EP3374351A1 - Modification cristalline thermodynamiquement stable du 2-méthyl-n-(5-méthyl-1,3,4-oxadiazol-2-yl)-3-(méthylsulfonyl)-4-(trifluorométhyl)benzamide - Google Patents
Modification cristalline thermodynamiquement stable du 2-méthyl-n-(5-méthyl-1,3,4-oxadiazol-2-yl)-3-(méthylsulfonyl)-4-(trifluorométhyl)benzamideInfo
- Publication number
- EP3374351A1 EP3374351A1 EP16793815.8A EP16793815A EP3374351A1 EP 3374351 A1 EP3374351 A1 EP 3374351A1 EP 16793815 A EP16793815 A EP 16793815A EP 3374351 A1 EP3374351 A1 EP 3374351A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- methyl
- benzamide
- crystal modification
- modification
- methylsulfonyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
- C07D271/113—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
-
- 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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Definitions
- the invention relates to the technical field of pesticides. More particularly, it relates to various crystal modifications, in particular the
- EP 1 314 724 A1 discloses two crystal structures of the herbicidal active substance sulcotrione.
- the benzamide known, for example, from WO 2012/126932 A1 (there Example No. 2-145 in Table 2) has herbicidal properties and is suitable for the production of crop protection agents which are used for weed control.
- benzamide preparable according to the disclosure of WO 2012/126932 A1 is not suitable for the production of user-friendly administration forms.
- User-friendly administration forms are, for example, suspension formulations in which the benzamide is finely ground in solid form is present.
- the benzamide preparable in accordance with the disclosure of WO 2012/126932 A1 is not suitable for the production of user-friendly administration forms.
- User-friendly administration forms are, for example, suspension formulations in which the benzamide is finely ground in solid form is present.
- the benzamide preparable in accordance with the disclosure of WO 2012/126932 A1 it has been found that the benzamide preparable in accordance with the disclosure of WO 2012/126932 A1
- Suspension formulations lead to crystal growth and as a result to clumping and precipitation, so that the suspension formulation is unusable.
- the crystal growth can occur spontaneously or over a longer period of time and can not be predicted.
- the object of the present invention was to provide a modification of the benzamide which overcomes these disadvantages and is suitable for the preparation of a storage-stable suspension formulation over a relatively long period of time.
- the benzamide occurs in seven crystal modifications, one of which is to be regarded as the thermodynamically stable or most stable one.
- thermodynamically stable crystal modification of the benzamide does not have the abovementioned disadvantages and is therefore particularly suitable for the preparation of suspension formulations such as suspoconcentrates, suspoemulsions and oil dispersions.
- thermodynamically stable benzamide according to the invention has the disadvantage that it works less well, can be filtered, cleaned and wetted with solvents.
- the poorer wettability is particularly observed in solvents such as water and aqueous solvents and thus makes it difficult to prepare suspension formulations.
- thermodynamically stable invention Crystal modification as crystal modification "A” and the others as crystal modifications "B", “C”, “D”, “E”, “F” and “G”.
- Single-crystal X-ray diffraction analysis was determined by using a M18X-HF rotating anode with ⁇ radiation from MACScience Co and a SMART CCD-1000 detector from Bruker-AXS.
- the data were processed with the programs SAINT-NT V 5.0 (data reduction, Bruker-AXS) and SADABS (absorption correction, Bruker-AXS).
- the structure solution and refinement was performed with SHELXTL NT version V5.1.
- the benzamide is usually in amorphous form, in the form of one of the crystal modifications described herein B to G or in a mixture of the amorphous form and the crystal modifications B to G.
- the thermodynamically stable crystal modification A of the benzamide can be
- thermodynamically stable crystal modification A treated at temperatures of 0 ⁇ to the boiling point of the solvent.
