CN109071463A - New model, the Its Preparation Method And Use of sulfentrazone - Google Patents
New model, the Its Preparation Method And Use of sulfentrazone Download PDFInfo
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- CN109071463A CN109071463A CN201780021722.7A CN201780021722A CN109071463A CN 109071463 A CN109071463 A CN 109071463A CN 201780021722 A CN201780021722 A CN 201780021722A CN 109071463 A CN109071463 A CN 109071463A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
- C07D249/12—Oxygen or sulfur atoms
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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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
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Abstract
The present invention describes novel crystal forms of sulfentrazone and preparation method thereof.Invention further describes the purposes that the analysis and the crystal that are carried out by various analysis to the crystal are used to prepare stable agrochemical formulations.Invention further describes use different solvents for crystal form preparation condition.The novel crystal forms are particularly suitable in Herbicidal combinations and for controlling undesired plant growth.
Description
Cross reference to related applications
This application claims the priority for No. 1608830.4 UK Patent Application submitted on May 19th, 2016, in
Appearance is incorporated herein by reference in their entirety.
Technical field
This disclosure has described N- [2,4- bis- chloro- 5- [4- (difluoromethyl) -4,5- dihydro -3- methyl -5- oxo -
1H-1,2,4- triazol-1-yls] phenyl] Methanesulfonamide (sulfentrazone (sulfentrazone)) crystal form, preparation method
And its purposes in agrochemical formulations.
Background technique
N- [2,4- bis- chloro- 5- [4- (difluoromethyl) -4,5- dihydro -3- methyl -5- oxo -1H-1,2,4- triazole -1-
Base] phenyl] Methanesulfonamide (sulfentrazone) be aryl triazolineone chemicals member.Sulfentrazone is before bud and after bud
Herbicide, and it is highly effective to the nutgrass flatsedge in turfgrass.It is by being referred to as the usual of proporphyrinogen oxidase (PPO) inhibition
Known binding mode controls weeds.The active constituent sulfentrazone is mainly absorbed by root, this can pass through the plant of soil treatment
In rhizome soil place research to identify.Therefore, the plant of soil treatment becomes necrosis and death afterwards at exposure in sunlight,
And the plant tissue of leaf contact leads to dry and necrosis.Sulfentrazone controls annual and perennial nutgrass flatsedge, cool-season grasses
And the broadleaf weeds in established season type, perennial grass.In addition to this, it is also used to from warm season turf and grass
High fox grass and nutgrass flatsedge are removed in ground annual bluegrass.
The molecular formula of sulfentrazone is C11H10Cl2F2N4O3S.Its chemical structure is
Usually by described in No. 4,818,275 United States Patent (USP) (it is incorporated herein by reference for all purposes)
The commercially available sulfentrazone of method production exists with the unformed state that fusing point is 75 DEG C to 78 DEG C.It has been found that place
Be not suitable for being prepared as composition or preparation in the sulfentrazone of unformed state, because it is easy to the direct light in aqueous solution
Solution.Direct photolysis occurs rapidly for the sulfentrazone aqueous solution being exposed in simulation daylight, and half-life period is about 1 to 12 hour.Therefore,
Showing the new model sulfentrazone of improved photolysis stability in aqueous solution to exploitation, there are demands.
Summary of the invention
In order to solve the problems, such as some or all of of existing amorphous forms sulfentrazone, it is prepared for the new of sulfentrazone
Stable crystal form.
In the first aspect, the present invention provides N- [2,4- bis- chloro- 5- [4- (difluoromethyl) -4,5- dihydro -3- methyl -
5- oxo -1H-1,2,4- triazol-1-yls] phenyl] Methanesulfonamide (sulfentrazone) novel crystal forms, referred to as " crystal modification I ",
At least three is presented in the X-ray powder diffraction figure (X-RPD) recorded at 25 DEG C using Cu-K α radiation with any combination in it
Following reflection as 2 θ ± 0.2 degree:
2 θ=6.3 ± 0.2 (1)
2 θ=6.8 ± 0.2 (2)
2 θ=12.1 ± 0.2 (3)
2 θ=17.0 ± 0.2 (4)
2 θ=17.6 ± 0.2 (5)
2 θ=18.5 ± 0.2 (6)
2 θ=19.1 ± 0.2 (7)
2 θ=19.9 ± 0.2 (8)
2 θ=21.6 ± 0.2 (9)
2 θ=22.6 ± 0.2 (10)
2 θ=24.3 ± 0.2 (11)
2 θ=24.6 ± 0.2 (12)
2 θ=28.5 ± 0.2 (13)
2 θ=29.0 ± 0.2 (14)
2 θ=32.2 ± 0.2 (15)
2 θ=34.4 ± 0.2 (16).
In one embodiment, at least 3 in following reflection are presented in crystal modification according to a first aspect of the present invention
A, 4,5,6,7,8 or whole (in any combination):
2 θ=6.3 ± 0.2 (1)
2 θ=6.8 ± 0.2 (2)
2 θ=12.1 ± 0.2 (3)
2 θ=17.0 ± 0.2 (4)
2 θ=18.5 ± 0.2 (6)
2 θ=19.1 ± 0.2 (7)
2 θ=21.6 ± 0.2 (9)
2 θ=24.6 ± 0.2 (12)
2 θ=29.0 ± 0.2 (14).
In second aspect, optionally according to the first aspect of the present invention, the present invention provides sulfentrazone crystal modifications
I is presented on about 3236,1741,1613,1483,1394,1318,1145,1096 and 1056cm-1In one or more waves
Number (cm-1, ± 0.2%) at characteristic group's vibration peak infrared (IR) spectrum.
In a third aspect, optionally according to first or second aspect of the invention, the present invention provides sulfentrazone knots
Brilliant variant I shows 126 DEG C -130 DEG C, optionally 127 DEG C -129 DEG C, optionally further 128 DEG C of fusing point.
In fourth aspect, optionally according to any one of present invention first to the third aspect, the present invention provides first
Sulphur grass amine crystal modification I, present endothermic fusion peak start from 125 DEG C and peak maximum at 128 DEG C, optionally further
Differential scanning calorimetry (DSC) distribution map of melting enthalpy with 73J/g.
