CN111362908B - Amorphous-state bicyclopyrone dimethylamine salt and preparation method and application thereof - Google Patents
Amorphous-state bicyclopyrone dimethylamine salt and preparation method and application thereof Download PDFInfo
- Publication number
- CN111362908B CN111362908B CN201811592942.8A CN201811592942A CN111362908B CN 111362908 B CN111362908 B CN 111362908B CN 201811592942 A CN201811592942 A CN 201811592942A CN 111362908 B CN111362908 B CN 111362908B
- Authority
- CN
- China
- Prior art keywords
- percent
- methyl
- amorphous
- salt
- chloro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic 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
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
- A01N33/18—Nitro compounds
-
- 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
- A01N37/18—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 containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/22—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 containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
-
- 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
- A01N37/36—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 containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
- A01N37/38—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 containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
- A01N37/40—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 containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
-
- 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
- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
- A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
- A01N39/04—Aryloxy-acetic acids; Derivatives thereof
-
- 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
- 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
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
-
- 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
-
- 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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
-
- 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
- A01N43/80—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 five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
-
- 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
-
- 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
-
- 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
- A01N47/12—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, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
-
- 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
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
-
- 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
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
-
- 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
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C211/03—Monoamines
- C07C211/04—Mono-, di- or tri-methylamine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
The invention belongs to the technical field of herbicide crystallization processes, and particularly relates to amorphous cyfluazifop-butyl dimethylamine salt and a preparation method and application thereof. The amorphous cyfluazifop-butyl dimethylamine salt exists in an amorphous form through X-ray powder diffraction detection, and an X-ray powder diffraction pattern of the amorphous cyfluazifop-butyl dimethylamine salt does not have sharp diffraction peaks and is basically shown in figure 1. The amorphous cyfluazifop-butyl dimethylamine salt has high solubility and high biological activity, and can be used for preventing and removing weeds.
Description
Technical Field
The invention belongs to the technical field of herbicide crystallization processes, and particularly relates to amorphous cyfluazifop-butyl dimethylamine salt and a preparation method and application thereof.
Background
Bicyclopyrone (structural formula:
) The compound is a newly developed HPPD inhibitor herbicide for treating postemergence stems and leaves of wheat fields, has excellent biological activity, can effectively prevent and kill various malignant gramineous weeds in the wheat fields, and has been granted in compound patents with the grant publication number: CN 105218449B.
Polymorphism refers to the phenomenon of solid states with different physicochemical properties formed by solid substances in two or more different spatial arrangements. Different crystal forms have different colors, melting points, dissolution properties, chemical stability, reactivity, mechanical stability and the like, and the physical and chemical properties or the processability sometimes directly influence the safety and the effective performance of the medicine. Therefore, research and control of crystal forms become important research content in the process of drug development.
Disclosure of Invention
The invention provides a novel herbicide amorphous-state cyflufenap dimethylamine salt and a preparation method and application thereof. The crystal form has high solubility and high biological activity, and can be used for preventing and removing common weeds in crop fields.
The technical scheme adopted by the invention is as follows:
an amorphous form of ciclopirox olamine salt, in amorphous form, as detected by X-ray powder diffraction.
It has an X-ray powder diffraction pattern without sharp diffraction peaks, and preferably, the X-ray powder diffraction pattern is substantially as shown in figure 1.
The preparation method of the amorphous cyfluazifop-butyl dimethylamine salt comprises the following steps: dissolving the bicyclopyrone dimethylamine salt in dichloromethane, methanol or ethyl acetate by stirring, performing rotary evaporation on the solvent at 40-60 ℃ under reduced pressure, and then performing mechanical grinding to obtain an amorphous state.
A herbicidal compounded composition comprising (i) the amorphous cyhalofop-butyl dimethylamine salt; preferably, also (ii) one or more other active ingredients and/or safeners; more preferably, (iii) an agrochemically acceptable formulation auxiliary.
Preferably, the adjuvant is selected from one or more of solvents, solid diluents, emulsifiers, wetting agents, dispersants, anti-freeze agents, anti-foaming agents and thickeners.
Selected solvents include, but are not limited to, the class of polar solvents: water, N-dimethylamide, dimethyl sulfoxide, N-alkylpyrrolidone, methanol, ethanol, ethylene glycol, isopropanol, ethylene glycol butyl ether, propylene glycol methyl ether, etc.; aromatic solvent oil series: toluene, xylene, 100 # solvent oil, 150# solvent oil, 180 # solvent oil, 200 # solvent oil, and the like; vegetable oils: castor oil, linseed oil, sesame oil, corn oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, and their corresponding methyl esterified vegetable oils and the like; ketones: cyclopentanone, cyclohexanone, cyclooctanone, 2-heptanone, isophorone, 4-hydroxy-4-methyl-2-pentanone, and the like; acetic acid esters: methyl acetate, ethyl acetate, propyl acetate, sec-butyl acetate, isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, and the like; the rest classes are: decanoamide, cyclohexanol, decanol, benzyl alcohol, tetrahydrofurfuryl alcohol, and the like.
The solid diluent selected may be water soluble or water insoluble. Water soluble solid diluents include, but are not limited to: salts such as alkali metal phosphates (sodium dihydrogen phosphate), alkaline earth metal phosphates, sulfates of sodium, potassium, magnesium and zinc, sodium and potassium chloride, sodium acetate, sodium carbonate and sodium benzoate, and sugars and sugar derivatives such as sorbitol, lactose, sucrose and mannitol, corn starch and the like. Examples of water insoluble solid diluents include, but are not limited to: clay, calcium carbonate, diatomite, white carbon black, calcium silicate, bentonite, magnesium aluminum silicate, kaolin and the like.
