CN106977458A - Amorphous state triazole sulphur humulone and its production and use - Google Patents

Amorphous state triazole sulphur humulone and its production and use Download PDF

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Publication number
CN106977458A
CN106977458A CN201710258005.8A CN201710258005A CN106977458A CN 106977458 A CN106977458 A CN 106977458A CN 201710258005 A CN201710258005 A CN 201710258005A CN 106977458 A CN106977458 A CN 106977458A
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triazole sulphur
amorphous state
sulphur humulone
humulone
triazole
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CN106977458B (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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    • 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

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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 field, and in particular to a kind of amorphous state triazole sulphur humulone and its production and use.A kind of amorphous state triazole sulphur humulone, through the detection of X ray powder diffractions is existed in unformed form, does not have sharp diffraction maximum in its X ray powder diffraction, it is preferable that its X-ray powder diffraction pattern is substantially as shown in Figure 2.The amorphous state triazole sulphur humulone of the present invention compares A crystal formations, physical and chemical stability is good, crystal transfer does not occur within being stored two months under 70 DEG C of high temperature, purity is not also reduced substantially, solubility is doubled in water simultaneously, the amorphous state of triazole sulphur humulone and the complex composition with other active ingredients, have extraordinary preventive effect, with good application prospect to rice terrace grassy weed and part broad leaved weed.

Description

Amorphous state triazole sulphur humulone and its production and use
Technical field
The invention belongs to herbicide crystallization processes technical field, and in particular to a kind of amorphous state triazole sulphur humulone 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 105503728B。
Amorphous state is a kind of form that material has polymorphism, is also a kind of special crystal form state.For tool There are the solid drugs of polymorphism, amorphous state is one kind in its a variety of crystal form state, the various reasons of amorphous state medicine Change property and drug effect is generally different from general crystal formation medicine.Therefore, in the polymorphic research of solid drugs, to amorphous state The further investigated of material has important scientific meaning.But because amorphous state is thermodynamic phase system, it is easy to occur crystalline substance Type changes, and this is also the main obstacle for perplexing amorphous state medicine.
Because triazole sulphur humulone is the equal report without its crystal formation in newly developed medicine, current various documents and patent Road, and 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 amorphous state triazole sulphur humulone and its production and use.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, available for rice terrace after seedling management of weeds.
Technical scheme, triazole sulphur humulone is prepared with reference to the method in CN 105503728B.It is wherein specific open , 2.1g (0.005mol) compound as are weighed in 100mL single-necked flasks, add 15mL acetonitriles and 1.0g (0.010mol) three Stirring is opened under the conditions of ethamine, ice-water bath.Weigh 1.0g (0.006mol) 1,3- dimethyl pyrazole -4- formyl chlorides and be dissolved in 10mL second Nitrile 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 knot Shu Hou, adds 100mL water and 100mL ethyl acetate, extracts branch vibration layer, organic layer is with after 100mL saturated common salts water washing 2 times Through anhydrous sodium sulfate drying, revolving removes organic solvent, obtains yellow-brown solid, it is light yellow to obtain 1.5g after being purified through column chromatography 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 or water etc., heating is stirred Mix to being completely dissolved, cooling stands still for crystals or slowly volatilized, dry, obtain A crystal formations.
On the basis of A crystal formations, the amorphous state of triazole sulphur humulone is have studied again.
A kind of amorphous state triazole sulphur humulone, through X-ray powder diffraction detection is existed in unformed form.
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, comprises the following steps：Triazole sulphur humulone stirring and dissolving is existed In dichloromethane, in 40-60 DEG C depressurize rotary evaporation of solvent, preferable temperature be 45-50 DEG C, after through mechanical lapping, obtain nothing Shape state.
A kind of weeding complex composition, including described amorphous state triazole sulphur humulone active ingredient and auxiliary agent.
The auxiliary agent is selected from solvent, solid diluent, emulsifying agent, wetting agent, dispersant, antifreezing agent, defoamer and thickening One or more in agent.
