CN106977458B - Amorphous state triazole sulphur humulone and its preparation method and application - Google Patents

Amorphous state triazole sulphur humulone and its preparation method and application Download PDF

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CN106977458B
CN106977458B CN201710258005.8A CN201710258005A CN106977458B CN 106977458 B CN106977458 B CN 106977458B CN 201710258005 A CN201710258005 A CN 201710258005A CN 106977458 B CN106977458 B CN 106977458B
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triazole sulphur
amorphous state
sulphur humulone
humulone
agent
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CN106977458A (en
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赵德
陈志祥
林贝贝
张兆真
彭学岗
张景远
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Qingdao Qing Yuan Compound Co Ltd
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Qingdao Qing Yuan Compound Co Ltd
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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
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention belongs to herbicide crystallization processes technical fields, and in particular to arrive a kind of amorphous state triazole sulphur humulone and its preparation method and application.A kind of amorphous state triazole sulphur humulone, through X-ray powder diffraction detection be in the form of unformed existing for, there is no sharp diffraction maximum in X-ray powder diffraction collection, it is preferable that its X-ray powder diffraction pattern basically as in Figure 2 shown in.Amorphous state triazole sulphur humulone of the invention compares A crystal form, physical and chemical stability is good, crystal transfer does not occur within storing two months under 70 DEG C of high temperature, purity does not also reduce substantially, solubility doubles in water simultaneously, the amorphous state of triazole sulphur humulone and complex composition with other effective components, have extraordinary preventive effect to paddy field gramineae weed and part broadleaf weeds, have a good application prospect.

Description

Amorphous state triazole sulphur humulone and its preparation method and application
Technical field
The invention belongs to herbicide crystallization processes technical fields, and in particular to a kind of amorphous state triazole sulphur humulone 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 105503728B。
Amorphous state is that there are a kind of forms of polymorphism, and a kind of special crystal form state for substance.For tool There are the solid drugs of polymorphism, amorphous state is one of its a variety of crystal form state, the various reasons of amorphous state drug Change property and drug effect is usually different from general crystal form drug.Therefore, in the polymorphic research of solid drugs, to amorphous state The further investigated of substance has important scientific meaning.But it since amorphous state is thermodynamic phase system, is easy to occur brilliant Type transformation, this is also the main obstacle for perplexing amorphous state drug.
Since triazole sulphur humulone is newly developed drug, without the report of its crystal form in current various documents and patent Road, and 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 amorphous state triazole sulphur humulone and its preparation method and application.It is described Amorphous state triazole sulphur humulone does not have sharp diffraction maximum in X-ray powder diffraction collection, and stability is good, solubility in water Height, it is good to control of weeds effect, it can be used for paddy field seedling Weed Control Effect after Improvement.
Technical solution of the present invention, triazole sulphur humulone is referring to the method preparation in CN 105503728B.It is wherein specific open , 2.1g (0.005mol) compound a is weighed in 100mL single-necked flask, and 15mL acetonitrile and 1.0g (0.010mol) three is added Ethamine 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 second Nitrile 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 knot 100mL water and 100mL ethyl acetate is added in Shu Hou, extracts branch vibration layer, after organic layer 100mL saturated common salt water washing 2 times It is dried over anhydrous sodium sulfate, revolving removes organic solvent, obtains yellow-brown solid, it is light yellow to obtain 1.5g after column Chromatographic purification 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 or water etc., heating is stirred It mixes to being completely dissolved, cooling stands still for crystals or slowly volatilizees, and it is dry, obtain A crystal form.
On the basis of A crystal form, and have studied the amorphous state of triazole sulphur humulone.
A kind of amorphous state triazole sulphur humulone, through X-ray powder diffraction detection be in the form of unformed existing for.
There is no sharp diffraction maximum in its X-ray powder diffraction collection, it is preferable that its X-ray powder diffraction pattern is basic It is upper as shown in Figure 2.
The preparation method of the amorphous state triazole sulphur humulone, comprising the following steps: triazole sulphur humulone stirring and dissolving exists In methylene chloride, in 40-60 DEG C of decompression rotary evaporation of solvent, preferable temperature is 45-50 DEG C, after through mechanical lapping, obtain nothing Shape state.
A kind of weeding complex composition, including the amorphous state triazole sulphur humulone effective component and auxiliary agent.
