Bingchun Inventor after: Dong Dezhen Inventor after: Yuan Jing Inventor after: Wei Wei Inventor after: Xing Jiahua Inventor after: Xu Tianming Inventor after: Zheng Zhiwen Inventor after: Chen Jie Inventor after: Peng Weili Inventor after: Xu Yonghua Inventor after: Kong Xiaolin Inventor after: Wei Youchang Inventor before: Zhu Bingchun Inventor before: Dong Dezhen Inventor before: Yuan Jing Inventor before: Wei Wei Inventor before: Xing Jiahua Inventor before: Xu Tianming Inventor before: Zheng Zhiwen Inventor before: Chen Jie Inventor before: Peng Weili Inventor before: Xu Yonghua Inventor before: Kong Xiaolin Inventor before: Wei Youchang |
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Effective date of registration: 20200220 Address after: 310051 Binjiang District Jiangnan Road, Zhejiang, No. 96, No. Co-patentee after: Zhejiang Research Institute of Chemical Industry, Ltd. Patentee after: Sinochem Lantian Co., Ltd. Co-patentee after: Sinochem Corporation Address before: 310012 No. 487, Stadium Road, Hangzhou, Zhejiang Co-patentee before: Zhejiang Research Institute of Chemical Industry, Ltd. Patentee before: Sinochem Lantian Co., Ltd. |