WO2016117675A1 - 置換ピラゾリルピラゾール誘導体とその除草剤としての使用 - Google Patents
置換ピラゾリルピラゾール誘導体とその除草剤としての使用 Download PDFInfo
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- WO2016117675A1 WO2016117675A1 PCT/JP2016/051823 JP2016051823W WO2016117675A1 WO 2016117675 A1 WO2016117675 A1 WO 2016117675A1 JP 2016051823 W JP2016051823 W JP 2016051823W WO 2016117675 A1 WO2016117675 A1 WO 2016117675A1
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- compound
- weeds
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- WASZSYLPEPFXBK-UHFFFAOYSA-N CCCC(Nc([n](-c1n[n](CCCC2)c2c1Cl)nc1)c1C#N)=O Chemical compound CCCC(Nc([n](-c1n[n](CCCC2)c2c1Cl)nc1)c1C#N)=O WASZSYLPEPFXBK-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P13/00—Herbicides; Algicides
- A01P13/02—Herbicides; Algicides selective
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
- C07D231/16—Halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
Definitions
- the present invention relates to a substituted pyrazolyl pyrazole derivative and use of the compound as a herbicide.
- the first mid-stage treatments in paddy rice are Nobies (Echinochloa oryzicola), Inhibibies (Echinochloa crus-galli var. Crus-galli), Echinochloa crus-galis var-formi. praticola) and proceedingsubie (generic name for Echinochloa crus-galli var. caudata) are effective in the treatment from the 2nd to the 3rd leaf stage, and the main weeds can be controlled by a single treatment ( Non-Patent Document 1 (reference). However, it is very difficult to control weeds when nobies grow to 3.5 leaf stages or more in the first mid-stage treatment agent in practical use. There is a great technological isolation in the control of the 5th leaf stage.
- maintaining the herbicidal effect over a long period of time is important in terms of reducing pesticide application, labor saving, and cost reduction, and is considered an essential performance for the first mid-term treatment agent.
- ALS acetolactic acid synthase
- weeds having resistance to ALS inhibitors have become a problem.
- herbicides that have a sufficient effect on the perennial Amodaka (Sagittaria trifolia) and Urikawa (Sagittaria pygmaea) ALS inhibitor-resistant biotypes.
- pyrazole derivatives have been put to practical use as herbicides, such as 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5-pyrazolyl p-toluenesulfonate (generic name: “pyrazolate”), 2- [4- (2,4-dichlorobenzoyl) -1,3-dimethylpyrazol-5-yloxy] acetophenone (generic name: “pyrazoxifene”), 2- [4- (2,4-dichloro-m-toluoyl) ) -1,3-Dimethylpyrazol-5-yloxy] -4′-methylacetophenone (generic name: “benzophenap”), etc.
- pyrazolate 2- [4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5-pyrazolyl p-toluenesulfonate
- 1- (3-chloro-4,5,6,7-tetrahydropyrazolo [1,5-a] pyridin-2-yl) -5 which is the compound of Example 4.73 described in Patent Document 1.
- -[Methyl (prop-2-ynyl) amino] pyrazole-4-carbonitrile (generic name: “pyraclonyl”, trade name: Pyraclone) is effective against a wide range of weeds, but it has a sufficient effect on old leaf nobies. In Japan, the scope of application of this drug alone to Nobies on registration is up to 1.5 leaf stage.
- Patent Document 1 discloses compounds that exhibit a herbicidal effect by pre- and post-emergence treatment on weeds that occur in upland fields, but does not describe leaf age. It cannot be said that it has sufficient effect on weeds.
- a herbicide having a broad herbicidal effect on upland weeds for example, isopropylammonium N- (phosphonomethyl) glycinate (generic name: “glyphosate isopropylamine salt”) is widely used. Problems such as the generation of weeds have occurred in recent years.
- the present invention has a broad herbicidal spectrum including weeds resistant to existing herbicides, can control important weeds of higher leaf age, which is a practical problem, and
- An object of the present invention is to provide a compound having excellent characteristics as a herbicide component, such as causing no phytotoxicity to crops.
- the present inventors have found that a pyrazolyl pyrazole derivative having a specific chemical structure has a broad herbicidal spectrum over a long period of time and is important for high leaf age.
