CN106946784B - Amorphous state polybenzobisoxazole humulone and its preparation method and application - Google Patents
Amorphous state polybenzobisoxazole humulone and its preparation method and application Download PDFInfo
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- CN106946784B CN106946784B CN201710302027.XA CN201710302027A CN106946784B CN 106946784 B CN106946784 B CN 106946784B CN 201710302027 A CN201710302027 A CN 201710302027A CN 106946784 B CN106946784 B CN 106946784B
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
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- 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
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Abstract
The invention belongs to herbicide crystallization processes technical fields, and in particular to arrive a kind of amorphous state polybenzobisoxazole humulone and its preparation method and application.A kind of amorphous state polybenzobisoxazole humulone, through X-ray powder diffraction detection be in the form of unformed existing for, there is no sharp diffraction maximum in X-ray powder diffraction collection, it is preferable that its X-ray powder diffraction pattern basically as in Figure 2 shown in.Amorphous state polybenzobisoxazole humulone of the invention compares A crystal form, physical and chemical stability is good, crystal transfer does not occur within storing two months under 55 DEG C of high temperature, purity does not also reduce substantially, solubility doubles in water simultaneously, the amorphous state of polybenzobisoxazole humulone and complex composition with other effective components, have extraordinary preventive effect to wheat paddock broadleaf weeds and part gramineae weed, have a good application prospect.
Description
Technical field
The invention belongs to herbicide crystallization processes technical fields, and in particular to arrive a kind of amorphous state polybenzobisoxazole humulone and its system
Preparation Method and purposes.
Background technique
The chemical name of polybenzobisoxazole humulone: 1,3- dimethyl -4- (2- (methyl sulphonyl) -4- (trifluoromethyl) benzoyl
Base) -1H- pyrazoles -5- base 1,3- dimethyl -1H- pyrazoles -4- carboxylate
Structural formula:
Polybenzobisoxazole humulone is the HPPD inhibitor class herbicide of newly developed wheat paddock stem and leaf treatment after seedling, has excellent life
Object activity, can effectively prevent and kill off a variety of malignant weeds of wheat paddock, compound patent has been authorized to, Authorization Notice No.: CN
103980202 B。
Amorphous state is that there are a kind of forms of polymorphism, and a kind of special crystal form state for substance.For tool
There are the solid drugs of polymorphism, amorphous state is one of its a variety of crystal form state, the various reasons of amorphous state drug
Change property and drug effect is usually different from general crystal form drug.Therefore, in the polymorphic research of solid drugs, to amorphous state
The further investigated of substance has important scientific meaning.But it since amorphous state is thermodynamic phase system, is easy to occur brilliant
Type transformation, this is also the main obstacle for perplexing amorphous state drug.
Since polybenzobisoxazole humulone is newly developed drug, without the report of its crystal form in current various documents and patent,
And it has been investigated that in most cases, polybenzobisoxazole humulone is all with the presence of A crystal form.
Summary of the invention
The present invention provides a kind of new herbicides amorphous state polybenzobisoxazole humulone and its preparation method and application.The nothing
Setting state polybenzobisoxazole humulone does not have sharp diffraction maximum in X-ray powder diffraction collection, and stability is good, and solubility is high in water, right
Control of weeds effect is good, can be used for wheat paddock seedling Weed Control Effect after Improvement.
Technical solution of the present invention, polybenzobisoxazole humulone is referring to the method preparation in 103980202 B of CN.By 1,3- dimethyl-
5- hydroxypyrazoles 2.5g (0.022mol), toluene 30mL are added in there-necked flask, are added with stirring 9.0g triethylamine (0.09mol).
For ice bath controlled at 5-10 DEG C, the toluene that 2- mesyl -4- trifluoromethyl benzoyl chloride 6.3g (0.022mol) is added dropwise is molten
Liquid, control reaction temperature are no more than 15 DEG C, are added dropwise, remove ice-water bath, and reaction 30min, TLC detection reaction is stirred at room temperature
(ethyl acetate: petroleum ether=4:1, GF254, UV colour developing), after fully reacting, is added acetone cyanohydrin 0.2g, stirring
Under be to slowly warm up to 45-50 DEG C reaction, TLC detection reaction (ethyl acetate: petroleum ether=2:1, GF254, UV colour developing), reacted
N- ethylsulfonyl-N- (4- Trifluoromethoxyphen-l) acetbromamide 9.0g (0.023mol) is added in Quan Hou, controls temperature 60-65
DEG C reaction 8hr, it is after the reaction was completed, cooling, 50mL water is added and stirs evenly.Divide and take organic layer, saturated common salt water washing recycles molten
To doing, residue column chromatography for separation obtains target product 7.1g, yield for agent: 48.1%,1HNMR(CDCl3, 300MHz): δ 1.441
(t, 3H), 1.961 (s, 3H), 3.292 (s, 3H), 3.622 (q, 2H), 3.737 (s, 3H), 4.612 (s, 2H), 7.310 (d,
2H), 7.359 (d, 2H), 7.549 (d, 1H), 7.946 (d, 1H), 8.303 (s, 1H).
6~embodiment of embodiment 60 changes reactant into corresponding pyrrole referring to the synthetic method of 1~embodiment of embodiment 5
Azole compounds and corresponding acyl chlorides or halides are reacted, and are made as numbered each formula (I) for being 006~060 in table 1
Close object.The test data of each compound of number 006~060 is listed in table 1.Polybenzobisoxazole humulone described herein is embodiment
Compound described in 21.
The polybenzobisoxazole humulone raw medicine being prepared is A crystal form, and on the basis of A crystal form, and the nothing for having studied polybenzobisoxazole humulone is fixed
Form.