- Another object of the invention is thus a process for preparing the thermodynamically stable crystal modification A of the benzamide, wherein the crystal modifications B to G of the benzamide are suspended in solvents and / or dissolved and until the quantitative conversion into the thermodynamically stable
- Suitable solvents which can be used in this process are e.g. lower alcohols such as methanol, ethanol, 2-propanol or ketones such as acetone, 2-butanone, which can also be used in admixture with water.
- lower alcohols or ketones are here referred to those compounds having one to ten carbon atoms, preferably one to five carbon atoms.
- Other suitable solvents are benzene, toluene and chlorobenzene. Preference is given to toluene and mixtures of ethanol and water, more preferably toluene and a mixture of ethanol and water in a ratio of 1: 1.
- the conversion into the thermodynamically stable crystal modification A takes place at temperatures less than 100, preferably at temperatures of from 0 ⁇ to 80 ⁇ , more preferably at temperatures of 20 to 8 0, most preferably at temperatures of 20 ⁇ to 40 ⁇ .
- the duration of the transformation depends on the temperature and the type of solvent. Furthermore, the duration of the conversion depends on whether seed crystals of crystal modification A are used.
- the conversion to crystal modification A at full dissolution of crystals of crystal modifications B to G at elevated temperature can be directly achieved by cooling crystallization to room temperature without the use of seed crystals.
- the cooling to room temperature is preferably carried out with a cooling rate of less than 25 °, particularly preferably with a cooling rate of less 20.
- the conversion of a suspension of crystal modifications A can usually be accomplished without the use of seed crystals over a period of 14 days.
- seed crystals of crystal modification A are used in the conversion of a suspension, a treatment time of 24 to 48 hours is generally sufficient to achieve a quantitative conversion of the crystals into the crystal modification A.
- the resulting crystals of crystal modification A are finally separated and dried to constant weight at room temperature or elevated temperature to remove the solvent.
- the stable crystal modification A can also be obtained by grinding under high pressure from the crystal modifications B to G or the amorphous form.
- Suitable pressure is a pressure of at least 5 bar.
- the crystal modification A is outstandingly suitable for the preparation of formulations, in particular suspension formulations of crop protection agents.
- the invention therefore also pesticides containing the crystal modification A of the benzamide alone or in admixture with excipients and carriers, as well as in admixture with other active ingredients.
- the invention also includes mixtures of the crystal modification A of the benzamide with the crystal modifications B to G of the benzamide, e.g. those which occur at any point of the inventive conversion process of the crystal modifications B to G in the crystal modification A.
- the benzamide of the stable crystal modification A is mixed with one or more other herbicides. Such mixtures also benefit from the advantageous properties of the inventive crystal modification A.
- the stable crystal modification A of the benzamide is generally suitable as starting material for the preparation of any of these benzamide containing crop protection formulations, even if the benzamide is no longer in this form after formulation, but about in dissolved form.
- the invention therefore also relates to processes for the preparation of the benzamide-containing crop protection formulations which use the stable crystal modification A of the benzamide, and to this benzamide-containing crop protection formulations obtained from the stable crystal modification A of the benzamide.
- the stable crystal modification A By using the stable crystal modification A, the safety for preparations of the benzamide is increased, thus reducing the risk of incorrect dosages.
- the stable crystal modification A of the benzamide can be converted in a known manner into the customary formulations, such as suspension concentrates, colloidal concentrates, dispersible concentrates, emulsifiable concentrates
- Compound be present in a concentration of about 0.5 to 90 wt .-% of the total mixture, i. in quantities sufficient to provide the necessary
- the formulations are prepared, for example, by stretching the stable crystal modification A of the benzamide with solvents and / or carriers, optionally using emulsifying and / or dispersing agents, and / or other excipients, e.g.
- the application is carried out in the usual way by contacting the undesired plants and / or their habitat with the active ingredient or its formulation.
- thermodynamically stable crystal modification A of the benzamide can be worked up, filtered and purified particularly well.
