CN106946783A - Triazole sulphur humulone C crystal form and its production and use - Google Patents
Triazole sulphur humulone C crystal form and its production and use Download PDFInfo
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- CN106946783A CN106946783A CN201710257455.5A CN201710257455A CN106946783A CN 106946783 A CN106946783 A CN 106946783A CN 201710257455 A CN201710257455 A CN 201710257455A CN 106946783 A CN106946783 A CN 106946783A
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- sulphur humulone
- triazole sulphur
- crystal form
- humulone
- triazole
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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
-
- 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
-
- 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
Abstract
The invention belongs to herbicide crystallization processes technical field, and in particular to a kind of triazole sulphur humulone C crystal form and its production and use.The X ray powder diffractograms of the triazole sulphur humulone C crystal form the θ of the angle of diffraction 2 be 6.8,7.6,9.4,11.1,13.1,13.5,14.6,15.5,16.1,16.9,18.0,19.3,19.4,20.9,21.9,23.3,23.6,23.8,24.8,25.5,26.1,26.8,27.8,28.9,30.1,31.3,33.2,34.3, there is characteristic peak at 36.0 degree, wherein 2 θ error ranges are in ± 0.2 °.The C crystal form of the triazole sulphur humulone of the present invention, after tested, have good stability, 70 DEG C of high-temperature storage two months, crystal formation 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 active ingredients, there is preferable preventive effect to rice terrace grassy weed and part broad leaved weed, effect is substantially better than A crystal formations.
Description
Technical field
The invention belongs to herbicide crystallization processes technical field, and in particular to a kind of triazole sulphur humulone C crystal form and its preparation
Method and purposes.
Background technology
The chemical name of triazole sulphur humulone：4- (the chloro- 3- of 2- ((3,5- dimethyl -1H- pyrazol-1-yls) 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 for the rice terrace after seedling cauline leaf process newly researched and developed, with excellent
Bioactivity, can effectively prevent and kill off a variety of malignant weeds of rice terrace, 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 the phenomenon of the solid state of physicochemical properties.In drug research field, polymorphic includes organic solvate, hydrate
Deng multicomponent crystal form.Medicine polymorphism is widely present in drug discovery process, is that organic micromolecule compound is intrinsic
Characteristic.Small-molecule drug can have infinite number of crystal accumulation mode-polymorphic in theory.Polymorphism not only by point
The space structure and functional group performance of son itself, the control of the internal factor such as intramolecular and intermolecular interaction, it is also
Designed, crystallized and purification condition, pharmaceutical adjunct selection, preparation process route and method of granulating and storage by medicine synthesising process
Deposit the influence of the aspects factor such as condition, packaging material.Different crystal forms have different colors, fusing point, dissolving, dissolving out capability,
Chemical stability, reactivity, mechanical stability etc., these physical and chemical performances or processability directly influence medicine sometimes
Safely, effectively performance.Therefore crystal formation research and control turn into the important research content in drug development process.
Because triazole sulphur humulone is the equal report without its crystal formation in newly developed medicine, current various documents and patent
Road.It has been investigated that in most cases, triazole sulphur humulone all exists with A crystal formations.
The content of the invention
The invention provides a kind of new herbicides triazole sulphur humulone C crystal form and its production and use.C crystal form is stable
Property it is good, solubility is big, and bioactivity is higher, available for preventing and kill off for paddy field weed.
