CN109071463A

CN109071463A - New model, the Its Preparation Method And Use of sulfentrazone

Info

Publication number: CN109071463A
Application number: CN201780021722.7A
Authority: CN
Inventors: 詹姆斯·蒂莫西·布里斯托
Original assignee: Jiangsu Rotam Chemical Co Ltd
Current assignee: Jiangsu Rotam Chemical Co Ltd
Priority date: 2016-05-19
Filing date: 2017-01-06
Publication date: 2018-12-21
Anticipated expiration: 2037-01-06
Also published as: GB201608830D0; GB2550399A; GB2550399B; TW201741289A; WO2017197909A1; TWI735574B; BR112017024524A2; CN109071463B

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

New model, the Its Preparation Method And Use of sulfentrazone

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

1. A N-[2,4-dichloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4 -Triazol-1-yl]phenyl]methanesulfonamide (sulfentrazone) crystalline modification I, which in the X-ray powder diffraction pattern (X-RPD) recorded at 25 ° C using Cu-Kα radiation as Any combination presents at least 3 of the following reflections as 2θ ± 0.2 degrees:

2θ＝6.3±0.2 (1)

2θ＝6.8±0.2 (2)

2θ＝12.1±0.2 (3)

2θ＝17.0±0.2 (4)

2θ＝17.6±0.2 (5)

2θ＝18.5±0.2 (6)

2θ＝19.1±0.2 (7)

2θ＝19.9±0.2 (8)

2θ＝21.6±0.2 (9)

2θ＝22.6±0.2 (10)

2θ＝24.3±0.2 (11)

2θ＝24.6±0.2 (12)

2θ＝28.5±0.2 (13)

2θ＝29.0±0.2 (14)

2θ＝32.2±0.2 (15)

2θ=34.4±0.2 (16).

2. Sulfentrazone crystalline modification I as claimed in claim 1 , which exhibits in any combination at least 3 of the following reflections in an X-ray powder diffraction pattern recorded with Cu-Kα radiation at 25° C.:

2θ＝6.3±0.2 (1)

2θ＝6.8±0.2 (2)

2θ＝12.1±0.2 (3)

2θ＝17.0±0.2 (4)

2θ＝18.5±0.2 (6)

2θ＝19.1±0.2 (7)

2θ＝21.6±0.2 (9)

2θ＝24.6±0.2 (12)

2θ=29.0±0.2 (14).

3. Sulfentrazone crystalline modification I as claimed in claim 1 or 2, which exhibits one or more ^of IR spectrum with characteristic functional group vibration peaks at wavenumber (cm ^-1 , ±0.2%).

4. Sulfentrazone crystalline modification I according to any one of claims 1 to 3, which exhibits a melting point of 126°C to 130°C, preferably 127°C to 129°C, further preferably 128°C.

5. Sulfentrazone crystalline modification I according to any one of claims 1 to 4, which exhibits an endothermic melting peak starting at 125° C. and a maximum peak at 128° C., further preferably having a melting of 73 J/g Differential scanning calorimetry (DSC) profile of enthalpy.

6. Sulfentrazone crystalline modification I as claimed in any one of claims 1 to 5, which is characterized by an X-ray powder diffraction pattern substantially as shown in Figure 2, and/or by substantially as characterized by an IR spectrum as shown in FIG. 1 , and/or by a DSC thermogram substantially as shown in FIG. 3 .

7. Sulfentrazone crystalline modification I according to any one of claims 1 to 6, obtainable by a method substantially as described in example 2 or 3.

8. Sulfentrazone crystalline modification I according to any one of claims 1 to 7, obtainable by a method according to any one of claims 9 to 14.

9. A method for preparing crystalline modification I of sulfentrazone according to any one of claims 1 to 5, the method comprising:

i) dissolving sulfentrazone in a solvent or a mixture of solvents;

ii) Precipitating the dissolved compound as crystalline modification I of sulfentrazone; and

iii) Isolation of the precipitated crystalline modification I.

10. The method of claim 9, wherein the sulfentrazone in step i) is amorphous sulfentrazone.

11. The method as claimed in claim 9 or 10, wherein the solvent is selected from the group consisting of xylene, benzene, chlorobenzene, dichlorobenzene, ethylbenzene, trifluorotoluene, mesitylene, nitrobenzene, ether, diethylbenzene ketone, methyl ethyl ketone, methanol, ethanol, isopropanol, acetonitrile or mixtures of the following: THF-hexane, ethyl acetate-hexane, dichloromethane-hexane, dichloromethane-methanol, THF- Water and methanol-water, and mixtures thereof.

12. The method of any one of claims 9 to 11, wherein the solvent comprises diethyl ketone, xylene, or mixtures thereof.

13. The method according to any one of claims 9 to 12, wherein step ii) comprises concentrating the solution and/or cooling and/or adding a solubility-reducing solvent and/or adding the crystalline modification I of sulfentrazone of seed crystals.

14. The method of claim 13, wherein step ii) is accomplished by cooling to about 0°C to 20°C.

15. A crystalline material comprising crystalline modification I of sulfentrazone obtained according to any one of the preceding claims and having a content of crystalline modification I of sulfentrazone of at least 98% by weight.

16. A composition comprising crystalline modification I of sulfentrazone as claimed in claims 1 to 8 and 15 and at least one auxiliary.

17. compositions as claimed in claim 16, wherein said auxiliary agent is selected from surfactant, diluent, wetting agent, dispersant, thickener, defoamer, antifreeze, preservative, antioxidant, Solid binders, inert fillers and mixtures thereof.

18. The composition of claim 17, wherein the composition may further comprise a dye and/or a drying agent.

19. The composition according to any one of claims 16 to 18 in the form of a suspension concentrate (SC), an oily suspension concentrate (OD), a soluble granule (SG), a dispersible liquid (DC), emulsifiable concentrate (EC), emulsion seed dressing, suspension seed dressing, granule (GR), microgranule (MG), suspoemulsion (SE) or water dispersible granule (WG).

20. The composition according to claim 19, in the form of a suspension concentrate (SC) or a water-dispersible granule (WG).

21. A method for controlling unwanted vegetation comprising applying a herbicidally effective amount of any one of claims 1 to 8 and 15 to said plant, plant part or the surrounding environment of said plant. Sulfentrazone crystalline modification I, or the composition as claimed in any one of claims 16-20.

22. Use of the crystalline modification I of sulfentrazone according to any one of claims 1 to 8 and 15, or the composition according to any one of claims 16 to 20, for weed control.

23. The crystalline modification I of sulfentrazone according to any one of claims 1 to 8, which is substantially as described above with reference to any one of the examples, figures or description.