- the benzamide in the stable crystal modification A shows excellent herbicidal activity against representatives of the group of both monocotyledonous and dicotyledonous plants. Examples include: Dicotyledonous plants of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea,
- the invention is therefore also the use of stable
- Crystal modification A of the benzamide for the preparation of a plant protection agent for the treatment of weed infestation is due to their high compatibility with crop plants for controlling undesirable plants in crops of, for example, wheat, barley, oats, rye, rice, corn, sugar beet, sugarcane, cotton and soybeans, especially in wheat, barley, oats and Rye, suitable.
- plants and parts of plants can be treated.
- plants are understood as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
- Crop plants can be plants that by conventional breeding and optimization methods or by
- Plant parts are to be understood as meaning all aboveground and subterranean parts and organs of the plants, such as shoot, leaf, flower and root, examples of which include leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, and roots, tubers and rhizomes.
- the plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.
- Treatment methods e.g. by dipping, spraying, evaporating, misting, spreading or brushing on.
- the inventive crystal modification A of the benzamide can, as already stated above, be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates, active substance-impregnated nature - and synthetic substances and Feinstverkapselitch in polymeric materials.
- customary formulations such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates, active substance-impregnated nature - and synthetic substances and Feinstverkapselitch in polymeric materials.
- formulations are prepared in a known manner, for. Example, by mixing the active compounds with extenders, that is liquid solvents and / or solid carriers, optionally with the use of surfactants, emulsifiers and / or dispersants and / or foam-forming agents.
- organic solvents can also be used as auxiliary solvents.
- Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols , as Butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
- Suitable solid carriers are: for example, ammonium salts and natural
- Minerals such as kaolins, clays, talc, chalk, quartz, attapulgite,
- silicic acid, alumina and silicates as solid carriers for granules are suitable: e.g. crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules
- suitable emulsifiers and / or foam formers are: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: e.g. Lignin sulphite liquors and methylcellulose.
- Adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-form polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins and synthetic phospholipids may be used in the formulations.
- Other additives may be mineral and vegetable oils.
- Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and
- Metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
- the formulations generally contain between 0, 1 and 95 percent by weight of the active ingredient in the inventive crystal modification A, preferably between 0.5 and 90%.
- the inventive crystal modification A of the benzamide can be used as such or in their formulations also in admixture with known herbicides and / or with substances which improve the crop plant compatibility ("safeners") for weed control, ready-to-use formulations or tank mixes being possible So also possible mixtures with weedkillers containing one or more known herbicides and a safener.
- Other known safeners which may be used for the mixtures include AD-67, BAS-145138, benoxacor, cloquintocet (-mexyl), cyometrinil, cyprosulfamides, 2,4-D, DKA-24, dichloromide, dymron, fenclorim, fenchlorazole (- ethyl), flurazoles, fluxofenim, furilazoles, isoxadifen (-ethyl), MCPA, mecoprop (-P), mefenpyr (-diethyl), MG-191, oxabetrinil, PPG-1292, R-29148.
- inventive crystal modification A of the benzamide can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules.
- the application is done in the usual way, eg by pouring, spraying, spraying, spreading.
- inventive crystal modification A of the benzamide can be applied both before and after emergence of the plants. It can also be incorporated into the soil before sowing.
- the amount of active ingredient used can vary within a substantial range. It depends essentially on the type of effect desired. In general, the application rates are between 1 g and 1 kg of active ingredient per hectare of soil surface, preferably between 5 g and 500 g per ha.
- Protoplastenfusion obtained plant species and plant varieties and their parts treated.
- transgenic plants and plant cultivars obtained by genetic engineering, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated.
- the term “parts” or “parts of plants” or “plant parts” has been explained above. Particularly preferred
- Plant varieties are understood to be plants having certain traits which have been obtained both by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be varieties, biotypes and genotypes.
- Growth conditions can also be superadditive ("synergistic") effects occur by the treatment according to the invention.