Technical scheme, triazole sulphur humulone is prepared with reference to the method in the B of CN 105503728.It is wherein specific public
Open, weigh 2.1g (0.005mol) compound as in 100mL single-necked flasks, add 15mL acetonitriles and 1.0g (0.010mol)
Stirring is opened under the conditions of triethylamine, ice-water bath.Weigh 1.0g (0.006mol) 1,3- dimethyl pyrazole -4- formyl chlorides and be dissolved in 10mL
Acetonitrile is placed in dropping funel, starts to be added dropwise under the conditions of ice-water bath.HPLC tracking reaction is complete to compound a reaction.Reaction
After end, 100mL water and 100mL ethyl acetate are added, branch vibration layer is extracted, organic layer 100mL saturated common salts water washing 2 times
By anhydrous sodium sulfate drying, revolving removes organic solvent, obtains yellow-brown solid, it is pale yellow to obtain 1.5g after being purified through column chromatography
Color pulverulent solids.As compound 01.HPLC contents 93.9%, yield 53.1%.Reaction equation sees below formula：
Embodiment 2 to embodiment 13 illustrates compound 02 in table 1 to the synthetic method of compound 13 respectively, itself and embodiment
1 is similar, and triazole sulphur humulone described herein is the compound described in embodiment 3.
The triazole sulphur humulone active compound prepared is A crystal formations, while triazole sulphur humulone active compound is dissolved in range of solvents：
Methanol, ethanol, 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 volatilize, dries, obtain A crystal formations.
On the basis of A crystal formations, C crystal form is have studied again.
A kind of triazole sulphur humulone C crystal form, X-ray powder diffraction spectrogram the θ of the angle of diffraction 2 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、
25.5th, 26.1,26.8,27.8,28.9,30.1,31.3,33.2,34.3, there is characteristic peak at 36.0 degree, wherein 2 θ error models
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, its X-ray powder diffraction pattern is substantially as shown in Figure 2.
The preparation method of the triazole sulphur humulone C crystal form, comprises the following steps：Triazole sulphur humulone is dissolved in dichloromethane
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, afterwards by crystal
In 90-110 DEG C of high temperature drying, C crystal form is obtained；
Or evaporate into triazole sulphur humulone heating for dissolving molten naturally in ethyl acetate, the mixed solvent of second alcohol and water
Agent volatilization is complete, 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, emulsifying agent, wetting agent, dispersant, antifreezing agent, defoamer
With the one or more in thickener.
Selected solvent includes but is not limited to polar solvent class：Water, N, N- dimethylformamides, dimethyl sulfoxide (DMSO), N- alkylated pyrazoles
Pyrrolidone, methanol, ethanol, 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-pentanones 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, phenmethylol and tetrahydrofurfuryl alcohol etc..
Selected solid diluent can be water-soluble or water-insoluble.Water-soluble solid diluent includes but is not limited to：
Salt, such as 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,
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
The ethoxylate of condensation product, alcohol with formaldehyde.
Dispersant 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 dispersant, polycarboxylic acid salt's dispersant
Deng.
Thickener includes but is not limited to：Guar gum, pectin, xanthans, alginates, methylcellulose, hydroxyethyl cellulose,
Carboxymethyl cellulose and aluminium-magnesium silicate etc..The thickener of synthesis includes the derivative of aforesaid kind, also including polyvinyl alcohol, gathers
Acrylamide, PVP, various polyethers and their copolymer and polyacrylic acid and their salt.
Other formulation ingredients can be used in the present invention, such as dyestuff, defoamer, drier.These compositions are ability
Field technique personnel know.
The composition also includes other active ingredients.