- the present inventors have found that it has excellent herbicidal efficacy against weeds, while having sufficient safety for cultivated crops, and has completed the present invention based on these findings. Accordingly, the present invention provides a compound represented by the following formula (I), a pyrazolyl pyrazole derivative.
- R 1 represents a chlorine atom or a bromine atom
- R 2 represents a cyano group or a nitro group
- R 3 is a C 3 -C 5 alkyl group (optionally substituted with one or more halogen atoms), C 2 -C 6 (optionally substituted with one or more halogen atoms).
- An alkenyl group, a C 2 -C 6 alkynyl group (optionally substituted by one or more halogen atoms), and a represents 3-5 (wherein R 3 is substituted by a halogen atom) And a compound represented by a straight-chain saturated hydrocarbon, and a compound in which R 1 is a chlorine atom, R 2 is a cyano group, and R 3 is a 3-chloropropyl group).
- R 1 represents a chlorine atom
- R 2 represents a cyano group
- R 3 is a C 3 -C 5 alkyl group (optionally substituted by one or more halogen atoms)
- C 2 -C 5 (optionally substituted by one or more halogen atoms) Represents an alkenyl group
- a represents 4.
- Halogen atom includes fluorine, chlorine, bromine and iodine atoms.
- Alkyl as referred to by itself or as part of a group can be linear or branched and includes, but is not limited to, for example, methyl, ethyl, n- or iso-propyl, n- , Iso-, sec- or tert-butyl, n-pentyl, and the like, each selected within the specified number of carbon atoms.
- Alkenyl group means an unsaturated hydrocarbon group which is linear or branched and has one or more double bonds in the molecule. Specific examples include groups, 1-propenyl group, 2-propenyl group, 2-butenyl group, 2-methyl-2-propenyl group, 3-methyl-2-butenyl group, 1,1-dimethyl-2-propenyl group and the like. Each of which is selected for each specified number of carbon atoms.
- Alkynyl group means an unsaturated hydrocarbon group which is linear or branched and has one or more triple bonds in the molecule, and is not limited to, for example, ethynyl group, 1 Specific examples include -propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1,1-dimethyl-2-propynyl group and the like. Selected by range. “Alkyl group”, “alkenyl group”, and “alkynyl group” may be such that at least one of the hydrogen atoms contained in these groups may be substituted by a halogen atom.
- this group can be substituted by more than one same or different halogen atoms.
- the compound of formula (I) can exist as a stereoisomer.
- stereoisomers can be enantiomers and diastereomers.
- Stereoisomers can be obtained from the mixtures obtained in the preparation by conventional separation methods, for example chromatographic separation steps.
- Stereoisomers can also be prepared by using stereoselective reactions, employing optically active starting materials and / or auxiliaries.
- the invention also relates to all stereoisomers and mixtures thereof which are encompassed by the compounds represented by formula (I) but are not specifically defined.
- the compound of the formula (II) can be synthesized from tetrahydro-2H-pyran-2-ylideneacetonitrile or 5-chlorovaleryl chloride according to the method described in WO93 / 10100 and WO94 / 08999.
- amidation reaction of the compound of formula (II) can be carried out with reference to known reaction conditions per se (see, for example, WO 94/08999, Tetrahedron Lett. 32, 4019 (1991)).
- the compound of the formula (I) provided by the present invention has an excellent herbicidal effect and is useful as a herbicide, as is apparent from the results of the herbicidal activity tests described in Test Examples 1 to 4 described later. is there.
- the compound of formula (I) of the present invention has activity against various types of agricultural and non-cultivated weeds.
- cultivated plants include, for example, gramineous plants such as rice, wheat, barley, corn, oat, sorghum, broad-leaved crops such as soybean, cotton, beet, sunflower, rapeseed, fruit trees, fruit vegetables, root vegetables, leaf vegetables, etc. Vegetables, lawn, etc., can be used for their cultivation.
- the compound of the present invention is herbicidal in various treatment methods such as soil treatment, soil admixture treatment and foliage treatment in flooded or non-flooded state against various weeds which are the following problems in paddy fields. Has efficacy. Although the weed is illustrated below, it is not limited to these examples.
