EP3316687A1 - Modification cristalline thermodynamiquement stable de 2-chloro-3-(méthylsulfanyl)-n-(1-méthyl-1h-tétrazol-5-yl)-4-(trifluorométhyl)benzamide - Google Patents

Modification cristalline thermodynamiquement stable de 2-chloro-3-(méthylsulfanyl)-n-(1-méthyl-1h-tétrazol-5-yl)-4-(trifluorométhyl)benzamide

Info

Publication number
EP3316687A1
EP3316687A1 EP16734325.0A EP16734325A EP3316687A1 EP 3316687 A1 EP3316687 A1 EP 3316687A1 EP 16734325 A EP16734325 A EP 16734325A EP 3316687 A1 EP3316687 A1 EP 3316687A1
Authority
EP
European Patent Office
Prior art keywords
benzamide
crystal modification
methyl
methylsulfanyl
tetrazol
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Withdrawn
Application number
EP16734325.0A
Other languages
German (de)
English (en)
Inventor
Hartmut Ahrens
Arnim Köhn
Christian Waldraff
Britta Olenik
Birgit Keil
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
Bayer CropScience AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer CropScience AG filed Critical Bayer CropScience AG
Publication of EP3316687A1 publication Critical patent/EP3316687A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
    • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D257/04—Five-membered rings
    • C07D257/06—Five-membered rings with nitrogen atoms directly attached to the ring carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
    • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D257/04—Five-membered rings
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • 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
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only 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.
  • EP 1 314 724 A1 discloses two crystal structures of the herbicidal active substance sulcotrione.
  • the benzamide known, for example, from WO 2012/028579 A1 (there Example No. 4-638 in Table 4) has herbicidal properties and is suitable for the
  • Benzamide which can be prepared is not suitable for the production of user-friendly administration forms.
  • user-friendly Dosage forms are, for example, suspension formulations in which the benzamide is finely ground in solid form. Practical testing has shown that the benzamide prepared in accordance with the disclosure of WO 2012/028579 A1 in suspension formulations leads to crystal growth and as a result to lumps and precipitations, so that the suspension formulation becomes 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 a thermodynamically metastable and in a thermodynamically stable crystal modification.
  • 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 suspooconcentrates, suspoemulsions and oil dispersions.
  • the benzamide preparable according to the disclosure of WO 2012/028579 A1 has the disadvantage that it works less well, can be filtered and cleaned. This disadvantage is overcome by the provision of the thermodynamically stable benzamide according to the invention.
  • An object of the invention is therefore a thermodynamically stable
  • metastable crystal modification I metastable crystal modification I
  • stable crystal modification II stable crystal modification II
  • the metastable crystal modification I has a characteristic Raman spectrum, which is shown in Figure 1, with the values of the band maxima in wavenumbers given in Table 1.
  • the X-ray powder diffractometry of the metastable crystal modification I shows characteristic peaks which are given in Table 2 for this crystal modification.
  • the accompanying X-ray diffractogram is shown in Figure 3.
  • the stable crystal modification II also exhibits a characteristic Raman spectrum, which is shown in FIG. 2, wherein the values of the band maxima in wavenumbers are also given in Table 1.
  • the X-ray powder diffractometry of the stable crystal modification II shows characteristic peaks for this crystal modification, which are also given in Table 2.
  • the accompanying X-ray diffractogram is shown in Figure 4.
  • 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 of the formula (I) per se can be prepared, for example, by one of the methods mentioned in WO 2012/028579 A1. Depending on the nature of the solvent used in the last purification step and the temperature control, the benzamide usually accumulates in amorphous form, in the form of the metastable crystal modification I described here or in a mixture of the amorphous form and the metastable crystal modification I.
  • thermodynamically stable crystal modification II of the benzamide can be any thermodynamically stable crystal modification II of the benzamide.
  • thermodynamically stable crystal modification II treated at temperatures of 0 ° C to 80 ° C.
  • Another object of the invention is thus a process for the preparation of the thermodynamically stable crystal modification II of the benzamide, wherein the Crystal modification I of the benzamide is suspended in solvents and / or dissolved and treated until the quantitative conversion into the thermodynamically stable crystal modification II at temperatures of 0 ° C to 80 ° C.
  • 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.
  • 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.
  • thermodynamically stable crystal modification II is carried out at temperatures below 100 ° C, preferably at temperatures of 0 ° C to 80 ° C, more preferably at temperatures of 20 ° C to 80 ° C, most preferably at temperatures of 20 ° C. up to 40 ° C.
  • the duration of the conversion depends on the temperature and the type of solvent. Furthermore, the duration of the conversion depends on whether seed crystals of crystal modification II are used. In general, the conversion to the crystal modification II at full dissolution of the crystals of the crystal modifications I at elevated
  • Temperature can be achieved directly 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 ° C, more preferably with a cooling rate of less than 20 ° C.
  • Crystal modifications I can usually be accomplished without the use of seed crystals over a 14 day period. If seed crystals of the crystal modification II are used in the conversion of a suspension, is
  • the obtained crystal of the crystal modification II are finally separated and dried to constant weight for removal of the solvent at room temperature or elevated temperature.
  • the stable crystal modification II can also be obtained by grinding under high pressure from the crystal modification I or the amorphous form.
  • Suitable pressure is a pressure of at least 5 bar.
  • crystal modification II is outstandingly suitable for the preparation of formulations, in particular suspension formulations of crop protection agents.
  • the invention therefore also serves to
  • the invention also includes mixtures of the crystal modification II of the benzamide with the crystal modification I of the benzamide, e.g. those which at any point in the inventive conversion process of the
  • Crystal modifications I occur in the crystal modification II. Preference is given to an active ingredient quality with more than 80% by weight of the crystal modification II of the benzamide, particularly preferably more than 90% by weight, very particularly preferably more than 95% by weight and most preferably more than 98% by weight .-%.