In the 5th aspect, optionally according to any one of first to fourth aspect of the present invention, the present invention provides first
Sulphur grass amine crystal modification I is characterized by X-ray powder diffraction figure shown in basically as in Figure 2, and/or by basic
Upper IR spectrum as shown in Figure 1 characterizes to characterize, and/or by DSC Thermogram substantially as shown in Figure 3.
In the 6th aspect, optionally according to any one of first to the 5th aspect of the present invention, the present invention provides first
Sulphur grass amine crystal modification I can be obtained by the substantially method as described in embodiment 2 or 3.
In the 7th aspect, optionally according to any one of first to the 6th aspect of the present invention, the present invention provides first
Sulphur grass amine crystal modification I, can through the invention eighth aspect method obtain.
It is significantly improved it has been found that the sulfentrazone crystal modification I has in terms of its photolysis stability.In addition, hair
It is now compared with the unformed sulfentrazone prepared according to the 4th, 818, No. 275 U.S. Patent Publication content, sulfentrazone crystallization
Variant I is easier to filter, crush or grind, and it was found that the preparation using crystal modification I preparation is steady after long term storage
Fixed.In addition, comparing with unformed state described in the 4th, 818, No. 275 United States Patent (USP), crystal modification I is being exposed to
There is lower propensity for degradation (photodissociation) after light.This allows to prepare commercial formulation such as suspending agent (SC) and water dispersible granules
(WG).For those reasons, crystal modification I is particularly suited for preparation commercial formulation.Due to its high photolysis stability, the methylsulphur
Careless amine crystal modification I assigns its preparation the desired long term storage phase.Therefore, appointing for sulfentrazone crystal modification I can be prepared
What preparation, these preparations will be disclosed in the following.
In eighth aspect, the present invention provides the method for preparing sulfentrazone crystal modification I, this method includes following step
It is rapid:
I) sulfentrazone is dissolved in the mixture of solvent or solvent；
It ii is) sulfentrazone crystal modification I by the compound precipitation of dissolution；And
Iii) the crystal modification I of precipitation and separation.
In an embodiment of eighth aspect present invention, the sulfentrazone in step i) is unformed sulfentrazone.
The method for being used to prepare unformed sulfentrazone is known in the art.Unformed sulfentrazone is with commercial size
It produces and obtainable.It is described in No. 4,818,275 United States Patent (USP) and is used to prepare the especially suitable of unformed sulfentrazone
The method of conjunction.
In an embodiment of eighth aspect present invention, which is selected from: halogenated hydrocarbons is (for example, chlorobenzene, bromobenzene, dichloro
Benzene, benzotrifluoride and trichloro-benzenes), ether is (for example, diethyl ether, ethyl propyl ether, n-butyl ether, methyl phenyl ethers anisole, phenetole, cyclohexyl first
Ether, dimethyl ether, glycol dimethyl ether, diphenyl ether, dipropyl ether, diisopropyl ether, di-n-butyl ether, diisobutyl ether, isoamyl ether, ethylene glycol
Dimethyl ether, isopropyl ether, methyl tertiary butyl ether, tetrahydrofuran, methyltetrahydrofuran, twoAlkane, dichlorodiethyl ether, methyl-four
The polyethers of hydrogen furans, ethylene oxide and/or propylene oxide), Nitrated hydrocarbons are (for example, nitromethane, nitroethane, nitropropane, nitre
Base benzene, chloronitrobenzene and ethylbenzene), aliphatic hydrocarbon, clicyclic hydrocarbon or aromatic hydrocarbon are (for example, pentane, n-hexane, normal heptane, just pungent
Alkane, nonane), cymene, the petroleum distillate that boiling range is 70 DEG C to 190 DEG C, hexamethylene, hexahydrotoluene, petroleum ether, ligroin,
Octane, benzene and dimethylbenzene), ester is (for example, malonate, n-butyl acetate (n-butyl acetate), methyl acetate, ethyl acetate, second
Sour isobutyl ester, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and ethylene carbonate) and fatty alcohol (for example, methanol, second
Alcohol, normal propyl alcohol, isopropanol, n-butanol and tert-pentyl alcohol), mesitylene, metacetone, methyl ethyl ketone, acetonitrile and its mixture.
In an embodiment of eighth aspect present invention, the solvent be selected from dimethylbenzene, benzene, chlorobenzene, dichloro-benzenes, ethylbenzene,
Benzotrifluoride, mesitylene, nitrobenzene, ether, metacetone, methyl ethyl ketone, methanol, ethyl alcohol, isopropanol, acetonitrile or below
Mixture: THF- hexane, ethylacetate-hexane, dichloromethane/hexane, methylene chloride-methanol, THF- water and methanol-water.This
Invention embodiment is also contemplated within the solvent mixture more than 2,3 or 4 kind of component.
In an embodiment of eighth aspect present invention, solvent is selected from or mixtures thereof metacetone, dimethylbenzene.
An embodiment according to a eighth aspect of the present invention, sulfentrazone crystal modification I are prepared in the following manner: being passed through
By unformed sulfentrazone at this below the reflux temperature or reflux temperature that environment temperature is heated to solvent or solvent mixture
Concentrate solution is dissolved into solvent or solvent mixture.It is optionally possible to prepare the concentrate solution under the reflux temperature of solvent.
The concentration of solution depends on solubility of the sulfentrazone in coordinative solvent or solvent mixture.
It, then will be by the concentration homogeneous solution of preparation in such as step (i) in an embodiment of eighth aspect present invention
It is cooled to room temperature or about 0 DEG C to 20 DEG C of temperature, to crystallize out desired crystal form from solvent.Sulfentrazone crystal modification I
Can crystallize out in the following manner: by by or solvent or solvent mixture do not removed to centainly by applying vacuum
Homogeneous solution is concentrated in volume, and is cooled to the reflux temperature of the solvent or solvent mixture or less.
It, can also be by the way that the crystal seed of desired crystal form be added during crystallization in an embodiment of eighth aspect present invention
(it can promote or accelerate to crystallize) generates sulfentrazone crystal modification I into the solution prepared in step (i).
Based on the weight for being used to prepare the sulfentrazone of concentrate solution in step (i), the crystalline substance that is added in the concentrate solution
Kind amount be usually by weight 0.001% to 10%, optionally 0.001% to 2.5%, optionally further 0.005% to
0.5%.Optionally, the boiling point lower than coordinative solvent or solvent mixture at a temperature of, these crystal seeds are added to the concentration
In solution.