The auxiliary agent is selected from solvent, solid diluent, emulsifier, wetting agent, dispersing agent, antifreezing agent, defoaming agent and thickening One of agent is a variety of.
Selected solvent includes but is not limited to polar solvent class: water, N, N- dimethylformamide, dimethyl sulfoxide, N- alkylated pyrazole Pyrrolidone, methanol, ethyl alcohol, ethylene glycol, isopropanol, butyl glycol ether, propylene glycol monomethyl ether etc.；Aromatic solvent naphtha series: toluene, two Toluene, No. 100 solvent naphthas, No. 150 solvent naphthas, No. 180 solvent naphthas, No. 200 solvent naphthas etc.；Plant oil: castor oil, linseed Oil, sesame oil, corn oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil and their corresponding methylated vegetable oils etc.；Ketone Class: cyclopentanone, cyclohexanone, cyclooctanone, 2-HEPTANONE, isophorone and 4- hydroxy-4-methyl-2-pentanone etc.；Acetate esters: acetic acid Methyl esters, ethyl acetate, propyl acetate, sec-butyl acetate, isoamyl acetate, hexyl acetate, heptyl acetate and octyl acetate etc.；Its Remaining class is such as: decyl amide, cyclohexanol, decyl alcohol, benzyl alcohol and tetrahydrofurfuryl alcohol.
Selected solid diluent can be water-soluble or water-insoluble.Water-soluble solid diluent includes but is not limited to: Salt, for example, alkali metal phosphate (sodium dihydrogen phosphate), alkali earth metal phosphate, sodium, potassium, the sulfate of magnesium and zinc, sodium chloride and Potassium chloride, sodium acetate, sodium carbonate and sodium benzoate and sugar and sugar derivatives, such as D-sorbite, lactose, sucrose and sweet dew Alcohol, cornstarch etc..The example of water-insoluble solid diluent includes but is not limited to: clay, calcium carbonate, diatomite, white carbon black, Calcium silicates, bentonite, aluminium-magnesium silicate and kaolin etc..
Wetting agent includes but is not limited to: alkyl sulfo succinate, laruate, alkyl sulfate, phosphate, ethyoxyl Fluorinated alohol, the silicone of ethoxylation, alkyl phenol ethoxylate, benzene sulfonate, alkyl-substituted benzene sulfonate, alkyl-alpha-alkene Sulfonated hydrocarbon, naphthalene sulfonate, alkyl-substituted naphthalene sulfonic acids alkali metal salt, naphthalene sulfonic acids alkali metal salt and alkyl-substituted napsylate With the ethoxylate of the condensation product of formaldehyde, alcohol.
Dispersing agent includes but is not limited to: sodium salt, calcium salt and the ammonium salt of lignin sulfonic acid；The sodium salt of copolymer-maleic anhydride and Ammonium salt；The sodium salt of the phenolsulfonic acid of condensation；Napsylate-formaldehyde condensation products；Phosphoric acid ester dispersing agent, polycarboxylic acid salt's dispersing agent Deng.
Thickener includes but is not limited to: guar gum, pectin, xanthan gum, alginates, methylcellulose, hydroxyethyl cellulose, Hydroxypropyl cellulose and carboxymethyl cellulose.The thickener of synthesis includes the derivative of aforesaid kind, further includes polyvinyl alcohol, poly- Acrylamide, polyvinylpyrrolidone, various polyethers and their copolymer and polyacrylic acid and their salt.
Other formulation ingredients, such as dyestuff, defoaming agent, desiccant etc. can be used in the present invention.These ingredients are ability Field technique personnel are known.
The composition further includes other effective components.
