CN107286095B - Polybenzobisoxazole humulone form D and its preparation method and application - Google Patents
Polybenzobisoxazole humulone form D and its preparation method and application Download PDFInfo
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- CN107286095B CN107286095B CN201710567914.XA CN201710567914A CN107286095B CN 107286095 B CN107286095 B CN 107286095B CN 201710567914 A CN201710567914 A CN 201710567914A CN 107286095 B CN107286095 B CN 107286095B
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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 polybenzobisoxazole humulone form D and its preparation method and application.The X-ray powder diffraction spectrogram of the polybenzobisoxazole humulone form D is to have characteristic peak at 7.421,7.738,10.82,13.701,15.54,18.941,19.641,21.299,22.019,23.041,23.44,23.96,24.621,26.6,30.38,34.399,38.319 degree in 2 θ of the angle of diffraction, wherein 2 θ error ranges are in ± 0.2 °.Polybenzobisoxazole humulone form D stability of the invention is good, and form D or the complex composition with other effective components, has preferable preventive effect to wheat paddock broadleaf weeds and part gramineae weed, effect is substantially better than A crystal form.
Description
Technical field
The invention belongs to herbicide crystallization processes technical fields, and in particular to a kind of polybenzobisoxazole humulone form D and its preparation side
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。
Polymorphism refers to solid matter with two or more different spaces arrangement mode, and formation has not
With physicochemical properties solid state the phenomenon that.In drug research field, polymorphic includes organic solvate, hydrate
Equal multicomponents crystal form.Drug polymorphism is widely present in drug discovery process, is that organic micromolecule compound is intrinsic
Characteristic.Theoretically small-molecule drug can have infinite number of crystal accumulation mode-polymorphic.Polymorphism not only by point
The space structure and functional group performance of son itself, the control of the internal factors such as intramolecular and intermolecular interaction, it is also
By medicine synthesising process design, crystallization and purification condition, pharmaceutical adjunct selection, preparation process route and method of granulating and storage
Deposit the influence of the aspects factor such as condition, packaging material.Different crystal forms have different colors, fusing point, dissolution, dissolving out capability,
Chemical stability, reactivity, mechanical stability etc., these physical and chemical performances or processability directly influence drug sometimes
Safely, effectively performance.Therefore crystal form research and control become the important research content in drug development process.
Since polybenzobisoxazole humulone is newly developed drug, without the report of its crystal form in current various documents and patent.
It has been investigated that the polybenzobisoxazole humulone raw medicine that synthesis obtains is with the presence of A crystal form.
Summary of the invention
The present invention provides a kind of new herbicides polybenzobisoxazole humulone form D and its preparation method and application, polybenzobisoxazole humulone D is brilliant
Type stability is good, good to control of weeds effect, 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, on the basis of A crystal form, and has studied form D.
A kind of polybenzobisoxazole humulone form D, X-ray powder diffraction spectrogram 2 θ of the angle of diffraction be 7.421,7.738,10.82,
13.701、15.54、18.941、19.641、21.299、22.019、23.041、23.44、23.96、24.621、26.6、
30.38, there is characteristic peak, wherein 2 θ error ranges are in ± 0.2 ° at 34.399,38.319 degree.Corresponding I/I0Value is respectively
17、27.2、58.9、8.3、20.2、20、11.6、100、12.6、14.6、34.3、14.9、12.3、12.8、7.4、6.6、4.5。
Preferably, X-ray powder diffraction pattern is shown basically as in Figure 2.
The preparation method of the polybenzobisoxazole humulone form D, comprising the following steps: polybenzobisoxazole humulone is dissolved in acetone or tetrahydro furan
It in muttering, is heated to after being completely dissolved, evaporates into solvent naturally and volatilize completely and finish, obtained crystal is form D.
Alternatively, polybenzobisoxazole humulone is dissolved in n-octyl alcohol, 55 DEG C are heated to, later, is cooled in 0-5 DEG C and stands still for crystals,
Filtering, the crystal obtained after dry are form D.
A kind of weeding complex composition, including the polybenzobisoxazole humulone form D and auxiliary agent.
