CN111362910A - Cyclopyraflutole dimethylamine salt B crystal form and preparation method and application thereof - Google Patents
Cyclopyraflutole dimethylamine salt B crystal form and preparation method and application thereof Download PDFInfo
- Publication number
- CN111362910A CN111362910A CN201811593030.2A CN201811593030A CN111362910A CN 111362910 A CN111362910 A CN 111362910A CN 201811593030 A CN201811593030 A CN 201811593030A CN 111362910 A CN111362910 A CN 111362910A
- Authority
- CN
- China
- Prior art keywords
- degrees
- percent
- dimethylamine salt
- dimethylamine
- salt
- 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.)
- Granted
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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/58—1,2-Diazines; Hydrogenated 1,2-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
- A01N43/64—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
- A01N43/90—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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention belongs to the technical field of herbicide crystallization processes, and particularly relates to a cyflufenac dimethylamine salt crystal form B, and a preparation method and application thereof. An X-ray powder diffraction spectrogram of the crystal form B of the ciclopirox flufenamate dimethylamine salt has characteristic peaks at diffraction angles 2 theta of 6.0 degrees, 7.0 degrees, 9.5 degrees, 10.0 degrees, 11.2 degrees, 11.9 degrees, 12.6 degrees, 13.1 degrees, 13.9 degrees, 14.6 degrees, 15.2 degrees, 16.1 degrees, 17.0 degrees, 17.3 degrees, 17.9 degrees, 18.7 degrees, 20.9 degrees, 21.9 degrees, 22.6 degrees, 23.0 degrees, 23.5 degrees, 24.2 degrees, 25.3 degrees, 26.5 degrees, 27.1 degrees, 28.2 degrees, 28.8 degrees, 29.9 degrees, 30.4 degrees, 31.5 degrees, 32.0 degrees, 32.8 degrees, 33.8 degrees, 34.4 degrees, 35.3 degrees, 35.9 degrees, 37.4 degrees, 38.4 degrees, 39.6 degrees, 40.4 degrees, 41.0 degrees, 42.1 degrees and 42.8 degrees, wherein the error range of the 2 theta is within +/-0.2 degrees. The cyflufen-ethyl flurtamone dimethylamine salt B has high solubility, good physical and chemical stability and higher 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 a cyflufenac dimethylamine salt crystal form B, 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 cyflufenan dimethylamine salt B crystal form and a preparation method and application thereof. The crystal form has good physical and chemical stability, high solubility and higher 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 X-ray powder diffraction spectrogram of the crystal form B of ciclopirox flutolscreen dimethylamine salt has characteristic peaks at diffraction angles 2 theta of 6.0 degrees, 7.0 degrees, 9.5 degrees, 10.0 degrees, 11.2 degrees, 11.9 degrees, 12.6 degrees, 13.1 degrees, 13.9 degrees, 14.6 degrees, 15.2 degrees, 16.1 degrees, 17.0 degrees, 17.3 degrees, 17.9 degrees, 18.7 degrees, 20.9 degrees, 21.9 degrees, 22.6 degrees, 23.0 degrees, 23.5 degrees, 24.2 degrees, 25.3 degrees, 26.5 degrees, 27.1 degrees, 28.2 degrees, 28.8 degrees, 29.9 degrees, 30.4 degrees, 31.5 degrees, 32.0 degrees, 32.8 degrees, 34.4 degrees, 35.3 degrees, 35.4 degrees, 38.4 degrees, 39.6 degrees, 40.4 degrees, 41.0 degrees, 42.1 degrees and 42.8 degrees, wherein the error range of the 2 theta is within +/-0.2 degrees.
Preferably, corresponding I/I0Are respectively corresponding I/I02.4, 100.0, 5.2, 3.1, 2.5, 73.0, 76.5, 4.9, 11.4, 11.5, 3.9, 16.4, 5.3, 4.3, 7.2, 7.8, 32.8, 19.7, 10.9, 13.0, 20.1, 1.6, 9.7, 4.5, 5.8, 10.6, 1.7, 3.4, 6.7, 1.2, 2.2, 4.6, 1.1, 3.1, 4.1, 2.8, 2.2, 2.1, 1.8, 5.5, 2.0, 3.3, 0.9, respectively.