A kind of amorphous state polybenzobisoxazole humulone, through X-ray powder diffraction detection be in the form of unformed existing for.
There is no sharp diffraction maximum in its X-ray powder diffraction collection, it is preferable that its X-ray powder diffraction pattern is basic
It is upper as shown in Figure 2.
The preparation method of the amorphous state polybenzobisoxazole humulone, comprising the following steps: by polybenzobisoxazole humulone stirring and dissolving in dichloro
In methane, in 25-35 DEG C of decompression rotary evaporation of solvent, preferable temperature is 30 DEG C, after through mechanical lapping, obtain amorphous state.
Or in methyl alcohol by polybenzobisoxazole humulone stirring and dissolving, in 60-70 DEG C of decompression rotary evaporation of solvent, preferable temperature 65
DEG C, after through mechanical lapping, obtain amorphous state.
Or by polybenzobisoxazole humulone stirring and dissolving in tetrahydrofuran, in 35-45 DEG C of decompression rotary evaporation of solvent, preferable temperature
Be 40 DEG C, after through mechanical lapping, obtain amorphous state.
A kind of weeding complex composition, including the amorphous state polybenzobisoxazole humulone effective component and auxiliary agent.
The auxiliary agent is selected from solvent, solid diluent, emulsifier, wetting agent, dispersing agent, antifreezing agent, defoaming agent and thickening
One of agent is a variety of.
Selected solvent includes but is not limited to polar solvent class: water, N, N- dimethylformamide, dimethyl sulfoxide, N- alkylated pyrazole
Pyrrolidone, methanol, ethyl alcohol, ethylene glycol, isopropanol, butyl glycol ether, propylene glycol monomethyl ether etc.；Aromatic solvent naphtha series: toluene, two
Toluene, No. 100 solvent naphthas, No. 150 solvent naphthas, No. 180 solvent naphthas, No. 200 solvent naphthas etc.；Plant oil: castor oil, linseed
Oil, sesame oil, corn oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil and their corresponding methylated vegetable oils etc.；Ketone
Class: cyclopentanone, cyclohexanone, cyclooctanone, 2-HEPTANONE, isophorone and 4- hydroxy-4-methyl-2-pentanone etc.；Acetate esters: acetic acid
Methyl esters, ethyl acetate, propyl acetate, sec-butyl acetate, isoamyl acetate, hexyl acetate, heptyl acetate and octyl acetate etc.；Its
Remaining class is such as: decyl amide, cyclohexanol, decyl alcohol, benzyl alcohol and tetrahydrofurfuryl alcohol.
Selected solid diluent can be water-soluble or water-insoluble.Water-soluble solid diluent includes but is not limited to:
Salt, for example, alkali metal phosphate (sodium dihydrogen phosphate), alkali earth metal phosphate, sodium, potassium, the sulfate of magnesium and zinc, sodium chloride and
Potassium chloride, sodium acetate, sodium carbonate and sodium benzoate and sugar and sugar derivatives, such as D-sorbite, lactose, sucrose and sweet dew
Alcohol, cornstarch etc..The example of water-insoluble solid diluent includes but is not limited to: clay, calcium carbonate, diatomite, white carbon black,
Calcium silicates, bentonite, aluminium-magnesium silicate and kaolin etc..
Wetting agent includes but is not limited to: alkyl sulfo succinate, laruate, alkyl sulfate, phosphate, ethyoxyl
Fluorinated alohol, the silicone of ethoxylation, alkyl phenol ethoxylate, benzene sulfonate, alkyl-substituted benzene sulfonate, alkyl-alpha-alkene
Sulfonated hydrocarbon, naphthalene sulfonate, alkyl-substituted naphthalene sulfonic acids alkali metal salt, naphthalene sulfonic acids alkali metal salt and alkyl-substituted napsylate
With the ethoxylate of the condensation product of formaldehyde, alcohol.
Dispersing agent includes but is not limited to: sodium salt, calcium salt and the ammonium salt of lignin sulfonic acid；The sodium salt of copolymer-maleic anhydride and
Ammonium salt；The sodium salt of the phenolsulfonic acid of condensation；Napsylate-formaldehyde condensation products；Phosphoric acid ester dispersing agent, polycarboxylic acid salt's dispersing agent
Deng.
Thickener includes but is not limited to: guar gum, pectin, xanthan gum, alginates, methylcellulose, hydroxyethyl cellulose,
Hydroxypropyl cellulose and carboxymethyl cellulose.The thickener of synthesis includes the derivative of aforesaid kind, further includes polyvinyl alcohol, poly-
Acrylamide, polyvinylpyrrolidone, various polyethers and their copolymer and polyacrylic acid and their salt.
Other formulation ingredients, such as dyestuff, defoaming agent, desiccant etc. can be used in the present invention.These ingredients are ability
Field technique personnel are known.
The composition further includes other effective components.