  • the benzamide of the stable crystal modification II is mixed with one or more other herbicides. Such mixtures also benefit from the advantageous properties of the inventive crystal modification II.
  • the stable crystal modification II of 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 rather in dissolved form.
  • the invention therefore also relates to processes for the preparation of
  • Crystal modification II increases the safety of preparations of benzamide and thus reduces the risk of incorrect dosages.
  • the stable crystal modification II of the benzamide can be converted in a known manner into the customary formulations, such as suspension concentrates, colloidal concentrates, dispersible concentrates, emulsifiable concentrates
  • the formulations are prepared, for example, by hiding the stable crystal modification II of the benzamide with solvents and / or carriers, optionally under
  • Auxiliaries such as Penetration aids.
  • 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 II of the benzamide can be worked up, filtered and purified particularly well.
  • the benzamide in the stable crystal modification II shows excellent herbicidal activity against representatives of the group of both monocotyledonous and dicotyledonous plants. Examples include:
  • the invention is therefore also the use of stable
  • Crystal modification II of the benzamide for the preparation of a crop protection agent for the treatment of weed infestation
  • the stable crystal modification II of the benzamide according to the invention is due to its high compatibility with crops to combat
  • 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 produced 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
  • Propagating material such as cuttings, tubers, rhizomes, offshoots and seeds.
  • the treatment according to the invention of the plants and plant parts with the inventive crystal modification II of the benzamide is carried out directly or by acting on their environment, habitat or storage space according to the usual treatment methods, e.g. by dipping, spraying, evaporating, misting, spreading or brushing on.
  • the inventive crystal modification II 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.
  • 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 such 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.
  • aromatics such as xylene, toluene, or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzene
  • Suitable solid carriers are: e.g. Ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite,
  • highly dispersed 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 of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks;
  • 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 carboxymethyl cellulose, natural and synthetic powdery, granular or latex-like polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural
  • Phospholipids such as cephalins and lecithins and synthetic phospholipids.
  • 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 II, preferably between 0.5 and 90%.
  • Kristallmod technik II of benzamide can be used as such or in their formulations in admixture with known herbicides and / or with substances that improve the crop plant compatibility ("safeners") for weed control, ready-made formulations or
  • Weedkillers containing one or more known herbicides and a safener are possible.
  • Acetochlor Acifluorfen (-sodium), Aclonifen, Alachlor, Alloxydim (-sodium),
  • Fluometuron Fluorochloridone, Fluoroglycofen (-ethyl), Flupoxam, Flupropacil, Flurpyrsulfuron (-methyl, -sodium), Flurenol (-butyl), Fluridone, Fluroxypyr (-butoxy-propyl, -meptyl), Flurprimidol, Flurtamone, Fluthiacet (-methyl), Fluthiamide,
  • Suitable safeners for the mixtures are, for example, AD-67, BAS-145138, benoxacor, cloquintocet (-mexyl), cyometrinil,
  • Cyprosulfamides 2,4-D, DKA-24, Dichlormid, Dymron, Fenclorim, Fenchlorazole (- ethyl), Flurazoles, Fluxofenim, Furilazoles, Isoxadifen (-ethyl), MCPA, Mecoprop (-P), Mefenpyr (-diethyl), MG-191, oxabetrinil, PPG-1292, R-29148.
  • active ingredients such as fungicides, insecticides, acaricides, nematicides, bird repellents,
  • Plant nutrients and soil conditioners are possible.
  • inventive crystal modification II 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, e.g. by pouring, spraying, spraying, sprinkling.
  • the inventive crystal modification II 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.
  • transgenic plants and plant cultivars are obtained by genetic engineering methods
  • 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 crops against drought or against water or soil salt content, increased flowering efficiency, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the crop
  • 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 tolerance to high or low temperatures, increased tolerance to dryness or to bottoms salt, increased flowering, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products , higher shelf life and / or workability of the harvested products. More and more
  • Transgenic plants are the major crops, such as cereals (wheat, rice), soybean, potato, cotton, oilseed rape and especially corn and fruit plants (with the fruits apples, pears, citrus fruits and grapes) mentioned, whereby in particular corn, in addition, soy, potato, cotton and oilseed rape
  • Bt plants are produced in the plants (hereinafter “Bt plants”). Traits also highlight the increased resistance of plants to fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and 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 e.g., "PAT” gene.
  • the genes which confer the desired properties can also be identified in
  • Bt plants are v.a. Maize varieties, but also cottons, soya and potato varieties sold under the trade names YIELD GARD® (e.g., corn, cotton, soy), KnockOut® (e.g., corn), StarLink® (e.g., corn),
  • Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato).
  • herbicide tolerant plants are v.a. Maize varieties, but also called cotton varieties and soybean, among the
  • Variant 1 0.1 g of the benzamide prepared according to the methods disclosed in WO 2012/028579 A1 were suspended in 0.5 ml of ethanol: water (1: 1). The suspension is shaken at 25 ° C and stirred for 24 hours at 20 to 25 ° C. Then another 0.5 ml of ethanol: water (1: 1) are added and stirred at 20 to 25 ° C for 8 days. The suspension is filtered and the residue is left open at room temperature until the solvent has evaporated. You get that
  • Variant 2 0.1 g of the benzamide prepared according to the methods disclosed in WO 2012/028579 A1 were suspended in 0.25 ml of toluene. The suspension is shaken at 25 ° C and stirred for 24 hours at 20 to 25 ° C. Then another 0.25 ml of toluene are added and stirred at 20 to 25 ° C for 6 days. Again, another 0.25 ml of toluene are added and stirred at 20 to 25 ° C for 2 days. The
  • An oil dispersion of the benzamide of the crystal modification II shows in comparison to an oil dispersion of the benzamide prepared according to the methods disclosed in WO 2012/028579 A1, even after several weeks of storage, no signs of lumping and precipitation.