More preferably, the X-ray powder diffraction pattern is substantially as shown in figure 1.
The preparation method of the crystal form B of the bicyclopyrone dimethylamine salt comprises the following steps:
weighing a certain amount of the cypioflutole, adding ethyl acetate, isopropyl acetate, butyl acetate, p-xylene, tetrahydrofuran, phenetole, chlorobenzene or dichloromethane, dissolving the materials just, adding a certain amount of dimethylamine into the solution to carry out salt forming reaction, separating out a solid, and drying at 35-50 ℃ to obtain a cypioflutole dimethylamine salt B crystal form;
or dissolving the cypioflutolamine dimethylamine salt in methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, sec-butanol, acetonitrile, tetrahydrofuran or 1, 4-dioxane, placing the mixture at the temperature of between 40 and 60 ℃ to slowly volatilize the solvent, and drying the obtained solid at the temperature of between 35 and 50 ℃ to obtain the cypioflutolamine dimethylamine salt B crystal form;
or adding the cypioflutolicacid dimethylamine salt into acetone, heating to 55-65 ℃ to dissolve the cypioflutolicacid dimethylamine salt, then placing the mixture in an environment of 0-4 ℃ to cool, filtering to obtain a precipitated solid, and drying at 35-50 ℃ to obtain the cypioflutolicacid dimethylamine salt B crystal form.
Or dissolving the cypioflutole dimethylamine salt in ethanol, and performing rotary evaporation at 55-65 ℃ to obtain the cypioflutole dimethylamine salt B crystal form.
A herbicidal compounded composition comprising (i) the crystalline form B of the diflufenican 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, phosphate esters, ethoxylated fluorinated alcohols, ethoxylated silicones, alkylphenol ethoxylates, benzene sulfonates, alkyl substituted benzene sulfonates, alkyl α -olefin sulfonates, naphthalene sulfonates, alkyl substituted alkali metal naphthalene sulfonates, condensates of alkali metal naphthalene sulfonates and alkyl substituted naphthalene sulfonates 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 mixed with the crystalline form B of the diflufenican dimethylamine salt of the present invention are, for example, those known from "the world wide technical universe of new pesticides", 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 crystal form B of the diflufenican dimethylamine salt has obvious synergistic effect when being applied with one or more of the herbicides.
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 crystalline form B of the bicyclopyrone dimethylamine salt or the herbicidal compounded composition on crops or in weed areas.
The invention also provides the application of the crystal form B of the bicyclopyrone dimethylamine salt or the weeding compound composition in controlling weeds; 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.
The crystal form B of the diflufenican dimethylamine salt has good physical and chemical stability and good water solubility through tests, the solubility in water is nearly twenty times larger than that of the diflufenican, and is nearly ten times larger than that of the diflufenican sodium salt, and the crystal form B or a compound composition of the crystal form B and other effective components has better control effect on gramineous weeds in wheat fields, and the effect is obviously better than that of the diflufenican and the sodium salt thereof.
Drawings
Figure 1 is an XRPD pattern of crystalline form B of the diflufenican dimethylamine 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
Instrument model Bruker D8advance, target Cu K α (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 0.25 kg of 40% 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.
Placing 1 kg of cypioflutole dimethylamine salt in a 10L flask, adding 2 liters of acetone, heating to 60 ℃, stirring until the raw materials are completely dissolved, gradually cooling to 0-4 ℃, cooling, filtering to obtain a precipitated solid, and drying at 45 ℃ to obtain cypioflutole dimethylamine B crystal form powder;
or adding 1 kg of the cyflutolanil obtained in the example 1 into 3 liters of ethyl acetate, isopropyl acetate, butyl acetate, p-xylene, tetrahydrofuran, phenetole, chlorobenzene or dichloromethane, stirring to completely dissolve the cyflutolanil, then adding 0.25 kg of 40% dimethylamine for reaction, separating out a solid, filtering, and drying at 45 ℃ to obtain the cyflutolanil dimethylamine salt B crystal form;
or dissolving 1 kg of the cypioflutolamine dimethylamine salt in 5 liters of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, sec-butanol, acetonitrile, tetrahydrofuran or 1, 4-dioxane, stirring to completely dissolve the cypioflutolamine dimethylamine salt, then placing the mixture at 50 ℃ to slowly volatilize the solvent, and drying the obtained solid at 45 ℃ to obtain the cypioflutolamine dimethylamine salt B crystal form;
or dissolving 1 kg of the cyflufenac dimethylamine salt in 6 liters of ethanol, and performing rotary evaporation at 60 ℃ to obtain the cyflufenac dimethylamine salt B crystal form.
Physical and chemical stability test
The content of the ciclopirox-fluridon and the sodium salt thereof obtained in the example 1 and the content of the ciclopirox-dimethylamine B crystal form thereof obtained in the example 2 are respectively tested by HPLC to be 97.2 percent, 98.0 percent and 98.0 percent, and then the three raw medicine powders are respectively placed in ovens at 25 ℃, 40 ℃, 55 ℃ and 70 ℃ for heat storage test for 2 months, and then the purity is tested, and the results are shown in the following table 1:
table 1 stability investigation of different samples
| Sample (I) | Cypriflutole | Cyclopyraflutole sodium salt | Crystal form B of bicyclopyrone dimethylamine salt |
| 25℃ | 97.2％ | 98.0％ | 98.0％ |
| 40℃ | 96.6％ | 97.8％ | 97.9％ |
| 55℃ | 96.1％ | 97.3％ | 97.6％ |
| 70℃ | 95.5％ | 96.5％ | 97.0％ |
As can be seen from the table 1, the crystal form B of the ciclopirox flurtamone and the sodium salt thereof and the ciclopirox diflufenican dimethylamine salt have better stability under different temperature conditions, particularly, the crystal form B still keeps good physical and chemical stability at the higher temperature of 55 ℃ and 70 ℃, the purity detection is equivalent to or slightly superior to that of the ciclopirox flurtamone and the sodium salt thereof, and the ciclopirox flurtamone and the dimethylamine salt thereof have good application prospect.
Determination of solubility in Water
Dissolving the ciclopirox and the sodium salt thereof obtained in example 1 and the ciclopirox dimethylamine salt B crystal form powder obtained in example 2 in pure water, shaking for 24h at 25 ℃ to fully dissolve the ciclopirox and the dimethylamine salt, centrifuging and filtering the solution, filtering the filtrate by a 0.22 mu m filter membrane, and measuring the solubility in water by HPLC (high performance liquid chromatography), wherein the results are shown in the following table 2:
table 2 water solubility test results for different samples
| Sample (I) | Solubility in pure Water (g/L) |
| Cypriflutole | 0.524 |
| Cyclopyraflutole sodium salt | 1.137 |
| Crystal form B of bicyclopyrone dimethylamine salt | 10.058 |
The results in table 2 show that compared with the crystal form B of the diflufenican dimethylamine salt, the solubility of the diflufenican dimethylamine salt is obviously increased.
Examples 1 and 2 formulation processing and field efficacy testing
The ciclopirox and the sodium salt thereof obtained in the example 1 and the ciclopirox dimethylamine salt B crystal form 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 the ciclopirox, the ciclopirox sodium salt and the ciclopirox dimethylamine salt B crystal form.
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 stem and leaf spray is adopted to spray evenly, the area of a cell is 30 square meters, and the average plant control effect (visual inspection) effect is investigated 45 days after each treatment is repeated for 4 times of pesticide application as shown in table 3.