Preferably, the auxiliary agent is selected from solvent, solid diluent, emulsifier, wetting agent, dispersing agent, antifreezing agent, defoaming agent
With one of thickener or 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 polybenzobisoxazole humulone form D of the invention is, such as " world pesticide new varieties
Technology is complete works of ", Scientia Agricultura Sinica technology publishing house, 2010.9 and document incorporated herein in known substance.Such as it is following
Mention various substances (remarks: the title of compound, perhaps for according to the common name of International Organization for standardization (ISO) or
For chemical name, there is code name when appropriate): Acetochlor, butachlor, alachlor, propisochlor, isopropyl methoxalamine, smart isopropyl
The left-handed naphthalene propionyl grass amine of alachlor, pretilachlor, propachlor, kecaoan, naphthalene propionyl grass amine, R-, propanil, mefenacet, double benzene
Acyl grass amine, diflufenican, N-alpha-chloroacetyl-N-isopropyl-o ethylaniline, beflubutamid, bromobutide, dimethenamid, dimethenamidP, ethoxy
Benzene grass amine, flufenacet, thenylchlor, metazachlor, isoxaben, flampropMmethyl, flampropMisopropyl, dipropyl
Pethoxamid, pethoxamid, chloranocryl, ring pretilachlor, mefluidide, monalide, delachlor, prynachlor, special fourth grass
Amine, xylachlor, dimethachlor, amine of taking to the greenwood, front three ring grass amine, clomeprop, propyzamide, valeryl benzene grass amine, card
Careless amine, suffer, tricyclic match careless amine, butenachlor, tebutam, benzyl grass amine, quinone duckweed amine, dichlofluanid, naproanilide, acetyl first grass
Amine, quinclorac, fenacet, pyrrole cyanogen grass amine, more grams of benzene grass be dead, chlorothiamid, chlorine phthalimide, fourth amidine amine, fluorine metazachlor, atrazine,
Simanex, prometryn, cyanatryn, symetryne, ametryn, propazine, dipropetryn, flur, terbutryn, Garagard, triazine fluorine
Careless amine, 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, three
Paracyanogen acid, Indaziflam, green sulphur is grand, metsulfuron-methyl, bensulfuron-methyl, chlorimuron, tribenuron-methyl, thifensulfuron methyl, pyrazosulfuron, methyl
Two sulphurs are grand, iodosulfuron-methyl-sodium, formamido group Sulfometuron Methyl, cinosulfuron, triasulfuron, sulfometuronmethyl, nicosulfuron, amine benzene sulphur
Grand, amidosulfuron, ethoxysulfuron, cypromisulfuron, rimsulfuron, azimsulfuron, pyridine ethyl methyl, monosulfmeturon, list are phonetic
Sulphur ester, flucarbazone, flupyrsulfuron-methyl-sodium, fluorine pyrazosulfuron, oxasulfuron, imazosulfuron, primisulfuronmethyl, procarbazone,
Prosulfuron, Sulfosulfuron, trifloxysulfuron, triflusulfuronmethyl, tritosulfuron, metsulfuron-methyl sodium salt, flucetosulfuron, first sulphur are phonetic
Sulphur is grand, orthosulfamuron, Propyrisulfuron (proxazuron-methyl), piperazine pyrazosulfuron, acifluorfen, fomesafen,
Lactofen, fluoroglycofen-ethyl, Oxyfluorfen, Mo 9 granular, aclonifen, ethoxyfen-ethyl, bifenox, fluoroform
Careless ether, chlomethoxyfen, fluorodifen, fluorination nitrofen, fluorine furan grass ether, nitrofen, first grass ether, diformazan grass ether, fluorine lactazone
Careless ether, fluofazone ester, Halosafen, chlortoluron, isoproturon, linuron, diuron, Sha flutter grand, fluometuron, benzthiazuron, methyl
Benzthiazuron, cumyluron, ethidimuron, isouron, terbufos benzthiazuron, buturon, bromax, methyldymron, phenobenzuron, methoxy kill
The grand, metobromuron of grass, metoxuron, afesin, telvar, Tupersan, fenuron, fluorine sulphur is grand, neburea, chloroxifenidium, herban, different