The suitable effective component that can be mixed with amorphous state polybenzobisoxazole humulone of the invention is, such as " world pesticide is new
Kind technology is complete works of ", Scientia Agricultura Sinica technology publishing house, 2010.9 and document incorporated herein in known substance.Such as
Various substances mentioned below (remarks: the title of compound, or for according to the common name of International Organization for standardization (ISO),
Or be chemical name, have code name when appropriate): Acetochlor, butachlor, alachlor, propisochlor, isopropyl methoxalamine, essence
The left-handed naphthalene propionyl grass amine of isopropyl methoxalamine, pretilachlor, propachlor, kecaoan, naphthalene propionyl grass amine, R-, propanil, mefenacet,
Diphenamide, diflufenican, N-alpha-chloroacetyl-N-isopropyl-o ethylaniline, beflubutamid, bromobutide, dimethenamid, dimethenamidP,
Ethobenzanid, flufenacet, thenylchlor, metazachlor, isoxaben, flampropMmethyl, flampropMisopropyl,
Allidochlor, pethoxamid, chloranocryl, ring pretilachlor, mefluidide, monalide, delachlor, prynachlor, spy
Butachlor, xylachlor, dimethachlor, amine of taking to the greenwood, front three ring grass amine, clomeprop, propyzamide, valeryl benzene grass
Amine blocks careless amine, suffer, tricyclic match careless amine, butenachlor, tebutam, benzyl grass amine, quinone duckweed amine, dichlofluanid, naproanilide, second
Acyl alachlor, quinclorac, fenacet, pyrrole cyanogen grass amine, benzene grass more grams of dead, chlorothiamid, chlorine phthalimides, fourth amidine amine, fluorine metazachlor, green bristlegrass
Go saliva, Simanex, prometryn, cyanatryn, symetryne, ametryn, propazine, dipropetryn, flur, terbutryn, Garagard, three
Piperazine benfluralin, cyprazine, proglinazine, trietazine, prometon, Gesadrual, nitrine be net, desmetryn, dimethametryn, cyclopropyl blueness saliva,
Green bristlegrass of going out saliva, another Ding Jin, Zhong Dingtong, Te Dingtong, methoxy third be net, cyanatryn, ipazine, chlorazine, atraton, weed eradication are logical, Radix Glycyrrhizae
Saliva, cyanuric acid, Indaziflam, green sulphur is grand, metsulfuron-methyl, bensulfuron-methyl, chlorimuron, tribenuron-methyl, thifensulfuron methyl, the phonetic Huang of pyrrole
Grand, mesosulfuron, iodosulfuron-methyl-sodium, formamido group Sulfometuron Methyl, cinosulfuron, triasulfuron, sulfometuronmethyl, the phonetic sulphur of cigarette
Grand, ethametsulfuron, amidosulfuron, ethoxysulfuron, cypromisulfuron, rimsulfuron, azimsulfuron, pyridine ethyl methyl, list are phonetic
Sulphur is grand, single phonetic sulphur ester, flucarbazone, flupyrsulfuron-methyl-sodium, fluorine pyrazosulfuron, oxasulfuron, imazosulfuron, primisulfuronmethyl,
Procarbazone, prosulfuron, Sulfosulfuron, trifloxysulfuron, triflusulfuronmethyl, tritosulfuron, metsulfuron-methyl sodium salt, fluorine pyrrole sulphur
Grand, Sulfonylurea, orthosulfamuron, Propyrisulfuron (proxazuron-methyl), piperazine pyrazosulfuron, acifluorfen, fluorine
Sulfanilamide (SN) grass ether, lactofen, fluoroglycofen-ethyl, Oxyfluorfen, Mo 9 granular, aclonifen, ethoxyfen-ethyl, first carboxylic weeding
Ether, fluoroform grass ether, chlomethoxyfen, fluorodifen, fluorination nitrofen, fluorine furan grass ether, nitrofen, first grass ether, diformazan grass
Ether, fluorine lactazone grass ether, fluofazone ester, Halosafen, chlortoluron, isoproturon, linuron, diuron, Sha flutter grand, fluometuron, benzene
Thiophene is grand, methabenzthiazuron, cumyluron, ethidimuron, isouron, terbufos benzthiazuron, buturon, bromax, methyldymron, acyl grass
Grand, methoxy daimuron, metobromuron, metoxuron, afesin, telvar, Tupersan, fenuron, fluorine sulphur is grand, neburea, chloroxifenidium,
It is herban, isonoruron, Alipur-O, thiazfluron, tebuthiuron, difenoxuron, different to fluon, methylamine methabenz thiazuron, Long Caote, front three
Urea, dimefuron, Monisouron, Anisuron, Methiuron, Chloreturon, four fluon, phenmedipham, phenmedipham-second
The careless spirit of ester, desmedipham, sulphur, terbucarb, oatax, Chem hoe, chlorpropham, benzyl dichloride grass ester, swep, chlorbufam,
Carboxazole, Chlorprocarb, Fenasulam, BCPC, CPPC, Carbasulam, Ding Caote, benthiocarb, vernolate,
Molinate, tri-allate, dimepiperate, esprocarb, pyributicarb, cycloate, Avadex, bactericide, second sulphur careless spy, orbencarb, gram grass
Suddenly, prosulfocarb, tiocarbazil, sulfuric acid, dimexan, Isopolinate, Methiobencarb, 2,4- d butyl ester, 2 first, 4 chlorine
Sodium, the different monooctyl ester of 2,4- drop, the different monooctyl ester of 2 first, 4 chlorine, 2,4- drop sodium salt, 2,4- drop dimethylamine salt, 2 first, 4 chloroethene thioesters, 2 first, 4 chlorine, 2,