Can be with the suitable active ingredient of the triazole sulphur humulone C crystal form mixing of the present invention, for example《World pesticide new product
The technology of kind is complete works of》, Scientia Agricultura Sinica technology publishing house, 2010.9 and document incorporated herein in known substance.For example with
Under the various material (remarks mentioned：The title of compound, or be the common name according to 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
The careless amine of the careless amine of careless amine, xylachlor, dimethachlor, amine of taking to the greenwood, front three ring, clomeprop, propyzamide, valeryl benzene,
The careless amine of card, suffer, the careless amine of three rings match, butenachlor, tebutam, the careless amine of benzyl, quinone duckweed amine, dichlofluanid, naproanilide, acetyl first
The careless amine of careless amine, quinclorac, fenacet, pyrrole cyanogen, dead many grams of benzene grass, chlorothiamid, chlorine phthalimide, fourth amidine amine, fluorine metazachlor, green bristlegrass are gone
Tianjin, Simanex, prometryn, cyanatryn, symetryne, ametryn, propazine, dipropetryn, SSH-108, terbutryn, Garagard, triazine
Benfluralin, cyprazine, proglinazine, trietazine, prometon, Gesadrual, nitrine are net, desmetryn, dimethametryn, the blue or green Tianjin of ring third, go out
Green bristlegrass Tianjin, another Ding Jin, Zhong Dingtong, Te Dingtong, methoxy third net, cyanatryn, ipazine, chlorazine, atraton, logical weed eradication, Radix Glycyrrhizae Tianjin,
Cyanuric acid, Indaziflam, grand green sulphur, metsulfuron-methyl, bensulfuron-methyl, chlorimuron, tribenuron-methyl, thifensulfuron methyl, pyrazosulfuron, first
The sulphur of base two is grand, iodosulfuron-methyl-sodium, formamido group Sulfometuron Methyl, cinosulfuron, triasulfuron, sulfometuronmethyl, nicosulfuron, amine benzene
Sulphur is grand, amidosulfuron, ethoxysulfuron, AC322140, 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 (promazine Sulfometuron 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, the careless ether of fluorine furan, nitrofen, the careless ether of first, the careless ether of diformazan,
Fluorine lactazone grass ether, AKH7088 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, grand fluorine sulphur, 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,
The careless spy of molinate, tri-allate, dimepiperate, esprocarb, pyributicarb, cycloate, Avadex, bactericide, second sulphur, orbencarb, gram grass
Suddenly, prosulfocarb, tiocarbazil, sulfuric acid, dimexan, Isopolinate, Methiobencarb, 2,4- d butyl ester, the chlorine of 2 first 4
Sodium, the different monooctyl ester of 2,4- drops, the different monooctyl ester of the chlorine of 2 first 4,2,4- drops sodium salt, 2,4- drops dimethylamine salt, the chloroethene thioesters of 2 first 4, the chlorine of 2 first 4,2,
4- drops propionic acid, high 2,4- drops propionate, 2,4- Embutoxs, Vi par, Vi par salt, Thistrol, 2,4,5-
Tears, 2,4,5- tears propionic acid, 2,4,5- tears butyric acid, the chloramines salt of 2 first 4, Mediben, 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 the standing grain of hydroxyl penta, 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
The careless phosphine of phosphine sulfide, piperazine, bialaphos, bensulide, butamifos, creeping weed phosphorus, cut down ridge phosphorus, double first amiprophos, dow crabgrass killer, imazapyr,
The careless ester of imazethapyr, imazaquin, imazamox, imazamox ammonium salt, AC 263222, miaow, chlorine fluorine pyrrole oxygen second
Acid, the different monooctyl ester of fluroxypyr, clopyralid, picloram, trichlopyr, dithiopyr, halogen grass are 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,
The careless amine of Methiozolin, fluazolate, pyraflufen-ethyl, pyrazolate, difenzoquat, pyrazoxyfen, benzofenap, pyrrole chlorine,
Pyrasulfotole, topramezone, Pyroxasulfone, cafenstrole, flupoxam, Amrol, amicarbazone, ethofumesate
Ketone, profluazone, sulfentrazone, Bencarbazone, benzfendizone, butafenacil, bromacil, isoprocil, lenacil,
The careless amine of terbacil, Flupropacil, cinidon-ethyl, Flumiclorac pentyl, flumioxazin, alkynes, 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
The careless phosphine of the careless amine of ester, thiadiazoles, phenisopham, hydroxyl humulone, ammonia chloranil, dioxybenzone, benzene flumetsulam, chlorine acyl, chloropon,
Alorac、Diethamquat、Etnipromid、Iprymidam、Ipfencarbazone、Thiencarbazone-methyl、
Pyrimisulfan, Chlorflurazole, Tripropindan, Sulglycapin, first sulphur nitralin,
Cambendichlor, the pyrimidine acid of ring third, rodethanii, benoxacor, fenclorim, flurazole, fenchlorazole, the careless quinoline of solution, oxabetrinil,
MG191, cyometrinil, DKA_24, 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 this triazole sulphur humulone C crystal form and the one or more in the above-mentioned herbicide enumerated
Compounding dispenser has obvious collaboration and synergistic effect.