Herban, Alipur-O, thiazfluron, tebuthiuron, difenoxuron, to fluon, methylamine methabenz thiazuron, Long Caote, front three isourea, dimefuron,
Monisouron, Anisuron, Methiuron, Chloreturon, four fluon, phenmedipham, phenmedipham-ethyl ester, desmedipham, sulphur
Careless spirit, terbucarb, oatax, Chem hoe, chlorpropham, benzyl dichloride grass ester, swep, chlorbufam, CarDoxazole,
ChlorprocarD, Fenasulam, DCPC, CPPC, CarDasulam, Ding Caote, benthiocarb, vernolate, molinate, wild wheat
It is fear, dimepiperate, esprocarb, pyributicarb, cycloate, Avadex, bactericide, the careless spy of second sulphur, orbencarb, pebulate, prosulfocarb, secondary
Careless pellet, sulfuric acid, dimexan, Isopolinate, MethioDencarD, 2,4- d butyl ester, 2 first, 4 chlorine sodium, 2,4- drop are different pungent
It is ester, 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 by 2,
4- drop propionate, 2,4- Embutox, Vi par, Vi par salt, Thistrol, 2,4,5- tears, 2,4,5- tears third
Acid, 2,4,5- tears butyric acid, 2 first, 4 chloramines salt, dicamba, erbon, Fenac, match pine, trichlorobenzoic acid, chloramben, methoxy
Trichlorobenzoic acid, diclofop-methyl, fluazifop, efficient fluazifop, haloxyfop-P-methyl, efficient haloxyfop, quizalofop-ethyl, smart quinoline
Standing grain spirit, fenoxaprop-P, fenoxapropPethyl, propaquizafop, cyhalofop-butyl, metamifop, clodinafop-propargyl, diclofop-methyl thiazole, alkynes
Standing grain spirit, the spirit of penta standing grain of hydroxyl, trifluoro dogstail oxime, isoxapyrifop, paraquat, diquat dibromide, oryzalin, ethalfluralin, isopropalin, first
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, sulphosate, piperazine grass phosphine,
Bialaphos, butamifos, creeping weed phosphorus, cut down ridge phosphorus, double first amiprophos, dow crabgrass killer, imazapyr, imazethapyr, miaow at bensulide
Azoles quinolinic acid, imazamox, imazamox ammonium salt, AC 263222, miaow grass ester, fluroxypyr, chlorine fluorine pyrrole oxygen second
The different monooctyl ester of acid, clopyralid, picloram, trichlopyr, dithiopyr, halogen grass are fixed, phenolate trichloropyridine, thiophene are careless
Pyridine, fluridone, chlorine Fampridine acid, diflufenzopyr, triclopyr butoxyethyl ester, Cliodinate, sethoxydim, alkene grass
Ketone, cycloxydim, alloxydimsodium, clefoxidim, butroxydim, tralkoxydim, tepraloxydim, Duthidazole, metribuzin, hexazinone,
Metamitron, ethiozin, Ametridione, AmiDuzin, Brominal, bromoxynil octanoate, ioxynil octanoate, ioxynil, enemy
Oxalic acid dinitrile, diphenatril, pyraclonil, chloroxynil, IodoDonil, weeding bromine, Flumetsulam, florasulam, five fluorine sulphurs
Careless amine, metosulam, cloransulammethyl, diclosulam, pyroxsulam, fluorine straw colour, bispyribac-sodium, pyribenzoxim, cyclic ester grass
Ether, KIH 6127, pyrithiobacsodium, benzobicylon, mesotrione, sulphur humulone, TemDotrione, Tefuryltrione,
It is Dicyclopyrone, Ketodpiradox, isoxaflutole, isoxachlorotole, Fenoxasulfone, Methiozolin, different
Third pyrrole grass ester, pyraflufen-ethyl, pyrazolate, difenzoquat, pyrazoxyfen, benzofenap, pyrrole chlorine grass amine, Pyrasulfotole, topramezone,
Pyroxasulfone, cafenstrole, flupoxam, Amrol, amicarbazone, azafenidin, profluazone, sulfentrazone,
DencarDazone, benzfendizone, butafenacil, bromacil, isoprocil, lenacil, terbacil, Flupropacil, Yin
Diindyl ketone grass ester, Flumiclorac pentyl, flumioxazin, alkynes grass amine, phthalein benzyl oxide, Flumezin, pentachlorophenol (sodium), dinoseb, dinoterb,
Dinoterb acetate, dinosam, Chemox PE, chlorine nitre phenol, medinoterb acetate, Di Lete, oxadiargyl, oxadiazon, pentoxazone, fluorine azoles grass