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, Hydroxypropyl cellulose and carboxymethyl cellulose.The thickener of synthesis includes the derivative of aforesaid kind, in addition to polyvinyl alcohol, poly- 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 amorphous state triazole sulphur humulone mixing of the present invention, for example《World pesticide New varieties technology is complete works of》, Scientia Agricultura Sinica technology publishing house, 2010.9 and document incorporated herein in known substance.Example Such as various material (remarks mentioned below：The title of compound, or be the generic name according to International Organization for standardization (ISO) Claim, or be chemical name, there is 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, The careless amine of terbuchlor, xylachlor, dimethachlor, amine of taking to the greenwood, front three ring, clomeprop, propyzamide, valeryl benzene grass The careless amine of amine, card, suffer, the careless amine of three rings match, butenachlor, tebutam, the careless amine of benzyl, quinone duckweed amine, dichlofluanid, naproanilide, second The careless amine of acyl alachlor, quinclorac, fenacet, pyrrole cyanogen, dead many grams of benzene grass, chlorothiamid, chlorine phthalimide, fourth amidine amine, fluorine metazachlor, green bristlegrass Go Tianjin, Simanex, prometryn, cyanatryn, symetryne, ametryn, propazine, dipropetryn, SSH-108, terbutryn, Garagard, three Piperazine benfluralin, cyprazine, proglinazine, trietazine, prometon, Gesadrual, nitrine are net, desmetryn, dimethametryn, the blue or green Tianjin of ring third, Green bristlegrass of going out Tianjin, another Ding Jin, Zhong Dingtong, Te Dingtong, methoxy third net, cyanatryn, ipazine, chlorazine, atraton, weed eradication are logical, radix glycyrrhizae Tianjin, cyanuric acid, Indaziflam, grand green sulphur, 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, AC322140, 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 (promazine Sulfometuron Methyl), piperazine pyrazosulfuron, acifluorfen, fluorine Sulfanilamide (SN) grass ether, lactofen, fluoroglycofen-ethyl, Oxyfluorfen, Mo 9 granular, aclonifen, ethoxyfen-ethyl, first carboxylic weeding The careless ether of ether, fluoroform, chlomethoxyfen, fluorodifen, fluorination nitrofen, the careless ether of fluorine furan, nitrofen, the careless ether of first, diformazan grass The careless ether of ether, fluorine lactazone, AKH7088 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, 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 amorphous state triazole sulphur humulone and one kind or many in the above-mentioned herbicide enumerated Planting 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 azoles humulone.
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 amorphous state triazole sulphur humulone or described weeding complex composition grass family in rice terrace is prevented and kill off is miscellaneous Application on grass and part broad leaved weed.
The amorphous state triazole sulphur humulone of the present invention compares A crystal formations, and physical and chemical stability is good, is stored under 70 DEG C of high temperature Do not occur crystal transfer within two months, purity is not also reduced substantially, while solubility is doubled in water, triazole sulphur humulone Amorphous state and the complex composition with other active ingredients, have non-to rice terrace grassy weed and part broad leaved weed Often good preventive effect, with good application prospect.
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 amorphous state triazole sulphur humulone crystal formation 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, Scanning range：3 ° -40 ° (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
3000 grams of triazole sulphur humulone A crystal formation active compounds are placed in 10L flask, dichloromethane 7L, stirring to raw material is added It is completely dissolved, is heated to 50 DEG C, rotate solvent, mechanical lapping is carried out after evaporating, you can obtains amorphous state triazole sulphur grass The powder of ketone.
Physical and chemical stability is tested
Amorphous state triazole sulphur two kinds of powder of humulone that the triazole sulphur humulone A crystal formations and embodiment 2 that embodiment 1 is obtained are obtained End, it is 95.5% to survey A crystal formations and amorphous state content by HPLC, afterwards, by both powder be respectively placed in 25 DEG C, 40 DEG C, inside 55 DEG C and 70 DEG C of baking ovens, place and carry out within 2 months heat storage experiment, crystal formation type and purity are tested afterwards, as a result be see the table below 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 amorphous state have good stabilization under different temperature conditionss Property, especially under 70 DEG C of higher temperatures, amorphous state still keeps good physical and chemical stability, and crystal formation does not change, Purity detecting is even slightly better than A crystal formations, significant.
Solubility test in water
Amorphous state triazole sulphur two kinds of powder of humulone that the triazole sulphur humulone A crystal formations and embodiment 2 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：
From the result of table 2, the amorphous state of triazole sulphur humulone compares A crystal formations, and solubility has obvious increase.