Preferably, other described active ingredients include but is not limited to：Isoproturon, propanil, bentazone, cyhalofop-butyl, fourth grass
Amine, dichloro quinolinic acid, mesotrione, pyraclonil, bromoxynil octanoate, clomazones, anilofos and one kind in azoles humulone or
It is a variety of.
The gross mass content of active ingredient is within 75%, within preferably 50% in the composition.
The formulation of the composition be suspending agent (SC), dispersible oil-suspending agent (OD), missible oil (EC), microemulsion (ME),
Granule (GR), suspension emulsion (SE) or water dispersible granules (WDG).
Described triazole sulphur humulone C crystal form or described weeding complex composition in rice terrace is prevented and kill off grassy weed and
Application on the broad leaved weed of part.
The C crystal form of the triazole sulphur humulone of the present invention, after tested, has good stability, 70 DEG C of high-temperature storage two months, and crystal formation is not
Change, purity is substantially undegraded, solubility increase connects by about one time in water, and C crystal form or the compounding with other active ingredients
Composition, has preferable preventive effect to rice terrace grassy weed and part broad leaved weed, and effect is substantially better than A crystal formations.
Brief description of the drawings
Fig. 1 is the XRPD collection of illustrative plates of the triazole sulphur humulone A crystal formations of embodiment 1 in the present invention.
Fig. 2 is the XRPD collection of illustrative plates of the triazole sulphur humulone C crystal form of embodiment 2 in the present invention.
Embodiment
The above to the present invention is described in further details by the following examples, but this should not be interpreted as to this
The scope for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair
Bright scope.
XRPD assay methods
INSTRUMENT MODEL：Bruker D8advance, target：Cu K α (40kV, 40mA), sample to detector distance：30cm,
Sweep limits：30-400(2 θ values), scanning step footpath：0.05s.
Embodiment 1
Triazole sulphur humulone active compound is prepared with reference to the B methods of CN 105503728.Again by 3000 grams of triazole sulphur humulone active compounds
It is placed in 10L flask, adds acetone 5L, is heated to 50 DEG C, stirring is completely dissolved to raw material, is cooled to 0 DEG C, stand 2 hours,
Filtering, 30 DEG C of normal pressure forced air dryings 5 hours, obtains the powder of triazole sulphur humulone A crystal formations.Or solvent volatilizees, it is complete to solvent
Volatilization is finished, and also can obtain the powder of triazole sulphur humulone A crystal formations.
Embodiment 2
2000 grams of triazole sulphur humulone A crystal formation active compounds are placed in 10L flask, dichloromethane 5L are added, heating stirring is extremely
Raw material is completely dissolved, and is progressively cooled to 10 DEG C or so, is stood 1 hour, is filtrated to get crystal, 110 DEG C of drying are 1 small afterwards
When, obtain C crystal form powder.
Embodiment 3
2000 grams of triazole sulphur humulone A crystal formation active compounds are placed in 10L flask, ethyl acetate 3L, ethanol 3L and water is added
1L, stirring is completely dissolved to raw material, is evaporated into solvent volatilization completely naturally afterwards and is finished, obtains the powder of triazole sulphur humulone C crystal form
End.