Wetting agents include, but are not limited to: alkyl sulfosuccinates, laurates, alkyl sulfates, phosphates, ethoxylated fluorinated alcohols, ethoxylated silicones, alkylphenol ethoxylates, benzenesulfonates, alkyl-substituted benzenesulfonates, alkyl alpha-olefin sulfonates, naphthalenesulfonates, alkyl-substituted alkali metal salts of naphthalenesulfonic acids, condensates of alkali metal salts of naphthalenesulfonic acids and of alkyl-substituted naphthalenesulfonic acids with formaldehyde, alcohol ethoxylates.
Dispersants include, but are not limited to: sodium, calcium and ammonium salts of lignosulfonic acid; sodium and ammonium salts of maleic anhydride copolymers; sodium salts of condensed phenolsulfonic acids; naphthalene sulfonate-formaldehyde condensates; phosphate dispersants, polycarboxylate dispersants, and the like.
Thickeners include, but are not limited to: guar gum, pectin, xanthan gum, alginates, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and magnesium aluminum silicate, among others. Synthetic thickeners include derivatives of the foregoing classes, and also include polyvinyl alcohols, polyacrylamides, polyvinyl pyrrolidones, various polyethers and copolymers thereof, and polyacrylic acids and salts thereof.
Other formulation ingredients, such as dyes, defoamers, desiccants, and the like, may be used in the present invention. These ingredients are well known to those skilled in the art.
Suitable active ingredients which may be admixed with the amorphous ciclopirox dimelamine salt of the present invention are, for example, those known from the "encyclopedia of New agricultural chemical products in the world", the Chinese agro-scientific and technical Press, 2010.9 and the references cited therein. For example, the various substances mentioned below (remarks: name of the compound, or common name according to the International organization for standardization (ISO), or chemical name, with code numbers where appropriate): acetochlor, butachlor, alachlor, propisochlor, metolachlor, s-metolachlor, pretilachlor, propyzamide, pretilachlor, napropamide, R-levulinyl-propyzamide, propanil, mefenacet, dibenzamide, diflufenican, flumetsulam, bromobutyrolac, dimethenamid, mefenacet, metazachlor, isoxaflutole, ryegrass methyl ester, loflutolane, diacrylamide, pethoxamide, butachlor, propisochlor, cyprosulfamide, flumetsulam, heptanoyl, isobutramine, propyzamide, terbutamid, dimethenamid, larvamide, trimethylcyclam, clofenamid, propyzamide, penoxulamide, carpronide, diflormid, trinitrol, butachlor, butafenacet, butachlor, benfluralin, bencarbzamide, pencyhalonil, metolachlor, bencarbzamide, pencyhalonil, buta, Grazing amine, bensulfuron, quinoxalamine, bensulfuron-methyl, naproxen, acetochlor, naphazel, thiachlor, pyraflufen, bensulfuron-methyl, prochloraz, clofenamide, butamidam, flupiram, atrazine, simazine, prometryn, cyanazine, simetryn, ametryn, prometryn, ipratron, flurazin, terbutryn, triazineone-flumetsulam, ciprofloxacin, glycazine, pradapazine, prometryn, simatong, azidezin, diuron, isopentetryn, cycloprozine, ametryn, terbuthylazine, terbuton, metocloprid, cyanazine, bentazon, clonazine, atrazine, metribuzin, cyanuric acid, indaziflazaflam, chlorsulfuron, meturon, bensulfuron, chlorimuron, tribenuron-methyl, thifensulfuron-methyl, pyrazosulfuron-methyl, sulfosulfuron-methyl, sulfometuron, Cinosulfuron, triasulfuron, sulfometuron-methyl, nicosulfuron, ethametsulfuron, amidosulfuron, ethoxysulfuron, cyclosulfamuron, rimsulfuron, azimsulfuron, primisulfuron-methyl, flusulfuron-methyl, flupyrsulfuron-methyl, epoxysulfuron, imazosulfuron, primisulfuron-methyl, prosulfuron, sulfosulfuron, trifloxysulfuron, triflusulfuron, metsulfuron-methyl sodium, flupyrazosulfuron, methisulfuron-methyl, primisulfuron, propysilfuron (Propyrisulfuron), metribusulfuron, acifluorfen-methyl, fomesafen, lactofen, fluoroglycofen-ethyl, oxyfen, prosulfuron, benfuresafen, trifloxysulfuron, metofen-ethyl, metofen, trifloxysulfuron, fluroxypyr, fluridone, benfop, benfluridone, benfurazolin, benfluridone, benfurbenflur, Dimethofen, oxyfluorfen, clofenflurate, Halosafen, chlortoluron, isoproturon, linuron, diuron, sifenuron, fluometuron, benzthiauron, methabenzuron, prosulfuron, sulfosulfuron, clomauron, clodinafuron, clofensulfuron, metoxuron, bromuron, metoxuron, meturon, fensulfuron, prosulfuron, subtilon, cuarone, metolachlor, cycloaroron, cyclouron, thifluuron, buthiuron, kuron, cumuron, metoxuron, methamidothion, metominosulfuron, trifolium, isoxafluron, isoxauron, moneuronon, aniron, methicuron, chloretron, clotururon, teuron, benuron, pennison, phenmedibensulfuron, bensulfuron, benazolin, propham, buthan, thiuron, buthan, benazolin, buthan, benazolin, buthan, benazol, Thiobencarb, merthiolane, diclofop, triallate, penoxsulam, pyributicarb, dichlorfon, edifenphos, ethiofen, prosulfocarb, clenbuterol, prosulfocarb, dichlorcarb, thiobencarb, dichlorphenate, Isopolinate, Methiobencarb, 2, 4-d butyl ester, 2 methyl 4-sodium chloride, 2, 4-d isooctyl ester, 2 methyl 4-chloroisooctyl ester, 2, 4-d sodium salt, 2, 4-d dimethylamine salt, 2 methyl 4-chloroethyl thioester, 2 methyl 4 chloride, 2, 4-d propionic acid, 2, 4-d propionate, 2, 4-d butyric acid, 2 methyl 4-chloropropionic acid, 2 methyl 4-chlorobutyric acid, 2,4, 5-d nasal discharge, 2,4, 5-d propionic acid, 2,4, 5-d butyric acid, 2-chloro-propionic acid, 2-chloro-4-d propionate, 2-d trichloroacetic acid, 2-d, triclocarb, triclopyr, triclop, Dichlorobenzoic acid, metocloprofenac, diclofop-methyl, fluazifop-P-ethyl, haloxyfop-methyl, haloxyfop-p-ethyl, quizalofop-p-ethyl, fenoxaprop-p-ethyl, propaquizafop-ethyl, clodinafop-ethyl, haloxyfop-ethyl, trifoliate-ethyl, clomazone, paraquat-p-ethyl, benfurazolin, clorflofop-methyl, benazolin-methyl, propafop-ethyl, butyfen-ethyl, chloroethafloxacin, aminofluanid, benazolin, chlorpropham, methamphrenalin, propamocarb-P-methyl, glufosinate, benfop-methyl, benfop-ethyl, benfop-methyl, benfop-ethyl, benfop-P, benfop-P, benfop-P, mex-P, mefenofos, me, Imazamox, imazapic ammonium salt, imazapic, imazamethabenz, fluroxypyr-meptyl, clopyralid, picloram, triclopyr, dithiopyr, haloxydine, triclopyr, thiazopyr, fluridone, aminopyralid, diflufenzopyr, butoxyethyl triclopyr, Cliodinate, sethoxydim, clethodim, bentazone, diclofen, clethodim, tralkoxydim, topramezone, buthiazole, metribuzin, azinone, metamitron, amitrizone, Amibuzin, bromoxynil octanoyl, ioxynil, dichlobenil, acetonitrile, pyraclonil, hydroxybensulam, Iodobonil, herbicidal bromine, flumetsulam, penoxsulam, sulfluramid, clofenapyr, flumetsulam, cuaminosulfame, sulfadiazinon, halosulfuron, sulfadiazinon, bispyribac-sodium, pyribenzoxim, pyriminobac-methyl, pyrithiobac-methyl, mesotrione, sulcotrione, Tembotrione, Tefuryltrione, Bicyclopyrone, kettopiradox, isoxaflutole, fenoxasul, Methiozolin, isopyrafen, pyraflufen, pyraflutole, difenzoquat, pyraclofen, pyraflufen, pyroxsulazole, pyraflufen, metamitron, carfentrazam, flumetsul, sulfentrazone, benconazole, bencarane, benflumethazine, isoxaflutole, cycloxathidin, terbacil, flapciclone, indoxacarb, flumiclorac, propyzamide, flumethazine, metoclopramide, carfentrazone, metoclopramide, metocloprofen, metoclopramide, metoclopr, Fentrazamide, pyrifluazifop-methyl, pyriminostrobin, bromogeramine, didaphylm, pyridaben, Pyridafol, quinclorac, chloroquinate, bentazon, pyridate, oxaziclomefone, benazolin, clomazone, isoxaprop-p-ethyl, isoproylether, propylclomefone, indanthrone, sodium chlorate, thatch, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoropropionic acid, moroxydine, fast grass, bromophenol oxime, triazasulam, imazazol, flurtamone, furbenfurathion, furbenfuresafen, ethafurazafenin, clofenac, fluorochloridone, fludioxonil, pyributicarb, acrolein, benfurazapyr-methyl, imazachlor, oatmeal, thiadiazolidine, linanine, hydroxybenzoquinone, amlodipine, metominophenidone, penoxsulam, dichlorophoron, alofen, metoclopramide, iprodione, pyraclofenapyr, iprodione, cammondiclor, aminocyclopyrachlor, thiocyananilide, clethodim, fenclorim, cloquintocet-mexyl, mefenpyr-diethyl, furazolidone, imazamox, isoxadifen, dichlormid, halauxin, DOW848, UBH-509, D489, LS 82-556, KPP-300, NC-324, NC-330, KH-218, DPX-N8189, SC-0744, CO535, DK-8910, V-53482, PP-600, MBH-001, DOWHOW-9201, ET-751, KIH-6127 and KIH-2023. Experiments prove that the amorphous cyflufenacet dimethylamine salt and one or more of the herbicides have obvious synergistic and synergistic effects.