4- drop propionic acid, high 2,4- drop propionate, 2,4- Embutox, Vi par, Vi par salt, Thistrol, 2,4,5-
Tears, 2,4,5- tears propionic acid, 2,4,5- tears butyric acid, 2 first, 4 chloramines salt, dicamba, erbon, Fenac, match pine, trichlorobenzoic acid, ammonia
Dichloro benzoic acid, methoxy trichlorobenzoic acid, diclofop-methyl, fluazifop, efficient fluazifop, haloxyfop-P-methyl, efficient pyrrole fluorine chlorine standing grain
Spirit, quizalofop-ethyl, Quizalotop-ethyl, fenoxaprop-P, fenoxapropPethyl, propaquizafop, cyhalofop-butyl, metamifop, clodinafop-propargyl,
Diclofop-methyl thiazole, chloroazifoppropynyl, the spirit of penta standing grain of hydroxyl, trifluoro dogstail oxime, isoxapyrifop, paraquat, diquat dibromide, oryzalin, second butylene fluorine
Spirit, isopropalin, nitralin, profluralin, prodiamine, benfluralin, fluchloraline, the spirit of amino second fluorine, dipropalin,
Chloroethene dipropalin, Methalpropalin, the third nitre phenol, glyphosate, Sha barnyard grass phosphine, glufosinate-ammonium, solid herbicide phosphorus, amiprophos-methyl, grass
Phosphine sulfide, piperazine grass phosphine, bialaphos, bensulide, butamifos, creeping weed phosphorus, cut down ridge phosphorus, double first amiprophos, dow crabgrass killer, imazapyr,
Imazethapyr, imazaquin, imazamox, imazamox ammonium salt, AC 263222, miaow grass ester, chlorine fluorine pyrrole oxygen second
Acid, the different monooctyl ester of fluroxypyr, clopyralid, picloram, trichlopyr, dithiopyr, halogen grass be fixed, trichlorine
Pyridol, thiazopyr, fluridone, chlorine Fampridine acid, diflufenzopyr, triclopyr butoxyethyl ester, Cliodinate,
Sethoxydim, clethodim, cycloxydim, alloxydimsodium, clefoxidim, butroxydim, tralkoxydim, tepraloxydim, Buthidazole, piperazine
Humulone, hexazinone, metamitron, ethiozin, Ametridione, Amibuzin, Brominal, bromoxynil octanoate, decoyl iodobenzene
Nitrile, ioxynil, dichlobenil, diphenatril, pyraclonil, chloroxynil, Iodobonil, weeding bromine, Flumetsulam, double fluorine
Sulphur grass amine, penoxsuam, metosulam, cloransulammethyl, diclosulam, pyroxsulam, fluorine straw colour, bispyribac-sodium, pyrimidine
Oxime grass ether, pyriftalid, KIH 6127, pyrithiobacsodium, benzobicylon, mesotrione, sulphur humulone, Tembotrione,
Tefuryltrione, Bicyclopyrone, Ketodpiradox, isoxaflutole, isoxachlorotole, Fenoxasulfone,
Methiozolin, fluazolate, pyraflufen-ethyl, pyrazolate, difenzoquat, pyrazoxyfen, benzofenap, pyrrole chlorine grass amine,
Pyrasulfotole, topramezone, Pyroxasulfone, cafenstrole, flupoxam, Amrol, amicarbazone, ethofumesate
Ketone, profluazone, sulfentrazone, Bencarbazone, benzfendizone, butafenacil, bromacil, isoprocil, lenacil,
Terbacil, Flupropacil, cinidon-ethyl, Flumiclorac pentyl, flumioxazin, alkynes grass amine, phthalein benzyl oxide, Flumezin, pentachloro-
Phenol (sodium), dinoseb, dinoterb, dinoterb acetate, dinosam, Chemox PE, chlorine nitre phenol, medinoterb acetate, Di Lete, oxadiargyl, evil
Humulone, pentoxazone, profluazol, fluthiacet, fentrazamide, flufenpyrethyl, pyrazon, brompyrazon, diformazan
Up to careless volt, Kusakira, grass pyridazone, grass rattle away pine, norflurazon, Pyridafol, dichloro quinolinic acid, quinmerac, Bentazon, rattle away
Careless spy, oxaziclomefone, benazolin, clomazone, cinmethylin, iso-propyl-ester nitrofen, propyl-ester nitorfen, indanofan, sodium chlorate, cogongrass
Withered, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoro propionic acid, grass are fast, herbage is fast, bromofenoxim, triazole sulphur, kill azoles, furan
Humulone, benfuresate, ethofumesate, phonetic careless amine, chlorine phthalandione, fluorochloridone, barnyard grass, methacrylaldehyde, bentranil, tridiphane, oat
Ester, thiadiazoles grass amine, phenisopham, hydroxyl humulone, ammonia chloranil, dioxybenzone, benzene flumetsulam, chlorine acyl grass phosphine, chloropon,
Alorac、Diethamquat、Etnipromid、Iprymidam、Ipfencarbazone、Thiencarbazone-methyl、
Pyrimisulfan, Chlorflurazole, Tripropindan, Sulglycapin, first sulphur nitralin,
Cambendichlor, cyclopropyl pyrimidine acid, rodethanii, benoxacor, fenclorim, flurazole, fenchlorazole, solve careless quinoline, oxabetrinil,
Oxalane, cyometrinil, desorpenic, mefenpyrdiethyl, furilazole, fluxofenim, isoxadifen, allyl dichloride amine, fluorine
Chloropyridine ester, DOW848, UBH-509, D489, LS 82-556, KPP-300, NC-324, NC-330, KH-218, DPX-
N8189、SC-0744、DOWCO535、DK-8910、V-53482、PP-600、MBH-001、KIH-9201、ET-751、KIH-
6127 and KIH-2023.And experiments verify that one of this amorphous state polybenzobisoxazole humulone and the above-mentioned herbicide enumerated or a variety of
Compounding application has apparent collaboration and synergistic effect.