Physical and chemical stability is tested
Triazole sulphur humulone three kinds of powder of C crystal form that the triazole sulphur humulone A crystal formations and embodiment 2,3 that embodiment 1 is obtained are obtained
End, surveys A crystal formations and two kinds of C crystal form contents by HPLC and is 95.0%, afterwards, by these three powder be respectively placed in 25 DEG C,
Inside 40 DEG C, 55 DEG C and 70 DEG C baking ovens, place and carry out within 2 months heat storage experiment, crystal formation type and purity are tested afterwards, is as a result seen below
Table 1：
The study on the stability of the triazole sulphur humulone different crystal forms of table 1
As shown in Table 1, triazole sulphur humulone A crystal formations and C crystal form have good stability under different temperature conditionss, especially
It is under 70 DEG C of higher temperatures, and C crystal form still keeps good physical and chemical stability, and crystal formation does not change, purity detecting
Even slightly it is better than A crystal formations, with good application prospect.
Solubility test in water
Triazole sulphur humulone three kinds of powder of C crystal form that the triazole sulphur humulone A crystal formations and embodiment 2,3 that embodiment 1 is obtained are obtained
End, is dissolved into pure water, and 24h is shaken at 25 DEG C, is allowed to fully dissolving, is filtered afterwards with filter paper, filtrate is after 0.22 μm
Solubility in water is determined with HPLC after filter membrane, flowing phased soln, 2 are as a result see the table below：
Solubility test result in the water of the triazole sulphur humulone different crystal forms of table 2
| Sample | Solubility (mg/L) in pure water |
| The triazole sulphur humulone A crystal formations of embodiment 1 | 6.1 |
| The triazole sulphur humulone C crystal form of embodiment 2 | 10.4 |
| The triazole sulphur humulone C crystal form of embodiment 2 | 10.5 |
From the result of table 2, the C crystal form of triazole sulphur humulone compares A crystal formations, and solubility has obvious increase.
Embodiment 1 and the preparation processing of embodiment 2 and crop field effect experiment
The triazole sulphur humulone C crystal form that the triazole sulphur humulone A crystal formations and embodiment 2 that embodiment 1 is obtained are obtained, according to identical
Formula, be processed into following preparation, Ju Ti Pei Fang is as follows：
5% triazole sulphur humulone OD
The emulsifying agent phenethyl phenol polyethenoxy ether of 5%+5% emulsifying agent calcium dodecyl benzene sulfonate of triazole sulphur humulone+8%+
The thickener fumed silica+20% of+2.5% thickener organobentonite of 4% emulsifying agent castor oil polyoxyethylene ether+2%
Decentralized medium soybean oil+decentralized medium methyl oleate is supplied
16% triazole sulphur humulone cyhalofop-butyl OD
The emulsifying agent phenethyl of 6%+6% emulsifying agent calcium dodecyl benzene sulfonate of triazole sulphur+10% cyhalofop-butyl of humulone+7%
The thickener vapor phase method of+2.5% thickener organobentonite of the emulsifying agent of phenol polyethenoxy ether+5% castor oil polyoxyethylene ether+2%
Silica+20%100# solvent naphthas+decentralized medium methyl oleate is supplied
30% triazole sulphur humulone bentazone WP
The wetting agent dodecyl sulphate of 5%+10% dispersant sodium lignin sulfonate of triazole sulphur+25% bentazone of humulone+3%
The filler of sodium+10% white carbon+filler kaolin is supplied
10% triazole sulphur humulone SC
The wetting agent of+4% dispersant phenethyl phenol polyethenoxy ether phosphate triethanolamine salt of 10% triazole sulphur humulone+2%
The antifreezing agent glycerine of+0.5% thickener carboxymethyl cellulose of the thickener of neopelex+0.25% xanthans+5%+
0.1% defoamer organic silicone oil+water is supplied
25% triazole sulphur humulone butachlor ME
