CN111362906B - Cyclopyraflutole-isopropylamine salt C crystal form and preparation method and application thereof - Google Patents
Cyclopyraflutole-isopropylamine salt C crystal form and preparation method and application thereof Download PDFInfo
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- 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
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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Abstract
The invention belongs to the technical field of herbicide crystallization processes, and particularly relates to a cyflufenac-isopropylamine salt C crystal form and a preparation method and application thereof. An X-ray powder diffraction spectrum of the crystalline form C of the ciclopirox monoisopropylamine salt has characteristic peaks at diffraction angles 2 theta of 6.9 degrees, 7.4 degrees, 8.3 degrees, 10.2 degrees, 11.3 degrees, 12.5 degrees, 14.0 degrees, 15.1 degrees, 16.3 degrees, 17.0 degrees, 18.0 degrees, 18.7 degrees, 19.2 degrees, 20.0 degrees, 20.6 degrees, 21.2 degrees, 21.7 degrees, 22.3 degrees, 23.0 degrees, 24.8 degrees, 25.9 degrees, 26.2 degrees, 27.5 degrees, 28.1 degrees, 28.4 degrees, 29.4 degrees, 30.3 degrees, 30.8 degrees, 31.3 degrees, 31.8 degrees, 33.4 degrees, 34.0 degrees, 34.7 degrees, 35.8 degrees, 37.0 degrees, 37.7 degrees, 38.2 degrees, 38.8 degrees, 40.1 degrees, 40.7 degrees, 42.6 degrees and 44.0 degrees, wherein the error range of the 2 theta is within +/-0.2 degrees. The cyflufenac monoisopropylamine salt C crystal form has the advantages of good physical and chemical stability, high solubility 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-isopropylamine salt C crystal form 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 cyflufenac monoisopropylamine salt C 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 spectrum of the crystalline form C of ciclopirox-flurtamone-isopropylamine salt has characteristic peaks at diffraction angles 2 theta of 6.9 degrees, 7.4 degrees, 8.3 degrees, 10.2 degrees, 11.3 degrees, 12.5 degrees, 14.0 degrees, 15.1 degrees, 16.3 degrees, 17.0 degrees, 18.0 degrees, 18.7 degrees, 19.2 degrees, 20.0 degrees, 20.6 degrees, 21.2 degrees, 21.7 degrees, 22.3 degrees, 23.0 degrees, 24.8 degrees, 25.9 degrees, 26.2 degrees, 27.5 degrees, 28.1 degrees, 28.4 degrees, 29.4 degrees, 30.3 degrees, 30.8 degrees, 31.3 degrees, 31.8 degrees, 33.4 degrees, 34.0 degrees, 34.7 degrees, 35.8 degrees, 37.0 degrees, 37.7 degrees, 38.2 degrees, 38.8 degrees, 40.1 degrees, 40.7 degrees, 42.6 degrees and 44.0 degrees, wherein the error range of the 2 theta is within +/-0.2 degrees.
Preferably, corresponding I/I03.5, 53.5, 8.9, 80.6, 12.7, 2.8, 100.0, 46.5, 19.3, 3.9, 12.8, 11.6, 18.9, 51.8, 10.3, 5.1, 12.9, 5.7, 26.1, 23.5, 25.8, 41.3, 12.9, 8.5, 9.4, 3.6, 14.3, 9.7, 4.7, 4.5, 3.2, 5.7, 27.9, 3.7, 5.0, 1.4, 2.7, 5.3, 2.1, 3.5, 3.0, 2.0, respectively.
More preferably, the X-ray powder diffraction pattern is substantially as shown in figure 1.
The preparation method of the crystalline form C of the bicyclopyrone monoisopropylamine salt comprises the following steps: dissolving the cyflufenac monoisopropylamine salt in methanol, stirring until the cyflufenac monoisopropylamine salt is completely dissolved, then adding 1-10 times of methyl tert-butyl ether by volume to separate out a large amount of solid crystals from the solution, and drying the obtained solid crystals to obtain the cyflufenac monoisopropylamine salt C crystal form.