- reduced application rates and / or extensions of the spectrum of action and / or an increase in the effect of the substances and agents that can be used according to the invention - also in combination with other agrochemical active ingredients - better plant growth of crops, increased tolerance of crops against high or low temperatures, increased Tolerance of the crop plants against drought or against water or soil salt content, increased Flowering performance, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher yields
- plants or plant varieties include all plants that received genetic material by the genetic modification, which gives these plants special beneficial properties ("traits"). Examples of such properties are better plant growth, increased
- Crops such as cereals (wheat, rice), soybean, potato, cotton, oilseed rape and especially maize and fruit plants (with the fruits apples, pears, citrus fruits and grapes) mentioned in particular corn, but also soybean, potato, cotton and oilseed rape be highlighted.
- Traits which are particularly emphasized are the increased defense of the plants against insects by toxins which are formed in the plants, in particular those which are produced by the genetic material from Bacillus thuringiensis (for example by the genes CrylA (a), CrylA (b), CrylA (c), CryllA, Cryl IIA, CrylIIB2, Cry9c, Cry2Ab, Cry3Bb and CrylF and combinations thereof) are produced in the plants (hereinafter "Bt plants”).
- Bt plants the increased defense of plants against fungi, bacteria and viruses by systemic acquired are also particularly emphasized
- SAR systemin
- phytoalexins elicitors
- resistance genes correspondingly expressed proteins and toxins.
- Traits which are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones.
- Sulfonylureas, glyphosate or phosphinotricin eg "PAT” gene.
- the genes which confer the desired properties can also be identified in
- Bt plants are v.a. Maize varieties, but also cottons, soybean and potato varieties, which are marketed under the trade names YIELD GARD® (eg corn, cotton, soya), KnockOut® (eg corn), StarLink® (eg corn), Bollgard® (cotton), Nucotn® ( Cotton) and NewLeaf® (potato).
- YIELD GARD® eg corn, cotton, soya
- KnockOut® eg corn
- StarLink® eg corn
- Bollgard® cotton
- Nucotn® Cotton
- NewLeaf® NewLeaf®
- Herbicide-resistant (conventionally grown herbicide-tolerant) plants also include the varieties sold under the name Clearfield® (e.g., corn). Of course, these statements also apply to future or future marketed plant varieties with these or future developed genetic traits.
- benzamide prepared according to the methods disclosed in WO 201 2/126932 A1 were suspended in 0.5 ml of methanol. The suspension is shaken at 25 for a total of 168 hours at intervals of 30 minutes each and left to stand. The benzamide is obtained in the thermodynamically stable
- thermodynamically stable crystal modification A In a first comparative experiment, the thermodynamically stable
- Crystal modification A in contrast to other modifications of this compound when mixed in water after 1 minute already 100% wettability.
- benzamide prepared according to the methods disclosed in WO 201 2/126932 A1 was dissolved in 10 ml of acetone at the boiling point. The solution is then allowed to stand at 23 in a crystallizing dish with a watch glass as cover until the solvent has completely evaporated. The benzamide is obtained in the
- benzamide prepared according to the methods disclosed in WO 201 2/126932 A1 was dissolved in 15 ml of methanol at the boiling point. The solution is then allowed to stand at 5 ° C. in a crystallizing dish with a clock as cover until the solvent has completely evaporated. The benzamide is obtained in the
- 0.1 g of the benzamide prepared according to the methods disclosed in WO 201 2/126932 A1 was dissolved in 15 ml of methanol at the boiling point. After addition of 50 ml of toluene, the solution is allowed to stand in a crystallizing dish with a watch glass as a cover at 23 until the solvent is completely evaporated.
- the benzamide is obtained in the crystal modification G.