The emulsifying agent calcium dodecyl benzene sulfonate of 3%+5% ethanol of triazole sulphur humulone+20% cyclohexanone of+22% butachlor+6%
The emulsifying agent phenethyl phenol polyethenoxy ether formaldehyde resin condensation product of+12% emulsifying agent phenethyl phenol polyethenoxy ether+5%+water is mended
Foot
40% triazole sulphur humulone dichloro quinolinic acid WDG
The wetting agent dodecyl sulphate of 6%+10% dispersant polycarboxylate of triazole sulphur+34% dichloro quinolinic acid of humulone+3%
The filler of sodium+10% white carbon+filler kaolin is supplied
10% triazole sulphur humulone isoproturon OD
The emulsifying agent polyoxyethylene nonyl phenyl of 6%+6% emulsifying agent calcium dodecyl benzene sulfonate of triazole sulphur+4% isoproturon of humulone+7%
The thickener fumed silica of+2% thickener organobentonite of the emulsifying agent of vinethene+5% AEO+2%+
Decentralized medium methyl oleate is supplied
4% triazole sulphur humulone amicarbazone GR
The dispersant napsylate of 3%+2% wetting agent lauryl sodium sulfate of triazole sulphur+1% amicarbazone of humulone+4%-
Formaldehyde condensation products+filler diatomite is supplied
Crop field effect test：After the leaf of paddy rice 3, barnyard grass (Changsha collection seed), moleplant seed (Hubei public security collection kind
Son) 3-4 leaf phases, hand sprayer, 30 kilograms/667m of the amount of being watered2, using cauline leaf spraying even spraying, 50 squares of plot area
Rice, it is as follows that often processing is repeated 4 times after dispenser average strain preventive effect (range estimation) effect of investigation in 45 days, is shown in Table 3.
The triazole sulphur humulone preparation of the different crystal forms of table 3 prevents and kill off direct sowing of rice field weed effect (%) --- dispenser 45d rear defences
Effect
Note：Test plot barnyard grass and show dichloro quinolinic acid certain resistance, 225g/hm2Dichloro quinolinic acid is anti-to barnyard grass
Effect<10%.
Embodiment 1 and the preparation processing of embodiment 3 and crop field effect experiment
The triazole sulphur humulone C crystal form that the triazole sulphur humulone A crystal formations and embodiment 3 that embodiment 1 is obtained are obtained, according to identical
Formula, be processed into following preparation, Ju Ti Pei Fang is as follows：
36% triazole sulphur humulone pretilachlor EC
The emulsifying agent 12 of 6%+10% cyclohexanone+10%N- methyl pyrrolidones of+30% pretilachlor of triazole sulphur humulone+6%
The emulsifying agent phenethyl phenol polyethenoxy ether formaldehyde resin of the emulsifying agent of alkyl benzene calcium sulfonate+12% NPE+2% contracts
Compound+solvent 100# solvent naphthas are supplied
4% triazole sulphur humulone pyraclonil OD
The emulsifying agent nonyl phenol of 3%+6% emulsifying agent calcium dodecyl benzene sulfonate of triazole sulphur+1% pyraclonil of humulone+7% gathers
The thickener vapor phase method titanium dioxide of+2% thickener organobentonite of+5% emulsifying agent castor oil polyoxyethylene ether of oxygen vinethene+2%
Silicon+decentralized medium methyl oleate is supplied
15% triazole sulphur humulone bromoxynil octanoate ME
The emulsifying agent detergent alkylate sulphur of 5%+5% ethanol of triazole sulphur humulone+20% cyclohexanone of+10% bromoxynil octanoate+6%
The sour emulsifying agent phenethyl phenol polyethenoxy ether formaldehyde resin condensation product of the emulsifying agent of calcium+12% phenethyl phenol polyethenoxy ether+5%+
Water is supplied
7% triazole sulphur humulone chlorine fluorine pyridine ester EC
The emulsifying agent ten of+15% cyclohexanone+10%N- methyl pyrrolidones of+1% chlorine fluorine pyridine ester of 6% triazole sulphur humulone+6%
The emulsifying agent phenethyl phenol polyethenoxy ether formaldehyde resin of+10% emulsifying agent NPE of dialkyl benzene sulfonic acids calcium+2%
Condensation product+solvent 100# solvent naphthas are supplied