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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)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

La présente invention concerne une modification cristalline thermodynamiquement stable du principe actif herbicide 2-chloro-3-(méthylsulfanyl)-N-(1-méthyl-1H-tétrazol-5-yl)-4-(trifluorométhyl)benzamide. Cette modification cristalline thermodynamiquement stable présente des avantages particuliers pour la stabilité de formulations de suspensions.
EP16734325.0A 2015-07-03 2016-06-30 Modification cristalline thermodynamiquement stable de 2-chloro-3-(méthylsulfanyl)-n-(1-méthyl-1h-tétrazol-5-yl)-4-(trifluorométhyl)benzamide Withdrawn EP3316687A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15175168 2015-07-03
PCT/EP2016/065248 WO2017005585A1 (fr) 2015-07-03 2016-06-30 Modification cristalline thermodynamiquement stable de 2-chloro-3-(méthylsulfanyl)-n-(1-méthyl-1h-tétrazol-5-yl)-4-(trifluorométhyl)benzamide

Publications (1)

Publication Number Publication Date
EP3316687A1 true EP3316687A1 (fr) 2018-05-09

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Application Number Title Priority Date Filing Date
EP16734325.0A Withdrawn EP3316687A1 (fr) 2015-07-03 2016-06-30 Modification cristalline thermodynamiquement stable de 2-chloro-3-(méthylsulfanyl)-n-(1-méthyl-1h-tétrazol-5-yl)-4-(trifluorométhyl)benzamide

Country Status (12)

Country Link
US (1) US20180208563A1 (fr)
EP (1) EP3316687A1 (fr)
JP (1) JP2018522870A (fr)
KR (1) KR20180022976A (fr)
CN (1) CN107846885A (fr)
AU (1) AU2016289664A1 (fr)
BR (1) BR112018000094A2 (fr)
CA (1) CA2990983A1 (fr)
EA (1) EA201890207A1 (fr)
MX (1) MX2018000308A (fr)
WO (1) WO2017005585A1 (fr)
ZA (1) ZA201708745B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10457651B2 (en) 2016-10-20 2019-10-29 Bayer Cropscience Aktiengesellschaft Method for producing 3-alkylsulfanyl-2-chloro-N-(1-alkyl-1H-tetrazol-5-yl)-4-trifluoromethyl-benzamides

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EA201992579A1 (ru) * 2017-05-04 2020-04-13 Байер Кропсайенс Акциенгезельшафт 4-дифторметилбензоиламиды с гербицидным действием

Family Cites Families (2)

* Cited by examiner, † Cited by third party
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]
UA109150C2 (xx) 2010-09-01 2015-07-27 Аміди n-(тетразол-5-іл)- або n-(триазол-5-іл)арилкарбонової кислоти та їх застосування як гербіцидів

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10457651B2 (en) 2016-10-20 2019-10-29 Bayer Cropscience Aktiengesellschaft Method for producing 3-alkylsulfanyl-2-chloro-N-(1-alkyl-1H-tetrazol-5-yl)-4-trifluoromethyl-benzamides

Also Published As

Publication number Publication date
MX2018000308A (es) 2018-03-14
BR112018000094A2 (pt) 2018-08-28
KR20180022976A (ko) 2018-03-06
WO2017005585A1 (fr) 2017-01-12
CN107846885A (zh) 2018-03-27
JP2018522870A (ja) 2018-08-16
ZA201708745B (en) 2018-11-28
AU2016289664A1 (en) 2018-01-25
US20180208563A1 (en) 2018-07-26
CA2990983A1 (fr) 2017-01-12
EA201890207A1 (ru) 2018-07-31

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