Preferably, other described effective components include but is not limited to: 2 first, 4 chlorine sodium, the different monooctyl ester of 2 first, 4 chlorine, 2,4-D butyl ester,
The different monooctyl ester of 2,4-D, 2 first, 4 chlorine dimethylamine salt, fluroxypyr, the different monooctyl ester of fluroxypyr, fluorine chloropyridine ester, dicamba,
Isoproturon, chlortoluron, diflufenican, fluorine pyrrole acyl grass amine, azoles humulone, fluoroglycofen-ethyl, fenoxapropPethyl, clodinafop-propargyl
(acid), tralkoxydim, pinoxaden, halosulfuronmethyl, mesosulfuron, flucarbazone, florasulam, pyroxsulam, piperazine grass
Ketone, prometryn, terbutryn, bentazone, Brominal, bromoxynil octanoate, flufenacet etc..
The gross mass content of effective component is within 75%, within preferably 50% in the composition.
The dosage form of the composition is suspending agent (SC), dispersible oil-suspending agent (OD), missible oil (EC), microemulsion (ME),
Granule (GR), suspoemulsion (SE) or water dispersible granules (WDG).
The amorphous state polybenzobisoxazole humulone or the weeding complex composition in preventing and kill off wheat paddock broadleaf weeds and
Application on the gramineae weed of part.
Amorphous state polybenzobisoxazole humulone of the invention compares A crystal form, and physical and chemical stability is good, stores two under 55 DEG C of high temperature
Crystal transfer does not occur within a month, purity does not also reduce substantially, while solubility doubles in water, and the nothing of polybenzobisoxazole humulone is fixed
Form and complex composition with other effective components, there have to wheat paddock broadleaf weeds and part gramineae weed to be very good
Preventive effect, have a good application prospect.
Detailed description of the invention
Fig. 1 is the XRPD map of the 1 polybenzobisoxazole humulone A crystal form of embodiment in the present invention.
Fig. 2 is the XRPD map of the 2 amorphous state polybenzobisoxazole humulone crystal form of embodiment in the present invention.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
XRPD measuring method
Instrument model: Bruker D8advance, target: Cu K α (40kV, 40mA), sample is to detector distance: 30cm,
Scanning range: 30-450(2 θ value), scanning step diameter: 0.05s.
Embodiment 1
Polybenzobisoxazole humulone raw medicine is prepared referring to 103980202 B method of CN.3000 grams of polybenzobisoxazole humulone raw medicines are placed in again
In the flask of 10L, Ethyl formate 5L is added, is heated to 50 DEG C, stirring is completely dissolved to raw material, is cooled to 0 DEG C, 2 hours are stood,
Filtering, 30 DEG C normal pressure forced air drying 5 hours, obtain the powder of polybenzobisoxazole humulone A crystal form.Or solvent volatilizees, until solvent is waved completely
It distributes complete, the powder of polybenzobisoxazole humulone A crystal form also can be obtained.
Embodiment 2
3000 grams of polybenzobisoxazole humulone A crystal form raw medicines are placed in the flask of 10L, methylene chloride 7L is added, are stirred complete to raw material
Fully dissolved is heated to 30 DEG C, rotates solvent, carries out mechanical lapping after evaporating, amorphous state polybenzobisoxazole humulone can be obtained
Powder；Or methanol 7L is added, in 65 DEG C of decompression rotary evaporation of solvent, after through mechanical lapping；Or tetrahydrofuran 7L is added,
In 40 DEG C of decompression rotary evaporation of solvent, after through mechanical lapping.
Physical and chemical stability experiment
By the polybenzobisoxazole humulone A crystal form that embodiment 1 obtains and two kinds of powder of amorphous state polybenzobisoxazole humulone that embodiment 2 obtains,
Surveying A crystal form and amorphous state content by HPLC is 96.0%, later, by both powder be respectively placed in 25 DEG C, 35 DEG C,
45 DEG C and 55 DEG C of baking ovens the insides place the heat storage experiment of progress in 2 months, later test crystal form type and purity, as a result see the table below 1:
The study on the stability of 1 polybenzobisoxazole humulone different crystal forms of table
As shown in Table 1, polybenzobisoxazole humulone A crystal form and amorphous state have good stability under the conditions of different temperature,
Especially under 55 DEG C of higher temperatures, amorphous state still keeps good physical and chemical stability, and crystal form does not change, purity
Detection is even slightly better than A crystal form, is of great significance.
Solubility test in water
By the polybenzobisoxazole humulone A crystal form that embodiment 1 obtains and two kinds of powder of amorphous state polybenzobisoxazole humulone that embodiment 2 obtains,
It is dissolved into pure water, is shaken at 25 DEG C for 24 hours, be allowed to sufficiently dissolve, be filtered later with filter paper, filtrate is filtered after 0.22 μm
Film, flow phased soln after with HPLC measurement water in solubility, as a result see the table below 2:
By 2 result of table, as it can be seen that the amorphous state of polybenzobisoxazole humulone compares, A crystal form, solubility have apparent increase.