In an embodiment of eighth aspect present invention, by general solid component isolation technics, such as filtering, centrifugation or
The sulfentrazone crystal modification I that the precipitating obtained from step (ii) is separated from solution is decanted.Then, isolated solid is used
Solvent washed once or repeatedly.Optionally, it is used to prepare concentration in step (i) by mentioned earlier in the solvent that the washing stage uses
One or more groups of solvent or solvent mixture used in solution are grouped as.According to the solubility of crystal, usually in room temperature
And washed between 0 DEG C using coordinative solvent or solvent mixture, to minimize as far as possible or avoid crystalline material corresponding
Loss in cleaning solvent.In an embodiment of eighth aspect present invention, dissolves and recrystallize sulfentrazone crystal modification
I.Can by any method cleaning solution and/or recrystallisation solvent be concentrated to obtain recyclable solid sulfentrazone.
In the 9th aspect, the present invention provides become comprising sulfentrazone crystallization obtained according to a eighth aspect of the present invention
The crystalline material of body I, it is by weight at least 98% sulfentrazone crystal modification I which, which has content,.
In the tenth aspect, the present invention provides a kind of composition, the composition includes according to the present invention first to the 7th
With the sulfentrazone crystal modification I and at least one auxiliary agent described in any one of the 9th aspect.
In the tenth one side, the present invention provides described in any one of according to the present invention first to the 7th and the 9th aspect
Sulfentrazone crystal modification I or the composition described according to a tenth aspect of the present invention be used for the purposes of Weeds distribution.
In an embodiment of tenth aspect present invention, the amount of sulfentrazone crystal modification I presses the weight of the composition
Meter is less than 90%, less than 75% optionally based on the weight of the composition, optionally further based on the weight of the composition
Less than 60%, about 50% optionally further still is calculated as by the weight of the composition.
It is known in the art for using unformed sulfentrazone as herbicide, and is used with commercial size.It has sent out
Existing, the sulfentrazone crystal modification I is also active in controlling undesirable plant such as weeds.Therefore, known in the art
It is public about the preparation of unformed sulfentrazone and the technology of application sulfentrazone, such as in existing technical literature described above
It opens, the sulfentrazone that the present invention is in crystal modification I can also be applied in a similar fashion.
Therefore, the present invention provides comprising as defined above in the Herbicidal combinations of the sulfentrazone of crystal modification I.
The present invention also provides use sulfentrazone crystal modification I to prepare the group for controlling undesirable plant (such as weeds)
The method for closing object.
The present invention also provides the method for controlling undesired plant growth, this method includes to the plant, plant
Any one of first to the 7th and the 9th aspect institute according to the present invention of part or surrounding plants environment application herbicidally effective amount
The sulfentrazone crystal modification I or the composition described according to a tenth aspect of the present invention stated.Therefore, this is provided for planting
The method that undesired plant is controlled in object, plant part, and/or its ambient enviroment, including the leaf or fruit, plant to plant
The sulfentrazone crystal modification I of the ambient enviroment of object part or plant application herbicidally effective amount.
In an embodiment of tenth aspect present invention, the composition is in the form of the following: suspending agent (SC), Oil-based Suspension
Agent (OD), soluble granule (SG), dispersible agent (DC), missible oil (EC), lotion seed dressing, suspension seed dressing, granule
(GR), fine granule (MG), suspoemulsion (SE) or water dispersible granules (WG).It can be in the known manner using suitable auxiliary agent, load
Body and solvent etc. include normal at these to be similar to mode known to unformed sulfanilamide (SN) humulone for sulfentrazone crystal modification I
In regulation agent.
In an embodiment of tenth aspect present invention, the composition is in the form of suspending agent (SC).
In an embodiment of tenth aspect present invention, the composition is in the form of water dispersible granules (WG).
In an embodiment of tenth aspect present invention, sulfentrazone crystal modification I can be to sufficiently achieve when application
The concentration of required dosage exists when to plant or its position, desirably by based on the weight of total mixture about 1% to about 75%
Concentration exists.For example, using cream if applicable by mixing water, solvent and carrier in sulfentrazone crystal modification I
Agent and/or dispersing agent and/or other auxiliary agents prepare preparation.
By by the sulfentrazone crystal modification I and at least one acceptable auxiliary agent of weeding, such as surfactant, liquid
Body diluent, solid diluent, wetting agent, dispersing agent, thickener, defoaming agent, antifreezing agent, preservative, antioxidant, solid are attached
Agent, inert filler and other formulation ingredients mixed to prepare these preparations.
Surfactant can be ionic or non-ionic emulsifier, dispersing agent or wetting agent.The reality that can be used
Example includes but is not limited to salt, ethylene oxide and the fatty alcohol of the salt of polyacrylic acid, the salt of lignin sulfonic acid, benzene sulfonic acid or naphthalene sulfonic acids
With fatty acid or with the condensation polymer of fatty amine, substituted phenol (especially alkyl phenol), sulfosuccinate ester salt, taurine derivatives
(especially alkyl taurine ester/salt) or polyethoxylated phenol or alcohol phosphate.
Liquid diluent includes but is not limited to water, N, N- dimethylformamide, dimethyl sulfoxide, N- alkyl pyrrolidone, second
Glycol, polypropylene glycol, propylene carbonate, dibasic ester, paraffin, alkylbenzene, alkylnaphthalene, glycerol, glyceryl triacetate, olive oil, castor oil,
Linseed oil, sesame oil, corn oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil and coconut oil, ketone (such as cyclohexanone, 2- heptan
Ketone, isophorone and 4- hydroxy-4-methyl-2-pentanone), acetic acid esters (such as hexyl acetate, heptyl acetate and octyl acetate) and
Alcohol (such as methanol, cyclohexanol, decyl alcohol, benzylalcohol and tetrahydrofurfuryl alcohol) and its mixture.
Solid diluent can be water-soluble or water-insoluble.Water-soluble solid diluent includes but is not limited to salt
Class, such as alkali metal phosphate (such as sodium dihydrogen phosphate), alkali earth metal phosphate, sodium, potassium, magnesium and zinc sulfate, sodium chloride
And potassium chloride, sodium acetate, sodium carbonate and sodium benzoate, and sugar and sugar derivatives such as sorbierite, lactose, sucrose and mannitol.