Preferably, the other active ingredients include, but are not limited to: diflufenican (CAS number: 83164-33-4), isoxaflutole (CAS number: 141112-29-0), clodinafop-propargyl (CAS number: 105512-06-9), pinoxaden (CAS number: 243973-20-8), isoproturon (CAS number: 34123-59-6), chlortoluron (CAS number: 15545-48-9), bromoxynil octanoate (CAS number: 1689-99-2), metribuzin (CAS number: 21087-64-9), pyridate (CAS number: 55512-33-9), amicarbazone (CAS number: 129909-90-6), 2-methyl 4-chloro (CAS number: 94-74-6), fluroxypyr (CAS number: 69377-81-7), halauxifen (CAS number: 943831-98-9), dicamba (CAS number: 1918-00-9), One or more of saflufenacil (CAS number: 372137-35-4), flufenacet (CAS number: 142459-58-3), metolachlor (CAS number: 178961-20-1), xaflufen (CAS number: 447399-55-5), pendimethalin (CAS number: 40487-42-1), mesosulfuron-methyl (CAS number: 208465-21-8), flucarbazone (CAS number: 181274-17-9), pyroxsulam (CAS number: 422556-08-9), prosulfocarb (CAS number: 52888-80-9) and derivatives thereof.
In the context of the present specification, if the abbreviated forms of the common name of the active compounds are used, all customary derivatives, such as esters and salts, and also isomers, in particular optical isomers, in particular one or more commercially available forms, are included in each case. If the generic name denotes esters or salts, all other customary derivatives, such as other esters and salts, free acids and neutral compounds, and also isomers, in particular optical isomers, in particular one or more commercially available forms, are also included in each case. The chemical name given for a compound means at least one compound covered by the generic name, with compounds generally being preferred. In the case of sulfonamides, such as sulfonylureas, salts also include those formed by exchange of cations with hydrogen atoms in the sulfonamide group. For example, 2-methyl-4-chloro derivatives include, but are not limited to: 2 methyl 4 chloro sodium salt, potassium salt, dimethyl ammonium salt, isopropyl amine salt, etc., and 2 methyl 4 chloromethyl ester, ethyl ester, isooctyl ester, ethyl thioester, etc.
In the context of the present invention, the salts of the compounds are preferably in the form of the respective alkali metal, alkaline earth metal or ammonium salts, preferably in the form of the respective alkali metal salts, more preferably in the form of the respective sodium or potassium salts, most preferably in the form of the respective sodium salts.
The total mass percentage of the active ingredients in the composition accounts for 1-95% of the total mass.
The safener is preferably one or more of isoxadifen (CAS: 163520-33-0), cyprosulfamide (CAS: 221667-31-8), mefenpyr (CAS: 135590-91-9), cloquintocet (CAS: 99607-70-2), gibberellic acid (CAS: 7-06-5), furilazole (CAS: 121776-33-8) and metacamifen (CAS: 129531-12-0).
The composition is in the form of aqueous Suspension (SC), dispersible oil suspension (OD), Emulsifiable Concentrate (EC), Microemulsion (ME), Granules (GR), Suspoemulsion (SE) or Water Dispersible Granules (WDG).
The invention also provides a method for controlling weeds in crops, which comprises applying a herbicidally effective amount of the amorphous cyfluazifop-butyl dimethylamine salt or the herbicidal compounded composition on crops or weed areas.
The invention also provides the use of the amorphous cyfluazifop-butyl dimethylamine salt or the weeding compound composition in weed control; preferably, it is used for controlling weeds in crops of useful plants, which are transgenic or treated by genome editing techniques.
Preferably, the crop is wheat, and the weed is a grass weed, such as alopecurus maytans, alopecurus japonicus etc.
Tests prove that the amorphous cyhalofop-butyl dimethylamine salt has good water solubility, the solubility in water is increased by about fifty times compared with cyhalofop-butyl, and is increased by about twenty five times compared with cyhalofop-butyl sodium salt, and the amorphous cyhalofop-butyl or the compound composition of the amorphous cyhalofop-butyl dimethylamine salt and other active ingredients has better control effect on gramineous weeds in wheat fields, and the effect is obviously better than that of cyhalofop-butyl and the cyhalofop-butyl sodium salt.
Drawings
Figure 1 is an XRPD pattern of amorphous ciclopirox dimelamine salt of example 2 of the present invention.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
XRPD determination method
The instrument model is as follows: bruker D8advance, target: cu ka (40kV, 40mA), sample-to-detector distance: 30cm, scanning range: 30-450(2 θ value), scan step size: 0.05 s.
Example 1
According to the CN 105218449B method, raw materials of the ciclopirox are prepared, then 1 kg of the ciclopirox reacts with 0.3 kg of 30% sodium hydroxide aqueous solution, a large amount of solid crystals are obtained through reaction, and the solid crystals are filtered and dried to obtain the powder of the sodium salt of the ciclopirox.
Example 2
1 kg of the ciclopirox-flurtamone obtained in example 1 was reacted with 0.27 kg of 50% aqueous dimethylamine solution to obtain a large amount of solid crystals, the solid was filtered and dried at 45 ℃ to obtain the powder of the ciclopirox-flurtamone dimethylamine salt.
Putting 1000 g of cypioflutole dimethylamine salt into a 10L flask, adding 3L of dichloromethane, methanol or ethyl acetate, heating and stirring until the raw materials are completely dissolved, carrying out rotary evaporation on the solvent at 50 ℃, and carrying out mechanical grinding after the solvent is completely evaporated to obtain amorphous cypioflutole dimethylamine salt powder.