Solubility test result in the water of 2 polybenzobisoxazole humulone different crystal forms of table
| Sample | Solubility (mg/L) in pure water |
| 2 amorphous state polybenzobisoxazole humulone of embodiment | 520 |
| 1 polybenzobisoxazole humulone A crystal form of embodiment | 240 |
Preparation processing and crop field effect experiment
It, will be according to such as by the polybenzobisoxazole humulone A crystal form that embodiment 1 obtains and the amorphous state polybenzobisoxazole humulone that embodiment 2 obtains
Lower formula, is processed into corresponding preparation, and specific formula is as follows:
5% polybenzobisoxazole humulone OD
+ 8% emulsifier phenethyl phenol polyethenoxy ether+4% of+5% emulsifier calcium dodecyl benzene sulfonate of 5% polybenzobisoxazole humulone
The dispersion of+2% thickener fumed silica+20% of+2.5% thickener organobentonite of emulsifier castor oil polyoxyethylene ether
Medium soybean oil+decentralized medium methyl oleate is supplied
8% polybenzobisoxazole humulone SC
+ 0.25% thickener of+2% wetting agent fatty alcohol polyoxyethylene ether of+4% dispersant polycarboxylate of 8% polybenzobisoxazole humulone
+ 0.1% defoaming agent organic silicone oil of+5% antifreezing agent glycerine of+0.5% thickener carboxymethyl cellulose of xanthan gum+water is supplied
40% polybenzobisoxazole humulone, 2 first, 4 chlorine sodium WP
+ 1.5% fatty alcohol polyoxyethylene ether of+6% sodium lignin sulfonate dispersing agent of 5% polybenzobisoxazole humulone, 4 chlorine sodium of+35%2 first+
5% precipitated silica+calcined kaolin is supplied
The different monooctyl ester EW of 27% polybenzobisoxazole humulone, 2 first, 4 chlorine
Different+3% phenethyl phenol polyethenoxy ether phosphoric acid of+15% cyclohexanone of monooctyl ester of 4 chlorine of+24.5%2 first of 2.5% polybenzobisoxazole humulone
+ 0.1% xanthan gum of+3% ethylene glycol of ester triethanolamine salt+3% castor oil polyoxyethylene ether of+2% phenethyl phenol polyethenoxy ether+
Water is supplied.
25% polybenzobisoxazole humulone 2,4-D butyl ester EC
+ 6% castor-oil plant of 2.5%+4% calcium dodecyl benzene sulfonate of polybenzobisoxazole humulone+22.5%2,4-D+10% isopropanol of butyl ester
Oily polyoxyethylene ether+150# aromatic solvent naphtha is supplied.
The 27% different monooctyl ester EC of polybenzobisoxazole humulone 2,4-D
+ 6% nonyl of+4% calcium dodecyl benzene sulfonate of different+15% cyclohexanone of monooctyl ester of 2.5% polybenzobisoxazole humulone+24.5%2,4-D
Base phenol polyethenoxy ether+100# aromatic solvent naphtha is supplied
17% polybenzobisoxazole humulone fluroxypyr ME
+ 8% maleic of+10% ethyl alcohol of 5% polybenzobisoxazole humulone+12% fluroxypyr+10% cyclopentanone of+10% cyclohexanone
+ 3% phenethyl phenol polyethenoxy ether formaldehyde resin condensation product of+8% phenethyl phenol polyethenoxy ether of di-sec-octyl sodium sulfonate+water is mended
Foot.
3% polybenzobisoxazole humulone fluorine chloropyridine ester EW
+ 3% polyoxyethylene nonyl phenyl of+10% cyclohexanone+10%150# solvent naphtha of+0.5% fluorine chloropyridine ester of 2.5% polybenzobisoxazole humulone
+ 3%+3% ethylene glycol of castor oil polyoxyethylene ether of+2% phenethyl phenol polyethenoxy ether of ethylene ether phosphate triethanolamine salt+water
It supplies.
30% polybenzobisoxazole humulone dicamba WP
+ 2.5% fatty alcohol polyoxyethylene ether of+6% calcium lignosulfonate dispersing agent of+25% dicamba of 5% polybenzobisoxazole humulone+
5% precipitated silica+calcined kaolin is supplied
20% polybenzobisoxazole humulone Brominal OD
+ 5% phenethyl phenol polyoxyethylene phosphonate triethanolamine salt of+17.5% Brominal of 2.5% polybenzobisoxazole humulone+
+ 8%+2% organobentonite of castor oil polyoxyethylene ether of 5% polyoxyethylene carboxylate+methyl oleate is supplied.
27% polybenzobisoxazole humulone bromoxynil octanoate EC
+ 4% calcium dodecyl benzene sulfonate of+24.5% bromoxynil octanoate+10%N- methyl pyrrolidone of 2.5% polybenzobisoxazole humulone
+ 5% fatty alcohol polyoxyethylene ether+100# aromatic solvent naphtha is supplied
35% polybenzobisoxazole humulone isoproturon SC
+ 5% phenethyl phenol polyoxyethylene phosphonate triethanolamine salt of+33.5% isoproturon of 1.5% polybenzobisoxazole humulone+
+ 0.2%+5% glycerine of xanthan gum of 2% pull open powder+water is supplied.
50% polybenzobisoxazole humulone terbutryn SC
+ 0.1% xanthan of+2% fatty alcohol polyoxyethylene ether of 2.5% polybenzobisoxazole humulone+5% naphthalene sulfonate of+47.5% terbutryn
+ 5% glycerine of glue+water is supplied.
35% polybenzobisoxazole humulone diflufenican SC
+ 2% rouge of+5% thermally coupled distillation columns triethanolamine salt of+30% diflufenican of 5% polybenzobisoxazole humulone
+ 0.15%+5% glycerine of xanthan gum of fat alcohol polyoxyethylene ether+excess water is supplied.
40% polybenzobisoxazole humulone fluorine pyrrole acyl grass amine SC
+ 2% nonylphenol polyoxyethylene ether of+15%+5% polycarboxylic acid salt's dispersing agent of fluorine pyrrole acyl grass amine of 25% polybenzobisoxazole humulone+
0.2%+5% glycerine of xanthan gum+excess water is supplied.
12% polybenzobisoxazole humulone flufenacet SC
+ 2% nonylphenol polyoxyethylene ether of+5% polycarboxylic acid salt's dispersing agent of+10% flufenacet of 2% polybenzobisoxazole humulone+
0.2%+5% glycerine of xanthan gum+excess water is supplied.