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 amorphous state triazole sulphur humulone of embodiment 2 13.6
The triazole sulphur humulone A crystal formations of embodiment 1 6.2
Preparation processing and crop field effect experiment
The amorphous state triazole sulphur humulone that the triazole sulphur humulone A crystal formations and embodiment 2 that embodiment 1 is obtained are obtained, will be by According to following formula, corresponding preparation is processed into, specific formula 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
12% triazole sulphur humulone cyhalofop-butyl OD
The emulsifying agent benzene second of 2.5%+6% emulsifying agent calcium dodecyl benzene sulfonate of triazole sulphur+9.5% cyhalofop-butyl of humulone+7% The thickener gas phase of+2.5% thickener organobentonite of+5% emulsifying agent castor oil polyoxyethylene ether of base phenol polyethenoxy ether+2% Method silica+20%200# solvent naphthas+decentralized medium methyl oleate is supplied
8% triazole sulphur humulone SC
The wetting agent AEO+0.25% of 8%+4% dispersant polycarboxylate of triazole sulphur humulone+2% is thickened The defoamer organic silicone oil of+5% antifreezing agent glycerine of+0.5% thickener carboxymethyl cellulose of agent xanthans+0.1%+water is supplied
18% triazole sulphur humulone dichloro quinolinic acid WP
The wetting agent dodecyl of 4%+10% dispersant sodium lignin sulfonate of triazole sulphur+14% dichloro quinolinic acid of humulone+3% The filler of sodium sulphate+10% white carbon+filler kaolin is supplied
12% triazole sulphur humulone isoproturon OD
The emulsifying agent phenethyl phenol of 4%+6% emulsifying agent calcium dodecyl benzene sulfonate of triazole sulphur+8% isoproturon 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+10%200# solvent naphthas+decentralized medium methyl oleate is supplied
28% triazole sulphur humulone propanil OD
The emulsifying agent phenethyl phenol of 3%+6% emulsifying agent calcium dodecyl benzene sulfonate of triazole sulphur+25% propanil 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% The solvent of silicon+20% decyl amide+decentralized medium methyl oleate is supplied
4% triazole sulphur humulone amicarbazone OD
The emulsifying agent benzene second of 2.5%+6% emulsifying agent calcium dodecyl benzene sulfonate of triazole sulphur+1.5% amicarbazone of humulone+7% The thickener vapor phase method of+3% thickener organobentonite of+5% emulsifying agent AEO of base phenol polyethenoxy ether+2% The decentralized medium of silica+10% rapeseed oil+decentralized medium methyl oleate is supplied
34% triazole sulphur humulone pretilachlor ME
The emulsifying agent DBSA of 5%+10% ethanol of triazole sulphur humulone+20% cyclohexanone of+29% pretilachlor+6% The emulsifying agent phenethyl phenol polyethenoxy ether formaldehyde resin condensation product of the emulsifying agent of calcium+12% phenethyl phenol polyethenoxy ether+5%+water Supply
30% triazole sulphur humulone butachlor EC
The emulsifying agent 12 of 3%+20% cyclohexanone+10%N- methyl pyrrolidones of+27% butachlor 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+5% contracts Compound+solvent 100# solvent naphthas are supplied
6% triazole sulphur humulone pyraclonil SC
The ethanol of 4.5%+4% dispersant phenethyl phenol polyethenoxy ether phosphate of+1.5% pyraclonil of triazole sulphur humulone three The thickener carboxymethyl cellulose+5% of+0.25% thickener xanthans of the wetting agent of amine salt+2% neopelex+0.5% The defoamer organic silicone oil of antifreezing agent glycerine+0.1%+water 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
6% triazole sulphur humulone chlorine fluorine pyridine ester EC
The emulsifying agent ten of+10% cyclohexanone+10%N- methyl pyrrolidones of+1% fluorine chloropyridine ester of 5% triazole sulphur humulone+6% The emulsifying agent phenethyl phenol polyethenoxy ether formaldehyde resin of+12% emulsifying agent NPE of dialkyl benzene sulfonic acids calcium+2% Condensation product+solvent 100# solvent naphthas are supplied
30% triazole sulphur humulone bentazone WDG
The wetting agent dodecyl sulphate of 3%+10% dispersant sodium lignin sulfonate of triazole sulphur+27% bentazone of humulone+3% The filler of sodium+10% white carbon+filler kaolin is supplied
7% triazole sulphur humulone mesotrione GR
The dispersant napsylate of 5%+2% wetting agent lauryl sodium sulfate of triazole sulphur+2% mesotrione of humulone+4%- Formaldehyde condensation products+filler diatomite is supplied