Determination of solubility in Water
The ciclopirox and its sodium salt obtained in example 1 and the amorphous ciclopirox dimethylamine salt obtained in example 2 were dissolved in pure water, shaken at 25 ℃ for 24h to be fully dissolved, then centrifuged and filtered, and the filtrate was filtered through a 0.22 μm filter membrane, and the solubility in water was determined by HPLC, the results are shown in table 1 below:
TABLE 1 test results of solubility in water of various samples
As can be seen from the results in table 1, the solubility of amorphous ciclopirox-flurtamone dimethylamine salt is significantly increased compared with ciclopirox-flurtamone and its sodium salt.
Examples 1 and 2 formulation processing and field efficacy testing
The ciclopirox and the sodium salt thereof obtained in the example 1 and the amorphous ciclopirox dimethylamine salt obtained in the example 2 are processed into the following preparation according to the same formula, wherein the specific formula is as follows, and the effective components A represent ciclopirox, ciclopirox sodium salt and the amorphous ciclopirox dimethylamine salt.
6％A OD
6 percent of A, 5 percent of calcium dodecyl benzene sulfonate, 5 percent of fatty alcohol-polyoxyethylene ether, 6 percent of castor oil-polyoxyethylene ether, 2.5 percent of organic bentonite, 2.5 percent of fumed silica, 5 percent of 150# solvent oil and methyl oleate
14% A diflufenican OD
6 percent of A, 8 percent of diflufenican, 5 percent of calcium dodecyl benzene sulfonate, 8 percent of fatty alcohol-polyoxyethylene ether, 4 percent of castor oil-polyoxyethylene ether, 2.0 percent of organobentonite, 1.0 percent of fumed silica, 10 percent of No. 150 solvent oil and methyl oleate
9% of A-isoxaflutole SC
6 percent of A, 3 percent of isoxaflutole, 5 percent of phenethylphenol polyoxyethylene ether phosphate dimethylamine salt, 1.5 percent of fatty alcohol-polyoxyethylene ether, 0.2 percent of xanthan gum, 2.2 percent of magnesium aluminum silicate, 0.1 percent of defoaming agent, 4 percent of glycol and water to complement
7.5% of A clodinafop-propargyl OD
6 percent of A, 1.5 percent of clodinafop-propargyl, 5 percent of calcium dodecyl benzene sulfonate, 5 percent of fatty alcohol-polyoxyethylene ether, 6 percent of castor oil polyoxyethylene ether, 2.0 percent of organobentonite, 2.0 percent of fumed silica, 10 percent of No. 150 solvent oil and methyl oleate
7.5% Azaolinate OD
6 percent of A, 1.5 percent of pinoxaden, 5 percent of calcium dodecyl benzene sulfonate, 5 percent of fatty alcohol-polyoxyethylene ether, 6 percent of castor oil polyoxyethylene ether, 2.0 percent of organobentonite, 2.0 percent of fumed silica, 20 percent of No. 150 solvent oil and methyl oleate
56% A isoproturon WDG
6% of A, 50% of isoproturon, 5% of sodium dodecyl sulfate, 8% of polycarboxylate dispersant, 2% of polyethylene glycol 4000, 5.0% of precipitated silica and kaolin
66% A-chlorotoluron WDG
6% of A, 60% of chlortoluron, 5% of sodium dodecyl sulfate, 8% of polycarboxylate dispersant, 2% of polyethylene glycol 4000, 5.0% of precipitated silica and kaolin
26% A bromoxynil octanoate OD
6 percent of A, 20 percent of bromoxynil octanoate, 5 percent of calcium dodecyl benzene sulfonate, 5 percent of fatty alcohol-polyoxyethylene ether, 6 percent of castor oil polyoxyethylene ether, 2.5 percent of organobentonite, 2.0 percent of fumed silica, 10 percent of No. 150 solvent oil and methyl oleate are complemented
12% A metribuzin OD
6 percent of A, 6 percent of metribuzin, 5 percent of calcium dodecyl benzene sulfonate, 5 percent of fatty alcohol-polyoxyethylene ether, 6 percent of castor oil polyoxyethylene ether, 2.5 percent of organic bentonite, 2.5 percent of fumed silica, 10 percent of 150# solvent oil and methyl oleate
32.3% of A-pyridate OD
2.3 percent of A, 30 percent of pyridate, 5 percent of calcium dodecyl benzene sulfonate, 5 percent of fatty alcohol-polyoxyethylene ether, 6 percent of castor oil polyoxyethylene ether, 2.8 percent of organic bentonite, 2.5 percent of fumed silica, 20 percent of No. 150 solvent oil and methyl oleate
13% A amicarbazone OD
6 percent of A, 7 percent of amicarbazone, 5 percent of calcium dodecyl benzene sulfonate, 5 percent of fatty alcohol-polyoxyethylene ether, 6 percent of castor oil polyoxyethylene ether, 2.3 percent of organic bentonite, 2.0 percent of fumed silica, 20 percent of 150# solvent oil and methyl oleate
26% A.2M 4 chloro SL
6% of A, 20% of 2-methyl-4-chloro, 6% of dimethylamine, 40% of ethanol, 10% of fatty alcohol-polyoxyethylene ether sodium sulfate and water
11% A.Fluroxypyr OD