The example of water insoluble solid diluent includes but is not limited to clay, synthetic silica and diatomite, calcium silicates and magnesium silicate,
Titanium dioxide, aluminium oxide, calcium oxide and zinc oxide and its mixture.
Wetting agent includes but is not limited to alkyl sulphosuccinates, laurate, alkyl sulfate, phosphate, acetylene series two
Alcohol, ethyoxyl fluorinated alohol, ethoxylated silicone, alkylphenol ethoxylate, benzene sulfonate, through alkyl-substituted benzene sulfonate,
Alpha-olefin alkyl sulfonate esters, napsylate, through alkyl-substituted napsylate, napsylate and through alkyl-substituted napsylate
With the condensation product and alcohol ethoxylate and its mixture of formaldehyde.Alkyl naphthalene sulfonic acid ester sodium salt is special to composition of the invention
It is useful.
Dispersing agent includes but is not limited to the sodium salt, calcium salt and ammonium salt of lignin sulfonic acid (optionally by polyethoxylated)；Horse
Come the sodium salt and ammonium salt of acid anhydride copolymer；It is condensed the sodium salt of phenolsulfonic acid；With naphthalene sulfonate-formaldehyde condensation product.Lignin sulfonic acid
Salt such as sodium lignin sulfonate is particularly useful to the present composition.Naphthalene sulfonate-formaldehyde condensation product such as naphthalene sulfonic acids and formaldehyde gather
It closes object and sodium salt is particularly useful to the present composition.
Thickener includes but is not limited to guar gum, pectin, casein, carrageenan, xanthan gum, alginates, Methyl cellulose
Element, hydroxyethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose and its mixture.Synthetic thickening agent includes front classification
Derivative, and there are also polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, various polyethers, their copolymers and poly-
Acrylic acid and their salt and its mixture.Alkyl polyvinylpyrrolidone is particularly useful to the present composition.
Defoaming agent includes can normally all substances for this purpose in agrochemical composition.Suitable defoaming
Agent is known in the art and is commercially available.Particularly preferred defoaming agent is dimethyl silicone polymer and perfluor alkane
The mixture of base phosphoric acid, the silicone antifoams agent that can be such as obtained from GE or Compton (Compton).
Preservative include can normally all substances for this purpose in such agrochemical composition,
It and is also well known in the art.It can be mentioned that suitable example include(come from Beyer Co., Ltd
(Bayer AG)) and(coming from Beyer Co., Ltd).
Antioxidant include can normally all substances for this purpose in agrochemical composition, such as in ability
It is known in domain.It is preferred that Butylated Hydroxytoluene.
Solid adhesive agent includes organic bond, including tackifier, such as cellulose or the cellulose being substituted, in powder,
The natural and synthetic polymer and inorganic binder of particle or form crystal lattice, such as gypsum, silica or cement.
Inert filler includes but is not limited to ground mineral, such as kaolin, aluminium oxide, talcum, chalk, quartz, bumps
Stick stone, montmorillonite and diatomite；Or synthesis ground mineral, such as the silicic acid of high degree of dispersion, aluminium oxide, silicate and calcium phosphate
And calcium monohydrogen phosphate.Suitable inert filler for particle includes for example, natural minerals (such as calcite, Dali for crushing and being classified
Stone, float stone, sepiolite and dolomite) or inorganic and organic abrasive material synthesis particle and organic material particle (such as
Sawdust, cocoanut shell, corncob and tobacco stem).
Other formulation ingredients can be used in the present invention, such as dyestuff, desiccant.These ingredients are those skilled in the art
Known to member.
In an embodiment of tenth aspect present invention, sulfentrazone crystal modification I may be present in preparation neutralize by
These preparations preparation other forms in, and as with other reactive compound (such as attractant, disinfectant, fungicide, mite killings
Agent, nematicide, fungicide, growth regulatory substance, herbicide, safener, fertilizer, semiochemical and other insecticides)
Or exist with the mixture of the reagent for improving plant performance.
It can be with the sulfentrazone crystal modification I of any aspect or embodiment according to the present invention to all plants, plant
Part and its ambient enviroment are handled.Herein, plant is understood to mean that all plant and plant population, such as phase
It hopes and undesirable wild plant or crop plants (including naturally occurring crop plants).Crop plants, which can be, to be passed through
Conventional breeding and optimization method combine the plant obtained by biotechnology and genetic engineering method or by these methods,
Including can with or cannot be by Plant cultivars that plant breeder's rights are protected and genetically modified plants.Plant part should be managed
Solution is all part and the organs above and below the ground for meaning plant, such as bud, leaf, needle, stem, stalk, flower, fructification, fruit, kind
Son, root, stem tuber and rhizome.Further comprise harvested material and trophism and genitality propagation material, such as cutting, block
Stem, separate living tissue, rhizome, offset, seed, single and multiple plant cells and any other plant tissue.
Directly plant, plant part and/or its ambient enviroment can be handled with composition or preparation of the invention,
Or composition or preparation is set to act on its ambient enviroment, habitat or storage space to carry out by conventional treatment method.These
The example of conventional treatment method include impregnate, is sprayed, vaporizes, being atomized, broadcasting sowing, in the case of propagation materials brushing and especially
One or more coatings are applied in the case of seed.
The benefit that the present invention farthest sees is growing when the Herbicidal combinations are applied to following useful plant
Crop in kill weeds when: leguminous plant (such as soybean), oilseed plant (such as sunflower), maize (corn) (including raise
Expect corn, pop corn (pop corn) and corn), cotton, cereal, barley, wheat, rice, oat, potato, beet, cultivation
Train crop (such as banana, fruit tree, rubber tree, nursery tree), liana, citrus, olive, beautification appearance of the city plant (amenity), vegetable
Dish (such as spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato, capsicum, garlic and leek), bush fruit are (such as
Blueberry), raspberry, Cranberry, flax, sorghum, gumbo, peppermint, rheum officinale, peanut spearmint (peanut spearmint), grass
Level ground grass, vine and sugarcane.In the present invention, processed soybeans, sunflower, peanut and sugarcane are particularly advantageous.
Everywhere in the description and claims of this application, the change of word " including (comprise) " and the word
Body (such as " including (comprising and comprises) ") refers to " including but not limited to ", and is not excluded for other parts, adds
Add agent, component, integer or step.In addition, odd number covers plural number, unless the context otherwise requires: particularly, using indefinite hat
In the case where word, unless the context otherwise requires, otherwise specification should be understood to consider plural number and odd number.