- Omodaka weeds such as Heramodaka (Arisma canaliculatum), Omodaka (Sagittaria trifolia), Urikawa (Sagittaria pygmaea), (Cyperus serotinus), firefly (Sirpus juncoides), Krogwei (Eleocharis ur kuroguwaii), Shirapus dine insidia (Sir
- dubia Scrophulariaceae weeds such as Amerikaazena (Lindernia dubia), Monochoria (Monochoria vaginalis), Monochoria korsakowii (Monochoria korsakowii) pontederiaceae weeds such as, pondweed (Potamogeton distinctus) potamogetonaceae weeds such as Rotala indica (Rotala indica) , Cranaceae weeds such as Amannia multiflora, Tacogi (Bidens tripartita), Asteraceae weeds such as Bidens frontosa, Aeschinomena dinosaurs, etc. ), Etc.
- Cruciferous weeds such as, knotweed (Persicaria longiseta), wild buckwheat (Fallopia convolvulus), bantams Niwa willow (Polygonum aviculare var.condensatum), Hirohamichiyanagi (Polygonum aviculare var. Monospeliense), Keharutade (Polygonum persicaria), Sanaetade (Persicaria lapathifolia var Incana), terrestrial weeds such as Persicaria lapathifolia var.
- Lapathifolia, siberian weeds such as Portulaca oleracea, Chenopodium albem, Kokasco (Chenopodium fififolium), Kochia scoparia, Azalea weeds (Atriplex patula), etc.
- Weeping weeds such as Commelina communis, Weikenosa (Lamium amplexicaule), Giantia bursam (Lamium purpureum), Rhinococcus bursas (Galeopsis tetrahit), How Euphorbiaceae weeds, thorns without cleavers (Galium spurium), cleavers (Galium spurium var.
- Echinospermon Rubia argyii, Rubiaceae weeds such as Galium aline, Viola mandashurica, Violet venoms such as Viola arvensis, Violet venomis, Ms.
- Broad-leaved weeds such as leguminous weeds such as Sesbania exaltata, Cassia obfusitolia, Sorghum bichor, encorders, and pears.
- the compound of the formula (I) of the present invention does not show any phytotoxicity that causes problems for paddy rice by any cultivation method such as direct sowing cultivation or transplantation cultivation of rice.
- the compound of the formula (I) of the present invention can be applied both before and after germination of a plant, and can also be mixed with soil before sowing.
- the dosage of the compound of formula (I) of the present invention can be varied over a wide range depending on the kind of the compound, the kind of the target plant, the application time, the place of application, the nature of the effect to be desired, etc.
- Can be exemplified as the active compound per are, in the range of about 0.01 to 100 g, preferably about 0.1 to 10 g.
- the compound of the formula (I) of the present invention can be used alone, but usually, according to a conventional method, a compounding aid is blended with the compound of the formula (I) and is not limited. Powder, Emulsion, Oil, Solubilizer, Suspo Emulsion, Fine Granule, Spray, DL Powder, Fine Granule F, Fine Granule F, Granule, Wettable Powder, Granulant, Flowable, Jumbo It is preferable to formulate and use it in any dosage form such as tablets, pastes, oily suspensions, aqueous solvents, granular aqueous solvents, liquids, and microcapsules.
- Formulation aids that can be used for formulation are not limited, and examples include solid carriers, liquid carriers, binders, thickeners, surfactants, antifreeze agents, and preservatives.
- Solid carriers include, but are not limited to, for example, talc, bentonite, montmorillonite, clay, kaolin, calcium carbonate, sodium carbonate, sodium bicarbonate, sodium sulfate, zeolite, starch, acid clay, diatomaceous earth, white carbon, vermiculite, slaked lime , Vegetable powder, alumina, activated carbon, saccharides, glass hollow body, silica sand, ammonium sulfate, urea and the like.
- liquid carriers include, but are not limited to, hydrocarbons (eg, kerosene, mineral oil, etc.); aromatic hydrocarbons (eg, toluene, xylene, dimethylnaphthalene, phenylxylylethane, etc.); chlorination Hydrocarbons (eg, chloroform, carbon tetrachloride, etc.); ethers (eg, dioxane, tetrahydrofuran, etc.); ketones (eg, acetone, cyclohexanone, isophorone, etc.); esters (eg, ethyl acetate, ethylene glycol acetate, Alcohols (eg, methanol, n-hexanol, ethylene glycol, etc.); polar solvents (eg, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc.); water, etc. .