- An old dispersion of the benzamide of the crystal modification A shows in comparison to an old dispersion of the benzamide prepared according to the in WO 2012/126932 A1
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- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Medicinal Preparation (AREA)
- Toxicology (AREA)
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP15193615 | 2015-11-09 | ||
PCT/EP2016/076620 WO2017080912A1 (fr) | 2015-11-09 | 2016-11-04 | Modification cristalline thermodynamiquement stable du 2-méthyl-n-(5-méthyl-1,3,4-oxadiazol-2-yl)-3-(méthylsulfonyl)-4-(trifluorométhyl)benzamide |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3374351A1 true EP3374351A1 (fr) | 2018-09-19 |
Family
ID=54541996
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16793815.8A Withdrawn EP3374351A1 (fr) | 2015-11-09 | 2016-11-04 | Modification cristalline thermodynamiquement stable du 2-méthyl-n-(5-méthyl-1,3,4-oxadiazol-2-yl)-3-(méthylsulfonyl)-4-(trifluorométhyl)benzamide |
Country Status (12)
Country | Link |
---|---|
US (1) | US10336716B2 (fr) |
EP (1) | EP3374351A1 (fr) |
JP (1) | JP2018534294A (fr) |
CN (1) | CN108349916A (fr) |
AU (1) | AU2016352566A1 (fr) |
BR (1) | BR112018009386A8 (fr) |
CA (1) | CA3004360A1 (fr) |
EA (1) | EA201891102A1 (fr) |
MX (1) | MX2018005818A (fr) |
UY (1) | UY36982A (fr) |
WO (1) | WO2017080912A1 (fr) |
ZA (1) | ZA201802523B (fr) |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10152459A1 (de) | 2001-10-24 | 2003-05-08 | Bayer Cropscience Ag | Neue thermodynamisch stabile Kristallmodifikation von [2-(2-Chloro-4-mesyl-benzoyl)cyclohexane-1,3-dione] |
ES2588999T3 (es) | 2011-03-22 | 2016-11-08 | Bayer Intellectual Property Gmbh | Amidas del ácido N-(1,3,4-oxadiazol-2-il)arilcarboxílico y su uso como herbicidas |
-
2016
- 2016-11-04 US US15/774,200 patent/US10336716B2/en not_active Expired - Fee Related
- 2016-11-04 MX MX2018005818A patent/MX2018005818A/es unknown
- 2016-11-04 JP JP2018521560A patent/JP2018534294A/ja active Pending
- 2016-11-04 CA CA3004360A patent/CA3004360A1/fr not_active Abandoned
- 2016-11-04 EP EP16793815.8A patent/EP3374351A1/fr not_active Withdrawn
- 2016-11-04 CN CN201680064785.6A patent/CN108349916A/zh active Pending
- 2016-11-04 BR BR112018009386A patent/BR112018009386A8/pt not_active Application Discontinuation
- 2016-11-04 WO PCT/EP2016/076620 patent/WO2017080912A1/fr active Application Filing
- 2016-11-04 AU AU2016352566A patent/AU2016352566A1/en not_active Abandoned
- 2016-11-04 EA EA201891102A patent/EA201891102A1/ru unknown
- 2016-11-10 UY UY0001036982A patent/UY36982A/es not_active Application Discontinuation
-
2018
- 2018-04-17 ZA ZA2018/02523A patent/ZA201802523B/en unknown
Also Published As
Publication number | Publication date |
---|---|
JP2018534294A (ja) | 2018-11-22 |
US20180319754A1 (en) | 2018-11-08 |
WO2017080912A1 (fr) | 2017-05-18 |
AU2016352566A1 (en) | 2018-05-10 |
EA201891102A1 (ru) | 2018-11-30 |
BR112018009386A8 (pt) | 2019-02-26 |
CA3004360A1 (fr) | 2017-05-18 |
UY36982A (es) | 2017-06-30 |
US10336716B2 (en) | 2019-07-02 |
BR112018009386A2 (pt) | 2018-11-13 |
MX2018005818A (es) | 2018-08-01 |
CN108349916A (zh) | 2018-07-31 |
ZA201802523B (en) | 2019-01-30 |
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