The suitable effective component that can be mixed with amorphous state triazole sulphur humulone of the invention is, such as " world pesticide New varieties technologies is complete works of ", Scientia Agricultura Sinica technology publishing house, 2010.9 and document incorporated herein in known substance.Example Such as various substances mentioned below (remarks: the title of compound, or for according to the generic name of International Organization for standardization (ISO) Claim, or be chemical name, have code name when appropriate): Acetochlor, butachlor, alachlor, propisochlor, isopropyl methoxalamine, The left-handed naphthalene propionyl grass amine of S-metolachlor, pretilachlor, propachlor, kecaoan, naphthalene propionyl grass amine, R-, propanil, benzene thiophene acyl grass Amine, diphenamide, diflufenican, N-alpha-chloroacetyl-N-isopropyl-o ethylaniline, beflubutamid, bromobutide, dimethenamid, efficient diformazan thiophene grass Amine, ethobenzanid, flufenacet, thenylchlor, metazachlor, isoxaben, flampropMmethyl, efficient wheat straw volt third Ester, allidochlor, pethoxamid, chloranocryl, ring pretilachlor, mefluidide, monalide, delachlor, prynachlor, Terbuchlor, xylachlor, dimethachlor, amine of taking to the greenwood, front three ring grass amine, clomeprop, propyzamide, valeryl benzene grass Amine blocks careless amine, suffer, tricyclic match careless amine, butenachlor, tebutam, benzyl grass amine, quinone duckweed amine, dichlofluanid, naproanilide, second Acyl alachlor, quinclorac, fenacet, pyrrole cyanogen grass amine, benzene grass more grams of dead, chlorothiamid, chlorine phthalimides, fourth amidine amine, fluorine metazachlor, green bristlegrass Go saliva, Simanex, prometryn, cyanatryn, symetryne, ametryn, propazine, dipropetryn, flur, terbutryn, Garagard, three Piperazine benfluralin, cyprazine, proglinazine, trietazine, prometon, Gesadrual, nitrine be net, desmetryn, dimethametryn, cyclopropyl blueness saliva, Green bristlegrass of going out saliva, another Ding Jin, Zhong Dingtong, Te Dingtong, methoxy third be net, cyanatryn, ipazine, chlorazine, atraton, weed eradication are logical, Radix Glycyrrhizae Saliva, cyanuric acid, Indaziflam, green sulphur is grand, metsulfuron-methyl, bensulfuron-methyl, chlorimuron, tribenuron-methyl, thifensulfuron methyl, the phonetic Huang of pyrrole Grand, mesosulfuron, iodosulfuron-methyl-sodium, formamido group Sulfometuron Methyl, cinosulfuron, triasulfuron, sulfometuronmethyl, the phonetic sulphur of cigarette Grand, ethametsulfuron, amidosulfuron, ethoxysulfuron, cypromisulfuron, rimsulfuron, azimsulfuron, pyridine ethyl methyl, list are phonetic Sulphur is grand, single phonetic sulphur ester, flucarbazone, flupyrsulfuron-methyl-sodium, fluorine pyrazosulfuron, oxasulfuron, imazosulfuron, primisulfuronmethyl, Procarbazone, prosulfuron, Sulfosulfuron, trifloxysulfuron, triflusulfuronmethyl, tritosulfuron, metsulfuron-methyl sodium salt, fluorine pyrrole sulphur Grand, Sulfonylurea, orthosulfamuron, Propyrisulfuron (proxazuron-methyl), piperazine pyrazosulfuron, acifluorfen, fluorine Sulfanilamide (SN) grass ether, lactofen, fluoroglycofen-ethyl, Oxyfluorfen, Mo 9 granular, aclonifen, ethoxyfen-ethyl, first carboxylic weeding Ether, fluoroform grass ether, chlomethoxyfen, fluorodifen, fluorination nitrofen, fluorine furan grass ether, nitrofen, first grass ether, diformazan grass Ether, fluorine lactazone grass ether, fluofazone ester, Halosafen, chlortoluron, isoproturon, linuron, diuron, Sha flutter grand, fluometuron, benzene Thiophene is grand, methabenzthiazuron, cumyluron, ethidimuron, isouron, terbufos benzthiazuron, buturon, bromax, methyldymron, acyl grass Grand, methoxy daimuron, metobromuron, metoxuron, afesin, telvar, Tupersan, fenuron, fluorine sulphur is grand, neburea, chloroxifenidium, It is herban, isonoruron, Alipur-O, thiazfluron, tebuthiuron, difenoxuron, different to fluon, methylamine methabenz thiazuron, Long Caote, front three Urea, dimefuron, Monisouron, Anisuron, Methiuron, Chloreturon, four fluon, phenmedipham, phenmedipham-second The careless spirit of