- hydrocarbons eg, kerosen
- binder and the thickener include, but are not limited to, for example, dextrin, sodium salt of carboxymethyl cellulose, polycarboxylic acid polymer compound, polyvinyl pyrrolidone, polyvinyl alcohol, sodium lignin sulfonate, calcium lignin sulfonate, Examples include sodium polyacrylate, gum arabic, sodium alginate, mannitol, sorbitol, bentonite minerals, polyacrylic acid and its derivatives, white carbon, natural sugar derivatives (for example, xanthan gum, guar gum, etc.).
- surfactant examples include, but are not limited to, for example, fatty acid salts, benzoates, alkylsulfosuccinates, dialkylsulfosuccinates, polycarboxylates, alkylsulfate esters, alkylsulfates, alkylarylsulfates.
- antifreezing agent examples include, but are not limited to, ethylene glycol, diethylene glycol, propylene glycol, and glycerin.
- preservatives include, but are not limited to, for example, benzoic acid, sodium benzoate, methyl paraoxybenzoate, butyl paraoxybenzoate, isopropylmethylphenol, benzalkonium chloride, chlorhexidine hydrochloride, hydrogen peroxide, gluconic acid Chlorhexidine, salicylic acid, sodium salicylate, zinc pyrithione, sorbic acid, potassium sorbate, dehydroacetic acid, sodium dehydroacetate, phenoxyethanol, 5-chloro-2-methyl-4-isothiazoline-3-one, 2-methyl-4-isothiazoline-3 Examples include isothiazoline derivatives such as -one, 2-bromo-2-nitropropane-1,3-diol, and salicylic acid derivatives.
- solid carriers liquid carriers, binders, thickeners, surfactants, antifreezing agents and preservatives described above can be used alone or in appropriate combination depending on the purpose of use.
- the blending ratio of the compound of the formula (I) of the present invention to the whole herbicidal composition of the present invention can be adjusted as necessary and is not particularly limited, but is usually about 0.01 to 90% by mass, for example, In the case of a powder or granule, it is preferably about 0.1 to 50% by mass, more preferably about 0.5 to 10% by mass, and in the case of an emulsion, wettable powder or granular wettable powder, it is 0. About 1 to 90% by mass is preferable, and about 0.5 to 50% by mass is more preferable.
- Example 1 Process for producing N- (1- (3-chloro-4,5,6,7-tetrahydropyrazolo [1,5-a] pyridin-2-yl) -4-cyanopyrazol-5-yl) isobutyramide (compound 1) 5-Amino-1- (3-chloro-4,5,6,7-tetrahydropyrazolo [1,5-a] pyridin-2-yl) pyrazole-4-carbonitrile (2.6 g) and acetonitrile (10 ml ) And isobutanoyl chloride (1.2 g) was slowly added dropwise thereto, and the mixture was heated to reflux for 5 hours.
- Formula (II) as a starting material was synthesized according to WO93 / 10100 and WO94 / 08999.
- Powder A compound of the formula (I) 10 parts by weight Talc 90 parts by weight is mixed and pulverized with a hammer mill.
- Wetting agent Compound of formula (I) 10 parts by weight Polyoxyethylene alkylaryl ether sulfate 22.5 parts by weight 67.5 parts by weight of white carbon are mixed, and this mixture is obtained by pulverizing with a hammer mill.
- Flowable agent Compound of formula (I) 10 parts by weight Polyoxyethylene alkyl ether phosphate 10 parts by weight Bentonite 5 parts by weight Ethylene glycol 5 parts by weight Water 70 parts by weight are mixed and pulverized using a wet pulverizer. An agent is obtained.
- Granules Compound of formula (I) 5 parts by weight Calcium lignin sulfonate 3 parts by weight Polycarboxylic acid salt 3 parts by weight Calcium carbonate 89 parts by weight are mixed, kneaded and extruded and granulated. Thereafter, the granules are obtained by drying and sizing. ⁇ Example of biological test>
- Paddy Field Weeding Test A 1 / 10,000 are pot was filled with paddy soil, kneaded with an appropriate amount of water and chemical fertilizer, seeded with nobier, kogi and firefly seeds, and maintained in a flooded state with a depth of 3 cm.
- the wettable powder of the target compound (I) shown in Table 1 prepared according to the formulation example was diluted with an appropriate amount of water, and 2.0 leaves of rice were transplanted into Nobies 3.5 leaves. The solution was dropped using a pipette so as to obtain a dose of. And after managing for 30 days in the glass room of average temperature 30 degreeC, those weeding effects were investigated.
- the evaluation of the herbicidal effect was compared with the state of the untreated group and the growth inhibition rate (%), and the evaluation of the phytotoxicity was shown in the following 11 steps by comparing the state of the complete weeding group and the growth inhibition rate (%).
- Control agent 1.36 (described in WO94 / 08999) Control agent 1.37 (described in WO94 / 08999) Control agent 1.9 (described in WO94 / 08999) Control agent 2.17 (described in WO94 / 08999) Control agent 4.187 (described in WO94 / 08999)
- Field Soil Treatment Test A 1/6000 are pot was filled with field soil, and seeds of barnyard grass, white rosy, and aubiu were sown and covered with soil.
- the wettable powder of the compound of the formula (I) shown in Table 1 prepared according to the formulation example is diluted with water to a predetermined dosage, and after spraying, before spraying weeds, the amount of sprayed water is 100 liters per 10 ares. Each soil surface was sprayed uniformly. And after managing for 30 days in the glass room of average temperature 30 degreeC, those weeding effects were investigated. The herbicidal effect was evaluated in the same manner as in Test Example 1. The results are shown in Table 3.
- Field crop foliage treatment test A 1/6000 are pot was filled with culture soil, seeds of bark, Shiroza and Aoubi were sown and covered with soil, and cultivated in a glass room with an average temperature of 25 ° C.
- the wettable powder of the target compound (I) shown in Table 1 prepared according to the preparation example is diluted with water to a predetermined dosage.
- the spray was uniformly sprayed on the weeds with a spraying water amount of 150 liters per 10 ares.
- those weeding effects were investigated. Evaluation of the herbicidal effect was performed in the same manner as in Test Example 1. The results are shown in Table 4.
- the bark is grown at the 4-5 leaf stage (plant height: 10-15 cm)
- the wettable powder of the target compound (I) shown in Table 1 prepared according to the formulation example is prepared in water so as to have a predetermined dosage. And sprayed uniformly on the weeds with a spraying water amount of 100 L per 10 ares. And after managing for 20 days in the glass room of average temperature 25 degreeC, those weeding effects were investigated. Evaluation of the herbicidal effect was performed in the same manner as in Test Example 1. The results are shown in Table 5.
- the compound of formula (I) of the present invention is useful as a harmful plant control agent because it has an excellent control effect against undesirable plants.
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Abstract
Description
しかしながら、雑草の種類は多岐にわたり、また各雑草の発芽及び生育時期は一様ではなく、さらに、多年生雑草の発生は長期におよぶ。そのため一回の除草剤散布ですべての雑草を防除することは非常に困難である。
従って本発明は、下記式(I)で示される化合物、ピラゾリルピラゾール誘導体を提供する。
R1は塩素原子、臭素原子を表わし、
R2はシアノ基、ニトロ基を表わし、
R3は(場合により、1個またはそれ以上のハロゲン原子によって置換された)C3~C5アルキル基、(場合により、1個またはそれ以上のハロゲン原子によって置換された)C2~C6アルケニル基、(場合により、1個またはそれ以上のハロゲン原子によって置換された)C2~C6アルキニル基を表わし、かつ
aは3~5を表わす
(ただし、R3はハロゲン原子によって置換されていない直鎖飽和炭化水素で表わされる化合物、および、R1は塩素原子、R2はシアノ基、R3は3-クロロプロピル基で示される化合物を除く)。
好ましくは、
R1が塩素原子を表わし、
R2がシアノ基を表わし、
R3が(場合により、1個またはそれ以上のハロゲン原子によって置換された)C3~C5アルキル基、(場合により、1個またはそれ以上のハロゲン原子によって置換された)C2~C5アルケニル基を表わし、かつ
aが4を表わす。
各置換基の前の「Ca~Cb」のごとき記載は、それぞれ該当する基中に炭素原子がa個~b個存在することを意味する。
「ハロゲン原子」には、フッ素、塩素、臭素及びヨウ素原子が包含される。
基それ自体または基の部分にいう「アルキル」は、直鎖状もしくは分枝鎖状であることができ、限定されるものでないが、例えば、メチル、エチル、n-もしくはiso-プロピル、n-、iso-、sec-もしくはtert-ブチル、n-ペンチルなどが挙げられ、各々の指定の炭素原子数の範囲で選択される。
「アルケニル基」は、直鎖状もしくは分枝鎖状で、且つ分子内に1個又は2個以上の二重結合を有する不飽和炭化水素基を意味し、限定されるものでないが、例えばビニル基、1-プロペニル基、2-プロペニル基、2-ブテニル基、2-メチル-2-プロペニル基、3-メチル-2-ブテニル基、1,1-ジメチル-2-プロペニル基等が具体例として挙げられ、各々の指定の炭素原子数の範囲で選択される。
「アルキニル基」は直鎖状又は分岐鎖状で、且つ分子内に1個又は2個以上の三重結合を有する不飽和炭化水素基を意味し、限定されるものでないが、例えばエチニル基、1-プロピニル基、2-プロピニル基、1-ブチニル基、2-ブチニル基、3-ブチニル基、1,1-ジメチル-2-プロピニル基等が具体例として挙げられ、各々の指定の炭素原子数の範囲で選択される。
「アルキル基」、「アルケニル基」、「アルキニル基」は、これらの基に含まれる水素原子の少なくとも1個がハロゲン原子により置換されていてもよく、例えばアルキル基を例に挙げると、限定されるものでないが、クロロメチル、ジクロロメチル、トリフルオロメチル、クロロエチル、ジクロロエチル、トリフルオロエチル、テトラフルオロプロピル、ブロモエチル、ブロモプロピル、クロロブチル、クロロヘキシル、ペルフルオロヘキシル基であることができ、各々の指定の炭素原子数の範囲で選択される。
イヌホウズキ(Solanum nigrum)、シロバナチョウセンアサガオ(Datura stramonium)などのナス科雑草、イチビ(Abutilon avicennae)、アメリカキンゴジカ(Sida spinosa)、セイヨウヒルガオ(Convolvulus arvensis)などのアオイ科雑草、マルバアサガオ(Ipomoea purpurea)などのヒルガオ科雑草、イヌビユ(Amaranthus lividus)、アオゲイトウ(Amaranthus retroflexus)、オオホナガアオゲイトウ(Amaranthus palmeri)、ヒユモドキ(Amaranthus tuberculatus)などのヒユ科雑草、オナモミ(Xanthium strumarium)、ブタクサ(Ambrosia artemisiifolia)、ハキダメギク(Galinsoga ciliata)、セイヨウトゲアザミ(Cirsium arvense)、ノボロギク(Senecio vulgaris)、ヒメジョオン(Stenactis annuus)、コゴメギク(Galinsoga parviflora)、アレチノゲシ(Sonchus arvensis)、ノゲシ(Sonchus oleraceus)、イヌカミツレ(Matricaria inodora)などのキク科雑草、イヌガラシ(Rorippa indica)、ノハラガラシ(Sinapis arvensis)、ナズナ(Capsella bursa―pastoris)、グンバイナズナ(Thlaspi arvense)などのアブラナ科雑草、イヌタデ(Persicaria longiseta)、ソバカズラ(Fallopia convolvulus)、チャボニワヤナギ(Polygonum aviculare var.condensatum)、ヒロハミチヤナギ(Polygonum aviculare var. monospeliense),ケハルタデ(Polygonum persicaria)、サナエタデ(Persicaria lapathifolia var. incana)、オオイヌタデ(Persicaria lapathifolia var. lapathifolia)などのタデ科雑草、スベリヒユ(Portulaca