20% triazole sulphur humulone anilofos OD
The emulsifying agent phenethyl phenol of 5%+6% emulsifying agent calcium dodecyl benzene sulfonate of triazole sulphur+15% anilofos of humulone+7% The thickener vapor phase method dioxy of+2% thickener organobentonite of the emulsifying agent of APEO+5% AEO+2% SiClx+decentralized medium methyl oleate is supplied
9% triazole sulphur humulone clomazone SE
The dispersant phenethyl phenol polyethenoxy ether phosphate triethanolamine salt of 5%+4% 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
6% triazole sulphur humulone azoles humulone OD
The emulsifying agent phenethyl of 4.5%+6% emulsifying agent calcium dodecyl benzene sulfonate of triazole sulphur+1.5% azoles humulone of humulone+7% The thickener vapor phase method two of+3% thickener organobentonite of the emulsifying agent of phenol polyethenoxy ether+5% AEO+2% Silica+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 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：Barnyard grass has certain resistance, 105g/hm to dichloro quinolinic acid in this experiment2Dichloro quinolinic acid is to barnyard grass preventive 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 amorphous state triazole sulphur humulone, it is characterised in that detect it is in unformed form through X-ray powder diffraction Exist.
2. a kind of amorphous state triazole sulphur humulone according to claim 1, it is characterised in that X-ray powder diffraction collection Above without sharp diffraction maximum, it is preferable that its X-ray powder diffraction pattern is substantially as shown in Figure 2.
3. the preparation method of amorphous state triazole sulphur humulone as claimed in claim 1 or 2, it is characterised in that comprise the following steps： By triazole sulphur humulone stirring and dissolving in dichloromethane, rotary evaporation of solvent is depressurized in 40-60 DEG C, preferable temperature is 45-50 DEG C, After through mechanical lapping, obtain amorphous state.
4. a kind of weeding complex composition, it is characterised in that：Including amorphous state triazole sulphur as claimed in claim 1 or 2 grass Ketone active 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 and diluted One or more in agent, emulsifying agent, wetting agent, dispersant, antifreezing agent, defoamer and thickener.
6. the weeding complex composition according to claim 4 or 5, it is characterised in that the composition also has including other Imitate composition.
7. weeding complex composition according to claim 6, it is characterised in that other described active ingredients are selected from isopropyl Grand, propanil, bentazone, cyhalofop-butyl, butachlor, dichloro quinolinic acid, mesotrione, pyraclonil, bromoxynil octanoate, Yi Evil grass One or more in pine, anilofos and azoles humulone.
8. weeding complex composition according to claim 6, it is characterised in that total matter of active ingredient in the composition It is within 75%, within preferably 50% to measure content.
9. weeding complex composition according to claim 4, it is characterised in that：The formulation of the composition be suspending agent, Dispersible oil-suspending agent, missible oil, microemulsion, granule, suspension emulsion or water dispersible granules.
10. the weeding described in amorphous state triazole sulphur humulone as claimed in claim 1 or 2 or claim 4-9 any one Application of the complex composition in rice terrace is prevented and kill off on grassy weed and part broad leaved weed.
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WO2018192047A1 (en) * 2017-04-19 2018-10-25 青岛清原化合物有限公司 Amorphous triazolesulcotrione, preparation method therefor, and use thereof
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
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
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
CN107836452A (en) * 2017-11-09 2018-03-27 青岛清原化合物有限公司 A herbicidal composition containing triazosulfotrione and its application
WO2019090814A1 (en) * 2017-11-09 2019-05-16 青岛清原化合物有限公司 Weeding composition with triazole sulcotrione and application thereof
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
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
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
WO2020133023A1 (en) * 2018-12-25 2020-07-02 青岛清原化合物有限公司 Amorphous cypyrafluone triethanolamine salt, preparation method therefor and use thereof

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