ester, desmedipham, sulphur, terbucarb, oatax, Chem hoe, chlorpropham, benzyl dichloride grass ester, swep, chlorbufam, Carboxazole, Chlorprocarb, Fenasulam, BCPC, CPPC, Carbasulam, Ding Caote, benthiocarb, vernolate, Molinate, tri-allate, dimepiperate, esprocarb, pyributicarb, cycloate, Avadex, bactericide, second sulphur careless spy, orbencarb, gram grass Suddenly, prosulfocarb, tiocarbazil, sulfuric acid, dimexan, Isopolinate, Methiobencarb, 2,4- d butyl ester, 2 first, 4 chlorine Sodium, the different monooctyl ester of 2,4- drop, the different monooctyl ester of 2 first, 4 chlorine, 2,4- drop sodium salt, 2,4- drop dimethylamine salt, 2 first, 4 chloroethene thioesters, 2 first, 4 chlorine, 2, 4- drop propionic acid, high 2,4- drop propionate, 2,4- Embutox, Vi par, Vi par salt, Thistrol, 2,4,5- Tears, 2,4,5- tears propionic acid, 2,4,5- tears butyric acid, 2 first, 4 chloramines salt, dicamba, erbon, Fenac, match pine, trichlorobenzoic acid, ammonia Dichloro benzoic acid, methoxy trichlorobenzoic acid, diclofop-methyl, fluazifop, efficient fluazifop, haloxyfop-P-methyl, efficient pyrrole fluorine chlorine standing grain Spirit, quizalofop-ethyl, Quizalotop-ethyl, fenoxaprop-P, fenoxapropPethyl, propaquizafop, cyhalofop-butyl, metamifop, clodinafop-propargyl, Diclofop-methyl thiazole, chloroazifoppropynyl, the spirit of penta standing grain of hydroxyl, trifluoro dogstail oxime, isoxapyrifop, paraquat, diquat dibromide, oryzalin, second butylene fluorine Spirit, isopropalin, nitralin, profluralin, prodiamine, benfluralin, fluchloraline, the spirit of amino second fluorine, dipropalin, Chloroethene dipropalin, Methalpropalin, the third nitre phenol, glyphosate, Sha barnyard grass phosphine, glufosinate-ammonium, solid herbicide phosphorus, amiprophos-methyl, grass Phosphine sulfide, piperazine grass phosphine, bialaphos, bensulide, butamifos, creeping weed phosphorus, cut down ridge phosphorus, double first amiprophos, dow crabgrass killer, imazapyr, Imazethapyr, imazaquin, imazamox, imazamox ammonium salt, AC 263222, miaow grass ester, chlorine fluorine pyrrole oxygen second Acid, the different monooctyl ester of fluroxypyr, clopyralid, picloram, trichlopyr, dithiopyr, halogen grass be fixed, trichlorine Pyridol, thiazopyr, fluridone, chlorine Fampridine acid, diflufenzopyr, triclopyr butoxyethyl ester, Cliodinate, Sethoxydim, clethodim, cycloxydim, alloxydimsodium, clefoxidim, butroxydim, tralkoxydim, tepraloxydim, Buthidazole, piperazine Humulone, hexazinone, metamitron, ethiozin, Ametridione, Amibuzin, Brominal, bromoxynil octanoate, decoyl iodobenzene Nitrile, ioxynil, dichlobenil, diphenatril, pyraclonil, chloroxynil, Iodobonil, weeding bromine, Flumetsulam, double fluorine Sulphur grass amine, penoxsuam, metosulam, cloransulammethyl, diclosulam, pyroxsulam, fluorine straw colour, bispyribac-sodium, pyrimidine Oxime grass ether, pyriftalid, KIH 6127, pyrithiobacsodium, benzobicylon, mesotrione, sulphur humulone, Tembotrione, Tefuryltrione, Bicyclopyrone, Ketodpiradox, isoxaflutole, isoxachlorotole, Fenoxasulfone, Methiozolin, fluazolate, pyraflufen-ethyl, pyrazolate, difenzoquat, pyrazoxyfen, benzofenap, pyrrole chlorine grass amine, Pyrasulfotole, topramezone, Pyroxasulfone, cafenstrole, flupoxam, Amrol, amicarbazone, ethofumesate Ketone, profluazone, sulfentrazone, Bencarbazone, benzfendizone, butafenacil, bromacil, isoprocil, lenacil, Terbacil, Flupropacil, cinidon-ethyl, Flumiclorac pentyl, flumioxazin, alkynes grass amine, phthalein benzyl oxide, Flumezin, pentachloro- Phenol (sodium), dinoseb, dinoterb, dinoterb acetate, dinosam, Chemox PE, chlorine nitre phenol, medinoterb acetate, Di Lete, oxadiargyl, evil Humulone, pentoxazone, profluazol, fluthiacet, fentrazamide, flufenpyrethyl, pyrazon, brompyrazon, diformazan Up to careless volt, Kusakira, grass pyridazone, grass rattle away pine, norflurazon, Pyridafol, dichloro quinolinic acid, quinmerac, Bentazon, rattle away Careless spy, oxaziclomefone, benazolin, clomazone, cinmethylin, iso-propyl-ester nitrofen, propyl-ester nitorfen, indanofan, sodium chlorate, cogongrass