oleracea)などのスベリヒユ科雑草、シロザ(Chenopodium album)、コアカザ(Chenopodium ficifolium)、ホウキギ(Kochia scoparia)、セイヨウハマアカザ(Atriplex patula)などのアカザ科雑草、コハコベ(Stellaria media)などのナデシコ科雑草、オオイヌノフグリ(Veronica persica)などのゴマノハグサ科雑草、ツユクサ(Commelina communis)などのツユクサ科雑草、ホトケノザ(Lamium amplexicaule)、ヒメオドリコソウ(Lamium purpureum)、タヌキジソ(Galeopsis tetrahit)などのシソ科雑草、コニシキソウ(Euphorbia supina)、オオニシキソウ(Euphorbia maculata)などのトウダイグサ科雑草、トゲナシヤエムグラ(Galium spurium)、ヤエムグラ(Galium spurium var. echinospermon)、アカネ(Rubia argyi)、シラホシムグラ(Galium aparine)などのアカネ科雑草、スミレ(Viola mandshurica)、マキバスミレ(Viola arvensis)などのスミレ科雑草、ノハラムラサキ(Myosotis arvensis)などのムラサキ科雑草、アメリカツノクサネム(Sesbania exaltata)、エビスグサ(Cassia obfusitolia)などのマメ科雑草などの広葉雑草、野性ソルガム(Sorghum bicolor)、オオクサキビ(Panicum dichotomiflorum)、ジョンソングラス(Sorghum halepense)、イヌビエ(Echinochloa crus-galli var.crus-galli)、メヒシバ(Digitaria ciliaris)、カラスムギ(Avena fatua)、オヒシバ(Eleusine indica)、エノコログサ(Setaria viridis)、スズメノテッポウ(Alopecurus aequalis)、スズメノカタビラ(Poa annua)、シバムギ(Agropyron repens)、ギョウギシバ(Cynodon dactylon)、オニメヒシバ(Digitaria sanguinalis)、キンエノコロ(Setaria pumila)、ノスズメノテッポウ(Alopecurus myosuroides)などのイネ科雑草、ハマスゲ(Cyperus rotundus)などのカヤツリグサ科雑草などが挙げられる。
以下の実施例により本発明を説明する。
5-アミノ-1-(3-クロロ-4,5,6,7-テトラヒドロピラゾロ[1,5-a]ピリジン-2-イル)ピラゾール-4-カルボニトリル(2.6g)にアセトニトリル(10ml)を加え、そこへイソブタノイルクロリド(1.2g)をゆっくりと滴下し、5時間加熱還流を行った。反応終了後、反応液に水を加え、酢酸エチルで抽出した。飽和炭酸水素ナトリウム水溶液で洗浄後、硫酸ナトリウムで乾燥し、溶媒を減圧留去した。得られた固体をイソプロピルエーテルで洗浄し、目的物(3.1g)を得た。
式(I)の化合物 10重量部
タルク 90重量部
を混合しハンマーミルで微粉砕することにより得られる。
式(I)の化合物 10重量部
ポリオキシエチレンアルキルアリールエーテル硫酸塩 22.5重量部
ホワイトカーボン 67.5重量部
を混合し、この混合物をハンマーミルで微粉砕することにより得られる。
式(I)の化合物 10重量部
ポリオキシエチレンアルキルエーテルリン酸塩 10重量部
ベントナイト 5重量部
エチレングリコール 5重量部
水 70重量部
を混合し、湿式粉砕機を用いて粉砕することによりフロアブル剤が得られる。
式(I)の化合物 15重量部
エトキシル化ノニルフェノール 10重量部
シクロヘキサノン 75重量部
を混合することにより乳剤が得られる。
式(I)の化合物 5重量部
リグニンスルホン酸カルシウム 3重量部
ポリカルボン酸塩 3重量部
炭酸カルシウム 89重量部
を混合し、水を加えて混練後押出し造粒する。その後乾燥、整粒することにより粒剤が得られる。
<生物試験実施例>
1/10000アールのポットに水田土壌を充填し、適量の水と化学肥料を加えて混練し、ノビエ、コナギ及びホタルイの種子を播種し、水深3cmの湛水状態を保った。
製剤例に準じて調製した表1に示す目的化合物(I)の水和剤を適量の水で希釈し、ノビエ3.5葉期に2.0葉期のイネを移植し、10アール当たり所定の薬量となるようにピペットを用いて滴下処理した。
そして平均気温30℃のガラス室で30日間管理した後に、それらの除草効果を調査した。
0(指数):0%~10%未満(生育抑制率)、
1:10%以上~20%未満、
2:20%以上~30%未満、
3:30%以上~40%未満、
4:40%以上~50%未満、
5:50%以上~60%未満、
6:60%以上~70%未満、
7:70%以上~80%未満、
8:80%以上~90%未満、
9:90%以上~100%未満、
10:100%
対照剤1.36(WO94/08999記載)
1/6000アールのポットに畑土壌を充填し、メヒシバ、シロザ、アオビユの種子を播種して覆土した。
製剤例に準じて調製した表1に示す式(I)の化合物の水和剤を所定の薬量になるように水で希釈し、播種後雑草発生前に10アール当たり100リットルの散布水量で各土壌表層に均一に噴霧処理した。
そして、平均気温30℃のガラス室で30日間管理した後に、それらの除草効果を調査した。
除草効果の評価は、前記試験例1と同様に行った。
その結果を表3に示す。
1/6000アールのポットに培土を充填し、メヒシバ、シロザ、アオビユ、の種子を播種して覆土し、平均気温25℃のガラス室で栽培した。