TABLE 3 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 3, 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 cyhalofop-butyl dimethylamine salt B crystal form 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 (10)
1. A crystalline form B of diflufenican dimethylamine salt is characterized in that: an X-ray powder diffraction spectrum has characteristic peaks at diffraction angles 2 theta of 6.0 degrees, 7.0 degrees, 9.5 degrees, 10.0 degrees, 11.2 degrees, 11.9 degrees, 12.6 degrees, 13.1 degrees, 13.9 degrees, 14.6 degrees, 15.2 degrees, 16.1 degrees, 17.0 degrees, 17.3 degrees, 17.9 degrees, 18.7 degrees, 20.9 degrees, 21.9 degrees, 22.6 degrees, 23.0 degrees, 23.5 degrees, 24.2 degrees, 25.3 degrees, 26.5 degrees, 27.1 degrees, 28.2 degrees, 28.8 degrees, 29.9 degrees, 30.4 degrees, 31.5 degrees, 32.0 degrees, 32.8 degrees, 33.8 degrees, 34.4 degrees, 35.3 degrees, 35.9 degrees, 37.4 degrees, 38.4 degrees, 39.6 degrees, 40.4 degrees, 41.0 degrees, 42.1 degrees, 42.8 degrees, wherein the error range of 2 theta is within +/-0.2 degrees.
2. The bicyclopyrone dimethylamine according to claim 1Salt form B characterized by: corresponding I/I02.4, 100.0, 5.2, 3.1, 2.5, 73.0, 76.5, 4.9, 11.4, 11.5, 3.9, 16.4, 5.3, 4.3, 7.2, 7.8, 32.8, 19.7, 10.9, 13.0, 20.1, 1.6, 9.7, 4.5, 5.8, 10.6, 1.7, 3.4, 6.7, 1.2, 2.2, 4.6, 1.1, 3.1, 4.1, 2.8, 2.2, 2.1, 1.8, 5.5, 2.0, 3.3, 0.9, respectively.
3. Crystalline form B of ciclopirox flurtamone dimethylamine salt according to claim 1 or 2, characterized in that: an X-ray powder diffraction pattern substantially as shown in figure 1.
4. A process for the preparation of crystalline form B of ciclopirox flurtamone dimethylamine according to any of the claims 1-3, characterized in that: the method comprises the following steps:
weighing a certain amount of the cypioflutole, adding ethyl acetate, isopropyl acetate, butyl acetate, p-xylene, tetrahydrofuran, phenetole, chlorobenzene or dichloromethane, dissolving the materials just, adding a certain amount of dimethylamine into the solution to carry out salt forming reaction, separating out a solid, and drying at 35-50 ℃ to obtain a cypioflutole dimethylamine salt B crystal form;
or dissolving the cypioflutolamine dimethylamine salt in methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, sec-butanol, acetonitrile, tetrahydrofuran or 1, 4-dioxane, placing the mixture at the temperature of between 40 and 60 ℃ to slowly volatilize the solvent, and drying the obtained solid at the temperature of between 35 and 50 ℃ to obtain the cypioflutolamine dimethylamine salt B crystal form;
or adding the cypioflutolicacid dimethylamine salt into acetone, heating to 55-65 ℃ to dissolve the cypioflutolicacid dimethylamine salt, then placing the mixture in an environment of 0-4 ℃ to cool, filtering to obtain a precipitated solid, and drying at 35-50 ℃ to obtain the cypioflutolicacid dimethylamine salt B crystal form.
Or dissolving the cypioflutole dimethylamine salt in ethanol, and performing rotary evaporation at 55-65 ℃ to obtain the cypioflutole dimethylamine salt B crystal form.
5. A weeding compound composition is characterized in that: comprising (i) crystalline form B of the bicyclopyrone dimethylamine salt of any of claims 1-3; preferably, also (ii) one or more other active ingredients and/or safeners; more preferably, (iii) an agrochemically acceptable formulation auxiliary.
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, chlortoluron, bromoxynil octanoate, metribuzin, pyridate, amicarbazone, 2-methyl-4-chloro, fluroxypyr, halauxifen, dicamba, saflufenacil, flufenacet, metolachlor, xaflufen, pendimethalin, mesosulfuron, flucarbazone, pyroxsulam, prosulfocarb and derivatives thereof.