6 percent of A, 5 percent of fluroxypyr, 5 percent of calcium dodecyl benzene sulfonate, 5 percent of fatty alcohol-polyoxyethylene ether, 6 percent of castor oil-polyoxyethylene ether, 2.3 percent of organobentonite, 2.0 percent of fumed silica, 12 percent of No. 150 solvent oil and methyl oleate
6.5% A.Fluorochloropyridine ester OD
6 percent of A, 0.5 percent of fluorochloropyridine ester, 5 percent of calcium dodecyl benzene sulfonate, 5 percent of fatty alcohol-polyoxyethylene ether, 6 percent of castor oil polyoxyethylene ether, 2.3 percent of organobentonite, 2.0 percent of fumed silica, 10 percent of No. 150 solvent oil and methyl oleate
18% A dicamba SL
6% of A + 12% of dicamba + 7% of dimethylamine + 40% of ethanol + 10% of fatty alcohol-polyoxyethylene ether sodium sulfate + water
8.5% A saflufenacil OD
6 percent of A, 2.5 percent of saflufenacil, 5 percent of calcium dodecyl benzene sulfonate, 5 percent of fatty alcohol-polyoxyethylene ether, 6 percent of castor oil polyoxyethylene ether, 2.5 percent of organobentonite, 2.0 percent of fumed silica, 10 percent of No. 150 solvent oil and methyl oleate
18% A-flufenacet OD
6 percent of A, 12 percent of flufenacet, 5 percent of calcium dodecyl benzene sulfonate, 5 percent of fatty alcohol-polyoxyethylene ether, 6 percent of castor oil-polyoxyethylene ether, 2.0 percent of organobentonite, 2.0 percent of fumed silica, 10 percent of 150# solvent oil and methyl oleate
14% A-S-metolachlor OD
6 percent of A, 8 percent of s-metolachlor, 5 percent of calcium dodecyl benzene sulfonate, 5 percent of fatty alcohol-polyoxyethylene ether, 6 percent of castor oil polyoxyethylene ether, 2.5 percent of organobentonite, 2.0 percent of fumed silica, 10 percent of No. 150 solvent oil and methyl oleate
12% A. Sulfonyl pyraflufen OD
6 percent of A, 6 percent of sulphone pyraflufen-ethyl, 5 percent of calcium dodecyl benzene sulfonate, 5 percent of fatty alcohol-polyoxyethylene ether, 6 percent of castor oil-polyoxyethylene ether, 2.5 percent of organic bentonite, 2.0 percent of fumed silica, 10 percent of No. 150 solvent oil and methyl oleate
22% A. pendimethalin OD
2 percent of A, 20 percent of pendimethalin, 5 percent of calcium dodecyl benzene sulfonate, 5 percent of fatty alcohol-polyoxyethylene ether, 6 percent of castor oil-polyoxyethylene ether, 2.5 percent of organic bentonite, 2.0 percent of fumed silica, 20 percent of 150# solvent oil and methyl oleate
6.6% A. mesosulfuron-methyl OD
6 percent of A, 0.6 percent of mesosulfuron, 5 percent of calcium dodecyl benzene sulfonate, 5 percent of fatty alcohol-polyoxyethylene ether, 6 percent of castor oil polyoxyethylene ether, 2.5 percent of organobentonite, 2.0 percent of fumed silica, 10 percent of No. 150 solvent oil and methyl oleate
8% A.Flucarbazone-sodium OD
6 percent of A, 2 percent of flucarbazone-sodium, 5 percent of calcium dodecyl benzene sulfonate, 5 percent of fatty alcohol-polyoxyethylene ether, 6 percent of castor oil polyoxyethylene ether, 2.5 percent of organic bentonite, 2.0 percent of fumed silica, 10 percent of No. 150 solvent oil and methyl oleate
6.6% A. Sulfoxaden OD
6 percent of A, 0.6 percent of pyroxsulam, 5 percent of calcium dodecyl benzene sulfonate, 5 percent of fatty alcohol-polyoxyethylene ether, 6 percent of castor oil polyoxyethylene ether, 2.5 percent of organobentonite, 2.0 percent of fumed silica, 10 percent of No. 150 solvent oil and methyl oleate
43% A-prosulfocarb OD
3 percent of A, 40 percent of prosulfocarb, 5 percent of calcium dodecyl benzene sulfonate, 5 percent of fatty alcohol-polyoxyethylene ether, 6 percent of castor oil polyoxyethylene ether, 2.5 percent of organic bentonite, 2.0 percent of fumed silica, 10 percent of 150# solvent oil and methyl oleate
Field effect test: after 3 leaves of wheat, the 3-4 leaf period of the Aleurea victoria L.and the 3-4 leaf period of the Aleurea victoria L.of Japan, an electric sprayer is added with water with the amount of 30 kg/667 m2The control effect (visual observation) of the average plant is investigated as follows by spraying stem leaves uniformly and spraying the stem leaves, wherein the area of the cell is 30 square meters, and the control effect (visual observation) of the average plant is investigated 45 days after each treatment is repeated 4 times of pesticide application, and is shown in table 2.
TABLE 2 weed control effect (%) of different preparations in wheat direct seeding field-control effect after 45 days of application
As can be seen from the table 2, compared with the effect of preventing and killing weeds in wheat direct seeding fields by using different preparations of the cyhalofop-butyl, the prevention effect of the amorphous cyhalofop-butyl dimethylamine salt is obviously higher than that of the cyhalofop-butyl and the sodium salt preparations thereof.