22% polybenzobisoxazole humulone, 2 first, 4 chlorine diformazan ammonium salt SC
+ 2% fatty alcohol polyoxy of 4+5% polycarboxylic acid salt's dispersing agent of chlorine diformazan ammonium salt of+19.5%2 first of 2.5% polybenzobisoxazole humulone
+ 0.3%+5% glycerine of xanthan gum of vinethene+excess water is supplied.
50% polybenzobisoxazole humulone chlortoluron WP
+ 5% precipitation method hard charcoal of+2.5% pull open powder of 1.5% polybenzobisoxazole humulone+10% sodium lignin sulfonate of+48.5% chlortoluron
Black+diatomite is supplied.
33% polybenzobisoxazole humulone prometryn WP
3% polybenzobisoxazole humulone+30% prometryn+8% naphthalene sulfonate+5% precipitation method of+1.5% fatty alcohol polyoxyethylene ether are white
Carbon black+calcined kaolin is supplied.
3% polybenzobisoxazole humulone azoles humulone WDG
+ 1% disintegrating agent polyvinyl alcohol of+5% pull open powder of 2.5% polybenzobisoxazole humulone+10% naphthalenesulfonate of+0.5% azoles humulone+
Filler diatomite is supplied.
14% polybenzobisoxazole humulone metribuzin WDG
+ 1% disintegrating agent polyethylene of+5% polyethylene glycol of 2.5% polybenzobisoxazole humulone+10% polycarboxylic acid salt of+11.5% metribuzin
Alcohol+filler diatomite is supplied.
3% polybenzobisoxazole humulone fluoroglycofen-ethyl EC
+ 5% benzene second of+5% calcium dodecyl benzene sulfonate of 2.5% polybenzobisoxazole humulone+15% cyclohexanone of+0.5% fluoroglycofen-ethyl
Base phenol polyethenoxy ether+100# aromatic solvent naphtha is supplied.
9% polybenzobisoxazole humulone fenoxapropPethyl EW
+ 8% dodecyl of+16% cyclohexanone+20%150# solvent naphtha of+6.5% fenoxapropPethyl of 2.5% polybenzobisoxazole humulone
+ 0.12% xanthan gum of+5% phenethyl phenol polyethenoxy ether formaldehyde resin condensation product of+8% nonylphenol polyoxyethylene ether of this sulfoacid calcium
+ water is supplied.
14% polybenzobisoxazole humulone clodinafop-propargyl EW
+ 4% basic sulfoacid calcium of dodecane of+20% cyclohexanone+20%150# solvent naphtha of+10% clodinafop-propargyl of 4% polybenzobisoxazole humulone+
+ 5%+0.15% xanthan gum of phenethyl phenol polyethenoxy ether formaldehyde resin condensation product of 8% castor oil polyoxyethylene ether+water is supplied.
17% polybenzobisoxazole humulone pinoxaden EW
+ 4% Nonyl pheno of+20% cyclohexanone+15%150# solvent naphtha of+12% pinoxaden of 5% polybenzobisoxazole humulone
+ 5% phenethyl phenol polyethenoxy ether formaldehyde resin condensation product of+3% fatty alcohol polyoxyethylene ether of ether phosphate triethanolamine salt+water
It supplies.
65% polybenzobisoxazole humulone tralkoxydim WDG
+ 1% disintegrating agent polyethylene of+5% pull open powder of 5% polybenzobisoxazole humulone+15% polycarboxylic acid salt's dispersing agent of+60% tralkoxydim
Alcohol+filler bentonite is supplied.
39% polybenzobisoxazole humulone halosulfuronmethyl WDG
The poly- second of+2.5% pull open powder of+20% polycarboxylic acid salt's dispersing agent of+24% halosulfuronmethyl of 15% polybenzobisoxazole humulone+5%
+ 1% disintegrating agent polyvinyl alcohol of glycol+filler diatomite is supplied.
7% polybenzobisoxazole humulone mesosulfuron OD
+ 5% Sorbitan alcohol ester of+5% maleic di-sec-octyl sodium sulfonate of+1.8% mesosulfuron of 5.2% polybenzobisoxazole humulone
+ 20% soya-bean oil of+3% fume colloidal silica of fat acid+3% organobentonite of+6% castor oil polyoxyethylene ether of polyoxyethylene ester+oil
Sour methyl esters is supplied.
11% polybenzobisoxazole humulone flucarbazone OD
+ 5% fatty alcohol of+5% aliphatic alcohol polyoxyvinethene phosphate triethanolamine salt of+6% flucarbazone of 5% polybenzobisoxazole humulone
+ 3%+20% soya-bean oil of organobentonite of+4% castor oil polyoxyethylene ether of polyoxyethylene ether+methyl oleate is supplied.
6% polybenzobisoxazole humulone florasulam OD
+ 5% maleic di-sec-octyl sodium sulfonate of+1% florasulam of 5% polybenzobisoxazole humulone+5% sorbitan fatty acid
+ 2.6%+25% soya-bean oil of organobentonite of+4% nonylphenol polyoxyethylene ether of polyoxyethylene ester+methyl oleate is supplied.
7% polybenzobisoxazole humulone pyroxsulam OD
+ 5% dehydration mountain of+5% aliphatic alcohol polyoxyvinethene phosphate triethanolamine salt of+2% pyroxsulam of 5% polybenzobisoxazole humulone
+ 3%+25% soya-bean oil of organobentonite of+6% nonylphenol polyoxyethylene ether of pears polyol fatty acid polyoxyethylene ester+methyl oleate is supplied.
38% polybenzobisoxazole humulone bentazone OD
+ 5% Nonyl pheno of+5% maleic di-sec-octyl sodium sulfonate of+36.5% bentazone of 1.5% polybenzobisoxazole humulone
+ 8%+0.5% organobentonite of castor oil polyoxyethylene ether of ether+methyl oleate is supplied.