Amine, fluthiacet, fentrazamide, flufenpyrethyl, pyrazon, brompyrazon, diformazan reach careless volt, Kusakira, careless pyridazone, grass
It rattles away pine, norflurazon, Pyridafol, dichloro quinolinic acid, quinmerac, Bentazon, pyridate, oxaziclomefone, benazolin, different
Oxadiazon, cinmethylin, iso-propyl-ester nitrofen, propyl-ester nitorfen, indanofan, sodium chlorate, Dalapon, trichloroacetic acid, monochloroacetic acid, six
Chlroacetone, tetrafluoro propionic acid, grass are fast, herbage is fast, bromofenoxim, triazole sulphur, kill azoles, is flurtamone, benfuresate, ethofumesate, phonetic
Careless amine, chlorine phthalandione, fluorochloridone, barnyard grass, methacrylaldehyde, bentranil, tridiphane, Bidisin, thiadiazoles grass amine, phenisopham, hydroxyl
Humulone, ammonia chloranil, dioxybenzone, benzene flumetsulam, chlorine acyl grass phosphine, chloropon, Alorac, Diethamquat,
Etnipromid、Iprymidam、IpfencarDazone、ThiencarDazone-methyl、Pyrimisulfan、
Chlorflurazole, Tripropindan, Sulglycapin, first sulphur nitralin, CamDendichlor, cyclopropyl pyrimidine acid,
Rodethanii, fenclorim, flurazole, fenchlorazole, solves careless quinoline, oxabetrinil, oxalane, cyometrinil, desorpenic, pyrrole at benoxacor
Azoles cloquitocet_mexyl, furilazole, fluxofenim, isoxadifen, allyl dichloride amine, fluorine chloropyridine ester, DOW848, UDH-509,
D489, LS 82-556, KPP-300, NC-324, NC-330, KH-218, DPX-N8189, SC-0744, DOWCO535, DK-
8910, V-53482, PP-600, MDH-001, KIH-9201, ET-751, KIH-6127 and KIH-2023.And experiments verify that originally
One of polybenzobisoxazole humulone form D and above-mentioned herbicide enumerated or the application of a variety of compoundings, which have, significantly cooperate with and synergy work
With.
Preferably, other 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 aqueous suspension agent (SC), oil-suspending agent (OD), missible oil (EC), microemulsion can be dispersed
(ME), granule (GR), suspoemulsion (SE) or water dispersible granules (WDG).
The polybenzobisoxazole humulone form D or the weeding complex composition are in controlling broad leaved weed in wheat field and part standing grain
Application on undergraduate course weeds.
Polybenzobisoxazole humulone form D stability of the invention is good, and form D or the complex composition with other effective components, right
Wheat paddock broadleaf weeds and part gramineae weed have preferable preventive effect, and effect is substantially better than A crystal form.
Detailed description of the invention
Fig. 1 is the XRPD map of 1 polybenzobisoxazole humulone A crystal form of embodiment in the present invention.
Fig. 2 is the XRPD map of embodiment 2-3 polybenzobisoxazole humulone form D 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: Druker D8advance, target: Cu K α (40kV, 40mA), sample is to detector distance: 30cm,
Scanning range: 3 ° -45 ° (2 θ value), scanning step diameter: 0.05s.
Embodiment 1
Polybenzobisoxazole humulone raw medicine is prepared referring to 103980202 B method of CN, is A crystal form.
Embodiment 2
3000 grams of polybenzobisoxazole humulone A crystal form raw medicines are placed in the flask of 10L, acetone is added or tetrahydrofuran 6L, heating are stirred
It mixes to raw material and is completely dissolved, volatilize naturally in 25 DEG C later, finished until acetone volatilizees completely, obtain polybenzobisoxazole humulone form D powder
End.
Embodiment 3
3000 grams of polybenzobisoxazole humulone A crystal form raw medicines are placed in the flask of 10L, n-octyl alcohol 6L is added, is heated to 55 DEG C, it
Afterwards, it is cooled in 0-5 DEG C and stands still for crystals, filter, the crystal obtained after dry is form D.