A herbicidal compounded composition comprising (i) the crystalline form C of the monoisopropylamine salt of ciclopirox; 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 that can be combined with the crystalline form C of the monoisopropylamine salt of ciclopirox according to the invention are, for example, those known in the "technical universe of new agricultural chemicals", 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, chlodine, ethiofencarb, prosperon, cleam, prosulfocarb, dichlorcarb, thiobencarb, promethan, isopoline, methiobenzoate, 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 isopropylamine salt, 2 methyl 4-chloroethyl thioester, 2 methyl 4 chloride, 2, 4-d propionic acid, high 2, 4-d propionate, 2, 4-d propionic acid, 2 methyl 4-c acid, 2 methyl 4-chloro-butyric acid, 2,4, 5-d nasal discharge, 2,4, 5-d propionic acid, 2,4, 5-d butyric acid, 2, 4-chloro-d benzoic acid, 2, 4-d trichloroacetic acid, 2, 5-d amine salt, triclocarb, triclopyr, 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 compound application of the crystalline form C of the pyriflutole-isopropylamine salt and one or more of the herbicides has 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 crystalline form C of the monoisopropylamine salt of bicyclopyrone or the herbicidal combination composition to the crops or the weed areas.
The invention also provides the application of the crystalline form C of the pyriflufenac-monoisopropylamine 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 test proves that the crystalline form C of the bicyclopyrone monoisopropylamine salt is good in physical and chemical stability and water solubility, the solubility of the bicyclopyrone in water is increased by more than ten times compared with that of the bicyclopyrone, and the solubility of the bicyclopyrone is increased by nearly six times compared with that of the bicyclopyrone sodium salt, and the crystalline form C or a compound composition of the bicyclopyrone monoisopropylamine salt and other effective components has a good preventing and removing effect on gramineous weeds in wheat fields, and the effect is obviously better than that of the bicyclopyrone.
Drawings
Figure 1 is an XRPD pattern of crystalline form C of bicyclopyrone monoisopropylamine 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 diameter: 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 cyflutolanil obtained in example 1 was reacted with 0.27 kg of 50% aqueous monoisopropylamine solution to give a large amount of solid crystals, which were filtered and dried to give cyflutolanil powder.
Placing 1000 g of cyflufenac monoisopropylamine salt into a 10L flask, adding 2L of methanol, heating and stirring until the raw materials are completely dissolved, then adding 7L of methyl tert-butyl ether, precipitating a large amount of crystals, filtering the solid, and drying to obtain cyflufenac monoisopropylamine salt C crystal form powder.
Physical and chemical stability test
The content of the ciclopirox-flurtamone and the sodium salt thereof obtained in the example 1 and the content of the ciclopirox-monoisopropylamine C crystal form powder obtained in the example 2 are respectively determined to be 97.2 percent, 98.0 percent and 98.0 percent by HPLC, and then the three raw medicine powders are respectively placed in ovens at 25 ℃, 40 ℃, 55 ℃ and 70 ℃ for 2 months to carry out a heat storage experiment, 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 | Cypriflutole monoisopropylamine salt crystal form C |
| 25℃ | 97.2％ | 98.0％ | 98.0％ |
| 40℃ | 96.6％ | 97.8％ | 97.9％ |
| 55℃ | 96.1％ | 97.3％ | 97.7％ |
| 70℃ | 95.5％ | 96.5％ | 97.3％ |
As can be seen from the table 1, the crystalline form C of the ciclopirox flurtamone and the sodium salt thereof and the ciclopirox monoisopropylamine salt have better stability under different temperature conditions, particularly, the crystalline form C still keeps good physicochemical 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 sodium salt thereof have good application prospect.
Determination of solubility in Water
Dissolving the powder of the bicyclopyrone and the sodium salt thereof obtained in example 1 and the powder of the crystal form C of the bicyclopyrone monoisopropylamine salt obtained in example 2 in pure water, shaking for 24 hours at 25 ℃ to fully dissolve the powder, centrifuging and filtering the solution, filtering the filtrate by using a 0.22 mu m filter membrane, and measuring the solubility in water by using 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 | 0.526 |
| Cyclopyraflutole sodium salt | 1.194 |
| Cypriflutole monoisopropylamine salt crystal form C | 6.375 |
As can be seen from the results in table 2, the solubility of the crystalline form C of the monoisopropylamine salt of ciclopirox is significantly increased compared to ciclopirox and its sodium salt.