メヒシバが1.0~2.0葉期に生育した時期に、製剤例に準じて調製した表1に示す目的化合物(I)の水和剤を所定の薬量になるように水で希釈し、10アール当たり150リットルの散布水量で雑草上に均一に噴霧処理した。
そして平均気温25℃のガラス室で3週間管理した後に、それらの除草効果を調査した。
除草効果の評価は前記試験例1と同様に行った。
その結果を表4に示す。
1/4500アールポットに畑土壌を充填し、メヒシバ、コゴメギク(Galinsoga parviflora)の種子を播種して覆土し、平均気温25度のガラス室で栽培した。
メヒシバが4~5葉期(草丈10~15cm)に生育した時期に、製剤例に準じて調製した表1に示す目的化合物(I)の水和剤を所定量の薬量になるように水で希釈し、10アール当たり100Lの散布水量で雑草上に均一に噴霧処理した。
そして平均気温25℃のガラス室で20日間管理した後に、それらの除草効果を調査した。
除草効果の評価は前記試験例1と同様に行った。
その結果を表5に示す。
Claims (7)
- 請求項1に記載の化合物であって、
R1が塩素原子を表わし、
R2がシアノ基を表わし、
R3が場合により、1個またはそれ以上のハロゲン原子によって置換されたC3~C5アルキル基、場合により、1個またはそれ以上のハロゲン原子によって置換されたC2~C5アルケニル基を表わし、かつ
aが4を表わす、化合物。 - 請求項1または2に記載の化合物の少なくとも1種の除草有効量を含む、除草剤組成物。
- 処方助剤をさらに含む、請求項3に記載の除草剤組成物。
- 請求項1または2に記載の化合物の少なくとも1種の有効量または請求項3または4に記載の除草剤組成物を、望ましくない植物または望ましくない植生の場所に施用することを含む、望ましくない植物の防除方法。
- 望ましくない植物を防除するための、請求項1または2に記載の化合物または請求項3または4に記載の除草剤組成物の使用。
- 請求項1または2に記載の化合物が有用植物の農作物中の望ましくない植物を防除するために使用される、請求項6に記載の使用。
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AU2016210164A AU2016210164B2 (en) | 2015-01-23 | 2016-01-22 | Substituted pyrazolyl-pyrazole derivative and use of same as herbicide |
BR112017011586-7A BR112017011586A2 (ja) | 2015-01-23 | 2016-01-22 | Use as a substitution pyrazolyl pyrazol derivative and its weed killer |
CA2971564A CA2971564A1 (en) | 2015-01-23 | 2016-01-22 | Substituted pyrazolylpyrazole derivative and use of same as herbicide |
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EP3248973A4 (en) * | 2015-01-23 | 2018-07-11 | Kyoyu Agri Co., Ltd. | Substituted pyrazolyl-pyrazole derivative and use of same as herbicide |
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EP3248973A4 (en) * | 2015-01-23 | 2018-07-11 | Kyoyu Agri Co., Ltd. | Substituted pyrazolyl-pyrazole derivative and use of same as herbicide |
US10258042B2 (en) | 2015-01-23 | 2019-04-16 | Kyoyu Agri Co., Ltd. | Substituted pyrazolylpyrazole derivative and use of same as herbicide |
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BR112017011586A2 (ja) | 2018-02-27 |
US20170367341A1 (en) | 2017-12-28 |
AU2016210164A1 (en) | 2017-06-29 |
EP3248974A1 (en) | 2017-11-29 |
KR20170103784A (ko) | 2017-09-13 |
AU2016210164B2 (en) | 2019-10-31 |
EP3248974A4 (en) | 2018-07-18 |
RU2017128810A3 (ja) | 2019-02-28 |
CN107108619A (zh) | 2017-08-29 |
RU2017128810A (ru) | 2019-02-25 |
AR103470A1 (es) | 2017-05-10 |
CA2971564A1 (en) | 2016-07-28 |
US10258041B2 (en) | 2019-04-16 |
TW201630909A (zh) | 2016-09-01 |
JPWO2016117675A1 (ja) | 2017-10-26 |
UA119999C2 (uk) | 2019-09-10 |
RU2692792C2 (ru) | 2019-06-27 |
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