6% triazole sulphur humulone mesotrione SC
The dispersant phenethyl phenol polyethenoxy ether phosphate triethanolamine salt of 5%+1% mesotrione of triazole sulphur humulone+4%
The antifreezing agent third of+0.5% thickener aluminium-magnesium silicate of+0.25% thickener xanthans of+2% wetting agent neopelex+5%
The defoamer of triol+0.1% organic silicone oil+water is supplied
10% triazole sulphur humulone clomazone SE
The dispersant phenethyl phenol polyethenoxy ether phosphate triethanolamine salt of 5%+5% clomazone of triazole sulphur humulone+4%
The antifreezing agent third of+0.5% thickener aluminium-magnesium silicate of+0.2% thickener xanthans of+6% emulsifying agent NPE+5%
The defoamer of triol+0.1% organic silicone oil+water is supplied
16% triazole sulphur humulone anilofos OD
The emulsifying agent phenethyl phenol of 6%+6% emulsifying agent calcium dodecyl benzene sulfonate of triazole sulphur+10% anilofos of humulone+7%
The thickener vapor phase method two of+2.6% thickener organobentonite of the emulsifying agent of APEO+5% AEO+2%
Silica+decentralized medium methyl oleate is supplied
6% triazole sulphur humulone azoles humulone OD
The emulsifying agent phenethyl phenol of 5%+6% emulsifying agent calcium dodecyl benzene sulfonate of triazole sulphur+1% azoles humulone of humulone+7% is gathered
The thickener vapor phase method titanium dioxide of+3% thickener organobentonite of+5% emulsifying agent AEO of oxygen vinethene+2%
Silicon+decentralized medium methyl oleate is supplied
Crop field effect test：After the leaf of paddy rice 3, barnyard grass (Changsha collection seed), moleplant seed (Hubei public security collection kind
Son) 3-4 leaf phases, hand sprayer, 30 kilograms/667m of the amount of being watered2, using cauline leaf spraying even spraying, 50 squares of plot area
Rice, it is as follows that often processing is repeated 4 times after dispenser average strain preventive effect (range estimation) effect of investigation in 45 days, is shown in Table 4.
The triazole sulphur humulone preparation of the different crystal forms of table 4 prevents and kill off direct sowing of rice field weed effect (%) --- dispenser 45d rear defences
Effect
Note：Test plot barnyard grass and show dichloro quinolinic acid certain resistance, 225g/hm2Dichloro quinolinic acid is anti-to barnyard grass
Effect<10%.
Embodiment above describes general principle, principal character and the advantage of the present invention, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, the original for simply illustrating the present invention described in above-described embodiment and specification
Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, and these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (10)
1. a kind of triazole sulphur humulone C crystal form, it is characterised in that：X-ray powder diffraction spectrogram the θ of the angle of diffraction 2 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、
23.8th, 24.8,25.5,26.1,26.8,27.8,28.9,30.1,31.3,33.2,34.3, there is characteristic peak at 36.0 degree, its
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
It is substantially as shown 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：Triazole sulphur humulone is dissolved in dichloromethane, 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 afterwards.
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 heating for dissolving evaporates into solvent volatilization completely, obtains C crystal form naturally in ethyl acetate, the mixed solvent of second alcohol and water.
6. a kind of weeding complex composition, it is characterised in that：It is brilliant including triazole sulphur humulone C described in claim 1-3 any one
Type and auxiliary agent, it is preferable that the auxiliary agent is selected from solvent, solid diluent, emulsifying agent, wetting agent, dispersant, antifreezing agent, froth breaking
One or more in agent and thickener.
7. weeding complex composition according to claim 6, it is characterised in that the composition also include other effectively into
Point, it is preferable that other described active ingredients be selected from isoproturon, propanil, bentazone, cyhalofop-butyl, butachlor, dichloro quinolinic acid,
One or more in mesotrione, pyraclonil, bromoxynil octanoate, clomazones, anilofos and azoles humulone.
8. weeding complex composition according to claim 7, it is characterised in that total matter of active ingredient in the composition
It is within 75%, within preferably 50% to measure content.
9. the weeding complex composition according to claim 6-8 any one, it is characterised in that：The formulation of the composition
For suspending agent, dispersible oil-suspending agent, missible oil, microemulsion, granule, suspension emulsion or water dispersible granules.
10. as described in the triazole sulphur humulone C crystal form or claim 6-9 any one as described in claim 1-3 any one
Application of the weeding complex composition in rice terrace is prevented and kill off on grassy weed and part broad leaved weed.
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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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| CN201710257455.5A CN106946783B (en) | 2017-04-19 | 2017-04-19 | Triazole sulphur humulone C crystal form and its preparation method and application |
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| CN107517978A (en) * | 2017-08-28 | 2017-12-29 | 青岛清原化合物有限公司 | A kind of ternary weeding composition and its application of the humulone of sulphur containing triazole and anilofos |
| CN107836452A (en) * | 2017-11-09 | 2018-03-27 | 青岛清原化合物有限公司 | A kind of Herbicidal combinations of humulone of sulphur containing triazole and its application |
| CN108558761A (en) * | 2018-05-21 | 2018-09-21 | 青岛清原化合物有限公司 | A kind of triazole sulphur humulone-salicylic acid eutectic and its preparation method and application |
| 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 |
| WO2019056537A1 (en) * | 2017-09-19 | 2019-03-28 | 青岛清原抗性杂草防治有限公司 | Herbicidal composition containing triazole sulcotrione and application thereof |
| CN112816569A (en) * | 2020-12-23 | 2021-05-18 | 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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| 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 |
| WO2019041582A1 (en) * | 2017-08-28 | 2019-03-07 | 青岛清原化合物有限公司 | Ternary weeding composition containing triazole sulcotrione and anilofos and application thereof |
| CN107517978A (en) * | 2017-08-28 | 2017-12-29 | 青岛清原化合物有限公司 | A kind of ternary weeding composition and its application of the humulone of sulphur containing triazole and anilofos |
| CN113016810B (en) * | 2017-09-19 | 2021-11-16 | 青岛清原抗性杂草防治有限公司 | Weeding composition containing triazasulam 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 |
| WO2019056537A1 (en) * | 2017-09-19 | 2019-03-28 | 青岛清原抗性杂草防治有限公司 | Herbicidal composition containing triazole sulcotrione and application thereof |
| CN113016810A (en) * | 2017-09-19 | 2021-06-25 | 青岛清原抗性杂草防治有限公司 | Weeding composition containing triazasulam and application thereof |
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| CN112998022A (en) * | 2017-11-09 | 2021-06-22 | 青岛清原化合物有限公司 | 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 |
| CN107836452A (en) * | 2017-11-09 | 2018-03-27 | 青岛清原化合物有限公司 | A kind of Herbicidal combinations of humulone of sulphur containing triazole and its application |
| WO2019223186A1 (en) * | 2018-05-21 | 2019-11-28 | 青岛清原化合物有限公司 | Triazole sulcotrione-salicylic acid co-crystal, preparation method thereof, and application thereof |
| CN108558761A (en) * | 2018-05-21 | 2018-09-21 | 青岛清原化合物有限公司 | A kind of triazole sulphur humulone-salicylic acid eutectic and its preparation method and application |
| CN112816569A (en) * | 2020-12-23 | 2021-05-18 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| PH12019502588A1 (en) | 2020-09-28 |
| CN106946783B (en) | 2019-04-19 |
| WO2018192046A1 (en) | 2018-10-25 |
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