Meanwhile, through a plurality of tests, the compound and the composition thereof can prevent and kill a plurality of key grassy weeds and broadleaf weeds. Tests on wheat, corn, rice, sugarcane, soybean, cotton, sunflower, potato, fruit trees, vegetables and the like under different application modes also show excellent selectivity and commercial value.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (16)
1. An amorphous form of ciclopirox olamine salt, characterised by the presence in amorphous form as detected by X-ray powder diffraction.
2. The amorphous diflufenican dimethylamine salt according to claim 1, wherein the amorphous diflufenican dimethylamine salt comprises: the X-ray powder diffraction pattern is substantially as shown in figure 1.
3. A process for the preparation of amorphous ciclopirox dimethylamine salt according to any of the claims 1-2, characterized in that: the method comprises the following steps: dissolving the bicyclopyrone dimethylamine salt in dichloromethane, methanol or ethyl acetate by stirring, performing rotary evaporation on the solvent at 40-60 ℃ under reduced pressure, and then performing mechanical grinding to obtain an amorphous state.
4. A weeding compound composition is characterized in that: comprising (i) the amorphous diflufenican dimethylamine salt of any of claims 1-2; (iii) an agrochemically acceptable formulation auxiliary.
5. A herbicidal combination according to claim 4, which further comprises (ii) one or more further active ingredients and/or safeners.
6. A herbicidal combination according to claim 5, wherein the further active ingredient is selected from one or more of diflufenican, isoxaflutole, clodinafop-propargyl, pinoxaden, isoproturon, chlorotoluron, bromoxynil octanoate, metribuzin, pyridate, amicarbazone, 2 methyl 4 chloro sodium salt, 2 methyl 4 chloro potassium salt, 2 methyl 4 chloro dimethyl ammonium salt, 2 methyl 4 chloro isopropyl amine salt, 2 methyl 4 chloro methyl ester, 2 methyl 4 chloro ethyl ester, 2 methyl 4 chloro isooctyl ester, 2 methyl 4 chloro ethyl thioester, fluroxypyr, fluroxypyridine, dicamba, saflufenacil, flufenacet, metolachlor, propyzamide, pyraflufen-ethyl, pendimethalin, mesosulfuron, flucarbazone, pyroxsulam, prosulfocarb.
7. A herbicidal compound composition according to claim 6, wherein the total mass percentage of the active ingredients in the composition accounts for 1-95% of the total amount.
8. A herbicidal compounded composition according to any one of claims 4 to 7, characterized in that: the formulation of the composition is water suspending agent, dispersible oil suspending agent, missible oil, microemulsion, granules, suspoemulsion or water dispersible granules.
9. A method of controlling weeds in crops of weeds, which comprises applying to the crop or the locus of weeds a herbicidally effective amount of the amorphous pyriflufenac dimethylamine salt according to any of claims 1 to 2 or the herbicidal combination according to any of claims 4 to 8.
10. The method of claim 9, wherein the crop is wheat and the weed is a grass weed.
11. The method according to claim 10, wherein the grassy weed is a alopecurus or a japanese alopecurus.
12. Use of the amorphous ciclopirox olamine salt according to any one of claims 1 to 2 or the herbicidal combination composition according to any one of claims 4 to 8 for weed control.
13. Use according to claim 12, for controlling weeds in crops of useful plants.
14. Use according to claim 13, wherein the useful crop is a transgenic crop or a crop treated with genome editing technology.
15. Use according to claim 13 or 14, wherein the crop is wheat and the weed is a grass weed.
16. Use according to claim 15, wherein the grassy weeds are alopecurus or alopecurus japonicus.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811592942.8A CN111362908B (en) | 2018-12-25 | 2018-12-25 | Amorphous-state bicyclopyrone dimethylamine salt and preparation method and application thereof |
| PCT/CN2018/124126 WO2020133018A1 (en) | 2018-12-25 | 2018-12-27 | Amorphous ciclopirox fluridone dimethylamine salt, preparation method therefor and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811592942.8A CN111362908B (en) | 2018-12-25 | 2018-12-25 | Amorphous-state bicyclopyrone dimethylamine salt and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111362908A CN111362908A (en) | 2020-07-03 |
| CN111362908B true CN111362908B (en) | 2021-03-12 |
Family
ID=71127378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811592942.8A Active CN111362908B (en) | 2018-12-25 | 2018-12-25 | Amorphous-state bicyclopyrone dimethylamine salt and preparation method and application thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN111362908B (en) |
| WO (1) | WO2020133018A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109819988A (en) * | 2019-01-28 | 2019-05-31 | 南京农业大学 | A kind of ring pyrrole fluorine humulone and chlortoluron administer resistance Alopecurus composition and its application |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012130685A1 (en) * | 2011-03-25 | 2012-10-04 | Bayer Cropscience Ag | Use of n-(tetrazol-4-yl)- or n-(triazol-3-yl)arylcarboxamides or their salts for controlling unwanted plants in areas of transgenic crop plants being tolerant to hppd inhibitor herbicides |