The preferred feature of each aspect of the present invention can be as combined described in any other aspect.Other spies of the invention
Sign will become apparent from following embodiment.In general, the present invention extends to this specification (including any appended right is wanted
Sum attached drawing) disclosed in feature any new feature or any new combination.Therefore, unless it is incompatible each other, otherwise, in conjunction with
Feature, integer, property, compound, chemical part or group described in particular aspects of the present invention, embodiment or embodiment are answered
When be interpreted as be suitable for any other aspect described herein, embodiment or embodiment.In addition, unless otherwise indicated, this
Any feature disclosed in text can be replaced by the alternative features for same or like purpose.
When for property reference upper and lower bound, it can also imply and be limited by the combination of any upper limit and any lower limit
A series of values.
In the present specification, unless otherwise indicated, performance refers at ambient conditions, i.e., under atmospheric pressure and about 20
The performance measured at a temperature of DEG C.
Terms used herein " about (about or around) " with numerical quantities or range when being used in combination, it is meant that slightly
It is micro- to be greater than or the slightly smaller than described numerical quantities or range, and for example deviate the numerical quantities or ± the 10% of the endpoints of ranges.
" ambient enviroment " used herein refer to the place of plant growth, the place that the plant propagation material of plant is sowed
Or the place of the plant propagation material of plant will be sowed.
It is (heavy including crystalline material that " precipitating " used herein refers to that solid material (sediment) is settled from liquid solution
Drop), wherein solid material exists with the amount for being greater than its solubility in the amount liquid solution.
Terms used herein " herbicidally effective amount " is such a chemical combination for referring to generate plant growth control effect
The combined amount of object or such compound.Control effect includes all deviations developed naturally with target plant, such as kill,
Development of plants and slow, the leaf of the one or more aspects of growth burn, albinism, dwarfing etc..
Unless otherwise indicated, all percentages are given with weight %.
Detailed description of the invention
The various features and aspect of present invention disclosed herein embodiment can be more clearly understood that by reference to attached drawing,
Attached drawing is intended to illustrate and illustrate and not limit the scope of the present invention, and wherein:
Fig. 1 is infrared (IR) spectrum of sulfentrazone crystal modification I；
Fig. 2 is the X-ray powder diffraction figure (X-RPD) of sulfentrazone crystal modification I；
Fig. 3 is differential scanning calorimetry (DSC) Thermogram of sulfentrazone crystal modification I；
Fig. 4 is the X-ray powder diffraction figure of unformed sulfentrazone.
Specific embodiment
The present invention will be described by following embodiment now, and wherein use following measuring technique, and these realities
Apply the purpose that example is merely to illustrate, and be not intended to be limited to scope of the present disclosure.
All X-ray diffractions are measured using following acquisition parameter in the reflection geometry at 25 DEG C using powder diffractometer
Figure:
| X ' Pert Pro MPD from PANalytical B.V. |
| θ compensates slit and graphite monochromator |
| Copper (K- α) radiation, 40kV, 40mA |
| Step-length: 0.03 degree of 2- θ |
| Gate time: 1.0 seconds |
| Maximum peak intensity: 1705 countings/second |
| Scanning range: 3-60 degree 2- θ |
For the sample of crystallization, 4cm is used-1Resolution and with 16 scanning times measure IR spectrum.It can be by such as Fig. 1
Shown in about 3236,1741,1613,1483,1394,1318,1145,1096 and 1056cm-1In one or more wave numbers
(cm-1, ± 0.2%) at characteristic group's vibration peak identify sulfentrazone crystal modification I.
All IR spectrum are obtained using following acquisition parameter:
All DSC Thermograms are obtained using following acquisition parameter:
Embodiment
Embodiment 1: unformed sulfentrazone (embodiment is prepared according to No. 4,818,275 Disclosure of U.S. patent
13, embodiment 14 and embodiment 15):
1. 1- (5- amino -2,4- dichlorophenyl) -3- methyl -4- difluoromethyl-Δ as intermediate2- 1,2,4- tri-
The preparation of oxazoline -5- ketone (embodiment 13)
Pyruvic acid of the step A- as intermediate, the synthesis of 2,4- dichloro phenylhydrazones
It is molten to stirring of 16.2g (0.07 mole) commercially available 2, the 4- dichloride phenyl hydrazine hydrochloric acid salt in 100ml ethyl alcohol
9.2g (0.11 mole) pyruvic acid in 100ml water is disposably added in liquid.The reaction mixture is stirred 10 minutes and led to
Obtained solid is collected by filtration, the pyruvic acid of 13.5g when obtaining dry, 2,4- dichloro phenylhydrazones, m.p.193 DEG C -194 DEG C.It will
The reaction repeated several times.
1- (2,4- dichlorophenyl) -3- methyl-Δ of the step B- as intermediate2The synthesis of -1,2,4- triazoline -5- ketone
To 13.6g (0.054 mole) pyruvic acid, 2,4- dichloro phenylhydrazones add in the stirred suspension in 100ml toluene
5.5g (0.054 mole) triethylamine.The reaction mixture becomes homogeneous, and adds 14.9g (0.054 mole) triphenyl phosphorus acyl group
Azide.After the completion of addition, which is heated to flowing back, wherein being stirred for 2 hours.By the reaction mixture
It is cooled to environment temperature and is extracted with the 1N aqueous sodium hydroxide of 300ml.By the extract with concentrated hydrochloric acid neutralize and
Solid sediment is collected by filtration.The solid is washed with water and is dried.1- (2,4- dichlorophenyl) -3- methyl-Δ2- 1,
The yield of 2,4- triazoline -5- ketone is 13.0g；m.p.174℃-175℃.By the reaction repeated several times.