Biological activity test is measured using indoor pot method: barnyard grass (Shandong Province Huangdao District proving ground wheat paddock) 3-4 leaf
Phase, ox chickweed (Xiuqian City of Jiangsu Province Siyang County acquires seed) 3-5 leaf phase, 3WP-2000 type walking spray tower (Ministry of Agriculture south
Capital agricultural machinery research institute), cauline leaf even spraying, every processing is repeated 4 times, and investigates average strain preventive effect (range estimation) effect within 30 days after application
Fruit is as follows, is shown in Table 3.
The polybenzobisoxazole humulone preparation eliminating weed in wheat field effect (%) of 3 different crystal forms of table --- preventive effect after application 45d
Note: shepherd's purse, ox chickweed have certain drug resistance, 7.5g/hm to florasulam in this test2Florasulam pair
Shepherd's purse, ox chickweed preventive effect < 10%.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (14)
1. a kind of amorphous state polybenzobisoxazole humulone, which is characterized in that its X-ray powder diffraction pattern is shown basically as in Figure 2.
2. the preparation method of amorphous state polybenzobisoxazole humulone as described in claim 1, which comprises the following steps:
(1) in methylene chloride by polybenzobisoxazole humulone stirring and dissolving, in 25-35 DEG C of decompression rotary evaporation of solvent, after through mechanical grinding
Mill, obtains amorphous state；
Or (2) by polybenzobisoxazole humulone stirring and dissolving in methyl alcohol, in 60-70 DEG C of decompression rotary evaporation of solvent, after through mechanical grinding
Mill, obtains amorphous state；
Or (3) by polybenzobisoxazole humulone stirring and dissolving in tetrahydrofuran, in 35-45 DEG C of decompression rotary evaporation of solvent, after through machine
Tool grinding, obtains amorphous state.
3. the preparation method of amorphous state polybenzobisoxazole humulone according to claim 2, which is characterized in that step (1) medium temperature
Degree is 30 DEG C.
4. the preparation method of amorphous state polybenzobisoxazole humulone according to claim 2, which is characterized in that step (2) medium temperature
Degree is 65 DEG C.
5. the preparation method of amorphous state polybenzobisoxazole humulone according to claim 2, which is characterized in that step (3) medium temperature
Degree is 40 DEG C.
6. a kind of amorphous state polybenzobisoxazole humulone being prepared using claim 2-5 any one the method.
7. a kind of weeding complex composition, it is characterised in that: including amorphous state polybenzobisoxazole humulone as described in claim 1 or 6
Effective component and auxiliary agent.
8. weeding complex composition according to claim 7, it is characterised in that: the auxiliary agent is selected from solvent, solid dilutes
One of agent, emulsifier, wetting agent, dispersing agent, antifreezing agent, defoaming agent and thickener are a variety of.
9. weeding complex composition according to claim 7 or 8, which is characterized in that the composition further includes that other have
Imitate ingredient.
10. weeding complex composition according to claim 9, which is characterized in that other described effective components are selected from 2 first 4
Chlorine sodium, the different monooctyl ester of 2 first, 4 chlorine, 2,4-D butyl ester, the different monooctyl ester of 2,4-D, 2 first, 4 chlorine dimethylamine salt, fluroxypyr, chlorine fluorine pyrrole oxygen
2-ethyl hexyl ethanoate, fluorine chloropyridine ester, dicamba, isoproturon, chlortoluron, diflufenican, fluorine pyrrole acyl grass amine, azoles humulone, second carboxylic
Fluofazone, fenoxapropPethyl, clodinafop-propargyl (acid), tralkoxydim, pinoxaden, halosulfuronmethyl, mesosulfuron, fluorine azoles sulphur
Grand, florasulam, pyroxsulam, metribuzin, prometryn, terbutryn, bentazone, Brominal, bromoxynil octanoate and fluorine thiophene grass
One of amine is a variety of.
11. weeding complex composition according to claim 9, which is characterized in that effective component is total in the composition
Mass content is within 75%.
12. weeding complex composition according to claim 11, which is characterized in that effective component is total in the composition
Mass content is within 50%.
13. weeding complex composition according to claim 7, it is characterised in that: the dosage form of the composition be suspending agent,
Dispersible oil-suspending agent, missible oil, microemulsion, granule, suspoemulsion or water dispersible granules.
14. weeding described in amorphous state polybenzobisoxazole humulone as described in claim 1 or 6 or claim 7-13 any one is multiple
Application with composition in preventing and kill off wheat paddock on broadleaf weeds and part gramineae weed.
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| PCT/CN2017/084909 WO2018201524A1 (en) | 2017-05-02 | 2017-05-18 | Amorphous biscarfentrazone and preparation method and use thereof |
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| CN107646848A (en) * | 2017-11-09 | 2018-02-02 | 青岛清原化合物有限公司 | A kind of Herbicidal combinations of humulone containing polybenzobisoxazole and its application |
| CN109329286B (en) * | 2018-07-14 | 2019-11-08 | 青岛清原化合物有限公司 | Binary Herbicidal combinations and its application comprising HPPD inhibitor class herbicide |
| CN111362913B (en) * | 2018-12-25 | 2021-03-12 | 青岛清原化合物有限公司 | Amorphous-state bicyclopyrone triethanolamine salt and preparation method and application thereof |
| CN109601548A (en) * | 2019-01-25 | 2019-04-12 | 河北省农林科学院粮油作物研究所 | A kind of prevention and treatment wheat paddock broadleaf weeds and gramineous weed weedicide composition |
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