Physical and chemical stability experiment
By the polybenzobisoxazole humulone A crystal form that embodiment 1 obtains and the polybenzobisoxazole humulone form D powder that embodiment 2-3 is obtained, pass through
HPLC surveys A crystal form and form D content is 96.0% or so, later, the raw medicine of both crystal forms is respectively placed in 25 DEG C, 40
DEG C, inside 55 DEG C and 70 DEG C of baking ovens, place the heat storage experiment of progresss in 2 months, test crystal form type and purity, as a result see the table below later
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 form D have good stability under the conditions of different temperature, especially
Under 70 DEG C of higher temperatures, crystal form still keeps good physical and chemical stability, and crystal form does not change, and purity detecting is even
Slightly it is better than A crystal form, has a good application prospect.
Preparation processing and indoor biometrics experiment
By the polybenzobisoxazole humulone A crystal form that embodiment 1 obtains and the polybenzobisoxazole humulone form D that embodiment 2-3 is obtained, according to matching as follows
Side, is processed into preparation, 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
+ 5% fatty alcohol polyoxyethylene ether+5% of+6% polycarboxylic acid salt's dispersing agent of 5% polybenzobisoxazole humulone, 4 chlorine sodium of+35%2 first
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+5% cyclohexanone of monooctyl ester of 4 chlorine of+24.5%2 first of 2.5% polybenzobisoxazole humulone
+ 3%+3% ethylene glycol of castor oil polyoxyethylene ether of+2% phenethyl phenol polyethenoxy ether of ester triethanolamine salt+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+5% cyclohexanone of monooctyl ester of 2.5% polybenzobisoxazole humulone+24.5%2,4-D
Phenol polyethenoxy ether+100# aromatic solvent naphtha is supplied
17% polybenzobisoxazole humulone fluroxypyr ME
+ 8% maleic di-sec-octyl sulphur of+10% ethyl alcohol of 5% polybenzobisoxazole humulone+10% cyclohexanone of+12% fluroxypyr
Sour+3% phenethyl phenol polyethenoxy ether formaldehyde resin condensation product of+8% phenethyl phenol polyethenoxy ether of sodium+water is supplied.
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
+ 5% fatty alcohol polyoxyethylene ether+5% of+6% polycarboxylic acid salt's dispersing agent of+25% dicamba of 5% polybenzobisoxazole humulone is heavy
Shallow lake method white carbon black+calcined kaolin is supplied
20% polybenzobisoxazole humulone Brominal EC
+ 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+5%N- methyl pyrrolidone of 2.5% polybenzobisoxazole humulone+
5% fatty alcohol polyoxyethylene ether+100# aromatic solvent naphtha is supplied
35% polybenzobisoxazole humulone isoproturon SC
+ 0.2% xanthan gum+5% of+2% pull open powder of 1.5% polybenzobisoxazole humulone+5% sodium lignin sulfonate of+33.5% isoproturon
Glycerine+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+10%+5% polycarboxylic acid salt's dispersing agent of fluorine pyrrole acyl grass amine 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% precipitated silica of+5% pull open powder of 1.5% polybenzobisoxazole humulone+10% sodium lignin sulfonate of+48.5% chlortoluron
+ diatomite is supplied.
33% polybenzobisoxazole humulone prometryn WP
+ 5% precipitation method hard charcoal of+5% fatty alcohol polyoxyethylene ether of 3% polybenzobisoxazole humulone+8% naphthalene sulfonate of+30% prometryn
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% phenethyl of+5% calcium dodecyl benzene sulfonate of 2.5% polybenzobisoxazole humulone+5% cyclohexanone of+0.5% fluoroglycofen-ethyl
Phenol polyethenoxy ether+100# aromatic solvent naphtha is supplied.
9% polybenzobisoxazole humulone fenoxapropPethyl EW
+ 10% ethyl alcohol+8% of+6% cyclohexanone+6%150# solvent naphtha of+6.5% fenoxapropPethyl of 2.5% polybenzobisoxazole humulone
Basic+5% phenethyl phenol polyethenoxy ether formaldehyde resin condensation product of+8% nonylphenol polyoxyethylene ether of sulfoacid calcium of dodecane+water is mended
Foot.