Withered, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoro propionic acid, grass are fast, herbage is fast, bromofenoxim, triazole sulphur, kill azoles, furan Humulone, benfuresate, ethofumesate, phonetic careless amine, chlorine phthalandione, fluorochloridone, barnyard grass, methacrylaldehyde, bentranil, tridiphane, oat Ester, thiadiazoles grass amine, phenisopham, hydroxyl humulone, ammonia chloranil, dioxybenzone, benzene flumetsulam, chlorine acyl grass phosphine, chloropon, Alorac、Diethamquat、Etnipromid、Iprymidam、Ipfencarbazone、Thiencarbazone-methyl、 Pyrimisulfan, Chlorflurazole, Tripropindan, Sulglycapin, first sulphur nitralin, Cambendichlor, cyclopropyl pyrimidine acid, rodethanii, benoxacor, fenclorim, flurazole, fenchlorazole, solve careless quinoline, oxabetrinil, Oxalane, cyometrinil, desorpenic, mefenpyrdiethyl, furilazole, fluxofenim, isoxadifen, allyl dichloride amine, fluorine Chloropyridine ester, DOW848, UBH-509, D489, LS 82-556, KPP-300, NC-324, NC-330, KH-218, DPX- N8189、SC-0744、DOWCO535、DK-8910、V-53482、PP-600、MBH-001、KIH-9201、ET-751、KIH- 6127 and KIH-2023.And experiments verify that one of this amorphous state triazole sulphur humulone and the above-mentioned herbicide enumerated or more Kind 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 Amine, dichloro quinolinic acid, mesotrione, pyraclonil, bromoxynil octanoate, clomazone, anilofos and azoles humulone.
The gross mass content of effective component is within 75%, within preferably 50% in the composition.
The dosage form of the composition is suspending agent (SC), dispersible oil-suspending agent (OD), missible oil (EC), microemulsion (ME), Granule (GR), suspoemulsion (SE) or water dispersible granules (WDG).
The amorphous state triazole sulphur humulone or weeding complex composition grass family in preventing and kill off paddy field is miscellaneous Application on grass and part broadleaf weeds.
Amorphous state triazole sulphur humulone of the invention compares A crystal form, and physical and chemical stability is good, stores under 70 DEG C of high temperature Crystal transfer does not occur within two months, purity does not also reduce substantially, while solubility doubles in water, triazole sulphur humulone Amorphous state and complex composition with other effective components, have paddy field gramineae weed and part broadleaf weeds non- Often good preventive effect, has a good application prospect.
Detailed description of the invention
Fig. 1 is the XRPD map of the 1 triazole sulphur humulone A crystal form of embodiment in the present invention.
Fig. 2 is the XRPD map of the 2 amorphous state triazole sulphur humulone crystal form of embodiment in the present invention.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair Bright range.
XRPD measuring method
Instrument model: Bruker D8advance, target: Cu K α (40kV, 40mA), sample is to detector distance: 30cm, Scanning range: 3 ° -40 ° (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
3000 grams of triazole sulphur humulone A crystal form raw medicines are placed in the flask of 10L, methylene chloride 7L, stirring to raw material is added It is completely dissolved, is heated to 50 DEG C, rotate solvent, carry out mechanical lapping after evaporating, amorphous state triazole sulphur grass can be obtained The powder of ketone.
Physical and chemical stability experiment
By the triazole sulphur humulone A crystal form that embodiment 1 obtains and amorphous state triazole sulphur two kinds of powder of humulone that embodiment 2 obtains End surveys A crystal form by HPLC and amorphous state content is 95.5%, later, both powder 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 triazole sulphur humulone different crystal forms of table
As shown in Table 1, triazole sulphur humulone A crystal form and amorphous state have good stabilization under the conditions of different temperature Property, especially under 70 DEG C of higher temperatures, amorphous state still keeps good physical and chemical stability, and crystal form does not change, Purity detecting is even slightly better than A crystal form, is of great significance.