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 5 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 comprising applying to the crop or to the locus of weeds a herbicidally effective amount of the crystalline form B of the pyriflufenacet dimethylamine salt according to any of claims 1 to 3 or the herbicidal combination according to any of claims 5 to 8; preferably, the crop is wheat and the weed is a grass weed (e.g., alopecurus maytans, alopecurus japonicus).
10. Use of the crystalline form B of ciclopirox flutolscreen dimethylamine salt according to any of the claims 1 to 3 or the herbicidal combination composition according to any of the claims 5 to 8 for controlling weeds, preferably for controlling weeds in crops of useful plants, said crops of useful plants being transgenic or crops treated by genome editing techniques; preferably, the crop is wheat and the weed is a grass weed (e.g., alopecurus maytans, alopecurus japonicus).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811593030.2A CN111362910B (en) | 2018-12-25 | 2018-12-25 | Cyclopyraflutole dimethylamine salt B crystal form and preparation method and application thereof |
| PCT/CN2018/124127 WO2020133019A1 (en) | 2018-12-25 | 2018-12-27 | Crystalline form b of cypyrafluone dimethylamine salt, and preparation method therefor and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811593030.2A CN111362910B (en) | 2018-12-25 | 2018-12-25 | Cyclopyraflutole dimethylamine salt B crystal form and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111362910A true CN111362910A (en) | 2020-07-03 |
| CN111362910B CN111362910B (en) | 2021-03-12 |
Family
ID=71127497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811593030.2A Active CN111362910B (en) | 2018-12-25 | 2018-12-25 | Cyclopyraflutole dimethylamine salt B crystal form and preparation method and application thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN111362910B (en) |
| WO (1) | WO2020133019A1 (en) |
Cited By (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 CN201811593030.2A patent/CN111362910B/en active Active
- 2018-12-27 WO PCT/CN2018/124127 patent/WO2020133019A1/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 |
Cited By (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 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2020133019A1 (en) | 2020-07-02 |
| CN111362910B (en) | 2021-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2930012A1 (en) | Composition of 1,5-dimethyl-6-thioxo-3-(2,2,7-trifluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2h-benzo[b][1,4]oxazin-6-yl)-1,3,5-triazinane-2,4-dione | |
| CN111362917B (en) | Amorphous-state bicyclopyrone monoisopropylamine salt and preparation method and application thereof | |
| CN115462385A (en) | Herbicidal composition containing phenyl isoxazolines with optical activity and application | |
| CN111362910B (en) | Cyclopyraflutole dimethylamine salt B crystal form and preparation method and application thereof | |
| CN111362909B (en) | Cypridinafulone dimethylamine salt C crystal form and preparation method and application thereof | |
| CN111362906B (en) | Cyclopyraflutole-isopropylamine salt C crystal form and preparation method and application thereof | |
| CN111362914B (en) | Cyclopyraflutole triethanolamine salt crystal form B and preparation method and application thereof | |
| CN111362905B (en) | Cyclopyraflutole-isopropylamine salt E crystal form 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 | |
| CN111362907B (en) | Cyclopyraflutole-isopropylamine salt D crystal form and preparation method and application thereof | |
| CN111362911B (en) | Cyclopyraflutole dimethylamine salt and preparation method and application thereof | |
| CN111362912B (en) | Cyclopyraflutole triethanolamine salt and preparation method and application thereof | |
| CN111362908B (en) | Amorphous-state bicyclopyrone dimethylamine salt and preparation method and application thereof | |
| CN111362915B (en) | Cyclopyraflutole-isopropylamine salt and preparation method and application thereof | |
| CN111362913B (en) | Amorphous-state bicyclopyrone triethanolamine salt and preparation method and application thereof | |
| CN111362919B (en) | Cyclopyraflutole dimethylamine salt D crystal form and preparation method and application thereof | |
| 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 | |
| CN114391014A (en) | Pyridazine compound and herbicide |
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 |