14% polybenzobisoxazole humulone clodinafop-propargyl EW
+ 8% basic sulfoacid calcium of dodecane of+10% butyl glycol ether of 4% polybenzobisoxazole humulone+10% cyclohexanone of+10% clodinafop-propargyl+
+ 5% phenethyl phenol polyethenoxy ether formaldehyde resin condensation product of 8% castor oil polyoxyethylene ether+water is supplied.
17% polybenzobisoxazole humulone pinoxaden EW
+ 10% butyl glycol ether+8% of+10% cyclohexanone+5%150# solvent naphtha of+12% pinoxaden of 5% polybenzobisoxazole humulone
Basic+5% phenethyl phenol polyethenoxy ether formaldehyde resin condensation product of+8% fatty alcohol polyoxyethylene ether of sulfoacid calcium of dodecane+water is mended
Foot.
65% polybenzobisoxazole humulone tralkoxydim WDG
+ 1% disintegrating agent polyvinyl alcohol of+5% pull open powder of 5% polybenzobisoxazole humulone+15% polycarboxylic acid salt of+60% tralkoxydim+fill out
Material bentonite is supplied.
39% polybenzobisoxazole humulone halosulfuronmethyl WDG
+ 1% poly- second of disintegrating agent of+5% polyethylene glycol of 15% polybenzobisoxazole humulone+20% polycarboxylic acid salt of+24% halosulfuronmethyl
Enol+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.
Indoor pot method measurement: barnyard grass (Shandong Province, proving ground, Huangdao District corn field) 3-4 leaf phase, ox chickweed (Jiangsu Province
Xiuqian City Siyang County acquires seed) the 3-5 leaf phase, 3WP-2000 type walking spray tower (Ministry of Agriculture's Nanjing agriculture mechanical investigations
Institute), cauline leaf even spraying, every processing is repeated 4 times, and average strain preventive effect (range estimation) effect of investigation in 30 days is as follows after application, is shown in Table 2.
The polybenzobisoxazole humulone preparation preventing weeding weeds effect (%) of 2 different crystal forms of table --- preventive effect after application 30d
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 (13)
1. a kind of polybenzobisoxazole humulone form D, it is characterised in that: X-ray powder diffraction spectrogram 2 θ of the angle of diffraction be 7.421,7.738,
10.82、13.701、15.54、18.941、19.641、21.299、22.019、23.041、23.44、23.96、24.621、
26.6, there is characteristic peak, wherein 2 θ error ranges are in ± 0.2 ° at 30.38,34.399,38.319 degree.
2. a kind of polybenzobisoxazole humulone form D according to claim 1, it is characterised in that: corresponding I/I0Value respectively 17,
27.2、58.9、8.3、20.2、20、11.6、100、12.6、14.6、34.3、14.9、12.3、12.8、7.4、6.6、4.5。
3. a kind of polybenzobisoxazole humulone form D according to claim 1 or 2, it is characterised in that: X-ray powder diffraction pattern base
It is as shown in Figure 2 in sheet.
4. the preparation method of polybenzobisoxazole humulone form D as described in claim 1-3 any one, it is characterised in that: including following step
It is rapid: polybenzobisoxazole humulone being dissolved in acetone or tetrahydrofuran, is heated to after being completely dissolved, solvent is evaporated into naturally and volatilizees completely
It finishes, obtained crystal is form D.
5. the preparation method of polybenzobisoxazole humulone form D as described in claim 1-3 any one, it is characterised in that: including following step
It is rapid: polybenzobisoxazole humulone being dissolved in n-octyl alcohol, is heated to 55 DEG C, later, is cooled in 0-5 DEG C and stands still for crystals, is filtered, after dry
Obtained crystal is form D.
6. a kind of weeding complex composition, it is characterised in that: including polybenzobisoxazole humulone form D described in claim 1-3 any one
And auxiliary agent.
7. a kind of weeding complex composition according to claim 6, it is characterised in that: the auxiliary agent is selected from solvent, solid
One of diluent, emulsifier, wetting agent, dispersing agent, antifreezing agent, defoaming agent and thickener are a variety of.
8. a kind of weeding complex composition according to claim 6, it is characterised in that: the composition further includes that other have
Imitate ingredient.
9. a kind of weeding complex composition according to claim 8, it is characterised in that: other described effective components are selected from 2
4 chlorine sodium of first, 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
The different monooctyl ester of fluoroacetic acid, fluorine chloropyridine ester, dicamba, isoproturon, chlortoluron, diflufenican, fluorine pyrrole acyl grass amine, azoles humulone, second
Fluoroglycofen, fenoxapropPethyl, clodinafop-propargyl, alkynes oxalic acid, tralkoxydim, pinoxaden, halosulfuronmethyl, mesosulfuron, fluorine
Azoles sulphur is grand, florasulam, pyroxsulam, metribuzin, prometryn, terbutryn, bentazone, Brominal, bromoxynil octanoate and fluorine
One of fenacet is a variety of.
10. weeding complex composition according to claim 8, it is characterised in that: effective component is total in the composition
Mass content is within 75%.
11. weeding complex composition according to claim 10, it is characterised in that: effective component is total in the composition
Mass content is within 50%.
12. according to weeding complex composition described in claim 6-11 any one, it is characterised in that: the agent of the composition
Type is aqueous suspension agent, dispersible oil-suspending agent, missible oil, microemulsion, granule, suspoemulsion or water dispersible granules.
13. being removed described in polybenzobisoxazole humulone form D as claimed in any one of claims 1-3 or claim 6-12 any one
Application of the careless complex composition in preventing and kill off wheat paddock on broadleaf weeds and part gramineae weed.
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| CN201710567914.XA CN107286095B (en) | 2017-07-13 | 2017-07-13 | Polybenzobisoxazole humulone form D and its preparation method and application |
| PCT/CN2017/093066 WO2019010716A1 (en) | 2017-07-13 | 2017-07-15 | Dicarfentrazone-ethyl crystalline form d, and preparation method therefor and use thereof |
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| CN113016811A (en) * | 2017-11-09 | 2021-06-25 | 青岛清原化合物有限公司 | Weeding composition containing topramezone and application thereof |
| CN111362906B (en) * | 2018-12-25 | 2021-03-05 | 青岛清原化合物有限公司 | Cyclopyraflutole-isopropylamine salt C crystal form and preparation method and application thereof |
| CN111362919B (en) * | 2018-12-25 | 2021-03-12 | 青岛清原化合物有限公司 | Cyclopyraflutole dimethylamine salt D crystal form 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980202A (en) * | 2014-05-27 | 2014-08-13 | 青岛清原化合物有限公司 | 4-benzoyl pyrazole compound with herbicidal activity |
| CN105230629A (en) * | 2015-11-17 | 2016-01-13 | 青岛清原抗性杂草防治有限公司 | Synergic weeding composition |
| CN105685049A (en) * | 2016-03-15 | 2016-06-22 | 青岛清原化合物有限公司 | Sorghum field weeding composition and application thereof |
| CN106070309A (en) * | 2016-06-21 | 2016-11-09 | 青岛清原抗性杂草防治有限公司 | Complex herbicidal composition containing polybenzobisoxazole oxadiazon and using method thereof |
| CN106305754A (en) * | 2016-10-13 | 2017-01-11 | 广东中迅农科股份有限公司 | Weeding composition containing dicarfentrazone, quinclorac and halosulfuron-methyl |
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| CN105503728B (en) * | 2015-12-31 | 2017-03-22 | 青岛清原化合物有限公司 | Pyrazole compounds or salts thereof and preparation method thereof, and weedicide composition and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980202A (en) * | 2014-05-27 | 2014-08-13 | 青岛清原化合物有限公司 | 4-benzoyl pyrazole compound with herbicidal activity |
| CN105230629A (en) * | 2015-11-17 | 2016-01-13 | 青岛清原抗性杂草防治有限公司 | Synergic weeding composition |
| CN105685049A (en) * | 2016-03-15 | 2016-06-22 | 青岛清原化合物有限公司 | Sorghum field weeding composition and application thereof |
| CN106070309A (en) * | 2016-06-21 | 2016-11-09 | 青岛清原抗性杂草防治有限公司 | Complex herbicidal composition containing polybenzobisoxazole oxadiazon and using method thereof |
| CN106305754A (en) * | 2016-10-13 | 2017-01-11 | 广东中迅农科股份有限公司 | Weeding composition containing dicarfentrazone, quinclorac and halosulfuron-methyl |
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