Solubility test in water
By the triazole sulphur humulone A crystal form that embodiment 1 obtains and amorphous state triazole sulphur two kinds of powder of humulone that embodiment 2 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:
By 2 result of table, as it can be seen that the amorphous state of triazole sulphur humulone compares, A crystal form, solubility have apparent increase.
Solubility test result in the water of 2 triazole sulphur humulone different crystal forms of table
Sample Solubility (mg/L) in pure water
2 amorphous state triazole sulphur humulone of embodiment 13.6
1 triazole sulphur humulone A crystal form of embodiment 6.2
Preparation processing and crop field effect experiment
It, will be by by the triazole sulphur humulone A crystal form that embodiment 1 obtains and the amorphous state triazole sulphur humulone that embodiment 2 obtains According to corresponding preparation as following formula, is processed into, 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
12% triazole sulphur humulone cyhalofop-butyl OD
+ 7% emulsifier benzene second of 2.5%+6% emulsifier calcium dodecyl benzene sulfonate of triazole sulphur+9.5% cyhalofop-butyl of humulone + 2% thickener gas phase of+2.5% thickener organobentonite of+5% emulsifier castor oil polyoxyethylene ether of base phenol polyethenoxy ether Method silica+20%200# solvent naphtha+decentralized medium methyl oleate is supplied
8% triazole sulphur humulone SC
The thickening of+2% wetting agent fatty alcohol polyoxyethylene ether+0.25% of 8%+4% dispersant polycarboxylate of triazole sulphur humulone + 0.1% defoaming agent organic silicone oil of+5% antifreezing agent glycerine of+0.5% thickener carboxymethyl cellulose of agent xanthan gum+water is supplied
18% triazole sulphur humulone dichloro quinolinic acid WP
+ 3% wetting agent dodecyl of 4%+10% dispersing agent sodium lignin sulfonate of triazole sulphur+14% dichloro quinolinic acid of humulone + 10% filler white carbon black of sodium sulphate+filler kaolin is supplied
12% triazole sulphur humulone isoproturon OD
+ 7% emulsifier phenethyl phenol of 4%+6% emulsifier calcium dodecyl benzene sulfonate of triazole sulphur+8% isoproturon 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+10%200# solvent naphtha+decentralized medium methyl oleate is supplied
28% triazole sulphur humulone propanil OD
+ 7% emulsifier phenethyl phenol of 3%+6% emulsifier calcium dodecyl benzene sulfonate of triazole sulphur+25% propanil 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 + 20% solvent decyl amide of silicon+decentralized medium methyl oleate is supplied
4% triazole sulphur humulone amicarbazone OD
+ 7% emulsifier benzene second of 2.5%+6% emulsifier calcium dodecyl benzene sulfonate of triazole sulphur+1.5% amicarbazone of humulone + 2% thickener vapor phase method of+3% thickener organobentonite of+5% emulsifier fatty alcohol polyoxyethylene ether of base phenol polyethenoxy ether + 10% decentralized medium rapeseed oil of silica+decentralized medium methyl oleate is supplied
34% triazole sulphur humulone pretilachlor ME
+ 6% emulsifier dodecyl benzene sulfonic acid of 5%+10% ethyl alcohol of triazole sulphur humulone+20% cyclohexanone of+29% pretilachlor + 5% emulsifier phenethyl phenol polyethenoxy ether formaldehyde resin condensation product of+12% emulsifier phenethyl phenol polyethenoxy ether of calcium+water It supplies
30% triazole sulphur humulone butachlor EC
+ 6% emulsifier 12 of 3%+20% cyclohexanone+10%N- methyl pyrrolidone of+27% butachlor of triazole sulphur humulone The contracting of+5% 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
6% triazole sulphur humulone pyraclonil SC
4.5%+4% dispersing agent phenethyl phenol polyethenoxy ether phosphate of+1.5% pyraclonil of triazole sulphur humulone, three ethyl alcohol + 0.5% thickener carboxymethyl cellulose+5% of+0.25% thickener xanthan gum of+2% wetting agent neopelex of amine salt + 0.1% defoaming agent organic silicone oil of antifreezing agent glycerine+water 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
6% triazole sulphur humulone chlorine fluorine pyridine ester EC
+ 6% emulsifier ten of+10% cyclohexanone+10%N- methyl pyrrolidone of+1% fluorine chloropyridine ester of 5% triazole sulphur humulone + 2% emulsifier phenethyl phenol polyethenoxy ether formaldehyde resin of+12% emulsifier nonylphenol polyoxyethylene ether of dialkyl benzene sulfonic acids calcium Condensation product+solvent 100# solvent naphtha is supplied
30% triazole sulphur humulone bentazone WDG
+ 3% wetting agent dodecyl sulphate of 3%+10% dispersing agent sodium lignin sulfonate of triazole sulphur+27% bentazone of humulone + 10% filler white carbon black of sodium+filler kaolin is supplied
7% triazole sulphur humulone mesotrione GR
+ 4% dispersing agent napsylate of 5%+2% wetting agent lauryl sodium sulfate of triazole sulphur+2% mesotrione of humulone- Formaldehyde condensation products+filler diatomite is supplied
20% triazole sulphur humulone anilofos OD
+ 7% emulsifier phenethyl phenol of 5%+6% emulsifier calcium dodecyl benzene sulfonate of triazole sulphur+15% anilofos of humulone + 2% thickener vapor phase method dioxy of+2% thickener organobentonite of+5% emulsifier fatty alcohol polyoxyethylene ether of polyoxyethylene ether SiClx+decentralized medium methyl oleate is supplied
9% triazole sulphur humulone clomazone SE
+ 4% dispersing agent phenethyl phenol polyethenoxy ether phosphate triethanolamine salt of 5%+4% 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
6% triazole sulphur humulone azoles humulone OD
+ 7% emulsifier phenethyl of 4.5%+6% emulsifier calcium dodecyl benzene sulfonate of triazole sulphur+1.5% azoles humulone of humulone + 2% thickener vapor phase method two of+3% thickener organobentonite of+5% emulsifier fatty alcohol polyoxyethylene ether of phenol polyethenoxy ether Silica+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 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: barnyard grass has certain resistance, 105g/hm to dichloro quinolinic acid in this test2Dichloro quinolinic acid to barnyard grass preventive effect < 10%.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within In the scope of protection of the invention.

Claims (11)

1. a kind of preparation method of amorphous state triazole sulphur humulone, which comprises the following steps: stir triazole sulphur humulone Mix dissolution in methylene chloride, in 40-60 DEG C of decompression rotary evaporation of solvent, after through mechanical lapping, obtain amorphous state.
2. the preparation method of amorphous state triazole sulphur humulone according to claim 1, which is characterized in that the temperature is 45-50℃。
3. a kind of amorphous state triazole sulphur humulone being prepared using method as claimed in claim 1 or 2.
4. a kind of weeding complex composition, it is characterised in that: have including amorphous state triazole sulphur humulone as claimed in claim 3 Imitate ingredient and auxiliary agent.
5. weeding complex composition according to claim 4, it is characterised in that: the auxiliary agent is selected from solvent, solid dilutes One of agent, emulsifier, wetting agent, dispersing agent, antifreezing agent, defoaming agent and thickener are a variety of.
6. weeding complex composition according to claim 4, which is characterized in that the composition further include other effectively at Point.
7. weeding complex composition according to claim 6, 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.
8. weeding complex composition according to claim 7, which is characterized in that total matter of effective component in the composition Measuring content is within 75%.
9. weeding complex composition according to claim 8, which is characterized in that total matter of effective component in the composition Measuring content is within 50%.
10. according to weeding complex composition described in claim 4-9 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.
11. weeding described in amorphous state triazole sulphur humulone as claimed in claim 3 or claim 4-10 any one is multiple Application with composition in preventing and kill off paddy field on gramineae weed and part broadleaf weeds.
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CN106977458B (en) * 2017-04-19 2019-08-09 青岛清原化合物有限公司 Amorphous state triazole sulphur humulone 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
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
CN107836452B (en) * 2017-11-09 2021-03-05 青岛清原化合物有限公司 Weeding composition containing triazasulam and application thereof
CN108283180A (en) * 2018-03-22 2018-07-17 合肥红佳科技信息有限公司 A kind of Herbicidal combinations containing dichloroquinoline humulone
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
CN111362913B (en) * 2018-12-25 2021-03-12 青岛清原化合物有限公司 Amorphous-state bicyclopyrone triethanolamine salt and preparation method and application thereof

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