1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyl-Δ of the step C- as intermediate2- 1,2,4- triazoles
The synthesis of quinoline -5- ketone
By 16.0g (0.065 mole) 1- (2,4- dichlorophenyl) -3- methyl-Δ2- 1,2,4- triazoline -5- ketone, 7.3g
The agitating solution of (0.13 mole) potassium hydroxide and 10.5g (0.03 mole) tetrabutylammonium bromide in 150ml tetrahydrofuran exists
It is cooling in ice bath, and dichlorodifluoromethane is bubbled into the reaction mixture.It removes ice bath and continues dichlorodifluoromethane
It is bubbled into the reaction mixture until observing its condensation in the dry-ice condenser for be connected to the reaction vessel.Addition is completed
Afterwards, the reaction mixture is stirred at ambient temperature 16 hours.By the powdered potassium hydroxide of other 6.7g (0.12 mole)
It is added in the reaction mixture, and be saturated again with dichlorodifluoromethane.The reaction mixture is stirred two hours so
After be diluted with water.The mixture is extracted with diethyl ether and combined extract is washed with water.Organic layer is done with sodium sulphate
It is dry, and filter.Filtrate is concentrated under reduced pressure, residue is obtained |.This residue is dissolved in methylene chloride and is made it through
Silicagel pad.Eluate is concentrated under reduced pressure, solid residue is obtained.The solid is precipitated from methylene chloride-heptane.1-
(2,4- dichlorophenyl) -3- methyl -4- difluoromethyl-Δ2The yield of -1,2,4- triazoline -5- ketone is 4.1g；m.p.108℃-
110℃.By the reaction repeated several times.
1- (2,4- bis- chloro- 5- the nitrobenzophenone) -3- methyl -4- difluoromethyl-Δ of step D- as intermediate2- 1,2,
The synthesis of 4- triazoline -5- ketone
To 4.0g (0.013 mole) 1- (2,4- dichlorophenyl) -3- methyl -4- difluoromethyl-Δ2- 1,2,4- triazolines-
5- ketone is slowly added 70% nitric acid of 1.2ml (0.015 mole) in the agitating solution in the 20ml concentrated sulfuric acid, while keeping this anti-
Answer mixture temperature at 25 DEG C.After the completion of addition, which is stirred 30 minutes at 25 DEG C, then pours into ice water
In.Obtained solid is collected by filtration.The solid is dissolved in methylene chloride and makes it through silicagel pad.Eluate is subjected to silicon
Plastic column chromatography.Use 1: 1- petroleum ether: methylene chloride is completed to elute.Suitable fraction is merged and is concentrated under reduced pressure.1-
(2,4- bis- chloro- 5- nitrobenzophenone) -3- methyl -4- difluoromethyl-Δ2The yield of -1,2,4- triazoline -5- ketone is 3.0g；
m.p.95℃-97℃.By the reaction repeated several times.
1- (5- amino -2,4- dichlorophenyl) -3- methyl -4- difluoromethyl-Δ of the step E- as intermediate2- 1,2,
The synthesis of 4- triazoline -5- ketone
To keep rate of the reaction mixture temperature lower than 35 DEG C to 2.5g (0.007 mole) 1- (2,4- bis- chloro- 5- nitros
Phenyl) -3- methyl -4- difluoromethyl-Δ2- 1,2,4- triazoline -5- ketone are in the agitating solution in 6ml acetic acid and 60ml water
The powdered iron of 2.5g (0.045 mole) is added batch-wise.After the completion of addition, which is stirred at 25 DEG C to 30 DEG C
Two hours.The reaction mixture is diluted with diethyl ether under stiring, is then filtered by diatomite.With 10% aqueous bicarbonate
The filtrate of stirring is become alkalinity by sodium solution and solid carbonic acid potassium.Organic layer is separated, with three parts of water washings, then uses sodium sulphate
It is dry.The mixture is filtered, and filtrate is concentrated under reduced pressure, obtains residue.The residue is passed through into column layer
Analysis method uses methylene chloride on silica gel: acetone is purified as eluent.Suitable fraction is merged and dense under reduced pressure
Contracting.1- (5- amino -2,4- dichlorophenyl) -3- methyl -4- difluoromethyl-Δ2The yield of -1,2,4- triazoline -5- ketone is
2.0g；m.p.133℃-135℃.By the reaction repeated several times.
1- 2. [2,4- bis- chloro- 5- [bis- (N- methyl sulphonyl) amino] phenyl] -3- methyl -4- difluoromethyl-Δ 2-1,
The preparation of 2,4- triazoline -5- ketone (embodiment 14)
Stir 1.2g (0.004 mole) 1- (5- amino -2,4- dichlorophenyl) -3- methyl -4- difluoromethyl -1,2,4- tri-
The solution of oxazoline -5- ketone and 0.95g (0.009 mole) triethylamine in 15ml methylene chloride, by the solution in ice/acetone bath
It is cooling.To keep rate of the reaction mixture temperature lower than 0 DEG C that 0.97g (0.009 mole) mesyl chloride is added dropwise.Addition needs completely
Want five minutes.After the completion of addition, which is heated up to environment temperature, wherein being stirred for 16 hours.After this,
Reaction mixture is concentrated under reduced pressure, residue is obtained.The residue is used into 50: 1- dichloromethane by silica gel column chromatography
Alkane-acetone is purified as eluent.Suitable fraction is merged and is concentrated under reduced pressure, solid is obtained.By the solid from
It is precipitated in acetone/heptane.1- [2,4- bis- chloro- 5- [bis- (N- methyl sulphonyl) amino] phenyl] -3- methyl -4- difluoromethyl -
The yield of 1,2,4- triazoline -5- ketone is 1.3g；m.p.213℃-214℃.
3. the preparation of sulfentrazone (embodiment 15)
Stir 0.8g (0.002 mole) 1- [2,4- bis- chloro- 5- [bis- (N- methyl sulphonyl) amino] phenyl] -3- methyl -
4- difluoromethyl -1,2, solution of the 4- triazoline -5- ketone in 10ml ethyl alcohol, and add the 0.14g (0.003 in 0.3ml water
Mole) sodium hydroxide.After the completion of addition, which is stirred 15 minutes, is then poured into the water of 100ml.It should
Mixture concentrated hydrochloric acid neutralizes and solid sediment is collected by filtration.N- [2,4- bis- chloro- 5- [4- (difluoromethyl) -4,5-
Dihydro -3- methyl -5- oxo -1H-1,2,4- triazol-1-yls] phenyl] yield of Methanesulfonamide (sulfentrazone) is 0.5g；
m.p.75℃-78℃。
The preparation of sulfentrazone crystal modification I
Crystallization of the embodiment 2- from dimethylbenzene
The unformed sulfentrazone sample (10g) prepared in such as embodiment 1 and dimethylbenzene (60ml) are put into togerther three necks
In round-bottomed flask.Gained slurries are heated to 90 DEG C to obtain homogeneous solution.The homogeneous solution is stirred to 2h at 90 DEG C and is incited somebody to action
Insoluble particles (if any) filtering, and the solution is slowly cooled to 20 DEG C to 25 DEG C.After cooling, microlite is formed,
And resulting Inhomogeneous charge object is stirred 2 hours at 20 DEG C.Then, slurries are filtered and with dimethylbenzene (3ml) at 20 DEG C
Washing.The crystal of filtering is dry at 60 DEG C under vacuum.The purity of gained crystallized product is about 98%, and it was found that recycling
The yield of the product in crystal be about 85%.
The crystal obtained by IR spectroscopic methodology, X-RPD and dsc analysis is the discovery that as shown in Figure 1, Figure 2 and Figure 3 respectively
Sulfentrazone crystal modification I.
The IR spectrum of sulfentrazone shows as shown in Figure 1 about 3235.67,1740.65,1613.45,1482.73,
1393.54,1318.30,1145.46,1095.85 and 1056.05cm-1In one or more wave numbers at functional group's feature vibration
Dynamic peak.
The DSC Thermogram of sulfentrazone, which shows, originates in 125.2 DEG C and heat absorption melting of the maximum peak at 128.3 DEG C
Peak, optionally further with the melting enthalpy of 73.42J/g as shown in Figure 3.
The X-ray powder diffraction figure of crystal shows the reflection in Fig. 2, and value is summarised in table 1.
The X-ray powder diffraction figure of 1. sulfentrazone crystal modification I of table reflects
Crystallization of the embodiment 3- from metacetone
Sulfentrazone (5g) sample prepared in such as embodiment 1 and metacetone (35ml) are put into togerther three neck round bottoms to burn
In bottle.Gained slurries are heated to 80 DEG C to obtain homogeneous solution.Gained hot solution is stirred to 2h at 80 DEG C and by insoluble
Grain (if any) filtering, and the solution is slowly cooled to 20 DEG C.After cooling, microlite is formed, and gained is non-
Matter mixture stirs 2 hours at 20 DEG C.Then, slurries are filtered, is washed at 20 DEG C with metacetone (3ml), and true
It is dry at 50 DEG C under sky.The purity of gained crystallized product is about 98%, and it was found that recycling yield is about 85%.
It is sulfentrazone by crystal characterization using IR spectroscopic methodology, X-ray powder diffraction and DSC as described in example 2 above
Crystal modification I.
The preparation of the unformed sulfentrazone suspending agent (SC) of embodiment 4-
The all components uniformly listed in mixing the following table 2, and it is (fragrant public by Willie A. Bach with promise mill (Dyno-Mill) is worn
Take charge of (Willy A.Bachofen AG) production) grinding gained mixture, to obtain suspending agent.
Table 2-SC preparation
The preparation of embodiment 5- sulfentrazone crystal modification I suspending agent (SC)
The all components uniformly listed in mixing the following table 3, and grinding (is produced) by Willie A. Bach's sweet smell company with promise mill is worn
Gained mixture, to obtain suspending agent.
Table 3-SC preparation
The preparation of the unformed sulfentrazone water dispersible granules (WG) of embodiment 6-
The all components listed in the following table 4 are mixed in high speed rotation grinding machine, is blended and grinds.Add enough water with
Obtain extrudable paste.Paste is extruded to form extrudate by mold or sieve.By wet extrudate in vacuum drying oven
It is dry at 70 DEG C, and then screened by 0.71mm to 2mm sieve, to obtain product granula.
Table 4-WG preparation
The preparation of embodiment 7- sulfentrazone crystal modification I water dispersible granules (WG)
The all components listed in the following table 5 are mixed in high speed rotation grinding machine, is blended and grinds.Add enough water with
Obtain extrudable paste.Paste is extruded to form extrudate by mold or sieve.By wet extrudate in vacuum drying oven
It is dry at 70 DEG C, and then screened by 0.71mm to 2mm sieve, to obtain product granula.
Table 5-WG preparation
The test of embodiment 8- photolysis stability
By the sulfentrazone sample dispersion that will be prepared in embodiment 4 to 7 in water to generate based on sulfentrazone weight
25% concentration carries out the test.Sulfentrazone suspension obtained by the 20mL of every kind of sample is added in quartz ampoule.In room
Under temperature, with the UV light Continuous irradiation pipe from UV lamp.The equal part of every part of suspension is taken out from the pipe with 20 minutes intervals
Sample is for analyzing.Each aliquot is determined by the high pressure liquid chromatography (HPLC) (HPLC) with reversed phase chromatography column and UV detection
The concentration of middle sulfentrazone.The test is repeated 5 times to ensure accuracy.
As a result it is summarized in the following table 6.
Table 6- photolysis stability test result
Surprisingly it has been found that being obtained in embodiment 5 and 7 compared with the unformed sulfentrazone product of embodiment 4 and 6
Crystallization sulfentrazone crystal modification I show very high photolysis stability.That is, in these violent test conditions
Under after sixty minutes, the few decomposition of embodiment 5 and 7 (include sulfentrazone crystal modification I) display.In contrast, 4 He of embodiment
The concentration of sulfentrazone (including unformed sulfentrazone) in 6 has halved.
Claims (23)
1. a kind of N- [2,4- bis- chloro- 5- [4- (difluoromethyl) -4,5- dihydro -3- methyl -5- oxo -1H-1,2,4- triazole -1-
Base] phenyl] Methanesulfonamide (sulfentrazone) crystal modification I, the X-ray powder recorded at 25 DEG C is being radiated using Cu-K α
The following reflection of at least three as 2 θ ± 0.2 degree is presented using any combination in last diffraction pattern (X-RPD):
2 θ=6.3 ± 0.2 (1)
2 θ=6.8 ± 0.2 (2)
2 θ=12.1 ± 0.2 (3)
2 θ=17.0 ± 0.2 (4)
2 θ=17.6 ± 0.2 (5)
2 θ=18.5 ± 0.2 (6)
2 θ=19.1 ± 0.2 (7)
2 θ=19.9 ± 0.2 (8)
2 θ=21.6 ± 0.2 (9)
2 θ=22.6 ± 0.2 (10)
2 θ=24.3 ± 0.2 (11)
2 θ=24.6 ± 0.2 (12)
2 θ=28.5 ± 0.2 (13)
2 θ=29.0 ± 0.2 (14)
2 θ=32.2 ± 0.2 (15)
2 θ=34.4 ± 0.2 (16).
2. sulfentrazone crystal modification I as described in claim 1 is radiating the X-ray recorded at 25 DEG C using Cu-K α
At least three in following reflection is presented with any combination in powder diagram:
2 θ=6.3 ± 0.2 (1)
2 θ=6.8 ± 0.2 (2)
2 θ=12.1 ± 0.2 (3)
2 θ=17.0 ± 0.2 (4)
2 θ=18.5 ± 0.2 (6)
2 θ=19.1 ± 0.2 (7)
2 θ=21.6 ± 0.2 (9)
2 θ=24.6 ± 0.2 (12)
2 θ=29.0 ± 0.2 (14).
3. sulfentrazone crystal modification I as claimed in claim 1 or 2, show about 3236,1741,1613,1483,
1394,1318,1145,1096 and 1056cm-1In one or more wave number (cm-1, ± 0.2%) at have characteristic group
The IR spectrum of vibration peak.
4. sulfentrazone crystal modification I as claimed any one in claims 1 to 3, show 126 DEG C to 130 DEG C, preferably
127 DEG C to 129 DEG C, further preferred 128 DEG C of fusing point.
5. sulfentrazone crystal modification I according to any one of claims 1 to 4 is presented endothermic fusion peak and starts from 125
DEG C and maximum peak at 128 DEG C, further preferably with 73J/g melting enthalpy differential scanning calorimetry (DSC) distribution map.
6. the sulfentrazone crystal modification I as described in any one of claims 1 to 5, shown in basically as in Figure 2
X-ray powder diffraction figure characterizes to characterize, and/or by IR spectrum substantially as shown in Figure 1, and/or by basic
DSC Thermogram as shown in Figure 3 is gone up to characterize.
7. such as sulfentrazone crystal modification I described in any one of claims 1 to 6, can by substantially such as embodiment 2 or
Method described in 3 obtains.
8. the sulfentrazone crystal modification I as described in any one of claims 1 to 7, can be by such as claim 9 to 14
Described in any item methods obtain.
9. a kind of method for preparing the sulfentrazone crystal modification I as described in any one of claims 1 to 5, this method includes:
I) sulfentrazone is dissolved in the mixture of solvent or solvent；
It ii is) sulfentrazone crystal modification I by the compound precipitation of dissolution；And
Iii) the crystal modification I of precipitation and separation.
10. method as claimed in claim 9, wherein the sulfentrazone in step i) is unformed sulfentrazone.
11. the method as described in claim 9 or 10, wherein the solvent be selected from dimethylbenzene, benzene, chlorobenzene, dichloro-benzenes, ethylbenzene,
Benzotrifluoride, mesitylene, nitrobenzene, ether, metacetone, methyl ethyl ketone, methanol, ethyl alcohol, isopropanol, acetonitrile or below
Mixture: THF- hexane, ethylacetate-hexane, dichloromethane/hexane, methylene chloride-methanol, THF- water and methanol-water, and
Its mixture.
12. the method as described in any one of claim 9 to 11, wherein the solvent include metacetone, dimethylbenzene or its
Mixture.
13. the method as described in any one of claim 9 to 12, wherein step ii) include concentrate solution and/or cooling and/
Or addition reduces the solvent of solubility and/or the crystal seed of the addition sulfentrazone crystal modification I.
14. method as claimed in claim 13, wherein step ii) it is realized by being cooled to about 0 DEG C to 20 DEG C.
15. a kind of crystalline material, it includes the sulfentrazone crystal modification I obtained according to any one of preceding claims, and
And the content of the sulfentrazone crystal modification I with by weight at least 98%.
16. a kind of composition, it includes as described in claim 1 to 8 and 15 sulfentrazone crystal modification I and at least one help
Agent.
17. composition as claimed in claim 16, wherein the auxiliary agent is selected from surfactant, diluent, wetting agent, dispersion
Agent, thickener, defoaming agent, antifreezing agent, preservative, antioxidant, solid adhesive agent, inert filler and its mixture.
18. composition as claimed in claim 17, wherein the composition can also include dyestuff and/or desiccant.
19. the composition as described in any one of claim 16 to 18, the composition are in the form of the following: suspending agent (SC), oil
Base suspending agent (OD), soluble granule (SG), dispersible agent (DC), missible oil (EC), lotion seed dressing, suspension seed dressing,
Granula (GR), fine granule (MG), suspoemulsion (SE) or water dispersible granules (WG).
20. composition as claimed in claim 19, the composition is in the form of suspending agent (SC) or water dispersible granules (WG).
21. a kind of method for controlling undesired plant growth comprising to the plant, plant part or the plant
Ambient enviroment application herbicidally effective amount the sulfentrazone crystal modification I as described in any one of claim 1 to 8 and 15,
Or the composition as described in any one of claim 16 to 20.
22. one kind sulfentrazone crystal modification I or such as claim 16 to 20 as described in any one of claim 1 to 8 and 15
Any one of described in composition be used for Weeds distribution purposes.
23. such as sulfentrazone crystal modification I described in any item of the claim 1 to 8, substantially such as above with reference to implementation
It is any described in example, attached drawing or specification.
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| GB1608830.4 | 2016-05-19 | ||
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| CN114044758A (en) * | 2021-11-08 | 2022-02-15 | 浙大宁波理工学院 | Synthesis method of intermediate for preparing triazolinone herbicide sulfentrazone |
| CN114181162A (en) * | 2021-11-08 | 2022-03-15 | 浙大宁波理工学院 | Preparation method of sulcarfentrazone-ethyl |
| CN114644599A (en) * | 2020-12-18 | 2022-06-21 | 南京理工大学 | Micro-reaction method for synthesizing phenyl tetra-substituted triazolinone herbicide intermediate by one-step nitration |
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| CA3175956A1 (en) * | 2020-03-20 | 2021-09-23 | Upl Limited | An agrochemical composition |
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| BR112017024524A2 (en) | 2018-07-24 |
| GB201608830D0 (en) | 2016-07-06 |
| CN109071463B (en) | 2022-04-29 |
| GB2550399A (en) | 2017-11-22 |
| WO2017197909A1 (en) | 2017-11-23 |
| TW201741289A (en) | 2017-12-01 |
| GB2550399B (en) | 2022-06-22 |
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