| CN105218449A (en) * | 2015-11-06 | 2016-01-06 | 青岛清原化合物有限公司 | Pyrazolone compound or its salt, preparation method, herbicidal composition and purposes |
| CN106070226A (en) * | 2016-06-07 | 2016-11-09 | 泰安市农业科学研究院 | A kind of ring pyrrole fluorine oxadiazon compositions and application thereof |
| CN106472517A (en) * | 2016-09-30 | 2017-03-08 | 江苏清原农冠杂草防治有限公司 | Synergistic herbicide compositions and its application |
| CN107629035A (en) * | 2017-10-24 | 2018-01-26 | 青岛清原化合物有限公司 | A kind of pyrazolone compound or its salt, herbicidal composition and purposes |
| CN107810963A (en) * | 2017-11-09 | 2018-03-20 | 青岛清原化合物有限公司 | A kind of Herbicidal combinations of the fluorine of pyrrole containing ring humulone and its application |
| CN109042675A (en) * | 2018-07-21 | 2018-12-21 | 青岛清原化合物有限公司 | Ternary weeding composition and its application comprising HPPD inhibitor class herbicide |
-
2018
- 2018-12-25 CN CN201811592942.8A patent/CN111362908B/en active Active
- 2018-12-27 WO PCT/CN2018/124126 patent/WO2020133018A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012130685A1 (en) * | 2011-03-25 | 2012-10-04 | Bayer Cropscience Ag | Use of n-(tetrazol-4-yl)- or n-(triazol-3-yl)arylcarboxamides or their salts for controlling unwanted plants in areas of transgenic crop plants being tolerant to hppd inhibitor herbicides |
| CN105218449A (en) * | 2015-11-06 | 2016-01-06 | 青岛清原化合物有限公司 | Pyrazolone compound or its salt, preparation method, herbicidal composition and purposes |
| CN106070226A (en) * | 2016-06-07 | 2016-11-09 | 泰安市农业科学研究院 | A kind of ring pyrrole fluorine oxadiazon compositions and application thereof |
| CN106472517A (en) * | 2016-09-30 | 2017-03-08 | 江苏清原农冠杂草防治有限公司 | Synergistic herbicide compositions and its application |
| CN107629035A (en) * | 2017-10-24 | 2018-01-26 | 青岛清原化合物有限公司 | A kind of pyrazolone compound or its salt, herbicidal composition and purposes |
| CN107810963A (en) * | 2017-11-09 | 2018-03-20 | 青岛清原化合物有限公司 | A kind of Herbicidal combinations of the fluorine of pyrrole containing ring humulone and its application |
| CN109042675A (en) * | 2018-07-21 | 2018-12-21 | 青岛清原化合物有限公司 | Ternary weeding composition and its application comprising HPPD inhibitor class herbicide |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2020133018A1 (en) | 2020-07-02 |
| CN111362908A (en) | 2020-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2493311B1 (en) | Synergistic herbicidal composition containing fluroxypyr and penoxsulam | |
| JP2006503083A (en) | Aryloxyphenoxypropionate and safener combination and its use for enhanced weed control | |
| CN111362917B (en) | Amorphous-state bicyclopyrone monoisopropylamine salt and preparation method and application thereof | |
| EP2685829A1 (en) | Synergistic herbicidal composition containing penoxsulam and pyroxsulam | |
| CN111362908B (en) | Amorphous-state bicyclopyrone dimethylamine salt and preparation method and application thereof | |
| CN111362913B (en) | Amorphous-state bicyclopyrone triethanolamine salt and preparation method and application thereof | |
| CN111362907B (en) | Cyclopyraflutole-isopropylamine salt D crystal form and preparation method and application thereof | |
| CN111362909B (en) | Cypridinafulone dimethylamine salt C crystal form and preparation method and application thereof | |
| CN111362905B (en) | Cyclopyraflutole-isopropylamine salt E crystal form and preparation method and application thereof | |
| CN111362914B (en) | Cyclopyraflutole triethanolamine salt crystal form B and preparation method and application thereof | |
| CN111362916B (en) | Cyclopyraflutole-isopropylamine salt F crystal form and preparation method and application thereof | |
| CN111362918B (en) | Cyclopyraflutole-isopropylamine salt B crystal form and preparation method and application thereof | |
| CN111362906B (en) | Cyclopyraflutole-isopropylamine salt C crystal form and preparation method and application thereof | |
| CN111362910B (en) | Cyclopyraflutole dimethylamine salt B crystal form and preparation method and application thereof | |
| AU2013217972A1 (en) | Polymorphs of N- (2 -methoxybenzoyl) -4- [ (methylaminocarbonyl) amino] benzenesulfonamide | |
| CN111362911B (en) | Cyclopyraflutole dimethylamine salt and preparation method and application thereof | |
| CN111362915B (en) | Cyclopyraflutole-isopropylamine salt and preparation method and application thereof | |
| CN111362912B (en) | Cyclopyraflutole triethanolamine salt and preparation method and application thereof | |
| CN111362919B (en) | Cyclopyraflutole dimethylamine salt D crystal form and preparation method and application thereof | |
| CN110099568B (en) | Polymorphs of herbicidal sulfonamides | |
| WO2016115883A1 (en) | A herbicidal composition and method of controlling plant growth | |
| CN108558761B (en) | Triazolesulfonylzone-salicylic acid eutectic crystal and preparation method and application thereof | |
| CN110551122B (en) | Substituted pyrazolyl pyrazole sulfonamide compound or salt and composition thereof acceptable as pesticide and application thereof | |
| WO2024073018A1 (en) | Biodegradable microparticles for reducing the volatility of bixolozone | |
| EA046113B1 (en) | FLUORINED PHENYLACETIC ACID DERIVATIVES IN A METHOD FOR WEED CONTROL |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |