CN106946783B - Triazole sulphur humulone C crystal form and its preparation method and application - Google Patents
Triazole sulphur humulone C crystal form and its preparation method and application Download PDFInfo
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- CN106946783B CN106946783B CN201710257455.5A CN201710257455A CN106946783B CN 106946783 B CN106946783 B CN 106946783B CN 201710257455 A CN201710257455 A CN 201710257455A CN 106946783 B CN106946783 B CN 106946783B
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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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- 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
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- 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 a kind of triazole sulphur humulone C crystal form and its preparation method and application.The C crystal form of triazole sulphur humulone of the invention, after tested, it has good stability, 70 DEG C high-temperature storage two months, crystal form does not change, and purity is substantially undegraded, solubility increase connects by about one time in water, and C crystal form or the complex composition with other effective components, there is preferable preventive effect to paddy field gramineae weed and part broadleaf weeds, 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 triazole sulphur humulone C crystal form and its preparation
Method and purposes.
Background technique
The chemical name of triazole sulphur humulone: 4- (the chloro- 3- of 2- ((3,5- dimethyl -1H- pyrazol-1-yl) methyl) -4- (first
Sulfonyl) benzoyl) -1,3- dimethyl -1H- pyrazoles -5- base -1,3- dimethyl -1H- pyrazoles -4- formic acid esters
Structural formula:
Triazole sulphur humulone is the HPPD inhibitor class herbicide of newly developed paddy field stem and leaf treatment after seedling, is had excellent
Bioactivity can effectively prevent and kill off a variety of malignant weeds of paddy field, and compound patent has been authorized to, Authorization Notice No.: CN
105503728 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 triazole sulphur humulone is newly developed drug, without the report of its crystal form in current various documents and patent
Road.It has been investigated that in most cases, triazole sulphur humulone is all with the presence of A crystal form.
Summary of the invention
The present invention provides a kind of new herbicides triazole sulphur humulone C crystal forms and its preparation method and application.C crystal form is stablized
Property is good, and solubility is big, and bioactivity is higher, can be used for preventing and kill off for paddy field weed.
Technical solution of the present invention, triazole sulphur humulone is referring to the method preparation in 105503728 B of CN.It is wherein specific public
It opens, weighs 2.1g (0.005mol) compound a in 100mL single-necked flask, 15mL acetonitrile and 1.0g (0.010mol) is added
Triethylamine opens stirring under the conditions of ice-water bath.It weighs 1.0g (0.006mol) 1,3- dimethyl pyrazole -4- formyl chloride and is dissolved in 10mL
Acetonitrile is placed in dropping funel, starts to be added dropwise under the conditions of ice-water bath.HPLC tracking is reacted to compound a fully reacting.Reaction
After, 100mL water and 100mL ethyl acetate is added, extracts branch vibration layer, organic layer is with 100mL saturated common salt water washing 2 times
After be dried over anhydrous sodium sulfate, revolving remove organic solvent, obtain yellow-brown solid, it is pale yellow to obtain 1.5g after column Chromatographic purification
Color pulverulent solids.As compound 01.HPLC content 93.9%, yield 53.1%.Reaction equation sees below formula:
Embodiment 2 to embodiment 13 illustrates the synthetic method of compound 02 in table 1 to compound 13 respectively, with embodiment
1 is similar, and triazole sulphur humulone described herein is compound described in embodiment 3.
The triazole sulphur humulone raw medicine being prepared is A crystal form, while triazole sulphur humulone raw medicine being dissolved in range of solvents:
Methanol, ethyl alcohol, isopropanol, acetone, butanone, acetonitrile, tetrahydrofuran, nitromethane, ethyl acetate, isopropyl acetate, isoamyl alcohol,
Methyl tertiary butyl ether, toluene, hexone, n-hexane, normal heptane, ether, chloroform, petroleum ether and water etc., stirring is extremely
It is completely dissolved, stands still for crystals or slowly volatilizees, it is dry, obtain A crystal form.
On the basis of A crystal form, and have studied C crystal form.
A kind of triazole sulphur humulone C crystal form, X-ray powder diffraction spectrogram 2 θ of the angle of diffraction be 6.8,7.6,9.4,11.1,
13.1、13.5、14.6、15.5、16.1、16.9、18.0、19.3、19.4、20.9、21.9、23.3、23.6、23.8、24.8、
25.5, there is characteristic peak, wherein 2 θ error models at 26.1,26.8,27.8,28.9,30.1,31.3,33.2,34.3,36.0 degree
It is trapped among in ± 0.2 °.Corresponding I/I0Respectively 41,87,24.7,100,37.2,26.4,19.2,23,17,29.5,24.8,
32.7、18、24.1、7.2、12.5、15.2、22.4、6.3、9.1、22.2、36、9.1、10、11.3、20.6、10.7、5.1、
4.6。
Preferably, X-ray powder diffraction pattern is shown basically as in Figure 2.
The preparation method of the triazole sulphur humulone C crystal form, comprising the following steps: triazole sulphur humulone is dissolved in methylene chloride
In, be heated to after being completely dissolved, be cooled to stand still for crystals and filter in 25 DEG C or 25 DEG C in volatilize naturally, later by crystal
In 90-110 DEG C of high temperature drying, C crystal form is obtained；
Or triazole sulphur humulone is dissolved by heating into the in the mixed solvent in ethyl acetate, second alcohol and water, it evaporates into naturally molten
Agent volatilization completely, obtains C crystal form.
A kind of weeding complex composition, including the triazole sulphur humulone C crystal form 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,
Carboxymethyl cellulose and aluminium-magnesium silicate etc..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 triazole sulphur humulone C crystal form of the invention is, such as " world pesticide new product
Kind of technology is complete works of ", Scientia Agricultura Sinica technology publishing house, 2010.9 and document incorporated herein in known substance.Such as with
Under mention various substances (remarks: the title of compound, or for according to the common name of International Organization for standardization (ISO), or
Person is chemical name, there is code name when appropriate): Acetochlor, butachlor, alachlor, propisochlor, isopropyl methoxalamine, essence are different
It is the left-handed naphthalene propionyl grass amine of methoxalamine, pretilachlor, propachlor, kecaoan, naphthalene propionyl grass amine, R-, propanil, mefenacet, double
Benzoyl grass amine, diflufenican, N-alpha-chloroacetyl-N-isopropyl-o ethylaniline, beflubutamid, bromobutide, dimethenamid, dimethenamidP, second
Oxygen benzene grass amine, flufenacet, thenylchlor, metazachlor, isoxaben, flampropMmethyl, flampropMisopropyl, two
Third pethoxamid, pethoxamid, chloranocryl, ring pretilachlor, mefluidide, monalide, delachlor, prynachlor, special fourth
Careless amine, xylachlor, dimethachlor, amine of taking to the greenwood, front three ring grass amine, clomeprop, propyzamide, valeryl benzene grass amine,
Block careless amine, suffer, tricyclic and matches careless amine, butenachlor, tebutam, benzyl grass amine, quinone duckweed amine, dichlofluanid, naproanilide, acetyl first
Careless amine, quinclorac, fenacet, pyrrole cyanogen grass amine, more grams of benzene grass be dead, chlorothiamid, chlorine phthalimide, fourth amidine amine, fluorine metazachlor, green bristlegrass are gone
Saliva, Simanex, prometryn, cyanatryn, symetryne, ametryn, propazine, dipropetryn, flur, terbutryn, Garagard, triazine
Benfluralin, cyprazine, proglinazine, trietazine, prometon, Gesadrual, nitrine are net, desmetryn, dimethametryn, cyclopropyl blueness saliva, go out
Green bristlegrass 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, pyrazosulfuron, first
Two sulphur of base is grand, iodosulfuron-methyl-sodium, formamido group Sulfometuron Methyl, cinosulfuron, triasulfuron, sulfometuronmethyl, nicosulfuron, amine benzene
Sulphur is grand, amidosulfuron, ethoxysulfuron, cypromisulfuron, rimsulfuron, azimsulfuron, pyridine ethyl methyl, monosulfmeturon, list
Phonetic sulphur ester, flucarbazone, flupyrsulfuron-methyl-sodium, fluorine pyrazosulfuron, oxasulfuron, imazosulfuron, primisulfuronmethyl, propyl benzene sulphur
Grand, prosulfuron, Sulfosulfuron, trifloxysulfuron, triflusulfuronmethyl, tritosulfuron, metsulfuron-methyl sodium salt, flucetosulfuron, first
Sulphur Sulfometuron Methyl, orthosulfamuron, Propyrisulfuron (proxazuron-methyl), piperazine pyrazosulfuron, acifluorfen, fluorine sulfanilamide (SN)
Careless ether, lactofen, fluoroglycofen-ethyl, Oxyfluorfen, Mo 9 granular, aclonifen, ethoxyfen-ethyl, bifenox,
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
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 triazole sulphur humulone C crystal form 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: isoproturon, propanil, bentazone, cyhalofop-butyl, fourth grass
One of amine, dichloro quinolinic acid, mesotrione, pyraclonil, bromoxynil octanoate, clomazone, anilofos and azoles humulone or
It is a variety of.
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 triazole sulphur humulone C crystal form or the weeding complex composition in preventing and kill off paddy field gramineae weed and
Application on the broadleaf weeds of part.
The C crystal form of triazole sulphur humulone of the invention has good stability after tested, 70 DEG C high-temperature storage two months, crystal form is not
Change, purity is substantially undegraded, and solubility increase connects by about one time in water, and C crystal form or compounds with other effective components
Composition has preferable preventive effect to paddy field gramineae weed and part broadleaf weeds, and effect is substantially better than A crystal form.
Detailed description of the invention
Fig. 1 is the XRPD map of 1 triazole sulphur humulone A crystal form of embodiment in the present invention.
Fig. 2 is the XRPD map of 2 triazole sulphur humulone C 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: 30-400(2 θ value), scanning step diameter: 0.05s.
Embodiment 1
Triazole sulphur humulone raw medicine is prepared referring to 105503728 B method of CN.Again by 3000 grams of triazole sulphur humulone raw medicines
It being placed in the flask of 10L, acetone 5L is added, be 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 triazole sulphur humulone A crystal form.Or solvent volatilizees, until solvent is complete
Volatilization finishes, and the powder of triazole sulphur humulone A crystal form also can be obtained.
Embodiment 2
2000 grams of triazole sulphur humulone A crystal form raw medicines are placed in the flask of 10L, methylene chloride 5L are added, heating stirring is extremely
Raw material is completely dissolved, and is gradually cooled to 10 DEG C or so, is stood 1 hour, crystal is obtained by filtration, 110 DEG C of drying are 1 small later
When, obtain C crystal form powder.
Embodiment 3
2000 grams of triazole sulphur humulone A crystal form raw medicines are placed in the flask of 10L, ethyl acetate 3L, ethyl alcohol 3L and water is added
1L, stirring are completely dissolved to raw material, are evaporated into solvent naturally later and are volatilized completely and finish, and the powder of triazole sulphur humulone C crystal form is obtained
End.
Physical and chemical stability experiment
By the triazole sulphur humulone A crystal form that embodiment 1 obtains and triazole sulphur humulone three kinds of powder of C crystal form that embodiment 2,3 obtains
End, surveying A crystal form and two kinds of C crystal form contents by HPLC is 95.0%, later, by these three powder be respectively placed in 25 DEG C,
Inside 40 DEG C, 55 DEG C and 70 DEG C baking ovens, the heat storage experiment of progress in 2 months is placed, crystal form type and purity is tested later, as a result sees below
Table 1:
The study on the stability of 1 triazole sulphur humulone different crystal forms of table
As shown in Table 1, triazole sulphur humulone A crystal form and C crystal form have good stability under the conditions of different temperature, especially
Under 70 DEG C of higher temperatures, C crystal form still keeps good physical and chemical stability for it, and crystal form does not change, purity detecting
Even slightly it is better than A crystal form, has a good application prospect.
Solubility test in water
By the triazole sulphur humulone A crystal form that embodiment 1 obtains and triazole sulphur humulone three kinds of powder of C crystal form that embodiment 2,3 obtains
End is dissolved into pure water, is shaken at 25 DEG C for 24 hours, is allowed to sufficiently dissolve, be filtered later with filter paper, filtrate is after 0.22 μm
Filter membrane, flow phased soln after with HPLC measurement water in solubility, as a result see the table below 2:
Solubility test result in the water of 2 triazole sulphur humulone different crystal forms of table
| Sample | Solubility (mg/L) in pure water |
| 1 triazole sulphur humulone A crystal form of embodiment | 6.1 |
| 2 triazole sulphur humulone C crystal form of embodiment | 10.4 |
| 2 triazole sulphur humulone C crystal form of embodiment | 10.5 |
By 2 result of table, as it can be seen that the C crystal form of triazole sulphur humulone compares, A crystal form, solubility have apparent increase.
Embodiment 1 and 2 preparation processing of embodiment and crop field effect experiment
By the triazole sulphur humulone A crystal form that embodiment 1 obtains and the triazole sulphur humulone C crystal form that embodiment 2 obtains, according to identical
Formula, be processed into following preparation, specific formula is as follows:
5% triazole sulphur humulone OD
+ 8% emulsifier phenethyl phenol polyethenoxy ether of 5%+5% emulsifier calcium dodecyl benzene sulfonate of triazole sulphur humulone+
+ 2% thickener fumed silica+20% of+2.5% thickener organobentonite of 4% emulsifier castor oil polyoxyethylene ether
Decentralized medium soybean oil+decentralized medium methyl oleate is supplied
16% triazole sulphur humulone cyhalofop-butyl OD
+ 7% emulsifier phenethyl of 6%+6% emulsifier calcium dodecyl benzene sulfonate of triazole sulphur+10% cyhalofop-butyl of humulone
+ 2% thickener vapor phase method of+2.5% thickener organobentonite of+5% emulsifier castor oil polyoxyethylene ether of phenol polyethenoxy ether
Silica+20%100# solvent naphtha+decentralized medium methyl oleate is supplied
30% triazole sulphur humulone bentazone WP
+ 3% wetting agent dodecyl sulphate of 5%+10% dispersing agent sodium lignin sulfonate of triazole sulphur+25% bentazone of humulone
+ 10% filler white carbon black of sodium+filler kaolin is supplied
10% triazole sulphur humulone SC
+ 2% wetting agent of+4% dispersing agent phenethyl phenol polyethenoxy ether phosphate triethanolamine salt of 10% triazole sulphur humulone
+ 5% antifreezing agent glycerine of+0.5% thickener carboxymethyl cellulose of+0.25% thickener xanthan gum of neopelex+
0.1% defoaming agent organic silicone oil+water is supplied
25% triazole sulphur humulone butachlor ME
+ 6% emulsifier calcium dodecyl benzene sulfonate of 3%+5% ethyl alcohol of triazole sulphur humulone+20% cyclohexanone of+22% butachlor
+ 5% emulsifier phenethyl phenol polyethenoxy ether formaldehyde resin condensation product of+12% emulsifier phenethyl phenol polyethenoxy ether+water is mended
Foot
40% triazole sulphur humulone dichloro quinolinic acid WDG
+ 3% wetting agent dodecyl sulphate of 6%+10% dispersant polycarboxylate of triazole sulphur+34% dichloro quinolinic acid of humulone
+ 10% filler white carbon black of sodium+filler kaolin is supplied
10% triazole sulphur humulone isoproturon OD
+ 7% emulsifier polyoxyethylene nonyl phenyl of 6%+6% emulsifier calcium dodecyl benzene sulfonate of triazole sulphur+4% isoproturon of humulone
+ 2% thickener fumed silica of+2% thickener organobentonite of+5% emulsifier fatty alcohol polyoxyethylene ether of vinethene+
Decentralized medium methyl oleate is supplied
4% triazole sulphur humulone amicarbazone GR
+ 4% dispersing agent napsylate of 3%+2% wetting agent lauryl sodium sulfate of triazole sulphur+1% amicarbazone of humulone-
Formaldehyde condensation products+filler diatomite is supplied
Crop field effect test: after 3 leaf of rice, barnyard grass (Changsha acquisition seed), semen euphorbiae (Hubei public security acquisition kind
Son) the 3-4 leaf phase, hand sprayer, 30 kilograms/667m of the amount of being watered2, even spraying is sprayed using cauline leaf, 50 squares of plot area
Rice, average strain preventive effect (range estimation) effect of investigation in 45 days is as follows after every processing is repeated 4 times application, is shown in Table 3.
The triazole sulphur humulone preparation of 3 different crystal forms of table prevents and kill off direct sowing of rice field weed effect (%) --- application 45d rear defence
Effect
Note: test plot barnyard grass shows dichloro quinolinic acid certain resistance, 225g/hm2Dichloro quinolinic acid is anti-to barnyard grass
Effect < 10%.
Embodiment 1 and 3 preparation processing of embodiment and crop field effect experiment
By the triazole sulphur humulone A crystal form that embodiment 1 obtains and the triazole sulphur humulone C crystal form that embodiment 3 obtains, according to identical
Formula, be processed into following preparation, specific formula is as follows:
36% triazole sulphur humulone pretilachlor EC
+ 6% emulsifier 12 of 6%+10% cyclohexanone+10%N- methyl pyrrolidone of+30% pretilachlor of triazole sulphur humulone
The contracting of+2% emulsifier phenethyl phenol polyethenoxy ether formaldehyde resin of+12% emulsifier nonylphenol polyoxyethylene ether of alkyl benzene calcium sulfonate
Object+solvent 100# solvent naphtha is closed to supply
4% triazole sulphur humulone pyraclonil OD
+ 7% emulsifier nonyl phenol of 3%+6% emulsifier calcium dodecyl benzene sulfonate of triazole sulphur+1% pyraclonil of humulone is poly-
+ 2% thickener vapor phase method titanium dioxide of+2% thickener organobentonite of+5% emulsifier castor oil polyoxyethylene ether of ethylene oxide ether
Silicon+decentralized medium methyl oleate is supplied
15% triazole sulphur humulone bromoxynil octanoate ME
+ 6% emulsifier detergent alkylate sulphur of 5%+5% ethyl alcohol of triazole sulphur humulone+20% cyclohexanone of+10% bromoxynil octanoate
Sour+5% emulsifier phenethyl phenol polyethenoxy ether formaldehyde resin condensation product of+12% emulsifier phenethyl phenol polyethenoxy ether of calcium+
Water is supplied
7% triazole sulphur humulone chlorine fluorine pyridine ester EC
+ 6% emulsifier ten of+15% cyclohexanone+10%N- methyl pyrrolidone of+1% chlorine fluorine pyridine ester of 6% triazole sulphur humulone
+ 2% emulsifier phenethyl phenol polyethenoxy ether formaldehyde resin of+10% emulsifier nonylphenol polyoxyethylene ether of dialkyl benzene sulfonic acids calcium
Condensation product+solvent 100# solvent naphtha is supplied
6% triazole sulphur humulone mesotrione SC
+ 4% dispersing agent phenethyl phenol polyethenoxy ether phosphate triethanolamine salt of 5%+1% mesotrione of triazole sulphur humulone
+ 5% antifreezing agent third of+0.5% thickener aluminium-magnesium silicate of+0.25% thickener xanthan gum of+2% wetting agent neopelex
+ 0.1% defoaming agent organic silicone oil of triol+water is supplied
10% triazole sulphur humulone clomazone SE
+ 4% dispersing agent phenethyl phenol polyethenoxy ether phosphate triethanolamine salt of 5%+5% clomazone of triazole sulphur humulone
+ 5% antifreezing agent third of+0.5% thickener aluminium-magnesium silicate of+0.2% thickener xanthan gum of+6% emulsifier nonylphenol polyoxyethylene ether
+ 0.1% defoaming agent organic silicone oil of triol+water is supplied
16% triazole sulphur humulone anilofos OD
+ 7% emulsifier phenethyl phenol of 6%+6% emulsifier calcium dodecyl benzene sulfonate of triazole sulphur+10% anilofos of humulone
+ 2% thickener vapor phase method two of+2.6% thickener organobentonite of+5% emulsifier fatty alcohol polyoxyethylene ether of polyoxyethylene ether
Silica+decentralized medium methyl oleate is supplied
6% triazole sulphur humulone azoles humulone OD
+ 7% emulsifier phenethyl phenol of 5%+6% emulsifier calcium dodecyl benzene sulfonate of triazole sulphur+1% azoles humulone of humulone is poly-
+ 2% thickener vapor phase method titanium dioxide of+3% thickener organobentonite of+5% emulsifier fatty alcohol polyoxyethylene ether of ethylene oxide ether
Silicon+decentralized medium methyl oleate is supplied
Crop field effect test: after 3 leaf of rice, barnyard grass (Changsha acquisition seed), semen euphorbiae (Hubei public security acquisition kind
Son) the 3-4 leaf phase, hand sprayer, 30 kilograms/667m of the amount of being watered2, even spraying is sprayed using cauline leaf, 50 squares of plot area
Rice, average strain preventive effect (range estimation) effect of investigation in 45 days is as follows after every processing is repeated 4 times application, is shown in Table 4.
The triazole sulphur humulone preparation of 4 different crystal forms of table prevents and kill off direct sowing of rice field weed effect (%) --- application 45d rear defence
Effect
Note: test plot barnyard grass shows dichloro quinolinic acid certain resistance, 225g/hm2Dichloro quinolinic acid is anti-to barnyard grass
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 (13)
1. a kind of triazole sulphur humulone C crystal form, it is characterised in that: X-ray powder diffraction spectrogram 2 θ of the angle of diffraction be 6.8,7.6,
9.4、11.1、13.1、13.5、14.6、15.5、16.1、16.9、18.0、19.3、19.4、20.9、21.9、23.3、23.6、
23.8, there is at 24.8,25.5,26.1,26.8,27.8,28.9,30.1,31.3,33.2,34.3,36.0 degree characteristic peak,
In 2 θ error ranges in ± 0.2 °.
2. a kind of triazole sulphur humulone C crystal form according to claim 1, it is characterised in that: corresponding I/I0Respectively 41,87,
24.7、100、37.2、26.4、19.2、23、17、29.5、24.8、32.7、18、24.1、7.2、12.5、15.2、22.4、6.3、
9.1、22.2、36、9.1、10、11.3、20.6、10.7、5.1、4.6。
3. a kind of triazole sulphur humulone C crystal form according to claim 1 or 2, it is characterised in that: X-ray powder diffraction pattern
Shown in basically as in Figure 2.
4. the preparation method of triazole sulphur humulone C crystal form as described in claim 1-3 any one, it is characterised in that: including following
Step: it in methylene chloride by the dissolution of triazole sulphur humulone, is heated to after being completely dissolved, is cooled in 25 DEG C and stands still for crystals and mistake
Filter or 25 DEG C in volatilize naturally, crystal is obtained into C crystal form in 90-110 DEG C of high temperature drying later.
5. the preparation method of triazole sulphur humulone C crystal form as described in claim 1-3 any one, it is characterised in that: by triazole sulphur
Humulone dissolves by heating the in the mixed solvent in ethyl acetate, second alcohol and water, evaporates into solvent volatilization naturally completely, obtains C crystal form.
6. a kind of weeding complex composition, it is characterised in that: including the crystalline substance of triazole sulphur humulone C described in claim 1-3 any one
Type and auxiliary agent.
7. weeding complex composition according to claim 6, which is characterized 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.
8. weeding complex composition according to claim 6, which is characterized in that the composition further include other effectively at
Point.
9. weeding complex composition according to claim 8, which is characterized in that other described effective components are selected from isopropyl
Grand, propanil, bentazone, cyhalofop-butyl, butachlor, dichloro quinolinic acid, mesotrione, pyraclonil, bromoxynil octanoate, different evil grass
One of pine, anilofos and azoles humulone are a variety of.
10. according to weeding complex composition described in claim 6-9 any one, which is characterized in that have in the composition
The gross mass content for imitating ingredient is within 75%.
11. weeding complex composition according to claim 10, which is characterized in that effective component is total in the composition
Mass content is within 50%.
12. according to weeding complex composition described in claim 6-9 and 11 any one, it is characterised in that: the composition
Dosage form be aqueous suspension agent, dispersible oil-suspending agent, missible oil, microemulsion, granule, suspoemulsion or water dispersible granules.
13. described in triazole sulphur humulone C crystal form as claimed in any one of claims 1-3 or claim 6-11 any one
Application of the weeding complex composition in preventing and kill off paddy field on gramineae weed and part broadleaf weeds.
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| CN201710257455.5A CN106946783B (en) | 2017-04-19 | 2017-04-19 | Triazole sulphur humulone C crystal form and its preparation method and application |
| PCT/CN2017/084899 WO2018192046A1 (en) | 2017-04-19 | 2017-05-18 | Triazolesulcotrione crystal form c, preparation method therefor, and use thereof |
| PH12019502588A PH12019502588A1 (en) | 2017-04-19 | 2019-11-19 | Crystal form c of sanzuohuangcaotong, preparation method and use thereof |
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| WO2019037313A1 (en) * | 2017-08-25 | 2019-02-28 | 青岛清原化合物有限公司 | Herbicidal composition containing triazole sulcotrione and application thereof |
| CN107517978B (en) * | 2017-08-28 | 2020-06-30 | 青岛清原农冠抗性杂草防治有限公司 | Ternary weeding composition containing triazophos-clomazone and anilofos and application thereof |
| CN113180051A (en) * | 2017-09-19 | 2021-07-30 | 青岛清原抗性杂草防治有限公司 | Weeding composition containing triazasulam and application thereof |
| CN112998022B (en) * | 2017-11-09 | 2021-09-21 | 青岛清原化合物有限公司 | Weeding composition containing triazasulam and application thereof |
| CN108558761B (en) * | 2018-05-21 | 2020-03-17 | 青岛清原化合物有限公司 | Triazolesulfonylzone-salicylic acid eutectic crystal and preparation method and application thereof |
| CN112816569B (en) * | 2020-12-23 | 2022-09-23 | 江苏省农产品质量检验测试中心 | High performance liquid chromatography analysis method for simultaneously determining content of triazophos-cotrione and anilofos in dispersible oil suspending agent |
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| CN105503728A (en) * | 2015-12-31 | 2016-04-20 | 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 |
| CN105724390A (en) * | 2016-04-28 | 2016-07-06 | 青岛清原抗性杂草防治有限公司 | Rice field herbicide composition and application thereof |
| CN106472517A (en) * | 2016-09-30 | 2017-03-08 | 江苏清原农冠杂草防治有限公司 | Synergistic herbicide compositions and its application |
| CN106508913A (en) * | 2016-10-11 | 2017-03-22 | 泰安市农业科学研究院 | Herbicide composition containing triazole sulcotrione and triazole napropamide and application thereof |
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| JP2001512726A (en) * | 1997-08-07 | 2001-08-28 | ビーエーエスエフ アクチェンゲゼルシャフト | Substituted 4-benzoylpyrazole |
| JP5416354B2 (en) * | 2007-02-02 | 2014-02-12 | 石原産業株式会社 | Herbicidal composition containing a benzoylpyrazole compound |
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| CN105503728A (en) * | 2015-12-31 | 2016-04-20 | 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 |
| CN105724390A (en) * | 2016-04-28 | 2016-07-06 | 青岛清原抗性杂草防治有限公司 | Rice field herbicide composition and application thereof |
| CN106472517A (en) * | 2016-09-30 | 2017-03-08 | 江苏清原农冠杂草防治有限公司 | Synergistic herbicide compositions and its application |
| CN106508913A (en) * | 2016-10-11 | 2017-03-22 | 泰安市农业科学研究院 | Herbicide composition containing triazole sulcotrione and triazole napropamide and application thereof |
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