Examples 1 and 2 formulation processing and field efficacy testing
The bicyclopyrone and the sodium salt thereof obtained in the example 1 and the bicyclopyrone monoisopropylamine salt C 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 bicyclopyrone, the bicyclopyrone sodium salt and the bicyclopyrone monoisopropylamine salt C 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 monoisopropylamine 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 monoisopropylamine, 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% A + 12% Dicamba + 7% monoisopropylamine + 40% ethanol + 10% sodium fatty alcohol Ether 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 average plant control effect (visual observation) was investigated 45 days after 4 application of the spray with stem and leaf spray evenly sprayed in a cell area of 30 square meters and each treatment, and is 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 cyflufenac, the preventing effect of the cyflufenac-isopropylamine salt C crystal form is obviously higher than that of the cyflufenac 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 (17)
1. A crystalline form C of bicyclopyrone monoisopropylamine salt, which is characterized in that: an X-ray powder diffraction spectrum has characteristic peaks at diffraction angles 2 theta of 6.9 degrees, 7.4 degrees, 8.3 degrees, 10.2 degrees, 11.3 degrees, 12.5 degrees, 14.0 degrees, 15.1 degrees, 16.3 degrees, 17.0 degrees, 18.0 degrees, 18.7 degrees, 19.2 degrees, 20.0 degrees, 20.6 degrees, 21.2 degrees, 21.7 degrees, 22.3 degrees, 23.0 degrees, 24.8 degrees, 25.9 degrees, 26.2 degrees, 27.5 degrees, 28.1 degrees, 28.4 degrees, 29.4 degrees, 30.3 degrees, 30.8 degrees, 31.3 degrees, 31.8 degrees, 33.4 degrees, 34.0 degrees, 34.7 degrees, 35.8 degrees, 37.0 degrees, 37.7 degrees, 38.2 degrees, 38.8 degrees, 40.1 degrees, 40.7 degrees, 42.6 degrees and 44.0 degrees, wherein the error range of the 2 theta is within +/-0.2 degrees.
2. The crystalline form C of bicyclopyrone monoisopropylamine salt according to claim 1, characterized in that: corresponding I/I03.5, 53.5, 8.9, 80.6, 12.7, 2.8, 100.0, 46.5, 19.3, 3.9, 12.8, 11.6, 18.9, 51.8, 10.3, 5.1, 12.9, 5.7, 26.1, 23.5, 25.8, 41.3, 12.9, 8.5, 9.4, 3.6, 14.3, 9.7, 4.7, 4.5, 3.2, 2,5.7、27.9、3.7、5.0、1.4、2.7、5.3、2.1、3.5、3.0、2.0。
3. Crystalline form C of bicyclopyrone monoisopropylamine 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 bicyclopyrone monoisopropylamine salt C, as claimed in any one of claims 1 to 3, wherein: the method comprises the following steps: dissolving the cyflufenac monoisopropylamine salt in methanol, stirring until the cyflufenac monoisopropylamine salt is completely dissolved, then adding 1-10 times of methyl tert-butyl ether by volume to separate out a large amount of solid crystals from the solution, and drying the obtained solid crystals to obtain the cyflufenac monoisopropylamine salt C crystal form.
5. A weeding compound composition is characterized in that: comprising (i) crystalline form C of the monoisopropylamine salt of ciclopirox according to any of claims 1 to 3, and (iii) agrochemically acceptable formulation auxiliaries.
6. A herbicidal combination according to claim 5, which further comprises (ii) one or more further active ingredients and/or safeners.
7. A herbicidal combination according to claim 6, 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.
8. A herbicidal compound composition according to claim 7, wherein the total mass percentage of the active ingredients in the composition accounts for 1-95% of the total amount.
9. A herbicidal compounded composition according to any one of claims 5 to 8, 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.
10. 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 crystalline form C of topramezone according to any one of claims 1 to 3 or a herbicidal combination according to any one of claims 5 to 9.
11. The method of claim 10, wherein the crop is wheat and the weed is a grass weed.
12. The method according to claim 11, wherein the grassy weed is a alopecurus or a japanese alopecurus.
13. Use of the crystalline form C of bicyclopyrone monoisopropylamine salt according to any one of claims 1 to 3 or the herbicidal re-formulation composition according to any one of claims 5 to 9 for controlling weeds.
14. Use according to claim 13, for controlling weeds in crops of useful plants.
15. Use according to claim 14, wherein the useful crop is a transgenic crop or a crop treated with genome editing technology.
16. Use according to claim 14 or 15, wherein the useful crop is wheat and the weed is a grass weed.
17. Use according to claim 16, wherein the grassy weeds are alopecurus or alopecurus japonicus.
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| PCT/CN2018/124122 WO2020133014A1 (en) | 2018-12-25 | 2018-12-27 | Crystalline form c of cypyrafluone monoisopropylamine salt, and preparation method therefor and use thereof |
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